JP2004217903A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel aromatic polycarbonate resin composition having a small decrease in molecular weight, high rigidity and significantly improved hydrolysis resistance.
SOLUTION: (A) A cation exchange capacity of 50 to 200 meq / 100 g per 100 parts by weight of an aromatic polycarbonate resin (A component), and 40% or more of the cation exchange capacity. 0.1 to 50 parts by weight of an organically modified layered silicate (component (B)) in which organic onium ions are ion-exchanged between layers at a ratio and the total content of chlorine and bromine atoms is 300 ppm or less. Aromatic polycarbonate resin composition comprising:
[Selection diagram] None

Description

  The present invention relates to an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and an organically modified layered silicate having a small amount of a contained component. In particular, the present invention relates to a novel aromatic polycarbonate resin composition having a small decrease in molecular weight, high rigidity, and significantly improved hydrolysis resistance.

  In recent years, the surface appearance and specific gravity of molded products have been improved by using clay minerals, especially layered silicates, as inorganic fillers and ion-exchanging the interlayer ions with various organic onium ions to facilitate dispersion in the resin. Many attempts have been made to improve the mechanical properties while maintaining the above conditions, especially for polyamide resins and polyolefin resins, and practical examples can be seen in these.

  However, at present, none of the resin compositions of aromatic polycarbonate resins in which these layered silicates or the like are finely dispersed have sufficient thermal stability and are poor in practicality. In other words, it has the same good surface appearance as a resin alone without an inorganic filler, etc., has the same rigidity as a resin reinforced with a reinforced filler, and exhibits practically sufficient thermal stability. At present, a thermoplastic resin composition comprising a thermoplastic resin has not been obtained.

  In general, as a means for improving the rigidity (flexural modulus) of a thermoplastic resin, mixing of a fibrous reinforcing material such as glass fiber and an inorganic filler has been performed. There are drawbacks in that the specific gravity increases and the surface appearance of the product is impaired.

  On the other hand, as one of the techniques for achieving a high flexural modulus with a relatively small amount of filler, a layered silicate as an inorganic filler, more preferably, an interlayer ion of such a layered silicate is ion-exchanged with various organic onium ions. A layered silicate obtained by finely dispersing in a thermoplastic resin, a layered silicate obtained by ion-exchanging interlayer ions between an aromatic polycarbonate resin and a layered silicate with various organic onium ions. Are also known (see Patent Documents 1 to 6).

  Examples of the organic onium ion for ion-exchanging interlayer ions of the layered silicate include an organic onium ion having an alkyl group having 12 or more carbon atoms represented by dimethyldioctadecyl ammonium ion and a polyethylene glycol chain. Have been proposed (see Patent Literature 2 and Patent Literature 3). Furthermore, for thermoplastic resins in general, a quaternary ammonium ion having 15 to 30 carbon atoms is preferable as an organic onium ion (see Patent Document 7), and a quaternary ammonium ion (or phosphonium ion) It has also been proposed that one of the organic groups has 8 or more carbon atoms and the other three organic groups are preferably organic onium ions having 1 to 4 carbon atoms (see Patent Document 8). ).

  On the other hand, Non-Patent Documents 1 to 3 discuss a resin composition of a polycarbonate resin / compatibilizer / organic fluoromica system by melt-kneading, and the composition shown as an example has a relatively low molecular weight. It discloses that the heat resistance is little reduced and the flexural modulus is excellent. However, in a polycarbonate resin composition containing an organically modified layered silicate, improvement of the hydrolysis resistance is an important technical problem, and at present, there is no sufficient knowledge on a method for solving the problem. That is, in these documents, there is no description or suggestion of a trace component contained in the layered silicate of the present invention, and by further reducing the trace component, the rigidity of the composition is improved and the resistance to hydrolysis is improved. There is no description or suggestion of improving decomposition. In addition, the composition is not completely suppressed in molecular weight reduction and has a poor hydrolysis resistance.Therefore, care must be taken not to lower the melting temperature during pelletization or to keep the storage conditions of the molded product at high temperature and high humidity. Was needed.

JP-A-3-215558 JP-A-7-207134 JP-A-7-228762 JP-A-7-331092 JP-A-9-143359 JP-A-10-60160 JP-A-2002-88255 WO 99/32403 (Japanese Unexamined Patent Publication No. 2001-526313) The 51st Annual Meeting of the Society of Polymer Science, Vol. 51 (No. 3), p. 669, 2002 Molding '02, p. 15, 2002 The 51st Symposium of the Society of Polymer Science, Vol. 51 (No. 11), p. 2645, 2002

  In view of the above problems, an object of the present invention is an aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin and an organically modified layered silicate, which suppresses a decrease in molecular weight, has high rigidity, and has high resistance. An object of the present invention is to provide a novel aromatic polycarbonate resin composition having significantly improved hydrolyzability.

  The present inventors have made intensive studies to achieve such an object, and as a result, are obtained by dispersing an organically modified layered silicate in an aromatic polycarbonate resin, and the layered silicate has a trace amount of a contained component in a specific range. Can solve the above-mentioned problem. The present inventors have conducted further intensive studies based on such a finding, and have completed the present invention.

  The present invention relates to (1) (B) a cation exchange capacity of 50 to 200 meq / 100 g per 100 parts by weight of the aromatic polycarbonate resin (component (A)), and 40 (C) of the cation exchange capacity. % Of the organic onium ion is exchanged between the layers, and 0.1 to 50 parts by weight of an organically modified layered silicate (B component) having a total content of chlorine atoms and bromine atoms of 300 ppm or less. The present invention relates to an aromatic polycarbonate resin composition to be blended.

  In a preferred embodiment of the present invention, (2) the component B is obtained by converting a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g to a chlorinated or brominated organic onium ion; The above-mentioned constitution (1), which is an organically modified layered silicate (B ′ component) having a total content of chlorine atoms and bromine atoms of not more than 300 ppm obtained by ion-exchanging at a ratio of 40% or more of the ion-exchange capacity. )) Is an aromatic polycarbonate resin composition.

  One preferred embodiment of the present invention is (3) further comprising (C) an organic compound having an affinity for the component A and having a hydrophilic component (component C), and 100 parts by weight of the component A The aromatic polycarbonate resin composition according to any one of the above-described constitutions (1) and (2), wherein the composition contains 0.1 to 50 parts by weight of the composition.

  One preferred embodiment of the present invention is (4) the aromatic polycarbonate resin composition according to the above-mentioned configuration (3), wherein the component C is a styrene-maleic anhydride copolymer.

  In another embodiment of the present invention, (5) (A) 100 parts by weight of an aromatic polycarbonate resin (component (A)) and (B) a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g are treated with an organic onium. Organically modified layered silicate having a total content of chlorine atoms and bromine atoms of 300 ppm or less, obtained by ion-exchanging with a chlorinated or brominated ion at a ratio of 40% or more of the cation exchange capacity. (B ′ component) A method for producing an aromatic polycarbonate resin composition containing an organically modified layered silicate in which a decrease in molecular weight at the time of molding is suppressed, wherein 0.1 to 50 parts by weight is melt-kneaded. is there.

  One of preferred embodiments of the present invention is that (6) together with the component A and the component B ', 0.1 to 50 parts by weight per 100 parts by weight of the component A, and (C) an affinity with the component A A method for producing an aromatic polycarbonate resin composition having the constitution (5), wherein an organic compound having a hydrophilic component (component C) is melt-kneaded.

  One preferred embodiment of the present invention is that (7) 0.1 to 50 parts by weight of the B 'component and 0.1 to 50 parts by weight of the C component are previously melt-kneaded per 100 parts by weight of the A component. And then melt-kneading the melt-kneaded product with 100 parts by weight of the component A, which is a method for producing an aromatic polycarbonate resin composition having the constitution (6).

  One preferred embodiment of the present invention is that (8) the ratio of the B ′ component to the C component is 1 to 300 parts by weight (preferably 30 to 150 parts by weight) per 100 parts by weight of the C component. (Preferably 50 to 120 parts by weight) of the aromatic polycarbonate resin composition of the above configuration (7).

  In one preferred embodiment of the present invention, (9) the B ′ component is obtained by converting a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g to a chlorinated or brominated organic onium ion. Ion exchange is performed at a rate of 40% or more of the cation exchange capacity, and the layered silicate after the ion exchange is washed with water until the total content of chlorine atoms and bromine atoms becomes 300 ppm or less. A method for producing an aromatic polycarbonate resin composition according to any one of the constitutions (5) to (8), which is a silicate.

