JP4381115B2 - Thermoplastic polycarbonate resin composition having flame retardancy and molded product thereof - Google Patents

Description

  The present invention relates to a thermoplastic polycarbonate resin composition imparted with flame retardancy by a thermoplastic polycarbonate resin derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure, and a molded article thereof. In particular, it is suitably used for thin conductive sheets and films that require flame retardancy. Specifically, it is used for home appliances and OA equipment that are highly demanded of flame retardancy.

  Thermoplastic polycarbonate resin is formed into various molded products by a simple and highly productive processing method such as injection molding, and is used in a wide range of industrial fields such as electrical and electronic equipment, OA equipment, heavy electrical machinery, precision machinery, and automotive fields. ing. On the other hand, a thermoplastic polycarbonate resin composition having flame retardancy obtained by adding a halogen compound or a phosphorus compound to a thermoplastic polycarbonate resin is used in OA equipment, home appliances, etc., which have a strong demand for flame retardancy. In recent years, the use of flame retardants containing no halogen has been studied in various ways due to the increasing interest in environmental issues, particularly in Europe.

  However, when using a phosphoric acid ester compound, red phosphorus, etc. as a flame retardant, a flame odor is generated during extrusion / molding, and there are problems such as adversely affecting mechanical and thermal properties. Therefore, various flame retardants that replace halogen compounds and phosphorus compounds have been studied.

  Examples of flame retardants that can replace the flame retardants listed above include silicone compounds. In recent years, a flame retardant resin composition in which a silicone compound is blended with a thermoplastic polycarbonate resin has been extensively studied and various proposals have been made.

  For example, a method in which an alkali (earth) metal salt of perfluoroalkanesulfonic acid and an organosiloxane having an alkoxy group, a vinyl group, and a phenyl group are blended in a polycarbonate resin (see Patent Document 1), and perfluoroalkanesulfonic acid in a polycarbonate resin. A method of blending an alkali metal salt or an alkaline earth metal salt with an organopolysiloxane containing an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group (see Patent Document 2), and Si— A method of blending any one or more of a silicone compound having an H bond and a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt (see Patent Document 3) has been proposed.

A non-silicone resin having an aromatic ring having a unit represented by the formula R ₂ SiO _1.0 and a unit represented by RSiO _1.5 , and having a weight average molecular weight of 10,000 or more and 270,000 or less. A method of blending (see Patent Document 4) has been proposed.

  However, the above-mentioned proposed polycarbonate resin composition has not been sufficiently flame retardant. For example, in the case of a thin sheet or film, there is a problem that a drip is generated, and it is not possible to comply with the flame retardant regulation for electrical equipment plastics defined by the US UL standards, and the 94VTM-1 rank cannot be achieved.

  On the other hand, a thermoplastic polycarbonate resin (component b) derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure has been disclosed as a resin and an optical member, but is effective for flame retardancy. It is unclear (see Patent Document 5). In addition, there is a description that a polycarbonate oligomer derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure has a flame-retardant effect on a thin molded article (see Patent Document 6). When molding a product, the oligomer component bleeds out, and there is a problem that the molded product becomes cloudy.

JP-A-6-306265 JP-A-6-336547 JP 2002-37997 A Japanese Patent Laid-Open No. 10-139964 JP-A-2001-342247 Japanese Patent Laid-Open No. 2002-220455

  The present invention is intended to solve the above-described conventional problems and the like, and has a good anti-drip performance even in a thin sheet or a film-shaped molded article, has excellent flame retardancy, and The object is to provide a thermoplastic polycarbonate resin composition having excellent heat resistance.

As a result of intensive research aimed at achieving the above object, the present inventors have made a thermoplastic polycarbonate resin (component a), a thermoplastic polycarbonate derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure. A resin (component b), an organic sulfonic acid metal salt (component c) and an organopolysiloxane (component d), and
Each of the above components is blended in the following ratio with respect to 100 parts by weight of the total amount of (component a) and (component b): a thermoplastic polycarbonate resin composition having flame retardancy (component a) 0.1 to 94.5 parts by weight (component b) 5 to 99.4 parts by weight (component c) 0.01 to 0.5 parts by weight (component d) 0.1 to 10 parts by weight It has been found that even a sheet or a film-like molded product has a good anti-drip performance, has excellent flame retardancy, and has excellent heat resistance, and has completed the present invention.

  The flame-retardant thermoplastic polycarbonate resin composition of the present invention and the molded product thereof include, as a flame retardant, a thermoplastic polycarbonate resin derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure, and organic Metal salt of sulfonic acid, organopolysiloxane (preferably (d-1) phenyl group-containing branched silicone resin, (d-2) Si-H group-containing silicone oil and / or (d-3) phenyl group, vinyl Group and an alkoxy group-containing silicone oil) in combination, so that not only thick molded products, but also thin sheet-shaped molded products, film-shaped molded products have good anti-drip performance, It has excellent flame resistance and excellent heat resistance. Therefore, it is useful for members that require flame retardancy.

The thermoplastic polycarbonate resin composition having flame retardancy and a molded product thereof according to the present invention are a heat derived from a thermoplastic polycarbonate resin (component a), a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure. A plastic polycarbonate resin (component b), an organic sulfonic acid metal salt (component c) and an organopolysiloxane (component d), and
Each of the above components is blended in the following ratio with respect to 100 parts by weight of the total amount of (component a) and (component b).
(Component a) 0.1 to 95 parts by weight, preferably 10 to 89.5 parts by weight (Component b) 5 to 99.9 parts by weight, preferably 10 to 89.5 parts by weight (Component c) 0.01 to 0.5 part by weight (component d) 0.1 to 10 parts by weight In addition, even if the proportion of (component a) is less than 0.1 part by weight, the proportion of (component b) is less than 5 parts by weight (component a) (Component b), which is not preferable because the polymer blend is less in any of the components, and a synergistic effect for improving flame retardancy cannot be obtained.

（式中、Ｒ_１〜Ｒ_４は、各々独立して、水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基又は炭素数１〜５のアルコキシ基を有することもできる。Ｒ_５〜Ｒ_８は、各々独立して、水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基又は炭素数１〜５のアルコキシ基を有することもできる。Ｒ_９は、炭素数１〜６の脂肪族基を表すか単に結合を表す。Ｘは、−Ｓｉ（Ｒ_１０）（Ｒ_１１）Ｏ−単位の単独重合体、又は２種以上の−Ｓｉ（Ｒ_１０）（Ｒ_１１）Ｏ−単位からなるブロック共重合体若しくはランダム共重合体を表し、重合度は０〜２００であり、Ｒ_１０〜Ｒ_１１は、各々独立して、水素、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基又は炭素数１〜５のアルコキシ基を有することもできる。）
一般式（２）

（Ｒ_１２〜Ｒ_１３は、各々独立して、水素、炭素数１〜１０のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数７〜１７のアラルキル基であり、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基又は炭素数１〜５のアルコキシ基を有することもできる。Ｙは、下記に列挙した二価の基の一であり、

