JP3438345B2 - Aromatic polyester composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polyester composition comprising an aromatic polyester and an intercalation compound having a layered silicate as a host and a quaternary ammonium ion as a guest.

[0002]

2. Description of the Related Art Conventionally, various fillers, for example, inorganic fibers such as glass fibers and carbon fibers, glass flakes, glass beads, mica and other inorganic powders have been compounded for the purpose of enhancing the strength and rigidity of aromatic polyester resins. Has been done. However, although these methods increase strength and rigidity, they have various drawbacks such as markedly impairing toughness, increasing specific gravity, and decreasing surface appearance. On the other hand, when a layered compound such as mica is used as a filler for aromatic polyester, it is known that the gas barrier property is improved in the film and the fiber has far-infrared radiation characteristics. ing. However, in general, an aromatic polyester mixed with mica has a decrease in smoothness and a decrease in toughness due to an increase in foreign matter in a film, a decrease in stability of a molten strand in a fiber-forming process in a fiber, a fluff, a decrease in toughness, etc. Had a drawback.

Disadvantages in mixing fillers with such aromatic polyesters are generally poor dispersion of the fillers or the size of the dispersed fillers, and the interface between the aromatic polyester matrix and the filler. It is thought that this is due to poor adhesion, and various measures have been made from this point of view. JP-A-64
JP-A-85119 describes mixing a polymer capable of forming an anisotropic melt, for example, a liquid crystalline aromatic polyester such as a copolymer of p-hydroxybenzoic acid and polyethylene terephthalate with a powdery filler such as talc. In this case, it is disclosed that the dispersion is facilitated by previously mixing the filler which is separably hardened with a binder such as an epoxy binder and is granulated, but it is possible to avoid the formation of aggregates having a diameter of about 1 mm. Is effective, but it is not always effective for dispersion of a unit layer of a filler having a layered structure, that is, a thin layer of several nanometers.

Japanese Patent Laid-Open No. 3-760 and Japanese Patent Laid-Open No. 3-4
No. 1149 discloses a polyester composition in which mica is dispersed in a polyester in the form of scale-like particles having a maximum length of 20 μm and a thickness of 0.01 to 1 μm, and such a polyester composition is added to a polycondensation reaction system. There is disclosed a method for producing by adding. In addition, JP-A-3-411
In Japanese Patent Publication No. 49, in addition to mica, polyethylene glycol,
A method is disclosed in which a dispersant such as an organic sulfonate, potassium metaphosphate, and dipotassium hydrogenphosphate is added together. However, although the mica dispersibility is improved to some extent by such a method, the thickness of the layered structure is 0.05 to 0.
It was not always satisfactory in terms of uniform dispersion at the unit layer level of about 1 μm.

JP-A-3-62846 discloses that a layered clay mineral containing a thermoplastic aromatic polyester, an organic onium ion-bonded layered clay mineral, and a compatibilizer is bound with an organic onium ion. Disclosed is a polyester composite material having a structure uniformly dispersed in a thermoplastic aromatic polyester and having a structure bridged by a molecular chain of the thermoplastic aromatic polyester, and a method for producing the same, by an affinity action of an agent. Although the tensile modulus and heat distortion temperature are improved and the water absorption rate is decreased under the specified conditions in boiling water, addition of a compatibilizer or the point of preventing the decrease in toughness, which is a general drawback of filler reinforced systems It was not satisfactory in terms of improving the balance between rigidity and toughness.

[0006]

An object of the present invention is to provide an aromatic polyester composition having excellent strength and rigidity, a good balance between rigidity and toughness, especially ductility, and a small increase in specific gravity and an excellent appearance on the molded surface. To provide.

[0007]

The present invention has been made to solve the above 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 quaternary class. The aromatic polyester composition is characterized by containing an interlayer compound containing ammonium ions as a guest in an amount of 0.5 to 10% by weight as an inorganic ash content.

