JP6542507B2 - Aromatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition, and more particularly to an aromatic polycarbonate resin composition excellent in flame retardancy, impact resistance and moist heat resistance and a molded article thereof.

  Because polycarbonate resins are excellent in heat resistance and impact resistance, they are widely and industrially widely used in many fields as raw materials for, for example, the automotive field, OA equipment field, electric / electronic field, and construction members. . On the other hand, the demand for the incombustibility of the synthetic resin material to be used is strong mainly in applications such as office automation equipment and home appliances, and a large number of flame retardants are being studied and developed in order to meet these demands. For synthetic resin materials, for example, not only 94HB in the horizontal combustion test of UL94 which is one of the standards of flame retardancy, but also those with good evaluation of flame retardancy in the vertical combustion test, that is, V-0 The higher grade of the three steps from V to V-2 is required.

  For example, as a method of improving the flame retardancy of polycarbonate resin, Japanese Patent Laid-Open No. 2003-49061 discloses a method of blending various flame retardants into polycarbonate resin, and Japanese Patent Laid-Open No. 2003-96290 discloses special phosphorus as a flame retardant JP-A-2003-105185 discloses a method of adding an acid ester, and a method of blending two types of ABS resin (acrylonitrile-butadiene-styrene copolymer).

  On the other hand, many studies have been made also in the method of producing polycarbonate resins. Among them, polycarbonate resins derived from aromatic dihydroxy compounds such as 2,2-bis (4-hydroxyphenyl) propane (hereinafter also referred to as "bisphenol A") are produced either by interfacial polymerization or melt polymerization. Industrialized by the method.

  According to this interfacial polymerization method, since polycarbonate resin is produced from bisphenol A and phosgene, toxic phosgene must be used. In addition, in this interfacial polymerization method, the apparatus is corroded by hydrogen chloride and sodium chloride by-produced and chlorine-containing compounds such as methylene chloride used in large amounts as a solvent, and impurities such as sodium chloride affecting the physical properties of the polymer And the difficulty in removing residual methylene chloride, and the generation of a large amount of wastewater. Thus, the actual situation is that the interfacial polymerization method has many environmental problems.

  On the other hand, according to the melt polymerization method, a polycarbonate resin is produced from an aromatic dihydroxy compound and a diaryl carbonate, and for example, an aromatic monohydroxy compound by-produced by transesterification reaction of bisphenol A and diphenyl carbonate in a molten state. It is possible to polymerize while removing. Unlike the interfacial polymerization method, this melt polymerization method has many environmental advantages such as using no solvent. However, since the resin obtained contains a naturally occurring different structure, and the concentration of terminal hydroxyl groups (terminal OH concentration) is relatively high, the impact resistance etc. can be obtained even if the conventional various flame retardants, ABS resin, etc. are blended. Satisfactory physical properties were not achieved in the mechanical strength and the heat and humidity resistance of the above.

  The inventors of the present invention have previously used a novel method of chain extension by linking the sealing end of an aromatic polycarbonate prepolymer with a diol compound as a method of achieving a high polymerization rate and obtaining a good quality aromatic polycarbonate resin. (See, for example, WO 2012/157766). According to these methods, a high polymerization degree aromatic polycarbonate resin having a Mw of about 30,000 to 100,000 is shortened by connecting the chained end of the aromatic polycarbonate prepolymer with a diol compound and chain-extending the same. It can be manufactured on time. Further, since the aromatic polycarbonate resin is produced by high-speed polymerization reaction, branching and crosslinking reaction due to long-term heat retention and the like can be suppressed, and the amount of different structure in the aromatic polycarbonate can be reduced. In addition, the terminal hydroxyl group concentration (terminal OH group concentration) is also reduced.

  With respect to the aromatic polycarbonate resin produced by a new method using a melt polymerization method in consideration of such an environment, a resin composition having improved flame retardancy has not been proposed yet.

Japanese Patent Application Publication No. 2003-49061 JP 2003-96290A JP 2003-105185 A WO 2012/157766

  The problem to be solved by the present invention is to provide an aromatic polycarbonate resin composition having good flame retardancy and improved impact resistance and moist heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have quality advantages such as a low degree of branching and a small number of different structures despite being a melt polymerization method, and in particular, specific cyclic carbonates. An aromatic polycarbonate resin composition having good flame resistance and having practically sufficient impact resistance and moist heat resistance when blended with an aromatic polycarbonate resin containing a specific amount or less and various flame retardants, and the same The article was found and the present invention was completed. That is, the present invention provides an aromatic polycarbonate resin composition shown below and a molded article thereof.

<1> An aromatic polycarbonate resin having a structural unit represented by the following general formula (I), a flame retardant, and a cyclic carbonate represented by the following general formula (II),
The aromatic polycarbonate, wherein the flame retardant is contained in 0.02 to 30 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin, and the cyclic carbonate is present at 3000 ppm or less with respect to the aromatic polycarbonate resin Resin composition:
General Formula (I):

(Wherein, R ₁ and R ₂ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 6 to 20 carbon atoms, or 6 carbon atoms And an aryl group of 6 to 20, a cycloalkoxy group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, p and q each represents an integer of 0 to 4; Represents a group selected from the group of Ia))

(Wherein R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₃ and R ₄ are each other And may form an aliphatic ring).
General formula (II):

(Wherein, Ra and Rb each independently represent a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom or a halogen atom Or C 3 -C 30 cycloalkyl group which may contain, C 6 -C 30 aryl group which may contain an oxygen atom or a halogen atom, or carbon number which may contain an oxygen atom or a halogen atom R 15 represents an alkoxy group of 1 to 15, or R a and R b may combine with each other to form a ring, and R _{5 to} R ₈ each independently represent a hydrogen atom, a halogen atom or a carbon number 1 to 5 represents a linear or branched alkyl group, and n represents an integer of 0 to 30).

<2> The flame retardant is at least one selected from the group consisting of sulfonic acid metal salt flame retardants, halogen-containing compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. The aromatic polycarbonate resin composition as described in 1>.

The aromatic polycarbonate resin composition as described in <1> or <2> which further contains 0.01-2.0 mass parts of polytetrafluoroethylene with respect to 100 mass parts of <3> above-mentioned aromatic polycarbonate resin.

<4> The aromatic polycarbonate resin composition according to any one of <1> to <3>, wherein the cyclic carbonate is a compound represented by the following general formula (IIa):
General formula (IIa):

(Wherein, Ra and Rb each independently represent a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom or a halogen atom Or C 3 -C 30 cycloalkyl group which may contain, C 6 -C 30 aryl group which may contain an oxygen atom or a halogen atom, or carbon number which may contain an oxygen atom or a halogen atom Or 1 to 15 alkoxy group, or Ra and Rb may be combined with each other to form a ring).

The <5> above-mentioned aromatic polycarbonate resin has a structural unit represented by the following general formula (III), The content is <1>-<4> which is less than 2000 ppm in the said aromatic polycarbonate resin. The aromatic polycarbonate resin composition according to any one of the following:
General formula (III):

(Wherein, X has the same meaning as <1>).

When the N value (structural viscosity index) of the <6> aromatic polycarbonate resin is represented by the following formula (1), the N value is 1.25 or less, in any one of <1> to <5> The aromatic polycarbonate resin composition as described.
N value = (log (Q 160 value)-log (Q 10 value)) / (log 160-log 10) (1)

The aromatic polycarbonate resin composition in any one of <1>-<6> whose terminal hydroxyl group content of <7> above-mentioned aromatic polycarbonate resin is 1000 ppm or less.

<8> The aromatic polycarbonate resin and the cyclic carbonate,
A high molecular weight forming step of causing the aromatic polycarbonate prepolymer and a diol compound represented by the following general formula (IV) to react in the presence of a transesterification catalyst to obtain a high molecular weight, and a by-product in the high molecular weight forming step The aromatic polycarbonate resin composition according to any one of <1> to <7>, which is obtained by a method including: a cyclic carbonate removing step of removing a part of the cyclic carbonate to be removed out of the reaction system:
Formula (IV):

(Wherein, Ra and Rb each independently represent a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom or a halogen atom Or C 3 -C 30 cycloalkyl group which may contain, C 6 -C 30 aryl group which may contain an oxygen atom or a halogen atom, or carbon number which may contain an oxygen atom or a halogen atom R 15 represents an alkoxy group of 1 to 15, or R a and R b may combine with each other to form a ring, and R _{5 to} R ₈ each independently represent a hydrogen atom, a halogen atom or a carbon number 1 to 5 represents a linear or branched alkyl group, and n represents an integer of 0 to 30).

<9> The aromatic polycarbonate resin composition according to <8>, wherein the diol compound is a compound represented by the following general formula (IVa):
Formula (IVa):

(Wherein, Ra and Rb each independently represent a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom or a halogen atom Or C 3 -C 30 cycloalkyl group which may contain, C 6 -C 30 aryl group which may contain an oxygen atom or a halogen atom, or carbon number which may contain an oxygen atom or a halogen atom Or 1 to 15 alkoxy group, or Ra and Rb may be combined with each other to form a ring).

<10> The diol compound is 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol The aromatic polycarbonate according to <8> or <9>, selected from the group consisting of: 2,2-diethylpropane-1,3-diol, and 2-methyl-2-propylpropane-1,3-diol Resin composition.

The molded article formed by shape | molding the aromatic polycarbonate resin composition in any one of <11> <1>-<10>.

  The aromatic polycarbonate resin composition of the present invention contains a specific cyclic carbonate at a content of a predetermined value or less, and is further blended with a flame retardant, so that it is excellent in flame retardancy and also has impact resistance and moist heat resistance. It has been greatly improved.

  In addition, the aromatic polycarbonate resin in the aromatic polycarbonate resin composition of the present invention polymerizes the aromatic polycarbonate at high speed by the reaction of the aromatic polycarbonate (prepolymer) and a linking agent comprising a diol compound having a specific structure. May be obtained by the following method. In that case, the aromatic polycarbonate resin has a high degree of branching while having a high molecular weight, and has a small number of different structures, so it has advantages in terms of mechanical strength and other inherent qualities of polycarbonate. In addition, since a skeleton derived from a diol compound is hardly contained in the resin, the resin is also excellent in heat stability (heat resistance). When the aromatic polycarbonate resin having such excellent properties contains a specific cyclic carbonate at a content of a predetermined value or less, not only the flame retardancy but also the impact resistance can be obtained by further blending various flame retardants. It is surprising to provide a resin composition in which the heat and humidity properties are also significantly improved.

1. Aromatic Polycarbonate Resin Composition The aromatic polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin having a structural unit represented by the following general formula (I) (hereinafter also referred to as "aromatic polycarbonate resin"), a flame retardant And a cyclic carbonate represented by the following general formula (II) (hereinafter, also referred to as “cyclic carbonate”) as an essential component.

  The aromatic polycarbonate resin composition of the present invention contains a specific cyclic carbonate at a content of a predetermined value or less, and is further excellent in flame retardance by being blended with a flame retardant, and the conventional aromatic polycarbonate resin composition Impact resistance and heat and humidity resistance are also greatly improved compared to products. The aromatic polycarbonate resin which can constitute such a resin composition is, for example, an aromatic polycarbonate prepolymer obtained by the reaction of an aromatic polycarbonate prepolymer obtained by a melt polymerization method and a linking agent comprising a diol compound having a specific structure. Can be obtained by the method of increasing the molecular weight. The aromatic polycarbonate resin obtained by such a method contains a specific amount of cyclic carbonate formed in the production process, and further, when the resin composition is made into a resin composition, an excellent flame resistance, Impact resistance, heat and humidity resistance can be provided. In addition to these essential components, the aromatic polycarbonate resin composition of the present invention can contain other components as long as the effects of the present invention are not impaired. Below, the said essential component and other components are explained in full detail.

