JPH07207134A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain an aromatic polycarbonate resin composition containing an intercalation compound containing a specific laminar silicate as a host and an organic onium ion as a guest, respectively, in a specific amount as an inorganic ash content and excellent in strength, stiffness, toughness, ductility, surface appearance of molding, melt fluidity and dimensional accuracy. CONSTITUTION:This composition contains an intercalation compound containing a laminar silicate having >=30mm equivalent/100g, preferably >=70mm equivalent/100g of cation exchange capacity as a host, and an organic onium ion (preferably a quaternary onium ion having preferably >= a 12C alkyl group, especially trimethyloctadecylammonium ion) as a guest, respectively, in an amount of 0.1-10wt.%, preferably 0.3-4wt.% as an inorganic ash content.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin composition containing a specific intercalation compound.

[0002]

2. Description of the Related Art Conventionally, for the purpose of improving the strength, rigidity or dimensional accuracy of aromatic polycarbonate resins, various fillers such as glass fibers, carbon fibers, inorganic fibers such as potassium titanate whiskers, glass flakes and glass. Inorganic powders such as beads, talc, mica, kaolin and wollastonite have been compounded. However, although these methods increase strength and rigidity, they have drawbacks such as impairing toughness, increasing specific gravity, and decreasing surface appearance. Disadvantages in mixing such fillers or inorganic powders are:
It is generally considered that this is caused by poor dispersion of the filler or too large a size of the dispersion, and poor adhesion at the interface with the matrix resin. Various attempts have been made such as pulverization and devising of the shape, but it was not always satisfactory.

In addition, the use of the filler generally causes a problem that the melt fluidity of the aromatic polycarbonate resin as well as the resin material is lowered. Furthermore, when inorganic fibers such as glass fibers are filled, the molding shrinkage in the orientation direction of the fibers decreases, but there is also a problem of dimensional accuracy anisotropy that the effect is hardly seen in the vertical direction. It was

As described above, the use of various inorganic fillers has been proposed for the purpose of improving the strength and rigidity of the aromatic polycarbonate resin, but the problems of lowering the toughness of the material and increasing the specific gravity are not always solved. This has not been done, and there is still a demand for improvement in melt fluidity, and there remains a problem in terms of improvement in dimensional accuracy.

[0005]

The object of the present invention is to provide excellent strength and rigidity, at the same time, without significantly impairing toughness, particularly ductility, and with little increase in specific gravity, excellent appearance of the molding surface and melt flowability, and dimensional accuracy. Is to provide an isotropically improved aromatic polycarbonate resin composition.

[0006]

The present invention has been made in order to solve the above-mentioned problems, and its gist is to use a layered silicate having a cation exchange capacity of 30 meq / 100 g or more as a host and a carbon number. An aromatic polycarbonate comprising an intercalation compound containing an organic onium ion having 12 or more alkyl groups as a guest in an amount of 0.1 to 10% by weight as an inorganic ash content.

The present invention will be described in more detail below. The aromatic polycarbonate resin used in the present invention comprises one or more kinds of bisphenols, which may contain polyhydric phenols as a copolymerization component, and carbonic acid esters such as bisalkyl carbonate, bisaryl carbonate and phosgene. It is produced by the reaction.

Specific examples of bisphenols include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane and 1,1-bis (4
-Hydroxyphenyl) propane, 2,2-bis (4-
Hydroxyphenyl) propane or bisphenol A, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) pentane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-
Methyl pentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxy-3-)
Methylphenyl) methane, bis (4-hydroxy-3-)
Methylphenyl) phenylmethane, 1,1-bis (4-
Hydroxy-3-methylphenyl) ethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane,
2,2-bis (4-hydroxy-3-ethylphenyl)
Propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (4-hydroxy-3-sec-butylphenyl) propane, 2,2
-Bis (4-hydroxy-3-sec-butylphenyl) propane, bis (4-hydroxyphenyl) phenylmethane, 1,1-bis (4-hydroxyphenyl)-
1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) dibenzylmethane, 4,4′-dihydroxydiphenylether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone, phenolphthalein and the like can be mentioned. Typical of these are bisphenol A, 1,1-bis (4-hydroxyphenyl) -1-phenylethane and 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-methylphenyl) propane and the like, and most commonly bisphenol A is used.