The present invention will be described in detail below. The aromatic polyester used in the present invention is a polyester having an aromatic ring in the molecular chain obtained by a condensation reaction of a dicarboxylic acid or its ester-forming derivative with a diol or its ester-forming derivative. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4'-dicarboxybiphenyl, and aromatic compounds such as the dicarboxylic acid represented by the formula (1). Group dicarboxylic acids, succinic acid, adipic acid, sebacic acid, 1,3-
Examples thereof include aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof, alone or in a mixture.

[0009]

[Chemical 1]

[In the formula (1), Z is an alkylene (C ₁ -C
_4), alkylidene _{(C 1 ~C 4), -} O -, - S-,
It is a group selected from —SO—, —SO ₂ — and —CO—. As the diol component, ethylene glycol, propylene glycol, 1,4-butanediol, 1,2-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol Aliphatic diol such as cyclohexanediol, etc., molecular weight 400-6,
000 long-chain glycols and the like, alone or in a mixture.

Examples of the aromatic polyesters include poly (ethylene terephthalate), poly (butylene terephthalate), poly (propylene terephthalate), poly (hexamethylene terephthalate), poly (cyclohexane dimethylene terephthalate) and other polyalkylene terephthalates, poly (ethylene terephthalate / ethylene isophthalate) copolymers,
Polyalkylene phthalate such as poly (butylene terephthalate / butylene isophthalate) copolymer, polyethylene naphthalate, polyalkylene naphthalate such as polybutylene naphthalate, aliphatic such as poly (butylene terephthalate / butylene dodecadioate) copolymer Examples thereof include polyalkylene terephthalate containing dicarboxylic acid. Among these, polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate and polycyclohexane dimethylene terephthalate are preferable, and polyethylene terephthalate and polybutylene terephthalate are most preferably used.

The molecular weight of the aromatic polyester used in the present invention is not particularly limited, but it is preferable to use a mixed solvent of phenol and tetrachloroethane in a weight ratio of 1: 1 and to measure the concentration at 30 g at a concentration of 1 g / dl. Intrinsic viscosity [η]
Is in the range of 0.5 to 3.0. When the intrinsic viscosity is lower than this range, the toughness is extremely lowered, and when the intrinsic viscosity is higher than this range, the melt viscosity is too large and problems in molding are likely to occur, which is not preferable.

The intercalation compound in the present invention is an intercalation compound having a layered silicate as a host and a quaternary ammonium salt as a guest. Here, the host means a compound composed of a molecule or an ion forming a basic skeleton, and the guest means a compound composed of a molecule or an ion incorporated therein by interaction with the host. An intercalation compound in which a quaternary ammonium ion is inserted (intercalated) in a layered silicate having a cation exchange capacity of 30 meq / 100 g or more has an extremely excellent cleavage dispersibility with respect to an aromatic polyester, and is an aromatic polyester. By containing 0.5 to 10% by weight of the inorganic ash content in the composition, an aromatic polyester composition having not only excellent rigidity but also a good balance between rigidity and ductility is provided.

The layered silicate used in the present invention includes:
Two octahedral sheet structures containing Al, Mg, Li, etc.
A 2: 1 type in which the tetrahedral sheet structure of iO ₄ is sandwiched is preferable, and specifically, montmorillonite, hectorite, fluorohectorite, saponite, beidellite,
Smectite clay minerals such as stevensite, Li-type fluorine teniolite, Na-type fluorine teniolite, swelling synthetic mica such as Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, vermiculite, fluorine vermiculite, halloysite, etc. It may be a synthetic one or a synthetic one.

Of these, swelling synthetic mica such as smectite clay minerals such as montmorillonite and hectorite, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica and the like are preferable, and Li type fluorine teniolite and Na type fluorine are particularly preferable. Swelling fluoromica such as teniolite and Na-type tetrasilicon mica are preferred. Li-type fluorine teniolite corresponds to the composition of the following formula (2), Na-type fluorine teniolite corresponds to the composition of the following formula (3), and Na-type tetrasilicon mica corresponds to the composition of the following formula (4). 3) and (4) show ideal compositions, and do not need to be in exact agreement.

