JPH069872A - Resin composition containing polyarylene thioether and polyamide - Google Patents

Abstract

PURPOSE:To provide the resin composition comprising a polyarylene sulfide and a polyamide and giving good mechanical properties even under thermally severe processing conditions. CONSTITUTION:The resin composition containing a polyarylene thioether and a polyamide is characterized in that at least a part of the polyarylene thioether is a one containing phthalic acid anhydride groups.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a polyarylene thioether and a polyamide.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as PP
A polyarylene thioether typified by S) (hereinafter, abbreviated as PATE) is a repeating arylene ether represented by the formula “—Ar—S—” (where —Ar— is an arylene group). It is a polymer having a unit as a main constituent element, and is used in a wide range of fields because it is excellent in heat resistance, flame resistance, chemical resistance, mechanical properties and the like.

Since PPS generally has poor impact resistance,
It has been proposed to blend PPS with polyamide to obtain a resin composition having improved impact resistance (Japanese Patent Publication No. Sho 59-1422). However, PP
Since S has an insufficient compatibility with polyamide, the surface condition of the obtained molded product is poor and the effect of improving the mechanical properties is not sufficient by simply blending both.

Macromol. Chem. vol. 1
91, 815-828 (1990), Telechelic polyphenylene thioether (Telechelic PP) having a functional group such as a carboxyl group at both ends.
It discloses a method for producing a block copolymer having a PPS block and a polyamide block by carrying out a polymerization reaction of a polyamide in the presence of S). According to this method, there is a possibility that a polymer having good mechanical properties can be obtained, but there is a drawback that the operation and treatment are complicated.

JP-A-3-231968 discloses a resin composition comprising a carboxyl group-containing PPS, a hydrogenated styrene-butadiene block copolymer and a polyamide. In the invention described in this publication, PP
It is intended to solve the problem of insufficient compatibility between PPS and polyamide by introducing a carboxyl group into S and making it reactive with an amino group at the terminal of the polyamide. This publication describes a carboxyl group-containing PP.
As S, 2,4 when the alkali metal sulfide and dihalobenzene are reacted in an organic amide to produce PPS,
A polymer obtained by coexisting a carboxyl group-containing aromatic halide such as -dichlorobenzoic acid or p-chlorobenzoic acid is used.

However, such a carboxyl group-introduced PPS is likely to cause decarboxylation to decompose the carboxyl group during melt blending or molding at high temperature, resulting in impairing the effect of introducing the functional group. It is estimated to be. Further, in the conventional method for producing a PPS containing a carboxyl group, since only a powdery polymer can be obtained, there are problems such as poor handleability.

JP-A-2-283763 discloses a modified PP obtained by reacting a polyphenylene sulfide resin prepared by a usual method with a carboxylic acid anhydride.
A resin composition obtained by compounding and kneading S and a thermoplastic resin such as a polyamide resin is disclosed. Specifically, this modification reaction is carried out by a method in which PPS powder and carboxylic acid anhydride are dry-blended, then melt-kneaded and extruded by an extruder set at 290 to 310 ° C. and pelletized. However, the modified P obtained by this method
PS does not have a sufficiently strong chemical bond between the carboxylic acid anhydride and PPS, and it is difficult to obtain satisfactory mechanical properties even with the resin composition of the modified PPS and polyamide.

On the other hand, the applicant of the present invention has proposed a method of polymerizing an alkali metal sulfide, a dihaloaromatic compound and a dihaloaromatic carboxylic acid in a polar solvent containing water in the presence of an alkaline earth metal compound. A patent application was previously filed for a method of producing PATE containing a carboxyl group in a granular form (Japanese Patent Application No. 2-410082;
No. 214,729), and a patent for a blend of the carboxyl group-containing PATE and polyamide (Japanese Patent Application No. 4-19507;
No. 51532). By introducing a carboxyl group into PATE, the compatibility between PATE and polyamide can be improved, but the thermal stability of the carboxyl group is insufficient, and if thermally difficult processing conditions are passed, it may be There is a drawback that it is difficult to obtain good mechanical properties.

[0009]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition of polyarylene sulfide and polyamide, which can obtain good mechanical properties even under thermally severe processing conditions. As a result of intensive studies to overcome the above-mentioned problems of the prior art, the present inventors have found that when a blend of PATE and polyamide is obtained, PATE containing phthalic anhydride groups is used as all or part of the PATE component. It has been found that a resin composition having excellent compatibility with each component and good mechanical properties can be obtained by using it.