Polyhydric phenols are used as a copolymerization component for the purpose of changing the rheological properties of aromatic polycarbonate resins and improving the surface abrasion properties, for example 1,1,1-tris (4-hydroxyphenyl). Examples include trisphenols such as ethane. The method for producing the aromatic polycarbonate resin used in the present invention is not limited, but an organic solvent and an alkaline water which dissolve the produced polymer from an alkali metal salt of bisphenol and a carbonate derivative active in nucleophilic attack as raw materials Interfacial polymerization method of polycondensation reaction at the interface of bisphenols, pyridine method of polycondensation reaction of bisphenols and carbonic acid ester derivative active in nucleophilic attack in organic base such as pyridine, bisphenols and bisalkyl carbonate or bis A melt polymerization method in which a carbonic acid ester such as an aryl carbonate is used as a raw material and melt polycondensation is generally known. Examples of the carbonic acid ester derivative active in the nucleophilic attack used in the interfacial polymerization method and the pyridine method include phosgene and carbodiimidazole. Among them, phosgene is the most common because it is easily available. Specific examples of the carbonic acid ester used in the melt polymerization method include (a) bisalkyl carbonate such as dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, and di-n-butyl carbonate. As the aryl carbonate, diphenyl carbonate, bis (2,
4-dichlorophenyl) carbonate, bis (2,4,
6-trichlorophenyl) carbonate, bis (2-nitrophenyl) carbonate, bis (2-cyanophenyl) carbonate, bis (4-methylphenyl) carbonate, bis (3-methylphenyl) carbonate, dinaphthylcarbonate and the like can be mentioned. . Of these, bisalkyl carbonates such as dimethyl carbonate and diethyl carbonate, diaryl carbonates such as diphenyl carbonate, bis (4-methylphenyl) carbonate, and bis (3-methylphenyl) carbonate are preferably used in view of easy availability of raw materials. Diphenyl carbonate is most preferably used because of its easy reaction.

The molecular weight of the aromatic polycarbonate resin used in the present invention is not particularly limited, but usually, in gel permeation chromatography (GPC) with a tetrahydrofuran (THF) solvent at 40 ° C., a single molecular weight dispersed polystyrene is used as a control. Weight average molecular weight Mw
Is 15,000 or more, preferably 2 from the viewpoint of toughness and moldability.
About 0000 to 80,000, most preferably 35,000
About 65000 is suitable.

The layered silicate used in the present invention includes:
Two octahedral sheet structures containing Al, Mg, Li, etc.
The 2: 1 type, which sandwiches the iO ₄ tetrahedral sheet structure, is suitable, and the thickness of one layer, which is the unit structure, is usually 9.5Å
It is a degree. Specifically, smectite clay minerals such as montmorillonite, hectorite, fluorohectorite, saponite, beidellite, and stevensite, Li,
Type fluorine teniolite, Na type fluorine teniolite, N
Examples of the swelling synthetic mica such as a-type tetra-silicon tetrafluoride mica and Li-type tetra-silicon fluoro-mica, vermiculite, fluorovermiculite, halloysite, etc. may be natural or synthetic.

In the present invention, the cation exchange capacity (CEC) of these layered silicates is 30 meq / 100 g.
It is necessary to be more than 50, but preferably 50 meq / 10
It is preferably 0 g or more, and more preferably 70 meq / 100 g or more. The cation exchange capacity is measured by determining the amount of methylene blue adsorbed. If the cation exchange capacity is less than 30 meq / 100 g, the amount of intercalation of organic onium ions between the layers becomes insufficient and the dispersibility in the aromatic polycarbonate resin deteriorates, resulting in strength and rigidity of the composition. Is not sufficiently increased and the appearance of the molded surface is deteriorated. Among these layered silicates due to their cation exchange capacity and availability, smectite clay minerals such as montmorillonite and hectorite,
Swelling synthetic mica such as Li-type fluoro-teniolite, Na-type fluoro-teniolite, and Na-type tetrasilicon-fluorine mica is preferably used. Particularly, montmorillonite obtained by refining bentonite is Li-type in terms of purity in view of availability. Swellable fluoromica such as fluoro-teniolite (the following formula A), Na-type fluoro-teniolite (the following formula B) and Na-type tetrasilicon mica (the following formula C) is most suitable for the present invention. The formulas A, B, and C show ideal compositions and do not need to be exactly the same.

