Flame-retardant polycarbonate resin composition and molded article thereof

Abstract

To provide a flame-retardant polycarbonate resin composition with excellent impact strength, flame retardancy and durability, and a molding thereof.SOLUTION: A flame-retardant polycarbonate resin composition contains, based on (A) a polycarbonate resin (A component) 100 pts.wt., (B) a polyorganosiloxane-containing graft copolymer (B component) 1-20 pts.wt., (C) a phosphazene containing at least 98.5 mol% of a phosphazene cyclic trimer (C component) 1-30 pts.wt., and (D) a drip inhibitor (D component) 0.05-2 pts.wt.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a flame-retardant polycarbonate resin composition and its molded articles. More specifically, the present invention relates to a flame-retardant polycarbonate resin composition and its molded articles that are excellent in impact strength, flame retardancy, and durability, obtained by adding a polycarbonate resin, a polyorganosiloxane-containing graft copolymer, a phosphazene containing 98.5 mol% or more of a phosphazene cyclic trimer, and a drip inhibitor. [Background technology]

[0002] Polycarbonate resin is used in many applications such as machine parts, automotive parts, electrical and electronic components, and office equipment parts due to its excellent properties such as mechanical strength, dimensional stability, and flame retardancy. However, enclosures used outdoors, such as outdoor electrical and electronic storage boxes for information and communication boxes, and junction boxes for solar power generation, require thin-walled flame retardancy, high impact resistance in low-temperature winter environments, and durability that resists degradation even when exposed to ultraviolet rays and wind and rain, as exemplified by the UL746C f1 rating certification. Conventional polycarbonate resins do not provide sufficient performance to meet these requirements.

[0003] Conventionally, in flame-retardant polycarbonate resins, it was common to use halogen-based flame retardants containing bromine atoms and other elements in combination with flame-retardant additives such as antimony trioxide. However, due to the problem of harmful substances being generated during combustion, there has been a growing interest in flame retardation methods that do not contain halogen compounds. For example, a method has been proposed in which polycarbonate resin is combined with a silicone / acrylic composite rubber graft copolymer, a phosphate ester-based flame retardant, and polytetrafluoroethylene as a drip-preventing agent (Patent Documents 1 and 2). On the other hand, in recent years, the ability to maintain performance over long-term use has become extremely important from the perspectives of product safety, reducing environmental impact by extending product lifespan, and manufacturer product warranties.

[0004] However, polycarbonate resin compositions containing these phosphate ester-based flame retardants have problems in that, in addition to insufficient heat resistance during long-term use, the incorporated phosphate ester-based flame retardants undergo hydrolysis, and the decomposition products accelerate the hydrolysis of the carbonate bonds in the polycarbonate resin, resulting in a significant decrease in properties such as impact strength and flame retardancy.

[0005] To solve these problems, for example, a method of compounding a rubber-modified graft polymer, a cyclic phenoxyphosphazene, and polytetrafluoroethylene with a polycarbonate resin has been proposed (Patent Document 3), and a resin composition containing a phosphazene and polytetrafluoroethylene, in which a phosphazene cyclic trimer is contained in an amount of 98.5 mol% or more, has been proposed (Patent Document 4).

[0006] In recent years, resin compositions containing impact modifiers in polycarbonate resins have been required to have durability that resists degradation even when exposed to ultraviolet rays and wind and rain, as exemplified by the UL746C f1 rating certification, in addition to heat resistance, due to the diversification of usage environments including indoors and outdoors, and the improvement of the utilization rate of recycled materials through closed recycling.

[0007] However, the conventional polycarbonate resin compositions containing impact modifiers described above did not adequately suppress the decrease in impact strength and flame retardancy after water exposure tests in the UL746C f1 rating certification. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2009-7487 [Patent Document 2] Japanese Patent Application Publication No. 11-21441 [Patent Document 3] Special Publication No. 2021-507053 [Patent Document 4] International Publication No. 2020 / 066535 [Overview of the project] [Problems that the invention aims to solve]

[0009] In view of the above, the object of the present invention is to provide a flame-retardant polycarbonate resin composition that is excellent in impact strength, flame retardancy, and durability. [Means for solving the problem]

[0010] The inventors conducted diligent research to solve the above problems and, as a result, discovered that a resin composition containing polycarbonate resin, a polyorganosiloxane-containing graft polymer, a phosphazene containing 98.5 mol% or more of a phosphazene cyclic trimer, and a drip inhibitor results in a flame-retardant polycarbonate resin composition with excellent impact strength, flame retardancy, and durability, thus completing the present invention. According to the present invention, the above problems are solved by the following items 1 to 6.

[0011] 1. A flame-retardant polycarbonate resin composition characterized by containing (A) 100 parts by weight of polycarbonate resin (component A), (B) 1 to 20 parts by weight of polyorganosiloxane-containing graft copolymer (component B), (C) 1 to 30 parts by weight of phosphazene (component C) containing 98.5 mol% or more of phosphazene cyclic trimer, and (D) 0.05 to 2 parts by weight of drip inhibitor (component D). 2. The flame-retardant polycarbonate resin composition according to item 1 above, wherein component A is an aromatic polycarbonate resin composed of a carbonate constituent unit (a-1) represented by the following formula (1) (excluding the following formula (3)) and a carbonate constituent unit (a-2) represented by the following formula (3), and the proportion of constituent unit (a-2) in the total constituent units is 5 mol% or more.

[0012] [ka]

[0013] (In the above equation (1), R 1 and R 2Each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. a and b 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 formula (2).)

[0014] [Chemical formula]

[0015] (In the above formula (2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. c is an integer of 1 to 10, and d is an integer of 4 to 7.)

[0016] [ka]

[0017] (In the above equation (3), R 1 and R 2 Each of these independently represents a group selected from an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted aralkyl group having 7 to 15 carbon atoms. 3 and R 4 Each of these independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, an optionally substituted aralkyl group having 7 to 15 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups of each type, they may be the same or different. a and b are natural numbers from 1 to 3, and W is at least one group selected from the group consisting of a single bond or a group represented by formula (2) above.

[0018] 3. The flame-retardant polycarbonate resin composition according to item 1 or 2 above, wherein component (B) is a silicone / acrylic composite rubber graft copolymer in which a vinyl polymer composed of one or more vinyl monomer units is grafted onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth)acrylate. 4. A flame-retardant polycarbonate resin composition according to any one of items 1 to 3 above, wherein the total amount of sodium ions and potassium ions contained in the resin composition is 1 to 40 ppm. 5. A flame-retardant polycarbonate resin composition according to any one of items 1 to 4 above, wherein component A is recycled polycarbonate resin. 6. A molded article obtained by molding any of the resin compositions described in item 1 to 5 above. [Effects of the Invention]

[0019] The flame-retardant polycarbonate resin composition of the present invention satisfies high levels of impact strength, flame retardancy, and durability, making it widely useful in various fields such as housing equipment, building materials, consumer goods, infrastructure equipment, automobiles, office automation / enterprise environment (OA / EE) applications, and other fields, and is particularly useful in outdoor applications where durability is required. Therefore, the industrial effects of the present invention are extremely significant. [Modes for carrying out the invention]

[0020] The details of the present invention will be described below.

[0021] (Component A: Polycarbonate resin) The polycarbonate resin used in the present invention is obtained by reacting a divalent phenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds.

[0022] 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.

[0023] In this invention, in addition to bisphenol A-based polycarbonates, which are general-purpose polycarbonates, it is also possible to use special polycarbonates manufactured using other divalent phenols as component A.

[0024] For example, polycarbonates (homopolymers or copolymers) using 4,4'-(m-phenylenediisopropylidene)diphenol (sometimes abbreviated as "BPM"), 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (sometimes abbreviated as "Bis-TMC"), 9,9-bis(4-hydroxyphenyl)fluorene, and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (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. It is preferable to use these divalent phenols other than BPA in an amount of 5 mol% or more, particularly 10 mol% or more, of the total divalent phenol components constituting the polycarbonate.

[0025] In particular, when high rigidity and better hydrolysis resistance are required, it is especially preferable that component A of the resin composition be one of the copolymer polycarbonates (1) to (3) below. (1) A copolymer polycarbonate in which, of 100 mol% of the divalent phenol component constituting the polycarbonate, 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 in which, of 100 mol% of the divalent phenol component constituting the polycarbonate, 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 in which, of 100 mol% of the divalent phenol component constituting the polycarbonate, 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%).

[0026] Furthermore, the polycarbonate resin used in the present invention is preferably an aromatic polycarbonate resin composed of a carbonate constituent unit (a-1) represented by the following formula (1) (excluding the following formula (3)) and a carbonate constituent unit (a-2) represented by the following formula (3), wherein the proportion of constituent unit (a-2) in the total constituent units is 5 mol% or more.

[0027] [ka]

[0028] (In the above equation (1), R 1 and R 2 Each of the following groups independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. a and b are integers from 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 formula (2).

[0029] [ka]

[0030] (In equation (2) above, R 11 ,R 12 ,R 13 ,R 14 ,R 15 ,R 16 ,R 17 and R 18 Each of these independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, R 19and R 20 Each of these independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group with 1 to 18 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, a cycloalkyl group with 6 to 20 carbon atoms, a cycloalkoxy group with 6 to 20 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, an aryl group with 6 to 14 carbon atoms, an aryloxy group with 6 to 10 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, an aralkyloxy group with 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. c is an integer from 1 to 10, and d is an integer from 4 to 7.

[0031] [ka]

[0032] (In the above equation (3), R 1 and R 2 Each of these independently represents a group selected from an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, and an optionally substituted aralkyl group having 7 to 15 carbon atoms. 3 and R 4 Each of these independently represents a group selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an optionally substituted cycloalkyl group having 6 to 15 carbon atoms, an optionally substituted aryl group having 6 to 15 carbon atoms, an optionally substituted aralkyl group having 7 to 15 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an optionally substituted cycloalkoxy group having 6 to 20 carbon atoms, an optionally substituted aryloxy group having 6 to 15 carbon atoms, an optionally substituted aralkyloxy group having 7 to 15 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups of each type, they may be the same or different. a and b are natural numbers from 1 to 3, and W is at least one group selected from the group consisting of a single bond or a group represented by formula (2) above.

[0033] As the carbonate structural unit (a-1), a carbonate structural unit (a-1) derived from bisphenol A is preferred, and as the carbonate structural unit (a-2), a carbonate structural unit (a-2) derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane (bisphenol C) is preferred.

[0034] These special polycarbonates may be used individually, or two or more may be mixed as appropriate. They can also be mixed with commonly used bisphenol A type polycarbonates.

[0035] The manufacturing methods and properties of these special polycarbonates 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.

[0036] Furthermore, among the various polycarbonates 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) Polycarbonate 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 having a Tg of 160-250°C, preferably 170-230°C, and a water absorption rate of 0.10-0.30%, preferably 0.13-0.30%, more preferably 0.14-0.27%.

