JP2003064248A - Aromatic polycarbonate resin composition and resin additive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin in which layered silicate is superfinely dispersed and has good rigidity and improved thermal deterioration of the aromatic polycarbonate resin. SOLUTION: Aromatic polycarbonate (component A) 10
0 parts by weight, having a cation exchange capacity of 50 to 200 meq / 100 g, and a layered silicate (component B) 0.1 in which organic onium ions are ion-exchanged at a rate of 40% or more of the exchange capacity. To 140 parts by weight and 0.1 to 70 parts by weight of polycaprolactone (component (C)).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aromatic polycarbonate resin composition comprising an aromatic polycarbonate and a layered silicate in which organic onium ions are ion-exchanged between layers and polycaprolactone (component C). . More specifically, the present invention relates to an aromatic polycarbonate resin composition having such a constitution, in which a layered silicate is finely dispersed in a resin matrix.

[0002]

2. Description of the Related Art Generally, an aromatic polycarbonate resin has excellent properties such as transparency, impact resistance, heat resistance and dimensional stability, and is widely used in applications such as OA equipment field and automobile field. ing. Due to recent technological trends such as lightness, thinness, shortness and smallness, good rigidity is required.

Conventionally, in order to improve rigidity, a material mixed with glass fiber or an inorganic filler has been used.
However, in some cases, a material having a lower specific gravity or a good surface appearance may be required. Therefore, attempts have been made to improve the rigidity and surface properties of the composition by ultrafinely dispersing an inorganic filler.

As a technique capable of addressing these problems, clay minerals, particularly layered silicates are used as inorganic fillers, and the interlayer ions are ion-exchanged with various organic onium ions to facilitate dispersion in the resin. In particular, many attempts have been made to improve the mechanical properties of the molded product while maintaining the surface appearance and specific gravity of the molded product in good condition, particularly in polyamide-based resins and polyolefin-based resins, and practical examples can be found in them.

Also in the aromatic polycarbonate resin composition, JP-A 03-215558 and JP-A 07-20 are available.
7134, JP 07-228762 A, JP 07
No. 331092, JP-A-09-143359, JP-A-10-60160 and the like attempt to improve dispersibility in an aromatic polycarbonate resin composition by devising an organic onium ion to be used and a mixing method. The method of doing is proposed. However, the aromatic polycarbonate resin in which the layered silicate or the like is finely dispersed is different from the polyamide-based resin and the polyolefin-based resin in that it easily hydrolyzes and has a problem of poor thermal stability, and therefore has sufficient practicality. The current situation is that it cannot be said.

Further, after the interlayer ions of the layered silicate are ion-exchanged with the organic onium ion, a polyamide monomer is inserted as a guest between the layers and polymerized to obtain a polyamide resin containing ultrafinely dispersed layered silicate. It has been proposed to produce an aromatic polycarbonate resin composition containing finely dispersed layered silicate by mixing the mixture with an aromatic polycarbonate resin and melt-kneading (Japanese Patent No. 3017232). However, such a resin composition is inferior in thermal stability and is not sufficiently practical.

Further, a layered silicate, a thermoplastic resin, an organic onium ion, and a solvent are individually charged into an extruder and melt-kneaded to produce an aromatic polycarbonate composite containing finely dispersed layered silicate. Has been proposed (Japanese Patent Laid-Open No. 2000-239397). However, since a large amount of solvent is put into an extruder and melt-kneaded, there is a manufacturing problem such as degassing of gas generated from the solvent, and further, organic onium ions and a solvent are mixed. Therefore, there is a problem that thermal deterioration of the aromatic polycarbonate resin due to the transesterification reaction is promoted.

On the other hand, Japanese Patent Laid-Open No. 2000-17157 discloses a composition comprising an aliphatic polyester and an organic clay complex obtained by treating a layered silicate with an organic cation, and a film comprising the composition is It is described that it has excellent strength, rigidity and biodegradability. However, this publication does not disclose a resin composition in which a layered silicate is ultrafinely dispersed in an aromatic polycarbonate.

As mentioned above, what is desired is an aromatic polycarbonate resin in which a layered silicate is ultrafinely dispersed, and in particular, a composition practically sufficient has not been achieved due to the problem of thermal stability. .