[0013]

Embedded image LiMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (A) NaMg ₂ Li (Si ₄ O ₁₀ ) F ₂ (B) NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ (C) Used in the present invention The organic onium ion is represented by ammonium ion, phosphonium ion, sulfonium ion, and onium ion derived from a heteroaromatic ring. The presence of the onium ion structure in the present invention makes it possible to introduce a hydrocarbon structure having a small intermolecular force between the layers of the negatively charged silicate layer, and the kind of the organic onium ion is not particularly limited. Not done. Among these, ammonium ion, phosphonium ion, and onium ion derived from a heteroaromatic ring are preferable from the viewpoint of easy availability and stability.

Examples of ammonium ions include primary ammonium such as dodecyl ammonium, hexadecyl ammonium and octadecyl ammonium, secondary ammonium such as methyl dodecyl ammonium, butyl dodecyl ammonium and methyl octadecyl ammonium, dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium and dimethyl. Tertiary ammonium such as octadecyl ammonium, diphenyl dodecyl ammonium, diphenyl octadecyl ammonium, quaternary ammonium having the same alkyl group such as tetraethyl ammonium, tetrabutyl ammonium, tetraoctyl ammonium, trimethyloctyl ammonium, trimethyl decyl ammonium, trimethyl dodecyl ammonium, Trimethyl tetradecyl Ammonium, trimethylhexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecadienyl ammonium and other trimethyl alkyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, Triethyl alkyl ammonium such as triethyl octadecyl ammonium, tributyl dodecyl ammonium, tributyl tetradecyl ammonium, tributyl hexadecyl ammonium, tributyl alkyl ammonium such as tributyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl ditetradecyl Dimethylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldioctadecadienylammonium, etc., dimethyldialkylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecyl Ammonium, diethyldialkylammonium such as diethyldioctadecylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldialkylammonium such as dibutyldioctadecylammonium, methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium Ammonium, dibenzyldihexadecyl ammonium Dibenzyldialkylammonium, trioctylmethylammonium, tridodecylmethylammonium, tritetradecylmethylammonium, etc. trialkylmethylammonium, trioctylethylammonium, tridodecylethylammonium, etc. trialkylethylammonium, trioctylbutylammonium , Trialkylbutylammonium such as tridodecylbutylammonium, quaternary ammonium having an aromatic ring such as trimethylbenzylammonium, and quaternary ammonium derived from an aromatic amine such as trimethylphenylammonium. Examples of the phosphonium ion include: Tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium , Trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, tributyloctadecylphosphonium, and the like, and quaternary phosphonium ions, and the heteroaromatic ring-derived onium ion includes ions such as pyridinium and quinolinium. To be

Among these organic onium ions, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, trimethyloctadecylammonium, triethyldodecylammonium are considered in view of the effectiveness of the hydrocarbon structure which contributes to the hydrophobicization between silicate layers. , Quaternary ammonium having one or more alkyl groups having 12 or more carbon atoms in one molecule such as triethyltetradecylammonium, triethylhexadecylammonium, triethyloctadecylammonium, dimethyldidodecylammonium, dimethylditetradecylammonium, dimethyldihexadecyl Ammonium, dimethyldioctadecyl ammonium, diethyl didodecyl ammonium, diethyl ditetradecyl ammonium, diethyl Quaternary ammonium having two alkyl groups having 12 or more carbon atoms in one molecule such as hexadecyl ammonium and diethyl dioctadecyl ammonium, trimethyl dodecyl phosphonium, trimethyl hexadecyl phosphonium, trimethyl octadecyl phosphonium, tributyl dodecyl phosphonium, tributyl hexadecyl phosphonium Having an alkyl group having 12 or more carbon atoms such as tributyl octadecylphosphonium
A quaternary onium ion such as a quaternary phosphonium is preferably used. Among them, trimethylhexadecyl ammonium,
Quaternary ammonium having one or more alkyl groups having 16 or more carbon atoms in one molecule such as trimethyloctadecyl ammonium, dimethylditetradecyl ammonium, dimethyldihexadecyl ammonium, and alkyl groups having 14 or more carbon atoms such as dimethyldioctadecyl ammonium Resin having a quaternary onium ion such as quaternary ammonium having two or more quaternary ammonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributylhexadecylphosphonium, tributyloctadecylphosphonium having 14 or more carbon atoms in one molecule It is more preferably used from the viewpoint of maintaining the toughness of the composition and easy availability, and most preferably trimethyloctadecyl ammonium ion, dimethyldihexadecyl ammonium ion, dimethyl di Kuta decyl ammonium ion,
Tributylhexadecylphosphonium ion and tributyloctadecylphosphonium ion are used. These organic onium ions can be used alone or as a mixture of plural kinds.