[0037] Here, the water absorption rate of polycarbonate 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 Tg (glass transition temperature) was determined by differential scanning calorimeter (DSC) measurement in accordance with JIS K7121.

[0038] Carbonyl halides, diester carbonates, or haloformates are used as carbonate precursors, specifically including phosgene, diphenyl carbonate, or dihaloformates of divalent phenols.

[0039] When producing a polycarbonate resin by interfacial polymerization of the divalent phenol and the carbonate precursor, a catalyst, an end-terminating agent, an antioxidant to prevent oxidation of the divalent phenol, etc., may be used as needed. The polycarbonate resin of the present invention also includes a branched polycarbonate resin copolymerized with a trifunctional or polyfunctional aromatic compound, a polyester carbonate resin copolymerized with an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a copolymerized polycarbonate resin copolymerized with a bifunctional alcohol (including alicyclic), and a polyester carbonate resin copolymerized with both such bifunctional carboxylic acid and bifunctional alcohol. Furthermore, a mixture of two or more of the obtained polycarbonate resins may also be used.

[0040] Branched polycarbonate resins can impart properties such as drip prevention to the resin composition of the present invention. Examples of trifunctional or polyfunctional aromatic compounds used in such branched polycarbonate resins include phloroglucin, phloroglucides, or 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptene-2, 2,4,6-trimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 4-{4-[1,1-bis(4- Examples include trisphenols such as hydroxyphenyl)ethyl]benzene}-α,α-dimethylbenzylphenol, tetra(4-hydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)ketone, 1,4-bis(4,4-dihydroxytriphenylmethyl)benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, among which 1,1,1-tris(4-hydroxyphenyl)ethane and 1,1,1-tris(3,5-dimethyl-4-hydroxyphenyl)ethane are preferred, and 1,1,1-tris(4-hydroxyphenyl)ethane is particularly preferred.

[0041] In branched polycarbonates, the constituent 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 constituent units derived from divalent phenols and those derived from such polyfunctional aromatic compounds.

[0042] Furthermore, especially in the case of molten transesterification, branched structural units may be produced as a side reaction. However, the amount of such branched structural units is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, and even more preferably 0.01 to 0.8 mol%, of the total 100 mol% of the constituent units derived from the divalent phenol.1 It can be calculated by 1H-NMR measurement.

[0043] 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.

[0044] The reaction methods used in the present invention for producing polycarbonate resin, such as interfacial polymerization, molten transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, are well-known methods described in various literatures and patent publications.

[0045] The viscosity-average molecular weight (M) of the polycarbonate resin is not particularly limited, but is preferably 1.8 × 10⁻⁶. 4 ~4.0×10 4 And more preferably 2.0 × 10 4 ~3.5×10 4 More preferably 2.2 × 10 4 ~3.0×10 4 The viscosity-average molecular weight is 1.8 × 10⁻⁶. 4 Polycarbonate resins with a viscosity-average molecular weight of less than 4.0 × 10⁻¹ may not provide good mechanical properties. On the other hand, a viscosity-average molecular weight of 4.0 × 10⁻¹⁰ 4 Resin compositions obtained from polycarbonate resins exceeding a certain value are less versatile due to their poor fluidity during injection molding.

[0046] Furthermore, the polycarbonate resin may be obtained by mixing resins whose viscosity-average molecular weight is outside the above range. In particular, the above range (5 × 10 4Polycarbonate resins having a viscosity-average molecular weight exceeding 7 × 10 exhibit improved entropy elasticity. As a result, they exhibit good moldability in gas-assisted molding and foam molding, which are sometimes used when forming reinforced resin materials into structural members. This improvement in moldability is even better than that of the branched polycarbonate. In a more preferred embodiment, component A has a viscosity-average molecular weight of 7 × 10 4 ~3×10 5 Polycarbonate resin (component A-1-1-1), and viscosity average molecular weight 1 × 10 4 ~3×10 4 It consists of polycarbonate resin (component A-1-1-2), and its viscosity-average molecular weight is 1.6 × 10⁻⁶. 4 ~3.5×10 4 Polycarbonate resin (component A-1-1) (hereinafter sometimes referred to as "high molecular weight component-containing polycarbonate resin") can also be used.

[0047] In such a polycarbonate resin containing high molecular weight components (component A-1-1), the molecular weight of component A-1-1-1 is 7 × 10⁻⁶. 4 ~2×10 5 Preferably, 8 × 10 4 ~2×10 5 More preferably 1 × 10 5 ~2×10 5 , particularly preferably 1 × 10 5 ~1.6×10 5 The molecular weight of component A-1-1-2 is 1 × 10⁻⁶. 4 ~2.5×10 4 Preferably, and more preferably, 1.1 × 10 4 ~2.4×10 4 More preferably 1.2 × 10 4 ~2.4×10 4 Particularly preferred is 1.2 × 10 4 ~2.3 × 10 4 That is the case.

[0048] A polycarbonate resin containing high molecular weight components (component A-1-1) can be obtained by mixing component A-1-1-1 and component A-1-1-2 in various proportions and adjusting them to satisfy a predetermined molecular weight range. Preferably, component A-1-1-1 is present in an amount of 2 to 40% by weight of component A-1-1, more preferably 3 to 30% by weight of component A-1-1-1, even more preferably 4 to 20% by weight of component A-1-1-1, and particularly preferably 5 to 20% by weight of component A-1-1-1.

[0049] Furthermore, methods for preparing component A-1-1 include (1) a method of independently polymerizing component A-1-1-1 and component A-1-1-2 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 A-1-1 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 A-1-1-1 and / or component A-1-1-2.

[0050] In this invention, the viscosity-average molecular weight is first calculated using the following formula: the specific viscosity (η SP The viscosity of the solution was determined using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of polycarbonate resin in 100 ml of methylene chloride at 20°C. Specific viscosity (η SP ) = (t-t0) / t0 [t0 is the number of seconds for the methylene chloride to fall, and t is the number of seconds for the sample solution to fall.] The specific viscosity (η) SP The viscosity-average molecular weight M is calculated from the following formula. η SP / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 -4 M 0.83 c = 0.7 Furthermore, the viscosity-average molecular weight of the polycarbonate resin in the flame-retardant polycarbonate resin composition of the present invention is calculated in the following manner. Specifically, the composition is mixed with methylene chloride in an amount 20 to 30 times its weight to dissolve the soluble components in the composition. These soluble components are collected by Celite filtration. The solvent is then removed from the resulting solution. The solid after solvent removal is thoroughly dried to obtain a solid of the components that dissolve in methylene chloride. The specific viscosity at 20°C is determined from a solution obtained by dissolving 0.7 g of this solid in 100 ml of methylene chloride in the same manner as above, and the viscosity-average molecular weight M is calculated from this specific viscosity in the same manner as above.

[0051] A polycarbonate-polydiorganosiloxane copolymer resin can also be used as the polycarbonate resin (component A) of the present invention. Preferably, the polycarbonate-polydiorganosiloxane copolymer resin is a copolymer resin containing a carbonate structural unit derived from a divalent phenol represented by the following formula (4) and a carbonate structural unit derived from a hydroxyaryl-terminated polydiorganosiloxane represented by the following formula (6).

[0052] [ka]

[0053] [In the above equation (4), R 1 and R 2 Each of the following groups independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. If there are multiple groups, they may be the same or different. e and f are integers from 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 formula (5).

[0054] [Chemical]

[0055] [In the above formula (5), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 each independently represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and R 19 and R 20 each independently represents a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, a cycloalkoxy group having 6 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. When there are a plurality of them, they may be the same or different. g is an integer from 1 to 10, and h is an integer from 4 to 7.]

[0056] [Chemical]

[0057] [In the above formula (6), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, and R 9 and R 10Each 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.

[0058] Examples of divalent phenols (I) that derive the carbonate constituent unit represented by formula (4) above 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, and 2,2-bis(4-hydroxy-3 ,3'-biphenyl)propane, 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, 2,2-bis(3-t-butyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 1,1-bis(3-cyclohexyl-4- Hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)diphenylmethane, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide , 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'-sulfonyldiphenol, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-diphenyldiphenyl sulfide, 1,3-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,Examples include 4-bis{2-(4-hydroxyphenyl)propyl}benzene, 1,4-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.

[0059] 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.

[0060] As hydroxyaryl-terminated polydiorganosiloxanes that derive the carbonate structural unit represented by formula (6) above, the following compounds are preferably used, for example.

[0061] [ka]

[0062] 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.

[0063] 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.

[0064] The polydiorganosiloxane content in 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, the resin exhibits excellent impact resistance and flame retardancy, while below the upper limit of this preferred range, a stable appearance that is less affected by molding conditions is easily obtained. The degree of polydiorganosiloxane polymerization and the polydiorganosiloxane content can be calculated by 1H-NMR measurement.

[0065] You may use only one hydroxyaryl-terminated polydiorganosiloxane(II), or you may use two or more. Furthermore, other comonomers besides the divalent phenol (I) and hydroxyaryl-terminated polydiorganosiloxane (II) can also be used in combination in an amount of 10% by weight or less relative to the total weight of the copolymer.

[0066] In the method for producing polycarbonate-polydiorganosiloxane copolymer resin, a mixed solution containing oligomers 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.

[0067] When generating divalent phenol(I) oligomers, the entire amount of divalent phenol(I) used may be converted into oligomers 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. Post-added monomers are added to expedite the subsequent polycondensation reaction, and do not need to be added if unnecessary. 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.

[0068] 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.

[0069] 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).

[0070] As the aforementioned solvent, various reaction-inert solvents, such as those used in the production of known polycarbonates, can be used individually or as a mixed solvent. Typical examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. Halogenated hydrocarbon solvents such as methylene chloride are particularly preferred.

[0071] 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.

[0072] In this way, after obtaining a mixed solution containing an oligomer of a dihydric phenol (I) having a terminal chloroformate group, while stirring the mixed solution, a hydroxyaryl-terminated polydiorganosiloxane (II) represented by the following formula (7) which is highly purified to a molecular weight distribution (Mw / Mn) of 3 or less is added to the dihydric phenol (I), and a polycarbonate-polydiorganosiloxane copolymer is obtained by interfacial polycondensation of the hydroxyaryl-terminated polydiorganosiloxane (II) and the oligomer.

[0073] [Chemical formula]

[0074] (In the above formula (7), R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, R 9 and R 10 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, p is a natural number, q is 0 or a natural number, and p + q is a natural number of 10 to 300. X is a divalent aliphatic group having 2 to 8 carbon atoms.)

[0075] 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).

[0076] The polycondensation reaction between the divalent phenol (I) oligomer and the hydroxyaryl-terminated polydiorganosiloxane (II) is carried out by vigorously stirring the above mixture.

[0077] 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.

[0078] 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.

[0079] 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.

