JP5481773B2 - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to a flame retardant aromatic polycarbonate resin composition and a flame retardant aromatic polycarbonate resin molded article that have excellent fluidity and exhibit high flame retardancy even when made into a very thin resin molded article. .

  Aromatic polycarbonate resin is a resin excellent in heat resistance, mechanical properties, and electrical properties, and is widely used in automobile materials, electrical / electronic equipment materials, housing materials, and the like. In particular, the flame-retardant aromatic polycarbonate resin composition is used as a member of OA / information equipment such as a computer, a notebook computer, a mobile phone, a printer, and a copying machine.

  In particular, in the field of electrical and electronic equipment, due to the recent miniaturization of mobile phones and digital cameras, etc., product casings and battery cases have become thinner, resulting in excellent fluidity and thinness. Even in such a case, a material having high flame retardancy is required.

  As means for imparting flame retardancy to aromatic polycarbonate resins, the use of halogen-based, phosphorus-based, organopolysiloxane-based, inorganic-based, metal salt-based flame retardants and flame retardant aids has been proposed. In particular, in recent years, organopolysiloxane flame retardants have been studied as flame retardants that do not generate harmful gases during fires or incineration, and that are safe and have little impact on the surrounding environment.

  Organopolysiloxane (hereinafter sometimes referred to as polyorganosiloxane or silicone) is composed of at least one of the following four structural units (M unit, D unit, T unit, Q unit). The organopolysiloxane having a branched structure in the main chain generally includes those containing T units and / or Q units.

  Many methods for imparting flame retardancy using organopolysiloxane have been proposed so far. Among them, a proposal has been made that an aromatic polycarbonate resin containing a branched structure by the above-mentioned T unit and / or Q unit is effective (for example, see Patent Document 1).

  It has also been proposed to use silicone powder (silica carrying a polyorganosiloxane polymer) (see, for example, Patent Document 2).

  However, the addition of organopolysiloxane alone does not provide sufficient flame retardancy, and the amount of organopolysiloxane added is large, resulting in a problem that the mechanical properties of the resin composition are lowered. there were.

  On the other hand, for the purpose of further improving the flame retardancy, a technique using an organopolysiloxane and a metal salt compound in combination has also been proposed (see, for example, Patent Documents 3 and 4). However, even in the methods described in these methods, there is a limit to improving the flame retardancy while maintaining other resin physical properties, and in particular, when the molded body is thin, it is difficult to obtain a stable flame retardancy. There was a general problem.

  On the other hand, by using a specific metal salt in a polycarbonate resin having a terminal hydroxyl group concentration of 3 to 60 mol%, a method for expressing oxygen shielding properties by thermally decomposing and carbonizing earlier at the time of thermal decomposition has been proposed ( For example, see Patent Document 5). However, only the addition of the metal salt compound is insufficient in both fire extinguishing property and sag-preventing property during combustion, and flame retardancy is still insufficient. In addition, even if the terminal hydroxyl group concentration of the polycarbonate resin is controlled, the effect of improving the flame retardancy is actually small, and it is still insufficient to achieve the flame retardancy of the thin resin molded product.

  Furthermore, a method has been proposed in which organopolysiloxane and polytetrafluoroethylene are used for a polycarbonate resin having a weight-average molecular weight of 15,000 to 25000 having a phenolic hydroxyl group terminal of 0.05 parts by weight or more (see, for example, Patent Document 6).

  However, as a result of studying such a polycarbonate resin composition by the present inventors, it has been found that while the fluidity is improved, the flame retardancy is still insufficient or the flame retardancy is deteriorated.

  By the way, in the case of an actual fire, unlike the combustion test of only the target sample in a laboratory, flammable gas is generated by the combustion of combustibles around the fire place, so it is easy to spread fire, etc. It is common to become. For example, it has been pointed out that in a fire caused by heat generation and ignition due to battery abnormality of a personal computer or a mobile phone, it is burnt violently by combustible gas from the battery.

  In order to prevent such a fire spread, as a member such as a casing or a rechargeable battery such as a power supply exterior (battery case), it has excellent flame extinguishing properties and flame retardancy even in a more easily combustible environment as described above. Although materials are desired, no description or suggestion from this point of view has been found in the above-described known technology.

Japanese Patent No. 3240972 Japanese Patent No. 3524192 Japanese Patent No. 3439710 Japanese Patent Laid-Open No. 11-217494 JP-A-8-295595 JP 2000-109668 A

  The object of the present invention is to maintain the excellent mechanical, thermal and electrical properties of aromatic polycarbonate resin in the flame retardant of aromatic polycarbonate resin with non-halogen and non-phosphorus compounds that have less impact on the surrounding environment. The present invention also provides a polycarbonate resin composition having improved fluidity and sufficient flame retardancy as a thin-walled resin molded body and preventing dripping during combustion, and a resin molded body formed by molding the polycarbonate resin composition.

  In particular, it has high flame retardancy even as a thin-walled resin molded product having a thickness of 0.8 mm or less, and has excellent flame retardancy even in a more combustible environment such as an increased oxygen concentration. An object of the present invention is to provide a group polycarbonate resin composition and a resin molded body formed by molding the same.

  In view of the above-mentioned problems, the present inventors, in a resin composition containing an aromatic polycarbonate resin, a metal compound, and an organopolysiloxane, react with the aromatic polycarbonate resin and the organopolysiloxane in the presence of a catalyst of the metal compound to cause noncombustibility. Focusing on the point that by forming the layer, dripping prevention and fire-extinguishing properties are improved, and flame retardancy is expressed, we have studied diligently.

  As a result, the aromatic polycarbonate resin having a specific amount of phenolic hydroxyl group unexpectedly further improves the formation of a non-combustible layer during combustion, has high flame retardancy even when made into a thin molded article, and has flame-retardant properties. It discovered that it might become an improved aromatic polycarbonate resin composition, and completed this invention.

That is, the gist of the present invention is that 0.001 to 1 part by weight of the metal compound (B) and 100 parts by weight of the aromatic polycarbonate resin (A), monofunctional M unit: R ¹ R ² R ³ SiO _{0. 5} , bifunctional D unit: R ⁴ R ⁵ SiO _1.0 , trifunctional T unit: R ⁶ SiO _1.5 and tetrafunctional Q unit: SiO _2.0 (where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each selected from the same or different monovalent hydrocarbon group having 1 to 6 carbon atoms which may be substituted. An aromatic polycarbonate resin composition containing 0.001 to 10 parts by weight of the organopolysiloxane compound (C), wherein the aromatic polycarbonate resin has a phenolic hydroxyl group content of 160 to 1500 ppm, the metal compound ( B) Yes An acid and / or an inorganic acid, a metal salt compound consisting of alkali metal and / or alkaline earth metals, the organopolysiloxane compound (C) comprises 90 to 100 mol% of T units, and the organopolysiloxane molecule It is related with the aromatic polycarbonate resin composition whose ratio of the phenyl group in all the organic substituents couple | bonded with the silicon atom in it is 80 to 100 weight%, and the resin molded object formed by shape | molding this.

  The aromatic polycarbonate resin composition of the present invention maintains the excellent mechanical, thermal, and electrical characteristics of the aromatic polycarbonate resin without using a halogen-based flame retardant or a phosphorus-based flame retardant containing chlorine or bromine. It is a flame retardant aromatic polycarbonate resin composition that has sufficient flame retardancy even when made into a thin-walled resin molded product, and in particular has dripping prevention properties during combustion.