  Another embodiment of the present invention relates to (10) (A) a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g per 100 parts by weight of an aromatic polycarbonate resin (component (A)). Aromatic polycarbonate resin composition containing 0.1 to 50 parts by weight of an organically modified layered silicate obtained by ion exchange with chlorinated or brominated ion at a ratio of 40% or more of the cation exchange capacity A method for suppressing a decrease in molecular weight during the forming process of the above, wherein the organically modified layered silicate is washed with water until the total content of chlorine and bromine atoms becomes 300 ppm or less after the ion exchange. This is a method for suppressing a decrease in molecular weight, characterized by using a silicate.

Hereinafter, the present invention will be described in detail.
<About component A>
A typical aromatic polycarbonate resin as the component A of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and the reaction may be performed by an interfacial polycondensation method, a melt transesterification method, a carbonate method. Examples include a prepolymer solid phase transesterification method and a ring opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) propane (commonly called “bisphenol A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 '-(p-phenylenediisopropylidene) diphenol, 4,4'-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- (Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, besides the bisphenol A-based polycarbonate resin which is a general-purpose aromatic polycarbonate resin, for the purpose of obtaining better hydrolysis resistance, a special aromatic polycarbonate resin using other dihydric phenols is used. It can be used as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Aromatic polycarbonate resins (homopolymers or copolymers) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) are polymers themselves. Has good hydrolysis resistance, so that it is suitable for applications where dimensional changes and dimensional stability due to water absorption are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the aromatic polycarbonate resin.

Particularly, when high rigidity and better hydrolysis resistance are required, the component A constituting the aromatic polycarbonate resin composition is the following copolymerized polycarbonate resin (1) to (3). Is particularly preferred.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, and still more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate resin. And a copolycarbonate resin having a BCF of 20 to 80 mol% (more preferably 25 to 60 mol%, and still more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate resin. And a copolycarbonate resin having a BCF of 5 to 90 mol% (more preferably 10 to 50 mol%, and still more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the aromatic polycarbonate resin. And a copolymer polycarbonate resin having a Bis-TMC of 20 to 80 mol% (more preferably 25 to 60 mol%, and still more preferably 35 to 55 mol%).

  These special aromatic polycarbonate resins may be used alone, or two or more kinds may be appropriately mixed and used. These can also be used by mixing with a commonly used bisphenol A type aromatic polycarbonate resin.

  The production method and properties of these special aromatic polycarbonate resins are described, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. It is described in detail.

Among the above-mentioned various aromatic polycarbonate resins, those in which the water absorption and Tg (glass transition temperature) are adjusted to the following ranges by adjusting the copolymer composition, etc., have the hydrolysis resistance of the polymer itself. Since it is good and has extremely low warpage after molding, it is particularly suitable in the field of, for example, a mirror or the like, where form stability is required.
(I) an aromatic polycarbonate resin having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and a Tg of 120 to 180 ° C, or (ii) a Tg of 160 to 180 Aroma having a temperature of 250 ° C, preferably 170 to 230 ° C, and a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%. Aromatic polycarbonate resin.

  Here, the water absorption of the aromatic polycarbonate resin was measured using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm and immersed in water at 23 ° C. for 24 hours in accordance with ISO62-1980. Value. Further, Tg (glass transition temperature) is a value determined by a differential scanning calorimeter (DSC) measurement based on JIS K7121.

  On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate, or the like is used, and specific examples include phosgene, diphenyl carbonate, and dihaloformate of dihydric phenol.

  In producing a polycarbonate resin from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, if necessary, a catalyst, a terminal stopper and an antioxidant for preventing the dihydric phenol from being oxidized. An agent may be used. Further, the aromatic polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a polyfunctional aromatic compound having three or more functional groups. Examples of the polyfunctional aromatic compound having three or more functional groups include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

When a polyfunctional compound that produces a branched polycarbonate resin is contained, the proportion thereof is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, and particularly preferably 0.01 to 1 mol%, based on the total amount of the aromatic polycarbonate resin. 0.8 mol%. In addition, particularly in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of such a branched structure is also 0.001 to 1 mol%, preferably 0.005 to 5 mol%, of the total amount of the aromatic polycarbonate resin. What is 0.9 mol%, especially preferably 0.01-0.8 mol% is preferable. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

  Further, the aromatic polycarbonate resin as the component A includes a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, and a bifunctional alcohol (including an alicyclic group). It may be a copolymerized polycarbonate resin and a polyester carbonate obtained by copolymerizing the bifunctional carboxylic acid and the bifunctional alcohol together. A mixture obtained by blending two or more of the obtained aromatic polycarbonate resins may be used.

  The aliphatic bifunctional carboxylic acid used here is preferably α, ω-dicarboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decane diacid), dodecandioic acid, tetradecandioic acid, octadecandioic acid, and icosane diacid, and cyclohexanedicarboxylic acid. And the like. Preferred are alicyclic dicarboxylic acids. As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecanedimethanol.

  Further, in the present invention, it is possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit.

  The aromatic polycarbonate resin as the component A in the resin composition of the present invention includes various aromatic resins such as the above-described polycarbonate resins having different dihydric phenols, polycarbonate resins containing a branching component, polyester carbonate, and polycarbonate-polyorganosiloxane copolymer. It may be a mixture of two or more of the aromatic polycarbonate resins. Further, a mixture of two or more kinds of polycarbonate resins having different production methods, polycarbonate resins having different terminal stoppers and the like can also be used.

  In the polymerization reaction of the aromatic polycarbonate resin, the reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is performed in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to promote the reaction, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound is used. You can also. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. As the monofunctional phenols, it is preferable to use monofunctional phenols such as phenol, p-tert-butylphenol and p-cumylphenol. Further, examples of the monofunctional phenols include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol, and tricontylphenol. Such terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the dihydric phenol and the carbonate ester are mixed while heating in the presence of an inert gas to form an alcohol or It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the pressure of the reaction system is reduced to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is about 1 to 4 hours.

  Examples of the carbonate ester include an ester such as an aryl group having 6 to 10 carbon atoms which may have a substituent, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, among which diphenyl carbonate is preferable. .

Further, a polymerization catalyst can be used to increase the polymerization rate. Examples of such polymerization catalysts include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salts and potassium salts of dihydric phenols; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide, and magnesium hydroxide; Catalysts such as nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Further, esterification reaction and transesterification of alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc. The catalyst used for the reaction can be used. The catalyst may be used alone or in combination of two or more. The use amount of these polymerization catalysts is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents, per 1 mol of the starting dihydric phenol. Selected by range.

  In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl, for the purpose of reducing the phenolic terminal group of the produced polycarbonate resin at a later stage or after completion of the polycondensation reaction. Compounds such as phenylphenyl carbonate can be added.

  Further, in the melt transesterification method, it is preferable to use a deactivator for neutralizing the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol per 1 mol of the remaining catalyst. Moreover, it is suitable to use it at a ratio of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm, based on the polycarbonate resin after polymerization. Examples of preferred quenching agents include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

  The viscosity average molecular weight of the aromatic polycarbonate resin as the component A is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength and the like are reduced, and when the viscosity average molecular weight is more than 50,000, the molding characteristics are deteriorated. The range is more preferably from 3,000 to 30,000, and even more preferably from 14,000 to 28,000. In this case, it is also possible to mix a polycarbonate resin having a viscosity average molecular weight outside the above-mentioned range as long as the moldability and the like are maintained. For example, a high molecular weight aromatic polycarbonate resin component having a viscosity average molecular weight exceeding 50,000 can be blended.

The viscosity average molecular weight referred to in the present invention is determined by first using a Ostwald viscometer from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. using a specific viscosity (η _SP ) calculated by the following equation. Asked,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight M is calculated by the following equation.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  The viscosity average molecular weight of the aromatic polycarbonate resin composition of the present invention is measured in the following manner. That is, the composition is dissolved in 20 to 30 times the weight of methylene chloride, and the soluble matter is collected by filtration through celite, the solution is removed and dried sufficiently, and the solid matter soluble in methylene chloride is removed. obtain. From a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride, the specific viscosity at 20 ° C. calculated by the above equation is measured by using an Ostwald viscometer.