ここに、Ｒ_１４〜Ｒ_１７は、各々独立して、水素、炭素数１〜１０のアルキル基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数６〜１２のアリール基を表すか、Ｒ_１４とＲ_１５、及び／又は、Ｒ_１６とＲ_１７が一緒に結合して、炭素数３〜１２の炭素環（但し、フルオレン構造を除く）又は複素環を形成する基を表し、これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基又は炭素数１〜５のアルコキシ基を有することもできる。ａは０〜２０の整数を表す。） Thermoplastic polycarbonate resin (component a)
In the present invention, two types of (component a) and (component b) are used as the thermoplastic polycarbonate resin. Therefore, the thermoplastic polycarbonate resin (component a) is precisely a thermoplastic polycarbonate resin other than the thermoplastic polycarbonate resin (component b) derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure. Should be understood. (Component a) may have a siloxane structure, but may be a thermoplastic polycarbonate resin derived from a dihydric phenol not having at least a fluorene structure.
More specifically, (component a) is a thermoplastic polycarbonate resin derived from a dihydric phenol represented by the following general formula (1) and a dihydric phenol represented by the following general formula (2), and / or It is a thermoplastic polycarbonate resin derived from a dihydric phenol represented by the formula (2), and the dihydric phenol unit of the general formula (1) is a dihydric phenol unit in the thermoplastic polycarbonate resin (component a). It is preferable that it is 0 to 50 weight% with respect to the total amount. From the viewpoints of good reactivity and availability at low cost, it is preferable to use a thermoplastic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane as (component a).
General formula (1)

(In the formula, R _{1 to} R ₄ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number It may also have an alkoxy group of 1 to 5. R _{5 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 2 to 5 carbon atoms. An alkenyl group, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent is a C 1-5 alkyl group or a carbon number 2 Having -5 alkenyl groups or C1-5 alkoxy groups Rukoto may .R ₉ is, .X _{is, -Si (R 10) (R} 11) a homopolymer of O- units representing a mere bond or represents an aliphatic group having 1 to 6 carbon atoms, or two It represents a block copolymer or a random copolymer composed of the above -Si (R ₁₀ ) (R ₁₁ ) O-unit, the degree of polymerization is 0 to 200, and R _{10 to} R ₁₁ are each independently Hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, In the case where the group has a carbon atom, it may have a C 1-5 alkyl group, a C 2-5 alkenyl group or a C 1-5 alkoxy group as a substituent.)
General formula (2)

(R _{12 to} R ₁₃ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms Y is one of the divalent groups listed below,

Here, R _{14 to} R ₁₇ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. Represents an aryl group, or R ₁₄ and R ₁₅ and / or R ₁₆ and R ₁₇ are bonded together to form a carbocyclic ring having 3 to 12 carbon atoms (excluding a fluorene structure) or a heterocyclic ring. In the case where these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. . a represents an integer of 0 to 20. )

（式中、Ｒ_１８〜Ｒ_２１は、各々独立して、水素原子、炭素数１〜５のアルキル基、炭素数６〜１２のアリール基、炭素数２〜５のアルケニル基、炭素数１〜５のアルコキシ基又は炭素数７〜１７のアラルキル基を表す。これらの基に炭素原子を有する場合には置換基として、炭素数１〜５のアルキル基、炭素数２〜５のアルケニル基又は炭素数１〜５のアルコキシ基を有することもできる。） Thermoplastic polycarbonate resin derived from dihydric phenol having siloxane structure and dihydric phenol having fluorene structure (component b)
In the present invention, the thermoplastic polycarbonate resin of (component b) is composed of a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure in order to impart flame retardancy by blending with the above (component a). Be guided. More specifically, (component b) is a thermoplastic polycarbonate resin derived from a dihydric phenol represented by the general formula (1) and a dihydric phenol represented by the following general formula (3), or a general formula ( A thermoplastic polycarbonate resin derived from a dihydric phenol represented by 1), a dihydric phenol represented by the general formula (2) and a dihydric phenol represented by the general formula (3), and thermoplastic Based on the total amount of dihydric phenol units in the polycarbonate resin, the dihydric phenol unit of the general formula (1) is 10 to 90% by weight, the dihydric phenol unit of the general formula (3) is 10 to 90% by weight, and the general formula The dihydric phenol unit (2) is preferably 0 to 80% by weight.
General formula (3)

(In the formula, R _{18 to} R ₂₁ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxy group or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or carbon (Also have an alkoxy group of 1 to 5)

As the dihydric phenol of the general formula (1) used in the present invention, it is general that R _{5 to} R ₈ of the general formula (1) are at least one selected from a methyl group and a phenyl group, Specifically, the following are exemplified.

  Two or more of these dihydric phenols can be used in combination. X preferably includes 1 to 100 dimethylsiloxanes or 1 to 100 diphenylsiloxanes, and random copolymers thereof. Among them, in particular, α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyl diphenyl random copolymer siloxane and α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane are used. At least one selected from the group is preferred.

  Specific examples of the dihydric phenol of the general formula (2) used in the present invention include 4,4′-biphenyldiol, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, and bis (4 -Hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1- Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane (bisphenol Z; BPZ), 2,2-bis (4-hydro Cis-3-methylphenyl) propane (dimethylbisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane ( Bisphenol AP (BPAP), bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-allylphenyl) propane, 3,3,5-trimethyl-1,1-bis (4-hydroxyphenyl) ) Cyclohexane (trimethylbisphenol-Z; TMBPZ) and the like. These can be used in combination of two or more. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

  Specific examples of the dihydric phenol of the general formula (3) used in the present invention include 9,9-bis (4-hydroxy-2-methylphenyl) fluorene and 9,9-bis (4-hydroxy-3- Methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methoxy-4-hydroxy) Phenyl) fluorene, 9,9-bis (3-ethoxy-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 4,5-dimethyl-9,9-bis ( 4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 3,6-dimethyl-9,9-bis (3- Chill-4-hydroxyphenyl) fluorene and 3,6-diphenyl-9,9-bis (4-hydroxyphenyl) fluorene, and the like. Among these, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxy-2-methylphenyl) fluorene are particularly preferable. preferable. Two or more of these compounds can be used in combination.

  Further, in the production of the thermoplastic polycarbonate resin described below, the carbonate ester-forming compound to be reacted with the above-mentioned various dihydric phenols includes, for example, phosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p- Bisallyl carbonates such as tolyl carbonate, di-p-chlorophenyl carbonate, dinaphthyl carbonate and the like can be mentioned. Two or more of these compounds can be used in combination.

  In the case of the thermoplastic polycarbonate resin (component a), the dihydric phenol of the general formula (1) and the dihydric phenol of the general formula (2) and / or the dihydric phenol of the general formula (2) are also used. In the case of a thermoplastic polycarbonate resin (component b) derived from a dihydric phenol having a structure and a dihydric phenol having a fluorene structure, the dihydric phenol of the general formula (1) and the dihydric phenol of the general formula (3), Alternatively, the dihydric phenol represented by the general formula (1), the dihydric phenol represented by the general formula (2), and the dihydric phenol represented by the general formula (3) are used as raw materials and reacted with a carbonate ester-forming compound, respectively. be able to. The reaction method is a known method used in producing a polycarbonate derived from bisphenol A, for example, a direct reaction between bisphenols and phosgene (phosgene method), or a transesterification reaction between bisphenols and bisaryl carbonate. A method such as (transesterification method) can be employed.