  The aromatic polycarbonate resin composition of the present invention having such features can be applied to a wide range of fields, for example, electric / electronic devices and parts thereof, OA devices, information terminal devices, mechanical components, home appliances, It is useful for various applications such as vehicle parts, building materials, various containers, leisure goods / miscellaneous goods, lighting equipment, etc., especially electrical / electronic equipment, OA equipment, information terminal equipment, home appliance housings, cover members, vehicle exteriors.・ It can be expected to be applied to exterior parts and interior parts.

  Electric and electronic devices, OA devices, information terminal devices, housings for household appliances, cover members include personal computers, game machines, television display devices, printers, copiers, scanners, fax machines, projectors, electronic notebooks and PDAs, electronic devices Desktop calculator, electronic dictionary, camera, video camera, mobile phone, battery case, drive and reader for recording media, mouse, numeric keypad, CD player, MD player, portable radio / audio player housing, cover, keyboard, buttons And a switch member.

  Hereinafter, the present invention will be described in more detail. In addition, the “group” possessed by various compounds means that it may have a substituent without departing from the scope of the present invention.

Aromatic polycarbonate resin (A)
Specifically, the aromatic polycarbonate resin used in the present invention is obtained by, for example, reacting an aromatic dihydroxy compound and a carbonate precursor, or a small amount of a polyhydroxy compound in combination with these. A linear or branched thermoplastic aromatic polycarbonate polymer or copolymer.

  The aromatic polycarbonate resin used in the present invention is not particularly limited, and any conventionally known one can be used. Moreover, the manufacturing method is also arbitrary and a conventionally well-known arbitrary method is employable. Specific examples include an interfacial polymerization method, a melt transesterification method, a pyridine method, a ring-opening polymerization method of a cyclic carbonate compound, and a solid phase transesterification method of a prepolymer.

  Specific examples of the aromatic dihydroxy compound used as a raw material in these polycarbonate resin production methods include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 2,2-bis. (3,5-dibromo-4-hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-tert-butyl) -4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 Bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4- Hydroxyphenyl) -1,1,1-trichloropropane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexachloropropane, 2,2-bis (4-hydroxyphenyl) ) -1,1,1,3,3,3-hexafluoropropane and other bis (hydroxyaryl) alkanes;

  Bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Hydroxyaryl) cycloalkanes;

  Cardostructure-containing bisphenols such as 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene; 4,4′-dihydroxydiphenyl ether; Dihydroxydiaryl ethers such as 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether;

  Dihydroxydiaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3 Dihydroxydiaryl sulfoxides such as 3,3'-dimethyldiphenyl sulfoxide;

  Examples include dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone; hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like.

  Among these, bis (4-hydroxyphenyl) alkanes are preferable, and 2,2-bis (4-hydroxyphenyl) propane [= bisphenol A] is particularly preferable from the viewpoint of impact resistance. These aromatic dihydroxy compounds may be used alone or in combination of two or more in any proportion.

  As the carbonate precursor to be reacted with the aromatic dihydroxy compound, carbonyl halide, carbonate ester, haloformate or the like is used. Specifically, for example, phosgene; diaryl carbonates such as diphenyl carbonate and ditolyl carbonate;

  Dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; dihaloformate of divalent phenol and the like. These carbonate precursors may also be used alone or in combination of two or more in any proportion.

  Next, the manufacturing method of the aromatic polycarbonate resin used for this invention is demonstrated. Of the methods for producing an aromatic polycarbonate resin, the interfacial polymerization method will be described first. In this production method, the polymerization reaction is usually carried out in the presence of an organic solvent inert to the reaction and an aqueous alkaline solution, and the pH is usually kept at 9 or higher, with an aromatic dihydroxy compound and, if necessary, a molecular weight modifier (end stopper). And an antioxidant for preventing oxidation of the aromatic dihydroxy compound, and after reacting with phosgene, a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added, and interfacial polymerization is carried out to obtain a polymer. Get a bonus.

  The addition of the molecular weight regulator is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. In addition, reaction temperature is 0-40 degreeC, for example, and reaction time is several minutes (for example, 10 minutes)-several hours (for example, 6 hours), for example.

  Specific examples of the organic solvent inert to the reaction include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene. Etc .; Examples of the alkali compound used in the alkaline aqueous solution include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.

  Examples of the molecular weight regulator include compounds having a monohydric phenolic hydroxyl group, and specifically include m-methylphenol, p-methylphenol, m-propylphenol, p-propylphenol. And p-tert-butylphenol and p-long chain alkyl-substituted phenol. The amount of the molecular weight regulator used is preferably 50 to 0.5 mol, more preferably 30 to 1 mol, per 100 mol of the aromatic dihydroxy compound.

  Polymerization catalysts include tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride Etc .;

  Next, the melt transesterification method will be described. The polymerization reaction in this production method is, for example, a transesterification reaction between a carbonic acid diester and an aromatic dihydroxy compound. Specific examples of the carbonic acid diester include dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate, diphenyl carbonate, and ditolyl carbonate. And substituted diphenyl carbonates. Among the carbonic acid diesters, diphenyl carbonate or substituted diphenyl carbonate is preferable, and diphenyl carbonate is particularly preferable.

  Further, the aromatic polycarbonate resin used in the present invention may be appropriately adjusted by any conventionally known method because the amount of terminal hydroxyl groups is a factor that greatly affects the flame retardancy. In the melt transesterification reaction, usually, the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of pressure reduction during the transesterification reaction are adjusted to obtain an aromatic polycarbonate having the desired molecular weight and terminal hydroxyl group content adjusted. Can do.

  Usually, in the melt transesterification reaction, an equimolar amount or more of a carbonic acid diester is used with respect to 1 mol of an aromatic dihydroxy compound, among which 1.01 to 1.30 mol, particularly 1.015 to 1.2 mol is used. preferable. Even if the amount of carbonic acid diester used is too small or too large, it is necessary to significantly reduce the reactivity and excessively increase the polymerization time, and it is difficult to adjust the hue and molecular weight and branch chain generation. There is a case. Further, as a more active adjustment method, there may be mentioned a method in which a terminal terminator is added separately during the reaction. Examples of the terminal terminator include monohydric phenols, monovalent carboxylic acids, and carbonic acid diesters.

  When producing polycarbonate by the melt transesterification method, a transesterification catalyst is usually used. Any conventionally known transesterification catalyst can be used. Specifically, for example, alkali metal compounds and / or alkaline earth metal compounds are preferred. In addition, a basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination.

  The transesterification reaction using the above raw materials is usually a reaction at a temperature of 100 to 320 ° C., and finally a melt polycondensation reaction while removing by-products such as aromatic hydroxy compounds under a reduced pressure of 2 mmHg or less. Can be done.

  The melt polycondensation can be performed by either a batch method or a continuous method. Among these, in consideration of the stability of the aromatic polycarbonate resin used in the present invention and the resin composition of the present invention, it is preferable to carry out in a continuous manner. As the catalyst deactivator used in the melt transesterification method, it is preferable to use a compound that neutralizes the transesterification reaction catalyst, such as a sulfur-containing acidic compound or a derivative formed therefrom.

  The amount of the compound that neutralizes the catalyst is preferably 0.5 to 10 equivalents, more preferably 1 to 5 equivalents, and more preferably 1 to the polycarbonate, with respect to the alkali metal contained in the catalyst. -100 ppm, preferably 1-20 ppm.

  The molecular weight of the aromatic polycarbonate resin used in the present invention is arbitrary and may be appropriately selected and determined, but a viscosity average molecular weight [Mv] converted from the solution viscosity is preferably 10,000 to 40,000. As described above, when the viscosity average molecular weight is 10,000 or more, the mechanical strength tends to be further improved, and the viscosity average molecular weight is more preferable when used for an application requiring high mechanical strength. On the other hand, by setting it as 40000 or less, it exists in the tendency to suppress and improve a fluid fall more, and is more preferable from a viewpoint of easy moldability.

