JPH06128472A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide a composition extremely satisfactory in compatibility of two kinds of resins, excellent in mechanical strength, heat-resistant rigidity, solvent resistance, etc., by adding a specific compatibilizing agent to a polyphenylene ether and a saturated polyester. CONSTITUTION:The composition comprises (A) a polyphenylene ether [preferably poly(2,6-dimethyl-1,4-phenylene ether), etc.], (B) a saturated polyester (preferably polyethylene terephthalate, etc.) and (C) an organic phosphorous acid compound of the formula [n is 1, 2; Ar is 6-30C (substituted)aryl; R is 2-18C alkylene, arylene when n is 1, and R is 4-18C alkyltetrayl, when n is 2] [preferably bis(norphenyl)pentaerythritol diphosphite, etc.] in an amount of 0.1-10 pts.wt. per 100 pts.wt. of the total amount of the components A and B. The composition is preferably prepared by melt-kneading the components A and B at a kneading temperature of 150-350 deg.C for a kneading time of <=20min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition containing polyphenylene ether (hereinafter referred to as "PPE"), a saturated polyester and a specific compatibilizer and having excellent mechanical strength. This product is used for connectors, ignition manifolds, coil sealing materials, gears, crankshafts, etc., which have excellent solvent resistance and heat resistance, and automobile parts,
It is an engineering plastic useful as an industrial material such as electric members.

[0002]

2. Description of the Related Art PPE has excellent heat resistance, dimensional stability,
It is used as an engineering plastic that has non-hygroscopic properties and electrical properties. However, the melt flowability is poor, molding processes such as injection molding or extrusion molding are difficult, and the molded product is inferior in solvent resistance and impact resistance.

On the other hand, saturated polyester typified by polybutylene terephthalate is widely used as an engineered plastic excellent in moldability, solvent resistance and mechanical strength in automobile parts, electric / electronic equipment parts and the like. However, it has the drawbacks that the molding shrinkage rate and the linear expansion rate are large, and that the reduction in rigidity at high temperatures is large.

Therefore, if a composition having good properties of PPE and saturated polyester and complementing undesired properties can be obtained, it becomes possible to provide an excellent resin material having a wide range of fields of use, and its industrial meaning. Can be said to be very large.

For this purpose, a composition obtained by simply melt-mixing both resins is disclosed, for example, in Japanese Patent Publication No. 51-21664.
It is described in JP-A-49-75662 and 59-159847. However, in such a simple blend system, the PPE and the saturated polyester have poor compatibility with each other, and thus the composition is unlikely to have a uniform and fine morphology. As a result, the impact resistance, heat rigidity, dimensional accuracy and solvent resistance of the obtained molded product did not show a satisfactory improvement effect worthy of the composition, and the appearance of the molded product deteriorates rather. .

A phosphorus compound (including a phosphorous acid compound) is added to the composition of PPE and polyester for the purpose of making it flame-retardant.
~ 15% by weight of U.S. Pat. No. 4,672,0
No. 86 is shown. However, in the tris (nonylphenyl) phosphite etc. exemplified here,
A composition having improved compatibility and good physical properties cannot be obtained.

It is generally known that the compatibility is improved by including a block or graft copolymer of PPE and saturated polyester in the composition.

Further, the reaction of directly synthesizing an ester from a hydroxy compound and a carboxylic acid using triphenyl phosphite as an ester condensing agent has been conventionally known. {Yamazaki, Higashi: Advances in Polymer Scien
ce, 38, 1, (1981)}. It is considered that by applying this reaction to the terminal hydroxyl group of PPE and the terminal carboxyl group of saturated polyester, a block copolymer of PPE and saturated polyester can be formed.

International Publication Number (PCT) WO91 / 082
Japanese Unexamined Patent Publication No. 50 discloses a method for producing a graft or block copolymer composed of PPE and polyester using a phosphite compound exemplified by triphenylphosphite and the like. However, this method requires removal of the phosphite compound remaining in the reaction from the composition, and even if it is removed, the performance of this resin composition containing the graft or block copolymer obtained is not satisfactory. It is enough. This is because the thermal stability of the phosphite compound used here is poor, and the reactivity as an ester condensing agent is insufficient, so the amount of the block or graft polymer produced is small and the compatibility is sufficient. This is probably because it does not improve.