  That is, in the phosgene method, the dihydric phenol of the general formula (1), the dihydric phenol of the general formula (2), and the divalent of the general formula (3) are usually present in the presence of an acid binder and a solvent as described above. A raw material appropriately selected from phenol is reacted with phosgene. Examples of the acid binder include pyridine and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Examples of the solvent include methylene chloride, chloroform, chlorobenzene, and xylene. Furthermore, in order to accelerate the polycondensation reaction, a catalyst such as a tertiary amine catalyst such as triethylamine is added as a molecular weight modifier, and a monofunctional compound such as phenol is added as a molecular weight modifier for adjusting the degree of polymerization. Further, if desired, an antioxidant such as sodium sulfite and hydrosulfite, phloroglucin, isatin bisphenol, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4 A small amount of a branching agent such as -hydroxyphenyl) -1,3,5-triisopropylbenzene may be added, and the reaction is usually in the range of 0 to 150 ° C., preferably 5 to 40 ° C. Although the reaction time depends on the reaction temperature, it is usually 0.5 minutes to 10 hours, preferably 1 minute to 2 hours, and it is desirable to maintain the pH of the reaction system at 10 or more during the reaction. .

  On the other hand, in the transesterification method, as described above, a raw material appropriately selected from the dihydric phenol of the general formula (1), the dihydric phenol of the general formula (2) and the dihydric phenol of the general formula (3) is used. Mix with aryl carbonate and react at elevated temperature under reduced pressure. The reaction is usually carried out at a temperature in the range of 150 to 350 ° C., preferably 200 to 300 ° C., and the degree of vacuum is preferably 1 mmHg or less at the end, and phenols derived from the bisaryl carbonate produced by the transesterification reaction Is distilled out of the system. The reaction time depends on the reaction temperature, the degree of reduced pressure and the like, but is usually about 1 to 6 hours. The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon, and the reaction may be performed by adding an antioxidant or a branching agent as desired.

  In the phosgene method and the transesterification method, in consideration of the reactivity of the dihydric phenol of the general formula (1), the dihydric phenol of the general formula (2) and the dihydric phenol of the general formula (3), the phosgene method is more preferable.

  When employing the phosgene method, examples of the tertiary amine polymerization catalyst used include triethylamine, tri-n-propylamine, tri-n-butylamine, N, N′-dimethylcyclohexylamine, N, N′-diethyl. Although there are aniline, diethylaminopyridine and the like, triethylamine is preferable from the viewpoint of catalyst activity and washing removal. The addition amount of the polymerization catalyst is preferably 0.001 to 5 mol% with respect to all bisphenols used.

  Furthermore, when employing the phosgene method, a small amount of a quaternary ammonium salt may be added in order to carry out the reaction efficiently. Specific examples include tetramethylammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium iodide and the like. Among these, trimethylbenzylammonium chloride and triethylbenzylammonium chloride are exemplified. preferable. In general, the quaternary ammonium salt is preferably used in an amount of 0.0005 to 5 mol% with respect to all bisphenols used.

  When a molecular weight regulator is used, the monofunctional compound is particularly preferably a monohydric phenol, specifically, phenol, butylphenol, octylphenol, nonylphenol, decanylphenol, tetradecanylphenol, heptadecanylphenol, octa Alkyl substituted phenols such as decanylphenol; hydroxybenzoic acid alkyl esters such as butyl hydroxybenzoate, octyl hydroxybenzoate, nonyl hydroxybenzoate, decanyl hydroxybenzoate, heptadecanyl hydroxybenzoate; butoxyphenol, octyloxyphenol, nonyloxy Alkyls such as phenol, decanyloxyphenol, tetradecanyloxyphenol, heptadecanyloxyphenol, octadecanyloxyphenol, etc. Oxy phenols are exemplified. The addition amount of this molecular weight regulator is 0.1-50 mol% with respect to all the bisphenols. Preferably, it is 0.5 to 10 mol%.

  The thermoplastic polycarbonate resin (component a) and the thermoplastic polycarbonate resin (component b) derived from a dihydric phenol having a siloxane structure and a dihydric phenol having a fluorene structure, which are the main components of the composition of the present invention, are both The intrinsic viscosity [η] at 20 ° C. in dichloromethane is preferably in the range of 0.2 to 1.0 dl / g. If the intrinsic viscosity [η] of the thermoplastic polycarbonate is lower than 0.2 dl / g, the mechanical strength of the thermoplastic polycarbonate resin composition of the present invention is low, and if it is higher than 1.0 dl / g, the moldability is inferior.

  In the thermoplastic polycarbonate resin (component a) used in the present invention, the dihydric phenol unit of the general formula (1) is preferably 0 with respect to the total amount of dihydric phenol units in the thermoplastic polycarbonate resin (component a). It is preferable to be ˜50 wt%, more preferably 0 to 30 wt%. The thermoplastic polycarbonate resin (component b) used in the present invention is preferably such that the dihydric phenol unit of the general formula (1) is based on the total amount of dihydric phenol units in the thermoplastic polycarbonate resin (component b). 10 to 90% by weight, more preferably 20 to 50% by weight. If it is less than 10% by weight, the effect as a flame retardant cannot be exhibited, which is not preferable. On the other hand, if it exceeds 90% by weight, the strength of the molded product cannot be maintained when (Concentration b) is added at a high concentration, which is inconvenient.

As the thermoplastic polycarbonate resin composition of the present invention, that is, when both (component a) and (component b) are combined, the dihydric phenol unit of the general formula (1) is preferably (component a) and ( It is preferably 1 to 50% by weight, more preferably 2 to 20% by weight, based on the total amount of all dihydric phenol units in component b).
When the dihydric phenol unit of the general formula (1) of the thermoplastic polycarbonate resin composition of the present invention is less than 1% by weight, the target flame retardancy (UL, 94VTM-1) is difficult to obtain. On the other hand, if it exceeds 20% by weight, the effect of improving the flame retardancy is not sufficiently recognized for the amount, and if it exceeds 50% by weight, it is represented by the general formulas (2) and (3). Regardless of the type of polyhydric phenol unit, the strength as a molded product cannot be maintained, which is inconvenient.

  The thermoplastic polycarbonate resin composition of the present invention preferably has a 1% heat loss temperature of 380 ° C. or higher and / or a 5% heat loss temperature of 430 ° C. or higher in thermogravimetric analysis under nitrogen. More preferably, the 1% heat loss temperature is 400 ° C. or higher and / or the 5% heat loss temperature is 450 ° C. or higher.

Organic sulfonic acid metal salt (component c)
The organic sulfonic acid metal salt (component c) used in the thermoplastic polycarbonate resin composition of the present invention is not particularly limited, and examples thereof include aliphatic sulfonic acid metal salts and aromatic sulfonic acid metal salts. The metal of the sulfonic acid metal salt is preferably an alkali metal, alkaline earth metal, etc., and the alkali metal and alkaline earth metal are sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium. And barium. A sulfonic acid metal salt may be used independently, and 2 or more types can also be mixed and used for it.

  The organic sulfonic acid metal salt is preferably a perfluoroalkane-sulfonic acid metal salt, an aromatic sulfonesulfonic acid metal salt or the like from the viewpoint of flame retardancy and thermal stability.

  Preferred examples of the perfluoroalkane-sulfonic acid metal salt include alkali metal salts of perfluoroalkane-sulfonic acid, alkaline earth metal salts of perfluoroalkane-sulfonic acid, and the like. Examples thereof include sulfonic acid alkali metal salts having 8 perfluoroalkane groups and sulfonic acid alkaline earth metal salts having 4 to 8 carbon perfluoroalkane groups.