<About component B>
The component B of the present invention has a cation exchange capacity of 50 to 200 meq / 100 g, and organic onium ions are ion-exchanged between layers at a ratio of 40% or more of the cation exchange capacity. And an organically modified layered silicate having a total bromine element content of 0.1% by weight or less. Here, the ratio of 40% means that, for example, when the cation exchange capacity of the layered silicate is 110 meq / 100 g, 44 meq / 100 g corresponding to 40% thereof is ion-exchanged with organic onium ions. Point. The term "organized layered silicate" is a general term for "layered silicate having a cation exchange capacity and being ion-exchanged between layers of organic onium ions". In the component B of the present invention, an organically modified layered silicate in which organic onium ions are ion-exchanged between layers at a ratio of substantially 100% (almost completely) is preferable.

  The organic onium ion compound in the organically modified layered silicate of the present invention is generally handled as a salt with anions such as a halogen ion, a hydroxide ion and an acetate ion. It is obtained by reacting such a salt compound of an organic onium ion with a layered silicate. Here, examples of the organic onium ion include an ammonium ion, a phosphonium ion, a sulfonium ion, an onium ion derived from a heteroaromatic ring, and the like. As the onium ion, any of primary, secondary, tertiary, and quaternary can be used. However, a quaternary onium ion is preferable.

  As the onium ion compound, those having various organic groups bonded thereto can be used. The organic group is typically an alkyl group, but may have an aromatic group, or may have an ether group, an ester group, a double bond, a triple bond, a glycidyl group, a carboxylic acid group, or an acid anhydride group. And various functional groups such as a hydroxyl group, an amino group, an amide group and an oxazoline ring.

  Specific examples of the organic onium ion include quaternary ammonium having the same alkyl group such as tetraethylammonium and tetrabutylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyl Octadecyl ammonium, and trimethylalkylammonium such as trimethylicosanilammonium, trimethylalkenylammonium such as trimethyloctadecenylammonium, trimethylalkadienylammonium such as trimethyloctadecadienylammonium, triethyldodecylammonium, triethyltetradecylammonium, Triethylhexadecyl ammonium And triethylalkylammonium such as triethyloctadecyl ammonium, tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium, and tributylalkylammonium such as tributyloctadecylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethylditetradecylammonium, dimethyl Dihexadecyl ammonium, dimethyl dioctadecyl ammonium, dimethyl dialkyl ammonium such as dimethyl didodecyl ammonium, dimethyl dialkenyl ammonium such as dimethyl dioctadecenyl ammonium, dimethyl dialkadienyl ammonium such as dimethyl dioctadecadenyl ammonium, Diethyldi Diethyl ammonium, such as decyl ammonium, diethyl ditetradecyl ammonium, diethyl dihexadecyl ammonium, and diethyl dioctadecyl ammonium, dibutyl dioctyl ammonium, dibutyl didecyl ammonium, dibutyl didodecyl ammonium, dibutyl ditetradecyl ammonium, dibutyl dihexadecyl ammonium Ammonium, dibutyl dialkyl ammonium such as dibutyl dioctadecyl ammonium, methyl benzyl dialkyl ammonium such as methyl benzyl dihexadecyl ammonium, dibenzyl dialkyl ammonium such as dibenzyl dihexadecyl ammonium, trioctyl methyl ammonium, tridodecyl methyl ammonium, and Tritetradecyl methyl ammonium Trialkylmethylammonium, trioctylethylammonium, tridodecylethylammonium and the like trialkylethylammonium, trioctylbutylammonium, tridecylbutylammonium and the like trialkylbutylammonium, trimethylbenzylammonium and the like aromatic ring Quaternary ammonium, quaternary ammonium derived from aromatic amines such as trimethylphenylammonium, triethyl [PAG] ammonium such as methyl diethyl [PEG] ammonium, and methyl diethyl [PPG], and methyl dimethyl bis [PEG] ammonium Alkyltris [PAG] ammonium such as ammonium dialkylbis [PAG] and ethyltris [PEG] ammonium; Nitrogen atom-ion can be cited phosphonium ion replacing a phosphorus atom. These organic onium ions can be used either singly or in combination of two or more. The notation “PEG” indicates polyethylene glycol, the notation “PPG” indicates polypropylene glycol, and the notation “PAG” indicates polyalkylene glycol. A polyalkylene glycol having a molecular weight of 100 to 1,500 can be used.

  The molecular weight of these organic onium ion compounds is more preferably from 100 to 600. More preferably, it is 150 to 500. When the molecular weight is more than 600, there is a tendency that heat deterioration of the aromatic polycarbonate resin is promoted in some cases or heat resistance of the aromatic polycarbonate resin composition is deteriorated. The molecular weight of such an organic onium ion refers to the molecular weight of a single organic onium ion not including a counter ion such as a halogen ion.

  Preferred embodiments of the organic onium ion include trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, methyltrioctylammonium, ethyltrioctylammonium, butyltrioctylammonium, triphenylmethylammonium, Organic onium ions such as trimethyloctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, methyltrioctylphosphonium, ethyltrioctylphosphonium, butyltrioctylphosphonium, and triphenylmethylphosphonium; Charcoal An alkyl group having 6 to 16 atoms (preferably having 7 to 14 carbon atoms, more preferably 8 to 11 carbon atoms) and an alkyl group having 1 to 4 carbon atoms (preferably having 1 to 3 carbon atoms) And more preferably a methyl group or an ethyl group, and more preferably a methyl group).

  In the present invention, a more preferred embodiment of the component B is a layered silicate ion-exchanged with an organic onium ion represented by the following general formula (I).

上記一般式（Ｉ）は次の条件を満足する。すなわち、Ｍは窒素原子またはリン原子であり、Ｒ^１およびＲ^２はそれぞれ炭素原子数６〜１６のアルキル基である。Ｒ^３は炭素原子数１〜１６のアルキル基であり、かつＲ^４は炭素原子数１〜４のアルキル基である。なお、Ｒ^１とＲ^２とは互いに同一の基であっても相異なる基であってもよく、また、Ｒ^３とＲ^４とは互いに同一の基であっても相異なる基であってもよい。

The general formula (I) satisfies the following condition. That is, M is a nitrogen atom or a phosphorus atom, and R ¹ and R ² are each an alkyl group having 6 to 16 carbon atoms. R ³ is an alkyl group having 1 to 16 carbon atoms, and R ⁴ is an alkyl group having 1 to 4 carbon atoms. Note that R ¹ and R ² may be the same group or different groups, and R ³ and R ⁴ may be the same group or different groups. Good.

A more preferred embodiment of the organic onium ion represented by the general formula (I) is (i) a case where R ³ is an alkyl group having 1 to 4 carbon atoms. More preferably, (ii) R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are each an alkyl group having 7 to 14 carbon atoms. More preferably, (iii) R ³ and R ⁴ are each an alkyl group having 1 to 4 carbon atoms, and R ¹ and R ² are an alkyl group having 8 to 11 carbon atoms. Of these, R ³ and R ⁴ are particularly preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably a quaternary ammonium ion of a methyl group.

  According to the more preferable embodiments (including the more preferable embodiments) of these (i) to (iii), the hydrolysis resistance of the resin composition is particularly excellent, and the thermoplastic resin composition of the present invention has a favorable hydrolysis resistance. Gives long-term practical properties.

In the above formula (I), any of R ^{1 to} R ⁴ can be selected from linear and branched.

  Examples of such suitable quaternary ammonium ions include dimethyldioctylammonium and dimethyldidecylammonium.

Layered silicate of component B is composed of a layer consisting of the octahedral sheet structure including SiO ₄ tetrahedra sheet structure and Al made of SiO ₂ chain, Mg, and Li, etc., distribution of exchangeable cations between the layers Silicate (silicate) or clay mineral (clay). These silicates (silicates) or clay minerals (clays) are represented by smectite-based minerals, vermiculite, halloysite, and swelling mica. Specifically, examples of smectite-based minerals include montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and stevensite, and examples of swelling mica include Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon. And swellable synthetic mica such as fluorine mica and Li-type tetrasilicon fluorine mica. These layered silicates can be used in both natural products and synthetic products. Synthetic products are produced, for example, by hydrothermal synthesis, melt synthesis, and solid-state reactions.

  Among layered silicates, swelling properties such as smectite clay minerals such as montmorillonite and hectorite, Li-type fluorine teniolite, Na-type fluorine teniolite, and Na-type tetrasilicon fluorine mica are considered from the viewpoint of cation exchange capacity and the like. Fluorine mica is preferably used, and montmorillonite and synthetic fluoromica obtained by purifying bentonite are more preferable in terms of purity and the like. Among them, synthetic fluorine mica which can obtain good mechanical properties is particularly preferable.