  The viscosity average molecular weight is preferably 12,000 to 40,000, particularly preferably 14,000 to 30,000. Two or more aromatic polycarbonate resins having different viscosity average molecular weights may be mixed. At this time, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range may be used.

Here, the viscosity average molecular weight [Mv] is obtained by using methylene chloride as a solvent and obtaining an intrinsic viscosity [η] (unit: dl / g) at a temperature of 20 ° C. using an Ubbelohde viscometer. , Η = 1.23 × 10 ⁻⁴ M ^0.83 . The intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [ηsp] at each solution concentration [C] (g / dl).

  When a branched polycarbonate is used as the aromatic polycarbonate resin used in the present invention, the production method is not particularly limited, and any conventionally known production method can be used. Specifically, for example, as described in JP-A-8-259687, JP-A-8-245782, etc., when an aromatic dihydroxy compound and a carbonic diester are reacted by a melting method (transesterification method), By selecting the catalyst conditions or the production conditions, an aromatic polycarbonate resin having a high structural viscosity index and excellent hydrolysis stability can be obtained without adding a branching agent.

  As another method, in addition to the aromatic dihydroxy compound and the carbonate precursor which are the raw materials of the polycarbonate resin described above, a trifunctional or higher polyfunctional aromatic compound is used, and the phosgene method or the melting method. (Transesterification method) includes a method of copolymerizing them.

  Specific examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl- 2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-3, 1,3,5-tri (4-hydroxyphenyl) ) Polyhydroxy compounds such as benzene, 1,1,1-tri (4-hydroxyphenyl) ethane;

  3,3-bis (4-hydroxyallyl) oxyindole (= isatin bisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like. Of these, 1,1,1-tri (4-hydroxyphenyl) ethane is preferred.

  The polyfunctional aromatic compound can be used by substituting a part of the aromatic dihydroxy compound, and the amount used is 0.01 to 10 mol%, particularly 0.1 to 0.1 mol, based on the aromatic dihydroxy compound. It is preferably 3 mol%.

  Specific examples of the branched structure contained in the aromatic polycarbonate resin obtained by the melting method (transesterification method) include the following general formulas (5) to (8).

（上述の一般式（５）〜（８）において、Ｘは、単結合、炭素数１〜８のアルキレン基、炭素数２〜８のアルキリデン基、炭素数５〜１５のシクロアルキレン基、炭素数５〜１５のシクロアルキリデン基、または、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ−、−ＳＯ_２−で示される２価の基からなる群より選ばれるものを示す。）

(In the above general formulas (5) to (8), X is a single bond, an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 15 carbon atoms, or the number of carbon atoms. 5-15 cycloalkylidene group or,, -O -, - S - , - CO -, - SO -, - SO 2 - in indicating chosen ones from the group consisting of divalent groups represented).

  The branched aromatic polycarbonate resin used in the present invention usually has a structural viscosity index N of 1.2 or more. By using this branched aromatic polycarbonate resin, a dripping prevention effect (dripping of molten resin ignited during combustion) This is preferable since the effect of preventing the increase is increased. Here, the structural viscosity index N is a value described in, for example, a known document (Shigeharu Onoki, “Rheology for chemists”, pages 15 to 16).

  The aromatic polycarbonate resin used in the present invention is required to have a phenolic hydroxyl group content of 160 ppm to 1500 ppm for improving flame retardancy, and is preferably 180 to 1200 ppm, particularly preferably 200 to 1000 ppm. Here, the phenolic hydroxyl group amount refers to the terminal hydroxyl group of the aromatic polycarbonate, but other than that, a structure in which a hydroxyl group is intentionally included in the structure is also included.

  It is preferable that the phenolic hydroxyl group content be 160 ppm or more because the reactivity with the organopolysiloxane is remarkably increased, a nonflammable layer is easily formed during combustion, and high flame retardancy tends to be obtained. When the phenolic hydroxyl group is 1500 ppm or more, the residence heat stability and color tone of the resin composition tend to decrease, and the production of such an aromatic polycarbonate is difficult due to problems such as gelation. As a result, the viscosity average molecular weight is remarkably increased, and the flowability of the resulting aromatic polycarbonate resin composition may be lowered.

  The unit of the amount of phenolic hydroxyl group is the weight of phenolic hydroxyl group expressed in ppm with respect to the weight of the aromatic polycarbonate resin, and the measuring method is colorimetric determination (Macromol. Chem. Chem. 88 215 (1965)).

  The aromatic polycarbonate resin having such a phenolic hydroxyl group can be appropriately adjusted by any conventionally known method. In particular, in the melt transesterification reaction, an aromatic polycarbonate having a desired molecular weight and terminal hydroxyl group content is usually adjusted by adjusting the mixing ratio of the carbonic acid diester and the aromatic dihydroxy compound and the degree of vacuum during the transesterification reaction. Since it can obtain easily, it is especially preferable.

  In the interfacial polymerization method, the amount of phenolic hydroxyl group can be controlled by the reaction conditions such as the reaction temperature, the amount of catalyst, the amount of terminal stopper, and the like. As such an example, for example, Japanese Patent No. 3692022 describes a method for producing an aromatic polycarbonate resin having a phenolic hydroxyl group content of 160 to 1500 ppm.

  The aromatic polycarbonate resin used in the present invention is not particularly limited as long as the amount of the phenolic hydroxyl group is within the above range, but the aromatic polycarbonate resin and aromatic dihydroxy compound produced by the interfacial polymerization method are not limited. It is preferable to mix and use an aromatic polycarbonate resin produced by a transesterification reaction with a carbonic acid diester, and the ratio may be determined by appropriately selecting.

  Compared with the melting method, the interfacial method is relatively easy to adjust the amount of phenolic hydroxyl groups in the resulting aromatic polycarbonate resin, and the amount of phenolic hydroxyl groups is 10 to 200 ppm. It is possible to manufacture the resin with high accuracy. Therefore, by using an aromatic polycarbonate resin by such an interface method, the amount of phenolic hydroxyl group can be adjusted to a desired value.

  In addition, the aromatic polycarbonate resin obtained by the interfacial method is usually in the form of granules, flakes, or powders, and the dispersibility of the components (B), (C), and (D) in the present invention is further improved. Since it can improve, it is preferable. In addition, the aromatic polycarbonate resin obtained by the melt transesterification method can be easily obtained in a highly dispersed state of additives such as a heat stabilizer, an antioxidant, and a release agent in the production process. By using together the aromatic polycarbonate resin produced by the interfacial polymerization method, the aromatic polycarbonate resin produced by the transesterification reaction of the aromatic dihydroxy compound and the carbonic acid diester, the above-described effects can be further improved.

  The aromatic polycarbonate resin used in the present invention is not limited to a polycarbonate resin alone (a polycarbonate resin alone is an embodiment containing only one type of polycarbonate resin, and includes, for example, a plurality of types of polycarbonate resins having different monomer compositions and molecular weights. In addition to an alloy (mixture) of a polycarbonate resin and another thermoplastic resin, for example, an oligomer having a siloxane structure for the purpose of further improving the flame retardancy, which is the object of the present invention, or A copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer, is also included.

  In addition, the aromatic polycarbonate resin used in the present invention may contain an aromatic polycarbonate oligomer in order to improve the appearance of the molded product and the fluidity. The viscosity average molecular weight [Mv] of the aromatic polycarbonate oligomer is preferably 1500 to 9500, particularly preferably 2000 to 9000. The aromatic polycarbonate oligomer is preferably 30% by weight or less of the aromatic polycarbonate resin.

