JP2001279097A - Polyarylene sulfide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To extremely improve the toughness and impact resistance of a molded product without deteriorating various kinds of properties of a polyarylene sulfide, such as heat resistance and chemical resistance. SOLUTION: This polyarylene sulfide composition comprises the polyarylene sulfide containing 50-100 μmol/g carboxyl group (a1) in the resin, and an epoxysilane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin composition which has excellent toughness and can be widely used for molded articles such as electric and electronic parts and automobile parts.

[0002]

2. Description of the Related Art Polyarylene sulfide typified by polyphenylene sulfide has excellent heat resistance, chemical resistance and the like, and is widely used in molded products such as electric and electronic parts and automobile parts. However, polyarylene sulfide was generally poor in toughness, and the molded product had insufficient impact strength and was very brittle.

As a technique for improving these, for example, JP-A-5-209054 discloses that the toughness and impact resistance of polyarylene sulfide are improved by reacting a modified polyarylene sulfide with an epoxy coupling agent. Techniques are disclosed.

[0004]

However, in this technique, in order to introduce a functional group capable of reacting with the epoxy compound, it was necessary to carry out modified copolymerization with a monomer having a functional group at the time of polymerization of polyarylene sulfide. The use of the modified copolymerized monomer is expensive in terms of cost, and also involves a problem that the production method becomes complicated because the polyarylene sulfide and the epoxy compound are reacted in an organic solvent in the presence of an alkali. Furthermore, copolymerization of the modified monomer makes it difficult to increase the molecular weight of the polyarylene sulfide due to the difference in monomer reactivity.

A method of reacting an epoxy-based coupling agent using a terminal functional group present in a resin of polyarylene sulfide is also known. However, from the viewpoint of maintaining the performance of polyarylene sulfide, the amount of the terminal group is reduced. Has a limit in increasing the toughness, and again, the effect of improving the toughness is not sufficient.

[0006] The problem to be solved by the present invention is to selectively increase the content of a functional group having reactivity with a coupling agent without particularly aiming at copolymerization.
An object of the present invention is to dramatically improve the toughness and impact resistance of a molded product without deteriorating various physical properties of polyarylene sulfide such as heat resistance and chemical resistance.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that by blending a polyarylene sulfide containing a specific amount of a specific functional group with an epoxy compound, the toughness and the toughness are improved. It has been found that a polyarylene sulfide composition having a significantly improved impact resistance can be obtained, and the present invention has been completed. The details will be described below.

That is, the present invention relates to a carboxyl group (a1)
(A) containing 50 to 100 μmol / g in a resin and a coupling agent (B) containing a functional group reactive with a carboxyl group
And a polyarylene sulfide resin composition comprising:

The polyarylene sulfide (A) used in the present invention has the following structure

Embedded image (Wherein R is a functional group reactive with H, an alkyl group or an acid or an alkali, and n is an integer of 0 to 4).
Of the various terminal functional groups present in the resin structure, the carboxyl group (a1) was converted to 50 to 100 μmol /
g.

In the present invention, among various terminal functional groups present in the resin structure of polyarylene sulfide,
By selectively increasing the content of the carboxyl group (a1) and adjusting the content to the range, the effect of improving the toughness and impact resistance by modification with the coupling agent (B) is dramatically increased.

The method for introducing the carboxyl group (a1) into the resin structure of the polyarylene sulfide is not particularly limited, but an alicyclic amide compound is used as a reaction solvent during the polymerization of the polyarylene sulfide. Efficient use of carboxyl group (a1)
Can be introduced. That is, in the method, the alicyclic amide compound is incorporated into the polyarylene sulfide resin structure as an aminoalkylcarboxyl group by hydrolysis during the polymerization of the polyarylene sulfide.

The amount of the carboxyl group (a1) present in the resin structure of the polyarylene sulfide is in the range of 50 to 100 μmol / g as described above, but may be in the range of 50 to 70 μmol / g. It is preferable because it has the effect of improving the toughness and impact resistance of the molded product, as well as excellent suppression of the generation of decomposition gas at the time of melting and excellent moldability. Further, in the present invention, the resin structure of the polyarylene sulfide further contains substantially no carboxylic acid metal salt (a2) such as a sodium salt or a potassium salt of a carboxyl group. Is not more than 15 μmol / g,
It is preferable because the effect of improving the toughness and impact resistance by the modification of the coupling agent (B) is dramatically increased.