The phthalic anhydride group-containing PATE is prepared by polymerizing an alkali metal sulfide and a dihalogen-substituted aromatic compound to produce PATE, in which a monohalogen-substituted phthalic acid compound is allowed to coexist and specific reaction conditions are applied. It can be easily obtained by adopting. It can also be obtained by causing PATE to act on an alkali metal sulfide to depolymerize it, and then reacting the depolymerized product with a monohalogen-substituted phthalic acid compound.

PAT having a phthalic anhydride group at this end
E has excellent compatibility with polyamide and P
Even at a temperature higher than the melting temperature of ATE, decomposition reaction such as decarboxylation does not occur, and it has excellent thermal stability. The present invention has been completed based on these findings.

[0012]

Thus, according to the present invention, in a resin composition containing a polyarylene thioether and a polyamide, at least a part of the polyarylene thioether is a phthalic anhydride group-containing polyarylene thioether. There is provided a resin composition containing the polyarylene thioether and the polyamide. Hereinafter, the present invention will be described in detail.

PATE The PATE used in the present invention has the formula "-Ar-S-".
(However, —Ar— is an arylene group), which is a polymer having a repeating unit of arylenthalotell represented by the main component. When "-Ar-S-" is defined as 1 mol (basic mol), the PATE used in the present invention is
The content of this repeating unit is usually 50 mol% or more, preferably 7
It is a polymer containing 0 mol% or more, more preferably 90 mol% or more. Such PATE is a known method of polymerizing an alkali metal sulfide and a dihalogen-substituted aromatic compound in a polar organic solvent (see, for example, JP-B-63-63).
No. 33775).

The polar organic solvent is generally an aprotic polar solvent which is stable to alkali at high temperature. As a specific example, for example, N,
Amide compounds such as N-dimethylformamide and N, N-dimethylacetamide; N-alkyl- such as N-methyl-ε-caprolactam, N-methylpyrrolidone and N-cyclohexylpyrrolidone, or N-cycloalkyl-
Lactam compounds; N, N-dialkylimidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone;
And tetraalkylurea compounds such as tetramethylurea; hexaalkylphosphoric acid triamides such as hexamethylphosphoric acid triamide; and mixtures of two or more thereof.

Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide. These can be used in the form of anhydrate, hydrate or aqueous mixture. Also, an alkali metal sulfide prepared in situ from alkali hydrosulfide can be used. These alkali metal sulfides may be used alone or in combination of two or more.

Examples of the dihalogen-substituted aromatic compound include dihalogen-substituted benzenes such as p-dihalobenzene and m-dihalobenzene; 2,3-dihalotoluene,
2,4-dihalotoluene, 2,6-dihalotoluene,
Dihalogen-substituted alkylbenzenes such as 3,4-dihalotoluene and 2,5-dihalo-p-xylene; Dihalogen-substituted arylbenzenes such as 2,5-dihalodiphenyl;
Dihalogen-substituted biphenyl such as 4,4′-dihalobiphenyl; dihalogen-substituted naphthalene such as 2,6-dihalonaphthalene and 1,5-dihalonaphthalene; and the like. The halogen element in the dihalogen-substituted aromatic compound is fluorine, chlorine, bromine, or iodine, which may be the same or different from each other.

Among the dihalogen-substituted aromatic compounds, the preferable one is dihalogen-substituted benzene, and particularly p
-Dichlorobenzene is preferred. These dihalogen-substituted aromatic compounds can be used alone or in combination of two or more. If necessary, trihalogen-substituted benzene, dihalogen-substituted aniline or the like may be used in combination as a minor component to adjust the molecular weight.

The PATE used in the present invention is 310 ° C.
And the melt viscosity measured at a shear rate of 1200 sec ^-1 is usually 100 to 7,000 poise, preferably 200 to 600.
The polymer is 0 poise, more preferably 300 to 5000 poise.