  Furthermore, as the aromatic polycarbonate resin used in the present invention, not only virgin raw materials but also aromatic polycarbonate resins regenerated from used products, so-called material recycled aromatic polycarbonate resins may be used. Used products include optical recording media such as optical disks, light guide plates, vehicle window glass, vehicle headlamp lenses, windshields, and other vehicle transparent members, water bottle containers, glasses lenses, soundproof walls, glass windows, waves, etc. A building member such as a plate is preferred. Also, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used. The regenerated aromatic polycarbonate resin is preferably 80% by weight or less, more preferably 50% by weight or less, among the aromatic polycarbonate resins used in the present invention.

Metal compound (B)
Metal compound used in the present invention and (B) shows that of the metal which can be a catalyst for complex formation of the organopolysiloxane and an aromatic polycarbonate resin at the time of combustion, a compound having such a catalytic function.

  Examples of such metal compounds include organic alkali (earth) metal salts and inorganic alkali (earth) metal salts. Among them, organic alkali (earth) metal salts have excellent dispersibility in aromatic polycarbonate resins. It is preferable because good appearance and flame retardancy tend to be obtained.

  The organic alkali (earth) metal salt in the present invention is formed between an organic acid or an organic acid ester and an alkali metal element or an alkaline earth metal element.

  Alkali metal elements used in organic alkali (earth) metal salts are lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and organic alkali (earth). The alkaline earth metal elements used for the metal salt are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba). Of these, sodium, potassium and cesium are preferable.

  Examples of organic acids used to produce organic alkali (earth) metal salts include organic sulfonic acids, carboxylic acids, phosphoric acids, boric acids, etc. Examples of organic acid esters include sulfonic acid esters, Phosphate ester etc. are mentioned. Of these, sulfonic acid and sulfonic acid ester are preferred.

  As an organic alkali (earth) metal salt (hereinafter sometimes referred to as an organic sulfonic acid metal salt) generated between an organic sulfonic acid and an alkali metal element or an alkaline earth element, an aliphatic sulfonic acid is used. And alkali (earth) metal salts of aromatic sulfonic acid.

  Examples of the aliphatic sulfonic acid include alkane sulfonic acid, sulfonic acid in which a part of the alkyl group of alkane sulfonic acid is substituted with a fluorine atom, and perfluoroalkane sulfonic acid. The above can be used in combination.

  Preferable examples of alkane sulfonic acid include methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, methyl butane sulfonic acid, hexane sulfonic acid, heptane sulfonic acid, octane sulfonic acid, decane sulfonic acid, dodecyl sulfonic acid and the like. These can be used, and one kind or two or more kinds can be used in combination. Moreover, alkanesulfonic acid in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

  On the other hand, preferred examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, Examples thereof include perfluoroheptane sulfonic acid and perfluorooctane sulfonic acid. Among them, those having 1 to 4 carbon atoms are particularly preferable. These can be used alone or in combination of two or more.

  Specific examples of such aliphatic sulfonic acid alkali (earth) metal salts include ethanesulfonic acid sodium salt, dodecylsulfonic acid sodium salt, perfluoromethanesulfonic acid sodium salt, and perfluoromethanesulfonic acid potassium salt. Perfluorobutanesulfonic acid lithium salt, perfluorobutanesulfonic acid sodium salt, perfluorobutanesulfonic acid potassium salt, perfluorobutanesulfonic acid cesium salt, and the like. Preference is given to potassium fluorobutanesulfonate.

  As an aromatic sulfonic acid alkali (earth) metal salt, as the aromatic sulfonic acid moiety, a monomeric or polymeric aromatic sulfide sulfonic acid, aromatic carboxylic acid and / or ester sulfonic acid, monomeric form Or polymeric aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfone sulfonic acid, aromatic ketone sulfonic acid, heterocyclic sulfonic acid , Aromatic sulfoxide sulfonic acid, condensates of aromatic sulfonic acid by methylene type bond, and the like.

  Aromatic sulfonic acid alkali (earth) metal salts having monomeric or polymeric aromatic sulfide sulfonic acid as the aromatic sulfonic acid moiety are described in JP-A No. 50-98539. Examples thereof include diphenyl sulfide-4,4′-disulfonic acid disodium, diphenyl sulfide-4,4′-disulfonic acid dipotassium, and the like. Examples of the sulfonic acid alkali (earth) metal salts of the aromatic carboxylic acid and ester described in JP-A-50-98540 include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polyethylene. Polysodium terephthalate and the like are preferred.

  Aromatic sulfonic acid alkali (earth) metal salts having monomeric or polymeric aromatic ether sulfonic acid as the aromatic sulfonic acid moiety are described in Japanese Patent Application Laid-Open No. 50-98542. For example, calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, polysodium poly (2,6-dimethylphenylene oxide) polysulfonate, poly (1,3-phenylene oxide) polysulfone Polysodium acid, poly (1,4-phenylene oxide) polysulfonic acid polysodium, poly (2,6-diphenylphenylene oxide) polysulfonic acid polypotassium, poly (2-fluoro-6-butylphenylene oxide) polysulfonic acid lithium, etc. Can be mentioned.

  Examples of the alkali (earth) metal salt of aromatic sulfonate sulfonate are described in JP-A No. 50-98544, and specifically, for example, sodium, potassium, cesium salts, and the like of benzene sulfonate sulfonate are preferable. .

  The monomeric or polymeric aromatic (earth) metal salt of aromatic sulfonate is described in Japanese Patent Application Laid-Open No. 50-98546. Specific examples thereof include sodium benzenesulfonate and potassium benzenesulfonate. , Cesium benzenesulfonate, rubidium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, sodium paratoluenesulfonate, potassium paratoluenesulfonate, cesium paratoluenesulfonate, rubidium paratoluenesulfonate, strontium paratoluenesulfonate , Magnesium paratoluenesulfonate, dipotassium metabenzene disulfonate, dipotassium parabenzene disulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl-3,3′- Calcium sulfonate and the like are preferable.

  Aromatic sulfonic acid alkali (earth) metal salts having monomeric or polymeric aromatic sulfonic acid as the aromatic sulfonic acid moiety are described in JP-A-52-54746, For example, sodium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3′-disulfonate, dipotassium diphenylsulfone-3,4′-disulfonate, and the like are preferable.

  An alkali (earth) sulfonate metal salt of an aromatic ketone is described in Japanese Patent Application Laid-Open No. 50-98547, specifically, for example, α, α, α-trifluoroacetophenone-4-sulfone. Sodium acid, benzophenone-3,3′-disulfonic acid dipotassium and the like are preferable.

  Heterocyclic sulfonic acid alkali (earth) metal salts are described in JP-A-50-116542. Specifically, for example, disodium thiophene-2,5-disulfonate, thiophene-2, Preference is given to dipotassium 5-disulfonate, calcium thiophene-2,5-disulfonate, sodium benzothiophene sulfonate and the like.

  Examples of the sulfonate alkali (earth) metal salt of aromatic sulfoxide are described in JP-A No. 52-54745, and specifically, for example, potassium diphenyl sulfoxide-4-sulfonate is preferable.

  Further, as a condensate of an alkali sulfonate alkali (earth) metal salt by a methylene bond, a formalin condensate of sodium naphthalene sulfonate, a formalin condensate of sodium anthracene sulfonate, or the like is preferable.