[0010]

SUMMARY OF THE INVENTION In consideration of the above problems, an object of the present invention is to improve thermal deterioration of an aromatic polycarbonate resin while finely dispersing a layered silicate to have good rigidity. An object is to provide an aromatic polycarbonate resin.

As a result of intensive studies conducted by the present inventor to achieve such an object, surprisingly, an aromatic polycarbonate, a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g, and polycaprolactone are used. It was found that the resin composition achieves fine dispersion of the layered silicate and has good thermal stability, and has completed the present invention.

[0012]

According to the present invention, 100 parts by weight of an aromatic polycarbonate (component A) has a cation exchange capacity of 50 to 200 meq / 100 g, and an organic onium ion has a cation exchange capacity of 40%. 0.1 to 140 parts by weight of layered silicate (component B) formed by ion exchange at a rate of not less than 100%, and polycaprolactone (component C) 0.1 to 70
The present invention relates to an aromatic polycarbonate resin composition composed of parts by weight.

The present invention more preferably relates to the above aromatic polycarbonate resin composition in which the C component has a number average molecular weight of 300 to 40,000.

The present invention more preferably relates to the above resin composition in which the component B is a layered silicate obtained by ion-exchange of organic onium ions between layers, and more preferably the organic onium ion. Is an organic phosphonium ion, and more preferably a resin composition in which the molecular weight of the organic onium ion is 100 to 600.

Further, the present invention preferably relates to the above aromatic polycarbonate resin composition obtained by melt-kneading the components B and C in advance and then melt-kneading the components with the component A.

The details of the present invention will be described below.

The aromatic polycarbonate which is the component A of the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid-state transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

As a typical example of the dihydric phenol,
2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) -3-methylbutane, 9,9-
Bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene and the like can be mentioned. In particular, a homopolymer of bisphenol A can be mentioned. Such an aromatic polycarbonate resin is preferable because it has excellent impact resistance.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

In producing an aromatic polycarbonate by reacting the above dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method,
If necessary, a catalyst, a terminal stopper, an antioxidant for preventing the dihydric phenol from oxidizing and the like may be used. The aromatic polycarbonate may be a branched polycarbonate obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.

When a polyfunctional compound which gives a branched polycarbonate is contained, such a proportion is 0.001 to 1 mol%, preferably 0.001 of the total amount of the aromatic polycarbonate.
It is 5 to 0.5 mol%, particularly preferably 0.01 to 0.3 mol%. Further, particularly in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of the branched structure is 0.
001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.01 to 0.3 mol%. The ratio can be calculated by ¹ H-NMR measurement.

Further, it may be a polyester carbonate obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include an aliphatic bifunctional carboxylic acid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The aliphatic difunctional carboxylic acid may be linear, branched or cyclic. The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Preferred examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid.

Further, it is also possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit.

The aromatic polycarbonate is a mixture of two or more of the above-mentioned polycarbonates having different dihydric phenols, polycarbonates containing a branching component, various polyester carbonates, and various aromatic polycarbonates such as polycarbonate-polyorganosiloxane copolymers. It may be one. Further, various kinds of polycarbonates having different production methods shown below, polycarbonates having different terminal stoppers, and the like can be used as a mixture of two or more kinds.

In the polymerization reaction of aromatic polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, tertiary amines such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds,
It is also possible to use a catalyst such as a quaternary phosphonium compound. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is 1
The pH during the reaction is preferably maintained at 9 or higher for about 0 minutes to 5 hours.

Further, in such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Specific examples of monofunctional phenols include, for example, phenol and p-tert.
-Butylphenol, p-cumylphenol and isooctylphenol. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, which is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1 to 4
It's about time.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, and among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salt and potassium salt of dihydric phenol, and water. A catalyst such as an alkaline earth metal compound such as calcium oxide, barium hydroxide or magnesium hydroxide, or a nitrogen-containing basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine or triethylamine can be used. In addition, alkali (earth) metal alkoxides, alkali (earth)
It is possible to use a catalyst which is usually used for esterification reaction and transesterification reaction of organic acid salts of metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds and the like. The catalyst may be used alone or in combination of two or more kinds. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × 1 with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 0 ^-3 equivalent, more preferably 1 x 10 ^{-7 to} 5 x 10 ^-4 equivalent.