The melt viscosity of the polyarylene sulfide (A) is not limited, but preferably has a melt viscosity at 300 ° C. of 20 to 10,000 poise from the viewpoint of fluidity of the composition.

The method for producing the polyarylene sulfide (A) is not particularly limited. For example, the step I: using an alkali metal sulfide (s1) as the sulfidizing agent (S); Alternatively, the alkali metal hydrosulfide (s2) and the alkali metal hydroxide (s3) are converted into (s
3) / (s2) is used in a molar ratio of 1 or less, and this is mixed with an alicyclic amide compound to form a mixed solution. Step II: The polyhalo aromatic compound (D) is added dropwise to the mixed solution. Step III: Next, after completion of the dropping of the polyhaloaromatic compound (D), after the consumption rate of (D) becomes 50% or more, the alkali metal hydroxide (s3) is added to the system. Step IV: Then, a method of treating with an acid is preferable because the amount of the carboxyl group (a1) can be selectively increased.

As the sulfidizing agent used in step I, the alkali metal sulfide (s1) may be used alone, or the alkali metal hydrosulfide (s2) and the alkali metal hydroxide (s3) may be replaced by the compound (s3) / (S2) molar ratio of 1
It is used in the following ratio. In the latter case, an alkali metal sulfide (s1) may be used in combination.
That is, by using the sulfidizing agent (S) under such conditions, when mixed with an alicyclic amide compound, it is possible to suppress the generation of excess alkali, and to significantly improve the molecular weight of polyarylene sulfide. it can.

In step I, the above-mentioned sulfidizing agent (S)
And an alicyclic amide compound to form a mixed solution. Specifically, an alkali metal sulfide (s1) is mixed with an alicyclic amide compound, or an alkali metal hydrosulfide (s2), an alkali metal hydroxide (s3) and an alicyclic amide compound are mixed (s3). / (S
There is a method of mixing under the condition that the molar ratio of 2) is 1 or less.

Here, the usable alkali metal sulfide (s1) is not particularly limited, and can be used as an anhydride or a hydrate of the alkali metal sulfide.
For example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesium sulfide, or a hydrate thereof, and the like, may be used each alone, or two or more kinds may be used in combination. . Among the alkali metal sulfides, sodium sulfide and potassium sulfide are preferable from the viewpoint of excellent reactivity, and sodium sulfide is particularly preferable.

When an anhydride is used as the alkali metal sulfide (s1), it may be used as an aqueous solution.

Further, these alkali metal sulfides (s1)
Can be obtained by preliminarily reacting an alkali metal hydrosulfide (s2) with an alkali metal base, or hydrogen sulfide and an alkali metal base in a reaction vessel, but it is also possible to use one prepared outside the reaction system. Good. Here, as the alkali metal base, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and the like, among which lithium hydroxide, sodium hydroxide and potassium hydroxide are preferred Particularly preferred is sodium hydroxide. These may be used alone or in combination of two or more.

The alkali metal hydrosulfide (s2) is not particularly limited, and may be used as an anhydride or a hydrate of the alkali metal sulfide. Examples thereof include lithium hydrosulfide, sodium hydrosulfide, and potassium hydrosulfide. , Rubidium hydrosulfide and cesium hydrosulfide, or hydrates thereof. These may be used alone, respectively.
Two or more kinds may be used as a mixture.

Among these alkali metal hydrosulfides, sodium bisulfide and potassium bisulfide are preferred from the viewpoint of excellent reactivity, and sodium bisulfide is particularly preferred. In addition,
In this adjustment, a small excess of an alkali metal base may be added in order to remove impurities present in trace amounts in the alkali metal sulfide and alkali metal hydrosulfide.

The alkali metal hydrosulfide can be obtained by reacting hydrogen sulfide with an alkali metal base, but a product prepared beforehand outside the reaction system may be used. As the alkali metal base, any of those described above can be used.

As the alkali metal hydroxide (s3),
Lithium hydroxide, sodium hydroxide, potassium hydroxide,
Rubidium hydroxide, cesium hydroxide and the like,
Among them, lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable because hydrolysis of the alicyclic amide compound is easy.
These may be used alone or in combination of two or more. The alkali metal hydroxide (s3) may be any of an anhydride, a hydrate, and an aqueous solution, but is preferably used in the form of an aqueous solution in order to be easily dissolved in an organic polar solvent as described above. Preferably, specifically,
The concentration is preferably in the range of 10 to 50% by weight. In this case, the water used is preferably water from which anions and cations that inhibit the reaction have been removed, such as distilled water and ion-exchanged water.