  On the other hand, the alkali (earth) metal salt of sulfate ester includes, in particular, the alkali (earth) metal salt of sulfate ester of monovalent and / or polyhydric alcohols. Specific examples of the sulfate of monohydric and / or polyhydric alcohols include methyl sulfate, ethyl sulfate, lauryl sulfate, hexadecyl sulfate, polyoxyethylene alkylphenyl ether sulfate, pentaerythritol. Monosulfuric acid ester of mono-, di-, tri-, and tetra-sulfuric acid, sulfuric acid ester of lauric acid monoglyceride, sulfuric acid ester of palmitic acid monoglyceride, and sulfuric acid ester of stearic acid monoglyceride. Of these, alkali (earth) metal salts of lauryl sulfate are preferable.

  Examples of other organic alkali (earth) metal salts used in the present invention include alkali (earth) metal salts of aromatic sulfonamides. Specifically, for example, saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonimide, N- (N′-benzylaminocarbonyl) sulfanilimide, and N- (phenylcarboxyl) sulfanilimide alkali (earth) ) Metal salts and the like.

  The organic alkali (earth) metal salt used in the present invention is preferably an alkali (earth) metal salt of aromatic sulfonic acid or an alkali (earth) metal salt of perfluoroalkanesulfonic acid.

  Moreover, the inorganic alkali (earth) metal salt in this invention is produced | generated between an inorganic acid and an alkali metal element, and an inorganic acid and an alkaline earth metal element, respectively.

  Examples of the alkali metal element include lithium, sodium, potassium, rubidium, and cesium, and sodium, potassium, and cesium are particularly preferable.

  The alkaline earth metal element used for the inorganic alkali (earth) metal salt is beryllium, magnesium, calcium, strontium, or barium, preferably magnesium or calcium.

  Examples of inorganic acids used to produce inorganic alkali (earth) metal salts include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, thiosulfuric acid, pyrosulfurous acid, dithionic acid, Examples thereof include nitric acid, nitrous acid, phosphoric acid, pyrophosphoric acid, boric acid, hexafluoroaluminic acid, hexafluorosilicic acid, hexafluorotitanic acid, hexafluorophosphoric acid, and tetrafluoroboric acid.

  Examples of inorganic alkali (earth) metal salts include alkali metal halides and alkaline earth halides comprising hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide and alkali metal elements or alkaline earth metal elements. Preference is given to metal salts, alkali metal sulfates and alkaline earth metal sulfates composed of sulfuric acid and alkali metal elements or alkaline earth metal elements.

Specific examples of the alkali metal halide salt and the alkaline earth metal halide salt include LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, MgF ₂ , MgCl ₂ MgBr ₂ , MgI ₂ , CaF ₂ , CaCl ₂ , CaBr ₂ , CaI ₂ . Of these, it is particularly preferable to use NaCl, NaBr, KCl, or KBr.

Specific examples of alkali metal sulfate and alkaline earth metal sulfate include Na ₂ SO ₄ , K ₂ SO ₄ , Cs ₂ SO ₄ , MgSO ₄ , CaSO ₄ , Na ₂ SO ₃ , K ₂ SO ₃ , MgSO ₃ , CaSO ₃ , Na ₂ SO ₃ , K ₂ SO ₃ , Cs ₂ SO ₃ , MgS ₂ O ₃ , CaS ₂ O ₃ , Na ₂ S ₂ O ₅ , K ₂ S ₂ O ₅ , MgS ₂ O ₅ , Examples thereof include CaS ₂ O ₅ , Na ₂ S ₂ O ₄ , K ₂ S ₂ O ₄ , MgS ₂ O ₄ , and CaS ₂ O ₄ . Among these, it is particularly preferable to use Na ₂ SO ₄ , K ₂ SO ₄ , or Cs ₂ SO ₄ .

Specific examples of inorganic alkali (earth) metal salts other than the above include NaNO ₃ , KNO ₃ , Mg (NO ₃ ) ₂ , Ca (NO ₃ ) ₂ , NaNO ₂ , KNO ₂ , Mg (NO ₂ ). ₂ , Ca (NO ₂ ) ₂ , Na ₃ PO ₄ , K ₃ PO ₄ , Mg ₃ (PO ₄ ) ₂ , Ca ₃ (PO ₄ ) ₂ , Na ₄ P ₂ O ₇ , K ₄ P ₂ O ₇ , Mg _{2 P 2 O 7, Ca 2} P 2 O 7, Na 2 B 4 O 7, K 2 B 4 O 7, MgB 4 O 7, CaB 4 O 7, Na 3 AlF 6, K 3 AlF 6, Mg 3 ( _{AlF 6) 2, Ca 3 (} AlF 6) 2, Na 2 SiF 6, K 2 SiF 6, MgSiF 6, CaSiF 6, Na 2 TiF 6, K 2 TiF 6, MgTiF 6, CaTiF 6, NaPF 6, KPF 6 , Mg (PF ₆ ) ₂ , Ca (PF ₆ ) ₂ , NaBF ₄ , KBF ₄ , Mg (BF ₄ ) ₂ , and Ca (BF ₄ ) ₂ may be mentioned.

  The content of the metal compound in the present invention is 0.001 to 1 part by weight, particularly 0.005 to 0.5 part by weight, particularly 0.01 to 0.3 part by weight based on 100 parts by weight of the aromatic polycarbonate resin. Part. When the content of the metal compound is less than 0.001 part by weight, the flame retardant effect is insufficient, and when it exceeds 1 part by weight, not only the effect reaches a peak, but also the thermal properties and mechanical properties such as a decrease in molecular weight are reduced. May reduce flame retardancy.

Organopolysiloxane (C)
The organopolysiloxane used in the present invention is composed of at least one of the following four units (M unit, D unit, T unit, Q unit).

  Specific examples of such organopolysiloxanes include M / D, M / D / T, M / D / T / Q, M / D / Q, M / T, and M / T. / Q, M / Q, D, D / T, D / T / Q, D / Q, T, T / Q combinations.

  Among them, organopolysiloxane having a branched structure in the main chain is preferable because it tends to exhibit good flame retardancy. Such organopolysiloxanes contain T units and / or Q units, and specifically include M / D / T, M / D / T / Q, M / D / Q, and M units. / T system, M / T / Q system, M / Q system, D / T system, D / T / Q system, D / Q system, T system, and T / Q system.

  Especially M / D / T, M / D / T / Q, M / T, M / T / Q, D / T, D / T / Q, T, T / Q, etc. What contains a T unit essential is preferable. On the other hand, the flame retardant effect may be insufficient because the molecular weight is too low in the M alone system. In addition, in the Q alone system, since the inorganic property is too strong, the dispersibility in the aromatic polycarbonate resin may be extremely lowered.

  The D-based organopolysiloxane naturally includes cyclic siloxanes such as D3 (trimer), D4 (tetramer), D5 (pentamer), and D6 (hexamer).

  Examples of such cyclic siloxane include hexamethylcyclotrisiloxane, hexaethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, 1,3,5,7-tetraethoxy- 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrapropoxycyclotetrasiloxane, 1,3,5,7-tetramethyl- Examples include 1,3,5,7-tetravinylcyclotetrasiloxane, dodecamethylcyclopentasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and the like.

The proportion of each unit in each combination described above is arbitrary, T units 9 0 to 100 mol% including.

  Further, the organopolysiloxane in the present invention may contain a hydroxyl group (silanol group) or an alkoxy group as a terminal group. The content of the end group is preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, and particularly preferably 2 to 7.5% by weight. Those with too little end group content are difficult to obtain due to difficulties in chemical industrial production, and those with more than 10 parts by weight cause self-condensation of the organopolysiloxane during kneading with the aromatic polycarbonate resin. As a result, the dispersibility in the aromatic polycarbonate is lowered, which may cause a reduction in the flame-retardant effect and hydrolysis of the aromatic polycarbonate resin composition.

  Among the above end groups, examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, and a butoxy group. Among these, a methoxy group and an ethoxy group are particularly preferable.