(1) Aromatic polycarbonate resin The aromatic polycarbonate resin composition of the present invention contains an aromatic polycarbonate resin (A) having a structural unit represented by the following general formula (I) as a main structural unit. Here, “main” means that the content of the structural unit represented by the general formula (I) in all structural units in the aromatic polycarbonate resin is 60 mol% or more, and 80 mol% or more Is preferably 90 mol% or more.

In general formula (I), R ₁ and R ₂ each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a cycloalkyl group having 6 to 20 carbon atoms, The aryl group having 6 to 20 carbons, the cycloalkoxy group having 6 to 20 carbons, or the aryloxy group having 6 to 20 carbons represents p, q represents an integer of 0 to 4, and X represents a single bond Or a group selected from the following group (Ia):

In general formula (Ia), R ₃ and R ₄ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, or R ₃ and R ₄ And may be bonded to each other to form an aliphatic ring.

  As an aromatic dihydroxy compound derived | led-out to the structural unit represented by said general formula (I), the compound represented by the following general formula (V) is mentioned.

In the general formula (V), R _{1 to} R ₂ , p, q and X are each the same as in the general formula (I).

  As such an aromatic dihydroxy compound, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2 -Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, Bis (4-hydroxyphenyl) diphenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-phen) Phenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (3,5-dibromo- 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methoxyphenyl) propane 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4 , 4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroki 3,3'-dimethyl diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone and the like.

  Among them, 2,2-bis (4-hydroxyphenyl) propane is preferable because of its stability as an aromatic dihydroxy compound, and further, because it is easy to obtain one having a small amount of impurities contained therein.

  In the present invention, for the purpose of control of glass transition temperature, improvement of fluidity and the like, plural kinds of the above-mentioned various aromatic dihydroxy compounds may be used in combination as needed.

  The aromatic polycarbonate resin may further contain other structural units other than the structural unit represented by General Formula (I). Examples of other structural units include heterostructural units having a branch represented by a structural unit represented by the following general formula (III), and structural units derived from a linking agent described later.

  In addition, X in the general formula (III) is the same as in the general formula (I).

  In the present invention, when the aromatic polycarbonate resin contains a structural unit represented by the general formula (III), its content is less than 2000 ppm by mass in the aromatic polycarbonate resin, preferably 1500 ppm or less, preferably 1000 ppm. The content is more preferably the following, more preferably 800 ppm or less, particularly preferably 700 ppm or less, and most preferably 600 ppm or less. When the content of the structural unit of the general formula (III) is less than 2000 ppm, the degree of branching of the aromatic polycarbonate resin tends to decrease and the thermal stability tends to be further improved. Also, these structural units are naturally occurring branched structures. Therefore, when the content of these structural units is a predetermined amount or more, it is difficult to easily control the degree of branching by the addition amount of the branching agent, and the compounding / dispersion with various flame retardants (B) is deteriorated. In some cases, disadvantages such as deterioration of flowability of the obtained aromatic polycarbonate resin composition and deterioration of moldability may occur.

  The structural unit of the general formula (III) is a kind of heterostructure which is likely to be by-produced during the production of the aromatic polycarbonate resin, and the aromatic polycarbonate resin of the present invention preferably has a small proportion of this heterostructure. Such an aromatic polycarbonate resin can be produced by a method including the step of polymerizing an aromatic polycarbonate prepolymer using a linking agent comprising a diol compound having a specific structure described later.

  Such an aromatic polycarbonate resin is linked using a diol compound as described later, and despite having a high molecular weight, a structural unit derived from the diol compound which is a linking agent in the obtained aromatic polycarbonate resin Since the amount of N is very small, it is possible to provide excellent qualities such as a low N value and a small proportion of different structural units while having the same skeleton as a conventional homopolycarbonate resin.

The lower limit of the content of the structural unit represented by the general formula (III) is not particularly limited, and may be, for example, the detection limit (the detection limit is usually about 1 ppm). The lower limit of the content of the structural unit represented by the general formula (III) in the aromatic polycarbonate resin is, for example, 1 ppm or more (detection lower limit), and in some cases, 5 ppm or more, and further 10 ppm or more. In addition, the content rate of the structural unit of said General formula (III) in this invention is the value calculated | required by < ¹ > H-NMR analysis.

When it is manufactured by the method of using the coupling agent containing the diol compound of the specific structure which the aromatic polycarbonate resin mentions later, the structural unit derived from the diol compound used at a high molecular weight formation process may be included. In that case, the content of the structural unit derived from the diol compound is, for example, 1 mol% or less and preferably 0.1 mol% or less with respect to the total structural unit amount of the high molecular weight aromatic polycarbonate resin. The content of the structural unit derived from the diol compound is a value determined by ¹ H-NMR analysis.

Furthermore, the terminal hydroxyl group concentration of the aromatic polycarbonate resin is preferably 1000 ppm or less, more preferably 800 ppm or less, still more preferably 600 ppm or less, and particularly preferably 500 ppm or less. When the terminal hydroxyl group concentration is 1000 ppm or less, the hydrolysis resistance tends to be improved. Generally, the terminal part in the aromatic polycarbonate resin has a structure sealed with an aromatic monohydroxy compound such as phenol, but a part may be a hydroxyl group. Therefore, the terminal hydroxyl group concentration of the aromatic polycarbonate resin is the concentration of hydroxyl group (OH group) in the aromatic polycarbonate resin. The terminal hydroxyl group concentration can be measured, for example, by ¹ H-NMR analysis.

  The weight average molecular weight (Mw) of the aromatic polycarbonate resin is preferably 35,000 to 100,000, more preferably 35,000 to 80,000, still more preferably 35,000 to 75,000, and particularly preferably 40,000. 000 to 65,000, and most preferably 40,000 to 50,000. The aromatic polycarbonate resin has high flowability while having high molecular weight. Therefore, if the weight average molecular weight is within this range, it exhibits good flame retardancy by blending with various flame retardants, and moldability and productivity when used for applications such as extrusion molding and injection molding are also good. is there. Furthermore, mechanical properties and moisture and heat resistance physical properties of the resulting molded article are improved.

  The molecular weight distribution (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) in the aromatic polycarbonate resin used in the present invention is, for example, 1.9 to 2.5, It is preferable that it is. In addition, a number average molecular weight (Mn) and a weight average molecular weight (Mw) are measured as polystyrene conversion value using GPC.

In the aromatic polycarbonate resin, the N value (structural viscosity index) represented by the following formula (1) is preferably 1.3 or less, more preferably 1.28 or less, and still more preferably 1.25 or less. , 1.23 or less is particularly preferred.
N value = (log (Q 160 value)-log (Q 10 value)) / (log 160-log 10) (1)

  In the above formula (1), the Q160 value represents a melt flow volume (ml / sec) measured at 280 ° C. and a load of 160 kg, and the Q10 value a melt flow per unit time measured at 280 ° C. and a load of 10 kg. Volume (ml / sec) is expressed.

  Structural viscosity index "N value" is used as an index of the degree of branching of polycarbonate resin. It is preferable that the N value in the aromatic polycarbonate resin of the present invention is low, the content of the branched structure is small, and the proportion of the linear structure is high. Generally, the aromatic polycarbonate resin tends to have high fluidity (Q value increases) when the ratio of the branched structure increases in the same Mw, but the aromatic polycarbonate resin obtained by the production method described later has an N value High fluidity (high Q value) can be achieved while keeping the

(2) Cyclic carbonate The aromatic polycarbonate resin composition of the present invention contains 3,000 ppm or less of a cyclic carbonate represented by the following general formula (II) with respect to the aromatic polycarbonate resin. The cyclic carbonates represented by the following general formula (II) are known compounds, can be obtained from reagent suppliers, or can be easily synthesized by known methods, and such compounds can be used as aromas of the present invention May be added to the group polycarbonate resin composition. Alternatively, the cyclic carbonate represented by the following general formula (II) may be by-produced in the production process of the aromatic polycarbonate resin. For example, the aromatic polycarbonate resin obtained by the production method described later may by-produce cyclic carbonate corresponding to the diol compound used as a linking agent in the production process, but even after removing it to the outside of the reaction system, A small amount of cyclic polycarbonate remains, and such cyclic polycarbonate is contained in the finally obtained aromatic polycarbonate resin. The presence of such cyclic carbonate at 3000 ppm or less tends to improve the flowability of the aromatic polycarbonate resin composition. In addition, the components constituting the aromatic polycarbonate resin composition are more uniformly mixed, and the moldability and strength tend to be improved. Furthermore, when a flame retardant is compounded, it is possible to have impact resistance superior to the prior art. In addition, when content of cyclic carbonate exceeds 3000 ppm, there may be a demerit, such as a fall of the mechanical strength of a resin composition.

In the general formula (II), each of Ra and Rb independently represents a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom Or a cycloalkyl group having 3 to 30 carbon atoms which may contain a halogen atom, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or an oxygen atom or a halogen atom It may represent a good C1-C15 alkoxy group, or Ra and Rb may combine with each other to form a C3-C8 ring. As said halogen atom, a fluorine atom is preferable. R _{5 to} R ₈ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. As said halogen atom, a fluorine atom is preferable. n represents an integer of 0 to 30.

  Each of Ra and Rb independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, Or an alkoxy group having 1 to 8 carbon atoms is preferable, a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable, and a linear or branched alkyl having 1 to 4 carbon atoms It is more preferably a group, and particularly preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or an i-butyl group.

Each of R _{5 to} R ₈ independently is preferably a hydrogen atom, a fluorine atom or a methyl group, and more preferably each is a hydrogen atom.

  The n is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

  The cyclic carbonate represented by the general formula (II) is preferably a compound represented by the following general formula (IIa). In general formula (IIa), Ra and Rb are respectively synonymous with in the above-mentioned general formula (II).

  The compound of the structure shown below is mentioned as a specific example of the said cyclic carbonate.

  The content of the cyclic carbonate contained in the aromatic polycarbonate resin composition of the present invention is 3000 ppm or less, preferably 1000 ppm or less, and more preferably 500 ppm or less based on the mass of the aromatic polycarbonate resin. It is more preferably 300 ppm or less, particularly preferably 100 ppm or less. The lower limit of the content of the cyclic carbonate is usually the detection limit, but is preferably 0.0005 ppm, more preferably 0.005 ppm, still more preferably 0.05 ppm, particularly preferably 0.1 ppm It is. The presence of the cyclic carbonate in such an amount may improve the fluidity of the aromatic polycarbonate resin composition. Furthermore, even when various additives such as stabilizers, UV absorbers, mold release agents, and colorants are added, the flowability (moldability), hue (YI value), moisture heat resistance and impact resistance are improved. Is possible. In addition, when content of cyclic carbonate is too high, there exists a demerit such as a fall of the intensity | strength of an aromatic polycarbonate resin composition etc., when too low, it is difficult for fluidity | liquidity to deteriorate or to have sufficient impact resistance May be

(3) Flame retardant The aromatic polycarbonate resin composition of the present invention can realize excellent flame retardancy by containing a flame retardant. The flame retardant is not particularly limited as long as it achieves the above object, but among them, a metal salt based flame retardant, a halogen containing compound based flame retardant, a phosphorus containing compound based flame retardant and a silicon containing compound based flame retardant It is preferable that it is at least one selected from In the aromatic polycarbonate resin composition of the present invention, the flame retardant may be used singly or in combination of two or more.