  The cation exchange capacity (also referred to as cation exchange capacity) of the layered silicate as the component B is required to be 50 to 200 meq / 100 g, preferably 80 to 150 meq / 100 g, and more preferably. Is 100 to 150 meq / 100 g. The cation exchange capacity is measured as a CEC value by the Schollenberger improved method, which is the official method in Japan as a soil standard analysis method.

The outline of such a method is as follows. A layered silicate sample is filled into an infiltration tube of a soil leaching apparatus having a length of 12 cm and an inner diameter of 1.3 cm so as to have a thickness of about 8 cm, and is infiltrated with 100 ml of a 1N ammonium acetate solution having a pH of 7 for 4 to 20 hours. And exchange leaching of cations. It is then washed with 100 ml of 80% methanol at pH 7 to remove excess ammonium acetate. Next, the sample is washed with 100 ml of a 10% aqueous potassium chloride solution to exchange and leach ammonium ions (NH ₄ ⁺ ) adsorbed on the sample. Finally, NH ₄ ⁺ in the leachate is quantified by a steam distillation method or Conway microdiffusion method, and the CEC is calculated. As the soil leaching device, a device commercially available as a glass set can be used. The Schollenberger method as the basis of the improved method is referred to in Soil Sci., 59, 13-24 (1945).

  The cation exchange capacity of the layered silicate is required to be at least 50 meq / 100 g in order to obtain good dispersibility in the aromatic polycarbonate resin as the component A. The heat deterioration of the polycarbonate resin composition increases, and accordingly, the influence of the aromatic polycarbonate resin composition of the present invention on the heat deterioration increases. This layered silicate preferably has a pH value of 9 to 11.5. When the pH value is higher than 11.5, the thermal stability of the aromatic polycarbonate resin composition of the present invention tends to decrease.

  For the ion exchange of organic onium ions into layered silicate, an organic onium ion compound (salt compound of organic onium ion) is added to the layered silicate dispersed in a polar solvent, and the ion exchange compound precipitated is collected. Can be created by doing Usually, in this ion exchange reaction, an organic onium ion compound is added at a ratio of 1.0 to 1.5 equivalents to 1 equivalent of the ion exchange capacity of the layered silicate, and almost all the metal ions between the layers are added to the organic onium ion. It is common to exchange with ions. However, controlling the exchange ratio with respect to the ion exchange capacity within a certain range is also effective in suppressing thermal deterioration of the aromatic polycarbonate resin. Here, the ratio of ion exchange with the organic onium ion is preferably 40% or more with respect to the ion exchange capacity of the layered silicate. The proportion of such ion exchange capacity is preferably 40-95%, particularly preferably 40-80%. Here, the exchange rate of the organic onium ion can be calculated by using a thermogravimeter or the like to determine the weight loss due to the thermal decomposition of the organic onium ion for the compound after the exchange.

  The composition ratio of the component B and the component A used in the present invention is 0.1 to 50 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the component A. Department. When the composition ratio is less than 0.1 part by weight, the effect of improving the mechanical properties of the aromatic polycarbonate resin is not seen. When the composition ratio is more than 50 parts by weight, the thermal stability of the composition is reduced and the practical aromatic polycarbonate resin is reduced. It is difficult to obtain a resin composition.

  The organically modified layered silicate of the present invention has a total content of chlorine atoms and bromine atoms of 300 ppm or less, preferably 250 ppm or less, more preferably 220 ppm or less. If the content of chlorine atoms and bromine atoms exceeds 300 ppm, the rigidity and hydrolysis resistance of the resin composition will deteriorate. In particular, the chlorine atom content is preferably low. On the other hand, as described later, it is also possible in the present invention to use a salt compound containing no chloride ion or bromine ion as an organic onium ion source in the organized layered silicate. In such a case, the content of chlorine atom or bromine atom can be made substantially zero. However, in practice, it is advantageous from the viewpoint of handling and cost to use an organic onium salt compound having a chlorine ion or a bromine ion, particularly a chloride ion as a counter ion. A resin composition containing atoms, especially chlorine atoms, is a practically preferred embodiment. Therefore, the lower limit of the total content of chlorine atoms and bromine atoms in the component B, and the lower limit of the content of chlorine atoms are preferably 10 ppm or more, preferably 50 ppm or more, and more preferably 100 ppm or more.

  The content of chlorine atoms and bromine atoms in the above-mentioned organized phyllosilicate is measured by ion chromatography.

  The following method is exemplified as a specific measuring method. That is, about 2 g of the organically modified layered silicate is precisely weighed, put into a 300 ml beaker, and 200 ml of distilled water is added. It is stirred for 1 hour at 1000 rpm with a stirrer using a stirrer. After stirring, the extracted suspension was diluted 10-fold with distilled water, and filtered (ADVANTEC: “Dismic-13cp” pore size: 0.20 μm and Nippon Dionex: “Dillex-IC” pore size: 0.22 μm) After filtration using, the amount of chlorine is quantified using an ion chromatograph (manufactured by Dionex: "DX-100").

  In order to produce the component B of the present invention, (i) use of an organic onium ion compound containing no chloride ion or bromine ion as a counter ion, and (ii) organic onium ion containing a small amount of impurities containing chlorine ion or bromine ion Use of the compound, (iii) sufficient washing and washing of the organically modified layered silicate after ion exchange using an organic onium ion compound containing chlorine ion or bromide ion as a counter ion (ie, an organic onium salt compound), and A method such as a combination thereof is preferably exemplified. Above all, from the viewpoint of work efficiency and productivity, it is important to carry out the method (iii), that is, to sufficiently wash the produced organically modified layered silicate to a predetermined chlorine atom and bromine atom content. The main cause of contamination of chlorine and bromine atoms in the organically modified layered silicate is by the use of such an organic onium ion compound, and its removal is also reduced to the specified amount of the present invention by a washing treatment using water with a small amount of impurities. It is possible to do.

  That is, in a preferred embodiment as the component B of the present invention, a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g is converted to a chlorinated or brominated organic onium ion at 40% of the cation exchange capacity. An organically modified layered silicate (B ′ component) having a total content of chlorine atoms and bromine atoms of 300 ppm or less, obtained by ion exchange at the above ratio, and a more preferred embodiment is the aforementioned B ′ The component is a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g, which is ion-exchanged with a chloride or bromide of an organic onium ion at a ratio of 40% or more of the cation exchange capacity. It is an organically modified layered silicate obtained by washing the layered silicate after exchange with water until the total content of chlorine atoms and bromine atoms becomes 300 ppm or less.

  Further, in order to reduce chlorine and bromine in the total amount of the resin composition, it is necessary to use a polycarbonate resin particularly having a sufficiently reduced chlorine impurity as the polycarbonate resin of the component A, and to use chlorine or bromine in the composition of the present invention. It is important not to compound a compound containing In particular, it is preferable to reduce the predetermined amount in the whole composition by paying attention to the amount of the inorganic compound having high ionicity.

  Regarding the reduction of the chlorine atom-containing impurities in the aromatic polycarbonate resin, for example, when the aromatic polycarbonate resin is treated with acetone, or when the aromatic polycarbonate resin powder is pelletized, water is forcibly forced in the middle of the vented extruder. It can be adjusted by various conventionally known methods, such as a method of injecting and performing a dechlorination compound, a method of non-solvent precipitation of an aromatic polycarbonate resin solution, and a further strengthening of a drying treatment. It is also possible to use an aromatic polycarbonate resin produced by a production method that does not require a chlorine-based organic solvent (for example, a melt polymerization method). On the other hand, since bromine element is not usually used in the production process and is not mixed therein, it does not substantially contain ordinary aromatic polycarbonate resin, or contains only a very small proportion as a catalyst. Therefore, the total content of chlorine atoms and bromine atoms (particularly the content of chlorine atoms) of the aromatic polycarbonate resin of the component A is preferably 50 ppm or less, more preferably 30 ppm or less, and further preferably 10 ppm or less. Such a content can be set to 1 ppm or less even in a phosgene-based aromatic polycarbonate resin using a chlorine-based organic solvent. It is possible to achieve the same level of content as a catalyst amount even in a melt-polymerized polycarbonate resin. In the present invention, among the aromatic polycarbonate resins obtained by the phosgene method, which can favorably perform terminal capping and have better thermal stability, those having reduced chlorine and bromine atom contents are more preferable.