[0016]

[Chemical 2]

A specific example of the swelling fluoromica is a swelling synthetic mica (trade name: ME1 manufactured by Corp Chemical Co., Ltd.).
00). In the present invention, the cation exchange capacity (CEC) of these layered silicates is usually 30 meq / 100 g or more, more preferably 50 meq / 100 g or more, and most preferably 70 meq / 10.
It is 0 g or more. The cation exchange capacity can be determined by measuring the adsorption amount of methylene blue. If the cation exchange capacity is less than 30 meq / 100 g, the intercalation amount of the quaternary ammonium ion between the planar macromolecular layers forming the layered silicate will be insufficient, and the intercalation compound to the aromatic polyester will be obtained. As a result, the strength and rigidity of the aromatic polyester composition are not sufficient and the appearance of the molded surface is also poor. Moreover, the cation exchange capacity of the layered silicate is 200 meq / 100 g from the viewpoint of cleavage.
The following is preferable.

The quaternary ammonium ion used in the present invention is usually treated as a salt with a halide ion. Specific examples of the quaternary ammonium ion include tetraethylammonium, quaternary ammonium having the same alkyl group such as tetrabutylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium, Triethyl alkyl ammonium such as trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecadienyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, triethyl octadecyl ammonium and other triethyl alkyl Ammonium, tri Chill dodecyl ammonium,
Tributylalkylammonium such as tributyltetradecylammonium, tributylhexadecylammonium, tributyloctadecylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethylditetradecylammonium, dimethyldihexadecylammonium, dimethyldioctadecylammonium, dimethyldioctadecem Nilammonium,
Dimethyldialkylammonium such as dimethyldioctadecadienylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, diethyldialkylammonium such as diethyldioctadecylammonium,
Dibutyldialkylammonium such as dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium, dibenzyl such as dibenzyldihexadecylammonium Trialkylmethylammonium such as dialkylammonium, trioctylmethylammonium, tridodecylmethylammonium, tritetradecylmethylammonium, trialkylethylammonium such as trioctylethylammonium, tridodecylethylammonium, trioctylbutylammonium, tridecylbutylammonium Trialkylbutylammonium such as monium, trimethyl Quaternary ammonium having an aromatic ring such as emissions Jill ammonium, quaternary ammonium derived from an aromatic amine such as trimethylphenyl ammonium, dialkyl bis [PEG] ammonium represented by the following formula (5)

[0019]

[Chemical 3]

(However, in the formula (5), R ¹ and R ² independently represent an alkyl group having 18 or less carbon atoms, and are integers such that m, n> 1. Also, 2 <m + n <60, preferably 10 ≤m
+ N ≦ 30, [PEG] represents a polyethylene glycol chain, and so on. ) Specific examples of the dialkylbis (PEG) ammonium represented by the formula (5) include dimethylbis [PEG] ammonium, diethylbis [PEG] ammonium and dibutylbis [PEG] ammonium.
Having a heteroaromatic ring such as ammonium, methylethylbis [PEG] ammonium, methyldodecylbis [PEG] ammonium, methyloctadecylbis [PEG] ammonium, etc., having a polyethylene glycol chain, quaternary ammonium, methylpyridinium, methylquinolinium, etc. Examples include ions such as onium. Among them, trimethyldodecyl ammonium, trimethyl tetradecyl ammonium, trimethyl hexadecyl ammonium, trimethyl octadecyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium,
Ion of quaternary ammonium having one alkyl group having 12 to 30 carbon atoms in one molecule such as triethylhexadecylammonium and triethyloctadecylammonium, dimethyldidodecylammonium, dimethylditetradecylammonium, dimethyldihexadecylammonium, Dimethyldioctadecyl ammonium, diethyl didodecyl ammonium, diethyl ditetradecyl ammonium, diethyl dihexadecyl ammonium,
Quaternary ammonium having two alkyl groups having 12 or more and 30 or less carbon atoms in one molecule such as diethyldioctadecyl ammonium, dimethylbis [PEG] ammonium, methylethylbis [PEG] ammonium, methyldodecylbis [PEG] ammonium, Ions such as quaternary ammonium having a polyethylene glycol chain such as methyloctadecylbis [PEG] ammonium are preferable from the viewpoint of maintaining the toughness of the aromatic polyester composition, and more preferably carbon numbers such as trimethylhexadecylammonium and trimethyloctadecylammonium. 14 carbon atoms such as quaternary ammonium having one or more alkyl groups of 16 or more in one molecule, dimethylditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl dioctadecyl ammonium Quaternary ammonium having two upper 25 an alkyl group in the molecule, dimethyl bis [PE
G] ammonium, an ion such as quaternary ammonium having a polyethylene glycol chain such as methyldodecylbis [PEG] ammonium, most preferably trimethyloctadecylammonium ion, dimethyldihexadecylammonium ion, dimethyldioctadecylammonium ion, methyldodecyl. Bis [PEG] ammonium ion. These quaternary ammonium ions can be used alone or as a mixture of plural kinds.