[Sulfonic acid metal salt flame retardants]
Examples of sulfonic acid metal salt-based flame retardants used in the present invention include aromatic sulfonic acid metal salts and aliphatic sulfonic acid metal salts. As metals of these metal salts, alkali metals, alkaline earth metals and the like can be mentioned as preferable examples. Examples of the alkali metal and alkaline earth metal include sodium, lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium.

  As the metal salt of sulfonic acid, from the viewpoint of flame retardancy and heat stability, metal salts of aromatic sulfone sulfonic acid and metal salts of perfluoroalkane-sulfonic acid are preferably selected.

  As the aromatic sulfone sulfonic acid metal salt, an aromatic sulfone sulfonic acid alkali metal salt and an aromatic sulfone sulfonic acid alkaline earth metal salt are preferable. The aromatic sulfone sulfonic acid alkali metal salt and the aromatic sulfone sulfonic acid alkaline earth metal salt may be a polymer.

  Specific examples of the aromatic sulfone sulfonic acid metal salt include sodium salt of diphenyl sulfone-3-sulfonic acid, potassium salt of diphenyl sulfone-3-sulfonic acid, and 4,4′-dibromodiphenyl sulfone-3-sulfonic acid. Sodium salt, potassium salt of 4,4'-dibromodiphenyl-sulfone-3-sulfone, calcium salt of 4-chloro-4'-nitrodiphenylsulfone-3-sulfonic acid, diphenylsulfone-3,3'-disulfonic acid Sodium salt, dipotassium salt of diphenyl sulfone-3,3'-disulfonic acid and the like can be mentioned.

  Examples of the perfluoroalkane-sulfonic acid metal salt include alkali metal salts of perfluoroalkane-sulfonic acid and alkaline earth metal salts of perfluoroalkane-sulfonic acid. Among them, alkali metal salts of sulfonic acid having a perfluoroalkane group having 4 to 8 carbon atoms, and alkali earth metal salts of sulfonic acid having a perfluoroalkane group having 4 to 8 carbon atoms are preferable.

  Specific examples of metal salts of perfluoroalkane-sulfonic acid include sodium perfluorobutane-sulfonate, potassium perfluorobutane-sulfonate, sodium perfluoromethylbutane-sulfonate, potassium perfluoromethylbutane-sulfonate, perfluoro Examples thereof include sodium octane-sulfonate, potassium perfluorooctane-sulfonate, tetraethyl ammonium salt of perfluorobutane-sulfonic acid, and the like. Among these, potassium perfluorobutane-sulfonate is preferable.

  It is preferable that the compounding quantity of the sulfonic-acid metal salt type flame retardant in the aromatic polycarbonate resin composition of this invention is 0.01-5 mass parts with respect to 100 mass parts of aromatic polycarbonate resin. The aromatic polycarbonate resin composition of the present invention can obtain sufficient flame retardancy when the blending amount of the sulfonic acid metal salt-based flame retardant is 0.01 parts by mass or more, and is 5 parts by mass or less The thermal stability is also fully satisfactory.

[Halogen-containing compound flame retardants]
Examples of halogen-containing compound flame retardants used in the present invention include tetrabromobisphenol A, tribromophenol, brominated aromatic triazine, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A epoxy polymer, decabromodiphenyl oxide, Examples thereof include tribromoallyl ether, tetrabromobisphenol A carbonate oligomer, ethylene bistetrabromophthalimide, decabromodiphenylethane, brominated polystyrene and the like.

  It is preferable that the compounding quantity of the halogen containing compound type flame retardant in the aromatic polycarbonate resin composition of this invention is 0.1-20 mass parts with respect to 100 mass parts of aromatic polycarbonate resin. The aromatic polycarbonate resin composition of the present invention can obtain sufficient flame retardancy when the compounding amount of the halogen-containing compound-based flame retardant is 0.1 parts by mass or more, and sufficient machinery when it is 20 parts by mass or less The strength can be maintained, and discoloration due to bleeding of the flame retardant tends not to occur.

[Phosphorus-containing compound flame retardant]
Examples of phosphorus-containing compound flame retardants used in the present invention include red phosphorus, coated red phosphorus, polyphosphate compounds, phosphate ester compounds, phosphazene compounds and the like. As a phosphoric acid ester compound, the phosphoric acid ester compound shown by the following general formula (VI) is mentioned.

R ₉ in the general formula (VI) , R ₁₀ , R ₁₁ And R ₁₂ Each independently represents a hydrogen atom or an organic group, R represents a divalent or higher organic group, a is 0 or 1, b is an integer of 1 or more, and c is a single atom. In the case of one compound, it is an integer of 0 or more, but a mixture of a plurality of compounds having different values of c may be used, and in this case, it is represented by the average value of c. However, R ₉ , R ₁₀ , R ₁₁ And R ₁₂ When c is 0, except when at the same time hydrogen is a hydrogen atom, R ₉ , R ₁₀ And R ₁₁ At least one represents an organic group.

R ₉ , R ₁₀ , R ₁₁ And the organic group represented by R ₁₂ includes, for example, an alkyl group which may be substituted, a cycloalkyl group, an aryl group and the like. Examples of the substituent in the case of substitution include an alkyl group, an alkoxy group, an alkylthio group, a halogen atom, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group and the like, and these substituents It may be a combined group (for example, an arylalkoxyalkyl group etc.) or a group obtained by combining these substituents by an oxygen atom, a sulfur atom, a nitrogen atom etc. (for example, an arylsulfonyl aryl group etc.).

  Examples of the divalent or higher organic group represented by R include an alkylene group, a cycloalkylene group, and an arylene group. Examples of the arylene group include a phenylene group which may have a substituent, a bisphenol, and a polynuclear group. The group etc. which are derived from phenols etc. are mentioned, The relative position of two or more free valences is arbitrary. Hydroquinone, resorcinol, 2,2-bis (4-hydroxyphenyl) methane (= bisphenol F), and 2,2-bis (4-hydroxyphenyl) propane are particularly preferable as the divalent or higher organic group. And arylene groups derived from bisphenol A), dihydroxybiphenyl, p, p′-dihydroxydiphenyl sulfone, dihydroxynaphthalene and the like.

  b is preferably an integer of 1 to 30, and c is preferably an integer of 1 to 10 or an average value thereof (in the case of the above mixture).

As specific examples of the phosphoric acid ester compound represented by the above general formula (VI), in the case of c = 0, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tri Cresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, diisopropyl phenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3 Dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate, c = 1 or more Case _of, R 9 _{to R 12} Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, tris, wherein is an alkyl group such as a methyl group, an ethyl group, a propyl group, or preferably a phenyl group optionally substituted with these alkyl groups. Polyphosphates such as oxybenzene triphosphate or mixtures thereof. Of these, triphenyl phosphate and various bis phosphates or mixtures thereof are preferred.

  It is preferable that the compounding quantity of the phosphorus containing compound type | system | group flame retardant in the aromatic polycarbonate resin composition of this invention is 0.1-20 mass parts with respect to 100 mass parts of aromatic polycarbonate resin. The aromatic polycarbonate resin composition of the present invention can obtain sufficient flame retardancy when the compounding amount of the phosphorus-containing compound-based flame retardant is 0.1 parts by mass or more, and the heat resistance when it is 20 parts by mass or less Sex is also fully satisfied.

[Silicon-containing compound flame retardant]
Examples of the silicon-containing compound-based flame retardant used in the present invention include silicone varnish, silicone resin having a substituent bonded to a silicon atom comprising an aromatic hydrocarbon group and an aliphatic hydrocarbon group having 2 or more carbon atoms, and a main chain Silicone compounds having an aromatic group in a branched structure and containing organic functional groups, silicone powders carrying a polydiorganosiloxane polymer which may have functional groups on the surface of silica powder, organopolysiloxane-polycarbonate Copolymer etc. are mentioned. Of these, silicone varnish is preferred.

The silicone varnish used in the present invention is mainly composed of a bifunctional unit [R ⁰ ₂ SiO] and a trifunctional unit [R ⁰ SiO _1.5 ], and a monofunctional unit [R ⁰ ₃ SiO _0.5 ] And / or a solution silicone resin of relatively low molecular weight which can contain tetrafunctional units [SiO ₂ ]. Here, R ⁰ is a hydrocarbon group having 1 to 12 carbon atoms or a hydrocarbon group having 1 to 12 carbon atoms substituted with one or more substituents, and the substituent includes an epoxy group, an amino group, a hydroxyl group And vinyl groups. It is possible to improve the compatibility with the aromatic polycarbonate resin (A) by changing the type of R ⁰ . Moreover, as a silicone varnish, although there exist a solvent-free silicone varnish and a silicone varnish containing a solvent, the silicone varnish which does not contain a solvent is preferable.

  The silicone varnish can be produced by hydrolysis of alkylalkoxysilane, and can be produced, for example, by hydrolysis of alkyltrialkoxysilane, dialkyldialkoxysilane, trialkylalkoxysilane, tetraalkoxysilane and the like. The molecular structure (crosslinking degree) and molecular weight can be controlled by adjusting the molar ratio of these raw materials, the hydrolysis rate and the like. Furthermore, although the alkoxysilane remains depending on the production conditions, if it remains in the composition, the hydrolysis resistance of the aromatic polycarbonate resin (A) may decrease, and there may be little or no residual alkoxysilane. desirable.

  The viscosity of the silicone varnish is usually less than 300 centistokes. If it exceeds 300 centistokes, the flame retardance may be insufficient. The viscosity of the silicone varnish is preferably 250 centistokes or less, more preferably 200 centistokes or less.

  It is preferable that the compounding quantity of the silicon-containing compound type flame retardant in the aromatic polycarbonate resin composition of this invention is 0.1-10 mass parts with respect to 100 mass parts of aromatic polycarbonate resin. Sufficient flame retardancy can be obtained in the aromatic polycarbonate resin composition of the present invention when the compounding amount of the silicon-containing compound-based flame retardant is 0.1 parts by mass or more, and heat resistance when it is 10 parts by mass or less I am satisfied enough.

  The aromatic polycarbonate resin composition of the present invention may use the following compounds in combination with the above flame retardant in order to achieve higher flame retardancy.

[Polytetrafluoroethylene]
In the present invention, it is preferable to use polytetrafluoroethylene in combination to achieve higher flame retardancy. Polytetrafluoroethylene is an anti-dripping agent, is easily dispersed in an aromatic polycarbonate resin, and exhibits a tendency to bond the resins by an external action such as shear force to form a fibrous material. Prevents burning of resin during flame and improves flame retardancy. Examples of polytetrafluoroethylene include those classified into type 3 according to ASTM standard, for example, as Mitsui 6 from DuPont Fluorochemicals Ltd., as Teflon 6J or Teflon 30J, or from Daikin Chemical Industries, Ltd. as Polyflon F 201L. What is marketed can be used.

  It is preferable that the compounding quantity of the polytetrafluoroethylene in the aromatic polycarbonate resin composition of this invention is 0.01-2.0 mass parts with respect to 100 mass parts of aromatic polycarbonate resin. When the blending amount of polytetrafluoroethylene is in the range of 0.01 to 2.0 parts by mass, the aromatic polycarbonate resin composition of the present invention can sufficiently obtain the melt dripping preventing effect at the time of combustion, and Excellent in appearance of molded products.