Phthalic anhydride group-containing PATE The phthalic anhydride group-containing PATE used in the present invention requires that the phthalic anhydride group is sufficiently chemically bonded to PATE. A preferable effect cannot be obtained by simply melt-extruding PATE and phthalic anhydride. Therefore, the phthalic anhydride group-containing PATE used in the present invention is
For example, in a method for producing PATE by polymerizing a dihalogen-substituted aromatic compound and an alkali metal sulfide in a polar organic solvent containing [I] water, a monohalogen-substituted phthalic acid compound is present in the polymerization reaction system. In addition, the ratio a / b of the mole number a of the charged dihalogen-substituted aromatic compound and the mole number b of the charged alkali metal sulfide was set to 0.
8 <a / b <1 range, [II] PATE in a polar organic solvent containing water is reacted with an alkali metal sulfide to depolymerize the main chain of PATE to depolymerize the end of the alkali thiolate. A compound having a group (depolymerized product) is obtained, and then the depolymerized product is reacted with a monohalogen-substituted phthalic acid compound. The method [I] is preferable for obtaining a phthalic anhydride group-containing PATE having a high molecular weight and a granular shape.

Examples of the monohalogen-substituted phthalic acid compound include 4-halophthalic acid, 3-halophthalic acid, and phthalic acid containing halophenyl group, halophenoxy group, halophenylthio group, halobenzenesulfonyl group, halobenzenesulfinyl group, A substituted phthalic acid derivative in which a halobenzyl group, a 2-halophenyl-2-propyl group, or the like is substituted can be given. The monohalogen-substituted phthalic acid compound is in the form of a salt with an alkali metal or alkaline earth metal (monometal phthalate or dimetal phthalate).
Can also be used as The halogen element in these monohalogen-substituted phthalic acid compounds is fluorine, chlorine, bromine, or iodine, respectively. Among these monohalogen-substituted phthalic acid compounds, especially, sodium hydrogen chlorophthalate, disodium chlorophthalate,
And chlorophthalic acid are preferably used.

A phthalic anhydride group-containing P is prepared by the above method [I].
When ATE is produced, the number of moles a of the charged dihalogen-substituted aromatic compound and the number b of moles of the charged alkali metal sulfide are charged.
When the ratio a / b is 0.8 or less, it is difficult to increase the molecular weight, and when it is 1 or more, it is difficult to introduce a phthalic acid group. The monohalogen-substituted phthalic acid compound is usually used in the range of 0.05 to 30 mol%, preferably 0.1 to 25 mol%, based on the total amount of the dihalogen-substituted aromatic compound. The total amount of the dihalogen-substituted aromatic compound and the monohalogen-substituted phthalic acid compound relative to 1 mol of the alkali metal sulfide is usually 0.81 to 1.42 mol, preferably 0.83 to 1.4.
It is in the range of 0 mol.

The amount of the polar organic solvent used is not particularly limited, but is usually the number of moles (total number of moles) of the total amount of the dihalogen-substituted aromatic compound and the monohalogen-substituted phthalic acid compound per 1 kg of the polar organic solvent. Is used in a range of 0.1 to 5 mol, preferably 0.5 to 3.5 mol. The polymerization reaction is carried out in a polar organic solvent containing water. The water content is usually 0.5 with respect to 1 kg of polar organic solvent.
The range is -30 mol, preferably 1-25 mol. A part of this water may be added during the polymerization reaction. When the alkali metal sulfide is a hydrate,
If necessary, the content of water can be adjusted by performing dehydration operation such as azeotropic distillation.

The monohalogen-substituted phthalic acid compound may be added to the reaction system at any time. For example, (1) a method of first charging the reaction system with the alkali metal sulfide, and (2) a reaction in which the alkali metal sulfide is present. A method of initiating polymerization by charging the system with a dihalogen-substituted aromatic compound,
(3) A method in which an alkali metal sulfide and a dihalogen-substituted aromatic compound are first charged to start a polymerization reaction, and then a monohalogen-substituted phthalic acid compound is added, and (4) a method in which these are combined.

When the monohalogen-substituted phthalic acid compound is added to the reaction system in a state of being dissolved in water, a basic compound may be added together, if desired. Further, in order to keep the polymerization reaction system alkaline, the polymerization reaction may be carried out by adding a basic compound. Examples of such a basic compound include hydroxides or oxides of alkali metals or alkaline earth metals, or a mixture of two or more thereof.