In the reaction by the melt transesterification method, in order to reduce the phenolic terminal group, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenyl carbonate are obtained at the latter stage or after the completion of the polycondensation reaction. Compounds such as phenyl carbonate can be added.

Further, in the melt transesterification method, it is preferable to use a deactivator which neutralizes the activity of the catalyst. The amount of the deactivator is 0.5 to 1 mol of the remaining catalyst.
It is preferably used in a proportion of 50 mol. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm, relative to the polycarbonate after polymerization. Preferable examples of the quenching agent include phosphonium salts such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

The molecular weight of the aromatic polycarbonate is not specified, but if the molecular weight is less than 10,000, the strength and the like will decrease, and if it exceeds 50,000, the moldability will decrease, so it is expressed as a viscosity average molecular weight. Total 10,000
0 to 50,000 is preferable, and 15,000 to 4
50,000 is more preferable, and 2 is more preferable.
It is from 30,000 to 35,000. In this case, it is naturally possible to mix with a polycarbonate having a viscosity average molecular weight outside the above range.

Particularly, a mixture with an aromatic polycarbonate having a viscosity average molecular weight of more than 50,000 has properties derived from its high entropy elasticity (anti-drip property, drawdown property, and property for improving melting property such as jetting improvement). Therefore, when good flame retardancy is required as in the resin composition of the present invention, it can be mentioned as one of the preferred embodiments.

More preferably, the viscosity average molecular weight is 80,0.
A mixture of 00 or more aromatic polycarbonates,
More preferably, it is a mixture with an aromatic polycarbonate having a viscosity average molecular weight of 100,000 or more. That is, those capable of observing a molecular weight distribution of two or more peaks by a measuring method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity average molecular weight in the present invention is calculated by the following formula:
Was obtained from a solution in which 0.7 g of aromatic polycarbonate was dissolved using an Ostwald viscometer. Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of methylene chloride drop, and t is the sample Solution drop seconds] The calculated specific viscosity is inserted by the following equation to obtain a viscosity average molecular weight M
Ask for. η _SP /c=[η]+0.45×[η] ² c (however, [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 was dissolved in 20 to 30 times its weight of methylene chloride, the soluble matter was collected by filtration through Celite, and the solution was removed and sufficiently dried to obtain a solid matter of methylene chloride-soluble matter. obtain. The specific viscosity at 20 ° C. calculated from the above equation from a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride is measured by using an Ostwald viscometer.

The phyllosilicate B component used in the present invention, SiO ₄ tetrahedral sheet structure and A consisting of SiO ₂ chain
A silicate (silicate) or clay mineral (clay) composed of a layer composed of a combination of an octahedral sheet structure containing l, Mg, Li, etc., with exchangeable cations coordinated between the layers.
Is. These are represented by, for example, smectite minerals, vermiculite, halloysite, and swelling mica. Specifically, as smectite minerals,
Montmorillonite, hectorite, fluorohectorite, saponite, beidellite, stevensite, etc.
As the swelling mica, Li-type fluorine teniolite, Na
Type fluorine teniolite, Na type tetrasilicon fluorine mica, Li
Examples include swelling synthetic mica such as type 4 silicon-fluorine mica. These layered silicates may be natural or synthetic. The synthetic product can be obtained by, for example, hydrothermal synthesis, melt synthesis, or solid reaction.

The cation exchange capacity of the layered silicate used in the present invention must be 50 to 200 meq / 100 g, preferably 80 to 150 meq / 100.
g or more, more preferably 100 to 150 meq / l
It is 00 g. The cation exchange capacity is measured as a CEC value by the Scholenberger modified method, which has become an official method in Japan as a soil standard analysis method. The cation exchange capacity of the layered silicate requires a cation exchange capacity of 50 meq / 100 g or more in order to obtain good dispersibility in the aromatic polycarbonate resin, but is larger than 200 meq / 100 g. Then, the influence on the thermal deterioration of the aromatic polycarbonate resin becomes large.