[0010]

DISCLOSURE OF THE INVENTION The present invention provides a novel thermoplastic resin composition which has improved compatibility between PPE and saturated polyester and is excellent in mechanical strength, heat resistance rigidity, solvent resistance and appearance of molded articles. The purpose is to provide.

[0011]

As a result of repeated studies to solve the above problems, the present inventors
It was found that an organic phosphite compound having one or more molecules in the molecule serves as a compatibilizing agent that significantly improves the compatibility between PPE and a saturated polyester, and that a resin composition having desirable physical properties can be obtained thereby, and the present invention is achieved. completed.

That is, the present invention provides the following component (A),
A thermoplastic resin composition containing (B) and (C).

(A) PPE (B) Saturated polyester (C) General formula (I)

[0014]

[Chemical 2]

(In the formula, n represents 1 or 2, Ar represents an aryl group having 6 to 30 carbon atoms or a substituted aryl group, and R represents
Represents an alkylene group having 2 to 18 carbon atoms or an arylene group when n is 1, and represents an alkyltetrayl group having 4 to 18 carbon atoms when n is 2. Ar may be the same or different), and the organic phosphite compound represented by the formula (A) may be 0.
1-10 parts by weight

[0016]

FUNCTION The mechanism by which an organic phosphite compound having one or more specific phosphite ester structures used in the present invention becomes a good compatibilizer is unknown. However, as a result of controlling the electronic state around the phosphorus atom and the stereoregulated state by imparting a structure having both a chelating substituent and an aromatic substituent to this organic phosphite compound, the reaction shown above { Yamazaki, Higashi: Advances in Polymer Sci
ence, 38, 1, (1981)}, it is speculated that the organophosphite compound of the present invention exhibits high reactivity.

As a result, a copolymer of PPE and a saturated polyester is produced in an amount sufficient to improve the compatibility between PPE and the saturated polyester and to obtain a thermoplastic resin composition having excellent physical properties. Conceivable.

The present invention will be described in detail below.

<PPE (A)> PPE of the component (A) is
General formula (II)

[0020]

[Chemical 3]

(Wherein R ¹ represents a halogen atom, a primary or secondary alkyl group, an aryl group, an aminoalkyl group, a halohydrocarbon group, a hydrocarbonoxy group or a halohydrocarbonoxy group, and R 1 ² represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, an aryl group, a haloalkyl group, a hydrocarbon oxy group or a halohydrocarbon oxy group)

It is a homopolymer or a copolymer having a structural unit represented by: Suitable examples of the primary alkyl group for R ¹ and R ² include methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, 2,
It is 3-dimethylbutyl, 2-, 3- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl groups are isopropyl, sec-butyl or 1-ethylpropyl. In many cases, R ¹ is an alkyl group or a phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and R ² is a hydrogen atom.

Specific examples of PPE (A) include poly (2,6-dimethyl-1,4-phenylene ether),
Poly (2,6-diethyl-1,4-phenylene ether), poly (2,6-dipropyl-1,4-phenylene ether), poly (2-ethyl-6-methyl-1,4-)
Phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol / 2, 3,6-triethylphenol copolymer, 2,6-diethylphenol / 2,3,6-trimethylphenol copolymer, 2,6
-Dipropylphenol / 2,3,6-trimethylphenol copolymer, graft copolymer obtained by graft-polymerizing styrene to poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol / 2, 3,
Examples thereof include a graft copolymer obtained by graft-polymerizing styrene to a 6-trimethylphenol copolymer.

A suitable homopolymer of PPE (A) is, for example, poly (2,6-dimethyl-1,4-phenylene ether). Suitable copolymers include 2,6
A random copolymer with dimethylphenol / 2,3,6-trimethylphenol.

The molecular weight of PPE (A) is preferably such that the intrinsic viscosity at 30 ° C. usually measured in chloroform is about 0.2 to 0.8 dl / g. Number average degree of polymerization is 25-
400.

PPE is usually produced by oxidative coupling of phenolic compounds. Numerous catalyst systems are known for the oxidative coupling polymerization of PPE. There is no particular limitation on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, and cobalt, usually in combination with various other substances (eg, US Pat. Nos. 4,042,056 and 3,306). , 8
No. 74, No. 3,306,875, No. 3,365.
No. 422, No. 3,639,656, No. 3,64
2,699, 3,733,299, and 3,8
No. 38,102, No. 3,661,848, No. 5,
No. 037,943, etc.).

<Saturated Polyester (B)> As the saturated polyester of the component (B), various polyesters can be used.