[0080] The reaction pressure can be reduced, atmospheric, or pressurized, but it is usually preferable to use atmospheric pressure or the self-pressure of the reaction system. The reaction temperature is selected from the range of -20 to 50°C, and since polymerization often generates heat, water cooling or ice cooling is desirable. The reaction time varies depending on other conditions such as the reaction temperature and cannot be specified in general terms, but it is usually carried out in 0.5 to 10 hours.

[0081] Depending on the circumstances, the obtained polycarbonate-polydiorganosiloxane copolymer resin may be subjected to appropriate physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking, partial decomposition, etc.) to obtain the desired reduced viscosity [η SP It can also be obtained as a polycarbonate-polydiorganosiloxane copolymer resin of [c].

[0082] The resulting reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer resin of the desired purity (degree of purification) by various post-treatment methods, such as known separation and purification methods.

[0083] The average size of polydiorganosiloxane domains in polycarbonate-polydiorganosiloxane copolymer resin molded articles is preferably in the range of 1 to 60 nm. More preferably, this average size is 3 to 55 nm, and even more preferably 5 to 50 nm. Below the lower limit of this preferred range, impact resistance and flame retardancy may not be sufficiently exhibited, and above the upper limit of this preferred range, impact resistance may not be stably exhibited.

[0084] Furthermore, it is preferable to include recycled polycarbonate resin as the polycarbonate resin. The recycled polycarbonate resin is preferably, for example, recycled polycarbonate resin obtained by crushing recovered material of molded products containing polycarbonate resin. The molded products may be used products. Preferred used products include various glazing materials such as soundproof walls, automobile windows, translucent roofing materials, and automobile sunroofs, transparent components such as windshields and automobile headlamp lenses, containers such as water bottles, light guide plates, eyeglass lenses, and optical recording media. In addition, crushed material obtained from unsuitable products, sprues, runners, etc., or pellets obtained by melting them can also be used.

[0085] (Component B: Polyorganosiloxane-containing graft copolymer) The flame-retardant polycarbonate resin composition of the present invention contains a polyorganosiloxane-containing graft copolymer as component B. The polyorganosiloxane-containing graft copolymer used in the flame-retardant polycarbonate resin composition of the present invention is not particularly limited, but it is preferably a graft copolymer obtained by graft copolymerizing a rubbery polymer containing polyorganosiloxane with a monomer component copolymerizable thereto. Furthermore, it is more preferably a silicone / acrylic composite rubber-based graft copolymer obtained by grafting a vinyl polymer composed of one or more vinyl monomer units onto a composite rubber containing polyorganosiloxane and polyalkyl (meth)acrylate. As a method for producing the graft copolymer, any method such as bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization may be used, and the copolymerization method may be single-stage grafting or multi-stage grafting, but examples of production methods disclosed in Japanese Patent Application Publication No. 2003-261629 and Japanese Patent Application Publication No. 2003-238639 can be cited.

[0086] The polyorganosiloxane-containing graft copolymer is not particularly limited as long as it contains polyorganosiloxane rubber. Examples include polyorganosiloxane rubber, and composite rubber (IPN type) consisting of polyorganosiloxane rubber and polyalkyl (meth)acrylate rubber. These can be used individually or in mixtures of two or more types.

[0087] Specific examples of monomer components that can be graft copolymerized with rubber components include aromatic vinyl compounds, vinyl cyanide compounds, (meth)acrylic acid ester compounds, epoxy group-containing (meth)acrylic acid ester compounds such as glycidyl (meth)acrylate; maleimide compounds such as maleimide, N-methylmaleimide, and N-phenylmaleimide; and α,β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid, and itaconic acid, and their anhydrides (e.g., maleic anhydride). These monomer components may be used individually or in combination of two or more.

[0088] Among these, aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid ester compounds are preferred in terms of mechanical properties and surface appearance. Specific examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and octyl (meth)acrylate.

[0089] Furthermore, the polyorganosiloxane-containing graft copolymer used in the present invention is preferably of the core / shell type from the viewpoint of impact resistance and surface appearance. Among these, a core / shell type graft copolymer is particularly preferred, in which at least one rubber component selected from polyorganosiloxane rubber and (IPN type) composite rubber consisting of polyorganosiloxane rubber and polyalkyl (meth)acrylate rubber forms the core layer, and a shell layer formed around it from at least one monomer component selected from aromatic vinyl compounds, vinyl cyanide compounds, and (meth)acrylic acid ester compounds.

[0090] Examples of such core / shell type polyorganosiloxane-containing graft copolymers include "Metablen (registered trademark, hereinafter the same) S-2001", "Metablen SRK-200", "Metablen S-2130", "Metablen S-2030", and "Metablen SX-005" from Mitsubishi Chemical Corporation, and "Kaneka (registered trademark) MR-01" from Kaneka Corporation.

[0091] The content of component B is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, and more preferably 5 to 10 parts by weight, per 100 parts by weight of component A. If the content of component B is below the lower limit, the decrease in impact strength and flame retardancy after the water exposure test in UL746C f1 rating certification is not suppressed, and if it exceeds the upper limit, the flame retardancy decreases.

[0092] (Component C: Phosphazene) The flame-retardant polycarbonate resin composition of the present invention contains phosphazene, which contains 98.5 mol% or more of a phosphophazene cyclic trimer as component C. When compounds other than phosphazene, such as phosphate esters or condensed phosphate esters, are used as phosphorus-based flame retardants, the decrease in impact strength and flame retardancy after the water exposure test in UL746C f1 rating certification is not suppressed. The phosphazene is not particularly limited as long as it does not contain halogen atoms and has a phosphazene structure in its molecule. The phosphazene structure referred to here is the structure represented by the formula: -P(R2)=N-[wherein R2 is an organic group]. Phosphazene is represented by the following formulas (8) and (9).

[0093] [ka]

[0094] [ka]

[0095] (In the formula, X1, X2, X3, and X4 represent organic groups that do not contain hydrogen, hydroxyl, amino, or halogen atoms. Also, n represents an integer between 3 and 10.) Examples of organic groups that do not contain halogen atoms represented by X1, X2, X3, and X4 in formulas (8) and (9) above include alkoxy groups, phenyl groups, amino groups, and allyl groups.

[0096] The C component, phosphazene, must contain 98.5 mol% or more of phosphazene cyclic trimers. The content is preferably in the range of 99 mol% to 100 mol%, and more preferably 99.5 mol% to 100 mol%. If the phosphazene cyclic trimer content is below the lower limit, the decrease in impact strength after the water exposure test in UL746C f1 rating certification will not be suppressed.

[0097] General methods for producing phosphazenes are described in European Patent Publication No. 728811 and International Publication No. 97 / 40092, among others.

[0098] During the manufacturing process, phosphazene produces cyclic tetramers and higher-grade oligomers as by-products in addition to cyclic trimers. However, the content of phosphazene cyclic trimers can be increased by purification using methods such as column chromatography.

[0099] Furthermore, the content of phosphazene cyclic trimers in phosphazene is 31 It can be quantified by PNMR (chemical shift, δ trimer 6.5-10.0 ppm, δ tetramer -10 to -13.5 ppm, higher-grade oligomers -16.5 to -25.0 ppm).

[0100] The content of component C is 1 to 30 parts by weight, preferably 1.5 to 25 parts by weight, and more preferably 2 to 20 parts by weight, per 100 parts by weight of component A. If the content of component C is below the lower limit, the flame retardant effect will not be obtained, and if it exceeds the upper limit, the decrease in impact strength after the water exposure test in UL746C f1 rating certification will not be suppressed.

[0101] (Component D: Drip prevention agent) The flame-retardant polycarbonate resin composition of the present invention contains a drip inhibitor as component D. The inclusion of this drip inhibitor makes it possible to achieve good flame retardancy without impairing the physical properties of the molded product.

[0102] Examples of drip inhibitors for component D 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.

[0103] 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.

[0104] Examples of commercially available PTFE products with such fibril-forming ability include Teflon® 6J from Mitsui DuPont Fluorochemicals Co., Ltd., and Polyflon MPA FA500 and F-201L from Daikin Industries, Ltd. Representative examples of commercially available aqueous dispersions of PTFE include Fluon AD-1 and AD-936 from Asahi ICI Fluoropolymers Co., Ltd., Fluon D-1 and D-2 from Daikin Industries, Ltd., and Teflon® 30J from Mitsui DuPont Fluorochemicals Co., Ltd.

[0105] 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 (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 A3800" (product name) from Mitsubishi Chemical Corporation and "BLENDEX B449" (product name) from GE Specialty Chemicals.

[0106] 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.

[0107] The content of component D is 0.05 to 2 parts by weight, preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1.2 parts by weight, per 100 parts by weight of component A. If the content of component D is below the lower limit, sufficient flame retardancy cannot be obtained, and if it exceeds the upper limit, the decrease in impact strength after the water exposure test in f1 rating certification cannot be suppressed.

[0108] Furthermore, examples of styrene monomers used in the organic polymer used in the polytetrafluoroethylene-based mixture 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.

[0109] The acrylic monomer used in the organic polymer used in the polytetrafluoroethylene-based mixture of the present invention includes a substituted (meth)acrylate derivative. Specifically, the acrylic monomer may be a substituted (meth)acrylate derivative 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.

[0110] 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.

[0111] The polytetrafluoroethylene-based mixture of 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.

[0112] The manufacturing process for the polytetrafluoroethylene-based mixture of 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.

[0113] 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 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.

[0114] The polytetrafluoroethylene-based mixture of the present invention was manufactured by suspension polymerization using the following procedure. 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.

[0115] 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.

[0116] 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.

[0117] The polytetrafluoroethylene contained in the coated branched PTFE is branched polytetrafluoroethylene. If the contained polytetrafluoroethylene is not branched polytetrafluoroethylene, the anti-dropping effect will be insufficient when the amount of polytetrafluoroethylene added is small. Branched polytetrafluoroethylene is particulate and preferably has 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 with 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 be poor. The number average molecular weight of the polytetrafluoroethylene used in this invention is 1 × 10⁻⁶ 4 ~1 × 10 7 Preferably, 2 × 10 6 ~9×10 6 Generally, polytetrafluoroethylenes with higher molecular weights are more preferable in terms of stability. They can be used in either powder or dispersion form. The branched polytetrafluoroethylene content in 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, per 100 parts by weight of the total weight of coated branched PTFE. When the proportion of branched polytetrafluoroethylene is within this range, good dispersibility of the branched polytetrafluoroethylene can sometimes be achieved.

[0118] (Other additives) (i) Phosphate stabilizers The flame-retardant polycarbonate resin composition of the present invention preferably contains a phosphorus-based stabilizer. The inclusion of this phosphorus-based stabilizer suppresses thermal decomposition during processing, thereby achieving good impact strength and flame retardancy. Examples of phosphorus-based stabilizers include phosphorous acid, phosphoric acid, phosphonic acid, phosphonic acid and their esters, as well as tertiary phosphines.