The layered silicate used in the present invention has a p
The value of H is preferably 7 to 10. pH value is 1
If it exceeds 0, the thermal stability of the aromatic polycarbonate resin tends to be deteriorated.

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

In the layered silicate of the component B used in the present invention, the organic onium ions are ion-exchanged between the layers of the layered silicate, so that the layer peeling due to shearing during blending with the aromatic polycarbonate resin is facilitated. , Good dispersion is promoted. Therefore, as the layered silicate of the component B of the present invention, an organic onium salt ion-exchanged between the layers is more preferable.

The organic onium ion is usually handled as a salt with a halogen ion or the like. Examples of the organic onium ion include ammonium ion, phosphonium ion, sulfonium ion, and onium ion derived from a heteroaromatic ring, and the onium ion is 1
Any of the secondary, secondary, tertiary and quaternary can be used, but the quaternary onium ion is preferred. Further, when phosphonium ions are used as onium ions, it is possible to obtain the advantage that the heat deterioration of the aromatic polycarbonate resin is small.
Therefore, an organic phosphonium ion is more preferable as the organic onium ion of the present invention.

As the ionic compound, those to which various organic groups are bound can be used. An alkyl group is typical as the organic group, but it may have an aromatic group, and may also have an ether group, an ester group, a double bond portion, a triple bond portion, a glycidyl group, a carboxylic acid group, an acid anhydride group. It may contain 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 and trimethylhexadecyl. Trimethylalkylammonium such as ammonium, trimethyloctadecylammonium, and trimethylicosanylammonium, trimethylalkenylammonium such as trimethyloctadecenylammonium, trimethylalkadienylammonium such as trimethyloctadecadienylammonium, triethyldodecylammonium, triethyltetraammonium Decyl ammonium, triethyl hexadecyl And triethylalkylammonium such as triethyloctadecylammonium, tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium, tributylalkylammonium such as tributyloctadecylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethylditetradecylammonium , Dimethyldihexadecylammonium, dimethyldioctadecylammonium, etc., dimethyldialkylammonium, dimethyldioctadecenylammonium, etc., dimethyldioctadecadienylammonium, etc., dimethyldialkadienylammonium, diethyldidodecyl Ammonium Diethyldialkylammonium such as diethylditetradecylammonium, diethyldihexadecylammonium, and diethyldioctadecylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, and dibutyldialkylammonium such as dibutyldioctadecylammonium , Methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium, dibenzyldialkylammonium such as dibenzyldihexadecylammonium, trioctylmethylammonium, tridodecylmethylammonium, and trialkylmethylammonium such as tritetradecylmethylammonium, Trioctylethylammonium, and tri Derived from trialkylethylammonium such as dodecylethylammonium, trioctylbutylammonium, trialkylbutylammonium such as tridecylbutylammonium, quaternary ammonium having an aromatic ring such as trimethylbenzylammonium, and aromatic amine such as trimethylphenylammonium Quaternary ammonium, methyldiethyl [PEG] onium. Trialkyl [PAG] ammonium such as methyl diethyl [PPG], dialkyl bis [PAG] ammonium such as methyl dimethyl bis [PEG] ammonium, alkyl tris [PAG] such as ethyl tris [PEG] ammonium.
Examples thereof include ammonium and phosphonium ions in which the nitrogen atom of the above ammonium ion is replaced with a phosphorus atom. It should be noted that these organic onium ions may be used either individually or in combination of two or more. The above "PEG" indicates polyethylene glycol, "PPG" indicates polypropylene glycol, and "PAG" indicates polyalkylene glycol.
The molecular weight of polyalkylene glycol is 100 to 1
The one of 500 can be used.

The molecular weight of these organic onium ion compounds is more preferably 100 to 600. It is more preferably 150 to 500. When the molecular weight is more than 600, there is a tendency that the heat deterioration of the aromatic polycarbonate resin is promoted or the heat resistance of the resin composition is impaired in some cases. The molecular weight of the organic onium ion refers to the molecular weight of a simple organic onium ion that does not contain counter ion components such as halogen ions. Further, using an alkyl group having 10 or less carbon atoms as the alkyl group in the organic onium ion compound structure is also a preferable method for suppressing thermal deterioration of the aromatic polycarbonate resin.

