JP3053211B2 - Polyarylen sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition. More specifically, the present invention relates to a polyarylene sulfide resin composition in which the crystallization rate of the polyarylene sulfide resin is significantly improved.

[Prior art] Polyarylene sulfide resin has recently attracted attention as an engineering plastic having excellent heat resistance, chemical resistance and flame retardancy. Demand is growing significantly in the field. However, when this resin is processed by injection molding, there is a problem that a molded product having a high crystallinity cannot be obtained unless the resin is molded at a high mold temperature because of a low crystallization rate.

In order to solve this problem, as a prior art, an oligomeric ester is added to a polyarylene sulfide resin (JP-A-62-45654) and another thioether is added (JP-A-62-230849). Japanese Patent Application Laid-Open No. 62-230850), a method of adding a carboxylic acid ester (Japanese Patent Application Laid-Open No. 62-230848), and a method of adding a specific aromatic phosphate ester (Japanese Patent Application Laid-Open No. 62-230850). However, in any of the methods, there is a problem that the heat resistance of the additive is poor, so that a vapor gas or a decomposition gas is generated at the time of molding.

The addition of silicone oil to polyphenylene sulfide resin is disclosed in JP-A-54-135845. This method has been studied for the purpose of improving the solder adhesion of the polyphenylene sulfide resin, but since the silicone oil used is not modified, the compatibility with the polyphenylene sulfide resin is poor, and bleed out from the surface of the molded product. In JP-A-59-20911, a reactive substituent, for example, an amino group, a carboxylic acid group or a hydroxyl group is introduced into a side chain of silicone oil, and is added to a polyphenylene sulfide resin to form a sealed electronic component. I have. Thereby, the adhesion between the polyphenylene sulfide resin and the lead frame and the moisture resistance are improved. Further, JP-A-62-138588, JP-A-63-138588
No. 17966 discloses a system in which a silicone oil in which a glycidyl group is introduced into the side chain of a silicone oil and a polyphenylene sulfide resin are blended, and a silicone oil in which an isocyanate group or a cyanate group is introduced into a side chain or a terminal is blended with a polyphenylene sulfide resin. In addition, a composition having improved slidability is disclosed. However, these methods have a drawback that the polyphenylene sulfide resin used has a small number of reactive terminals, so that the silicone oil is not uniformly dispersed in the resin and bleeds out from the surface of the molded product.

In recent years, attempts have been made to improve the gas separation performance by nitrating polyphenylene sulfide resin with fuming nitric acid or the like, then aminating with a reducing agent such as palladium, and grafting a siloxane oligomer to the polyphenylene sulfide resin. . However, in this method, the sulfide portion of the polyphenylene sulfide resin is partially oxidized to sulfoxide and sulfonic acid, which deviates from the properties of the polyphenylene sulfide resin and becomes thermally unstable. Further, since the introduction ratio of amino groups is high, silicone oil is excessively introduced and further reacts with the side chain of polyphenylene sulfide resin, so that the improvement of the crystallization promoting effect aimed at by the present invention cannot be obtained.

[Problems to be Solved by the Invention] The present invention solves the above problems, further remarkably accelerates the crystallization speed, and can sufficiently crystallize even when molded at a mold temperature lower than that of the conventional polyarylene sulfide resin. It provides a composition.

Means for Solving the Problems The present inventors have conducted intensive studies in view of the above-mentioned current situation, and as a result, have identified a silicone oil in which a part of the polyarylene sulfide resin has been modified to an amino group and a terminal epoxy group has been modified. It has been found that the crystallization rate is remarkably improved by adding a small amount, and the present invention has been completed.

That is, the present invention relates to (A) 80% to 99.5% by weight of a polyarylene sulfide resin containing 0.01 to 5.0% by mole of an amino group per phenylene sulfide unit, and (B) a silicone oil having a terminal epoxy group-modified silicone oil represented by the following general formula: To 0.5% by weight of a polyarylene sulfide resin composition.