When an onium ion having an alkyl group having 14 or more carbon atoms is used, the melt flowability of the composition is greatly improved as a secondary preferable effect, and moldability, molding strain, high birefringence, etc. are improved. Can be done. This is considered to be because the presence of a relatively long chain alkyl group improves the molecular mobility of the matrix resin. An intercalation compound that is preferably used as a raw material for the resin composition of the present invention and has a cation exchange capacity of 30 meq / 100 g or more as a host and an organic onium ion as a guest is an organic onium ion negatively. Known techniques for reacting with clays containing layer lattices and exchangeable cations (see, for example, Japanese Examined Patent Publication No.
No. 1-5492, JP-A No. 60-42451, etc.), and the onium ion is intercalated between the layers. Preparation of the intercalation compound is described in, for example, Japanese Patent Application No. 5-2451.
No. 99, Japanese Patent Application No. 5-245200, etc., and the reaction and purification method in the case of inserting a quaternary ammonium ion.

The amount of the organic onium ion in the intercalation compound is 0.8 with respect to the cation exchange capacity of the starting layered silicate.
There is no particular limitation as long as it is in the range of 2.0 to 2.0 equivalents, but it will be about 1.0 to 1.3 equivalents under normal reaction conditions. If this amount is less than 0.8 equivalents, the dispersibility in the aromatic polycarbonate resin is lowered, and if it is more than 2.0 equivalents, the free compounds derived from the onium ions become remarkable, and the thermal stability at the time of molding is lowered, May cause smoke, mold contamination, odor, etc.

The water content of the intercalation compound is 7 wt% or less, preferably 5 wt% or less in order to reduce undesired side reactions such as hydrolysis during mixing with the aromatic polycarbonate resin.
% Or less, most preferably 3 wt% or less. When the water content exceeds 7 wt%, the molecular weight decrease due to hydrolysis of the aromatic polycarbonate becomes remarkable,
The toughness of the composition is greatly reduced. In the aromatic polycarbonate resin composition of the present invention, the layered silicate has an inorganic ash content of 0.1 to 10% by weight, preferably 0.3 to 8% by weight, more preferably from the viewpoint of maintaining toughness and manifesting a reinforcing effect. Is 0.3 to 5% by weight, and most preferably 0.3 in terms of ductility.
Up to 4% by weight. Here, the amount of inorganic ash means the weight fraction of the residue obtained by completely burning off the organic component of the aromatic polycarbonate composition in an electric furnace at 650 ° C. If the amount of the inorganic ash is less than 0.1% by weight, the elastic modulus is not significantly improved, while if it exceeds 10% by weight, the toughness is greatly reduced.
Either case is not preferable. When adding the intercalation compound, they may be used alone or in combination.

The intercalation compound of the present invention, in which an organic onium ion is intercalated into a layered silicate having a specific cation exchange capacity, has an extremely excellent cleavage dispersibility with respect to an aromatic polycarbonate resin matrix, and has an excellent cleavage dispersibility in the resin matrix. It is finely dispersed and extremely efficiently improves the strength and rigidity while maintaining the ductility of the aromatic polycarbonate resin, exhibits a low isotropic molding shrinkage ratio in the injection molded product, and greatly reduces the melt viscosity.

In the present invention, in the exchange of the interlayer cation of the layered silicate having a cation exchange ability by the organic onium ion, the hydrophobicity between the layers is changed by controlling the structure of the organic onium ion, and the organic structure is controlled. Cleavage dispersion can be easily achieved even by a simple means such as mechanical shearing force in a molten aromatic polycarbonate resin due to the synergistic effect of reducing the interlayer attractive force and increasing the interlayer distance by intercalation of onium ions.