Here, as the alicyclic amide compound, N
-Methylpyrrolidone (NMP), N-cyclohexylpyrrolidone (NCP), N-methylcaprolactam and the like. Among them, N-methylpyrrolidone (NMP) is preferable in that it has good reactivity with an alkali metal hydroxide. In the present invention, the alicyclic amide compound functions also as a reaction solvent. The amount used depends on the type of the solvent to be used and the amount of water with respect to the solvent in the system, and is not particularly limited, but the viscosity of the reaction system capable of performing a uniform polymerization reaction is maintained. In order to maintain the productivity of the sulfidizing agent, the amount is preferably in the range of 1.0 to 6.0 mol per 1 mol of the sulfur source in the sulfidizing agent used for the polymerization. Further, in order to further increase the productivity, the range is preferably 2.5 to 4.5 mol per 1 mol of the sulfur source in the sulfidizing agent (S).

Next, as step II, polymerization is carried out while dropping the polyhaloaromatic compound (D). The polyhalo aromatic compound (D) that can be used here is not particularly limited, but for example, p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 1,2,3-trihalobenzene, 1,2,2 4-trihalobenzene, 1,3,5-trihalobenzene, 1,2,3,4-tetrahalobenzene, 1,2,3,5-tetrahalobenzene, 1,2,2
4,5-tetrahalobenzene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1-methoxy-2,5
-Dihalobenzene, 4,4'-dihalobiphenyl, 3,
5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5
-Dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p'-dihalodiphenyl ether, 4,4'-dihalobenzophenone,
4,4'-dihalodiphenyl sulfone, 4,4'-dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide and the like can be mentioned.

Among these, p-dihalobenzene,
m-Dihalobenzene, 4,4'-dihalobenzophenone and 4,4'-dihalodiphenylsulfone are preferably used, and p-dihalobenzene and m-dihalobenzene are particularly preferred. Here, as the dihalobenzene such as p-dihalobenzene and m-dihalobenzene, those having an alkyl group having 1 to 18 carbon atoms as a substituent on the aromatic ring can also be preferably used. The halogen atom in each of the above polyhalo aromatic compounds (D) is preferably a chlorine atom or a bromine atom.

Also, a copolymer containing two or more different reaction units can be obtained by an appropriate selection combination of the polyhalo aromatic compound (D). The specific combination is not particularly limited, and two or more arbitrarily selected from the above can be appropriately combined. Specifically, p-dichlorobenzene and 4,4′- It is preferable to use in combination with dichlorobenzophenone or 4,4'-dichlorophenylsulfone since polyarylene sulfides having various excellent physical properties can be obtained. When two or more dihaloaromatic compounds are used with p-dihalobenzene as a component, 70 mol% of p-dihalobenzene in the polyhaloaromatic compound (D) is used.
Or more, preferably 90 mol% or more, more preferably 99 mol% or more.
It is preferable to use it in a proportion of at least mol% from the viewpoint of excellent toughness improving effect.

The amount of the polyhaloaromatic compound (D) used is desirably in the range of 0.8 to 1.3 moles, preferably 0.9 to 1.3 moles, per mole of the sulfur source in the sulfidizing agent (S) used.
The range of 1.10 mol is preferred from the viewpoint that a polymer having excellent physical properties, that is, a higher molecular weight polyarylene sulfide can be obtained.

Incidentally, in order to form the terminal of the produced polymer,
Alternatively, a monohalo compound may be used in combination with the polyhalo aromatic compound (D) in order to control the polymerization reaction or the molecular weight.

The polymerization conditions in the step II are not particularly limited, but in order to suppress side reactions, 2
The reaction is preferably performed at a relatively low temperature of 00 to 230 ° C.

Next, in Step III, after the dropping of the polyhaloaromatic compound (S) is completed, after the consumption rate of the polyhaloaromatic compound (D) becomes 50% or more, the alkali metal hydroxide (s3) Is added to the reaction system.

The consumption rate referred to here is derived from the ratio of the remaining amount of the polyhaloaromatic compound and the charged amount at a certain point in time. In the present invention, the content of the carboxyl group (a1) in the final product polyarylene sulfide is dramatically increased by adding the alkali metal hydroxide (s3) after the consumption rate becomes 50% or more. Can be increased.