(Where R ₁ , R ₂ , R ₃ , R ₄ are an alkyl group, an aryl group, R ₅ ,
R ₆ is an alkylene group, an arylene group, X ₁ and X ₂ are a glycidyl group, a glycidyl ether group, a glycidyl ester group,
It is a group selected from a cyclic aliphatic epoxy group, a hydrogen atom, an alkyl group and an aryl group. However, at least one of X ₁ and X ₂ is a group selected from a glycidyl group, a glycidyl ether group, a glycidyl ester group, and a cycloaliphatic epoxy group. n is 30 to 1000. Hereinafter, the present invention will be described in detail.

The amino group-containing polyarylene sulfide resin used as the component (A) of the present invention has a repeating unit of the general formula
1 selected from crystalline polymers represented by Ar-S
Species or two or more species, in which an amino group is introduced into the main chain and / or the terminal group. Here specifically
Ar-S includes those composed of the following structural units.

(However, in the formula, R ₇ and R ₈ each represent a hydrogen atom, an alkyl group, a phenyl group, an alkoxy group, a nitro group, a halogen atom, an alkylene glycol group, a hydroxyl group, a nitrile group, a carboxyl group, a sulfonic acid group or an amino group. In the formula, X represents methylene, ethylene, isopropyl, ether or ketone.) However, an amino group-containing polyphenylene sulfide resin is particularly preferred. The main chain structure of the amino group-containing polyphenylene sulfide resin has the general formula Other components may be copolymerized as long as the structure having a repeating unit represented by the formula contains at least 70 mol%, preferably at least 90 mol%.

The amino group content in the amino group-containing polyarylene sulfide resin (hereinafter abbreviated as amino group-containing PAS) used in the present invention is 0.01 to 5.
0 mol%, preferably 0.05 to 3.0 mol%, more preferably 0.1 to 2.0 mol%. Amino group content is 5.0
If it exceeds mol%, the heat resistance of the polyarylene sulfide resin is significantly reduced, which is not preferable. If the amount is less than 0.01 mol%, the effect of the present invention is small, and it is difficult to achieve the object of the present invention.

The structure of the amino group-containing PAS used in the present invention may be either linear or branched obtained by heat treatment, or may be a mixture thereof.

However, a polyarylene sulfide resin having an amino group introduced at the terminal is particularly preferred.

In addition, the melt viscosity of PAS containing amino groups (shear rate 100
(Second) ⁻¹ , melt viscosity at 300 ° C.) is 100 to 100,000 poise, preferably 200
Those having a poise of up to 50,000 poise, more preferably 300 to 30,000 poise are suitably used. In addition, if it is a branched product obtained by heat treatment, the melt viscosity after heat treatment is preferably 1.5 times or more, preferably 3 times or more, more preferably 5 times or more the melt viscosity before heat treatment. And 150-15000
0 poise, preferably 300 to 50,000 poise, more preferably 500 to 3,000 poise is used.

The heat treatment referred to herein means increasing the melt viscosity using a ribbon blender or the like in an air or nitrogen atmosphere at 180 to 270 ° C.

If the melt viscosity exceeds 100,000 poise, the moldability deteriorates, which is not preferable. If the melt viscosity is less than 50 poise, the chemical resistance inherent in the polyarylene sulfide resin decreases, which is not preferable.

The above-mentioned amino group-containing PAS can be produced, for example, by the following method.

(A) When reacting an alkali metal sulfide with a dihalobenzene in an organic amide solvent, a general formula [1] (X) _m Ar (NH ₂ ) _n [1] (where X is halogen and Ar is carbon (6) an aromatic hydrocarbon group represented by Formulas 6 to 18, m is an integer of 1 to 4, and n is an integer of 1 to 4.) The polymerization is carried out in the presence of an amino group-containing aromatic halide represented by the following formula:

(B) When reacting an alkali metal sulfide with a dihalobenzene in an organic amide solvent, the general formula [2] (NH ₂ ) _X Ar ′ (NO ₂ ) _y [2] (where Ar ′ is the number of carbon atoms) 6 to 18 aromatic hydrocarbon groups, x
Is an integer of 0 to 4, y is an integer of 1 to 4, provided that when x is 0, y is an integer of 2 to 4. (3) a method of polymerizing in the presence of an aromatic nitro compound represented by the formula (in this case, the nitro group is reduced to generate an amino group).