(4) Other components In the aromatic polycarbonate resin composition of the present invention, a rubbery polymer, a heat resistant stabilizer, an antioxidant, a mold release agent, an ultraviolet absorber, a dye, as long as the effects of the present invention are not impaired. Pigments and other additives may be blended.

[Rubber polymer]
In addition to the above-mentioned essential components, a rubbery polymer can be added to the aromatic polycarbonate resin composition of the present invention for the purpose of improving impact resistance. The rubbery polymer refers to a polymer having a glass transition temperature of 0 ° C. or less, particularly −20 ° C. or less, and includes a polymer obtained by copolymerizing a rubbery polymer with a monomer component copolymerizable therewith. . As the rubbery polymer used in the present invention, any conventionally known one which can be generally blended into an aromatic polycarbonate resin to improve its impact resistance can be used.

  Specific examples of the rubbery polymer include polyalkyl acrylate rubbers such as polybutadiene rubber, polyisoprene rubber, polybutyl acrylate, poly (2-ethylhexyl acrylate) and butyl acrylate / 2-ethylhexyl acrylate copolymer; polyorganosiloxane rubber In addition to silicone rubbers, etc., butadiene-acrylic composite rubber, IPN type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, styrene-butadiene rubber, ethylene-α-olefin rubber (ethylene-propylene rubber, ethylene -Butene rubber, ethylene-octene rubber and the like), ethylene-acrylic rubber, fluororubber and the like. Two or more of these may be used in combination. Among these, from the viewpoint of impact resistance, any one selected from the group of polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber consisting of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber The species is preferred.

  Specific examples of monomer components copolymerizable with the rubbery polymer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, etc. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methyl maleimide and N-phenyl maleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and the like Anhydrides (for example, maleic anhydride etc.) etc. are mentioned. Two or more of these monomer components may be used in combination. Among these, from the viewpoint of impact resistance, preferably any one selected from the group of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds and (meth) acrylic acid compounds And more preferably (meth) acrylic acid ester compounds. Specific examples of (meth) acrylic acid ester compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate and the like Be

  The rubbery polymer used in the present invention is preferably of the core / shell type graft copolymer from the viewpoint of impact resistance. In this case, the core layer is at least one rubber component selected from the group consisting of polybutadiene-containing rubber, polybutyl acrylate-containing rubber, and IPN (Interpenetrating polymer network) type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber. And the shell layer is preferably formed of (meth) acrylic acid ester, acrylonitrile-styrene copolymer.

  Preferred specific examples of the core / shell type graft copolymer include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-butadiene copolymer (MB), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer Polymer (MABS), methyl methacrylate-acrylic rubber copolymer (MA), acrylonitrile-styrene-acrylic rubber copolymer (ASA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic · acrylic Examples include butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methyl methacrylate- (acrylic silicone IPN rubber) copolymer and the like. Two or more of these may be used in combination.

  Further, as a product of the core / shell type graft copolymer, for example, “Stafroid MG1011” manufactured by Ganz Chemical Co., Ltd., “Paraloid EXL 2315”, “EXL 2602” manufactured by Rohm and Haas Japan Ltd., Examples include EXL series such as EXL 2603 ", KM series such as" KM 330 "and" KM 336 P ", KC series such as" KCZ 201 ", and" Metabrene S-2001 "and" SRK-200 "manufactured by Mitsubishi Rayon.

  Specific examples of other rubbery polymers include styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), Examples thereof include styrene-ethylene / propylene-styrene block copolymer (SEPS), acrylonitrile-butadiene rubber-styrene copolymer (ABS), acrylonitrile-ethylene-propylene rubber-styrene copolymer (AES) and the like.

  The content of the rubbery polymer is, for example, 0.5 to 40 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 25 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin and the polyethylene terephthalate resin. It is a department. When the content of the rubbery polymer is 1 part by mass or more, the impact resistance tends to be improved, and when it is less than 40 parts by mass, the rigidity, the heat resistance, and the moist heat resistance tend to be improved.

[Heat resistant stabilizer]
As the heat resistant stabilizer, known ones such as triphenylphosphine (P-Ph ₃ ) can be used.

[Antioxidant]
As an antioxidant, for example, tris- (2,4-di-t-butylphenyl) phosphite, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) Propionate, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-) 4-hydroxyphenyl) propionate], triethylene glycol-bis-3- (3-t-butyl-4-hydroxy-5-methylphenylpropionate), 3,9-bis [2- {3- (3-t) -Butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane Triphenyl phosphite, trisnonylphenyl phosphite, tris- (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphos Phonite, tricresyl phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like can be mentioned. Among these, tris- (2,4-di-t-butylphenyl) phosphite and n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-t-butylphenyl) propionate are preferred.

[Release agent]
As a mold release agent, a full ester of aliphatic alcohol and aliphatic carboxylic acid is preferably used. The full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid used in the present invention is, in particular, one or more of a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a polyhydric aliphatic alcohol And at least one kind of a full esterified product of monoaliphatic carboxylic acid, and a fully esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, polyvalent aliphatic alcohol and monoester The combined use with a full ester of an aliphatic carboxylic acid improves the mold release effect, suppresses gas generation during melt-kneading, and reduces mold deposit.

  As the full esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, preferred is a full esterified product of stearyl alcohol and stearic acid (stearyl stearate), and a fully esterified product of behenyl alcohol and behenic acid (behenyl behenate) As the full ester of polyhydric aliphatic alcohol and monoaliphatic carboxylic acid, a full ester of glycerin serine and stearic acid (glycerin tristearate), a full ester of pentaerythritol and stearic acid (pentaerythritol tetramer) Stearylate is preferred, and pentaerythritol tetrastearate is particularly preferred.

[UV absorber]
The aromatic polycarbonate resin composition of the present invention can optionally contain a UV absorber. By containing an ultraviolet absorber, the weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved.

  Examples of UV absorbers include inorganic UV absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oganilide compounds, malonic acid ester compounds, hindered amine compounds and the like An ultraviolet absorber etc. are mentioned. Among these, organic UV absorbers are preferable, and benzotriazole compounds are more preferable. By selecting the organic ultraviolet absorber, the mechanical properties of the aromatic polycarbonate resin composition of the present invention become good.

  Examples of the benzotriazole compound include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] -Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-Chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2′-hydroxy-3 ′, 5 '-Di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2,2' And -methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like. Among these, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N -Benzotriazol-2-yl) phenol] is preferable, and 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole is more preferable. Commercially available products of such benzotriazole compounds include, for example, “Seasorb 701”, “Seasorb 705”, “Seasorb 703”, “Seasorb 702”, “Seasorb 704”, “Seasorb 709” manufactured by Cipro Chemical Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 583”, “Chemsorb 71”, “Chemsorb 72” by Chemi-Pro Chemical Co., “Cysorb SO 541” by Cytec Industries, “LAC by Adeka” “32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinuvin P” manufactured by Ciba Specialty Chemicals, “Tinuvin 234”, “Tinuvin 326”, “ Tinuvin 327 "," tinuvin 328 "," tinuvin 329 " Etc. The.

[Dye and pigment]
The aromatic polycarbonate resin composition of the present invention may optionally contain dyes and pigments. By containing dyestuffs and pigments, the hiding power and weatherability of the aromatic polycarbonate resin composition of the present invention can be improved, and the designability of the resulting molded article can be improved.

  Examples of dyes and pigments include inorganic pigments, organic pigments, organic dyes and the like.

  Examples of inorganic pigments include sulfide pigments such as carbon black, cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc flower, red iron oxide, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black, copper-iron black; chromic acid pigments such as yellow lead and molybdate orange; Russian pigments and the like can be mentioned.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo dyes, perinones, perylene dyes, quinacridones, dioxazine dyes, and iso dyes. Condensed polycyclic dyes and pigments such as indolinone type and quinophthalone type; Anthraquinone types, heterocyclic types, methyl type dyes and the like.

  Among these, titanium oxide, carbon black, cyanine type, quinoline type, anthraquinone type, phthalocyanine type compounds and the like are preferable from the viewpoint of thermal stability.

  Dyeing pigments are aromatic like polystyrene masterbatch of carbon black (40% carbon black, RB904G made by Koshigaya Kasei Co., Ltd.) for the purpose of improving handling property at the time of extrusion and dispersibility improvement in the resin composition. Polycarbonate resins or those which are masterbatched with other rubbery polymers may also be used.

  The aromatic polycarbonate resin composition of the present invention may be, for example, an antistatic agent, an inorganic filler, an antifogging agent, an antiblocking agent, or a fluid, as long as the desired physical properties are not significantly impaired. Various additives such as a quality improver, a sliding property modifier, a plasticizer, a dispersant, an antibacterial agent, a hydrolysis stabilizer, a toughening agent, a filler, a lubricant, and a crystal nucleating agent can be contained.

  The mixing method and mixing time of the additives and the like in the aromatic polycarbonate resin composition of the present invention are not particularly limited. For example, as the mixing time, during the polymerization reaction or at the completion of the polymerization reaction, such as aromatic polycarbonate etc. The polycarbonate can be added in a molten state, such as in the middle of kneading, or after blending with a solid polycarbonate such as pellets or powder, it is also possible to knead with an extruder or the like.

<Method of producing aromatic polycarbonate resin>
Although the manufacturing method in particular of aromatic polycarbonate resin contained in the aromatic polycarbonate resin composition of this invention is not restrict | limited, It is preferable that it is obtained by the manufacturing method shown below. By taking the production method described below, an aromatic polycarbonate resin containing a cyclic carbonate having a specific structure at a desired content rate with a low degree of branching, a low content of different structure, a low concentration of terminal hydroxyl groups and a desired content It can be manufactured.

  That is, a preferable method for producing an aromatic polycarbonate resin comprises reacting an aromatic polycarbonate prepolymer with a diol compound represented by the following general formula (IV) (hereinafter, also referred to as a "diol compound") in the presence of a transesterification catalyst Manufacturing to obtain a high molecular weight aromatic polycarbonate resin, and a cyclic carbonate removing step of removing at least a part of cyclic carbonate by-produced in the high molecular weight step out of the reaction system. It is a method.

In the general formula (IV), each of Ra and Rb independently represents a hydrogen atom, a halogen atom, an oxygen atom or a linear or branched alkyl group having 1 to 30 carbon atoms which may contain a halogen atom, an oxygen atom or It may contain a cycloalkyl group having 3 to 30 carbon atoms which may contain a halogen atom, an aryl group having 6 to 30 carbon atoms which may contain an oxygen atom or a halogen atom, or an oxygen atom or a halogen atom It may represent an alkoxy group having 1 to 15 carbon atoms, or Ra and Rb may be bonded to each other to form a ring. As a halogen atom, a fluorine atom is preferable.
R _{5 to} R ₈ each independently represent a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 5 carbon atoms. As said halogen atom, a fluorine atom is preferable. n represents an integer of 0 to 30.

  Each of Ra and Rb independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, Or an alkoxy group having 1 to 8 carbon atoms is preferable, a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms is more preferable, and a linear or branched alkyl having 1 to 4 carbon atoms It is more preferably a group, and particularly preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or an i-butyl group.

Each of R _{5 to} R ₈ independently is preferably a hydrogen atom, a fluorine atom or a methyl group, and more preferably each is a hydrogen atom.

  The n is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably 1.

  More preferable as the diol compound represented by the general formula (IV) is a compound represented by the following general formula (IVa). In general formula (IVa), Ra and Rb are the same as in general formula (IV).