[0119] 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, tris(diethylphenyl) phosphite, tris(di-iso-propylphenyl) phosphite, tris(di-n-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert- Examples include 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, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl} pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

[0120] 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, and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite.

[0121] 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, with triphenyl phosphate and trimethyl phosphate being preferred.

[0122] 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(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, and bis Examples include (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, with tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite and bis(di-tert-butylphenyl)-phenyl-phenylphosphonite being preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite and bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite being more preferred. Such phosphonite compounds can be used in combination with phosphite compounds having an aryl group substituted with two or more alkyl groups, and this is preferable.

[0123] Examples of phosphonate compounds include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

[0124] 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.

[0125] The phosphorus-based stabilizers described above can be used not only individually but also in combination of two or more. Among the phosphorus-based stabilizers described above, phosphonite compounds or phosphite compounds represented by the following general formula (10) are preferred.

[0126] [ka]

[0127] (In formula (10), R and R' represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

[0128] As described above, tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite is preferred as the phosphonite compound, and stabilizers mainly composed of this phosphonite are commercially available as Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS), both of which can be used.

[0129] Furthermore, among the above formula (10), the more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.

[0130] Distearyl pentaerythritol diphosphite is commercially available as ADEKA Stab PEP-8 (trademark, manufactured by ADEKA Corporation) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and both are available for use. Bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite is commercially available as Songnox 6260W (trademark, manufactured by Song Wong), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgaofos 126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and all are available for use. Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite is commercially available as ADEKA Stab PEP-36 (trademark, manufactured by ADEKA Corporation) and is readily available. Bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite is commercially available as ADEKA Stab PEP-45 (trademark, manufactured by ADEKA Corporation) and Doverphos S-9228 (trademark, manufactured by Dover Chemical), both of which are also available.

[0131] The phosphorus-based stabilizers described above can be used alone or in combination of two or more. The content of the phosphorus-based stabilizer is preferably 0.01 to 1.0 parts by weight, more preferably 0.03 to 0.8 parts by weight, and even more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of component A. When the content is within the above range, a thermal decomposition suppression effect during processing is achieved, and a decrease in impact strength is less likely to occur.

[0132] (ii) Phenolic stabilizers The flame-retardant polycarbonate resin composition of the present invention may contain a phenolic stabilizer. Examples of phenolic stabilizers include hindered phenols, semi-hindered phenols, and less-hindered phenol compounds, but hindered phenol compounds are particularly preferred from the viewpoint of providing a heat-stable formulation for polypropylene resins. 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, and 2,6-di-tert-butyl-4-(N,N-dimethylaminomethyl)pheno. 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-dimethylenebis(6-α-methylbenzyl-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-hydroxy-5-methylphenyl) [Loxyphenyl)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-hydroxy-5-methylphenyl)propionyloxy]-1,1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-di-thiobis(2,6-di-tert-butylphenol), 4,4'-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy- 3,5-di-tert-butylanilino)-1,3,5-triazine, N,N'-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl) Droxyphenyl) 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-butyl-4-hydroxy-5-methylphenyl)acetyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, 1,3,5-trimethyl-2,4Examples include 6-tris(3-tert-butyl-4-hydroxy-5-methylbenzyl)benzene and tris(3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferably used, and furthermore, (3,3', 3'', 5,5',5''-hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, represented by the following formula (11), and 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, represented by the following formula (12), are more preferably used as they excel at suppressing the deterioration of mechanical properties due to thermal decomposition during processing.

[0133] [ka]

[0134] [ka]

[0135] The above-mentioned phenolic stabilizers can be used alone or in combination of two or more. The content of the phenolic stabilizer is preferably 0.05 to 1.0 parts by weight, more preferably 0.07 to 0.8 parts by weight, and even more preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of component A. When the content is within the above range, a thermal decomposition suppression effect during processing is achieved, and a decrease in impact properties is less likely to occur.

[0136] (iii) UV absorbers The flame-retardant polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber. Examples of UV absorbers include benzophenone-based compounds such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-bendyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridebenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodium sulfoxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl)methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0137] Examples of benzotriazole derivatives 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, 2-(2-hydroxy-3,5-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole, and 2-(2-hydroxy-5-tert-octylphenyl)benzotri Examples include polymers having a 2-hydroxyphenyl-2H-benzotriazole skeleton, such as azoles, 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, as well as copolymers of 2-(2'-hydroxy-5-methacryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer, and copolymers of 2-(2'-hydroxy-5-acryloxyethylphenyl)-2H-benzotriazole with vinyl monomers copolymerizable with the monomer.

[0138] Examples of hydroxyphenyltriazine compounds include 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, examples include compounds in which the phenyl group of the above example 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.

[0139] Examples of cyclic iminoester systems include 2,2'-p-phenylenebis(3,1-benzoxazine-4-one), 2,2'-m-phenylenebis(3,1-benzoxazine-4-one), and 2,2'-p,p'-diphenylenebis(3,1-benzoxazine-4-one).

[0140] Examples of cyanoacrylate compounds include 1,3-bis-[(2'-cyano-3',3'-diphenylacryloyl)oxy]-2,2-bis[(2-cyano-3,3-diphenylacryloyl)oxy]methyl)propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl)oxy]benzene.

[0141] Furthermore, the above-mentioned ultraviolet absorber may also be a polymer-type ultraviolet absorber obtained by copolymerizing such ultraviolet-absorbing monomer and / or photostable monomer with a monomer such as alkyl (meth)acrylate, by adopting the structure of a monomer compound that can undergo radical polymerization. Suitable examples of the ultraviolet-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic iminoester skeleton, and a cyanoacrylate skeleton in the ester substituent of a (meth)acrylic acid ester.

[0142] Among the above compounds, in the present invention, a compound represented by any of the following formulas (13), (14), and (15) is more preferably used.

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] The above-mentioned UV absorbers can be used individually or in combination of two or more types. The amount of UV absorber is preferably 0.1 to 3 parts by weight, more preferably 0.12 to 2 parts by weight, and even more preferably 0.15 to 1 part by weight, per 100 parts by weight of component A. When the amount of UV absorber is within the above range, sufficient light resistance is achieved, and appearance defects and deterioration of physical properties due to gas generation are less likely to occur.

[0147] (iv) Hindered amine light stabilizers The flame-retardant polycarbonate resin composition of the present invention may contain a hindered amine light stabilizer. Hindered amine light stabilizers are generally called HALS (Hindered Amine Light Stabilizer) and are compounds having a 2,2,6,6-tetramethylpiperidine skeleton in their structure, for example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-methoxy-2,2 6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine, 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine, 4-(phenylcarbon Lubamoyloxy)-2,2,6,6-tetramethylpiperidine, bis(2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidyl) oxalate, bis(2,2,6,6-tetramethyl-4-piperidyl) malonate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) adipate, bis(2,2,6,6-tetramethyl-4-piperidyl) terephthalate Bis(1,2,2,6,6-pentamethyl-4-piperidyl) carbonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) oxalate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) malonate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) adipate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) terephthalate, N,N'-bis-2,2,6,6-Tetramethyl-4-piperidinyl-1,3-benzenedicarboxamide, 1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)ethane, α,α'-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene, bis(2,2,6,6-tetramethyl-4-piperidyltrylene-2,4-dicarbamate, bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene-1,6-dicarbamate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3, 5-Tricarboxylate, N,N',N'',N'''-Tetrakis-(4,6-bis-(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4-yl)amino)-triazine-2-yl)-4,7-diazadecane-1,10-diamine, dibutylamine·1,3,5-triazine·N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine polycondensate, poly[{6-(1,1,3,3-tetramethyl [Tributyl)amino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4-piperidyl)imino}], tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3, Examples include 4-tricarboxylate, 1-[2-{3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine, and condensates of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β',β'-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethanol.

[0148] Hindered amine light stabilizers can be broadly classified into three types based on the bonding partner of the nitrogen atom in the piperidine skeleton: NH type (hydrogen bonded to the nitrogen atom), NR type (alkyl group (R) bonded to the nitrogen atom), and N-OR type (alkoxy group (OR) bonded to the nitrogen atom). However, when applied to polycarbonate resins, it is preferable to use the low-basic NR type or N-OR type from the viewpoint of the basicity of the hindered amine light stabilizer.

[0149] Among the above compounds, the compounds represented by the following formulas (16) and (17) are more preferably used in the present invention.

[0150] [ka]

[0151] [ka]

[0152] Hindered amine light stabilizers can be used alone or in combination of two or more types. The content of the hindered amine light stabilizer is preferably 0 to 1 part by weight, more preferably 0.05 to 1 part by weight, even more preferably 0.08 to 0.7 parts by weight, and particularly preferably 0.1 to 0.5 parts by weight, per 100 parts by weight of component A. When the content of the hindered amine light stabilizer is within the above range, it is less likely that appearance defects due to gas generation and a decrease in impact properties due to the decomposition of the polycarbonate resin will occur, and sufficient light resistance will be achieved.

[0153] (v) Release agent The flame-retardant polycarbonate resin composition of the present invention preferably contains a release agent to improve productivity during molding and reduce distortion of molded products. Known release agents can be used. Examples include saturated fatty acid esters, unsaturated fatty acid esters, polyolefin waxes (such as polyethylene wax and 1-alkene polymers; those modified with functional group-containing compounds such as acid modification can also be used), silicone compounds, fluorine compounds (such as fluorine oils represented by polyfluoroalkyl ethers), paraffin wax, and beeswax. Among these, fatty acid esters are particularly preferred as release agents. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. The aliphatic alcohol may be a monohydric alcohol or a polyhydric alcohol of two or more hydric values. The number of carbon atoms in the alcohol is in the range of 3 to 32, more preferably 5 to 30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, ceryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. Polyhydric alcohols are more preferred in the fatty acid esters of the present invention.

[0154] On the other hand, aliphatic carboxylic acids are preferably those having 3 to 32 carbon atoms, and particularly preferably those having 10 to 22 carbon atoms. Examples of such aliphatic carboxylic acids include saturated aliphatic carboxylic acids such as decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, 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 having 14 to 20 carbon atoms are preferred. Saturated aliphatic carboxylic acids are particularly preferred. Stearic acid and palmitic acid are particularly preferred.

[0155] 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.

[0156] The fatty acid ester of the present invention 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. The acid value of the fatty acid ester of the present invention is preferably 20 or less, more preferably in the range of 4 to 20, and even more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially 0. Furthermore, the hydroxyl value of the fatty acid ester is more preferably in the range of 0.1 to 30. Furthermore, the iodine value is preferably 10 or less. The iodine value can be substantially 0. These properties can be determined by the method specified in JIS K 0070.