And the like.

Examples of the amino group-containing halogen compound represented by the general formula [1] include m-fluoroaniline, o-chloroaniline, m-chloroaniline, p-chloroaniline,
2,3-dichloroaniline, 2,4-dichloroaniline, 2,5
-Dichloroaniline, 2,6-dichloroaniline, 3,4-dichloroaniline, 3,5-dichloroaniline, 2-amino-4-chlorotoluene, 2-amino-6-chlorotoluene, 4-amino -2-chlorotoluene, 3-chloro-1,
2-phenylenediamine, m-bromoaniline, 3,5-dibromoaniline, m-iodoaniline, 4-chloro-1,
2-phenylenediamine, 5-chloro-1,3-phenylenediamine and mixtures thereof, especially 5-chloro-1,3-phenylenediamine, p-chloroaniline,
3,5-Dichloroaniline is preferably used.

Examples of the aromatic nitro compound represented by the general formula [2] include o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 1,2,3-trinitrobenzene, 1,2,4-trinitrobenzene, , 3,5-Trinitrobenzene, 1,2,3,5-tetranitrobenzene, 1,2,4,5-tetranitrobenzene, o-nitroaniline, m-nitroaniline, p-nitroaniline, 3-nitro-2 -Aminotoluene, 4-nitro-2-aminotoluene, 5-nitro-2-aminotoluene, 6-nitro-2-aminotoluene, 4-nitro-3-aminotoluene, 6-nitro-3-aminotoluene, 2 -Nitro-4-aminotoluene, 3-nitro-4-aminotoluene, 2,4-dinitroaniline, 2,5-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, 2,4,6 − Linitroaniline, 3-nitro-1,2-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 2-nitro-1,4-phenylenediamine, 4, 6-dinitro-1,2-phenylenediamine, 4,6
-Dinitro-1,3-phenylenediamine, 1-amino-
2-nitronaphthalene, 1-amino-3-nitronaphthalene, 1-amino-4-nitronaphthalene, 1-amino-5-nitronaphthalene, 1-amino-6-nitronaphthalene, 1-amino-7-nitronaphthalene, 1-amino-8-nitronaphthalene, 2-amino-1-nitronaphthalene, 2-amino-3-nitronaphthalene, 2-amino-4-nitronaphthalene, 2-amino-5-nitronaphthalene, 2-amino-6 -Nitronaphthalene, 2-
Amino-7-nitronaphthalene, 2-amino-8-nitronaphthalene, 1-amino-2,4-dinitronaphthalene, 1-amino-4,5-dinitronaphthalene, 1-amino-4,8-dinitronaphthalene, 2 -Amino-1,5-dinitronaphthalene, 2-amino-1,6-dinitronaphthalene, 2-amino-1,8-dinitronaphthalene, 2-amino-4,5-dinitronaphthalene, 9,10-dinitroanthracene and And mixtures thereof.

The amino group-containing aromatic halide or aromatic nitro compound may be added at once with the dihalobenzene, or may be added to the system after the polymerization of the alkali metal sulfide and the dihalobenzene has started. May be.

As the alkali metal sulfide used in the above production method,
Lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof may be used even in the form of a hydrate. A preferred alkali metal sulfide is sodium sulfide.

These alkali metal sulfides are obtained by reacting an alkali metal hydrosulfide with an alkali metal base, or hydrogen sulfide with an alkali metal base, but may be prepared in situ prior to the addition of dihalobenzene to the polymerization system. Also, it is acceptable to use one adjusted outside the system.