  Specific examples of perfluoroalkane-sulfonic acid metal salt include perfluorobutane-sodium sulfonate, perfluorobutane-potassium sulfonate, perfluoromethylbutane-sodium sulfonate, perfluoromethylbutane-potassium sulfonate, perfluoro Examples include octane-sodium sulfonate, potassium perfluorooctane-sulfonate, and tetraethylammonium salt of perfluorobutane-sulfonic acid.

  The aromatic sulfonesulfonic acid metal salt is preferably an aromatic sulfonesulfonic acid alkali metal salt, an aromatic sulfonesulfonic acid alkaline earth metal salt, or the like. The acid alkaline earth metal salt may be a polymer.

  Specific examples of the aromatic sulfonesulfonic acid metal salt include sodium salt of diphenylsulfone-3-sulfonic acid, potassium salt of diphenylsulfone-3-sulfonic acid, and 4,4′-dibromodiphenyl-sulfone-3-sulfonic acid. Sodium salt, potassium salt of 4,4′-dibromodiphenylsulfone-3-sulfone, calcium salt of 4-chloro-4′-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3′-disulfonic acid di Examples thereof include sodium salts and dipotassium salts of diphenylsulfone-3,3′disulfonic acid.

  The compounding amount of the organic sulfonic acid metal compound (component c) is 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the total amount of (component a) + (component b). If the blending amount is less than 0.01 parts by weight, the flame retardant effect is reduced. If the blending amount is more than 0.5 parts by weight, not only a further improvement in the flame retardant effect can be expected, but also foaming of the molded product and poor appearance are caused. .

Organopolysiloxane (component d)
The organopolysiloxane (component d) used in the thermoplastic polycarbonate resin composition of the present invention is a thermoplastic polycarbonate resin (component) derived from a dihydric phenol having the siloxane structure and a dihydric phenol having a fluorene structure. There is no particular limitation as long as it has a flame retardant effect in cooperation with b) or an organic sulfonic acid metal salt (component c).
(D-1) Phenyl Group-Containing Branched Silicone Resin Preferred examples of the organopolysiloxane (component d) used in the present invention include phenyl group-containing branched silicone resins. The substance (d-1) is preferably an organopolysiloxane having a phenyl group bonded to a silicon atom in the molecule, represented by the following average composition formula (4). Moreover, this organopolysiloxane may be used individually by 1 type, or may use 2 or more types from which a composition and a structure differ.
Average composition formula (4)
(R ₂₂ ) _m (R ₂₃ ) _n (OR ₂₄ ) _p (OH) _q SiO _{(4-mnpq) / 2}
Wherein R ₂₂ is a phenyl group, R ₂₃ is a monovalent hydrocarbon group having 1 to 6 carbon atoms (excluding the phenyl group), and R ₂₄ is a monovalent hydrocarbon group having 1 to 4 carbon atoms. M, n, p, q are 0.5 ≦ m ≦ 2.0; 0.1 ≦ n ≦ 2.3; 0 ≦ p ≦ 0.2; 0 ≦ q ≦ 0.3; (The number satisfies the requirement of 9 ≦ m + n + p + q ≦ 2.8.)

  Furthermore, the phenyl group-containing branched silicone resin has a branched structure in the molecule. The branched structure referred to here is a T unit and / or Q which will be described later as a siloxane unit indicating the structure of organopolysiloxane. Defined as containing units.

This organopolysiloxane has a phenyl group bonded to a silicon atom in the molecule from the viewpoint of dispersibility in a thermoplastic polycarbonate resin and a flame-retarding effect. M corresponding to the number of substituted moles of the group (R ₂₂ ) is in the range of 0.5 ≦ m ≦ 2.0, preferably in the range of 0.6 ≦ m ≦ 1.4.

On the other hand, R ₂₃ is a monovalent hydrocarbon group having 1 to 6 carbon atoms (excluding the phenyl group), and by containing an appropriate amount of this substituent, the three-dimensional structure of the organopolysiloxane molecule containing a bulky phenyl group is included. This has the effect of reducing the obstacles and improving the spatial freedom, facilitating the overlapping of the phenyl groups and enhancing the flame retarding effect. Accordingly, R ₂₃ includes an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group, and an alkenyl having 2 to 6 carbon atoms such as a vinyl group, an allyl group, and a butenyl group. Groups are preferred. In particular, a methyl group and a vinyl group are preferred from the viewpoint of reducing steric hindrance and industrially. To achieve the effect as described _above, 0.1 ≦ n ≦ 2.3 in the range content with the value of n in the above formula (4) _{R 23,} preferably 0.5 ≦ n ≦ 2. A range of zero.

R _{24 in} the alkoxy group of the above formula (4) is a monovalent hydrocarbon group having 1 to 4 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. A group is exemplified, and a methyl group is particularly preferably used industrially. The value of p corresponding to the residual alkoxy group content is preferably 0.2 or less.

  In addition, silanol groups contained in organopolysiloxane may remain for reasons of production method, have low reactivity and hardly contribute to flame retardancy, but storage stability and thermoplastic polycarbonate resin From the viewpoint of stability and moldability during melt processing, the content is preferably 0.3 or less in terms of q in the above formula (4).

  The molecular weight of such a phenyl group-containing branched silicone resin is not particularly limited, but if the molecular weight is too large or too small, the dispersibility in the thermoplastic polycarbonate resin and the flame retarding effect will be insufficient. Therefore, in the above formula (4), 0.9 ≦ m + n + p + q ≦ 2.8, preferably 1.1 ≦ m + n + p + q ≦ 2.4. Furthermore, the weight average molecular weight is preferably 2,000 or more, more preferably in the range of 2,000 to 50,000, and particularly preferably in the range of 3,000 to 15,000.

  Such a phenyl group-containing branched silicone resin can be produced by a conventionally known method. For example, according to the structure of the desired organopolysiloxane, the corresponding organochlorosilanes may be co-hydrolyzed in the presence of alcohol having 1 to 4 carbon atoms to remove by-product hydrochloric acid and low-boiling components. You can get things. In addition, when using alkoxysilanes having an organic residue such as phenyl group or methyl group in the molecule, silicone oil or cyclic siloxane as a starting material, an acid catalyst such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc. is used, In some cases, water for hydrolysis is added to advance the polymerization reaction, and then the acid catalyst and low-boiling components used are similarly removed to obtain the desired organopolysiloxane. In addition, in order to make silanol group content into the above-mentioned range, it is also possible to block the silanol group remaining after hydrolysis by reacting with a silylating agent such as hexamethyldisilazane or trimethylchlorosilane.

(D-2) Si-H group-containing silicone oil Further, the preferred organopolysiloxane (component d) used in the present invention may be a Si-H group-containing silicone oil. This substance (d-2) is an organopolysiloxane having a methyl group bonded to a silicon atom and a hydrogen atom (Si-H group) in the molecule and does not contain an aromatic hydrocarbon group. As long as it is a thing, it may be linear or may have a branched structure. Specifically, various silicone compounds having a methyl group and a Si—H group at any one of a side chain, a terminal, and a branch point in a molecular structure, or a plurality of sites can be used effectively. Moreover, the said organopolysiloxane may be used individually by 1 type, or may use 2 or more types from which a composition and a structure differ.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units.
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _{1/2 and} other monofunctional siloxane units D units: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO, etc. Unit T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (C ₆ H ₅ ) SiO _3/2 , (CH ₂ ═CH) SiO _3/2 trifunctional siloxane units Q units etc: tetrafunctional siloxane represented by SiO ₂ As the structure of the position various organopolysiloxanes, specifically, _{M 2,} D _n as rational _{formula, T p, M m D n} , M m T p, M m Q q, M m D n T p, M _m D _n Q _q , M _m T _p Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q , and D _n T _p Q _q are mentioned. structure preferred organopolysiloxane used as -H group-containing silicone oil _is a _{M m D n, M m T} p, M m D n T p, M m D n Q q, more preferred structure, M _m D _n, a _M m _D n _{T p.}

  Here, the coefficients m, n, p, and q in the above formula are positive numbers representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the degree of polymerization of the organopolysiloxane. When any of m, n, and p is a numerical value of 2 or more, the 1-3 functional siloxane units with the coefficient are two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. be able to.