[0157] The release agent content is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and even more preferably 0.05 to 0.5 parts by weight, per 100 parts by weight of component A. Within this range, the flame-retardant polycarbonate resin composition has good release properties and roll release properties. In particular, such an amount of fatty acid ester can provide a flame-retardant polycarbonate resin composition with good release properties and roll release properties without impairing a good hue.

[0158] (vi) dyes and pigments The flame-retardant polycarbonate resin composition of the present invention can further contain various dyes and pigments to provide molded articles exhibiting 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 flame-retardant polycarbonate resin composition that can be colored with minute amounts of dyes and pigments and exhibits vivid color development can also be provided.

[0159] 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 during the molding process of polycarbonate resin.

[0160] Other dyes besides the bluing agents and 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 resin composition of the present invention can be further enhanced by incorporating metallic pigments to obtain better metallic colors. Suitable metallic pigments include those having a metal coating or metal oxide coating on various plate-shaped fillers.

[0161] The content of the above-mentioned dye pigment is preferably 0.00001 to 1 part by weight, and more preferably 0.00005 to 0.5 parts by weight, per 100 parts by weight of component A.

[0162] (vii) Other heat stabilizers The flame-retardant polycarbonate resin composition of the present invention may also contain other heat stabilizers besides the phosphorus-based and phenol-based stabilizers described above. Such other heat stabilizers are preferably used in combination with either of these stabilizers or antioxidants, and are particularly preferably used in combination with both. Suitable examples of such other heat stabilizers include lactone-based stabilizers, such as those represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (details of such stabilizers are described in Japanese Patent Publication No. 7-233160). Such compounds are commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS), and these compounds can be used. Furthermore, stabilizers mixed with such compounds and various phosphite compounds and hindered phenol compounds are commercially available. For example, Irganox HP-2921 manufactured by the above company is a suitable example. Such pre-mixed stabilizers can also be used in the present invention. The amount of lactone-based stabilizer added is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, per 100 parts by weight of component A.

[0163] Other examples of stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Such stabilizers are particularly effective when the resin composition is applied to rotational molding. The amount of such sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.

[0164] (viii) Filling material The flame-retardant polycarbonate resin composition of the present invention may contain various fillers as reinforcing fillers, to the extent that the effects of the present invention are exhibited. Examples include silicate minerals, calcium carbonate, glass fibers, glass beads, glass balloons, glass milled fibers, glass flakes, carbon fibers, carbon flakes, carbon beads, carbon milled fibers, graphite, expanded graphite, vapor-deposited ultrafine carbon fibers (fiber diameter less than 0.1 μm), carbon nanotubes (fiber diameter less than 0.1 μm and hollow), fullerenes, metal flakes, metal fibers, metal-coated glass fibers, metal-coated carbon fibers, metal-coated glass flakes, silica, metal oxide particles, metal oxide fibers, metal oxide balloons, various whiskers (potassium titanate whiskers, aluminum borate whiskers, and basic magnesium sulfate, etc.), boron compounds (boron nitride, etc.), and laser direct structuring agents. These reinforcing fillers may be included individually or in combination of two or more. The content of these fillers is preferably 1 to 300 parts by weight, more preferably 5 to 280 parts by weight, per 100 parts by weight of component A.

[0165] (ix) Impact modifier The flame-retardant polycarbonate resin composition of the present invention may contain, to the extent that the effects of the present invention are exhibited, impact modifiers other than polyorganosiloxane-containing graft copolymers in addition to the polyorganosiloxane-containing graft copolymer. For example, a rubbery polymer (component ix-1) or an aromatic vinyl-(hydrogenated) conjugated diene type block copolymer (component ix-2) is preferably used.

[0166] (component ix-1: rubbery polymer) The rubbery polymer used in this invention refers to a polymer obtained by copolymerizing a rubber component with a vinyl monomer or a mixture thereof in one or more steps.

[0167] Examples of rubber components include polybutadiene, diene copolymers (e.g., random and block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, and copolymers of alkyl (meth)acrylate and butadiene), polyisoprene, copolymers of ethylene and α-olefins (e.g., random and block copolymers of ethylene-propylene, random and block copolymers of ethylene-butene), copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (e.g., ethylene-vinyl acetate copolymers), non-conjugated diene polymers of ethylene and propylene (e.g., ethylene-propylene-hexadiene copolymers), and acrylic rubbers (e.g., polybutyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate). Among these, polybutadiene, diene copolymers, polyisoprene, acrylic rubber, and ethylene, propylene, and non-conjugated diene polymers are more readily expressed, and among these, diene copolymers are particularly preferred.

[0168] The weight-average particle size of the rubber particles in the rubber component is preferably in the range of 0.10 to 1.0 μm, more preferably 0.15 to 0.8 μm, and even more preferably 0.20 to 0.5 μm. When the weight-average particle size of the rubber particles is within the above range, the impact improvement effect due to the addition of the graft polymer is preferably exhibited, and the dispersion state with the polycarbonate resin is good, which is preferable as it does not cause a decrease in impact.

[0169] In this invention, the weight-average particle diameter of the rubber particles is a value measured by a transmission electron microscope. Specifically, a drop of the rubbery polymer in emulsion state was placed on a mesh for transmission electron microscopy measurement, stained with osmium tetroxide or ruthenium tetroxide vapor, and then the stained rubbery polymer sample was photographed with a transmission electron microscope (TECNAI G2, manufactured by FEI, accelerating voltage 120kv). The weight-average particle diameter was calculated from 200 rubber particles in the captured image using image processing software (Nexus NewQube).

[0170] Here, the diene polymer is a copolymer obtained by polymerizing such that the main constituent unit, 1,3-butadiene, is preferably 50 to 100% by weight, more preferably 65 to 100% by weight, and even more preferably 75 to 100% by weight, and a vinyl monomer, such as styrene, which can copolymerize with it, is preferably 50 to 0% by weight, more preferably 35 to 0% by weight, and even more preferably 25 to 0% by weight. It is preferable that the main constituent unit, 1,3-butadiene, is within the above range because sufficient impact properties can be obtained.

[0171] Examples of vinyl monomers used in component ix-1 include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, chlorostyrene, dibromostyrene, and tribromostyrene; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate; and alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. In addition to the above monomers, other examples include vinyl ether monomers, vinylidene halogenated monomers, and vinyl monomers having a glycidyl group, such as glycidyl acrylate.

[0172] Furthermore, among the aforementioned vinyl monomers, those that also function as crosslinkable monomers are copolymerizable with butadiene or other vinyl monomers and are compounds containing two or more independent C=C bonds within their molecules. Examples include aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; α,β-unsaturated carboxylic acid esters, trimethacrylate or triacrylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate; allyl esters of α,β-unsaturated carboxylic acids such as allyl acrylate and allyl methacrylate; and di- or trialyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine. One or more of these vinyl monomers and crosslinkable monomers can be used.

[0173] Furthermore, when forming diene-based rubber components, chain transfer agents (initiators) such as t-dodecyl mercaptan may be used in the polymerization reaction as needed. When preparing the latex of this diene-based rubber component, a particle size-enhancing agent is added to control the weight-average particle size of the diene-based rubber component. Examples of such particle size-enhancing agents include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, and aluminum sulfate; organic salts such as calcium acetate and magnesium acetate; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and succinic acid; and their organic acid anhydrides, as well as polymer latex containing carboxylic acids.

[0174] Styrene polymers are a preferred choice for rubbery polymers. Styrene polymers are preferred because they possess good moldability, moderate fluidity, and heat resistance, thus maintaining a balance of these properties.

[0175] Such styrene-based polymers are polymers or copolymers of aromatic vinyl compounds in which a vinyl group or an alkylethenyl group (a vinyl group modified with an alkyl group) is bonded to a benzene ring, and polymers obtained by copolymerizing these with other vinyl monomers and rubber components that can be copolymerized with them as needed.

[0176] Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromstyrene, dibromstyrene, fluorostyrene, and tribromstyrene, with styrene being particularly preferred.

[0177] Other vinyl monomers copolymerizable with aromatic vinyl compounds include vinyl cyanide compounds and (meth)acrylic acid ester compounds. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. Examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. The notation (meth)acrylate indicates that it includes both methacrylate and acrylate, and the notation (meth)acrylic acid ester indicates that it includes both methacrylic acid ester and acrylic acid ester. Methyl methacrylate is a particularly suitable (meth)acrylic acid ester compound.

[0178] Other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth)acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, and α,β-unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid.

[0179] Examples of rubbery polymers copolymerizable with the above aromatic vinyl compounds include polybutadiene, polyisoprene, diene copolymers (e.g., random and block copolymers of styrene-butadiene, acrylonitrile-butadiene copolymers, and copolymers of alkyl (meth)acrylates and butadiene), copolymers of ethylene and α-olefins (e.g., random and block copolymers of ethylene-propylene, random and block copolymers of ethylene-butene), copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene-methacrylate copolymers and ethylene-butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyls (e.g., ethylene-vinyl acetate copolymers), non-conjugated diene polymers of ethylene and propylene (e.g., ethylene-propylene-hexadiene copolymers), and acrylic rubbers (e.g., polybutyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate). Among these, polybutadiene, polyisoprene, or diene copolymers are more readily expressed, with polybutadiene being particularly preferred.

[0180] Specific examples of the styrene-based polymers mentioned above include resins made from styrene-based polymers such as HIPS resin, ABS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and SMA resin, as well as styrene-based thermoplastic elastomers (e.g., (hydrogenated) styrene-butadiene-styrene copolymer, (hydrogenated) styrene-isoprene-styrene copolymer). The notation (hydrogenated) means that both unhydrogenated and hydrogenated resins are included.

[0181] Among these, rubber-reinforced styrene polymers such as HIPS resin, ABS resin, AES resin, ASA resin, MBS resin, MABS resin, MAS resin, and styrene-based thermoplastic elastomers are particularly preferred.

[0182] As described above, among these, those having a diene copolymer rubber component are preferred, and ABS resin and MBS resin are particularly preferred. ABS resin and MBS resin exhibit the effects of the present invention favorably in that they have good impact resistance. Here, AES resin is a copolymer resin mainly composed of acrylonitrile, ethylene-propylene rubber, and styrene; ASA resin is a copolymer resin mainly composed of acrylonitrile, styrene, and acrylic rubber; MABS resin is a copolymer resin mainly composed of methyl methacrylate, acrylonitrile, butadiene, and styrene; MAS resin is a copolymer resin mainly composed of methyl methacrylate, acrylic rubber, and styrene; and SMA resin is a copolymer resin mainly composed of styrene and maleic anhydride (MA).

[0183] Furthermore, such styrene-based resins may have high stereoregularity, such as syndiotactic polystyrene, due to the use of catalysts such as metallocene catalysts during their manufacture. In addition, depending on the circumstances, polymers and copolymers with a narrow molecular weight distribution, block copolymers, and polymers and copolymers with high stereoregularity obtained by methods such as anionic living polymerization and radical living polymerization can also be used.