Preferred examples of the organic onium ion include trimethyl-n-octyl ammonium, trimethyl-n-decyl ammonium, trimethyl-n-dodecyl ammonium, trimethyl-n-hexadecyl ammonium, trimethyl-n-octadecyl ammonium,
Methyl tri-n-octyl ammonium, ethyl tri-
n-octyl ammonium, butyl tri-n-octyl ammonium, triphenylmethyl ammonium, trimethyl-n-octyl phosphonium, trimethyl-n-
Decylphosphonium, trimethyl-n-dodecylphosphonium, trimethyl-n-hexadecylphosphonium,
Examples thereof include trimethyl-n-octadecylphosphonium, methyltri-n-octylphosphonium, ethyltri-n-octylphosphonium, butyltri-n-octylphosphonium and triphenylmethylphosphonium.

The ion exchange of the organic onium ion to the layered silicate is carried out by adding the organic onium ion to the layered silicate dispersed in a polar solvent and collecting the deposited ion exchange compound. You can Usually, this ion exchange reaction is performed by adding an organic onium ion compound to the ion exchange capacity of the layered silicate in an amount of 1.0 to 1.
It is general to add 5 equivalents to exchange almost all of the interlayer metal ions with organic onium ions. However, suppressing this exchange ratio to a lower level also suppresses thermal deterioration of the aromatic polycarbonate resin. It is effective in the above. The ratio of ion exchange with the organic onium ion is 40% or more, preferably 40 to 80%, with respect to the ion exchange capacity of the layered silicate. If this exchange ratio is less than 40%, it becomes difficult to synthesize the ion exchange compound.

The exchange rate of the organic onium ion can be calculated by obtaining the weight loss of the compound after exchange by thermolysis of the organic onium ion using a thermogravimetric measuring device.

The polycaprolactone used as the C component in the present invention has a good compatibility with the organic onium salt of the B component, thereby promoting delamination due to shearing during melt-kneading, and at the same time the organic onium ion. It is presumed that the components are preventing the aromatic polycarbonate from attacking. Polycaprolactone is represented by the following repeating unit.

[0050]

[Chemical 1]

Such polycaprolactone can be produced, for example, by ring-opening polymerization of caprolactone in the presence of a catalyst such as an acid, a base or an organometallic compound. The end of polycaprolactone may be subjected to end treatment such as esterification or etherification. The molecular weight of polycaprolactone is not particularly limited, but is 3 in terms of number average molecular weight.
00-40,000 is preferable, 400-30,000
Is more preferable, 400 to 15,000 is further preferable, and 500 to 12,000 is particularly preferable. Molecular weight is 4
When it exceeds 10,000, polycaprolactone may have a low delamination effect on the layered silicate, and in some cases good dispersibility may not be obtained in the aromatic polycarbonate resin.

In the above, the composition ratio of the component B is 0.1 to 140 parts by weight with respect to 100 parts by weight of the component A,
1 to 120 parts by weight is preferable, 2 to 60 parts by weight is more preferable, and 3 to 40 parts by weight is further preferable. If it is less than 0.1 parts by weight, the effect of improving rigidity cannot be obtained, and if it exceeds 120 parts by weight, the aromatic polycarbonate is significantly deteriorated, which is not preferable. Further, the proportion of the net layered silicate is preferably 0.05 to 100 parts by weight, more preferably 0.5 to 70 parts by weight, and further preferably 1 to 35 parts by weight, relative to 100 parts by weight of the component A. The net amount of layered silicate in the composition can be calculated by thermally decomposing the resin component and the like of the resin composition using a thermogravimetric analyzer (TGA), and determining the weight reduction (others. If used in combination with inorganic filler, etc., subtract that amount).

The composition ratio of the component C is 0.1 to 70 parts by weight, preferably 1 to 50 parts by weight, more preferably 1 to 40 parts by weight, and 1 to 20 parts by weight with respect to 100 parts by weight of the component A. Is more preferable and 1 to 15 parts by weight is particularly preferable.
If it is less than 0.1 part by weight, the effect of improving rigidity cannot be obtained. 70
If it exceeds the amount by weight, the heat resistance of the aromatic polycarbonate is lowered and the practicality is lowered.