  The Si-H group-containing silicone oil has at least a methyl group and a Si-H group in any of 1 to 3 functional siloxane units, M units, D units, and T units in the above formula, and is aromatic carbonized. Other organic groups that these siloxane units can have, although they do not have a hydrogen group, include an alkyl group such as an ethyl group, a propyl group, a butyl group, and a hexyl group, a cycloalkyl group such as a cyclohexyl group, Examples thereof include alkenyl groups such as vinyl group and allyl group. Among these, an alkyl group having 1 to 4 carbon atoms such as an ethyl group or a propyl group or a vinyl group is preferable.

The Si—H group content in such an organopolysiloxane is not particularly limited, but is preferably 0.3 mol / 100 g or more from the viewpoint of flame retardancy. The Si-H group content referred to here is the number of moles of Si-H groups contained per 100 g of organopolysiloxane, which was generated per unit weight of organopolysiloxane by the alkali decomposition method. It can be determined by measuring the volume of hydrogen gas. For example, when 122 ml of hydrogen gas is generated per 1 g of organopolysiloxane at 25 ° C., the Si—H group content is 0.5 mol / 100 g according to the following calculation formula.
122 × 273 / (273 + 25) ÷ 22400 × 100≈0.5
In the present invention, an organopolysiloxane having a Si—H group content in the range of 0.3 to 1.6 mol / 100 g can be particularly preferably used.

  The molecular weight of such Si—H group-containing silicone oil is not particularly limited, but from the viewpoint of dispersibility in thermoplastic polycarbonate resin and improved mobility during combustion, the weight average molecular weight is It is preferable to set it as 10,000 or less. On the other hand, when the molecular weight is too small, there are many components that volatilize out of the system when melt-mixed with the resin, and the flame retardancy effect is not exhibited, and there is a risk of causing defects such as molding defects due to the volatile components. Therefore, it is preferable to use an organopolysiloxane having a weight average molecular weight of 600 to 10,000, particularly 1,000 to 8,000.

  Such Si—H group-containing silicone oil can be produced by a conventionally known method. For example, according to the structure of the target organopolysiloxane, the target product can be obtained by cohydrolyzing the corresponding organochlorosilanes and removing by-product hydrochloric acid and low-boiling components. In addition, when starting from silicone oils having organic residues such as Si-H bonds or methyl groups in the molecule, cyclic siloxanes or alkoxysilanes, acid catalysts such as hydrochloric acid, sulfuric acid, methanesulfonic acid, etc. are used. In some cases, water for hydrolysis is added to allow the polymerization reaction to proceed, and then the target organopolysiloxane can be obtained by similarly removing the acid catalyst and low boiling point used. .

(D-3) Phenyl group, vinyl group and alkoxy group-containing silicone oil The preferred organopolysiloxane (component d) used in the present invention may be a phenyl group, vinyl group and alkoxy group-containing silicone oil. The oil referred to here includes oil that is branched because of its low molecular weight. The substance (d-3) is preferably an organopolysiloxane having a phenyl group, a vinyl group and an alkoxy group bonded to a silicon atom in the molecule represented by the following average composition formula (5). Moreover, this organopolysiloxane may be used individually by 1 type, or may use 2 or more types from which a composition and a structure differ.
Average composition formula (5)
(R ₂₅ ) _l (R ₂₆ ) _m (R ₂₇ ) _n (OR ₂₈ ) _p (OH) _q SiO _{(4-1-mnpq) / 2}
(In the formula, R ₂₅ represents a phenyl group, R ₂₆ represents a vinyl group, R ₂₇ represents an alkyl group having 1 to 6 carbon atoms, R ₂₈ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, , M, n, p, q are 0.5 ≦ l ≦ 2.0; 0.1 ≦ m ≦ 0.6; 0 ≦ n ≦ 1.4; 0.2 ≦ p ≦ 2.0; q ≦ 0.2; 0.95 ≦ l + m + n + p + q ≦ 2.8.

This organopolysiloxane has a phenyl group and a vinyl group bonded to a silicon atom in the molecule because of its dispersibility in a thermoplastic polycarbonate resin and flame retardancy. From the viewpoint of imparting this characteristic, l corresponding to the number of moles of substitution of the phenyl group (R ₂₅ ) per 1 mol of silicon atoms is in the range of 0.5 ≦ l ≦ 2.0, preferably 0.5 ≦ l ≦ 1.5. Range. Similarly, m corresponding to the number of moles of the vinyl group (R ₂₆ ) per mole of silicon atoms is in the range of 0.1 ≦ m ≦ 0.6, preferably in the range of 0.15 ≦ m ≦ 0.4. is there.

On the other hand, R ₂₇ is an alkyl group having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. From the point of view, it is preferable from an industrial point of view, and the content thereof is the value of n in the above formula (5) in the range of 0.1 ≦ n ≦ 1.4, preferably in the range of 0.2 ≦ n ≦ 1.0. is there.

In addition, by adding an alkoxy group to the organopolysiloxane, the drip is caused by the combination of the organopolysiloxane and the aromatic polycarbonate resin by the oxidative degradation crosslinking of the alkoxy group at the time of combustion to form a flame retardant layer in the combustion part. May be prevented. R _{28 in} the alkoxy group of the above formula (5) is a monovalent hydrocarbon group having 1 to 4 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, or an isobutyl group. Illustratively, a methyl group is particularly preferably used industrially. An alkyl group having 5 or more carbon atoms has low reactivity as an alkoxy group, and a flame retarding effect cannot be expected when an alkoxy group is introduced. Further, if the number of alkoxy groups is too large, the result is a low molecular weight organopolysiloxane, which increases the loss rate due to vaporization by heat before crosslinking reaction during combustion. ) In the range of 0.2 ≦ p ≦ 2.0, preferably 0.4 ≦ p ≦ 1.2.

  In addition, silanol groups contained in organopolysiloxane may remain for reasons of production method, have low reactivity and hardly contribute to flame retardancy, but storage stability and thermoplastic polycarbonate resin From the viewpoint of stability and moldability during melt processing, the content is preferably 0.2 or less in terms of q in the above formula (5).

  The phenyl group, vinyl group and alkoxy group-containing organopolysiloxane may be linear or have a branched structure, but from the above-mentioned T unit and / or Q unit in the molecule. What has the branched structure which becomes is more preferable.

  The molecular weight of such a phenyl group, vinyl group and alkoxy group-containing silicone oil is not particularly limited, but dispersibility and flame retardancy in thermoplastic polycarbonate resin can be achieved even if the molecular weight is too large or too small. In the above formula (5), the range is 0.95 ≦ l + m + n + p + q ≦ 2.8, preferably 1.5 ≦ l + m + n + p + q ≦ 2.6. The weight average molecular weight is preferably in the range of 410 to less than 2,000, and more preferably in the range of 600 to 1,500.