[0184] Among these, acrylonitrile-butadiene-styrene copolymer resin (ABS resin) is preferred. It is also possible to use a mixture of two or more styrene-based polymers.

[0185] The ABS resin used in this invention is a mixture of a thermoplastic graft copolymer obtained by graft polymerizing a vinyl cyanide compound and an aromatic vinyl compound onto a diene-based rubber component, 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, methyl (meth)acrylate, ethyl acrylate, 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 the content of these is 15% by weight or less of the ABS resin component. Furthermore, various conventionally known initiators, chain transfer agents, emulsifiers, etc., can be used in the reaction as needed.

[0186] In the ABS resin of 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.

[0187] Furthermore, it is well known that ABS resin contains vinyl cyanide compounds and aromatic vinyl compounds that are not grafted onto the diene rubber component, and the ABS resin of the present invention may also contain free polymer components generated during such polymerization. The reduced viscosity of the copolymer consisting of such free vinyl cyanide compounds and aromatic vinyl compounds is preferably 0.2 to 1.0 dl / g, more preferably 0.3 to 0.7 dl / g, as determined by the method described above at 30°C.

[0188] Furthermore, the proportion of grafted vinyl cyanide compounds and aromatic vinyl compounds is preferably 20-200% (by weight) relative to the diene rubber component, and more preferably 20-70%.

[0189] The ABS resin may be manufactured by any of the following methods: bulk polymerization, suspension polymerization, or emulsion polymerization, but bulk polymerization is particularly preferred. Representative examples of such bulk polymerization methods include the continuous bulk polymerization method (the so-called Toray method) described in Chemical Engineering, Vol. 48, No. 6, p. 415 (1984), and the continuous bulk polymerization method (the so-called Mitsui Toatsu method) described in Chemical Engineering, Vol. 53, No. 6, p. 423 (1989). Any of these ABS resins can be suitably used as the ABS resin of the present invention. Furthermore, the copolymerization method may be one-step or multi-step. Additionally, 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 manufacturing method can also be suitably used.

[0190] The aforementioned ABS resin is more preferable in terms of good thermal stability and hydrolysis resistance if the alkali (earth) metal content is reduced. The alkali (earth) metal content in the styrene-based resin is preferably less than 100 ppm, more preferably less than 80 ppm, even more preferably less than 50 ppm, and particularly preferably less than 10 ppm. From this point of view, ABS resin produced by the bulk polymerization method is suitably used. Furthermore, in relation to such good thermal stability and hydrolysis resistance, when an emulsifier is used in the ABS resin, the emulsifier is preferably sulfonates, and more preferably alkyl sulfonates. When a coagulant is used, the coagulant is preferably sulfuric acid or an alkaline earth metal salt of sulfuric acid.

[0191] Another rubbery polymer suitable for the present invention is one that does not contain styrene. Polymers that do not contain styrene have good moldability, moderate fluidity and heat resistance, as well as excellent chemical resistance, and are preferred rubbery polymers for maintaining a balance of these properties. Examples of polymers that do not contain styrene include polymers obtained by copolymerizing vinyl monomers other than styrene and rubber components that do not contain styrene.

[0192] Other vinyl monomers besides styrene include vinyl cyanide compounds and (meth)acrylic acid ester compounds. Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, with acrylonitrile being particularly preferred. Examples of (meth)acrylic acid ester compounds include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate. The notation (meth)acrylate indicates that it includes both methacrylate and acrylate, and the notation (meth)acrylic acid ester indicates that it includes both methacrylic acid ester and acrylic acid ester. Methyl methacrylate is a particularly suitable (meth)acrylic acid ester compound.

[0193] Other vinyl monomers besides vinyl cyanide compounds and (meth)acrylic acid ester compounds include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide monomers such as maleimide, N-methylmaleimide, and N-phenylmaleimide, and α,β-unsaturated carboxylic acids and their anhydrides such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid.

[0194] Examples of rubber components that do not contain styrene include polybutadiene, polyisoprene, styrene-free diene copolymers (e.g., acrylonitrile-butadiene copolymers, and copolymers of alkyl (meth)acrylate and butadiene), copolymers of ethylene and α-olefins (e.g., ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers), copolymers of ethylene and unsaturated carboxylic acid esters (e.g., ethylene-methacrylate copolymers, and ethylene-butyl acrylate copolymers), copolymers of ethylene and aliphatic vinyl (e.g., ethylene-vinyl acetate copolymers), non-conjugated diene polymers of ethylene and propylene (e.g., ethylene-propylene-hexadiene copolymers), and acrylic rubbers (e.g., polybutyl acrylate, poly(2-ethylhexyl acrylate), and copolymers of butyl acrylate and 2-ethylhexyl acrylate). Among these, polybutadiene, polyisoprene, or diene copolymers, acrylic rubber, and silicone rubber are more readily expressed, with polybutadiene being particularly preferred.

[0195] The weight-average particle size of the rubber particles of the rubber polymer that does not contain styrene is preferably in the range of 0.10 to 1.0 μm, more preferably 0.15 to 0.8 μm, and even more preferably 0.20 to 0.5 μm. When the weight-average particle size of the rubber particles is within the above range, the impact improvement effect due to the addition of graft polymer is less likely to decrease, which is preferable, and the dispersion state with the polycarbonate resin is good, which is preferable as it does not result in a decrease in impact.

[0196] The weight-average particle size of the rubber particles was measured using a transmission electron microscope. Specifically, a drop of the rubbery polymer in emulsion form was placed on a mesh for transmission electron microscopy measurement, stained with osmium tetroxide or ruthenium tetroxide vapor, and then the stained rubbery polymer sample was photographed using a transmission electron microscope (TECNAI G2, FEI, accelerating voltage 120kV). The weight-average particle size was calculated from 200 rubber particles in the captured image using image processing software (Nexus NewQube).

[0197] Here, the diene-based rubber component is a copolymer obtained by polymerizing such that the main constituent unit, 1,3-butadiene, is preferably 50 to 100% by weight, more preferably 65 to 100% by weight, and even more preferably 75 to 100% by weight, and a vinyl monomer represented by methyl methacrylate copolymerizable with it is preferably 50 to 1% by weight, more preferably 35 to 1% by weight, and even more preferably 25 to 1% by weight. It is preferable that the main constituent unit, 1,3-butadiene, be within the above range because sufficient impact properties can be obtained.

[0198] Examples of vinyl monomers used in the formation of this diene-based rubber component include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, and alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. In addition to the above monomers, other examples include vinyl ether monomers, vinylidene halogenated monomers, and vinyl monomers having a glycidyl group such as glycidyl acrylate.

[0199] Furthermore, among the aforementioned vinyl monomers, those that can also be crosslinkable monomers are compounds that can copolymerize with butadiene or vinyl monomers and contain two or more independent C=C bonds within the molecule. Examples include aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; α,β-unsaturated carboxylic acid esters, trimethacrylate or triacrylic acid esters of polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate; allyl esters of α,β-unsaturated carboxylic acids such as allyl acrylate and allyl methacrylate; and di- or triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine.

[0200] The vinyl monomer and the crosslinkable monomer can each be one or more types.

[0201] Furthermore, when forming diene-based rubber components, chain transfer agents (initiators) such as t-dodecyl mercaptan may be used in the polymerization reaction as needed. When preparing the latex of this diene-based rubber component, a particle size-enhancing agent is added to control the weight-average particle size of the diene-based rubber component. Examples of such particle size-enhancing agents include inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, magnesium sulfate, and aluminum sulfate; organic salts such as calcium acetate and magnesium acetate; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and succinic acid; and their organic acid anhydrides, as well as polymer latex containing carboxylic acids.

[0202] A styrene-free rubbery polymer is prepared by graft polymerization of an alkyl (meth)acrylate monomer, or a mixture of alkyl (meth)acrylate and other monomers copolymerized therewith, in one or multiple steps, onto the latex of the rubbery component having the above-described structure.

[0203] In other words, the monomers used in the aforementioned graft polymerization include alkyl (meth)acrylates such as methyl methacrylate and ethyl methacrylate, and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate, as well as styrenes such as styrene, α-methylstyrene, or various halogen-substituted and / or alkyl-substituted styrenes, and vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether. Furthermore, the aforementioned crosslinkable vinyl monomers can also be used in combination with the vinyl monomers. When used in combination with alkyl (meth)acrylates, one or more of these vinyl monomers and crosslinkable monomers can be used.

[0204] In graft polymerization, it is preferable to use 60 to 10 parts by weight of monomer or monomer mixture per 40 to 90 parts by weight of diene rubber component latex, more preferably 58 to 15 parts by weight per 42 to 85 parts by weight, and even more preferably 55 to 20 parts by weight per 45 to 80 parts by weight. Furthermore, when using monomer mixtures, it is preferable that the alkyl (meth)acrylate monomer constitutes at least 25% by weight, more preferably 40% by weight, of the total monomer mixture.

[0205] Graft polymerization itself can be carried out in a single step by adding the monomer or monomer mixture all at once, or it can be carried out in multiple steps by adding the monomer or monomer mixture in two or more separate steps.

[0206] Emulsion polymerization is used as the graft polymerization method. When performing this graft copolymerization, persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate, organic peroxides such as t-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, and diisopropylbenzene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile can be used as polymerization initiators. In addition, the above-mentioned oxidizing agent compounds can be combined with sulfites, bisulfites, thiosulfates, metalloid salts, sodium formaldehyde sulfoxylate, dextrose, etc., and used as redox initiators.

[0207] The reaction temperature in graft copolymerization can be appropriately selected within a range of, for example, 40 to 80°C, depending on the type of polymerization initiator used. Furthermore, for emulsion polymerization, known emulsifiers can be appropriately used as emulsifiers for the rubbery polymer latex.

[0208] The resulting styrene-free rubber polymer is either spray-dried (directly powdered) with an appropriate antioxidant and, if necessary, other additives added to the reaction solution, or without any additives, or by adding a coagulant such as an acid like sulfuric acid, hydrochloric acid, or phosphoric acid, or a salt like calcium chloride or sodium chloride, to the reaction solution to coagulate it, and then further heat-treated to solidify it. After that, it is dehydrated, washed, and finally dried into a powder for use.

[0209] (component ix-2: aromatic vinyl-(hydrogenated) conjugated diene type block copolymer) The aromatic vinyl-(hydrogenated) conjugated diene block copolymer used as component ix-2 is generally used to improve the impact resistance of resin compositions, and examples include ABA-type triblock copolymer and AB-type diblock copolymer.

[0210] A-B type and A-B-A type block copolymer rubber additives include thermoplastic rubbers containing one or two aromatic vinyl blocks (usually styrene blocks) and rubber blocks (such as partially hydrogenated butadiene blocks). Mixtures of these triblock copolymers and diblock copolymers are particularly useful.