As described above, the alkali metal hydroxide (s3) used in Step III can be used alone or as an aqueous solution of the alkali metal hydroxide. At this time, the water used is preferably water excluding anions and cations that inhibit the reaction, such as distilled water and ion-exchanged water, as in step I. The amount of the alkali metal hydroxide (s3) used in the step III is not particularly limited, but the sulfidizing agent (S) used in the step I used is not limited.
A ratio of 1.03 to 1.10 mol per 1 mol is preferable because the effect of the present invention becomes remarkable.

The reaction temperature after adding the alkali metal hydroxide (s3) in the system in this step III is not particularly limited, but is preferably 200 to 300 ° C.
Further, the reaction is preferably performed at a temperature of 220 to 260 ° C.

The reaction vessel used in the reactions of Steps I to III is not particularly limited, but a polymerization vessel whose liquid contact part is made of titanium, chromium, zirconium, or the like is used. In both the reactions of Step II and Step II, it is preferable to carry out the reaction under an inert gas atmosphere.
Examples of the inert gas include nitrogen, helium, argon, and the like. Among them, nitrogen is preferable in terms of economy and ease of handling.

At the end of the reaction, the polymer obtained in Step III is recovered by directly removing the solvent by heating the reaction mixture as it is, or adding an acid or a base, and then heating under reduced pressure or normal pressure to remove the solvent. Water, acetone,
A method of washing once or twice or more with a solvent such as methyl ethyl ketone or alcohol, and further neutralizing, washing with water, filtering and drying; and

After completion of the reaction, water, acetone, methyl ethyl ketone, alcohols, ethers,
Solvents such as halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons (soluble in the polymerization solvent used and at least poor solvent for the produced polymer) are added with a precipitant. To precipitate the solid product such as polymer, inorganic salt, etc., and then filter, wash and dry it. After the reaction is completed, the reaction mixture is added to the reaction solvent (or equivalent solubility to low molecular weight polymer). Organic solvent), and the mixture is stirred, filtered to remove the low molecular weight polymer, washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, or alcohols, and then neutralized, washed with water, and filtered. Separate and drying methods are included.

In each of the above-mentioned methods, drying may be carried out under vacuum, or may be carried out in air or in an atmosphere of an inert gas such as nitrogen.

The polyarylene sulfide (A) thus obtained is then treated with an acid as step IV.
Examples of the acid used here include hydrochloric acid, sulfuric acid, carbonic acid, acetic acid and the like. The method of treatment is not particularly limited, but a method in which the obtained slurry is washed with water, and an acid is added to adjust the pH to 6.5 or less, and the washing is further repeated with water.

The polyarylene sulfide (A) thus obtained can be used as it is for various molding materials, but can be thickened by heat treatment in air or oxygen-enriched air or under reduced pressure. Yes, after performing such a thickening operation as needed, it may be used for various molding materials.

The heat treatment temperature varies depending on the treatment time and the atmosphere in which the treatment is carried out, and thus cannot be unconditionally specified. The heat treatment may be performed in a molten state at a temperature equal to or higher than the melting point of the polymer using an extruder or the like.
It is preferable to carry out the reaction at a temperature not higher than the melting point plus 100 ° C.

The amount of the carboxyl group (a1) contained in the polyarylene sulfide (A) is measured by the following method.

(Measurement of Microscopic FT-IR) An appropriate amount of polyarylene sulfide, which is an object to be measured, is pressed and formed into a disk-shaped sample for measurement. Next, the sample is set on a microscopic FT-IR apparatus and measurement is performed. Separately, p-
Chlorophenylacetic acid was mixed in a predetermined amount in polyarylene sulfide, and the absorption curve obtained by the same operation was 1705 cm ^-1 with respect to the absorption intensity of 2666 cm ^-1.
The numerical value obtained from the calibration curve obtained by plotting the relative intensity of the absorption intensity of the above is the μmol / g of the amount of carboxyl groups (a1) contained in the polyarylene sulfide.

Further, polyarylene sulfide (A)
And the composition of the coupling agent (B) and the coupling agent (B), the denatured state can be confirmed by microscopic FT-IR measurement.
That is, the absorption peak of the C ＝ O stretching vibration derived from the carboxyl group at 1705 cm −1 disappears due to the reaction, and 1740 cm −1.
A new absorption peak of C ＝ O stretching vibration derived from an ester bond appears at cm-1.