In the present invention, the method for mixing the layered silicate and the aromatic polycarbonate resin is not particularly limited,
When an intercalation compound is used, it is essential that the aromatic polycarbonate resin is melted under mechanical shearing, and the compound can be added at any stage within this range. For example, a method of adding to the aromatic polycarbonate raw material before polymerization and stirring and mixing with the melt polymerization of the aromatic polycarbonate, a method of adding and stirring and mixing before or after the melt polymerization of the aromatic polycarbonate before or after the melt polymerization of the aromatic polycarbonate, or after the chip formation. Although it can be mixed by any method such as a method of adding it to the aromatic polycarbonate resin and melt-mixing with a kneader such as an extruder, a method using a kneader is preferable from the viewpoint of productivity, convenience and versatility. Above all, it is preferable to use a twin-screw extruder having high shear efficiency, and it is most preferable to use a twin-screw extruder with a vent capable of efficiently removing water contained in the intercalation compound. The aromatic polycarbonate resin composition of the present invention, as long as the object of the present invention is not impaired, various conventional addition components as necessary, such as glass fibers, inorganic fibers such as carbon fibers, glass flakes, glass beads, mica, etc. Inorganic powder, various plasticizers, stabilizers, colorants, flame retardants, etc. can be added.

Further, in the aromatic polycarbonate resin composition of the present invention, a thermoplastic resin or a thermoplastic elastomer, for example, a polyamide resin, which is blended with an ordinary aromatic polycarbonate resin as needed, is used as long as the object of the present invention is not impaired. , Aromatic polyester resin, polyarylate resin, ABS resin, polyphenylene ether resin,
Polyarylene sulfide resin, epoxy resin, phenoxy resin, polystyrene resin, maleic anhydride modified polystyrene resin, polystyrene resin modified with a compound having an epoxy group, aromatic polycarbonate polysiloxane copolymer, polyester elastomer, acid anhydride group or Styrene-based thermoplastic elastomer modified with a compound having an epoxy group, acrylic rubber, core-shell type acrylic rubber, MBS rubber and the like may be added.

[0023]

EXAMPLES The present invention will be described in more detail below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

[Evaluation Items and Measuring Method] [Tensile Test] According to ASTM D-638. The yield strength (abbreviated as YS, unit kg / cm ² ), elastic modulus (abbreviated as TM, unit kg / cm ² ) and elongation at break (abbreviated as UE, unit%) were measured.

[Observation of Surface Appearance] The surface smoothness of injection-molded articles was compared by visual evaluation. [Melted Strand Transparency] Visual evaluation was performed as a simple evaluation of the dispersed state. [Molding Shrinkage Ratio] It was determined by injection-molding a flat plate using a 2 mm thick, 8 cm square film gate mold and measuring the dimensions in the flow direction (MD) and in two directions, MD and the vertical direction (TD).

[Melt Flowability] The minimum filling injection pressure (kg / cm ² ) at the time of injection molding was evaluated. [Molecular weight] Gel permeation chromatography with tetrahydrofuran solvent (HLC-8 manufactured by Tosoh Corporation)
020, column: GMHXL, temperature: 40 ° C.), weight average molecular weight M with monomolecular weight dispersed polystyrene as a control.
w was measured.

[Layered Silicate Used] Table 1 shows the name, mineral name, type, cation exchange capacity (abbreviated as CEC) measured by the methylene blue adsorption method, and manufacturer of the layered silicate used. Also, as an intercalation compound, a commercially available organic bentonite, Sven 74 (manufactured by Toyoshun Kogyo Co., Ltd.,
An intercalation compound mainly composed of montmorillonite and dimethyldioctadecyl ammonium ion) was also used.

[0028]

[Table 1]

[Preparation Method of Intercalation Compound] Layered silicate about 10
0 g was precisely weighed and dispersed in 10 liters of water at room temperature with stirring. To this, 1.2 times equivalent of onium ion hydrochloride of CEC of the layered silicate was added and stirred for 6 hours. The purified precipitated solid was filtered off, then washed with stirring in 25 liters of demineralized water, and then filtered off again. This washing and filtering operation was performed at least three times, and it was confirmed by the silver nitrate test of the washing liquid that chloride ions could not be detected. The solid obtained is 3-7.
After air drying in the day, crush in a mortar and dry with warm air at 50 ° C for 3 ~
After 10 hours, it was crushed again in a mortar. Drying conditions vary depending on the type of guest onium ion, but the maximum particle size is 1
Securing pulverizability of about 100 μm and 120
The amount of residual water evaluated by thermogravimetric reduction when kept at 1 ° C for 1 hour was 2-3 wt% as an index. As the ash content of the intercalation compound, the weight fraction of the residue when kept at 500 ° C. for 3 hours under a nitrogen stream was adopted and used for calculation of the theoretical ash content of Examples and Comparative Examples.