The monofunctional M unit contained in the organopolysiloxane used in the present invention is R ¹ R ² R ³ SiO _0.5 and the bifunctional D unit is R ⁴ R ⁵ SiO _1.0 . Trifunctional T units are each represented by R ⁶ SiO _1.5 . Here, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each selected from the same or different monovalent hydrocarbon groups having 1 to 6 carbon atoms, which may be substituted, for example, Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group and cyclohexyl group, alkenyl groups such as vinyl group and allyl group, and aryl groups such as phenyl, and methyl group and phenyl group are particularly preferable.

The content of aryl groups, particularly phenyl groups, in the organopolysiloxane greatly affects the moldability, transparency, mechanical strength, and flame retardancy of the aromatic polycarbonate resin composition. The higher the phenyl group content in the organopolysiloxane, the higher the dispersibility and compatibility with the aromatic polycarbonate resin, and the better the moldability, transparency, mechanical strength, and flame retardancy. Therefore, the proportion of the phenyl groups in the total organic substituents attached to silicon atoms in the organopolysiloxane molecule, Ru 8 0-100 wt% der.

  The organopolysiloxane used in the present invention may contain a functional group such as an epoxy group, an alkoxy group, a hydrosilyl (SiH) group, or a vinyl group in addition to the organic group described above in the molecule. By containing these special functional groups, the compatibility with the aromatic polycarbonate resin is improved, the reactivity at the time of combustion is improved, and as a result, flame retardancy may be increased.

  The weight average molecular weight of the organopolysiloxane used in the present invention is not particularly limited, but is usually 450 to 100,000, preferably 750 to 20,000, more preferably 1000 to 10,000, and particularly preferably 1500 to 5,000. Those having a weight average molecular weight that is too small are difficult to obtain due to difficulty in chemical industrial production, and may not be suitable for use in which the heat resistance of the silicone resin is extremely low. If the weight average molecular weight is too large, the flame retardancy tends to decrease because of poor dispersibility, and the mechanical properties of the resin composition tend to decrease. The weight average molecular weight is usually measured by GPC (gel permeation chromatograph).

  The content of the organopolysiloxane component in the present invention is 0.001 to 10 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. If the content of the organopolysiloxane component is too small, the resulting polycarbonate resin composition will have insufficient flame retardancy and dripping prevention properties. Conversely, if the content is too large, the appearance of the polycarbonate resin molded product will be poor and the mechanical strength will be reduced. In some cases, heat resistance and thermal stability may be reduced.

  Therefore, the content of the organopolysiloxane in the present invention is preferably 0.03 to 7 parts by weight, more preferably 0.1 to 5 parts by weight, particularly 0.5 to 0.5 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin. The amount is preferably 3.5 parts by weight. The organopolysiloxane used in the present invention may be used alone or in combination of two or more in any ratio.

  Moreover, you may use what mixed and / or impregnated organopolysiloxane with inorganic fillers, such as a silica powder, a talc powder, and calcium carbonate. By impregnating such an inorganic filler, particularly silica powder, it is possible to improve the dispersibility in the aromatic polycarbonate resin.

  As an organopolysiloxane impregnated with such an inorganic filler, for example, a powder of polydimethylsiloxane having a viscosity of 60000 cSt supported on silica (Toray Dow Corning Silicone Co., Ltd., Trefil F202, containing polydimethylsiloxane) Amount 60% by weight) and the like.

Fluoropolymer (D)
The resin composition in the present invention may further contain a fluoropolymer for the purpose of enhancing flame retardancy and dripping prevention. As such a fluoropolymer, any conventionally known one can be used, and among these, a fluoroolefin resin is preferred. As the fluoroolefin resin, a polymer or copolymer containing a fluoroethylene structure is usually used. Specifically, for example, difluoroethylene resin, tetrafluoroethylene resin, tetrafluoroethylene / hexafluoropropylene copolymer resin, and the like are used. Can be mentioned. Among these, tetrafluoroethylene resin and the like are preferable, and as this fluoroethylene resin, a fluoroethylene resin having fibril forming ability is preferable.

  Specific examples of the fluoroethylene resin having fibril-forming ability used in the present invention include Teflon (registered trademark) 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd., Polyflon F201L manufactured by Daikin Chemical Industries, and Polyflon F103. . Examples of the aqueous dispersion of fluoroethylene resin include Teflon (registered trademark) 30J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Fullon D-1 manufactured by Daikin Chemical Industries. Furthermore, in the present invention, a fluoroethylene polymer having a multilayer structure obtained by polymerizing vinyl monomers can also be used, and specific examples include METABRENE A-3800 manufactured by Mitsubishi Rayon Co., Ltd.

  The content of the fluoropolymer in the present invention is 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. If the fluoropolymer content is too low, the resulting polycarbonate resin composition will have insufficient flame retardancy and dripping prevention properties. Conversely, if it is too high, the appearance of the polycarbonate resin molded product will be poor and the mechanical strength will be reduced. There is a case.

  Therefore, the content of the fluoropolymer in the present invention is preferably 0.05 to 0.45 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin, and more preferably 0.075 to 0.4 parts by weight, particularly 0. 0.1 to 0.35 parts by weight is preferable.

Other Components The aromatic polycarbonate resin composition of the present invention may contain other resins and various resin additives as long as they do not impair the object of the present invention.

  Examples of other resins include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, and polybutylene terephthalate resin; polystyrene resin, high impact polystyrene resin (HIPS), and acrylonitrile-styrene copolymer (AS resin). Styrene resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin); polyethylene Polyolefin resins such as resins and polypropylene resins; Polyamide resins; Polyimide resins; Polyetherimide resins; Polyurethane resins; Polyphenylene ether resins; Resins; polysulfone resins; polymethacrylate resins, polylactic acid (PLA), polybutylene succinate (PBS) resin, and the like. These may be used in combination of two or more types may be used alone.

  As various resin additives, any conventionally known heat stabilizer, antioxidant, mold release agent, ultraviolet absorber, dye / pigment, flame retardant, anti-dripping agent, antistatic agent, antifogging agent, lubricant -An anti-blocking agent, a fluidity improver, a plasticizer, a dispersant, a fungicide, etc. may be appropriately selected and used. Two or more of these may be used in combination. Hereinafter, the additive used for the flame-retardant aromatic polycarbonate resin composition of the present invention will be described.

  Examples of the heat stabilizer include phosphorus compounds. As the phosphorus compound, any conventionally known compound can be used. Specifically, for example, phosphorus oxo acids such as phosphoric acid, phosphonic acid, phosphorous acid, phosphinic acid and polyphosphoric acid; acidic pyrophosphate metal salts such as acidic sodium pyrophosphate, acidic potassium pyrophosphate and acidic calcium pyrophosphate; phosphoric acid Group 1 or Group 2B metal phosphates such as potassium, sodium phosphate, cesium phosphate, and zinc phosphate; organic phosphate compounds, organic phosphite compounds, organic phosphonite compounds, and the like. Among these, the organic phosphate compound represented by the following general formula (13) and / or the organic phosphite compound represented by the following general formula (14) are preferable.

O = P (OH) _m (OR) _3-m (13)
(In the above formula, R represents an alkyl group or an aryl group, which may be the same or different, and m represents an integer of 0 to 2.)

（式中、Ｒ’はアルキル基またはアリール基を示し、それぞれ同一でも、異なっていてもよい。）

(In the formula, R ′ represents an alkyl group or an aryl group, which may be the same or different.)

  In general formula (13), R is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and particularly preferably an alkyl group having 2 to 25 carbon atoms. M is preferably 1 or 2.