In the present invention, the cation exchange capacity is 30.
The intercalation compound having a layered silicate (milli-equivalent / 100 g or more) as a host and a quaternary ammonium ion as a guest is a known technique for reacting an organic onium ion with a clay containing a negative layer lattice and an exchangeable cation (for example, a special technique). It can be produced according to JP-A-61-2492, JP-A-60-42451, etc.). The insertion of the quaternary ammonium ion between the layers of the layered silicate is carried out using a polar solvent, preferably water, methanol, ethanol, propanol,
It depends on an ion exchange reaction which proceeds in a protic solvent such as butanol and a mixed solvent of two or more kinds of these. Preferred solvents for producing the intercalation compound of the present invention are water, methanol and ethanol, but water is most suitable unless the solubility of the quaternary ammonium salt is extremely low.

The quaternary ammonium ion is usually reacted in an amount of 1 to 3 equivalents, preferably 1.0 to 1.5 equivalents, relative to the cation exchange capacity of the layered silicate. Reaction yield (insertion rate)
Varies slightly depending on the solubility of the quaternary ammonium ion in the solvent and the reaction temperature. The amount of the quaternary ammonium ion in the generated intercalation compound is not particularly limited as long as it is in the range of 0.8 to 2.0 equivalents with respect to the cation exchange capacity of the layered silicate as a raw material, but under normal reaction conditions. It becomes 1.0 to 1.3 equivalents. When this amount is less than 0.8 equivalent, dispersibility in the aromatic polyester is lowered, and when it is more than 2.0 equivalent, a free compound derived from a quaternary ammonium ion becomes prominent, and thermal stability at the time of molding is lowered, May cause smoke, mold contamination, odor, etc.

After the intercalation reaction of the quaternary ammonium ion, the generated intercalation compound is subjected to a stirring washing step in a solvent and a separation step such as centrifugation or filtration in order to remove excess ions remaining other than between the layers. Purification is carried out by an appropriate method such as batch washing or continuous washing in which a solvent is continuously flown for washing. The degree of purification can be confirmed, for example, when a quaternary ammonium halide is used as a raw material, an aqueous silver nitrate solution is added to the washing solution, and white silver halide is not produced. If this purification is insufficient, the thermal stability at the time of molding is lowered by the free compound derived from quaternary ammonium ion,
May cause smoke, mold contamination, odor, etc. The amount of water after purification of the intercalation compound is set to 1 in order to reduce undesired side reactions such as hydrolysis during mixing with the aromatic polyester.
It is controlled to 0 wt% or less, preferably 5 wt% or less, and more preferably 3 wt% or less. When the water content exceeds 10 wt%, the molecular weight of the aromatic polyester is significantly reduced due to the hydrolysis of the aromatic polyester, and the toughness of the aromatic polyester composition is significantly reduced.