Further, the weight ratio of the B component to the C component (weight of the B component / weight of the C component) is preferably 0.2 to 10, more preferably 0.5 to 5, and further preferably 1 to 3. Further, the weight ratio of the net layered silicate in the component B to the component C is preferably 0.1 to 8, more preferably 0.3 to 3, and even more preferably 0.5 to 2. Therefore, it is preferable that the higher the proportion of the layered silicate of the component B, the more the content of the polycaprolactone of the component C. However, in such a case, it is preferable from the viewpoint of strength that the molecular weight of the polycaprolactone is relatively high. Is. On the other hand, in order to disperse the layered silicate, it is preferable that the molecular weight of polycaprolactone is relatively low. Therefore, when the layered silicate is relatively small, the molecular weight of polycaprolactone is preferably low, and when the layered silicate is relatively large, the molecular weight of polycaprolactone is preferably high. In the present invention, a preferable relationship between the two is represented by the following formula.

0.036x + 2.7 ≦ log (Mp) ≦
0.036x + 3.2 (where x represents the amount (% by weight) of the net layered silicate in the component B in 100% by weight of the resin composition, and Mp represents the number average molecular weight of polycaprolactone) Examples of the aromatic polycarbonate resin composition include a phosphoric acid ester such as trimethyl phosphate, triphenyl phosphite, trisnonyl phenyl phosphite, distearyl pentaerythritol diphosphite, and bis (2,6-
Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tris (2,4-di-t
ert-Butylphenyl) phosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, and bis (2,4-di-ter).
t-Butylphenyl) pentaerythritol diphosphite and other phosphites, tetrakis (2,4-di-)
A phosphonous ester such as tert-butylphenyl) -4,4′-biphenylenediphosphonite may be contained in an amount of 0.001 to 1% by weight based on the total composition. Since this further improves the thermal stability, it is preferable to include the above-mentioned various phosphorus compounds in the predetermined amounts.

Further, to the extent that the object of the present invention is not impaired,
Other thermoplastic resin (for example, polyamide, polyacetal, modified polyphenylene ether, other styrene resin such as ABS resin, acrylic resin, polyolefin resin, polyphenylene sulfide, etc.), flame retardant (for example, brominated epoxy resin, bromine) Polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonamide compound, etc.), flame retardant aid (eg sodium antimonate, antimony trioxide) etc),
Anti-dripping agent (polytetrafluoroethylene having fibril forming ability), nucleating agent (eg sodium stearate, ethylene-sodium acrylate), antioxidant (eg hindered phenol compound), impact You may mix | blend a improver, a ultraviolet absorber, a light stabilizer, a mold release agent, a lubricant, a coloring agent, etc.

Further, in the present invention, various commonly known fillers such as glass fiber, carbon fiber, glass flake, wollastonite, kaolin clay, mica, and talc can be used in combination depending on the purpose of use. Glass fibers, carbon fibers, glass flakes and the like are suitable for improving the strength and impact resistance of the resin composition. The shape of the filler can be freely selected from fibrous, flake, spherical and hollow shapes.

Any method may be used to produce the aromatic polycarbonate resin composition of the present invention. For example, a method of pre-mixing each component, and optionally other components, then melt-kneading and pelletizing can be mentioned. Examples of the premixing means include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer. In the pre-mixing, granulation may be carried out by an extrusion granulator or a briquetting machine, depending on the case. After premixing, the mixture is melt-kneaded by a melt-kneader typified by a vented 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 constant temperature stirring container, but a vented twin-screw extruder is preferable.

Further, in the melt-kneading of the aromatic polycarbonate resin composition of the present invention with a melt-kneading machine, the layered silicate of the component B and the polycaprolactone of the component C are melt-kneaded in advance, and then the melt-kneaded product. Melt kneading with the aromatic polycarbonate as the component A is particularly preferable because the decrease in the molecular weight of the aromatic polycarbonate is suppressed.
Specifically, for example, (i) B component and C component are melt-kneaded by a vent type twin-screw extruder and pelletized, and then melt-kneaded with A component again, or (ii) B component and C component. The components were charged from the main feed port of the vent type twin-screw extruder, and part or all of the component A was already melt-kneaded from the feed port provided in the middle stage of the twin-screw extruder. The method of throwing into a state is mentioned.