The polymerization reaction is usually carried out in an atmosphere of an inert gas such as nitrogen or argon at 150 to 300 ° C., preferably 1
It is carried out at a temperature range of 80 to 280 ° C. for 0.5 to 30 hours, preferably 1 to 20 hours. The polymerization reaction is
It is also possible to raise the temperature in multiple stages of two or more stages, for example, 2
There is a method in which the first stage polymerization is carried out at a temperature of 35 ° C. or lower, and then the second stage polymerization is carried out by raising the temperature to 240 ° C. or higher. Particularly, in the two-stage polymerization reaction, when the temperature is raised to 240 ° C. or higher in the latter stage, according to the water-added two-stage polymerization method in which water is added before or after the temperature rise (see Japanese Patent Publication No. 63-33775), PA with phthalic anhydride group with high molecular weight and more excellent melt stability
Easy to get TE.

After completion of the polymerization reaction, PA having a phthalic acid group
TE is obtained, but if present in the form of a metal salt of phthalic acid, it is treated with acidic water to form the phthalic acid. If the produced polymer is washed and then dried, a dehydration reaction occurs and a phthalic anhydride group-containing PATE is obtained.

When the phthalic anhydride group-containing PATE is produced by the method [II], for example, PATE and alkali metal sulfide are mixed in a water-containing polar organic solvent having 0.1 to 20 mol of water per 1 kg of the polar organic solvent. 200 to 3
A depolymerization product having an alkali thiolate group at at least one terminal is prepared by performing a depolymerization reaction at 00 ° C. for 0.1 to 30 hours, and then a monohalogen-substituted phthalic acid compound is added to the depolymerization product at 200 to 200 ° C. The reaction is carried out at a temperature of 300 ° C, preferably 240 to 280 ° C.

The amount of the phthalic anhydride group contained in the phthalic anhydride group-containing PATE is determined by measuring the absorbance at 1850 cm ^-1 , which is the characteristic absorption band of the phthalic anhydride group, in the infrared absorption spectrum of the PATE by the transmission method. The absorbance ratio divided by the absorbance at 1900 cm ^-1 , which is the out-of-plane bending overtone absorption band, is 100.
When expressed by an IR index (%) multiplied by, usually 2% or more,
It is preferably at least 3%. With the phthalic anhydride group-containing PATE having an IR index of less than 2%, the effect of introducing the phthalic anhydride group is too small, and the physical properties are not so different from the case of using the unmodified PATE.

Similar infrared absorption is detected even when PATE and phthalic anhydride are mixed and melt extruded only. However, in this case, when remelting extraction is performed with N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) described below, phthalic anhydride is removed and the infrared characteristic absorption band is no longer detected.
That is, in this method, a sufficiently strong chemical bond is not formed between PATE and phthalic anhydride. On the other hand, the phthalic anhydride group-containing polyarylene thioether used in the present invention has an IR after remelting treatment by NMP.
The index is preferably 2% or more, more preferably 3% or more.

Remelting treatment by NMP means polymer 5
0 g together with 500 g of NMP, 30 g of water and 4 g of NaOH was placed in a 1 liter autoclave, and after nitrogen substitution, the polymer was remelted (dissolved) by heating while stirring, and then immediately cooling while continuing stirring, sieving, washing with NaOH,
And a treatment of washing with HCl and drying.

Polyamide The polyamide used in the present invention is not particularly limited,
Known ones can be used. Specific examples include aliphatic polyamides, aromatic polyamides, polyamide elastomers, amorphous polyamides, copolyamides, mixed polyamides, and the like. Typical examples are polycaproamide (nylon 6), polyundecane amide (nylon 11), Polydodecane amide (nylon 12), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), nylon MXD6, nylon 6
Examples thereof include copolyamides such as / Nylon 66 and mixed polyamides thereof.

Resin Composition The resin composition of the present invention is a resin composition containing a PATE component and a polyamide component, which is a phthalic anhydride group-containing PAT.
Use E as all or part of the PATE component. The preferred composition ratio of the resin composition of the present invention is as follows. (A) PATE: 0 to 98.5% by weight, preferably 0
89% by weight, more preferably 0-72% by weight. (B) phthalic anhydride group-containing PATE: 0.5 to 99% by weight, preferably 1 to 90% by weight, more preferably 3 to 8%
0% by weight. (C) Polyamide: 99.5 to 1% by weight, preferably 9
9 to 10% by weight, more preferably 97 to 20% by weight.

PA containing phthalic anhydride group used in the present invention
Since TE has excellent compatibility with polyamide, when both are blended, the dispersibility is remarkably improved as compared with the case where unmodified PATE is used. In addition, unmodified P
When used in combination with ATE, PAT containing phthalic anhydride group
E also acts as a compatibilizer for PATE and polyamide. PATE component (PATE and phthalic anhydride group-containing P
The blend ratio of ATE) and polyamide can be appropriately determined according to the purpose of use. Phthalic anhydride group-containing P
When ATE is used as a compatibilizer, it exerts an excellent effect even in a very small amount.