Next, in the coupling agent (B) containing a functional group having a reactivity with a carboxyl group, the functional group having a reactivity with a carboxyl group is not particularly limited. , A hydroxyl group or the like, but in the present invention, an epoxy group is preferable from the viewpoint of reactivity with a carboxyl group. Therefore, as the coupling agent (B), an epoxy coupling agent is used. It is preferred that

Such an epoxy-based coupling agent includes 1
It contains one or more epoxy groups per molecule,
Although not particularly limited, an epoxysilane coupling agent represented by 3-glycidoxypropyltrimethoxysilane and 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, or an epoxy group having two epoxy groups per molecule. Bisphenol A type, bisphenol F type, alicyclic type, cresol novolak type, epoxy resin represented by phenol novolak type and the like containing epoxy resin or more are included, but epoxy silane cups are excellent in improving the toughness and impact resistance. Ring agents are particularly preferred.

Next, the mixing ratio of the coupling agent (B) in the composition is not particularly limited, but the effect of the present invention is remarkable, and the amount of the coupling agent (B) is relative to the polyarylene sulfide (A). Therefore, a ratio of 0.1 to 40% by weight is preferable.

The composition of the present invention has the object of the present invention in order to further improve the performance such as strength, heat resistance and dimensional stability in addition to the above-mentioned components (A) and (B). They can be used in combination with various fillers as long as they are not damaged.

Examples of the filler include a fibrous filler and an inorganic filler. As the fibrous filler, glass fiber, carbon fiber, silane glass fiber, ceramic fiber, aramid fiber, metal fiber, potassium titanate, silicon carbide,
Fibers such as calcium sulfate and calcium silicate, and natural fibers such as wollastonite can be used. Examples of the inorganic filler include barium sulfate, calcium sulfate, clay, viroferrite, bentonite, sericite, zeolite, mica, mica, talc, atalpargite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, and glass beads. Can be used.

In addition, a small amount of a releasing agent, a coloring agent, a heat stabilizer, a UV stabilizer, a foaming agent, a rust inhibitor, a flame retardant, etc. Lubricants can be included. Further, similarly, the following synthetic resins and elastomers can be mixed and used.
These synthetic resins include polyester, polyamide,
Polyimide, polyetherimide, polycarbonate,
Polyphenylene ether, polysulfone, polyethersulfone, polyetheretherketone, polyetherketone, polyarylene, polyethylene, polypropylene, polytetrafluoroethylene, polydifluoroethylene, polystyrene, ABS resin, epoxy resin, silicone resin, phenol Resins, urethane resins, liquid crystal polymers and the like can be mentioned, and elastomers include polyolefin-based rubber, fluorine rubber, silicone rubber and the like.

Since the polyarylene sulfide composition of the present invention also has various properties such as heat resistance and dimensional stability inherent to polyarylene sulfide, it can be used for, for example, electrical connection of a connector, a printed circuit board, and a molded molded article. Injection molding or compression molding of automotive parts such as electronic parts, lamp reflectors and various electrical components, interior materials such as various buildings, aircraft and automobiles, or precision parts such as OA equipment parts, camera parts and watch parts. Or, it is useful as a material for various molding processes such as extrusion molding or pultrusion molding of composites, sheets, pipes, etc., or as a material for fibers or films.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

(Synthesis of Polyarylene Sulfide) Synthesis Example 1 A 4 liter stainless steel (titanium-lined) autoclave with stirring blades connected to a temperature sensor, a cooling tower, a dropping tank, and a dropping pump was charged with sodium sulfide hydrate (hereinafter Na2
804.2 g (5.0 mol) of N-
1983 g of methyl-2-pyrrolidone (hereinafter abbreviated as NMP)
(20 mol) was charged at room temperature, and the temperature was raised to 205 ° C. under a nitrogen atmosphere with stirring to distill 315.0 g of water. Thereafter, the system was closed, the temperature was further raised to 220 ° C., and 735.0 g of paradichlorobenzene (hereinafter abbreviated as p-DCB)
(5.0 mol) was added dropwise. After stirring at 220 ° C. for 3 hours, 12.5 g (0.15 mol) of 48% sodium hydroxide was added. Thereafter, the temperature was raised to 250 ° C., and the mixture was stirred for 2 hours. The slurry obtained after cooling was poured into 20 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. After stirring and washing this cake again with 5 liters of hot water for 1 hour,
Filtered. This operation was repeated twice. This cake is reslurried with 5 liters of hot water again, hydrochloric acid is added and the pH is adjusted.
Was adjusted to 4.0, stirred for 1 hour, and then filtered. Next, the cake was stirred again with 5 liters of hot water for 1 hour, washed, and filtered. This operation was repeated twice, followed by filtration and drying overnight (120 ° C.) with a hot air drier to obtain 508 g (yield 94%) of a white powdery polymer.