[0211] Examples of the above aromatic vinyl monomers include aromatic vinyls such as styrene and α-methylstyrene. In addition to aromatic vinyl monomers, alkyl methacrylate esters such as methyl methacrylate and ethyl methacrylate; alkyl acrylate esters such as ethyl acrylate and n-butyl acrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as methyl vinyl ether and butyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene halides such as vinylidene chloride and vinylidene bromide; vinyl monomers having a glycidyl group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and ethylene glycol glycidyl ether can be used.

[0212] Furthermore, aromatic polyfunctional vinyl compounds such as divinylbenzene and divinyltoluene; polyhydric alcohols such as ethylene glycol dimethacrylate and 1,3-butanediol diacrylate; crosslinkable monomers such as allyl carboxylic acid esters such as trimethacrylic acid ester, triacrylic acid ester, allyl acrylate, and allyl methacrylate, and di- and triallyl compounds such as diallyl phthalate, diallyl sebacate, and triallyl triazine can also be used in combination. These vinyl monomers and crosslinkable monomers can be used singly or in combination of two or more.

[0213] A suitable method for producing an aromatic vinyl-(hydrogenated) conjugated diene type block copolymer is disclosed, for example, in JP-A-8-301929. Typical examples of the aromatic vinyl-(hydrogenated) conjugated diene type block copolymer include, but are not particularly limited to, a styrene-butadiene block copolymer called SBR, a styrene-butadiene-styrene block copolymer called SBS, and a styrene-isoprene-styrene block copolymer called SIS, which are obtained by hydrogenating the butadiene polymer block and the isoprene polymer block respectively, and are generally called SEBS (polystyrene-poly(ethylene / butylene) block-polystyrene copolymer), SEPS (polystyrene-poly(ethylene / propylene) block-polystyrene copolymer), SEP (polystyrene-poly(ethylene / propylene) block copolymer), and SEEPS (polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene copolymer).

[0214] Further, the above-mentioned block copolymer may be used which is modified with a modifying compound having one or more functional groups selected from a hydroxyl group, an amide group, an amino group, a carboxylic acid group, an acid anhydride group, a glycidyl group, a mercapto group, and derivatives thereof.

[0215] As a suitable aromatic vinyl-(hydrogenated) conjugated diene type block copolymer, the weight ratio of the aromatic vinyl compound to the (hydrogenated) conjugated diene is in the range of 5 / 95 to 95 / 5, preferably 10 / 90 to 90 / 10, and further, it is composed of a hydrogenated block copolymer in which 50% or more of the unsaturated bonds based on the conjugated diene of the block copolymer are hydrogenated. Here, when the weight ratio of the vinyl aromatic compound to the conjugated diene constituting the block copolymer is in the range of 5 / 95 to 95 / 5, the effect of improving the impact resistance can be obtained, and the heat resistance and rigidity of the resin composition are less likely to decrease, which is preferable.

[0216] Such A-B and A-B-A block copolymers are commercially available from numerous suppliers, under the trade name KRATON from Kraton Polymers, and under the trade name SEPTON from Kuraray Co., Ltd.

[0217] The content of component ix is ​​preferably 0.1 to 50.0 parts by weight, more preferably 1.0 to 48.0 parts by weight, and even more preferably 2.5 to 45.0 parts by weight, per 100 parts by weight of component A. When the content of component E is within the above range, impact resistance is sufficient and flame retardancy is less likely to decrease.

[0218] (x) Other resins or elastomers The 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, polyolefin resins such as polypropylene and polyethylene, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins, polysulfone resins, polymethacrylate resins, phenolic resins, epoxy resins, cyclic polyolefin resins, polylactic acid resins, polycaprolactone resins, and thermoplastic fluororesins (such as polyvinylidene fluoride resin).

[0219] Examples of elastomers include isobutylene / isoprene rubber, ethylene / propylene rubber, acrylic elastomers, polyester elastomers, and polyamide elastomers.

[0220] (xi) Other additives In addition, the flame-retardant polycarbonate resin composition of the present invention may contain small amounts of well-known additives to impart various functions or improve the properties of the molded article. 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 such as carbon black and titanium dioxide), light diffusing agents (e.g., acrylic crosslinked particles, silicone crosslinked particles, ultrathin glass flakes, calcium carbonate particles), fluorescent dyes, inorganic phosphors (e.g., phosphors with aluminate as the matrix crystal), antistatic agents, nucleating agents, inorganic and organic antimicrobial agents, photocatalytic antifouling agents (e.g., fine particle titanium dioxide, fine particle zinc oxide), radical generators, infrared absorbers (heat absorbers), and photochromic agents.

[0221] (Content of sodium and potassium ions in the flame-retardant polycarbonate resin composition) The total amount of sodium ions and potassium ions contained in the flame-retardant polycarbonate resin composition of the present invention is preferably 1 to 40 ppm. More preferably 1.5 to 38 ppm, even more preferably 2 to 36 ppm, even more preferably 2.5 to 35 ppm, particularly preferably 3 to 35 ppm, and most preferably 3.5 to 34 ppm. When the total amount of sodium ions and potassium ions contained in the resin composition is 40 ppm or less, the decrease in impact strength and flame retardancy after the water exposure test in UL746C f1 rating certification is suppressed. However, since most of the sodium ions and potassium ions contained in the resin composition originate from the polymerization reaction residues of components A, B, C, and D, if the amount is less than 1 ppm, the polymerization of components A, B, C, and D itself may be greatly restricted, so a lower limit of 1 ppm or more is sufficient.

[0222] The amounts of sodium and potassium ions contained in the flame-retardant polycarbonate resin composition are determined by elemental analysis using ICP-AES analysis. The elemental analysis using ICP-AES is performed as follows: The sample is heated and decomposed with sulfuric acid and nitric acid, then diluted to a fixed volume with ultrapure water to prepare the test solution. Qualitative and quantitative analysis of the elements in the test solution is then performed using ICP-AES (SPS5100 model, manufactured by SII Nanotechnology).

[0223] (Manufacturing of flame-retardant polycarbonate resin composition) Any method can be used to produce the flame-retardant polycarbonate resin composition of 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, or extruder mixer, and then the premix may be granulated using an extruder or briquetting machine as needed, followed by melt-kneading in a melt-kneader such as a vented twin-screw extruder, and then pelletized using a pelletizer.

[0224] Other methods include supplying each component independently to a melting and mixing machine, such as a vented twin-screw extruder, or pre-mixing some of the components before supplying them to the melting and mixing machine independently of the remaining components. An example of a method for pre-mixing some of the components is to pre-mix components other than components A and B, and then mix them with the resins of components A and B or supply them directly to the extruder.

[0225] One method of pre-mixing is, for example, if component A is in powder form, a masterbatch of the additive can be produced by blending a portion of the powder with the additive to be blended, and then using this masterbatch. Another method is to supply one component independently from the middle of the melt extruder. If there is a liquid component to be blended, a so-called liquid injection device or liquid additive device can be used to supply it to the melt extruder.

[0226] Preferably, an extruder equipped with a vent capable of removing moisture from the raw material and volatile gases generated from the molten and kneaded resin is used. A vacuum pump is preferably installed in the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. It is also possible to install a screen in the zone in front of the extruder die to remove foreign matter mixed into the extrusion raw material, thereby removing foreign matter from the resin composition. Examples of such screens include wire mesh, screen changers, and sintered metal plates (disc filters, etc.).

[0227] Other types of melting and mixing machines include twin-screw extruders, Banbury mixers, mixing rolls, single-screw extruders, and multi-screw extruders with three or more shafts.

[0228] As described above, the extruded resin is either directly cut and pelletized, or strands are formed and then cut in a pelletizer to form pellets. If it is necessary to reduce the influence of external dust and other contaminants during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the production of such pellets, various methods already proposed for polycarbonate resins for optical discs can be used to appropriately narrow the shape distribution of the pellets, reduce miscuts, reduce fine powder generated during transportation or transport, and reduce air bubbles (vacuum bubbles) generated inside the strands and pellets. These formulations can enable high-cycle molding and reduce the rate of defects such as silver. The shape of the pellets can be general shapes such as cylinders, prismatics, and spheres, but cylinders are more preferable. The diameter of such cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.3 mm. On the other hand, the length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 3.5 mm.

[0229] (Molded article made from the flame-retardant polycarbonate resin composition of the present invention) The flame-retardant polycarbonate resin composition of the present invention can be used to produce various products by injection molding pellets obtained by the method described above. In such injection molding, molded products can be obtained using injection molding methods such as injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including those by injection of supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding, depending on the purpose. The advantages of these various molding methods are already widely known. Furthermore, molding can be performed using either a cold runner system or a hot runner system.

[0230] (Impact strength) For the flame-retardant polycarbonate resin composition of the present invention, the value obtained by measuring the notched Charpy impact strength of the test piece at 23°C in accordance with ISO179 is preferably 20 kJ / m 2 or more, more preferably 25 kJ / m 2 or more, still more preferably 30 kJ / m 2 or more. When the value obtained by measuring the notched Charpy impact strength is less than the respective appropriate ranges, it is difficult to apply in various applications. Although the upper limit is not particularly limited, it can exhibit sufficient performance at 100 kJ / m 2 or less.

[0231] (Impact strength at extremely low temperature) For the polycarbonate resin composition of the present invention, the value obtained by measuring the notched Charpy impact strength of the test piece cooled to -30°C in accordance with ISO179 is preferably 10 kJ / m 2 or more, more preferably 20 kJ / m 2 or more, still more preferably 30 kJ / m 2 or more. When the value obtained by measuring the notched Charpy impact strength is less than the above lower limit, it is difficult to apply in outdoor structural members, various housing members, and automotive-related parts for extremely cold regions. Although the upper limit is not particularly limited, it can exhibit sufficient performance at 100 kJ / m 2 or less.

[0232] (Flame retardancy) For the flame-retardant polycarbonate resin composition of the present invention, in the vertical burning test in accordance with UL94, the UL94 flame retardant rating of the test piece is preferably V-1 or higher, more preferably V-0. When the flame retardant rating is lower than V-1, it is difficult to apply in members that require a high degree of flame retardancy.

[0233] (Durability) The polycarbonate resin composition of the present invention preferably has a retention rate expressed by the following formula, which is determined from the notched Charpy impact strength of a test specimen measured at 23°C before and after a water exposure test in accordance with UL746C, and more preferably 55% or more, even more preferably 60% or more, particularly preferably 65% ​​or more, and most preferably 70% or more. If the retention rate is below the above lower limit, it is difficult to apply to structural members for outdoor use, various housing members, and automotive-related parts. Retention rate (%) = (Charpy impact strength after water exposure test / Charpy impact strength before water exposure test) × 100 Furthermore, it is desirable that the UL94 flame retardancy rating of the test specimen be maintained after conducting a water exposure test in accordance with UL746C. If the flame retardancy rating is not maintained, it will be difficult to apply the material to structural components, various enclosure components, and automotive parts intended for outdoor use.