The intercalation compound used in the present invention has a maximum particle size after purification of 500 μm or less, preferably 100 μm or less, more preferably 50 μm or less, and most preferably 10 μm or less.
It is desirable to grind the particles to have a particle size of less than μm so that they can be applied to a wide range of dispersion methods having different shearing efficiencies. In the aromatic polyester composition of the present invention, the amount of the inorganic compound in the interlayer compound is usually 0.5 to 10% by weight, preferably 0.7 to 5% by weight, more preferably 1 to 5% by weight, based on the aromatic polyester composition. 3% by weight is contained. The amount of inorganic ash is 650 as compared with the organic component of the aromatic polyester composition.
It can be determined from the weight fraction of the residue completely burned out in an electric furnace at ℃. If the amount of the inorganic ash is less than 0.5% by weight, the elastic modulus is not significantly improved, while if it exceeds 10% by weight, the deterioration of the matrix aromatic polyester is promoted by the influence of the quaternary ammonium ion component in the intercalation compound. It is not preferable because it has drawbacks such as a problem in molding. The intercalation compounds may be used alone or in combination. The compounding amount of the intercalation compound is 0.5 to 40 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the aromatic polyester.
Parts by weight.

In the present invention, the method for mixing the intercalation compound and the aromatic polyester is not particularly limited, but the mixing method is preferably carried out in a molten state of the aromatic polyester under mechanical shearing. . For example, a method of stirring and mixing with the melt polymerization of the aromatic polyester after addition to the aromatic polyester raw material before polymerization, a method of stirring and mixing during the melt polymerization of the aromatic polyester or after the melt polymerization before chip formation, or after chip formation. Although it can be mixed by any method such as a method of adding it to the aromatic polyester 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 polyester composition of the present invention comprises:
As long as the purpose of the present invention is not impaired, various conventionally used additive components, for example, glass fibers, inorganic fibers such as carbon fibers, glass flakes, glass beads, inorganic powders such as mica, various plasticizers, stabilizers, coloring Agents and flame retardants can be added. Further, in the aromatic polyester composition of the present invention, a thermoplastic resin or a thermoplastic elastomer, such as a polyamide resin or an aromatic polycarbonate resin, which is blended with a usual aromatic polyester as required unless the object of the present invention is impaired. , ABS resin, polyphenylene ether resin, polyarylene sulfide resin, epoxy resin, phenoxy resin, maleic anhydride modified polyolefin resin, polyolefin resin modified with an epoxy group-containing compound, polyester elastomer, modified with an epoxy group-containing compound Styrenic thermoplastic elastomer, acrylic rubber, core-shell type acrylic rubber, etc. may be added.

[0027]

EXAMPLES The present invention will be described in more detail with reference to examples 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. Yield strength (abbreviated as YS, unit kg / cm ² ) and elongation at break (U
Abbreviated as E, unit%) was measured.

[Bending Test] According to ASTM D-790. The yield strength (abbreviated as FS, unit kg / cm ² ) and flexural modulus (abbreviated as FM, unit kg / cm ² ) were measured. [Oxygen Permeation Rate] Oxygen Permeation Tester O manufactured by MOCON, USA
23 ° C, relative humidity 90 by X-TRAN10 / 50H
% Was measured. For the measurement, a film with a thickness of about 100 μm was formed by hot press molding, and the result was 25 μm.
It was expressed as the amount of oxygen permeated per 1 m ² and 24 hours when converted per thickness. [Observation of Surface Appearance] The surface smoothness of the injection molded product and the pressed film were compared by visual evaluation. [Inorganic ash content of composition] About 1.5 g of a molded piece of the composition was precisely weighed and determined from the weight fraction of the residue after the organic matter was completely burned in an electric furnace at 650 ° C.

[Layered silicate used] Table 1 shows the names, mineral names and types of the layered silicates used, the cation exchange capacity (abbreviated as CEC) measured by the methylene blue adsorption method, and the manufacturers.