The resin composition of the present invention may contain other components in addition to the PATE component and the polyamide within a range not impairing the object of the present invention. Other components include, for example, glass fibers, fillers such as carbon fibers, resin modifiers such as ethylene glycidyl methacrylate, elastomers, other thermoplastic resins, thermosetting resins,
Examples include coupling agents, lubricants, stabilizers, nucleating agents and the like.

The method for preparing the resin composition of the present invention includes:
There is no particular limitation, but preferably the PATE component and the polyamide are premixed by a Henschel mixer, a tumbler, etc., and if necessary, a filler such as glass fiber is added and further mixed, and then melt-kneaded by using an extruder. Then, the method of pelletizing is used.

[0036]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The methods for measuring the physical properties are as shown below.

(1) IR index of phthalic anhydride group content The phthalic anhydride group-containing PATE was hot-pressed at 320 ° C., then put in ice water and rapidly cooled.・ Elmer (Per
It was measured by FT-IR1760 manufactured by Kin Elmer). From the obtained spectrum, the absorbance ratio at 1850 cm ^-1 , which is the characteristic absorption band of the phthalic anhydride group, is divided by the absorbance at 1900 cm ^-1 , which is the CH out-of-plane bending angle overtone absorption band, and is multiplied by 100 (%). ).

(2) Melt viscosity A Capirograph (manufactured by Toyo Seiki Seisakusho) was used to obtain a temperature of 3
The measurement was performed under the conditions of 10 ° C. and a shear rate of 1200 sec ⁻¹ .

(3) Melting point (Tm) and glass transition temperature (Tg) A sheet obtained by hot pressing a polymer at 320 ° C. and then rapidly cooling the same was Perkin Elmer (Perkin Elmer).
The measurement was performed using a differential scanning calorimeter (DSC) manufactured by Elmer) in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min.

(4) Thermogravimetric analysis Using a thermogravimetric analyzer (TGA) manufactured by METTLER CORPORATION, 2
It was carried out at 0 ° C./min in a nitrogen stream.

(5) Breaking Elongation The melt-kneaded resin composition was vacuum dried at 100 ° C. for 8 hours, hot pressed at 320 ° C., and then rapidly cooled to about 200.
A sheet having a thickness of μm was prepared. After the sheet was crystallized at 200 ° C. for 1 hour, it was cut into a strip with a width of 10 mm, and this was used as a test piece with a sample length of 20 mm and a pulling speed of 4 mm / min.
A tensile test was performed at a temperature of 23 ° C. to determine the breaking elongation.

(6) Observation of Dispersion State With respect to the quenched sheet prepared in the above (5), after etching polyamide with hydrochloric acid, scanning electron microscope (SEM)
The dispersed state was observed with. The diameter of the blending component of the dispersed phase is 4
When a large number of particles having a size of μm or more were contained, it was evaluated as coarse dispersion, and when the size of dispersed particles was less than 4 μm in diameter, it was evaluated as fine dispersion.

Reference Example 1 (Synthesis Example of PATE Containing Phthalic Anhydride Group) 3200 g of NMP and 1351.1 g of hydrous sodium sulfide (8.00 mol as S content) were charged into a titanium-lined autoclave, and after nitrogen substitution, While gradually raising the temperature to 200 ° C., 1373.8 g of an NMP solution containing 543.1 g (30.15 mol) of water and 0.17 mol of hydrogen sulfide were distilled out. Then, p-dichlorobenzene 1116.5 g
(7.59 mol), NMP1540.2 g, and water 3
After feeding 2.7 g and reacting at a temperature of 220 ° C. for 4.5 hours, 282 g (15.7 mol) of water, 175.9 g (0.790 mol) of sodium hydrogen 4-chlorophthalate, and hydroxylation were further added. 31.32 g (0.78) of sodium
(3 mol) was injected under pressure, the temperature was raised to 255 ° C., and the reaction was carried out for 5 hours.

The obtained reaction mixture was sieved with a 100 mesh screen to separate the granular polymer, then washed with acetone 3 times, washed with water 4 times, and washed with HCl water while adjusting the pH to 3 with HCl water. After 5 times, dehydration and drying (1
Granular polymer (Polymer A) after 10 ° C for 8 hours
Was obtained with a yield of 73%. The physical properties of Polymer A were as follows. Phthalic anhydride group content IR index: 28.4%,
Melt viscosity: 1340 poise, Tm: 276 ° C, Tg: 9
0 ° C.