  Such a phenyl group, vinyl group, and alkoxy group-containing silicone oil can be produced by a conventionally known method. For example, according to the structure of the target organopolysiloxane, the corresponding organochlorosilanes are partially co-hydrolyzed in the presence of an alcohol having 1 to 4 carbon atoms to remove by-product hydrochloric acid and low-boiling components. Can be obtained. In addition, when starting from alkoxysilanes having an organic residue such as phenyl group, vinyl group or methyl group, silicone oil or cyclic siloxane in the molecule, an acid catalyst such as hydrochloric acid, sulfuric acid or methanesulfonic acid is used. In some cases, the target organopolysiloxane is obtained by removing the acid catalyst and low-boiling components used in the same manner after the polymerization reaction has progressed by adding water for partial hydrolysis. Can do.

  The compounding quantity of organopolysiloxane (component d) is 0.1-10 weight part with respect to 100 weight part of total amounts of (component a) + (component b), Preferably it is 1-5 weight part. When the blending amount is less than 0.1 parts by weight, the flame retardant effect is lowered. When the blending amount is more than 10 parts by weight, not only a further improvement in the flame retardant effect can be expected, but also gas generation during molding processing, appearance of the molded product Invite a defect. (Component d) may be at least one of (d-1), (d-2), and (d-3), but (d-1) a phenyl group-containing branched silicone resin and (d- 2) Si-H group-containing silicone oil and / or (d-3) phenyl group, vinyl group and alkoxy group-containing silicone oil are preferably used in combination, and in that case, (component d) blending ratio in 100% by weight Is particularly preferably (d-1) / (d-2) / (d-3) = 40 to 90/0 to 30/0 to 30% by weight.

Thermoplastic polycarbonate resin composition The thermoplastic polycarbonate resin composition of the present invention can contain various thermoplastic resins, additives and the like within a range in which the effects of the present invention are exhibited.

  Other thermoplastic resins other than polycarbonate resins include, for example, polyester (polyethylene terephthalate, polyolefin terephthalate, etc.), polyamide, polyethylene, polypropylene, polystyrene, acrylonitrile / styrene (AS) resin, acrylonitrile / butadiene / styrene (ABS) resin. And polymethyl methacrylate. Further, as the elastomer, for example, isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and thermoplastic elastomers such as MBS and MAS which are core shell type elastomers are also included. Can be used.

  Other various additives include, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fiber, glass bead, glass balloon, milled fiber, glass flake, carbon fiber, carbon flake, carbon bead, carbon milled Fiber, metal flake, metal fiber, metal coated glass fiber, metal coated carbon fiber, metal coated glass flake, silica, ceramic particle, ceramic fiber, aramid particle, aramid fiber, polyarylate fiber, graphite, conductive carbon black, various whiskers Etc.), heat stabilizers, UV absorbers, light stabilizers, mold release agents, lubricants, sliding agents (PTFE particles, etc.), colorants (pigments such as carbon black and titanium oxide, dyes), light diffusing agents (acrylic) Crosslinked particles, silicone crosslinked particles, ultrathin glass flakes , Calcium carbonate particles, etc.), fluorescent brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (fine titanium oxide, fine particles Zinc oxide and the like), impact modifiers typified by graft rubber, infrared absorbers, and photochromic agents can be blended.

  As a method for preparing the thermoplastic polycarbonate resin composition of the present invention, various conventionally known methods can be used and are not particularly limited. For example, a method of mixing a thermoplastic resin powder and other components, a melt-kneading method of mixing and kneading a thermoplastic resin melt and other components, or a solution in which a thermoplastic resin is dissolved in a solvent A method of suitably removing the solvent after dispersing other components is preferably used.

  The thermoplastic polycarbonate resin composition of the present invention comprises the above components (component a), (component b), (component c) and (component d), and various additive components used as necessary, and kneaded. Can be prepared. For the blending and kneading, a commonly used method, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a kneader, a multi screw extruder or the like is used. It can be done by a method. In addition, the heating temperature at the time of kneading | mixing is normally chosen in the range of 240-330 degreeC. The flame retardant polycarbonate resin composition thus obtained is applied to various known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, etc. As above, it can be used to manufacture various molded products.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. In addition, the obtained polycarbonate resin composition was evaluated according to the following procedure.

[Evaluation methods]
1. Intrinsic viscosity:
The intrinsic viscosity [η] (dl / g) is determined from a 0.5 g / 100 ml dichloromethane resin solution at 20 ° C. and a Huggins constant of 0.45.
2. Flame retardance:
2-1. Flame retardant V test:
According to UL-94V, the flame retardance of a 1.6 mm thick test piece (width 12 mm, length 127 mm) was evaluated.
2-2. Flame retardant VTM test:
In accordance with UL-94 VTM, the flame retardancy of a film-shaped test piece (width 50 mm, length 200 mm) having a thickness of 150 μm was evaluated.
2-3. Number of drops:
In accordance with UL-94V, when a flame-retardant evaluation of a 1.6 mm thick test piece (width 12 mm, length 127 mm) and a film test piece 150 μm thick (width 50 mm, length 200 mm) according to UL-94VTM The total number of times of dropping from each test piece until 5 test pieces were extinguished.
3. Heat-resistant:
Using TGA-50 (manufactured by Shimadzu Corporation), a 1% heat loss temperature (temperature increase rate: 20 ° C./min) was measured under a nitrogen stream (50 ml / min).
4). Appearance observation:
The test piece of 1.6 mm × 12 mm × 127 mm is visually observed and evaluated as follows.
○: A test piece with no gloss and excellent gloss.
X: A test piece in which a flow mark is generated and gloss is inferior.
5. Comprehensive evaluation:
Overall evaluation was performed based on the measurement results obtained by all the evaluation methods 2 to 4.
(Circle): The Example and comparative example which were favorable by all the evaluation methods.
X: Example and comparative example in which results were not good even in any one evaluation.
[Examples 1 to 13, Comparative Examples 1 to 9]

  The following raw materials (component a), (component b), (component c), (component d) are weighed in the ratios shown in Tables 1 and 2, and (component a), (component b), (component c) and (Component d) was premixed with a super mixer, then melted and kneaded at a temperature of 270 to 290 ° C. with a vented 40 mm extruder, and then cooled to obtain pellets. This pellet was dried in a 120 ° C. hot air dryer for 6 hours, and then tested with an injection molding machine (Sumitomo Neomat N350 / 120 Cycap) at a cylinder temperature of 290 ° C. and a mold temperature of 100 ° C. at 1.6 mm × 12 mm × 127 mm. A piece was molded and used for the flame retardancy V test, and further used for observation of the appearance of the test piece. Similarly, a pellet preliminarily dried at 120 ° C. was molded into a film having a thickness of 150 μm at 300 ° C. using a compression molding machine to obtain a test film. This test film was used for various measurements in the flame-retardant VTM test.

[raw materials]
Synthesis examples of polycarbonate resins used in Examples and Comparative Examples and other raw materials are as follows.