  It is preferable that the aromatic polycarbonate resin composition of the present invention further contains a compound (component C) having an affinity for the aromatic polycarbonate resin (component A) and having a hydrophilic component.

<About the C component>
The composition of the C component produces good affinity for both aromatic polycarbonate resins and phyllosilicates, especially organically modified phyllosilicates. Affinity for both aromatic polycarbonate resin and layered silicate, especially organically modified layered silicate, improves the compatibility of the two components, and the layered silicate is finely and stably dispersed in the aromatic polycarbonate resin. Become like

  The function of the C component relating to the dispersion of the organically modified layered silicate is the same as that of a compatibilizer for polymer alloy (compatibilityizer) used for compatibilizing heterogeneous polymers with each other. Therefore, the component C is preferably a polymer obtained by polymerizing a monomer rather than a low molecular compound. Further, the polymer also has excellent thermal stability during kneading. The average number of repeating units of the polymer needs to be 2 or more, preferably 5 or more, more preferably 10 or more. On the other hand, at the upper limit of the average molecular weight of the polymer, the number average molecular weight is preferably 2,000,000 or less. If the upper limit is not exceeded, good moldability is obtained.

  The basic structure of the component C of the present invention includes, for example, (i) a component having an affinity for an aromatic polycarbonate resin (α) and a hydrophilic component (β) separately in a molecule, and (ii) a molecule. Those having an affinity for the aromatic polycarbonate resin as a whole (α) and having a hydrophilic component (β) in a part thereof are exemplified.

  The component having an affinity for the aromatic polycarbonate resin in the present invention (hereinafter sometimes referred to as α according to the above) will be described. As described above, the component C functions in the same manner as the compatibilizer in the polymer alloy, so that α is required to have the same affinity for the polymer as the compatibilizer. Therefore, α can be largely classified into a non-reactive type and a reactive type.

In the non-reaction type, the affinity is good when the following factors are present. That is, between the aromatic polycarbonate resin and α, (i) similarity in chemical structure, (ii) similarity of solubility parameter (difference in solubility parameter is within 1 (cal / cm ³ ) ^1/2 , that is, about 2.05 (MPa) within ^1/2 ), (iii) intermolecular interactions (hydrogen bonding, ionic interactions, etc.) and pseudo-attractive interactions unique to random polymers. It is necessary to have. These factors are known as indices for judging the affinity between the compatibilizer and the polymer on which the polymer alloy is based.

  In the reaction type, various types known as functional groups having reactivity with the aromatic polycarbonate resin in the compatibilizer can be used. For example, a carboxyl group, a carboxylic anhydride group, an epoxy group, an oxazoline group, an ester group, an ester bond, a carbonate group, and a carbonate bond can be exemplified.

Among these, α is preferably a non-reactive type, and particularly, the solubility parameter ((MPa) ^1/2 ) is close (the difference between the solubility parameter of the aromatic polycarbonate resin and α is 2 or less in absolute value) Is preferred because it exhibits good affinity.

For example Examples of the polymer component which satisfies the solubility parameter [delta] _alpha according the aromatic polycarbonate resin, aromatic polyester (polyethylene terephthalate, polybutylene terephthalate, and typified cyclohexanedimethanol copolymerized polyethylene terephthalate), And polyester-based polymers such as aliphatic polyesters (typified by polycaprolactone). Specific examples thereof include styrene polymers, alkyl (meth) acrylate polymers, and acrylonitrile polymers (polystyrene, styrene-maleic anhydride copolymer, polymethyl methacrylate, styrene-methyl methacrylate copolymer, and styrene-acrylonitrile copolymer). Vinyl polymer).

Next, the hydrophilic component of component C in the present invention (hereinafter sometimes referred to as β as described above) will be described. Such a hydrophilic component is selected from a functional group having a hydrophilic group (organic atomic group having strong interaction with water) and a hydrophilic polymer component (polymer segment). Examples of the functional group of the hydrophilic group include the following groups (1) to 3)) according to the Chemical Dictionary (Kyoritsu Shuppan, 1989), and the following 1) and a strongly hydrophilic group such as a sulfine group. And 2) below, a carboxylic anhydride group, an oxazoline group, a formyl group, a pyrrolidone group, and the like.
1) strong hydrophilic _{groups: -SO 3 H, -SO 3 M} , -OSO 3 H, -OSO 3 H, -COOM, -NR 3 X (R: alkyl group, X: a halogen atom, M: alkali metal , _-NH 4), etc.,
2) slightly smaller hydrophilic group _{having: -COOH, -NH 2, -CN,} -OH, -NHCONH 2 or the like,
3) Hydrophilic or little _{groups: -CH 2 OCH 3, -OCH 3} , -COOCH 3, -CS etc.

  Examples of the hydrophilic polymer component of the component C include polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyacrylic acid metal salt (including chelate type), polyvinylpyrrolidone, polyacrylamide, and polyhydroxyethyl methacrylate. . Among these, polyalkylene oxide, polyvinyl alcohol, polyacrylic acid, polyvinyl pyrrolidone, and polyhydroxyethyl methacrylate are preferably exemplified. As the polyalkylene oxide, polyethylene oxide and polypropylene oxide are preferred.

  In both the monomer having a hydrophilic group and the hydrophilic polymer component, β preferably has an acidic functional group (hereinafter sometimes simply referred to as “acid group”). The acidic group suppresses thermal deterioration of the aromatic polycarbonate resin during melt processing.

  Examples of the acidic group include a phosphonic acid group and a phosphinic acid group in addition to a carboxylic acid, a carboxylic anhydride group, a sulfonic acid group, and a sulfinic acid group, and a carboxylic acid and a carboxylic anhydride group are preferable.

  When β is a monomer having a hydrophilic group, the ratio of β in the component C of the present invention is 60 to 10,000 as a functional group equivalent, which is the molecular weight per functional group, and 70 to 8,000 Preferably, it is more preferably from 80 to 6,000, and still more preferably from 100 to 3,000. When β is a hydrophilic polymer segment, β is suitably in the range of 5 to 95% by weight, preferably 10 to 90% by weight, in 100% by weight of the component C. Especially, 30 to 70% by weight is more preferable, and 30 to 50% by weight is further preferable.

  As preferred embodiments of the component C of the present invention, “a polymer having an affinity for an aromatic polycarbonate resin and having an acidic functional group”, “a polymer having an affinity for an aromatic polycarbonate resin and a polyalkylene oxide segment” A polymer having an affinity for an aromatic polycarbonate resin and having an oxazoline group, or a polymer having an affinity for an aromatic polycarbonate resin and having a hydroxyl group. And "a polymer having an affinity for an aromatic polycarbonate resin and having an acidic functional group" and a "polymer having an affinity for an aromatic polycarbonate resin and having a polyalkylene oxide segment". In the polymer of the preferred embodiment as the C component, its molecular weight is preferably in the range of 10,000 to 1,000,000 in weight average molecular weight, more preferably in the range of 50,000 to 500,000. The weight average molecular weight is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line with a standard polystyrene resin.

  Among them, a polymer having an affinity for an aromatic polycarbonate resin and having an acidic functional group is preferable, and more preferably having an affinity for an aromatic polycarbonate resin and comprising a carboxyl group and / or a derivative thereof. It is a polymer having a functional group. Further, from the viewpoint of the effect of maintaining the heat resistance of the aromatic polycarbonate resin, the polymer is preferably one having an aromatic ring component in the main chain and one having a styrene component in the main chain. From the above points, a styrene-containing polymer (component C1) having a functional group consisting of a carboxyl group and / or a derivative thereof is particularly suitable as the component C of the present invention. Here, the styrene-containing polymer refers to a polymer containing, as a polymer component, a repeating unit obtained by polymerizing an aromatic vinyl compound such as styrene.

  The styrene-containing polymer (component C1) having a functional group comprising a carboxyl group and / or a derivative thereof particularly suitable as the component C of the present invention will be described in detail. The ratio of the functional group comprising a carboxyl group and / or a derivative thereof is preferably from 0.1 to 12 meq / g, more preferably from 0.5 to 5 meq / g. Here, one equivalent in the C1 component means that one mole of a carboxyl group is present, and such a value can be calculated by back titration with potassium hydroxide or the like.