For example, as one of them, there may be mentioned a thermoplastic polyester produced by condensing a dicarboxylic acid or a lower alkyl ester thereof, an acid halide or an acid anhydride derivative and a dihydroxy compound according to a usual method.

Specific examples of the aliphatic or aromatic dicarboxylic acid suitable for producing the polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and terephthalic acid. acid,
Isophthalic acid, phthalic acid, p, p'-dicarboxydiphenyl sulfone, p-carboxyphenoxyacetic acid, p-
Carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, 2,
Examples thereof include 6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and the like, or a mixture of these carboxylic acids.

The aliphatic diol suitable for producing the saturated polyester (B) is a straight chain alkylene glycol having 2 to 12 carbon atoms, for example, ethylene glycol, 1,3.
-Propanediol, 1,4-butanediol, 1,6
Examples include-hexanediol and 1,12-dodecanediol. As the aromatic diol, there are p-xylene glycol, pyrocatechol, resorcinol, hydroquinone, and alkyl-substituted derivatives of these compounds. Other suitable diols also include 1,4-cyclohexanedimethanol.

Other preferable saturated polyesters (B) include polyesters obtained by ring-opening polymerization of lactone. For example, polypivalolactone, poly (ε-caprolactone) and the like. In addition, as another preferable polyester, a polymer (Ther
There is polyester as motoropic Liquid Crystal Polymer: TLCP). Typical polyesters that fall into these categories are Eastman Kodak's X7G, Dartco's Xydar, Sumitomo Chemical's Econoll, and Hextocelanese's Vectra.

Among the saturated polyesters (B) listed above, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PB).
N), poly (1,4-cyclohexanedimethylene terephthalate) (PCT), liquid crystalline polyester and the like are the saturated polyester (B) suitable for the thermoplastic resin composition of the present invention.

<Organic phosphite compound (C)> The organic phosphite compound (C) used in the present invention is excellent in thermal stability and has a structure having both a chelate substituent and an aromatic substituent. It is an organic phosphite compound in which the electronic state around atoms and the steric regulation state are controlled, and has the general formula (I)
Indicated by.

Specific examples of Ar include a phenyl group; 2-, 3- or 4-methylphenyl, 2,4-
Or 2,6-dimethylphenyl, 2,3,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,4- or 2,6-diethylphenyl, 2,
3,6-triethylphenyl, 2-, 3- or 4-
tert-butylphenyl, 2,4- or 2,6-di-
tert-butylphenyl, 2,4,6-tri-tert-butylphenyl, 2,6-di-tert-butyl-4-methylphenyl, 2,6-di-tert-butyl-4-ethylphenyl, 2- A substituted phenyl group such as 3- or 4-nonylphenyl and biphenyl; or a naphthyl group.

As a concrete example of R, when n is 1,
1,2-phenylene group; polymethylene groups such as ethylene, propylene, trimethylene, tetramethylene, 2,2-dimethyltrimethylene or hexamethylene, and the like, and when n is 2, the following pentaerythritol-derived Examples thereof include a tetrayl group represented by the general formula (III).

[0036]

[Chemical 4]

(In the formula, each X is a hydrogen atom or a carbon number of 1 to
6 represents an alkyl group)

Among these, preferred compounds represented by the general formula (I) are exemplified. Here, as the name of the compound,
For example, 3,9-bis (2,6-di-tert-butyl-4-
Methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane [formula (IV)], generally bis (2,6-di-tert-butyl-4- It is shown according to the nomenclature called methylphenyl) pentaerythritol diphosphite.

[0039]

[Chemical 5]

That is, (phenyl) (1,3-propanediol) phosphite, (4-methylphenyl)
(1,3-propanediol) phosphite, (2,6
-Dimethylphenyl) (1,3-propanediol) phosphite, (4-tert-butylphenyl) (1,3-
Propanediol) phosphite, (2,4-di-tert
-Butylphenyl) (1,3-propanediol) phosphite, (2,6-di-tert-butylphenyl)
(1,3-propanediol) phosphite, (2,6
-Di-tert-butyl-4-methylphenyl) (1,3-
Propanediol) phosphite,