Before the polymerization by adding dihalobenzene, the water in the system is preferably removed by distillation or the like so as to be about 4 mol or less per 1 mol of alkali metal sulfide. It is also possible to vary the amount.

Examples of the dihalobenzene used in the above production method include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene and 1-chloro-4. -Bromobenzene and the like, and preferable examples thereof include p-dihalobenzene such as p-dichlorobenzene.

When the content is less than 30 mol% based on p-dihalobenzene, m-dihalobenzene such as m-dichlorobenzene or o-
O-dihalobenzene such as dichlorobenzene, dichloronaphthalene, dibromonaphthalene, dichlorodiphenylsulfone, dichlorobenzophenone, dichlorodiphenylether, dichlorodiphenylsulfide, dichlorodiphenyl, dibromodiphenyl and dichlorodiphenylsulfoxide. Copolymerization of a dihalo aromatic compound is not a problem. Furthermore, polyhalo aromatic compounds containing three or more halogens per molecule, such as trichlorobenzene, tribromobenzene, triiodobenzene,
It is also possible to copolymerize tetrachlorobenzene, trichloronaphthalene, tetrachloronaphthalene and the like.

As the polymerization solvent used in the above-mentioned production method, a polar solvent is preferable, and particularly, an aprotic organic amide which is stable to alkali at high temperature is preferable. Some examples of the organic amide used in the above production method include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, Examples include N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethylsulfoxide, sulfolane, tetramethylurea and the like, and mixtures thereof.

Polymerization is performed at 200 to 300 ° C, preferably at 220 to 280 ° C for 0.5 to 3
It is carried out with stirring for 0 hour, preferably 1 to 15 hours.

Recovery of the amino group-containing PAS from the reaction mixture thus obtained may be performed by using a conventional conventional technique,
For example, after collecting the solvent by distillation, flashing, etc.,
Examples of the method include a method of washing and collecting the polymer with water, a method of filtering the reaction mixture to collect a solvent, and then washing and collecting the polymer with water.

After the reaction, the amount of amino groups in the amino group-containing PAS is determined by gas chromatograph of unreacted amino group-containing aromatic halides and aromatic nitro compounds in the polymerization solvent after the reaction,
It can be determined by back-calculating the amount of amino groups in the polymer.

The silicone oil modified with a terminal epoxy group as the component (B) used in the present invention is a cyclic aliphatic epoxy group obtained by oxidizing and epoxidizing a double bond such as a glycidyl group, a glycidyl ether group, a glycidyl ester group, cyclohexene or cyclopentadiene. And so on. The epoxy group-modified silicone oil is of a type in which an epoxy group is introduced into a side chain or a terminal group, but the effect of the present invention is not exhibited at all if the epoxy group is not introduced into a terminal of the silicone oil.

The terminal-epoxy-group-modified silicone oil is, for example, a homopolymer such as dimethylsiloxane, methylphenylsiloxane, trimethylfluoropropylsiloxane, or 2
It is selected from at least one kind of copolymer and is represented by the following general formula.

Here, R ₁ , R ₂ , R ₃ , and R ₄ in the above structural formula are an alkyl group,
An aryl group, R ₅ and R ₆ are an alkylene group, an arylene group,
X ₁ and X ₂ represent a glycidyl group, a glycidyl ether group, a glycidyl ester group, a cycloaliphatic epoxy group, a hydrogen atom,
It is a group selected from an alkyl group and an aryl group. However, at least one of X ₁ and X ₂ is a group selected from a glycidyl group, a glycidyl ether group, a glycidyl ester group, and a cycloaliphatic epoxy group. n is 30 to 1000, preferably n is 40 to 900. Here, it is not preferable that n is smaller than 30, since it slightly evaporates when kneading with PAS containing an amino group. On the other hand, when n exceeds 1000, it is not industrially available.

Table 1 shows examples of commercially available silicone oils.

Next, the viscosity of the terminal epoxy group-modified silicone oil suitable for use in the present invention is not particularly limited as long as it is in the range of 10 to 20,000 cs (25 ° C.), but is preferably in the range of 50 to 8000 cs.