  In general formula (IVa), Ra and Rb each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and a linear or branched alkyl group having 1 to 4 carbon atoms And is preferably a linear or branched alkyl group having 2 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, or an isobutyl group, and an ethyl group or a propyl group. , Butyl and isobutyl are particularly preferred.

  As the diol compound, for example, 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, 2,2-diethylpropane-1,3-diol, 2-methyl-2-propylpropane-1,3-diol, propane-1,2-diol, propane-1,3-diol, ethane-1,2-ethane Diol (1,2-ethylene glycol), 2,2-diisoamylpropane-1,3-diol, 2-methylpropane-1,3-diol and the like can be mentioned.

  Moreover, the compound which has the following structural formula as another example of the said diol compound is mentioned.

  Among these, 2-butyl-2-ethylpropane-1,3-diol, 2,2-diisobutylpropane-1,3-diol, 2-ethyl-2-methylpropane-1,3-diol, 2,2 Particular preference is given to diethylpropane-1,3-diol and 2-methyl-2-propylpropane-1,3-diol.

[Aromatic polycarbonate prepolymer]
An aromatic polycarbonate prepolymer (hereinafter, also referred to as “prepolymer” or “PP”) used in a method for producing an aromatic polycarbonate resin has a structure represented by the above general formula (I) which constitutes the aromatic polycarbonate resin It is a polycondensation polymer as a main repeating unit.

  Such an aromatic polycarbonate prepolymer is obtained by a known transesterification method in which an aromatic dihydroxy compound derived from the structural unit represented by the general formula (I) is reacted with a carbonic diester in the presence of a basic catalyst, or It can be easily obtained by any known interfacial polycondensation method in which the aromatic dihydroxy compound is reacted with phosgene or the like in the presence of an acid binder.

  As an aromatic dihydroxy compound which derives the structural unit represented by said general formula (I), the compound represented by said general formula (V) is mentioned.

  The aromatic polycarbonate prepolymer may be one synthesized by an interfacial polymerization method or one synthesized by a melt polymerization method, and may be one synthesized by a method such as solid phase polymerization method or thin film polymerization method. May be Further, it is also possible to use polycarbonate etc. recovered from used products such as used disc molded products. These polycarbonates may be mixed and used as a pre-reaction polymer. For example, a polycarbonate polymerized by an interfacial polymerization method and a polycarbonate polymerized by a melt polymerization method may be mixed, or a polycarbonate polymerized by a melt polymerization method or an interfacial polymerization method and a polycarbonate recovered from a used disc molded article or the like You may mix and use.

  As the aromatic polycarbonate prepolymer, an end-capped aromatic polycarbonate prepolymer satisfying a specific condition is preferable. That is, at least a part of the aromatic polycarbonate prepolymer is sealed with an end group or an end phenyl group derived from an aromatic monohydroxy compound (hereinafter collectively referred to as "sealing end group"). preferable.

The proportion of the capping end groups is preferably 60 mol% or more based on the total amount of ends. In addition, the terminal phenyl group concentration (the ratio of the capping terminal group to the total constituent units) is 2 mol% or more, preferably 2 to 20 mol%, and more preferably 2 to 12 mol%. When the terminal phenyl group concentration is 2 mol% or more, the reaction with the diol compound proceeds rapidly, and the effects unique to the present invention are particularly prominent. The ratio of the amount of end of closure to the total amount of end of prepolymer can be analyzed by ¹ H-NMR analysis of the prepolymer.

In addition, it is possible to measure the terminal hydroxyl group concentration by spectrometry with a Ti complex. Furthermore, the terminal hydroxyl group concentration can also be measured by ¹ H-NMR analysis. As a terminal hydroxyl group concentration by the same evaluation, 1,500 ppm or less is preferable, and 1,000 ppm or less is more preferable. At the hydroxyl group end within the above range, a sufficient effect of high molecular weight formation tends to be obtained by a transesterification reaction with a diol compound.

  The “total end group content of the aromatic polycarbonate prepolymer” referred to herein is calculated as, for example, if there are 0.5 mol of non-branched polycarbonate (ie, chain polymer), the total amount of end groups is 1 mol. . The same applies to "the total amount of terminal groups of the aromatic polycarbonate resin".

  Specific examples of the capping end group include phenyl end group, cresyl end group, o-tolyl end group, p-tolyl end group, p-t-butylphenyl end group, biphenyl end group, o-methoxycarbonylphenyl end group And p-cumylphenyl end groups and the like.

  Among these, a capping end group composed of a low boiling point aromatic monohydroxy compound which is easily removed from the reaction system by a transesterification reaction with a diol compound is preferred, and a phenyl end group, a p-tert-butylphenyl end group Is more preferred.

  Such capping end groups can be introduced by using an endcapping agent in the preparation of the aromatic polycarbonate prepolymer in the interfacial process. Examples of the terminator include p-tert-butylphenol, phenol, p-cumylphenol, long-chain alkyl-substituted phenol and the like. The amount of termination agent used can be appropriately determined according to the desired terminal amount of the aromatic polycarbonate prepolymer (that is, the molecular weight of the desired aromatic polycarbonate prepolymer), the reactor, the reaction conditions, and the like.

  In the melting method, a sealing end group can be introduced by using a carbonic diester such as diphenyl carbonate in excess with respect to the aromatic dihydroxy compound at the time of producing the aromatic polycarbonate prepolymer. Although depending on the apparatus and reaction conditions used for the reaction, specifically, the amount of carbonic diester is usually 1.00 to 1.30 moles and 1.02 to 1.20 moles relative to 1 mole of the aromatic dihydroxy compound. It is preferred to use. Thereby, an aromatic polycarbonate prepolymer satisfying the amount of the sealing end is obtained.

  As the aromatic polycarbonate prepolymer, it is preferable to use an end-capped polycondensation polymer obtained by reacting (ester exchange reaction) an aromatic dihydroxy compound with a carbonic acid diester.

  When producing an aromatic polycarbonate prepolymer, a polyfunctional compound having three or more functional groups in one molecule can be used in combination with the above-mentioned aromatic dihydroxy compound. As such a polyfunctional compound, a compound having a phenolic hydroxyl group and a carboxyl group is preferably used.

  Further, when producing an aromatic polycarbonate prepolymer, a dicarboxylic acid compound may be used in combination with the above-mentioned aromatic dihydroxy compound to form a polyester carbonate. As the dicarboxylic acid compound, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid and the like are preferable, and these dicarboxylic acids are preferably reacted as an acid chloride or an ester compound. Moreover, when manufacturing polyester carbonate resin, when making the sum total of the said dihydroxy component and a dicarboxylic acid component into 100 mol%, it is preferable to use in 0.5-45 mol%, 1 It is more preferable to use in the range of -40 mol%.

  The molecular weight of the aromatic polycarbonate prepolymer is preferably 5,000 to 35,000, more preferably 15,000 to 35,000, and still more preferably 20,000 to 35,000. An aromatic polycarbonate prepolymer in the range of 1,000 is particularly preferred.

  The use of an aromatic polycarbonate prepolymer having a molecular weight within this range eliminates the need to carry out the preparation of the prepolymer at high temperature, high shear and long time and / or because the aromatic polycarbonate prepolymer itself has low viscosity. There is a tendency that it is not necessary to carry out the reaction with the diol compound at high temperature, high shear and long time.

[Cyclic carbonate]
In the above-mentioned production method, the molecular weight of the aromatic polycarbonate prepolymer is made high by causing the diol compound to act on the end-capped aromatic polycarbonate prepolymer in the presence of a transesterification catalyst under reduced pressure conditions. The reaction proceeds rapidly under mild conditions to achieve high molecular weight. That is, the reaction between the diol compound and the aromatic polycarbonate prepolymer proceeds faster than the reaction in which the aliphatic polycarbonate unit is generated by the transesterification reaction after the aromatic polycarbonate prepolymer undergoes a cleavage reaction by the diol compound.

  Here, in the method of reacting the diol compound having the specific structure, the reaction is caused by the reaction of the aromatic polycarbonate prepolymer and the diol compound, and a cyclic compound derived from the diol compound having a structure corresponding to the structure of the diol compound. Cyclic carbonate is by-produced. Then, by removing the by-produced cyclic carbonate out of the reaction system, the molecular weight of the aromatic polycarbonate prepolymer proceeds, and finally, it is almost the same as that of a conventional homopolycarbonate (for example, a homopolycarbonate resin derived from bisphenol A). An aromatic polycarbonate resin having the same structure is obtained. Since the cyclic carbonate can not be completely removed even by this removal step, the production method using the diol compound having the structure represented by the above general formula (IV) of the present invention is a polycarbonate of the conventional melting method. Compared with the manufacturing method, it has the advantage that high molecular weight can be obtained at high speed.

  The details of the structure of the cyclic carbonate are as described above.

  Although the reaction mechanism by which cyclic carbonate is by-produced along with the above-mentioned high molecular weight formation is not necessarily clear, for example, the mechanism shown in the following scheme (a) or (b) can be considered. The production method using a diol compound having a structure represented by the above general formula (IV) of the present invention comprises reacting an aromatic polycarbonate prepolymer with a diol compound as a linking agent, and connecting the aromatic polycarbonate prepolymer with a high molecular weight It is intended to remove the cyclic carbonate having a structure corresponding to the structure of the by-produced diol compound as well as the reaction system, and it is not limited to a specific reaction mechanism within the range.

Scheme (a):

Scheme (b):

  The high molecular weight-ized aromatic polycarbonate resin obtained by the production method using a diol compound having a structure represented by the general formula (IV) hardly contains a structural unit derived from a diol compound, and the resin skeleton is a homopolycarbonate It is almost the same as resin.

  That is, since the structural unit derived from the diol compound which is the linking agent is not contained in the skeleton or is very small if contained, the thermal stability is extremely high and the heat resistance is excellent. On the other hand, while having the same skeleton as a conventional homopolycarbonate resin, excellent quality such as low N value, small proportion of structural units having different structures, excellent in color tone, and the like can be provided.

Below, the detailed conditions of the manufacturing method of aromatic polycarbonate resin are demonstrated.
(I) Addition of Diol Compound The diol compound represented by the above general formula (IV) is added to and mixed with the aromatic polycarbonate prepolymer, and a polymerization reaction (ester exchange reaction) is performed in the polymerization reactor.

  The amount of the diol compound used is preferably 0.01 to 1.0 mol, more preferably 0.1 to 1.0 mol based on 1 mol of the total terminal group weight of the aromatic polycarbonate prepolymer. Preferably, it is 0.2 to 0.7 mole. However, when one having a relatively low boiling point is used, an excess amount may be added in advance in consideration of the possibility of part of the reaction leaving the system without volatilizing due to volatilization depending on the reaction conditions. For example, up to 50 moles, preferably 10 moles, more preferably 5 moles can be added per mole of the total amount of terminal groups of the aromatic polycarbonate prepolymer.

  The addition and mixing method of the diol compound is not particularly limited, but when using a compound having a relatively high boiling point (boiling point of about 350 ° C. or higher) as the diol compound, the diol compound has a degree of vacuum of 10 torr (1333 Pa or less) It is preferable to supply the polymerizing reactor directly under high vacuum. As for the said pressure reduction degree, 2.0 torr or less (267 Pa or less) is more preferable, and 0.01-1 torr (1.3-133 Pa or less) is more preferable. If the degree of reduced pressure at the time of supplying the diol compound to the high molecular weight polymerization reactor is insufficient, the cleavage reaction of the prepolymer main chain by the by-product (phenol) proceeds, and the reaction time for high molecular weight polymerization You may have to make it longer.