  Examples of the compound or monomer having a functional group consisting of a carboxyl group and / or a derivative thereof (hereinafter, simply referred to as “carboxyl groups”) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, acrylamide, and methacrylamide. Derivatives of maleic anhydride such as carboxylic acid and its derivatives, maleic anhydride, citraconic anhydride, N-phenylmaleimide, N-methylmaleimide, and chelate structures formed by glutarimide structure and acrylic acid and polyvalent metal ions And the like. Among these, a monomer having a functional group containing no metal ion or nitrogen atom is preferable, and a monomer having a carboxyl group and a carboxylic anhydride group is more preferable. Among these, maleic anhydride is particularly preferred.

  Further, as the styrene monomer compound, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethylstyrene, chlorostyrene, Dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene and the like can be used, but styrene is particularly preferred.

  Further, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as a copolymerization component.

  Among the styrene-containing polymers having carboxyl groups, preferred in the present invention are styrene-containing copolymers obtained by copolymerizing monomers having a functional group consisting of a carboxyl group and / or a derivative thereof. is there. A particularly preferred embodiment is a styrene-maleic anhydride copolymer.

  Regarding the composition of the styrene-containing copolymer obtained by copolymerizing the above-mentioned monomer having a carboxyl group, 1 to 30% by weight (particularly 5 to 25% by weight) of the component from the monomer having a carboxyl group is used. It is preferable to use a styrene-based monomer compound component containing 99 to 70% by weight (particularly 95 to 75% by weight) and another copolymerizable compound component containing 0 to 29% by weight. A copolymer containing 1 to 30% by weight (particularly 5 to 25% by weight) of a monomer having the following formula, and 99 to 70% by weight (particularly 95 to 75% by weight) of a styrene monomer compound is particularly preferred.

  The molecular weight (weight average molecular weight) of the component C1, which is a preferred embodiment of the component C of the present invention, is preferably in the range of 10,000 to 1,000,000, and more preferably in the range of 50,000 to 500,000. The weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line with a standard polystyrene resin.

  A polymer having a polyalkylene oxide segment suitable as the component C of the present invention, particularly a preferable polyetherester copolymer (component C2) will be described.

  The polyetherester copolymer is a polymer produced by performing polycondensation from dicarboxylic acid, alkylene glycol, and poly (alkylene oxide) glycol, and derivatives thereof. Particularly preferred examples include poly (alkylene oxide) glycol having a polyalkylene oxide unit represented by the following formula (II) or a derivative thereof (C2-I component), and alkylene glycol containing at least 65 mol% of tetramethylene glycol. Alternatively, it is a copolymer produced from a derivative thereof (C2-II component), a dicarboxylic acid containing at least 60 mol% of terephthalic acid or a derivative thereof (C2-III component).

（ここで、Ｘは一価の有機基を表し、ｎおよびｍはいずれも０を含む整数であり、かつ１０≦（ｎ＋ｍ）≦１２０である。ｍが２以上の場合Ｘは互いに同一および異なる態様のいずれも選択できる。）

(Where X represents a monovalent organic group, n and m are each an integer including 0, and 10 ≦ (n + m) ≦ 120. When m is 2 or more, Xs are the same or different from each other Any of the embodiments can be selected.)

X is _-CH 3 in the above formula _{(II), -CH 2 Cl,} -CH 2 Br, at least one substituent selected from _-CH 2 I, and _-CH 2 OCH ₃ are preferred.

  The copolymerization ratio of the C2-I component is 30 to 80% by weight, more preferably 40 to 70% by weight of the total glycol component.

  In the C2-II component of the polyetherester copolymer of the C2 component, a diol other than tetramethylene glycol can be copolymerized. Examples of such a diol include ethylene glycol, trimethylene glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, 1,4-cyclohexanediol, and 1,4-cyclohexanedimethanol. The content of tetramethylene glycol in the C2-II component is at least 65 mol%, preferably at least 75 mol%, more preferably at least 85 mol%.

  A dicarboxylic acid of a polyetherester copolymer or a derivative thereof (in the C2-III component, a dicarboxylic acid other than terephthalic acid (including those having a carboxyl group of more than 2) can be copolymerized. , Isophthalic acid, phthalic acid, adipic acid, sebacic acid, azelaic acid, dodecane diacid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid. The polymer is particularly suitable as the component C. In the C2-III component, terephthalic acid is at least 60 mol%, preferably at least 70 mol%, more preferably at least 75 to 95 mol%.

  Other suitable C components include styrene-containing copolymers containing oxazoline groups as hydrophilic groups. Styrene monomer compounds forming such a copolymer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, tert-butylstyrene, α-methylvinyltoluene, dimethyl Styrene, chlorostyrene, dichlorostyrene, bromostyrene, dibromostyrene, vinylnaphthalene, and the like can be used. Further, other compounds copolymerizable with these compounds, such as acrylonitrile and methacrylonitrile, may be used as a copolymerization component. Among them, styrene (2-isopropenyl-2-oxazoline) -styrene-acrylonitrile copolymer is particularly preferable.

  The composition ratio of the component C of the present invention is preferably 0.5 to 50 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the component A. When the amount is less than 0.5 part by weight, the effect of dispersing the layered silicate is not sufficient, and the effect of suppressing the thermal deterioration of the aromatic polycarbonate resin may be insufficient. If the amount exceeds 50 parts by weight, impact resistance and heat resistance may be reduced.

  The aromatic polycarbonate resin composition of the present invention may further contain a reinforcing filler other than the component B as long as the effects of the present invention are exhibited. Various commonly known fillers such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, talc and various whiskers (potassium titanate whisker, aluminum borate whisker, etc.) are used as the reinforcing filler. Can be used together. The shape can be freely selected from fibrous, flake, spherical, and hollow shapes. Glass fiber, carbon fiber, glass flake and the like are suitable for improving the strength and impact resistance of the aromatic polycarbonate resin composition. On the other hand, in order to more effectively utilize the extremely good surface appearance (surface smoothness) of the resin composition of the present invention, the size of the reinforcing filler is preferably minute. Specifically, in the case of a fibrous filler, its fiber diameter is, and in the case of a plate-like filler or a granular filler, its size is preferably 5 μm or less, more preferably 4 μm or less, and still more preferably 3 μm or less. preferable. The lower limit is appropriately about 0.05 μm. Examples of such a minute reinforcing filler include talc, wollastonite, kaolin clay, and various whiskers. The compounding amount of the reinforcing filler is suitably 50% by weight or less per 100% by weight of the wholly aromatic polycarbonate resin composition, preferably in the range of 0.5 to 50% by weight, more preferably in the range of 1 to 35% by weight. . If the amount is more than 50% by weight, the moldability deteriorates and the effect of the present invention cannot be obtained, which is not preferable.

  Further, within the range not impairing the object of the present invention, other thermoplastic resins other than the compound that may be used as the component C (for example, polystyrene, syndiotactic polystyrene resin, AS resin (acrylonitrile-styrene copolymer mainly) Resins), MS resins (resins mainly composed of methyl methacrylate-styrene copolymer) and ABS resins (various styrene-containing (co) polymer resins such as resins mainly composed of acrylonitrile-styrene-butadiene copolymer), acrylic resins, and Polyamide resin, polyacetal resin, aromatic polyester resin, liquid crystal polyester resin, polyolefin resin, crystalline thermoplastic resin such as syndiotactic polystyrene resin and polyphenylene sulfide resin), flame retardant (for example, brominated epoxy) Fat, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic amide compound, alkali (earth) metal salt of organic sulfonate, silicone Flame retardant, etc.), flame retardant aids (eg, sodium antimonate, antimony trioxide, etc.), anti-dripping agents (eg, polytetrafluoroethylene having fibril-forming ability), nucleating agents (eg, sodium stearate, ethylene-acryl) Sodium oxide, etc.), antioxidants (eg, hindered phenolic compounds, sulfur type antioxidants, etc.), impact modifiers, ultraviolet absorbers, light stabilizers, release agents, lubricants, coloring agents (dyes, Inorganic pigments, etc.) and optical brighteners . These various additives can be utilized in a known amount in formulating the aromatic polycarbonate resin.

  The hydrolysis resistance of the resin composition of the present invention can be further improved by further containing a partial ester and / or full ester (component D) of a higher fatty acid and a polyhydric alcohol. Although the cause of the improvement of the hydrolysis resistance is not clear, it is presumed that it has an action of trapping and neutralizing an ionic compound causing the hydrolysis.