The amount of the component (B) is from 0.5% by weight to 20% by weight, preferably from 1% by weight to 10% by weight, based on the total amount of the components (A) and (B). Here, when the addition amount of the component (B) is less than 0.5% by weight, the crystallization promoting effect becomes small, which is not preferable. On the other hand, if the amount exceeds 20% by weight, the mechanical properties are remarkably reduced, which is not preferable.

When a nucleating agent is used in combination with the composition of the present invention, the crystallization rate is further increased, and the effect of the present invention is further increased. Crystal nucleating agents used for this purpose include silica, kaolin,
Inorganic substances such as talc, Hytron, boron nitride, etc., and organic carboxylic acid metal salts such as calcium stearate, aluminum stearate, calcium benzoate, sodium oxalate, disodium phthalate, trisodium trimellitate, tetrapotassium pyromellitate Or a polymer having a higher boiling point than the polyarylene sulfide used,
For example, polyether ether ketone, polyether ketone, polyphenylene sulfide ketone and the like are effective.

It is sufficient that the addition amount of these nucleating agents is 0.05% by weight to 10% by weight based on the total weight of the composition of the present invention,
Preferably it is 0.1% to 5% by weight. 0.05 added
If the amount is less than the weight percentage, the effect of promoting crystallization may be reduced. On the other hand, if it exceeds 10% by weight, the mechanical properties are undesirably reduced.

Further, the composition of the present invention may contain, if necessary, various substances to be filled in a general molding resin composition. Such materials include fibrous (eg, carbon fiber, glass fiber, aramid fiber, asbestos fiber,
Potassium titanate fiber, etc., scale-like (mica, graphite, glass flake, aluminum flake, etc.)
Or powdered (calcium carbonate, clay, zinc sulfate, etc.) reinforcing and non-reinforcing fillers, pigments and other colorants, light and heat stabilizers, mold release agents, plasticizers, flame retardants, A foaming agent or a special additive such as a polymer toughness imparting agent may, for example, be mentioned. The amount of the filler is 70% by weight or less, preferably 60% by weight or less based on the composition of the present invention. If the amount exceeds 70% by weight, the fluidity during molding may be poor.

Further, if necessary, polyethylene, polybutadiene,
Polyisoprene, polychloroprene, polystyrene, polybutene, poly α-methylstyrene, polyvinyl acetate,
Polyamide such as polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, nylon 46, polyethylene terephthalate, polybutylene terephthalate , Polyarylate, polyester such as liquid crystal polymer, polyurethane, polyacetator
, Polycarbonate, polyphenylene oxide, polysulfone, polyethersulfone, polyallylsulfone, polyetherketone, polyetheretherketone, polyphenylenesulfideketone, polyimide,
Polyamide imide, silicone resin, phenoxy resin,
One or more homopolymers such as fluororesins, random or block, and graft copolymers may be used in combination.

The resin composition of the present invention is obtained by melt-kneading the above components (A) and (B). For example,
After the components (A) and (B) are mixed at room temperature, they can be melt-kneaded using a roll kneader, a single-screw kneader, a twin-screw kneader, or the like, and pelletized. Alternatively, the component (B) may be diluted with a solvent, then dispersed in the component (A), and the solvent in the mixture may be removed.

Next, the temperature of the melt kneading is 5 ° C. to 100 ° C. higher than the melting point of the amino group-containing PAS, and particularly preferably 10 ° C. to 7 ° C.
0 ° C higher temperature. If the kneading is performed at a temperature lower than 5 ° C. from the melting point of the amino group-containing PAS, the dispersibility of the component (B) is poor and the effect is small. Also, the melting point of the amino group-containing PAS is 1
When kneaded at a temperature of 00 ° C. or higher, decomposition, coloring or other abnormal reactions occur, which is not preferable. The pellets thus obtained can be formed into an arbitrary shape by means of ordinary injection molding, extrusion molding, compression molding and the like.