(Phenyl) (1,2-ethanediol)
Phosphite, (4-methylphenyl) (1,2-ethanediol) phosphite, (2,6-dimethylphenyl) (1,2-ethanediol) phosphite, (4-
tert-butylphenyl) (1,2-ethanediol) phosphite, (2,4-di-tert-butylphenyl)
(1,2-ethanediol) phosphite, (2,6-
Di-tert-butylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-
Methylphenyl) (1,2-ethanediol) phosphite, (2,6-di-tert-butyl-4-methylphenyl) (1,4-butanediol) phosphite;

Diphenylpentaerythritol diphosphite, bis (2-methylphenyl) pentalithritol diphosphite, bis (3-methylphenyl) pentaerythritol diphosphite, bis (4-methylphenyl) pentaerythritol diphosphite, Bis (2,4-dimethylphenyl) pentaerythritol diphosphite, bis (2,6-dimethylphenyl) pentaerythritol diphosphite, bis (2,3,6-
Trimethylphenyl) pentaerythritol diphosphite, bis (2-tert-butylphenyl) pentaerythritol diphosphite, bis (3-tert-butylphenyl) pentaerythritol diphosphite, bis (4
-Tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl)
Pentaerythritol diphosphite, bis (2,6-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite,
Bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (biphenyl) pentaerythritol diphosphite, dinaphthyl pentaerythritol diphosphite A fight etc. are mentioned.

Of these, more preferred organic phosphite compounds (C) are bis (nonylphenyl) pentaerythritol diphosphite and bis (2,4-di-te).
Examples include rt-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite.

The thermoplastic resin composition of the present invention decomposes these organic phosphorous acid compounds (hydrolysis, thermal decomposition, etc.).
It may contain a compound generated by.

<Composition Ratio of Constituent Components> The mixing ratios of PPE (A), saturated polyester (B) and organic phosphorous acid compound (C) contained in the composition of the present invention are as follows. That is, the component (A) is the resin composition (A) + (B) in view of the balance of heat resistance rigidity, solvent resistance and molding processability.
It is preferably 10 to 90% by weight, more preferably 20 to 80% by weight, and the component (B) is preferably 90 to 10% by weight, more preferably 80 to 20% by weight, based on the total amount of 100% by weight. .

In the resin composition, if the component (A) is less than 10% by weight, the effect of improving the heat resistance is small, and conversely, if it exceeds 90% by weight, the solvent resistance and molding processability are deteriorated.

When the component (B) is less than 10% by weight in the resin composition, the effect of improving solvent resistance and molding processability is small, and
If it exceeds 90% by weight, the heat resistance is not sufficient.

The organic phosphite compound as the component (C) is 0.1 parts by weight per 100 parts by weight of the total amount of the components (A) and (B).
-10 parts by weight, preferably 0.1-8 parts by weight, more preferably 0.1-4 parts by weight. If it is less than 0.1 part by weight, the effect of addition of the component (C) is small and the effect of improving the physical properties of the resin composition is insufficient. If it exceeds 10 parts by weight, the appearance of the molded product may be difficult, which is not preferable.

<Additional Components> Components other than the above components (A), (B) and (C) can be added to the thermoplastic resin composition of the present invention. For example, well-known antioxidants, weather resistance improvers, metallic soaps 0.01 to components (A) and (B) are used.
5 wt%; plasticizer, fluidity improver 5-30 wt%; nucleating agent 0.5-2 wt%; flame retardant 3-15 wt% can be used as additional components. Further, organic fillers, inorganic fillers, reinforcing agents, especially glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc.
Addition of 0 to 45% by weight is effective in improving rigidity, heat resistance, dimensional accuracy and the like. Further, 0.5 to 5% by weight of a colorant and a dispersant thereof can be added.

Further, an impact strength improver, particularly polystyrene, polycarbonate, polyamide, styrene-butadiene copolymer rubber or a hydride thereof, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, and further those Α, β-unsaturated carboxylic acid anhydride modified product or a modified product with a glycidyl ester or an unsaturated glycidyl ether, or a copolymer composed of an unsaturated epoxy compound and ethylene, or an unsaturated epoxy compound, ethylene and an ethylenically unsaturated compound The addition of a copolymer and the like is effective for improving the strength of the composition.

The above impact strength improvers may be used alone or in combination of two or more. The blending amount of the impact strength improver varies depending on the physical properties used as a guide, but in the case of improving the balance between rigidity and impact strength of the composition, it is 5 to 30% by weight in the resin composition.