ａは平均３９ (Component a)
[Synthesis Example 1] Synthesis of PC (a1) A polyorganosiloxane compound (X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was added to 42 liters of an 8.8% (w / v) aqueous sodium hydroxide solution. 0.35 kg, 2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as BPA) 6.65 kg and hydrosulfite 20 g were added and dissolved. To this was added 36 liters of methylene chloride, and 3.50 kg of phosgene was blown at a rate of 0.12 kg / min while stirring at 15 ° C. After completion of the blowing, 158 g of p-tert-butylphenol (hereinafter abbreviated as PTBP) was added, and stirring was continued vigorously for 10 minutes, and further 10 ml of triethylamine was added, followed by stirring for about 1 hour for polymerization.

a is an average of 39

The polymerization solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washed with water until the washing liquid had a conductivity of 10 μS / cm or less, to obtain a purified resin liquid. The obtained purified resin liquid was slowly added dropwise to 60 ° C. hot water that was vigorously stirred to solidify the polymer while removing the solvent. The solid was filtered and dried to obtain a white powdery polymer. This polymer had an intrinsic viscosity [η] at a temperature of 20 ° C. of 0.48 dl / g in a 0.5 g / dl solution containing methylene chloride as a solvent. This synthesized copolymer polycarbonate is hereinafter abbreviated as PC (a1). The results obtained above polymer was analyzed from the infrared absorption spectrum, absorption by siloxane bond position of 1000～1100Cm ^-1, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, due to an ether bond in a position near 1240 cm ^-1 Absorption was observed, and it was confirmed to have a siloxane bond and a carbonate bond. Moreover, the absorption derived from a hydroxyl group was hardly recognized by the position of 3650-3200cm < ^-1 >. When the monomers in this polymer were measured by GPC analysis, all the monomers were 20 ppm or less. As a result of combining them, this polymer was recognized as a polycarbonate polymer having the same copolymerization ratio as the charged composition.

[Synthesis Example 2] Synthesis of PC (a2)
A copolymer polycarbonate was synthesized in the same manner as in Synthesis Example 1 except that the polyorganosiloxane compound used in Synthesis Example 1 was changed to 1.14 kg and BPA was changed to 6.46 kg. The intrinsic viscosity of the obtained copolymer polycarbonate was 0.45 dl / g. This synthesized copolymer polycarbonate is hereinafter abbreviated as PC (a2). From the infrared absorption spectrum analysis and the like, it was confirmed that the polymer had a polycarbonate polymer structure equivalent to that of Synthesis Example 1 except for the polymerization ratio of this polymer.

[Synthesis Example 3] Synthesis of PC (a3)
The same as Synthesis Example 1 except that the polyorganosiloxane compound used in Synthesis Example 1 was changed to 4.45 kg of 2,2-bis (4-hydroxy-3-methylphenyl) propane and BPA was changed to 2.64 kg. Copolycarbonate was synthesized. The intrinsic viscosity of the obtained copolymer polycarbonate was 0.51 dl / g. This synthesized copolymer polycarbonate is hereinafter abbreviated as PC (a3). The results obtained above polymer was analyzed from the infrared absorption spectrum, absorption by carbonyl group at the position in the vicinity of 1770 cm ^-1, observed absorption by ether bond position near 1240 cm ^-1, was confirmed to have a carbonate bond It was. Moreover, the absorption derived from a hydroxyl group was hardly recognized by the position of 3650-3200cm < ^-1 >. When the monomers in this polymer were measured by GPC analysis, all the monomers were 20 ppm or less. As a result of combining them, this polymer was recognized as a polycarbonate polymer having the same copolymerization ratio as the charged composition.

PC1 from bisphenol A: Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon S-2000, intrinsic viscosity 0.53 dl / g, hereinafter abbreviated as BPAPC1.
PC2 from bisphenol A: Mitsubishi Gas Chemical Co., Ltd., trade name: Iupilon E-1000, intrinsic viscosity 0.61 dl / g, hereinafter abbreviated as BPAPC2.

(Component b)
[Synthesis Example 4] Synthesis of PC (b1) A polyorganosiloxane compound (X-22-1827 manufactured by Shin-Etsu Chemical Co., Ltd.) having the following structure was added to 30 liters of an aqueous 8.8% (w / v) sodium hydroxide solution. 2.60 kg, 3.91 kg (hereinafter abbreviated as BCFL) of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 0.49 kg of BPA and 20 g of hydrosulfite were added and dissolved. To this was added 30 liters of methylene chloride, and 1.81 kg of phosgene was blown at a rate of 0.12 kg / min while stirring at 15 ° C. After completion of the blowing, 88 g of PTBP was added, and vigorous stirring was continued for 10 minutes, and 50 ml of triethylamine was further added, followed by polymerization for about 1 hour.

ジメチル体の合計の平均が２６。
ジフェニル体の合計の平均が１３。

The average of the total dimethyl form is 26.
The average of the total diphenyl form is 13.

  Thereafter, the same treatment as in Synthesis Example 1 was carried out, and the intrinsic viscosity of the obtained copolymer polycarbonate was 0.28 dl / g. This synthesized copolymer polycarbonate is hereinafter abbreviated as PC (b1). From the infrared absorption spectrum analysis and the like, this polymer was recognized as a polycarbonate polymer having the same copolymerization ratio as the charged composition.

[Synthesis Example 5] Synthesis of PC (b2) Copolymerization was performed in the same manner as in Synthesis Example 4 except that 2.60 kg of the polyorganosiloxane compound used in Synthesis Example 1 was used instead of the polyorganosiloxane compound used in Synthesis Example 4. Polycarbonate was synthesized. The intrinsic viscosity of the obtained copolymer polycarbonate was 0.29 dl / g. This synthesized copolymer polycarbonate is hereinafter abbreviated as PC (b2). From the infrared absorption spectrum analysis and the like, this polymer was recognized as a polycarbonate polymer having the same copolymerization ratio as the charged composition.

(Si component other than component b)
[Synthesis Example 6] Synthesis of PC (b3) A copolymeric polycarbonate was synthesized in the same manner as in Synthesis Example 4 except that PTBP was changed to 123 g. The intrinsic viscosity of the obtained copolymer polycarbonate was 0.13 dl / g, and it was an oligomer. This synthesized copolymer polycarbonate is hereinafter abbreviated as PC (b3).

(Component c)
Pearl fluoroalkanesulfonic acid metal salt: Perfluorobutanesulfonic acid potassium salt (Megafac F-114P manufactured by Dainippon Ink & Chemicals, Inc.). Hereinafter, it is abbreviated as metal salt 1.
Aromatic sulfone sulfonic acid metal salt: Diphenyl sulfone sulfonic acid potassium salt (KSS manufactured by UCB). Hereinafter, it is abbreviated as metal salt 2.

(Component d)
Phenyl group-containing branched silicone resin: A silicone resin having a phenyl group and a methyl group as substituents and having a branched structure (in the above average composition formula (4), R ₂₃ = methyl group, m = 0.96, n = 0. 68, p = 0, q = 0.02, and a weight average molecular weight of 9,000). Hereinafter, it is abbreviated as d1.
Si-H group-containing silicone oil: Silicone oil having a methyl group, Si-H group as a substituent, and not containing an aromatic hydrocarbon group or a branched structure (Si-H group content is 1.57 mol / 100 g, weight average) The one having a molecular weight of 5,500 was used. Hereinafter, it is abbreviated as d2.
Silicone oil containing phenyl group, vinyl group and alkoxy group: Silicone oil having phenyl group, vinyl group, methyl group and methoxy group as substituents and having a branched structure (in the above average composition formula (5), R ₂₇ = methyl group) R ₂₈ = methyl group, l = 0.75, m = 0.25, n = 0.75, p = 0.5, q = 0, and the weight average molecular weight is 850). Hereinafter, it is abbreviated as d3.