[Examples] Next, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The crystallization rate of the polyarylene sulfide resin composition used in the following examples was measured using an amorphous sample obtained by quenching a molten sample, and using a DSC (manufactured by Seiko Denshi Kogyo KK, DSC- The evaluation was performed by measuring the cold crystallization temperature (Tc) when the temperature was raised at a heating rate of 10 ° C./min with a 200 type). In addition, analysis of amino groups introduced into the polyarylene sulfide resin is carried out by quantifying unreacted amino group-containing aromatic halides and aromatic nitro compounds in the polymerization solvent after the reaction is completed by gas chromatography, and determining amino groups in the polymer. The amount of the group was determined by back calculation.

Reference Example 1 (polyarylene sulfide) Internal volume 530 equipped with stirrer, dehydration tower and jacket
N-methyl-2-pyrrolidone (NMP) 110
And sodium sulfide (Purity: Na ₂ S 60.2% by weight) 61.1Kg
And heated with a jacket under agitation.
Dehydration was performed through a dehydration tower until 0 ° C was reached. At this time, the extract of 13.5 mainly consisting of water was distilled off. Next, 68.7 Kg of p-dichlorobenzene and NMP48 were added, and the temperature was raised to 225 ° C over 2 hours, reacted at 225 ° C for 2 hours, then raised to 250 ° C over 30 minutes, and further increased to 250 ° C. The reaction was carried out at 3 ° C. for 3 hours.

After completion of the reaction, the reaction mixture was transferred to a solvent recovery device equipped with a stirrer, a jacket and a vacuum line. At this time, NMP3
0 has been added. Subsequently, the mixture is heated under reduced pressure to obtain mainly N
A distillate 210 consisting of MP was distilled off.

Subsequently, water 200 was added to form a water slurry,
After heating and stirring for 15 minutes, the polymer was recovered by centrifugation.

Further, the polymer was returned to the solvent collector, water 200 was added, and the mixture was heated and stirred at 100 ° C. for 30 minutes. After cooling, the polymer powder was recovered by a centrifuge.

 This operation was repeated twice.

The obtained polymer was transferred to a jacketed ribbon blender and dried. The polyarylene sulfide resin thus produced was introduced into a ribbon blender having an inner volume of 150, and heated to 250 ° C. in the air with stirring to perform a heat treatment for 5 hours. The melt viscosity before the heat treatment was 500 poise, and the melt viscosity after the heat treatment was 3200 poise. The polyarylene sulfide thus obtained is designated as (I).

Reference Example 2 (PAS containing amino group) Instead of 68.7 kg of p-dichlorobenzene in Reference Example 6, 68.0 kg of p-dichlorobenzene and 5-chloro-1,3-
The amino group-containing PAS obtained in the same manner as in Reference Example 1 except that 0.68 kg of phenylenediamine is used is referred to as (II).

The melt viscosity of the obtained polymer was 550 poise, and the amino group content was 0.51 mol%.

Reference Example 3 (Amino Group-Containing PAS) The amino group-containing PAS produced in Reference Example 2 was introduced into a ribbon blender having an internal volume of 150, and heated to 250 ° C. in air with stirring to perform a heat treatment for 5 hours. The amino group-containing PAS thus obtained is referred to as (III).

The melt viscosity after the heat treatment was 3,400 poise, and the amino group content was 0.50 mol%.

Examples 1 to 3 The amino group-containing PAS (II) of Reference Example 2 and a glycidyl group-terminated silicone oil (Shin-Etsu Silicone, manufactured by Shin-Etsu Chemical Co., Ltd.) were used in the amounts shown in Table 2 in a Labo Plastomill mixer R-60. The mixture was melt-kneaded at 300 ° C. and 75 rpm for 5 minutes by using (manufactured by Toyo Seiki). The cold crystallization temperature (Tc) and melting point (Tm) of the kneaded sample were determined by DSC (Seiko Denshi Kogyo Co., Ltd., DS
C-200). The results are shown in Table 2.