  In general formula (14), R ′ is preferably an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms. Preferable specific examples of the organic phosphite represented by the general formula (7) include distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

  The content of these phosphorus compounds is preferably 0.001 to 1 part by weight with respect to 100 parts by weight of the aromatic polycarbonate resin, particularly 0.01 to 0.7 parts by weight, particularly 0.03 to 0 parts. .5 parts by weight is preferred.

  Examples of the antioxidant include hindered phenol antioxidants. Specifically, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate Thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-tert- Butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl ] Phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-( Citylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-tert- Butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4,6-bis ( Octylthio) -1,3,5-triazin-2-ylamino) phenol and the like, and two or more of these may be used in combination.

  Among the above, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate is preferred. These two phenolic antioxidants are commercially available from Ciba Specialty Chemicals under the names “Irganox 1010” and “Irganox 1076”.

  The content of the antioxidant is usually 0.001 to 1 part by weight, preferably 0.01 to 0.5 part by weight, based on 100 parts by weight of the aromatic polycarbonate resin. If the content is too small, the effect is insufficient. Conversely, if the content is too large, the effect reaches its peak and is not economical.

  Specific examples of the release agent include aliphatic carboxylic acids, alcohol esters thereof, aliphatic hydrocarbon compounds having a number average molecular weight of 200 to 15000, polysiloxane silicone oil, and the like.

  Examples of the aliphatic carboxylic acid include saturated or unsaturated, linear or cyclic aliphatic 1 to 3 carboxylic acids. Among these, monovalent or divalent carboxylic acids having 6 to 36 carbon atoms are preferable, and aliphatic saturated monovalent carboxylic acids having 6 to 36 carbon atoms are particularly preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, mellicic acid, tetrariacontanoic acid, and montanic acid. , Adipic acid, azelaic acid and the like.

  As the aliphatic carboxylic acid in the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. Examples of the alcohol moiety of the ester include saturated or unsaturated, linear or cyclic, monovalent or polyhydric alcohols, which may have a substituent such as a fluorine atom or an aryl group. Among them, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and saturated aliphatic monovalent or polyhydric alcohols having 30 or less carbon atoms are particularly preferable.

  Specific examples of such alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaol. Examples include erythritol. The aliphatic carboxylic acid ester may contain an aliphatic carboxylic acid and / or alcohol as an impurity, and may be a mixture of a plurality of aliphatic carboxylic acid esters.

  Specific examples of the aliphatic carboxylic acid ester include beeswax (a mixture based on myricyl palmitate), stearyl stearate, behenyl behenate, stearyl behenate, glycerin monopalmitate, glycerin monostearate, glycerin diester. Examples thereof include stearate, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate and the like.

  Examples of the aliphatic hydrocarbon having a number average molecular weight of 200 to 15000 include liquid paraffin, paraffin wax, microwax, polyethylene wax, Fischer-Tropsch wax, and α-olefin oligomer having 3 to 12 carbon atoms. Here, the aliphatic hydrocarbons also include alicyclic hydrocarbons, and these hydrocarbon compounds may be partially oxidized.

  Among these aliphatic hydrocarbons, paraffin wax, polyethylene wax, or a partial oxide of polyethylene wax is preferable, and paraffin wax and polyethylene wax are particularly preferable. The number average molecular weight is preferably 200 to 5,000. These aliphatic hydrocarbons may be a single substance, or may be a mixture of various constituent components and molecular weights, as long as the main component is within the above range.

  Examples of the polysiloxane-based silicone oil include dimethyl silicone oil, phenylmethyl silicone oil, diphenyl silicone oil, fluorinated alkyl silicone, and the like, and these may be used alone or in combination of two or more.

  The content of the release agent in the present invention is usually 0.001 to 2 parts by weight, preferably 0.01 to 1 part by weight, with respect to 100 parts by weight of the aromatic polycarbonate resin. If the content of the release agent is too low, the release effect is not sufficiently exhibited. Conversely, if the content is too high, degradation of the hydrolysis resistance of the aromatic polycarbonate resin or mold contamination during injection molding occurs. There is a case.

  Specific examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, and organic ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, and triazine compounds. Among them, organic ultraviolet absorbers are preferable. In particular, benzotriazole compounds, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2, 4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2 ′-(1,4-phenylene) bis [4H-3,1-benzoxazine-4- ON], [(4-methoxyphenyl) -methylene] -propanedioic acid-dimethyl ester is preferred.

  Specific examples of the benzotriazole compound include condensates of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol. Specific examples of other benzotriazole compounds include 2-bis (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3 ′, 5′-di-tert-butyl-2′-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3,5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy- 3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2,2′-methyl Ren-bis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] [methyl-3- [3-tert-butyl-5- (2H- Benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol] condensate. These may be used alone or in combination of two or more at any ratio.

  Among these benzotriazole compounds, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H -Benzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazin-2-yl] -5- (octyloxy) phenol, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6 -(2N-benzotriazol-2-yl) phenol] and the like are preferable.

  Content of the ultraviolet absorber in this invention is 0.01-3 weight part normally with respect to 100 weight part of aromatic polycarbonate resin, Preferably it is 0.1-1 weight part. If the content of the ultraviolet absorber is too small, the effect of improving the weather resistance may be insufficient. Conversely, if the content is too large, problems such as mold deposit may occur.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes. Inorganic pigments include, for example, sulfide pigments such as carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc -Oxide pigments such as iron-based brown, titanium-cobalt-based green, cobalt-green, cobalt-blue, copper-chromium-based black, copper-iron-based black; chromic acid such as chrome, molybdate orange Pigments: ferrocyan pigments such as bitumen.

  Organic pigments and organic dyes include: phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine And condensed polycyclic dyes such as isoindolinone and quinophthalone; anthraquinone, heterocyclic, and methyl dyes.

  These may be used alone or in combination of two or more at any ratio, and from the viewpoint of thermal stability, titanium oxide, carbon black, cyanine series, quinoline series, anthraquinone series, phthalocyanine series compounds and the like are preferable. .

  The content of the dye / pigment is usually 5 parts by weight or less, particularly 3 parts by weight or less, and particularly preferably 2 parts by weight or less with respect to 100 parts by weight of the aromatic polycarbonate resin. If the content of the dye / pigment is too large, the impact resistance may decrease.

  A conventionally well-known arbitrary thing can be used as a flame retardant, and you may use together 2 or more types in arbitrary ratios. Of these, organometallic salt flame retardants, silicone flame retardants, and inorganic compound flame retardants (auxiliaries) that have a very low possibility of environmental pollution are preferred. Inorganic compound flame retardant (auxiliary) agents include talc and mica. , Kaolin, clay, silica powder, fumed silica, and glass flakes.

  The content of the flame retardant in the present invention is usually 0.0001 to 30 parts by weight, particularly 0.01 to 25 parts by weight, particularly 0.1 to 20 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin. Preferably there is. If the content of the flame retardant is too small, the flame retardant effect becomes insufficient. Conversely, if the content is too large, the heat resistance and mechanical properties may be significantly reduced.

Production of Aromatic Polycarbonate Resin Composition The aromatic polycarbonate resin composition of the present invention is characterized by containing a specific amount of the above-mentioned organopolysiloxane and metal compound in an aromatic polycarbonate resin. And the manufacturing method in particular is not restrict | limited, What is necessary is just to select and select suitably from the conventionally well-known arbitrary manufacturing methods of a resin composition.

  Specifically, the method for producing the aromatic polycarbonate resin composition of the present invention includes, for example, the above-described aromatic polycarbonate, a metal compound component, and, if necessary, other additive components such as a tumbler or a Henschel mixer. Examples thereof include a method of premixing using various mixers and then melt-kneading with a Banbury mixer, a roll, a brabender, a single-screw kneading extruder, a twin-screw kneading extruder, a kneader or the like.