(Silicone component other than component d)
[Synthesis Example 7] Synthesis of organopolysiloxane described in JP-A-6-336547 An organopolysiloxane was synthesized according to Production Example 1 of JP-A-6-336547. A light brown transparent liquid was obtained and identified as methylpolysiloxane having a methoxy group by NMR measurement. Hereinafter, it is abbreviated as d4.

Table 1

Table 2

Table 3

  As shown in Tables 1 to 3, as is apparent from the comparison between Examples 1 to 4 and Comparative Examples 1 to 4, the one containing PC (b1) is used to prevent dropping when the film-like molded product is burned. Excellent performance and improved flame retardancy. And it turns out that it is excellent in heat resistance and the external appearance of a molded article. Moreover, although Comparative Example 5 is excellent in the anti-dropping performance at the time of burning the film-like molded product, it has a 1% heat loss temperature of less than 380 ° C. and is not excellent in heat resistance, and the appearance of the molded product. It turns out that it is inferior.

  In Comparative Example 6, the content of PC (b1) contained in the resin composition is less than the lower limit of the present invention. In Comparative Example 7, organopolysiloxane (component d) is not contained in the resin composition, and both are film-like. The anti-dropping performance at the time of burning the molded product is not excellent, and the flame retardancy cannot be improved. In Comparative Example 8, the content of the metal salt 1 is less than the lower limit of the present invention, and the flame retardancy is not excellent. Further, in Comparative Example 9, the content of the metal salt 1 exceeds the upper limit of the present invention, the flame retardancy is not excellent, and the object is not achieved even in the appearance of the molded product.

As an application example of the present invention, there can be mentioned applications related to molding materials in the electric / electronic field, OA equipment field, and automobile field.

Claims (13)

Thermoplastic polycarbonate resin (component a), thermoplastic polycarbonate resin derived from dihydric phenol having a siloxane structure and dihydric phenol having a fluorene structure (component b), organic sulfonic acid metal salt (component c), and organopolysiloxane (Component d) and
A flame retardant thermoplastic polycarbonate resin composition, wherein each of the above components is blended in the following ratio with respect to 100 parts by weight of the total amount of (component a) and (component b).
(Component a) 0.1 to 95 parts by weight (Component b) 5 to 99.9 parts by weight (Component c) 0.01 to 0.5 parts by weight (Component d) 0.1 to 10 parts by weight (Component a) is a thermoplastic polycarbonate resin derived from a dihydric phenol represented by the following general formula (1) and a dihydric phenol represented by the following general formula (2), and / or the general formula (2) And the dihydric phenol unit of the general formula (1) is 0 with respect to the total amount of dihydric phenol units in the thermoplastic polycarbonate resin. The thermoplastic polycarbonate resin composition having flame retardancy according to claim 1, which is ˜50 wt%.
General formula (1)

(In the formula, R _{1 to} R ₄ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms. Or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a carbon number It may also have an alkoxy group of 1 to 5. R _{5 to} R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 2 to 5 carbon atoms. An alkenyl group, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, the substituent is a C 1-5 alkyl group or a carbon number 2 Having -5 alkenyl groups or C1-5 alkoxy groups Rukoto may .R ₉ is, .X _{is, -Si (R 10) (R} 11) a homopolymer of O- units representing a mere bond or represents an aliphatic group having 1 to 6 carbon atoms, or two It represents a block copolymer or a random copolymer composed of the above -Si (R ₁₀ ) (R ₁₁ ) O-unit, the degree of polymerization is 0 to 200, and R _{10 to} R ₁₁ are each independently Hydrogen, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, In the case where the group has a carbon atom, it may have a C 1-5 alkyl group, a C 2-5 alkenyl group or a C 1-5 alkoxy group as a substituent.)
General formula (2)

(R _{12 to} R ₁₃ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 5 carbon atoms Y is one of the divalent groups listed below,

Here, R _{14 to} R ₁₇ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. Represents an aryl group, or R ₁₄ and R ₁₅ and / or R ₁₆ and R ₁₇ are bonded together to form a carbocyclic ring having 3 to 12 carbon atoms (excluding a fluorene structure) or a heterocyclic ring. In the case where these groups have a carbon atom, the substituent may have an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. . a represents an integer of 0 to 20. ) (Component b) is a thermoplastic polycarbonate resin derived from a dihydric phenol represented by the general formula (1) and a dihydric phenol represented by the following general formula (3), or represented by the general formula (1). In the thermoplastic polycarbonate resin derived from the dihydric phenol represented by the general formula (2) and the dihydric phenol represented by the general formula (3), and in the thermoplastic polycarbonate resin Based on the total amount of dihydric phenol units, the dihydric phenol unit of the general formula (1) is 10 to 90% by weight, the dihydric phenol unit of the general formula (3) is 10 to 90% by weight, of the general formula (2) 2. The flame retardant thermoplastic polycarbonate resin composition according to claim 1, wherein the dihydric phenol unit is 0 to 80% by weight.
General formula (3)

(In the formula, R _{18 to} R ₂₁ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 1 carbon atoms. 5 represents an alkoxy group or an aralkyl group having 7 to 17 carbon atoms, and when these groups have a carbon atom, as a substituent, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or carbon (Also have an alkoxy group of 1 to 5) When both (component a) and (component b) are combined, the dihydric phenol unit of general formula (1) is based on the total amount of all dihydric phenol units in (component a) and (component b), It is 1 to 50 weight%, The thermoplastic polycarbonate resin composition which has a flame retardance in any one of Claims 1-3 characterized by the above-mentioned. The thermoplastic polycarbonate resin composition having flame retardancy according to any one of claims 1 to 4, wherein (Component d) is a phenyl group-containing branched silicone resin. (Component d) (d-1) phenyl group-containing branched silicone resin, (d-2) Si-H group-containing silicone oil and / or (d-3) phenyl group, vinyl group and alkoxy group-containing silicone oil A thermoplastic polycarbonate resin composition having flame retardancy according to claim 5, wherein The flame retardancy according to any one of claims 1 to 4, wherein, in thermogravimetric analysis under nitrogen, the 1% heat loss temperature is 380 ° C or higher and / or the 5% heat loss temperature is 430 ° C or higher. A thermoplastic polycarbonate resin composition. The thermoplastic polycarbonate resin composition having flame retardancy according to claim 1 or 2, wherein (component a) is a thermoplastic polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane. object. 2. The flame-retardant thermoplastic polycarbonate resin composition according to claim 1, wherein (Component c) is a pearl fluoroalkanesulfonic acid metal salt or an aromatic sulfonesulfonic acid metal salt. _{5. The} thermoplastic polycarbonate resin having flame retardancy according to claim 1, wherein R _{5 to} R _{8 in} the general formula (1) are at least one selected from a methyl group and a phenyl group. Composition. The dihydric phenol represented by the general formula (1) is α, ω-bis [3- (o-hydroxyphenyl) propyl] polydimethyl-diphenyl random copolymer siloxane and α, ω-bis [3- (o- The thermoplastic polycarbonate resin composition having flame retardancy according to any one of claims 1 to 4, which is at least one selected from the group consisting of (hydroxyphenyl) propyl] polydimethylsiloxane. A molded article obtained by molding the flame-retardant thermoplastic polycarbonate resin composition according to any one of claims 1 to 11. The molded article according to claim 12, wherein the molded article is in the form of a sheet or a film.