  Here, the higher fatty acid refers to an aliphatic carboxylic acid having 10 to 32 carbon atoms, and specific examples thereof include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecanoic acid (palmitic acid). ), Saturated aliphatic carboxylic acids such as heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, icosanoic acid, docosanoic acid, hexacosanoic acid, and palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaene Unsaturated aliphatic carboxylic acids such as acid and cetreic acid can be exemplified. Among them, aliphatic carboxylic acids having 10 to 22 carbon atoms are preferable, and those having 14 to 20 carbon atoms are more preferable. Particularly, a saturated aliphatic carboxylic acid having 14 to 20 carbon atoms, particularly stearic acid and palmitic acid, are preferred. An aliphatic carboxylic acid such as stearic acid is usually a mixture containing another carboxylic acid component having a different number of carbon atoms in many cases. As the D component, an ester compound obtained from stearic acid or palmitic acid in the form of a mixture containing other carboxylic acid components produced from such natural fats and oils is preferably used.

  On the other hand, polyhydric alcohols having 3 to 32 carbon atoms are more preferable. Specific examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (eg, decaglycerin), pentaerythritol, dipentaerythritol, diethylene glycol, propylene glycol, and the like.

  The higher fatty acid ester of the component D is more preferably a partial ester. The acid value of the component D is preferably 20 or less (can take substantially 0), and the hydroxyl value is more preferably in the range of 20 to 500 (more preferably 50 to 400). Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be determined by a method specified in JIS K0070.

  Among them, particularly preferred as the D component is a partial ester of a higher fatty acid containing stearic acid as a main component and glycerin, and this partial ester is, for example, “RIQUEMAL S-100A” from Riken Vitamin Co., Ltd. It can be easily obtained from the market under the trade name of

  The aromatic polycarbonate resin composition of the present invention preferably contains a phosphorus-based heat stabilizer. Examples of such a phosphorus-based heat stabilizer include phosphate esters such as trimethyl phosphate, triphenyl phosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4). -Methylphenyl) pentaerythritol-diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, and Phosphites such as bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite Aromatic polycarbonate such as phosphonite Compounds widely known as the phosphorus-based heat stabilizer is preferably exemplified. The phosphorus-based heat stabilizer preferably contains 0.001 to 1% by weight, more preferably 0.01 to 0.5% by weight, and more preferably 0.01 to 0.2% by weight, based on 100% by weight of the total composition. It is even more preferred that it comprises% by weight. By adding such a phosphorus-based heat stabilizer, the heat stability is further improved, and good molding characteristics can be obtained.

  To produce the aromatic polycarbonate resin composition of the present invention, any method is employed. For example, there can be mentioned a method in which each component and optionally other components are premixed, then melt-kneaded, and pelletized. Examples of premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the pre-mixing, granulation can also be carried out by an extrusion granulator or a briquetting machine, if necessary. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent-type twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a thermostatic stirring vessel. A multi-screw extruder represented by a vented twin-screw extruder is preferable. By using such a multi-screw extruder, the organically modified layered silicate is finely dispersed in the base resin with a strong shearing force. On the other hand, since the dispersion is performed in the presence of the action of reducing the size of the interlayer, exposure of ions between the layers to the outside is suppressed. As a result, a higher balance between good dispersion and thermal stability is achieved.

  Further, in the melt kneading of the aromatic polycarbonate resin composition of the present invention by a melt kneader, the following embodiment is more preferable. That is, a compound having an affinity for the organically modified layered silicate of the component B and the aromatic polycarbonate resin of the component A and having a hydrophilic component (component C), particularly preferably a carboxyl group and / or a derivative thereof. And a styrene-based polymer (component C1) having a functional group consisting of Thereafter, the melt-kneaded product and the aromatic polycarbonate resin of the component A are melt-kneaded by a multi-screw extruder. Such a melt-kneading method is preferable for improving the thermal stability of the aromatic polycarbonate resin. This is a preferred melt-kneading method for the aromatic polycarbonate resin since the decrease in the molecular weight is particularly suppressed. This is considered to be because the C component sufficiently interacts with the B component when the B component and the C component are melt-kneaded in advance, and a predetermined effect is efficiently obtained. Therefore, according to the present invention, after melt-kneading the components B and C in advance, the melt-kneaded product and the component A are melt-kneaded using a multi-screw extruder. A method for producing a resin composition is provided.

  More specifically, for example, (i) a method of melt-kneading the components B and C with a vented twin-screw extruder to form a pellet, and then melt-kneading with the component A again, or (ii) mixing the component B with the component B The component C is introduced from the main supply port of the vented twin-screw extruder, and part or all of the component A is already melt-kneaded with the components B and C from the supply port provided in the middle stage of the twin-screw extruder. The method of throwing into the state where it was put is mentioned. In the method in which the components B and C are melt-kneaded in advance, a part of the component A may be included during the melt-kneading.

  The aromatic polycarbonate resin composition of the present invention can be used to produce various products by injection molding the pellets produced as described above. In such injection molding, not only ordinary molding methods but also, as appropriate, injection compression molding, injection press molding, gas assist injection molding, foam molding (including injection by supercritical fluid), insert molding, A molded article can be obtained by using an injection molding method such as in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, sandwich molding, and ultra-high-speed injection molding. The advantages of these various molding methods are already widely known. For the molding, either a cold runner method or a hot runner method can be selected.

  Further, the aromatic polycarbonate resin composition of the present invention can be used in the form of various shaped extruded products, sheets, films and the like by extrusion molding. For forming a sheet or film, an inflation method, a calendar method, a casting method, or the like can be used. Furthermore, it is also possible to form a heat-shrinkable tube by performing a specific stretching operation. Further, the aromatic polycarbonate resin composition of the present invention can be formed into a hollow molded article by rotational molding, blow molding or the like.

  The aromatic polycarbonate resin composition of the present invention has good rigidity and further has good thermal stability. Therefore, the resin molded product obtained as described above is manufactured under a wide range of molding processing conditions that have no practical problem, and has good rigidity and good surface appearance. More specifically, according to the present invention, a resin molded article formed from the aromatic polycarbonate resin composition of the present invention, the value of the arithmetic average roughness Ra of the surface measured according to JIS B0601 Is 0.1 μm or less, and the value of the flexural modulus measured in accordance with ASTM D790 is 2,500 MPa or more. Worth more. Conventionally, in order to improve the bending elastic modulus of a resin molded product, it was common to mix a reinforcing material on a fiber or an inorganic filler, but in that case, the surface roughness is significantly reduced, This is because a product that can achieve the above balance has not been obtained.

  The value of the arithmetic surface roughness Ra of the resin molded product is more preferably 0.08 μm or less, and further preferably 0.05 μm or less. The lower limit largely depends on the mold used for molding, but about 0.001 μm is appropriate. The value of the flexural modulus is more preferably 2,800 MPa or more, and still more preferably 3,000 MPa or more. On the other hand, the upper limit is suitably 8,000 MPa, preferably 7,000 MPa, and more preferably 6,000 MPa.

  By subjecting the resin molded article of the present invention to surface modification, a surface modified molded article having excellent smoothness can be obtained. The term “surface modification” here means a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot-dip plating, etc.), painting, coating, printing, etc. And a method used for a general aromatic polycarbonate resin can be applied. In these surface modifications, the surface smoothness of the resin molded product to be modified greatly affects the surface properties after the modification. However, when the resin molded product of the present invention is used, a molded product having excellent surface smoothness is obtained. Can be obtained. Generally, these surface modifications are performed not only for surface modification and function addition, but also for the purpose of enhancing the surface smoothness of the resin molded product.If the surface smoothness is poor, it is necessary to increase the thickness of the modification. However, the resin molded product of the present invention can be efficiently modified with a small thickness. That is, the thickness is preferably 50 μm or less because the effects of the present invention are exhibited. Further, the thickness is more preferably 20 μm or less, still more preferably 5 μm or less, and still more preferably 2 μm or less. As the lower limit, 0.001 μm or more is appropriate. Further, with respect to the value of the arithmetic average roughness Ra measured according to JIS B0601 in a single resin molded product having no metal layer or metal oxide layer, surface modification is performed with a thickness of 500 times or less of the Ra. When carried out, the characteristics of the resin molded product of the present invention are utilized, and the thickness is more preferably 200 times or less, more preferably 100 times or less, and particularly preferably 50 times or less of Ra. A preferable surface modification method in the present invention is a method with a small modified thickness such as vapor deposition and plating.