  On the other hand, when using a compound having a relatively low boiling point (boiling point less than about 350 ° C.) as the diol compound, the aromatic polycarbonate prepolymer and the diol compound can also be mixed at a relatively gentle degree of reduced pressure. For example, after mixing an aromatic polycarbonate prepolymer and a diol compound at a pressure close to normal pressure to form a prepolymer mixture, the prepolymer mixture is subjected to a high molecular weight reaction under reduced pressure conditions, whereby the boiling point is relatively low. Even if it is a diol compound, volatilization is minimized and there is no need to use it in excess.

(Ii) Transesterification (polymerization reaction)
The temperature used for the transesterification reaction (polymerization reaction) of the aromatic polycarbonate prepolymer and the diol compound is preferably in the range of 240 ° C. to 320 ° C., more preferably 260 ° C. to 310 ° C., 280 ° C. to 310 ° C. Is more preferred.

  Moreover, as a pressure reduction degree, 13 kPaA (100 torr) or less is preferable, 1.3 kPaA (10 torr) or less is more preferable, and 0.67 to 0.013 kPaA (5 to 0.1 torr) is more preferable.

  Examples of the transesterification catalyst (hereinafter also referred to as "catalyst") used for the transesterification reaction include basic compounds, and examples include alkali metal compounds and / or alkaline earth metal compounds, nitrogen-containing compounds, and the like.

  As such compounds, organic acid salts such as alkali metals or alkaline earth metals, inorganic salts, oxides, hydroxides, hydrides and alkoxides, quaternary ammonium hydroxides and salts thereof, amines, etc. are preferable. These compounds may be used alone or in combination of two or more.

  As an alkali metal compound, for example, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, lithium carbonate, sodium acetate, sodium acetate, potassium acetate, cesium acetate, acetic acid Lithium, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium tetraphenylborate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate , Dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, sodium gluconate, disodium salt of bisphenol A, dipotassium salt of dipotassium salt, disodium salt of dibasic acid, dilithium salt of dibasic acid, dilithium salt of phenol Potassium salt, potassium salt, cesium salt and lithium salt and the like.

  As the alkaline earth metal compound, for example, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, magnesium carbonate, calcium carbonate, strontium carbonate And barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenylphosphate and the like.

  As the nitrogen-containing compound, for example, a quaternary having an alkyl group such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, trimethyl benzyl ammonium hydroxide and / or an aryl group, etc. Ammonium hydroxides, tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2- Imidazoles such as phenylimidazole and benzimidazole; ammonia; tetramethylammonium borohydride; tetrabutylammonium borohydride; Eniruhou tetrabutyl ammonium, basic or basic salts such as tetraphenyl borate tetraphenyl ammonium, and the like.

  As the transesterification catalyst, for example, salts of zinc, tin, zirconium and lead are preferably used, and specific examples thereof include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin chloride ( IV), tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate etc. Can be mentioned. These may be used alone or in combination of two or more.

These catalysts are generally used in a ratio of 1 × 10 ⁻⁹ to 1 × 10 ⁻³ mol, and 1 × 10 ⁻⁷ to 1 ×, based on 1 mol in total of the aromatic dihydroxy compounds constituting the prepolymer. Preferably, it is used in a ratio of 10 ^-5 moles.

(Iii) Cyclic Carbonate Removal Step At the same time as the aromatic polycarbonate prepolymer is made to be high molecular weight by the above high molecular weight conversion reaction to obtain an aromatic polycarbonate resin having a desired molecular weight, at least one of cyclic carbonates by-produced in the reaction Remove the part out of the reaction system. By removing at least a part of the by-produced cyclic carbonate out of the reaction system, the polymerization reaction of the aromatic polycarbonate prepolymer proceeds.

  As a method for removing the cyclic carbonate, there may be mentioned, for example, a method of distilling away from the reaction system together with phenol and unreacted diol compound which are also by-produced as well. The temperature in the case of distillation from the reaction system is preferably in the range of 240 ° C to 320 ° C, more preferably 260 ° C to 310 ° C, and more preferably 280 ° C to 310 ° C.

  The removal of the cyclic carbonate is performed on at least a part of the by-produced cyclic carbonate. The preferable upper limit of the residual amount of cyclic carbonate to be by-produced is 3000 ppm. That is, in the production method using the diol compound having the structure represented by the general formula (IV), the cyclic carbonate having the structure represented by the general formula (II) is 3000 ppm or less, preferably 1000 ppm or less, more preferably The aromatic polycarbonate resin is obtained at a content of at most 500 ppm, particularly preferably at most 300 ppm. The lower limit of the content of the cyclic carbonate having the structure represented by the general formula (II) is usually a detection limit value, and preferably 0.0005 ppm. The cyclic carbonate content is a value measured by GC-MS.

  The cyclic carbonate distilled out of the reaction system can then be recovered and recycled (recycled) through steps such as hydrolysis and purification. The phenol distilled off together with the cyclic carbonate can be similarly recovered, supplied to the diphenyl carbonate production process and reused.

  The step of increasing the molecular weight and the step of removing the cyclic carbonate do not necessarily need to be separate steps physically and temporally, and are actually performed simultaneously. In a preferred production method of the present invention, an aromatic polycarbonate and a diol compound are reacted in the presence of a transesterification catalyst to obtain an aromatic polycarbonate resin having a high molecular weight, and a cyclic product by-produced in the high molecular weight reaction. And a step of removing at least a part of the carbonate out of the reaction system.

(Iv) Other Production Conditions The weight average molecular weight (Mw) of the aromatic polycarbonate resin after reaction is the weight average molecular weight (Mw) of the aromatic polycarbonate prepolymer by the transesterification reaction of the aromatic polycarbonate prepolymer and the diol compound It is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more.

  The type of the apparatus in the transesterification reaction with the diol compound, the material of the pot, etc. may be any known one, and may be carried out continuously or batchwise. The reaction apparatus used for carrying out the above reaction was equipped with paddle blades, grid blades, glasses blades, etc. even if it is a vertical type equipped with vertical mixing blades, Max Blend stirring blades, helical ribbon type stirring blades etc. A horizontal type or an extruder type equipped with a screw may be used, and it is preferable to use a reaction device in which these are appropriately combined in consideration of the viscosity of the polymer. It is preferable to use a rotary blade having good horizontal stirring efficiency and a unit capable of reducing pressure, and more preferably a twin-screw extruder or a horizontal reactor having a polymer seal and having a degassing structure.

  The material of the device is preferably a stainless steel such as SUS310, SUS316 or SUS304, or a material that does not affect the color tone of the polymer, such as nickel or nitrided steel. Further, the inside of the apparatus (the part in contact with the polymer) may be subjected to buffing or electrolytic polishing, or may be plated with metal such as chromium.

  A catalyst deactivator may be applied to the high molecular weight aromatic polycarbonate resin. Generally, known catalyst deactivators include known acidic substances and the like, and catalyst deactivation by the addition of these catalyst deactivators is preferably carried out. As these catalyst deactivators, for example, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, p-toluenesulfonic acid Aromatic sulfonates such as tetrabutylammonium salts, stearic acid chloride, butyric acid chloride, benzoyl chloride, organic halides such as toluenesulfonic acid chloride, benzyl chloride, alkyl sulfates such as dimethyl sulfate, phosphoric acids, phosphorous acids, etc. Can be mentioned.

  Among these, catalyst deactivators selected from the group consisting of paratoluenesulfonic acid, butyl paratoluenesulfonate, tetrabutylphosphonium salt of dodecylbenzenesulfonic acid, and tetrabutylammonium salt of paratoluenesulfonic acid are preferable.

  The addition amount of the catalyst deactivator is not particularly limited, but is preferably 3 ppm or more, and more preferably 5 ppm or more with respect to the aromatic polycarbonate resin. When the content of the catalyst deactivator is 3 ppm or more, the effect of improving the thermal stability of the aromatic polycarbonate resin composition of the present invention can be expected. Although the upper limit in particular of catalyst deactivator content is not restrict | limited, 30 ppm or less is preferable and 20 ppm or less is more preferable.

  The addition of the catalyst deactivator can be mixed with the polycarbonate resin by a conventionally known method after the completion of the high molecular weight formation reaction. For example, after dispersing and mixing with a high speed mixer represented by a turnbull mixer, a Henschel mixer, a ribbon blender, a super mixer, a method of melt-kneading with an extruder, a Banbury mixer, a roll or the like is appropriately selected.

  After catalyst deactivation, a step of degassing the low boiling point compound in the aromatic polycarbonate resin at a pressure of 0.013 to 0.13 kPaA (0.1 to 1 Torr) at a temperature of 200 to 350 ° C. may be provided. For this purpose, a horizontal apparatus such as a paddle blade, a grid blade or an eyeglass blade, or a stirring blade having an excellent surface renewal capability, or a thin film evaporator is preferably used. Preferably, it is a twin-screw extruder or a horizontal reactor having a polymer seal and having a vent structure.

<Method of producing aromatic polycarbonate resin composition of the present invention>
The method for producing the aromatic polycarbonate resin composition is not particularly limited as long as the aromatic polycarbonate resin composition of the present invention can be obtained. That is, there is no restriction | limiting in particular about the mixing method of a flame retardant, the said additive, etc., and mixing time. For example, as mixing time, during the polymerization reaction (for example, the above-mentioned high molecular weight formation reaction) of the aromatic polycarbonate resin or at the end of the polymerization reaction, or after deactivating the catalyst used for the polymerization reaction with the catalyst deactivator, pelletize A resin composition can be manufactured by adding an additive at any time before and mixing with aromatic polycarbonate resin. In addition, although it can add in the state which aromatic polycarbonate resin melt | dissolved in the middle of kneading | mixing etc., such as aromatic polycarbonate resin, it is possible to knead by an extruder etc., after blending with polycarbonate of solid states, such as pellets or powder. It is. For example, in a state where the aromatic polycarbonate resin containing a specific amount of cyclic carbonate is melted, a flame retardant, the above-mentioned additive and the like may be added and mixed to adjust. Also, even if the aromatic polycarbonate resin containing a specific amount of cyclic carbonate is in the solid state such as pellets or powder, after blending the solid state aromatic polycarbonate resin etc. with the flame retardant or the above-mentioned additives, It is also possible to knead with an extruder or the like.

2. Molded Article The aromatic polycarbonate resin composition of the present invention can be preferably used for various molded articles, various members and the like obtained by injection molding, blow molding, extrusion molding, rotational molding, compression molding and the like. When used in these applications, the resin composition of the present invention may be used alone or in a blend with another polymer. Depending on the application, processing such as hard coating may be preferably used.

  Particularly preferably, the aromatic polycarbonate resin composition of the present invention is used for extrusion molding, injection molding and the like. Because of having excellent mechanical properties, examples of molded products obtained include extruded products, precision parts and injection molded products, raw materials in the automotive field, OA equipment field, electronic and electrical fields, etc., raw materials in the general industrial field Etc., but not limited thereto.

  Specific examples of molded articles include various raw materials in the field of electrics and electronics, various raw materials in the automobile and aircraft industries, other optical equipment parts, in-vehicle products such as trains and automobiles, various building members, copiers, facsimiles, personal computers such as personal computers Various parts of equipment, Various parts materials of home appliances such as TVs and microwaves, Electronic parts applications such as connectors and IC trays, Protective members such as helmets, protectors and protective surfaces, Members of different medical devices, etc. But not limited thereto. As described above, particularly preferable applications of the aromatic polycarbonate resin composition of the present invention of the present invention include molded articles which require high strength (high Charpy strength), high heat and humidity resistance, and precise moldability.