Therefore, according to the present invention, 50 to 200 milliequivalents / 1 per 100 parts by weight of polycaprolactone.
Provided is a resin additive having a cation exchange capacity of 00 g and obtained by melt-kneading 1 to 200 parts by weight of a layered silicate in which organic onium ions are ion-exchanged between layers. A preferred embodiment of such layered silicate is the same as the component B of the present invention. Therefore, the cation exchange capacity is preferably 80 to 1
50 meq / 100 g, more preferably 100-1
It is 50 meq / 100 g, and as the organic onium ion, phosphonium ion is particularly preferable. Further, the preferred embodiment of polycaprolactone is also the same as the component C of the present invention. In such an additive for resins, the proportion of polycaprolactone and layered silicate is 50 to 200 meq / 100 with respect to 100 parts by weight of polycaprolactone.
The layered silicate having a cation exchange capacity of g and having an organic onium ion ion-exchanged between layers is more preferably 5 to 80 parts by weight, further preferably 10 to 70 parts by weight. Further, such resin additives can be applied to various thermoplastic resins, but are particularly suitable for aromatic polycarbonate resins. The ratio is 100 aromatic polycarbonate resin.
It is preferable to add 1 to 100 parts by weight of such a resin additive per part by weight to form a resin composition containing the components A, B and C of the present invention.

[0061]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples. The present invention is not limited to this. The evaluation was performed by the following methods (1) to (6).

(1) Melt-kneading of B component and C component "Method 1", in which A component, B component and C component are premixed without melt kneading and then melt kneaded by an extruder, B component and C component The case where the components were kneaded in advance was described as "method 2". In addition, after kneading the two components, after dry blending the B component and the C component, if the C component is C-1 to C-2, after heating and stirring for one day in a stirring constant temperature bath maintained at a temperature of 150 ° C. It was left to cool, pulverized and used. When the C component was C-3, the mixture was heated and stirred for a whole day and night in a stirrable constant temperature bath kept at a temperature of 200 ° C., and then allowed to cool and used.

(2) An injection molding machine (TOSHIBA MACHINE: IS-150EN) was used to test the layered silicate content test piece.
Cylinder temperature is 260 ° C, mold temperature is 80 ° C, molding cycle is 40 seconds, the molded test piece is cut, put into a crucible and weighed.
After holding for a while, the mixture was allowed to cool, and the ash residue remaining in the crucible was weighed to measure the layered silicate content.

(3) Molecular weight A test piece was molded under the same conditions as in (2), and the viscosity average molecular weight of the test piece was measured by the method described in the text.

(4) Impact Value An impact test piece having a thickness of 3.2 mm was molded under the same conditions as in (2) and measured by the method according to ASTM-D256.

(5) Bending elastic modulus Bending test pieces were molded under the same conditions as in (1), and were subjected to ASTM-D.
It was measured by a method according to 790.

(6) Appearance evaluation A flat plate having a thickness of 2 mm was molded under the same conditions as in (1), and the surface appearance of the molded product was visually evaluated. When the silicate aggregates were not seen at all and the surface gloss was excellent, it was ○, when a little silicate aggregates were observed, and when the surface gloss was slightly inferior, silicate aggregates were found and the surface gloss was observed. When inferior, it was evaluated as x.

[Examples 1 to 13 and Comparative Examples 1 to 5] The components shown in Table 2 were dry blended at the blending ratio shown in Table 2, and then
Using a twin-screw extruder with a vent [Kobe Steel Co., Ltd .: KTX30] equipped with a screw having a diameter of 30 mmφ, L / D = 33.2 and two kneading zones, a cylinder temperature of 26
The mixture was melt-kneaded at 0 ° C., extruded, and strand-cut to obtain pellets, and the obtained pellets were dried at 100 ° C. for 5 hours by a hot air circulation dryer. After drying, a test piece for evaluation was prepared by an injection molding machine as described above.