[0031]

[Table 1] 1) Milli-equivalent / 100g

[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, 1.4 times equivalent of ammonium ion hydrochloride of CEC of the layered silicate was added and stirred for 6 hours. The purified sedimentable solid was filtered off, then washed with stirring in 30 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
After air-drying for 7 days, it was crushed in a mortar and further dried with warm air at 50 ° C. for 3-10 hours, and then crushed again in the mortar. Drying conditions vary depending on the type of guest's ammonium ion, but the residual water content evaluated by securing pulverizability with a maximum particle size of about 100 μm and thermogravimetric reduction when kept at 120 ° C. for 1 hour under a nitrogen stream is shown. The index was set to be 2 to 3 wt%.
Regarding the blending amount of the intercalation compound, first, the ash content in the intercalation compound was measured for the weight fraction of the residue when kept at 500 ° C. for 3 hours under a nitrogen stream, and based on this value, the ash content in the composition The (theoretical ash content) was adjusted to a predetermined value.

Examples 1 to 5 Chips of polybutylene terephthalate (Novadwool 5020, manufactured by Mitsubishi Kasei Co., Ltd., Novadwool is a registered trademark [η] = 1.2) and the intercalation compounds shown in Table 2 are theoretical ash. Blended so that the amount is 2 wt%, and using a twin-screw extruder TEM35B manufactured by Toshiba Machine Co., Ltd., the barrel temperature is set to 250 ° C. and the screw rotation speed is set to 150.
Melt kneading was performed under the conditions of rpm to form chips. The obtained chips were subjected to injection molding machine J28SA manufactured by Japan Steel Works, Ltd. with a barrel temperature of 260 ° C. and a mold surface measurement temperature of 82 to 84.
C., injection / cooling = 15/15 seconds, molding was performed under the conditions of maximum injection speed, and a tensile test, a bending test, and a surface appearance observation were performed for evaluation. Also, the amount of inorganic ash of the composition was determined.

Example 6 In Example 1, an intercalation compound obtained from ME100 and methyldodecylbis [PEG] ammonium chloride (see footnote ^{1 in} Table 2) chloride was used, and the theoretical ash content was 1.6 wt%. The same procedure as in Example 1 was carried out except that [Example 7] In Example 4, the theoretical ash content was 0.7 w.
The same procedure as in Example 4 was performed except that t% was set. [Example 8] In Example 1, the theoretical ash content was 5 wt%.
The same procedure as in Example 1 was carried out except that

Comparative Example 1 The procedure of Example 1 was repeated except that ME100 was used instead of the intercalation compound. [Comparative Example 2] The same procedure as in Example 1 was repeated except that Osmos N was used instead of the intercalation compound in Example 5. [Comparative Example 3] In Example 5, the theoretical ash content was set to 0.05.
The same procedure as in Example 5 was performed except that the content was changed to wt%.

[Comparative Example 4] The procedure of Example 5 was repeated except that the theoretical ash content was changed to 11 wt%. [Comparative Example 5] The same procedure as in Example 1 was carried out except that an interlayer compound obtained from dimonite and trimethyloctadecyl ammonium chloride was used.

Comparative Example 6 The procedure of Example 1 was repeated except that 5 wt% of A-61 was used instead of 2 wt% of the intercalation compound. [Comparative Example 7] The same procedure as in Example 1 was repeated except that Kunipia F and 12-aminododecanoic acid hydrochloride were used as the intercalation compound and the theoretical ash content was 1.6 wt%. It was

[Comparative Example 8] In Example 1, a compound obtained from Kunipia F and 12-aminododecanoic acid hydrochloride was used as the intercalation compound, the theoretical ash content was set to 1.6 wt%, and at the same time, 3-glycidyloxypropyl was used. The same procedure as in Example 1 was carried out except that 0.025 wt% of trimethoxysilane (manufactured by Nippon Unicar Co., Ltd., silane coupling agent A-187) was added.

[Comparative Example 9] In Example 1, a compound obtained from Kunipia F and 12-aminododecanoic acid hydrochloride was used as the intercalation compound, the theoretical ash content was set to 1.6 wt%, and at the same time, polycaprolactone (Daicel chemistry) was used. (stock)
The same procedure as in Example 1 was carried out except that 2.5 wt% of Praxel H1P, Praxel was a registered trademark, and the molecular weight was 10,000).