<Production Method and Molding Method of Thermoplastic Resin Composition>
Melt kneading is preferable as a method for obtaining the thermoplastic resin composition of the present invention. In this regard, a kneading method generally used for thermoplastic resins can be applied. For example, each of the powdery or granular components, together with the additives described in the section of the additional components, if necessary, is uniformly mixed by a Henschel mixer, a super mixer, a ribbon blender, a V-type blender, etc., and then uniaxially or It can be kneaded with a multi-screw kneading extruder, roll, Banbury mixer, Labo Plastomill (Bravender), or the like. The kneading order of each component is not particularly limited.

The kneading temperature and the kneading time can be arbitrarily selected depending on the conditions such as the desired production amount of the block or graft polymer and the kind of the kneading machine. The kneading temperature is 150 to 3
The kneading time at 50 ° C. is preferably 20 minutes or less. When the kneading temperature is 350 ° C and the kneading time exceeds 20 minutes, PPE
The heat deterioration of (A), the saturated polyester (B) or the organic phosphite compound (C) becomes a problem, and the physical properties and the appearance of the molded product may be deteriorated.

The method of molding the thermoplastic resin composition of the present invention is not particularly limited, and a molding method generally used for thermoplastic resins, that is, injection molding,
Various molding methods such as blow molding, extrusion molding and press molding can be applied.

[0055]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following, parts and percentages are based on weight.

Examples 1 to 6 and Comparative Examples 1 to 6 The components used are as follows.

PPE (A): Poly (2,6-dimethyl-1,4) manufactured by Nippon Polyether Co., Ltd.
-Phenylene ether): Intrinsic viscosity measured in chloroform at 30 ° C. 0.30 dl / g (marked H-30 in the table), 0.41 dl / g (marked H-41 in the table) and 0.5
3 kinds of 1 dl / g (indicated as H-51 in the table).

Saturated polyester (B): 1) Polybutylene terephthalate: Novador 5010 grade (trade name) manufactured by Mitsubishi Kasei: Gel permeation chromatography (GP
C) polystyrene equivalent number average molecular weight (Mn) 30,000, weight average molecular weight (Mw) 99.00
0 (denoted as PBT-1 in the table). Kanebo K-128 grade (trade name): GPC
Polystyrene-converted Mn = 42,000,
Mw = 116,000 (denoted as PBT-2 in the table). 2) Polyethylene terephthalate: PBX-1 manufactured by Kanebo
Grade (trade name): Intrinsic viscosity 0.65 dl / g (PE in the table
T).

Organic phosphorous acid compound (C): 1) Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite: MARK PEP-36 (trade name) manufactured by Asahi Denka Co., Ltd .: (Indicated as A in the table). 2) Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite: MARK PEP-24G (trade name) manufactured by Asahi Denka Co., Ltd. (denoted as B in the table). 3) Triphenylphosphite: manufactured by Tokyo Chemical Industry Co., Ltd. (denoted by C in the table). 4) Distearyl pentaerythritol diphosphite: Asahi Denka Co., Ltd .: MARK PEP-8 (trade name) (denoted by D in the table). 5) Tris (nonylphenyl) phosphite: MARK-1178 (trade name) manufactured by Asahi Denka Co., Ltd. (denoted by E in the table).

Impact resistance improver: Hydrogenated styrene-butadiene block copolymer: Shell Chemical Co., Ltd., Kraton G-1651 grade (trade name):
(Indicated as SEBS in the table).

Each component according to the composition ratio shown in Table 1 was kneaded using a lab blast mill kneader (trade name) manufactured by Toyo Seiki Seisaku-sho, Ltd. for 10 minutes at a preset temperature of 250 ° C. and a rotation speed of 180 rpm, and then pulverized. A granular composition was obtained.

[0062]

[Table 1]

The characteristics of the composition obtained are CS183 manufactured by Custom Scientific.
Test pieces injection-molded at a temperature of 280 ° C. using an MMX Minimax injection molding machine (trade name) were measured and evaluated by the following methods. The results are shown in Table 1.

Upon kneading and molding, polybutylene terephthalate, polyethylene terephthalate, resin composition and the like were used after being dried under reduced pressure at 120 ° C. for 5 hours in advance.

(1) Impact strength: A test piece having a length of 31.5 mm, a width of 6.2 mm, and a thickness of 3.2 mm was injection-molded, and the mini-max Izod impact tester CS-138TI manufactured by Custom Scientific Co., Ltd. The mold was used to measure the Izod impact strength without notch at 23 ° C.