[0234] Furthermore, the polycarbonate resin composition of the present invention preferably has a total burning time of 50 seconds or less, more preferably 40 seconds or less, even more preferably 35 seconds or less, and particularly preferably 30 seconds or less, in the UL94 flame retardancy test of the test specimen before and after a water exposure test in accordance with UL746C. If the total burning time exceeds the above upper limit, it is difficult to apply to components that require a high degree of flame retardancy. [Examples]

[0235] The embodiments for carrying out the present invention are a combination of preferred ranges of the above requirements, and representative examples are described in the following examples. Of course, the present invention is not limited to these embodiments. Unless otherwise specified, parts in the examples refer to parts by weight, and % refers to weight percent. The evaluation was carried out by the method described below.

[0236] (1) Measurement of sodium ion and potassium ion content in the resin composition The pellets obtained by the method described below were heated and decomposed with sulfuric acid and nitric acid, then diluted to a fixed volume with ultrapure water to prepare the test solution. The sodium and potassium ions in the test solution were quantified using ICP-AES (SPS5100, manufactured by SII Nanotechnology).

[0237] (2) Evaluation of resin composition (i) Charpy impact strength Using ISO bending test specimens with a thickness of 3 mm obtained by the method described below, the notched Charpy impact strength was measured in accordance with ISO 179 under an atmosphere of 23°C or -30°C. (ii) Flame retardant Combustion tests were conducted using 1.5 mm thick UL test specimens obtained by the following method, in accordance with the UL94 vertical combustion test defined by Underwriter Laboratory, Inc., USA. The results were classified and evaluated as V-0, V-1, V-2, and not V. In addition, the UL test after the water exposure test evaluated flame retardancy, including the total burning time. (iii) Durability (a) Charpy impact strength retention rate after water exposure test in UL746C f1 rating certification ISO bending test specimens with a thickness of 3 mm obtained by the method described below were immersed in 70°C hot water for 7 days in accordance with the UL746C water exposure test specified by Underwriter Laboratories, Inc. in the United States. After that, the notched Charpy impact strength was measured in an atmosphere of 23°C according to ISO 179. From these results, the retention rate of the notched Charpy impact strength was calculated using the following formula. Charpy impact strength retention rate (%) = (Charpy impact strength after water exposure test / initial Charpy impact strength) × 100 (b) Flame retardancy after water exposure test in UL746C f1 rating certification UL test specimens with a thickness of 1.5 mm obtained by the method described below were immersed in 70°C hot water for 7 days in accordance with the UL746C water exposure test specified by Underwriter Laboratories, Inc., USA. Afterward, a combustion test was conducted according to the UL94 vertical combustion test specified by Underwriter Laboratories, Inc., USA. The results were classified and evaluated as V-0, V-1, V-2, and not V. The total burning time is also shown in Table 1.

[0238] [Examples 1-19, Reference Example 1, Comparative Examples 1-9] The mixture was supplied from the first feed port of the extruder with the compositions shown in Tables 1 and 2. This mixture was obtained by mixing the premixture (i) below with the other components in a V-type blender. Specifically, (i) is a mixture of component D, a drip inhibitor, and component A, a polycarbonate resin, which was uniformly mixed by shaking the entire polyethylene bag so that component D constituted 2.5% by weight. The amount of mixture supplied was precisely measured using a weighing instrument [Kubota Corporation CWF]. Extrusion was performed using a 30 mmφ vented twin-screw extruder (Japan Steel Works Ltd. TEX30α-38.5BW-3V), with a screw rotation speed of 230 rpm, a discharge rate of 25 kg / h, and a vent vacuum of 3 kPa, by melt-kneading to obtain pellets. The extrusion temperature was 280°C from the first feed port to the die section. A portion of the obtained pellets was dried in a hot air circulating dryer at 100°C for 6 hours, and then ISO bending test specimens (ISO179) and UL test specimens were formed using an injection molding machine at a cylinder temperature of 280°C and a mold temperature of 80°C. The components represented by the symbols in Table 1 are as follows:

[0239] (Component A) A-1: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 25,100, produced by conventional methods from bisphenol A and phosgene; manufactured by Teijin Limited, product name: Panlite L-1250WQ) A-2: Aromatic polycarbonate resin (polycarbonate resin powder with a viscosity-average molecular weight of 20,900, produced by conventional methods from bisphenol A and phosgene, manufactured by Teijin Limited, product name: Panlite L-1225WS) A-3: Polycarbonate resin manufactured by the following method In a reactor equipped with a thermometer, stirrer, and reflux condenser, 3,844 parts of 48% sodium hydroxide aqueous solution and 22,380 parts of deionized water were charged. 1,992 parts of 2,2-bis(4-hydroxy-3-methylphenyl)propane (Bis-C, manufactured by Honshu Chemical, 7.78 mol), 1,773 parts of 2,2-bis(4-hydroxyphenyl)propane (Bis-A, manufactured by Nippon Steel Chemical, 7.78 mol), and 7.53 parts of hydrosulfite (manufactured by Wako Pure Chemical Industries) were dissolved in these mixtures. Then, 13,210 parts of methylene chloride were added, and under stirring, 2,000 parts of phosgene were blown in over approximately 60 minutes at 15-25°C. After the phosgene was blown in, 640 parts of 48% sodium hydroxide aqueous solution and 93.2 parts of p-tert-butylphenol were added, stirring was resumed, and after emulsification, 3.24 parts of triethylamine were added, and the reaction was completed by stirring at 28-33°C for 1 hour. After the reaction was complete, the product was diluted with methylene chloride and washed with water, then acidified with hydrochloric acid and washed with water again, and the washing with water was repeated until the conductivity of the aqueous phase was approximately the same as that of deionized water to obtain a methylene chloride solution of polycarbonate resin. Next, this solution was passed through a filter with a mesh size of 0.3 μm and then dropped into warm water in a kneader with an isolation chamber having a foreign matter outlet in the bearing part, and the polycarbonate resin was flakebed while the methylene chloride was distilled off. Subsequently, the liquid-containing flakes were crushed and dried to obtain a powdered polycarbonate resin. The viscosity-average molecular weight was 20,000. A-4: Recycled polycarbonate resin (recycled polycarbonate resin pellets with a viscosity-average molecular weight of 20,000, recycled from polycarbonate resin sheets) A-5: Recycled polycarbonate resin (recycled polycarbonate resin pellets with a viscosity-average molecular weight of 20,500, recycled from polycarbonate resin headlamp lenses) A-6: Recycled polycarbonate resin (recycled polycarbonate resin pellets with a viscosity-average molecular weight of 20,000, recycled from polycarbonate resin water bottles)

[0240] (B component) B-1: Methyl methacrylate, butyl acrylate, dimethylsiloxane copolymer (Mitsubishi Chemical Corporation's Metabrane SX-005 (product name)) B-2: Methyl methacrylate, butyl acrylate, dimethylsiloxane copolymer (Mitsubishi Chemical Corporation's Metabrane S-2001 (product name)) B-3: Polyorganosiloxane-containing graft copolymer with a polyorganosiloxane rubber component of 60-70% by weight (KANEACE MR-01 (product name) manufactured by Kaneka Corporation) B-4 (Comparative Example): Methyl methacrylate-butadiene-styrene copolymer (Mitsubishi Chemical Corporation, Metabrene E-870A (product name))

[0241] (C component) C-1: Cyclic phenoxyphosphazene in which the content of the k=1 trimer in the following formula (18) is 100 mol% C-2; A cyclic phenoxyphosphazene in which the content of the k=1 trimer in formula (18) below is 98.5 mol%, the content of the k=2 tetramer is 1 mol%, and the content of the k=3 or greater polymer is 0.5 mol. C-3 (Comparative Example): A cyclic phenoxyphosphazene in which the content of the k=1 trimer in formula (18) below is 98 mol%, the content of the k=2 tetramer is 1.5 mol%, and the content of the k=3 or higher polymer is 0.5 mol. C-4 (Comparative Example): A cyclic phenoxyphosphazene in which the content of the k=1 trimer in formula (18) below is 70 mol%, the content of the k=2 tetramer is 20 mol%, and the content of the k=3 or higher polymer is 10 mol%.

[0242] [ka]

[0243] (D component) D-1: Drip prevention agent (polytetrafluoroethylene, manufactured by Mitsubishi Chemical Corporation, Metabren A-3750 (product name)) (Other ingredients) STB-1: Phosphorus-based heat stabilizer (Tris(2,4-di-tert-butylphenyl) phosphite, Irgafos 168 (product name) manufactured by BASF Japan Ltd.) STB-2: Phenolic heat stabilizer (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, molecular weight 531, manufactured by BASF Japan Ltd., Irganox 1076 (product name)) UVA: Benzotriazole-based UV absorber (ADEKA Corporation's ADEKA Stab LA-31 (product name)) WAX: Pentaerythritol fatty acid ester-based release agent (Rikester EW-400 (product name) manufactured by Riken Vitamin Co., Ltd.)

[0244] [Table 1]

[0245] [Table 2] [Industrial applicability]

[0246] The flame-retardant polycarbonate resin composition of the present invention satisfies high levels of impact strength, flame retardancy, and durability, making it widely useful in various fields such as housing equipment, building materials, daily living materials, infrastructure equipment, automobiles, OA / EE applications, and other fields, and is particularly useful in outdoor applications where durability is required.

Claims

1. A flame-retardant polycarbonate resin composition characterized by containing (A) 100 parts by weight of polycarbonate resin (component A), (B) 1 to 20 parts by weight of polyorganosiloxane-containing graft copolymer (component B), (C) 1 to 30 parts by weight of phosphazene (component C) containing 98.5 mol% or more of phosphazene cyclic trimers, and (D) 0.05 to 2 parts by weight of drip inhibitor (component D), wherein component A is an aromatic polycarbonate resin containing a carbonate structural unit (a-1) derived from 2,2-bis(4-hydroxyphenyl)propane and a carbonate structural unit (a-2) derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane.

2. The flame-retardant polycarbonate resin composition according to Claim 1, wherein the proportion of constituent unit (a-2) in the total constituent units is 5 mol% or more.

3. The flame-retardant polycarbonate resin composition according to claim 1 or 2, wherein component (B) is a silicone / acrylic composite rubber graft copolymer obtained by grafting a vinyl polymer composed of one or more vinyl monomer units onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth)acrylate.

4. A flame-retardant polycarbonate resin composition according to any one of claims 1 to 3, wherein the total amount of sodium ions and potassium ions contained in the resin composition is 1 to 40 ppm.

5. A flame-retardant polycarbonate resin composition according to any one of claims 1 to 4, wherein component A is recycled polycarbonate resin.

6. A molded article obtained by molding a resin composition according to any one of claims 1 to 5.

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