Examples 4 to 5 The same conditions as in Example 1 were used, except that the amino group-containing PAS (III) of Reference Example 3 and the terminal glycidyl group-modified silicone oil (Shin-Etsu Silicone, manufactured by Shin-Etsu Chemical Co., Ltd.) were used in the mixing ratio shown in Table 2. By melt kneading.

Cold crystallization temperature (Tc), melting point (Tm) of sample after kneading
Was measured by DSC. The results are shown in Table 2.

Comparative Example 1 The amino group-containing PAS (II) of Reference Example 2 was melt-kneaded in the same manner as in Example.

Determine the cold crystallization temperature (Tc) and melting point (Tm) of the sample after kneading.
Measured by DSC. The results are shown in Table 2.

Comparative Example 2 The amino group-containing PAS (III) of Reference Example 3 was melt-kneaded in the same manner as in Example.

Determine the cold crystallization temperature (Tc) and melting point (Tm) of the sample after kneading.
Measured by DSC. The results are shown in Table 2.

Comparative Example 3 Polyarylene sulfide (I) of Reference Example 1 was melt-kneaded in the same manner as in Example.

Determine the cold crystallization temperature (Tc) and melting point (Tm) of the sample after kneading.
Measured by DSC. The results are shown in Table 2.

Comparative Examples 4 to 6 The polyarylene sulfide (I) of Reference Example 1 and a glycidyl group-modified silicone oil (Shin-Etsu Silicone;
(Shin-Etsu Chemical Co., Ltd.) and melt kneading in the same manner as in the examples with the blending amounts shown in Table 2.

Determine the cold crystallization temperature (Tc) and melting point (Tm) of the sample after kneading.
Measured by DSC. The results are shown in Table 2.

Comparative Example 7 The amino group-containing PAS (II) of Reference Example 2 and an unmodified silicone oil (Shin-Etsu Silicone KF96; manufactured by Shin-Etsu Chemical Co., Ltd.) were melt-kneaded in the amounts shown in Table 2 in the same manner as in Example. .

Determine the cold crystallization temperature (Tc) and melting point (Tm) of the sample after kneading.
Measured by DSC. The results are shown in Table 2.

Comparative Example 8 The amino group-containing PAS (II) of Reference Example 2 and the side chain glycidyl group-modified silicone oil (Shin-Etsu Silicone KF103; manufactured by Shin-Etsu Chemical Co., Ltd.) were used in the same manner as in the Examples, with the blending amounts shown in Table 2. It was melt-kneaded.

Determine the cold crystallization temperature (Tc) and melting point (Tm) of the sample after kneading.
Measured by DSC. The results are shown in Table 2.

[Effects of the Invention] According to the present invention, by adding a terminal epoxy group-modified silicone oil to an amino group-modified polyarylene sulfide resin, a resin composition having a remarkably fast crystallization rate without affecting the melting point of the resin is provided. Can be obtained, and a sufficiently crystallized molded article can be obtained even in injection molding at a low mold temperature.

Claims (1)

(57) [Claims] (A) 80% to 99.5% by weight of a polyarylene sulfide resin containing 0.01 to 5.0% by mole of amino groups per phenylene sulfide unit; (B) a silicone oil modified with a terminal epoxy group-modified silicone oil represented by the following general formula: A polyarylene sulfide resin composition comprising from 0.5% by weight to 0.5% by weight. (Where R ₁ , R ₂ , R ₃ , R ₄ are an alkyl group, an aryl group, R ₅ ,
R ₆ is an alkylene group, an arylene group, X ₁ and X ₂ are a glycidyl group, a glycidyl ether group, a glycidyl ester group,
It is a group selected from a cyclic aliphatic epoxy group, a hydrogen atom, an alkyl group and an aryl group. However, at least one of X ₁ and X ₂ is a group selected from a glycidyl group, a glycidyl ether group, a glycidyl ester group, and a cycloaliphatic epoxy group. n is 30 to 1000. )