[Comparative Example 10] The same procedure as in Example 5 was repeated except that stearylamine was used as the ammonium ion in the interlayer compound. [Comparative Example 11] The procedure of Example 5 was repeated except that aniline hydrochloride was used as the ammonium ion of the interlayer compound. [Comparative Example 12] The procedure of Example 1 was repeated except that the intercalation compound was not added.

[0041]

[Table 2]

[0042]

[Table 3]

1) [PEG] means a polyethylene glycol chain. Total number of (CH ₂ CH ₂ O) units is 1
It was about 15 in the molecule. 2) Silane coupling agent manufactured by Nippon Unicar Co., Ltd .: 3
-Glycidyloxypropyltrimethoxysilane. 3) PLACCEL-H1P (molecular weight 10,000) manufactured by Daicel Chemical Industries, Ltd.

Example 9 In Example 6, polyethylene terephthalate (RT543, manufactured by Nippon Unipet Co., Ltd. [η] =
0.8) is used, the theoretical ash content is 3 wt% instead of 1.6 wt%, and the barrel temperature setting of the twin-screw extruder is 280.
Melt kneading was performed in the same manner as in Example 6 except that the temperature was changed to 0 ° C. to obtain chips of the composition. The oxygen transmission rate of this composition is 28
It measured with the press film molded at 0 degreeC, and the external appearance of the press film was also observed. Also, using an injection molding machine J28SA manufactured by Toshiba Machine Co., Ltd., a barrel temperature of 280 ° C., a mold surface measured temperature of 28 to 32 ° C., injection / cooling = 10/20.
Second, a tensile test piece was molded under the condition of maximum injection speed and a tensile test was performed.

Comparative Example 13 The procedure of Example 9 was repeated, except that ME100 was used instead of the intercalation compound. [Comparative Example 14] The procedure of Example 9 was repeated except that the intercalation compound was not used.

[0046]

[Table 4]

1) See footnote in Table 2.

[0048]

The aromatic polyester composition of the present invention is
The strength and elastic modulus are remarkably improved, the toughness shown by tensile elongation at break is not significantly reduced, and the surface appearance of the injection-molded product is also good. Low specific gravity, good surface appearance, high strength, high rigidity, and high toughness. It is applied to various machine parts, automobile parts, electric / electronic parts, films, packaging materials, fibers, etc. by taking advantage of its high gas barrier property.

The melt strand of the composition of the present invention has good spinnability, and a fibrous molded article having both strength and toughness can be easily obtained. Furthermore, the composition of the present invention has improved oxygen barrier properties and tensile strength without impairing toughness and surface smoothness, and is also useful as a film or packaging material that requires gas barrier properties.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Manabu Kawa 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Mitsubishi Kasei Co., Ltd. (56) Reference JP-A-3-62846 (JP, A) (58) ) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 67/00-67/02

Claims (6)

(57) [Claims] 1. A cation exchange capacity of 30 meq / 10
An aromatic polyester composition comprising an interlayer compound having 0 g or more of a layered silicate as a host and a quaternary ammonium ion as a guest in an amount of inorganic ash of 0.5 to 10% by weight. 2. The cation exchange capacity is 30 meq / 10.
An aromatic polyester composition comprising an interlayer compound having 0 g or more of a layered silicate as a host and a quaternary ammonium ion as a guest in an amount of 0.5 to 40 parts by weight per 100 parts by weight of the aromatic polyester. 3. The aromatic polyester composition according to claim 1, wherein the aromatic polyester is polyalkylene terephthalate. 4. The fragrance according to any one of claims 1 to 3, wherein the quaternary ammonium ion is a quaternary ammonium ion having an alkyl group having 12 or more carbon atoms and / or a polyethylene glycol chain. Group polyester composition. 5. The aromatic polyester composition according to claim 1, wherein the layered silicate is swellable fluoromica. 6. A compatibilizer is not contained.
The aromatic polyester resin composition according to claim 1.
object.