The symbols showing the components shown in Table 2 are as follows. (Component A) A: Aromatic polycarbonate resin having a viscosity average molecular weight of 23,700 (manufactured by Teijin Chemicals; Panlite L-1250) (Component B) The details of the component B are shown in Table 1. Show. The cation exchange capacity of the layered silicate is a value measured by the Scholenberger method shown in the text. Ion exchange of organic onium ions into these layered silicates was performed by the following method.

[Method for producing intercalation compound] Layered silicate about 1
00 g was precisely weighed and stirred and dispersed in 10 liters of water at room temperature. Onium ion bromide was added thereto in various equivalent amounts, and the mixture was stirred for 6 hours. The precipitated solid formed was filtered off, washed with stirring in 30 liters of demineralized water, and then filtered off again. The washing and filtering operations were repeated 3 times. The obtained solid was air-dried for 3 to 7 days, then crushed in a mortar, and then dried in warm air at 50 ° C. for 3 to 10 hours (depending on the type of guest onium ion), and again the maximum particle size was 100 μm in the mortar.
It was crushed to a certain extent. The amount of residual water evaluated by thermogravimetric reduction when kept at 120 ° C. for 1 hour under a nitrogen stream by such warm air drying was set to 2 to 3% by weight. The ion exchange ratio of the onium ion was determined by measuring the weight fraction of the residue of the ion-exchanged layered silicate when it was held at 500 ° C. for 3 hours under a nitrogen stream.

[0071]

[Table 1]

(Component C) C-1: Polycaprolactone having a number average molecular weight of 1,250 (manufactured by Daicel Chemical Industries; Praxel PCL212) C-2: polycaprolactone having a number average molecular weight of 4,000 (manufactured by Daicel Chemical Industries; Praxel PCL240) ) C-3: Polycaprolactone having a number average molecular weight of 10,000 (manufactured by Daicel Chemical Industries; Praxel H1P) C-4: Nylon 6 (manufactured by Ube Industries; Ube Nylon 101)
5B) C-5: Polycaprolactone having a number average molecular weight of 70,000 (manufactured by Daicel Chemical Industries; Praxel H7) Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP) was used as another component depending on the sample.

[0073]

[Table 2]

As is clear from Table 2, from Examples 1 to 13, the layered silicate obtained by ion-exchange of the organic onium ion as the component B between the layers and the polycaprolactone as the component C were added in a specific range. By doing so, it can be seen that the composition has excellent thermal stability since it exhibits a high rigidity and a good impact value. Further, it can be seen that the melt-kneading of the B component and the C component in advance shows a higher level of rigidity and thermal stability.

[0075]

INDUSTRIAL APPLICABILITY The aromatic polycarbonate resin composition of the present invention has high rigidity and thermal stability, and is useful in a wide range of applications such as OA equipment parts such as covers and housings, automobile parts, etc. Effects are exceptional.

Continued front page    F-term (reference) 4F070 AA47 AA50 AC22 AD06 AE01                       FA03 FA13 FA17 FC06                 4J002 CF192 CG001 DJ006 FB086                       FD016 GN00 GQ00

Claims (6)

[Claims] 1. Aromatic polycarbonate (component A) 10
Layered silicate (component B) 0.1 having 0 parts by weight, a cation exchange capacity of 50 to 200 meq / 100 g, and an organic onium ion ion-exchanged at a ratio of 40% or more of the exchange capacity. An aromatic polycarbonate resin composition consisting of ˜140 parts by weight and 0.1 to 70 parts by weight of polycaprolactone (component C). 2. The C component has a number average molecular weight of 30.
The aromatic polycarbonate resin composition according to claim 1, which is 0 to 40,000. 3. The resin composition according to claim 1, wherein the molecular weight of the organic onium ion in the component B is 100 to 600. 4. The resin composition according to claim 1, wherein the organic onium ion in the component B is an organic phosphonium ion. 5. The resin composition according to claim 1, wherein the component B and the component C are melt-kneaded in advance and then the component A is melt-kneaded.
The aromatic polycarbonate resin composition according to any one of items 1 to 4. 6. Melting 1 to 200 parts by weight of a layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g with respect to 100 parts by weight of polycaprolactone, and organic onium ions being ion-exchanged between layers. Kneaded resin additive.