Reference Example 2 (Synthesis Example of PATE Containing Phthalic Anhydride Group) 108 g of polyphenylene sulfide (melt viscosity 2800 poise) manufactured by Kureha Chemical Industry Co., Ltd. was placed in a titanium-lined autoclave.
P500 g, sodium hydroxide 7 g, and hydrous sodium sulfide 8.43 g (0.05 mol as S content) were charged, water 8.8 g was added, and the atmosphere was replaced with nitrogen.
The temperature was raised to 0 ° C., the reaction was carried out for 30 minutes to depolymerize, and then the mixture was cooled to room temperature. Next, 17.8 g (0.08 mol) of sodium hydrogen 4-chlorophthalate and 48.6 g of water were added, and the temperature was raised to 255 ° C. to react for 2 hours.

The polymer was separated from the obtained reaction mixture, immersed in HCl water adjusted to pH 1 with stirring, washed with water, dehydrated and dried to obtain a polymer (polymer B). The physical properties of Polymer B were as follows.
Phthalic anhydride group content IR index: 215%, melt viscosity:
10 poise or less, Tm: 284 ° C, Tg: 82 ° C.

Reference Example 3 (Synthesis Example of PATE Containing Carboxyl Group) In a titanium-lined autoclave, 8000 g of NMP and 3360 g of sodium sulfide hydrous (19.99 mol as S content, water content 5)
3.6% by weight), and 60 g of calcium hydroxide (0.
81 mol) was charged and the atmosphere was replaced with nitrogen, and then gradually 200 ° C.
NMP solution 240 containing 1260 g of water while heating to 240
0 g and 0.50 mol of hydrogen sulfide were distilled off. Then p
2646 g (18.00 mol) of dichlorobenzene,
384 g (2.01 mol) of 3,5-dichlorobenzoic acid,
And 3000 g of NMP are supplied, and at a temperature of 220 ° C., 5
After reacting for a period of time, 1000 g (55.6 mol) of water was further added under pressure, the temperature was raised to 255 ° C., and a reaction was conducted for 5 hours.

The obtained reaction mixture was sieved with a 100 mesh screen to separate the granular polymer, washed with acetone, then immersed in water adjusted to pH 1 for 2 hours with stirring, and then washed with water. A white granular polymer (Polymer C) was obtained with a yield of 50% through dehydration and drying.
In the infrared absorption spectrum of Polymer C, absorption was observed at 1700 cm ^-1 , and the calcium content determined by ion chromatography was only 60 ppm. From this, it was confirmed that 3,5-dichlorobenzoic acid was certainly copolymerized and that the carboxylic acid was present as an acid. Physical properties of polymer C were as follows. Carboxylic acid component content determined by oxygen analysis: 9.5 mol%, Tm: 274 ° C., Tg: 83 ° C.,
Melt viscosity: 50 poise.

<Thermogravimetric Analysis Test> The results of thermogravimetric analysis of Polymer A and Polymer C are shown in FIG. The monocarboxyl group-containing PATE (Polymer C) shows a decrease in thermogravimetry, which is considered to be due to decarboxylation, in the relatively low temperature region, while the phthalic anhydride group-containing PATE is present.
(Polymer A) does not show such a decrease in thermogravity. In addition, polyphenylene sulfide having no functional group (Kureha Chemical Industry Co., Ltd., melt viscosity 1400 poise))
The result of thermogravimetric analysis of (PPS-D) is shown in FIG. As is clear from comparison between FIG. 1 and FIG. 2, the results of thermogravimetric analysis of the phthalic anhydride group-containing PATE (Polymer A) are the same as those of the unmodified PATE, and the thermal stability of the phthalic anhydride group is extremely high. It turns out that it is very good. Therefore, the resin composition of the present invention can obtain good mechanical properties without loss of functional groups even under severe processing conditions. On the other hand, monocarboxyl-containing PATE
In the case of (Polymer C), decarboxylation occurs during melt-kneading with polyamide, and functional groups are lost, so that the expected compatibilizing effect is not exhibited.