  The aromatic polycarbonate resin composition of the present invention can be applied to parts that could not be used as a resin material conventionally by taking advantage of the above characteristics. In particular, the present invention can be used for applications requiring extremely high surface smoothness and rigidity, which could not be achieved unless a conventional glass molded product or a precision cut metal product was used. Such applications include, for example, mirrors arranged in optical precision equipment, polygon mirrors arranged in laser type copying / printing apparatuses, and hard disks.

  Further, the aromatic polycarbonate resin composition of the present invention is useful for various applications such as various electronic / electric devices, OA devices, vehicle parts, machine parts, other agricultural materials, fishing materials, transport containers, packaging containers, and miscellaneous goods. is there. Since the aromatic polycarbonate resin composition of the present invention is also excellent in moldability, it is also suitable for various thin molded products. Specific examples of the thin injection molded products include various housing molded products such as a battery housing, Lens tube, memory card, speaker cone, disk cartridge, surface illuminator, mechanical parts for micromachine, nameplate, PC housing, CD and DVD drive tray and chassis, copier tray and chassis, LCD device direct backlight Light diffusion plate (especially a direct-type backlight light diffusion plate for a large liquid crystal display device (large liquid crystal television of 15 inches or more)) and an IC card.

  The aromatic polycarbonate resin composition of the present invention is a novel aromatic polycarbonate resin composition having a small decrease in molecular weight, high rigidity, and significantly improved hydrolysis resistance. Further, the aromatic polycarbonate resin composition of the present invention has melt viscosity characteristics suitable for both injection molding and extrusion molding, and is excellent in moldability. Therefore, the aromatic polycarbonate resin composition of the present invention can be used in the fields of electric and electronic parts, OA equipment parts, automobile parts, agricultural materials, fishery materials, transport containers, and packaging containers, in addition to the specific uses described above. It is useful in a wide range of fields, such as the field of electrical and electronic components, the field of OA equipment, and the field of automobile parts, and the industrial effects achieved are outstanding.

  The embodiments of the present invention considered by the present inventors to be the best present are those in which the preferable ranges of the above requirements are summarized. For example, representative examples thereof are described in the following Examples. Of course, the present invention is not limited to these embodiments.

Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to these. In addition, the measurement of various characteristics in an Example was based on the following method. The following raw materials were used.
(1) Layered silicate content A test piece was molded and molded by an injection molding machine (manufactured by FANUC Co., Ltd .: AUTOSHOT T series model 150D) at a cylinder temperature of 260 ° C, a mold temperature of 80 ° C, and a molding cycle of 50 seconds. A test piece was cut into a crucible, weighed, heated to 600 ° C., kept for 6 hours, allowed to cool, and the amount of layered silicate was measured by weighing the incinerated residue remaining in the crucible. .

(2) Chlorine Content in Layered Silicate About 2 g of the organic layered silicate was precisely weighed, placed in a 300 ml beaker, and 200 ml of distilled water was added. It was stirred for 1 hour at 1000 rpm with a stirrer using a stirrer. After stirring, the extracted suspension was diluted 10-fold with distilled water, and filtered (ADVANTEC: “Dismic-13cp” pore size: 0.20 μm and Nippon Dionex: “Dillex-IC” pore size: 0.22 μm) After filtration using, the amount of chlorine was quantified using an ion chromatograph (manufactured by Dionex: "DX-100"). No bromine was detected.

(3) Viscosity average molecular weight in aromatic polycarbonate resin composition A test piece was molded under the same conditions as in (1) above, and the viscosity average molecular weight of the test piece was measured by the method described in the text.

(4) Flexural Modulus A test piece of the same shape (dimensions: length 127 mm × width 12.7 mm × thickness 6.4 mm) molded under the same conditions as in (1) above was measured at a temperature of 23 ° C. and a relative humidity of 50% RH. Under an atmosphere, the flexural modulus (MPa) was measured by a method based on ASTM-D790. The larger the value, the better the rigidity of the molded resin composition.

(5) Hydrolysis resistance A test piece of the same shape (dimensions: 127 mm long x 12.7 mm wide x 6.4 mm thick) molded under the same conditions as in (1) above was used at an atmosphere of 65 ° C and 85% relative humidity. The viscosity-average molecular weights of the treated and untreated samples were left to stand for 500 hours. The difference was defined as ΔM. The smaller the value (ΔM), the better the hydrolysis resistance of the molded resin composition.
The following were used as raw materials.

(A component: aromatic polycarbonate resin)
A-1: Bisphenol A-type aromatic polycarbonate resin powder (manufactured by Teijin Chemicals Ltd., Panlite 1-1250WP, viscosity-average molecular weight 23,900, chlorine content 40 ppm, manufactured by Teijin Chemicals Co., Ltd .; bromine content is recognized) Could not be done)

(B component and other than B component)
B-1: Synthetic mica (DMA-80E: manufactured by Topy Industries, Ltd.) was almost completely ion-exchanged with onium ion chloride (didecyldimethylammonium chloride) and filtered off. The chlorine element content after drying was 948 ppm.
B-2: Synthetic mica (DMA-80E: manufactured by Topy Industries, Ltd.) was almost completely ion-exchanged with onium ion chloride (didecyldimethylammonium chloride). After rinsing with a portion of ion-exchanged water, the mixture was filtered again. The chlorine content after drying was 613 ppm.
B-3: Synthetic mica (DMA-80E: manufactured by Topy Industries, Ltd.) was almost completely ion-exchanged with onium ion chloride (didecyldimethylammonium chloride). After washing with stirring in a portion of ion-exchanged water using a stirrer, the mixture was filtered off again. The chlorine content after drying was 208 ppm.

(C component)
C-1: Styrene-maleic anhydride copolymer (manufactured by Nova Chemical Japan Co., Ltd .: “DYLARK 332-80”, maleic anhydride content: about 15% by weight)

[Examples 1 and 2, and Comparative Examples 1 and 2]
The components B and C were dry-blended at the mixing ratios shown in Table 1, and then a twin-screw extruder (Toshiba Machine Co., Ltd .: TEM-58SS) equipped with a screw having a diameter of 58 mm and two kneading zones was used. The mixture was melt-kneaded at a cylinder temperature of 200 ° C., extruded, and strand-cut to obtain pellets. The pellets and the A component were mixed in the proportions shown in Table 1, and 0.1 part by weight of trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd .: TMP) and fatty acid ester (RIKEN Vitamin Co., Ltd., per 100 parts by weight of the A component). ): Rikemar S-100A) 0.05 parts by weight were added and dry-blended, and then a vented twin-screw extruder equipped with a screw having a diameter of 30 mm, L / D = 33.2, and two kneading zones ((Co. ) Using Kobe Steel: KTX30), the mixture was melt-kneaded at a cylinder temperature of 280 ° C, extruded, and strand cut to obtain pellets.

  The obtained pellets were dried at 100 ° C. for 5 hours using a hot-air circulation dryer. After drying, the test piece was molded using an injection molding machine (manufactured by FANUC Corporation: AUTOSHOT T series model 150D) at a cylinder temperature of 260 ° C, a mold temperature of 80 ° C, and a molding cycle of 50 seconds. Table 1 shows the measurement results for these.

  As is evident from the above table, the aromatic polycarbonate resin composition of the present invention has an excellent aromaticity with good hydrolyzability, good rigidity and good heat stability as the content of the specific component in the B component is small. It is clear that this will result in an aromatic polycarbonate resin composition.

Claims (4)

  (B) A cation exchange capacity of 50 to 200 meq / 100 g per 100 parts by weight of the aromatic polycarbonate resin (A component), and an organic onium having a cation exchange capacity of 40% or more of the cation exchange capacity. An aromatic polycarbonate obtained by ion-exchanging ions between layers and further comprising 0.1 to 50 parts by weight of an organically modified layered silicate (component B) having a total content of chlorine atoms and bromine atoms of 300 ppm or less. Resin composition.   The component B is obtained by ion-exchanging a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g with a chlorinated or brominated organic onium ion at a ratio of 40% or more of the cation exchange capacity. The aromatic polycarbonate resin composition according to claim 1, which is an organically modified layered silicate (component B ') having a total content of chlorine atoms and bromine atoms of 300 ppm or less, obtained by the above method.   Furthermore, 0.1 to 50 parts by weight of (C) an organic compound having an affinity for the component A and having a hydrophilic component (component C) is contained in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the component A. The aromatic polycarbonate resin composition according to claim 2.   The polycarbonate resin composition according to claim 3, wherein the C component is a styrene-maleic anhydride copolymer.