  EXAMPLES The present invention will be described by way of examples, but the present invention is not limited by these examples. In addition, the measured value in an Example is an analysis and physical-property evaluation of the obtained aromatic polycarbonate or aromatic polycarbonate resin composition (Hereafter, when it is common to both, it may be called "aromatic polycarbonate."). , The following method or apparatus was used to measure.

<Physical property evaluation method>
(1) Weight average molecular weight (Mw) and number average molecular weight (Mn)
Using GPC, chloroform was used as a developing solvent, and a standard curve (molecular weight distribution = 1) of standard polystyrene (Tosoh Corp., “PStQuick MP-M”) was used to prepare a calibration curve. The elution time and molecular weight value of each peak were plotted from the measured standard polystyrene, and approximation with a cubic equation was performed to obtain a calibration curve. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were determined as polystyrene conversion values from the following formula.

[a formula]
Mw = ((Wi x Mi) ((Wi)
Mn = Σ (Ni × Mi) ÷÷ (Ni)
Here, i is the i-th dividing point when dividing the molecular weight M, Wi is the i-th weight, Ni is the number of the i-th molecule, and Mi is the i-th molecular weight. Also, the molecular weight M represents the polystyrene molecular weight value at the same elution time of the calibration curve.

(2) Molecular weight distribution (Mw / Mn)
It calculated | required from the following calculation formulas from polystyrene conversion weight average molecular weight (Mw) and polystyrene conversion number average molecular weight (Mn).

[a formula]
Molecular weight distribution = Mw / Mn

[Measurement condition]
Device: Tosoh Co., Ltd. HLC-8320 GPC
column:
Guard column: TSKguardcolumn SuperMPHZ-M x 1 analytical column: TSKgel SuperMultipore HZ-M x 3 solvent: HPLC grade chloroform Injection volume: 10 μL
Sample concentration: 0.2 w / v% HPLC grade chloroform solution Solvent flow rate: 0.35 ml / min
Measurement temperature: 40 ° C
Detector: RI

(3) Terminal hydroxyl group concentration (ppm)
It measured by observing a terminal hydroxyl group from the analysis result of < ¹ > H-NMR. The terminal hydroxyl group concentration in the prepolymer (PP) by ¹ H-NMR was prepared by dissolving 0.05 g of the resin sample in 1 ml of deuterated chloroform (containing 0.05 w / v% TMS), and ¹ H-NMR at 23 ° C. It asked by measuring. Specifically, from the integral ratio of the hydroxyl group peak of 4.7 ppm and the phenyl and phenylene groups (terminal phenyl group and phenylene group derived from BPA skeleton) in the vicinity of 7.0 to 7.5 ppm, the terminal hydroxyl group concentration in PP (OH Concentration) was calculated. The terminal hydroxyl group concentration in the aromatic polycarbonate resin can also be measured and calculated in the same manner.

In addition, the detail of the measurement conditions of ¹ H-NMR is as follows.
Device: LA-500 (500 MHz) manufactured by Nippon Denshi Co., Ltd.
Measuring nucleus: ¹ H
relaxation delay: 1s
x_angle: 45deg
x_90_width: 20 μs
x_plus: 10 μs
scan: 500times

(4) Terminal phenyl group concentration (capping terminal group concentration, Ph terminal concentration; mol%):
^It calculated | required by the following numerical formula from the analysis result of < ¹ > H-NMR.

Specifically, 0.05 g of a resin sample is dissolved in 1 ml of deuterated chloroform (containing 0.05 w / v% TMS), and a ¹ H-NMR spectrum is measured at 23 ° C. The terminal phenyl group content and terminal phenyl group concentration of PP were measured from the integral ratio of a phenyl group and a phenylene group (derived from BPA skeleton) in the vicinity of 7.0 to 7.3 ppm. The details of the measurement conditions of ¹ H-NMR are the same as described above.

  The total amount of terminal groups of the polymer can be calculated from the above-mentioned terminal hydroxyl group concentration and terminal phenyl group concentration.

(5) Heterostructure amount 0.05 g of a resin sample is dissolved in 1 ml of deuterated chloroform (containing 0.05 w / v% TMS) and polymerized at 23 ° C. using a nuclear magnetic resonance analyzer ¹ H-NMR. The amount of different structures in the polycarbonate (PC) was measured. The following different amounts of heterostructure (ppm) were determined by ¹ H-NMR assignment of Ha and Hb described in P. 7659 in the literature, Polymer 42 (2001) 7653-6661. The measurement conditions for ¹ H-NMR are the same as described above.

[Calculation]
The signals of Ha (near 8.01 ppm) and Hb (near 8.15 ppm) in the different structural unit and the phenyl and phenylene groups (a terminal phenyl group and a phenylene group derived from BPA skeleton) around 7.0 to 7.5 ppm The amount of different structure was calculated from the integral ratio of the signal.

(6) N value With respect to an aromatic polycarbonate (sample) dried at 120 ° C. for 5 hours using an enhanced flow tester CFT-500D (manufactured by Shimadzu Corporation), the hole diameter is 1.0 mmφ and the length is 10 mm The melt flow volume per unit time measured with a die at 280 ° C and a load of 160 kg is taken as a Q160 value, and the melt flow volume per unit time measured with a 280 ° C and a load of 10 kg as a Q10 value. It calculated | required by the following Formula (1).
N value = (log (Q 160 value)-log (Q 10 value)) / (log 160-log 10) (1)

(7) Flow value (Q value)
The flow value (Q value) of pellets of the aromatic polycarbonate resin composition dried at 100 ° C. for 5 hours according to the method described in JIS K 7210 Appendix C was evaluated. The measurement was carried out using a flow tester CFT-500D manufactured by Shimadzu Corporation, using a die with a hole diameter of 1.0 mmφ and a length of 10 mm, at a test temperature of 280 ° C., a test force of 160 kg / cm ² and a remaining heat time of 420 sec. The amount of molten resin (× 0.01 cm ³ / sec) was measured.

(8) Impact resistance After the pellets of the aromatic polycarbonate resin composition are dried at 100 ° C. for 5 hours, a cylinder temperature of 260 ° C., a mold by an injection molding machine (“SG75 Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.) Injection molding is performed under conditions of temperature 80 ° C. and molding cycle 50 seconds, ISO multipurpose test pieces (4 mm thick) are molded, and under each condition of 23 ° C., Charpy impact test (notched, based on ISO-179 standard) A unit: kJ / m ² ) was performed.

(9) Wet heat test Pellets of the aromatic polycarbonate resin composition are dried at 100 ° C. for 5 hours, and cylinder temperature 260 ° C., mold temperature by an injection molding machine (“SG 75 Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.) Injection molding was carried out under conditions of 80 ° C. and molding cycle of 50 seconds, ISO multipurpose test pieces (3 mm thickness) were molded, and a steam pressure tester (“HASTEST PC-S III” manufactured by Hirayama Mfg. Co., Ltd.) was used. The wet heat treatment was carried out by holding in water vapor at 100 ° C. for 24 hours. The test pieces after the wet heat treatment were cut with scissors and the flow value (Q value) was measured. The difference between the Q value after wet heat treatment and the flow value (Q value) before wet heat treatment was taken as ΔQ.

(10) Flammability evaluation (UL 94)
After drying the pellet of the aromatic polycarbonate resin composition at 120 ° C. for 5 hours, the cylinder temperature is 270 ° C., the mold temperature is 80 ° C., and the molding cycle is 50 seconds with an injection molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) The injection molding was performed under the following conditions to form a UL test specimen having a length of 125 mm, a width of 13 mm, and a thickness of 1.0 mm. The obtained UL test specimen is conditioned for 48 hours in a thermostatic chamber with a temperature of 23 ° C and a humidity of 50%, and the UL94 test prescribed by Underwriters Laboratories (UL) in the United States (plastic for parts of equipment The combustion test was conducted in accordance with the material combustion test).

(11) Measurement Method of Cyclic Carbonate Content in Resin 10 g of the sample resin was dissolved in 100 ml of dichloromethane and added dropwise to 1000 ml of methanol with stirring. The precipitate was filtered off and the solvent in the filtrate was removed. The obtained solid was analyzed by GC-MS under the following measurement conditions. The detection limit value under this measurement condition is 0.0005 ppm.
[GC-MS measurement conditions]
Measuring device: Agilent HP 6890/5973 MSD
Column: Capillary column DB-5MS, 30m × 0.25mm ID, film thickness 0.5μm
Temperature rising condition: 50 ° C (5 min hold)-300 ° C (15 min hold), 10 ° C / min
Inlet temperature: 300 ° C, implantation amount: 1.0 μl (split ratio 25)
Ionization method: EI method Carrier gas: He, 1.0 ml / min
Aux temperature: 300 ° C
Mass scan range: 33-700
Solvent: Chloroform for HPLC Internal standard substance: 2,4,6-trimethylol phenol

  The chemical purity of each of the diol compounds used in the following Examples and Comparative Examples is 98 to 99%, the chlorine content is 0.8 ppm or less, alkali metals, alkaline earth metals, titanium and heavy metals (iron, nickel, The content of each of chromium, zinc, copper, manganese, cobalt, molybdenum and tin) is 1 ppm or less. Chemical purity of aromatic dihydroxy compound and diester of carbon dioxide is 99% or more, chlorine content is 0.8 ppm or less, alkali metals, alkaline earth metals, titanium and heavy metals (iron, nickel, chromium, zinc, copper, manganese, cobalt, The content of each of molybdenum and tin is 1 ppm or less.

  In the following examples, 2,2-bis (4-hydroxyphenyl) propane may be abbreviated as "BPA", prepolymer as "PP", hydroxyl group as "OH group" and phenyl group as "Ph".

<Preparation of Aromatic Polycarbonate Resin Composition>
(1) Production of Aromatic Polycarbonate Resin [Production Example of Polycarbonate 1: PC-1]
(Prepolymer production process)
66.480 kg (291.209 moles) of 2,2-bis (4-hydroxyphenyl) propane, 70.179 kg (327.610 moles) of diphenyl carbonate and 0.17 μmole / mole of cesium carbonate as a catalyst The (number of moles relative to (4-hydroxyphenyl) propane) was placed in a 300 L reactor equipped with a stirrer and a distillation apparatus, and the system was replaced under a nitrogen atmosphere. The degree of vacuum was adjusted to 0.046 MPa (345 torr), and the raw material was heated and melted at 160 ° C. and stirred for 1 minute.

  Thereafter, while gradually raising the temperature and reducing the degree of vacuum over 9 hours, transesterification was carried out while removing and condensing phenol distilled from the reaction system with a cooling pipe. Finally, the inside of the system is kept at 260 ° C., the degree of reduced pressure is set to 0.05 kPa (0.38 torr) or less, and the system is kept for 1 hour to obtain an aromatic polycarbonate prepolymer (hereinafter sometimes abbreviated as "PP-E"). The

  The polystyrene reduced weight average molecular weight (Mw) of the obtained aromatic polycarbonate prepolymer (PP-E) was 27,900, the OH concentration was 280 ppm, and the phenyl end concentration (Ph end concentration) was 5.8 mol%. The OH concentration is a value calculated from NMR, and indicates the concentration of OH groups contained in all the polymers. The Ph end concentration is a value calculated from NMR, and indicates the concentration of all phenylene groups and terminal phenyl groups (including phenyl groups substituted with hydroxyl groups) in the phenyl ends.