Synthesis Example 2 33.3 g (0.4%) of 48% sodium hydroxide to be added was added.
Mol), and synthesized and purified in the same manner as in Synthesis Example 1 to obtain 503 g (yield: 93%) of a white powdery polymer.

(Measurement of Micro FT-IR) The polyarylene sulfide used in each of Examples and Comparative Examples was subjected to the pretreatment as described above, and then pressed into a disk by a press.
The measurement was performed with a microscopic FT-IR device. As an example, an FT-IR chart of the polymer used in Example 1 is shown in FIG. Of these absorptions, the relative intensity of the absorption at 1705 cm-1 with respect to the absorption at 2666 cm-1 was determined. A calibration curve was prepared by a method described separately below, and the content of the carboxyl group in the measurement sample was determined.

(Preparation of Calibration Curve) After the polyarylene sulfide used in Comparative Example 1 described below was pretreated as described above, a predetermined amount of p-chlorophenylacetic acid was added as a standard substance, and FT-IR measurement was performed. And the relative intensity of the above-mentioned absorption with respect to the amount added. The result is shown in FIG.

(Method of Adjusting Composition) The polyarylene sulfide composition used in each of Examples and Comparative Examples was prepared by mixing polyarylene sulfide and 3-glycidoxypropyltrimethoxysilane at a ratio of 99.5 wt / 0.5 wt. With a Labo Plastomill (Toyo Seiki)
It was adjusted by melting and kneading at ℃. The melt viscosity and impact strength of the obtained composition were evaluated.

(Measurement of Melt Viscosity) The melt viscosity (η) of the polyarylene sulfide composition was measured using a Koka type flow tester (300 ° C., shear rate 100 / sec, nozzle hole diameter 0.5 mm, length 1.0 mm).

(Evaluation of Toughness and Impact Resistance) The toughness of the compositions obtained in each of Examples and Comparative Examples was evaluated by a bending test. Specifically, the polyarylene sulfide composition prepared by the above-described method was heated to 300 ° C. using a small extruder.
After melt-kneading in the form of pellets, using a small injection molding machine, the thickness is 2.0 mm, the width is 10.0 mm, and the length is 60.
A 0 mm sample piece was prepared, and a bending test was performed using this sample piece. The bending test was performed with a span length of 30.0 m.
m, the test speed was 1.5 mm / min.

Examples 1 to 3 and Comparative Example 1 As shown in Table 1, polyarylene sulfide having a predetermined melt viscosity characteristic and containing a predetermined amount of a carboxyl group was mixed with 3-glycidoxypropyltrimethoxysilane. The composition was blended by the above adjustment method, and the melt viscosity and toughness of the composition were evaluated.

[0061]

[Table 1] In the table, PPS1 is PPS manufactured by Dainippon Ink and Chemicals, Inc.
"DSP C-102".

[0062]

According to the present invention, a polyarylene sulfide composition containing a specific amount of a specific functional group and an epoxy compound are blended to provide a polyarylene sulfide composition having significantly improved toughness and impact resistance. Can be provided.

[Brief description of the drawings]

FIG. 1 shows FT- of the polymer obtained in Synthesis Example 1.
It is an IR chart figure.

FIG. 2 is a correlation diagram showing a calibration curve showing a correlation between a relative intensity of absorption in FT-IR measurement and a carboxyl group content.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 CD052 CD062 CN011 EX066 FD010 GL00 GM00 GN00 GQ01 GQ05 4M109 AA01 EA13 EB06 EC03

Claims (4)

[Claims] 1. The method according to claim 1, wherein the carboxyl group (a1) is contained
A polyarylene sulfide resin composition comprising, as essential components, a polyarylene sulfide (A) containing 100 μmol / g and a coupling agent (B) containing a functional group reactive with a carboxyl group. object. 2. A polyarylene sulfide (A) having 3
The composition according to claim 1, wherein the composition has a melt viscosity at 00C of 20 to 1000 poise. 3. The composition according to claim 1, wherein the coupling agent (B) containing a functional group reactive with a carboxyl group is an epoxy coupling agent. 4. The composition according to claim 1, wherein the amount of the coupling agent (B) is from 0.1 to 40% by weight based on the polyarylene sulfide (A).