[Examples 1 to 8 and Comparative Examples 1 to 3] The polymer components shown in Table 1 were uniformly dry blended and dried in a vacuum dryer at 95 ° C. under a vacuum of 1 mmHg or less for about 8 hours. The water was sufficiently removed. Then, using a Labo Plastomill mixer (manufactured by Toyo Seiki Co., Ltd.), the mixture was melt-kneaded at 300 ° C. for about 4 minutes. A test piece was prepared for each melt-kneaded product, the breaking elongation was measured, and the dispersed state was observed. The results are shown in Table 1.

[0051]

[Table 1] (Footnote) (1) PPS-D: Polyphenylene sulfide (Kureha Chemical Industry Co., Ltd., melt viscosity 1400 poise) (2) Nylon 66: Polyamide (Hoechst Celanese Co., Ltd.)

[Reference Example 4] A titanium-lined autoclave was charged with 3200 g of NMP and 135 hydrated sodium sulfide.
After charging 1.1 g (8.00 mol as S content), 53.9 g (0.24 mol) of sodium hydrogen 4-chlorophthalate, and 9.6 g (0.24 mol) of sodium hydroxide, and performing nitrogen substitution, While gradually raising the temperature to 200 ° C,
NMP solution 1 containing 543.1 g (30.15 mol) of water
373.8 g and 0.17 mol of hydrogen sulfide were distilled off. Then, 1139.5 g of p-dichlorobenzene (7.75)
Mol), NMP1540.2g, and water 32.7g are supplied, and after making it react at the temperature of 220 degreeC for 4.5 hours, 211g (11.7mol) of water was further press-fitted and it heated up at 255 degreeC. The reaction was carried out for 5 hours.

Thereafter, the post-treatment was carried out in the same manner as in Reference Example 1 to obtain a granular polymer (Polymer E) with a yield of 78%. The conversion rate of p-dichlorobenzene at the completion of the first-stage polymerization was 91%. Physical properties of polymer E were as follows. Phthalic anhydride group content IR index: 16.0%, melt viscosity: 100
0 poise, Tm: 277 ° C, Tg: 89 ° C.

Reference Example 5 PATE having a melt viscosity of about 1400 poise (Fortron KPSW21 manufactured by Kureha Chemical Industry Co., Ltd.)
4) (PPS-D) with phthalic anhydride in a weight ratio of 98 /
After dry blending at a ratio of 2, twin screw extruder BT-3
No. 0 was used to extrude and pelletize at a maximum setting temperature of 310 ° C. to obtain a melt-modified polymer a. The melt-modified polymer a had a phthalic anhydride group content of 119% by IR index.
Similarly, the PATE was dry blended with sodium hydrogen 4-chlorophthalate at a weight ratio of 98/2, and then the maximum set temperature of 310 was obtained using a twin-screw extruder BT-30.
It was extruded and pelletized at 0 ° C. to obtain a melt-modified polymer b. The phthalic anhydride group content of the melt-modified polymer b was 29% by IR index.

Measurement of IR index after remelting treatment by NMP
Constant Then, the molten modified polymer a, b and Reference Example 4 made polymer E, were performed remelting treatment with NMP, and the evaluation of the amount of functional groups by subsequent IR. That is, 50 g of each polymer was separately placed in a 1 liter autoclave, and 500 g of NMP, 30 g of water and 4 g of NaOH were added,
After purging with nitrogen, the temperature was raised from room temperature to 255 ° C. in about 1 hour to melt the polymer, and heating was stopped immediately after reaching 255 ° C. with stirring. And about 1.5 up to about 80 ℃
Cooled in time. The slurry taken out after cooling was sieved with a 100 mesh sieve and then washed with NaOH (pH: 1 to remove phthalic acid extracted by the remelting treatment with NMP).
2.5) Wash three times with HCl to obtain the acid form (pH:
2) Two times were carried out, and after drying, a quenched press sheet was prepared at 320 ° C., and the phthalic anhydride group content was examined by infrared absorption spectrum measurement.

Regarding the IR index, the melt-modified polymers a and b were both 0% and the polymer E was 12%. That is,
In a system in which PATE is mixed with phthalic anhydride or sodium hydrogen 4-chlorophthalate and melt-extruded,
The content of phthalic anhydride is shown, but when remelted and extracted with NMP, the infrared characteristic absorption band of phthalic anhydride is not detected, and the spectrum is the same as that of PATE. On the other hand, in the polymer E, the presence of phthalic anhydride is clearly confirmed even after the remelting treatment with NMP. Therefore, it can be seen that the bonding force of the phthalic acid group is different from that in the simple mixing and melt extrusion methods.