(2) Tensile strength: A tensile test piece having a parallel length of 7 mm and a parallel portion diameter of 1.5 mm was injection-molded, and a tensile tester CS-183TE type manufactured by Custom Scientific was used to pull at a tensile speed of 1 cm. A tensile test was performed under the condition of / min to measure stress at break and elongation at break.

For Examples 1 to 3 and Comparative Examples 1 to 4, a scanning electron microscope (S-2400 manufactured by Hitachi, Ltd.) was used as a measure for improving the compatibility by using the organic phosphite compound (C). Shows the dispersed particle size of PPE domains dispersed in a matrix of polybutylene terephthalate.

Examples 7 to 12 and Comparative Examples 7 to 10 According to the composition ratio of each component shown in Table 2, melt kneading and injection molding were carried out in the same manner as in Examples 1 to 6, and the physical properties were evaluated. The results are shown in Table 2.

[0069]

[Table 2]

Examples 13 and 14 and Comparative Examples 11 and 12,
13 According to the composition ratio of each component shown in Table 3, after thoroughly mixing each component with a super mixer, using a twin screw extruder manufactured by Japan Steel Works (trade name: TEX-44 twin screw extruder), Set temperature 210 ℃, screw rotation speed 150rpm, discharge rate 4
Kneading was performed under the condition of 0 kg / hour to obtain pellets. During this kneading, degassing under reduced pressure was performed at the post-venting section.

The characteristics of the obtained composition were evaluated and molded in the same manner as in Examples 1 to 6 for Example 13 and Comparative Examples 11 and 12.

Regarding Example 13 and Comparative Examples 11 and 12, the reaction rate of PPE was measured as a measure of the amount of block or graft polymer produced, which improves the compatibility by using the organic phosphite compound (C). It was calculated by the formula.

PPE reaction rate (%) = 100 × (α-β) / α α: Total weight of PPE component in composition β: Weight of unreacted PPE component in composition

Β was determined according to the following. Chloroform /
Hexafluoroisopropanol mixed solution (volume ratio 1:
The composition of PPE and polybutylene terephthalate weighed in 1) is dipped in and swollen. Tetrahydrofuran and chloroform were sequentially added to the solution phase, and unreacted P was added from the solution phase.
The PE component was isolated and weighed to give β.

The molding / evaluation in Example 14 and Comparative Example 13 was performed using an in-line screw injection molding machine (IS-90B manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 260 ° C. and a mold cooling temperature of 80 ° C. The injection-molded test pieces were measured and evaluated by the following methods. Before injection molding, vacuum dry at 120 ° C for 5 minutes.
I went on time.

(1) Impact strength: ISO R180-1
According to the 969 (JIS K 7110) notched Izod impact test, the measurement was performed using an Izod impact tester manufactured by Toyo Seiki Seisakusho.

(2) Tensile strength: ISO R527-66
According to (JIS K 7113) tensile strength, measurement was performed using an Instron tester. The results are shown in Table 3.

[0078]

[Table 3]

Examples 15 and 16 and Comparative Examples 14 and 15 Kneading was carried out in the same manner as in Examples 1 to 6 except that polyethylene terephthalate was used instead of polybutylene terephthalate, and the temperature of the kneader was set to 260 ° C. Molded to obtain a test piece for evaluation of physical properties. This test piece was heat-treated in a hot air drier at a temperature of 120 ° C. for 4 hours to sufficiently crystallize polyethylene terephthalate, and then, Examples 1 to 6 were performed.
The physical properties were evaluated by the same method as. The results are shown in Table 4.

[0080]

[Table 4]

[0081]

INDUSTRIAL APPLICABILITY The resin composition of the present invention has a remarkably improved compatibility between the component (A) and the component (B), and has a high rigidity and a mechanical strength balance having the characteristics inherent in each component. It is an excellent thermoplastic resin composition.

Claims (1)

[Claims] 1. A thermoplastic resin composition containing the following components (A), (B) and (C). (A) Polyphenylene ether (B) Saturated polyester (C) General formula (I) (In the formula, n represents 1 or 2, Ar represents an aryl group having 6 to 30 carbon atoms or a substituted aryl group, and R represents an alkylene group having 2 to 18 carbon atoms or an arylene group when n is 1. Represents an alkyltetrayl group having 4 to 18 carbon atoms when n is 2. Ar may be the same or different, and the organic phosphite compound represented by the formulas (A) and (B) may be used. 0.1 to 10 parts by weight per 100 parts by weight of