JP2003073545A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide resin composition which has low extractability and low burr-formability in an excellent balance and is especially useful for the applications for e.g. parts for refrigerant compressors. SOLUTION: This polyphenylene sulfide resin composition comprises (a) 100 pts.wt. of polyphenylene sulfide resin and (b) 10 to 100 pts.wt. of a fibrous inorganic filler, and has an extraction amount of <=0.3 wt.% by a Soxhlet extraction method comprising a total reflux extraction using chloroform for 5 hours, a melt viscosity (320 deg.C, a shear rate of 5,000 sec<-1> ) of <=150 Pa.s, and a melt viscosity ratio of >=2.3 at a shear rate of 500 sec<-1> and a shear rate of 5,000 sec<-1> at 320 deg.C (the melt viscosity at the shear rate of 500 sec<-1> at 320 deg.C/the melt viscosity at the shear rate of 5,000 sec<-1> at 320 deg.C).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a low chloroform extractability (hereinafter referred to as low extractability) of an oligomer component and a molding die such as a compressor part used in a refrigerant. The present invention relates to a polyphenylene sulfide resin composition which is useful for applications in which a resin is flown out from the gap of the cavity and solidified, so-called burrs are reduced (hereinafter referred to as low burrs). is there.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter P
Abbreviated as PS resin. ) Has excellent properties such as heat resistance, rigidity, dimensional stability, and flame retardancy as an engineering plastic. Therefore, it is suitable for various electrical parts, mechanical parts, automobile parts, etc., mainly for injection molding. Used for purposes.

However, in applications such as compressor parts used in a refrigerant, eluates centering on a few to a dozen polymer oligomer components contained in the PPS resin float in the refrigerant, and the inside of the compressor There are problems such as clogging of the capillaries. Further, the PPS resin causes a large amount of burrs during injection molding, and the burrs of a molded product that peels off in a refrigerant cause clogging of the capillaries in the compressor, so careful deburring is essential.

[0004] Several studies aimed at the low extractability of PPS resins have been made so far. For example, P
A method of repeatedly boiling PS resin with deionized water for a long time to reduce oligomer components (JP-A-55-156342).
No.), a method of repeatedly washing and extracting a PPS resin with dimethylformamide to reduce oligomer components (Japanese Patent Laid-Open No. 62-143933). However, in the methods described in these, since the PPS resin is simply washed to remove the oligomer component, the resulting PPS resin has a melt viscosity (320 ° C.) even when blended with the fibrous inorganic filler. , Shear rate of 5000 sec ^-1 ) is 150P
Shear rate less than a · s or less or 320 ° C. 50
The melt viscosity ratio between 0 sec ^-1 and 5000 sec ^-1 is 2.3.
However, a composition excellent in low burr property cannot be obtained.

In addition, some studies have been made so far to reduce the occurrence of burrs during injection molding of PPS resin. For example, a method of adding an alkali metal organophosphate compound to a PPS resin (JP-A-64-54066) and a method of adding a silane compound to a PPS resin (JP-A-63-251).
No. 430), but in the methods described therein, neither oxidative crosslinking nor washing of the PPS resin with an organic solvent and acid treatment are carried out. Therefore, when it is used in contact with a refrigerant, it floats in the refrigerant. Not only a large amount of eluate that melts but also melt viscosity (320 ° C, shear rate 5000 sec
^-1) is 150 Pa · s less than or less, or 320 ° C. should not be less than the ratio of the melt viscosity shear rate 500 sec ^-1 and 5000Sec ^-1 is 2.3 in, obtained only insufficient low burr resistance even .

[0006]

As described above, there is no conventional technique capable of achieving both low extraction property and low burr property,
Therefore, a PPS resin composition having a low extractability and a low burr property has never been used for a refrigerant compressor part.

Therefore, the inventors of the present invention have made earnest studies for the purpose of developing a PPS resin excellent in the above-mentioned performance required for the PPS resin, that is, both low extraction property and low burr property, and as a result, it floats in the refrigerant. It was found that the degree of elution of the component can be determined by using the chloroform extraction amount as an index, and further, the chloroform extraction amount of the PPS resin composition, 320 ° C., shear rate 5
Melt viscosity measured under the condition of 000 sec ^-1 and 32
Shear rate at 0 ° C 500sec ^-1 and 5000sec
The inventors have found that a PPS resin composition having both excellent low extraction property and low burr property can be obtained by setting the ratio of the melt viscosity of ^-1 within a specific range, and arrived at the present invention.