(High molecular weight process)
An aromatic polycarbonate prepolymer (PP-E) is melted at a resin temperature of 280 ° C. by a melter (two-screw extruder), continuously fed to a kneader with a rotation number of 180 rpm and heated beforehand to 300 ° C. at a speed of 13300 g / hr. did.

At the same time, 3000 g of 2-butyl-2-ethylpropane-1,3-diol (BEPG), which is a diol compound, is heated and melted at 75 to 80 ° C. in a coupling agent adjustment tank equipped with an anchor wing, and the amount is 0.005 mol / L. 82 ml of an aqueous solution of cesium carbonate (Cs ₂ CO ₃ ) was added thereto, the mixture was stirred, and dehydration treatment was carried out at 0.1 torr for 1 hour (final water content is below the detection limit). BEPG containing the obtained catalyst was continuously supplied to the kneader at a rate of 124 g / hr together with PP-E.

BEPG is continuously supplied at a flow rate of 0.25 mol per mol of the total terminal amount (terminal phenyl group content) of PP-E, and cesium carbonate (Cs ₂ CO ₃ ) as a catalyst is 0. 0 per mol of BPA. It was continuously fed at a rate of 33 μmol / mol.

  Subsequently, a mixture of PP-A and BEPG to which cesium carbonate is added is supplied to the horizontal stirring reactor at a flow rate of 13425 g / hr via a transport tube kept warm at 280 ° C. from the kneader outlet to carry out a polymerization reaction of high molecular weight. The The internal pressure of the horizontal stirring reactor at this time was 0.5 torr, and the resin temperature was 300.degree.

  The liquid level is controlled so that the average residence time of the horizontal stirring reactor is 60 minutes, and phenol and cyclic carbonate (5-butyl-5-ethyl-1,3-dioxane- by-produced simultaneously with the polymerization reaction) Evaporation of 2-on) was carried out. The stirring blades of the horizontal stirring reactor were stirred at 20 rpm.

  Furthermore, 5 ppm of butyl para-toluenesulfonate (p-TSB) as a catalyst deactivator and n- as an antioxidant are added to the aromatic polycarbonate resin obtained after conducting the linked high molecular weight reaction in the horizontal stirring reactor. 1000 ppm of octadecyl 3- (3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate (IRGANOX 1076, manufactured by BASF) was kneaded by a twin-screw kneader. The polystyrene equivalent weight average molecular weight (Mw) of the obtained aromatic polycarbonate resin is 42300, the molecular weight distribution (Mw / Mn) is 2.4, and the N value of the obtained polycarbonate resin is 1.19, the terminal hydroxyl group concentration is The amount of different structure (PSA) was 500 ppm, and the content of cyclic carbonate was 1 ppm (Table 1).

[Production Example of Polycarbonate 2: PC-2]
64.662 kg (283.245 mol) of 2,2-bis (4-hydroxyphenyl) propane, 63.710 kg (297.41 mol) of diphenyl carbonate and 1.0 μmol / mol of cesium carbonate as a catalyst The (number of moles relative to (4-hydroxyphenyl) propane) was placed in a 300 L reactor equipped with a stirrer and a distillation apparatus, and the system was replaced under a nitrogen atmosphere. The degree of vacuum was adjusted to 0.046 MPa (345 torr), and the raw material was heated and melted at 160 ° C. and stirred for 1 minute.

  Thereafter, while the temperature was raised gradually and the degree of reduced pressure was gradually reduced over 10 hours, transesterification was carried out while removing and condensing phenol distilled from the reaction system with a cooling pipe. Finally, the inside of the system was adjusted to 260 ° C., the degree of vacuum was reduced to 0.05 kPa (0.38 torr) or less, and the system was held for an additional 1 hour to obtain an aromatic polycarbonate prepolymer (PP-F).

  The polystyrene reduced weight average molecular weight (Mw) of the obtained aromatic polycarbonate prepolymer (PP-F) was 30,000, the OH concentration was 1200 ppm, and the phenyl end concentration (Ph end concentration) was 2.0 mol%. The OH concentration is a value calculated from NMR, and indicates the concentration of OH groups contained in all the polymers. The Ph end concentration is a value calculated from NMR, and indicates the end concentration of all phenylene groups and phenyl groups in the phenyl end (including a phenyl group substituted with a hydroxyl group).

  An aromatic polycarbonate prepolymer (PP-F) is melted at a resin temperature of 280 ° C by a melter (two-screw extruder), continuously fed to a kneader with a rotation speed of 140 rpm and heated beforehand to 300 ° C at a speed of 13300 g / hr. did.

  Subsequently, the aromatic polycarbonate prepolymer (PP-F) was supplied to the horizontal stirring reactor at a flow rate of 13300 g / hr via a transport pipe kept at 280 ° C. from the outlet of the kneader, to carry out a polymerization reaction of high molecular weight. The internal pressure of the horizontal stirring reactor at this time was 0.5 torr, and the resin temperature was 300.degree.

  The liquid level was controlled so that the average residence time of the horizontal stirring reactor was 120 minutes, and the phenol produced as a by-product was distilled off simultaneously with the high molecular weight conversion reaction. The stirring blades of the horizontal stirring reactor were stirred at 20 rpm.

  Furthermore, for the polycarbonate resin obtained after conducting the coupled high molecular weight reaction in the horizontal stirring reactor, 5 ppm of butyl p-toluenesulfonate (p-TSB) as a catalyst deactivating agent and 3- (3, 1000 ppm of octadecyl (Irganox 1076, manufactured by BASF AG), 5-di-tert-butyl-4-hydroxyphenyl) propanoate, was kneaded using a twin-screw kneader. The polystyrene equivalent weight average molecular weight (Mw) of the obtained polycarbonate resin is 44700, the molecular weight distribution (Mw / Mn) is 2.6, the N value of the obtained polycarbonate resin is 1.29, the terminal hydroxyl group concentration is 1100 ppm, the heterostructure The amount of (PSA) was 2000 ppm. Cyclic carbonate was not detected (Table 1).

2) Preparation of Aromatic Polycarbonate Resin Composition [Example 1 and Comparative Examples 1 to 3]
The PC-1 or PC-2 prepared according to the above preparation example and various additives are compounded at a mass ratio shown in Table 2 and mixed in a tumbler for 20 minutes, and then made by Japan Steel Works, Ltd. equipped with 1 vent ( It supplied to TEX30HSST), and knead | mixed on the conditions of 200 rpm of screw rotation speeds, and the amount of discharge of 20 kg / hour, and the barrel temperature of 280 degreeC. Thereafter, the molten resin extruded in the form of strands was quenched in a water tank and pelletized using a pelletizer to obtain pellets of the aromatic polycarbonate resin composition. For each aromatic polycarbonate resin composition, Charpy impact test, combustion test, and measurement of Q value (before and after wet heat treatment) were performed according to the above-described physical property evaluation method and evaluated. The results are shown in Table 2.

The additives used in the preparation of the aromatic polycarbonate resin composition are shown below.
-Flame retardant: Perfluorobutane sulfonic acid potassium salt (Bayowet C4, manufactured by LANXESS Co., Ltd.)
Elastomer: Polybutadiene core / polymethyl methacrylate shell copolymer (Paraloid EXL 2603, manufactured by Toha Chemical Industry Co., Ltd.)
-PTFE: polytetrafluoroethylene (Teflon 6J, Mitsui-Dupont Fluorochemicals Co., Ltd.)
CB: carbon black polystyrene masterbatch. 40% carbon black,
Koshigaya Kasei Co., Ltd. RB904G
Releasing agent: PTS: pentaerythritol tetrastearate (Roxyol VPG 861, manufactured by Cognis Japan Ltd.)
Antioxidant: ADK 2112; tris (2,4-di-t-butylphenyl) phosphite (Adekastab 2112, manufactured by Asahi Denka Co., Ltd.)
-UV absorber: TINUVIN 329; 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole (TINUVIN 329, manufactured by Ciba Specialty Chemicals)

  As shown in Table 2, the aromatic polycarbonate resin composition of Example 1 has high Charpy impact strength in a Charpy impact test as compared to the aromatic polycarbonate resin compositions of Comparative Examples 1 to 3. I understand. In addition, the change in Q value before and after wet heat treatment is smaller in the aromatic polycarbonate resin composition of Example 1 than in Comparative Examples 1 and 2, and the change in fluidity of the composition is obtained before and after the wet heat treatment. It was sufficiently suppressed that it was shown to be excellent in heat and humidity resistance. Furthermore, while the flame retardancy of the aromatic polycarbonate resin composition of Comparative Examples 2 and 3 was insufficient as a result of the combustion test, the aromatic polycarbonate resin composition of Example 1 had the highest level (V- It was also shown to have a flame retardance of 0).

  The aromatic polycarbonate resin composition of the present invention contains a specific cyclic carbonate at a content of a predetermined value or less, and is further blended with various flame retardants, so it is excellent in flame retardancy and also has impact resistance and moist heat resistance. It has been greatly improved. Therefore, the aromatic polycarbonate resin composition of the present invention can be used in the fields of electrics and electronics, automobiles and aircraft industry, other optical equipment parts, automotive products such as trains and automobiles, various building members, office machines such as copiers and facsimiles, personal computers In various fields such as various component materials, it can be effectively used as a material of products that require high strength (high Charpy strength), high moisture and heat resistance, and precise formability.

Claims (5)

Aromatic polycarbonate resins having a structural unit represented by the following general formula (I) and having a weight average molecular weight in the range of 40,000 to 100,000, a flame retardant, and a table of the following general formula (II a ) Containing cyclic carbonates,
The terminal hydroxyl group concentration of the aromatic polycarbonate resin is 1000 ppm or less, and the aromatic polycarbonate resin has a structural unit represented by the following general formula (III), and its content is represented by the general formula (I) Less than 2000 ppm in an aromatic polycarbonate resin having structural units
The flame retardant is an alkali metal salt of sulfonic acid having a C 4-8 perfluoroalkane group, and the flame retardant is 0.01 to 5 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin An aromatic polycarbonate resin composition, which is contained, and wherein the cyclic carbonate is present at 0.1 ppm or more and 3000 ppm or less with respect to the aromatic polycarbonate resin:
General Formula (I):

(Wherein, p and q represent 0, X represents a group selected from the group of lower Symbol (Ia))

(Wherein, _{R 3} and _{R 4,} to display the methyl group)
General formula (IIa):

(Wherein, Ra is an ethyl group and Rb is a butyl group)
General formula (III):

(Wherein, X is as defined above).   The aromatic polycarbonate resin composition according to claim 1, further comprising 0.01 to 2.0 parts by mass of polytetrafluoroethylene with respect to 100 parts by mass of the aromatic polycarbonate resin. The aromatic polycarbonate resin composition according to claim 1 or 2 , wherein the N value is 1.25 or less when the N value (structural viscosity index) of the aromatic polycarbonate resin is represented by the following formula (1). .
N value = (log (Q 160 value)-log (Q 10 value)) / (log 160-log 10) (1) The aromatic polycarbonate resin and the cyclic carbonate are
In the polymerizing step, the aromatic polycarbonate prepolymer and 2-butyl-2-ethylpropane-1,3-diol are reacted in the presence of a transesterification catalyst to polymerize, and the polymerizing step The aromatic polycarbonate resin composition according to any one of claims 1 to 3 , which is obtained by a method including: a cyclic carbonate removing step of removing a part of the by-produced cyclic carbonate out of the reaction system . The molded article formed by shape | molding the aromatic polycarbonate resin composition as described in any one of Claims 1-4 .