[Examples 9 to 14 and Comparative Examples 4 to 7] Table 2
Dry-blend each polymer component shown in 10
After vacuum drying at 5 ° C for 10 hours, twin-screw extruder BT-30
Was extruded and pelletized at a maximum set temperature of 285 ° C. Next, each of the obtained pellets was vacuum-dried at 105 ° C. for 10 hours, and then the 75T injection molding machine was used, the mold temperature was 145 ° C.
Were molded into a tensile test piece and an Izod impact test piece. Table 2 shows the mixed composition of the sample and the mechanical property evaluation results. The tensile test was carried out at a tensile speed of 5 mm / min based on ASTM-D638. The Izod impact test was based on ASTM-D256.

[0058]

[Table 2]

(Footnote) (1) PPS-D: polyphenylene sulfide (Kureha Chemical Industry Co., Ltd., melt viscosity 1400 poise) (2) Nylon 66: polyamide (Hoechst Celanese Co., Ltd.) (3) Tensile test is absolutely dry And measure. (4) The Izod impact test was performed after adjusting the temperature and humidity at 23 ° C and 50% humidity. * Anti-notch: Reverse notch

[0060]

EFFECTS OF THE INVENTION The present invention provides a resin composition containing a PATE component and a polyamide, which can easily obtain good mechanical properties even under severe processing conditions.

[Brief description of drawings]

FIG. 1 PATE containing phthalic anhydride group (Polymer A)
3 is a chart showing the results of thermogravimetric analysis of monocarboxyl group-containing PATE (polymer C).

FIG. 2 is a chart showing the results of thermogravimetric analysis of polyphenylene sulfide.

Claims (4)

[Claims] 1. A resin composition containing a polyarylene thioether and a polyamide, wherein at least a part of the polyarylene thioether is a polyarylene thioether containing a phthalic anhydride group. . 2. The resin composition according to claim 1, wherein the phthalic anhydride group-containing polyarylene thioether has an IR index of 2% or more after remelting treatment with N-methyl-2-pyrrolidone. [However, the IR index after the remelting treatment with N-methyl-2-pyrrolidone is a value measured by the following method. First, 50 g of the polymer was placed in a 1 liter autoclave, 500 g of N-methyl-2-pyrrolidone, 30 g of water, and 4 g of NaOH were added, and after nitrogen substitution, the polymer was melted by heating, and then immediately cooled while stirring, The slurry taken out after cooling was sieved with a 100 mesh sieve and washed with NaOH (pH: 12.
5) 3 times, washed with HCl (pH: 2) 2 to convert to acid form 2
Carry out times. Then, the washed polymer was dried, hot-pressed at 320 ° C., put into ice water and rapidly cooled, and the infrared absorption spectrum of the transmission method was measured by FT-IR1760 manufactured by Perkin-Elmer Co., Ltd. From the spectrum obtained, the absorbance ratio at 1850 cm ^-1 , which is the characteristic absorption band of the phthalic anhydride group, is divided by the absorbance at 1900 cm ^-1 , which is the CH out-of-plane bending angle overtone absorption band, to obtain an absorbance ratio of 100.
The numerical value (IR index:%) multiplied by is calculated. ] 3. A method for producing PATE by polymerizing a dihalogen-substituted aromatic compound and an alkali metal sulfide in a polar organic solvent containing [I] water, wherein the phthalic anhydride group-containing polyarylene thioether comprises A monohalogen-substituted phthalic acid compound is allowed to be present in the polymerization reaction system, and the ratio a / b between the mole number a of the charged dihalogen-substituted aromatic compound and the mole number b of the charged alkali metal sulfide is 0.8 <a / b <. Method of setting to the range of 1, or [II]
In a polar organic solvent containing water, PATE is reacted with an alkali metal sulfide to obtain a depolymerized product having an alkali thiolate group at the terminal by depolymerization for cutting the main chain of PATE, and then to the depolymerized product. The resin composition according to claim 1 or 2, which is obtained by a method of reacting a monohalogen-substituted phthalic acid compound. 4. Polyarylene thioethers 0 to 98.
5% by weight, phthalic anhydride group-containing polyarylene thioether 0.5 to 99% by weight, and polyamide 99.5
The resin composition according to any one of claims 1 to 3, containing 1% by weight.