Examples 1 to 12 Flakes of bisphenol A polycarbonate (Novarex 7025PJ, weight average molecular weight Mw = 45,000, manufactured by Mitsubishi Kasei Co., Ltd., Novarex is a registered trademark) and the intercalation compounds shown in Table 2 were used. Compounded with a twin-screw extruder TEM35 manufactured by Toshiba Machine Co., Ltd.
Barrel temperature is set to 280 ℃ by B, screw speed is 15
Melt extrusion was performed into chips by using a vent under the condition of 0 rpm. The obtained chips were molded by an injection molding machine J28SA manufactured by Japan Steel Works, Ltd. under the conditions of a barrel temperature of 280 ° C., a mold surface measured temperature of 80 ° C., injection / cooling = 10/10 seconds, and an injection speed maximum, Tensile test pieces, bending test pieces and flat plates were obtained. The composition has an ash content of about 1.5 g
Was precisely weighed, and the weight fraction of the residue in which the organic matter was completely burned out in an electric furnace at 650 ° C. was adopted.

Comparative Example 1 The same melt extrusion experiment as in Examples 1 to 12 was carried out without adding an intercalation compound. [Comparative Examples 2 to 5] As the organic onium ion of the intercalation compound, those having no alkyl group having 12 or more carbon atoms shown in Table 2 were used to perform the same melt extrusion experiment as in Examples 1 to 12.

Comparative Example 6 Instead of the intercalation compound, Table-2
Examples 1 to 1 using the natural montmorillonite described in 1.
The same melt extrusion experiment as in 2 was performed. [Comparative Example 7] The cation exchange capacity (CE
The same melt extrusion experiment as in Example 7 was carried out using a layered silicate having C) of less than 30 meq / 100 g.

Comparative Example 8 The same melt extrusion experiment as in Examples 1 to 12 was conducted using natural mica which is a general-purpose layered filler shown in Table 2. [Comparative Examples 9 to 10] Examples 8 to 10 as described in Table 2
The same melt extrusion experiment as in 12 was performed, but the ash content was 0.1
It was blended so as to be less than 10% by weight and more than 10% by weight.

The evaluation results of the examples and comparative examples are shown in Table 2 for the amount of ash, the tensile test, the surface appearance, and the transparency of the molten strand.
The molecular weight, melt fluidity, and molding shrinkage are shown in Table 3, respectively. From Table 2, it can be seen that the compositions of the examples of the present invention show a remarkable improvement in strength and elastic modulus by the addition of a small amount of an inorganic substance as compared with the addition of mica (Comparative Example 8) and the tensile elongation at break (U
In the case of using an intercalation compound of an organic onium ion having no alkyl group having 12 or more carbon atoms, the injection molded article has a good surface appearance with little decrease in toughness as shown in E) (Comparative Examples 2 to 5). It is also understood that the layered silicate is superior to the case where the cation exchange capacity is small (Comparative Example 7). Further, from Table 3, it can be seen that the compositions of the examples of the present invention have a significantly improved melt flowability and an isotropically improved molding shrinkage ratio.

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

The aromatic polycarbonate resin composition obtained by the present invention is excellent in strength and rigidity, at the same time does not significantly impair toughness, particularly ductility, and has a small increase in specific gravity and an excellent molded surface appearance and melt flowability. Moreover, it gives the result that the dimensional accuracy is improved isotropically. The aromatic polycarbonate resin composition obtained by the present invention has various properties such as low specific gravity, good surface appearance, high strength, high rigidity, high toughness, low molding shrinkage, and good melt fluidity. It can be applied to machine parts, automobile parts, electric / electronic parts, sheets, films, packaging materials, etc.

Claims (2)

[Claims] 1. A cation exchange capacity of 30 meq / 10
Aromatic polycarbonate resin containing 0.1 to 10% by weight of inorganic ash as an intercalation compound having 0 g or more of a layered silicate as a host and an organic onium ion having an alkyl group having a carbon number of 12 or more as a guest Composition. 2. The aromatic polycarbonate resin composition according to claim 1, wherein the organic onium ion having an alkyl group having 12 or more carbon atoms is a quaternary onium ion having an alkyl group having 12 or more carbon atoms. object.