  Alternatively, the resin composition may be produced by mixing each component in advance, or by mixing only a part of the components in advance, supplying the mixture to an extruder using a feeder, and melt-kneading the mixture. Furthermore, a resin composition obtained by mixing some components in advance and supplying them to an extruder and melt-kneading is used as a master batch, and again mixed with other components and melt-kneaded to produce a resin composition. You can also.

  In particular, in the method for producing the aromatic polycarbonate resin composition of the present invention, the above-described organopolysiloxane or metal compound is masterbatched with a resin component in advance to produce a resin composition, whereby dispersibility and further extrusion work. This is preferable because of improved properties. Further, from the viewpoint of improving the dispersibility of the metal compound described above, it can be kneaded after dissolving it in a solvent such as water or an organic solvent in advance.

Production of Resin Molded Body The aromatic polycarbonate resin molded body of the present invention can obtain the above-described aromatic polycarbonate resin composition of the present invention by any conventionally known resin molding method. The method for producing the resin molded body is not particularly limited, and a molding method generally used for thermoplastic resins can be used.

  Specifically, as a method for producing a resin molded body, for example, a general injection molding method, an ultra-high speed injection molding method, an injection compression molding method, a two-color molding method, a hollow molding method such as gas assist, and a heat insulating mold are used. Molding method used, molding method using rapid heating mold, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method Method, thermoforming method, rotational molding method, laminate molding method, press molding method and the like. A molding method using a hot runner method can also be used.

  In particular, when an electric / electronic device member such as a battery case is used as the resin molding, molding by injection molding is preferable from the viewpoint of molding speed and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples, unless the summary is exceeded. “Part” means “part by weight”.

Resin pellet production Each component listed in Table 1 was blended in the ratio (weight ratio) listed in Table 3, mixed for 20 minutes with a tumbler, and then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent. The molten resin, which was kneaded under the conditions of a screw rotation speed of 200 rpm, a discharge rate of 15 kg / hour, and a barrel temperature of 260 ° C. and extruded into a strand, was rapidly cooled in a water tank and pelletized with a pelletizer.

  In addition, when two or more kinds of polycarbonate resins are used in combination, the amount of the phenolic hydroxyl group of the polycarbonate resin is, for example, an aromatic polycarbonate resin A (part by weight) having an amount of phenolic hydroxyl group of X (ppm) and Y (ppm). When using the aromatic polycarbonate resin B (parts by weight), it was determined as X × A + Y × B / (A + B).

Preparation of UL Test Specimen Pellets obtained by the above production method were dried at 120 ° C. for 5 hours, and then a cylinder temperature of 300 ° C. and a mold temperature of 80 using a J50-EP injection molding machine manufactured by Nippon Steel. A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was formed by injection molding under the conditions of ° C and a molding cycle of 30 seconds.

Preparation of test piece for flame extinction test After drying the pellet obtained by the above-mentioned production method at 120 ° C. for 5 hours, using a J50-EP type injection molding machine manufactured by Nippon Steel Works, cylinder temperature 300 ° C., mold temperature 80 A test piece having a length of 124 mm, a width of 6 mm, and a thickness of 3 mm was formed by injection molding under the conditions of C. and a molding cycle of 30 seconds.

Flame Retardancy Test The flame retardant evaluation of each aromatic polycarbonate resin composition was conducted by conditioning a UL test sample for 48 hours in a temperature-controlled room at 23 ° C. and 50% humidity. UL) It was performed in accordance with UL94 test (combustion test of plastic material for equipment parts) defined by UL. UL94V is a method for evaluating flame retardancy from the after-flame time and drip properties after indirect flame of a burner for 10 seconds on a test piece of a predetermined size held vertically, V-0, V- In order to have flame retardancy of 1 and V-2, it is necessary to satisfy the criteria shown in Table 2 below.

  Here, the afterflame time is the length of time for which the test piece continues to be flammable after the ignition source has been moved away, and the drip cotton ignition is a mark approximately 300 mm below the lower end of the test piece. This is determined by whether the cotton used is ignited by a drip from the specimen. Moreover, when one of the five samples did not satisfy the above criteria, it was evaluated as NR (not rated) because V-2 was not satisfied.

Flame extinction test Using candle method combustion tester D (manufactured by Toyo Seiki Seisakusho) in accordance with JIS K7201-2, oxygen index OI (%) is fixed at 30%, each sample is indirect flame for 10 seconds, flame is The time from release to complete extinction was measured, and the average value of three times was determined. It shows that flame-extinguishing property is so high that this value is small.

Flowability Evaluation Resin pellets of the resin composition are dried at 120 ° C. for 4 hours or more, and using a high load type flow tester, the flow rate Q value of the composition per unit time at 280 ° C. and a load of 160 kgf / cm 2 ( Unit: ml / s) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used. It shows that it is excellent in fluidity | liquidity, so that Q value is high.

Claims (10)

0.001 to 1 part by weight of the metal compound (B) with respect to 100 parts by weight of the aromatic polycarbonate resin (A), monofunctional M unit: R ¹ R ² R ³ SiO _0.5 , bifunctional D Unit: R ⁴ R ⁵ SiO _1.0 , trifunctional T unit: R ⁶ SiO _1.5 and tetrafunctional Q unit: SiO _2.0 (where R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are each selected from monovalent hydrocarbon groups having 1 to 6 carbon atoms which may be substituted.) Organopolysiloxane compound ( C) is an aromatic polycarbonate resin composition containing 0.001 to 10 parts by weight of the aromatic polycarbonate resin and having a phenolic hydroxyl group content of 160 to 1500 ppm, wherein the metal compound (B) contains an organic acid and / Or inorganic acid A metal salt compound consisting of alkali metal and / or alkaline earth metals, the organopolysiloxane compound (C) comprises 90 to 100 mol% of T units and, bonded to the silicon atom in the organopolysiloxane molecule An aromatic polycarbonate resin composition, wherein the proportion of phenyl groups in all organic substituents is 80 to 100% by weight. 2. The aromatic polycarbonate resin composition according to claim 1, wherein the proportion of phenyl groups in all organic substituents bonded to silicon atoms in the organopolysiloxane molecule is 100% by weight. The aromatic polycarbonate resin composition according to claim 1 or 2 , wherein the aromatic polycarbonate resin (A) has a phenolic hydroxyl group content of 200 to 1200 ppm. The aromatic polycarbonate resin according to any one of claims 1 to 3 , wherein the aromatic polycarbonate resin (A) is an aromatic polycarbonate resin produced by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester. Resin composition. The aromatic polycarbonate resin (A) is composed of an aromatic polycarbonate resin produced by an interfacial polymerization method, an aromatic polycarbonate resin produced by a transesterification reaction between an aromatic dihydroxy compound and a carbonic acid diester. Item 5. The aromatic polycarbonate resin composition according to any one of Items 1 to 4 . Furthermore, 0.001-0.5 weight part of fluoropolymer (D) is contained with respect to 100 weight part of aromatic polycarbonate resin (A), The Claim 1 thru | or 5 characterized by the above-mentioned. Aromatic polycarbonate resin composition. To any one of claims 1 to 6, characterized in that flame retardancy evaluation in compliance with UL94 test by the test piece having a thickness of 0.8mm obtained by molding the aromatic polycarbonate resin composition is V-0 The aromatic polycarbonate resin composition described. An aromatic polycarbonate resin molded article obtained by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 7 . The resin molded article according to claim 8 , which is an electric / electronic device member. It is a battery case, The resin molding of Claim 8 characterized by the above-mentioned.