[0008]

That is, the present invention is
A Soxhlet extraction method, which is a polyphenylene sulfide resin composition prepared by blending (b) 10 to 100 parts by weight of a fibrous inorganic filler with respect to 100 parts by weight of a polyphenylene sulfide resin, and performing total reflux extraction with chloroform for 5 hours. Extraction amount is less than 0.3% by weight, and melt viscosity (320 ° C, shear rate 5000 sec ^-1 ) is 150P.
a · s or less and a shear rate of 5 at 320 ° C.
Ratio of melt viscosity between 00 sec ^-1 and 5000 sec ^-1 (32
Melt viscosity at shear rate of 500 sec ^-1 at 0 ° C / 32
It is a polyphenylene sulfide resin composition having a melt viscosity of 5000 sec ⁻¹ at 0 ° C. of 2.3 or more.

Among them, (a) an uncrosslinked polyphenylene resin having a melt viscosity of 30 to 70 Pa · s at 320 ° C. and a shear rate of 500 sec ⁻¹ which has been washed with an organic solvent and acid treatment, and (b) a fibrous inorganic filler. A polyphenylene sulfide resin composition containing 10 to 100 parts by weight of (c) a silane compound and having a Soxhlet extraction method in which a total reflux extraction is performed with chloroform for 5 hours to give an extraction amount of 0.
3% by weight or less, 320 ° C., shear rate 5000 se
the melt viscosity at c ⁻¹ is 150 Pa · s, and
Ratio of the melt viscosity (shear rate at 320 ° C: 500 se
A polyphenylene sulfide resin composition having a melt viscosity of c ⁻¹ / melt viscosity of 5000 sec ⁻¹ at 320 ° C. of 2.3 or more is particularly preferable.

This preferred polyphenylene sulfide resin composition is (a) an uncrosslinked polyphenylene which is acid-treated after being washed with an organic solvent and has a melt viscosity of 30 to 70 Pa · s at 320 ° C. and a shear rate of 500 sec ⁻¹ . (B) fibrous inorganic filler 10 to sulfide resin
100 parts by weight and (c) a silane compound are blended, the amount of extraction by Soxhlet extraction method, which is a total reflux extraction with chloroform for 5 hours, is 0.3% by weight or less, 320 ° C., shear rate: 5000 sec ^−1. melt viscosity at is not more than 150 Pa · s, and polyphenylene sulfide ratio of the melt viscosity (melt viscosity of 5000Sec ^-1 in the melt viscosity / 320 ° C. in a shear rate of 500 sec ^-1 at 320 ° C.) is 2.3 or more It is produced by the method for producing a resin composition.

The polyphenylene sulfide resin composition of the present invention is preferably used for parts for refrigerant compressors.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula.

[0013]

[Chemical 1]

The repeating unit represented by the above structural formula is 70
From the viewpoint of heat resistance, a polymer containing at least 90 mol%, especially at least 90 mol% is preferable.

In the PPS resin, less than 30 mol% of the repeating unit can be composed of a repeating unit having the following structure.

[0016]

[Chemical 2]

The cross-linked PPS resin is a PPS resin which has undergone a step of oxidatively cross-linking such a polymer at a high temperature of 200 to 260 ° C. in the presence of oxygen, and an uncross-linked PPS resin is a PPS resin. In the presence of 200-260
PP that does not go through the process of oxidative crosslinking at a high temperature such as ℃
S resin.

Generally, PPS resins include, for example, polymers having a relatively small molecular weight obtained by a production method represented by JP-B-45-3368 and JP-B-52-122.
There is a non-crosslinked polymer which is substantially linear and has few impurities, which is obtained by the production method represented by JP-B No. 40.

The difference between the former and the latter is the presence or absence of an alkali metal carboxylate as a polymerization aid in the polymerization system.

The former is a polymer in which the degree of polymerization does not increase and the molecular weight is relatively small and the oligomer component is predominantly contained because the alkali metal carboxylate is not added to the polymerization system. Poor, poor toughness, flexibility and impact resistance. Therefore, such a polymer can be oxidatively crosslinked at a high temperature of 200 to 260 ° C. in the presence of oxygen to have a high molecular weight, reduce oligomer components, and improve toughness, flexibility and impact resistance.

In the latter, since an alkali metal carboxylate is added to the polymerization system, a PPS resin having a high degree of polymerization, a relatively high molecular weight and a relatively low content of an oligomer component can be obtained.

PPS used for the production of the composition of the present invention
As the resin, either the former PPS resin or the latter PPS resin can be used. The former, that is, as the PPS resin, for example, a PPS resin produced through a polymerization process typified by JP-B-45-3368 is used in the presence of oxygen.
When a PPS resin that is oxidatively crosslinked at a high temperature of 0 to 260 ° C. is used, the oxidative crosslinking temperature, time and degree of oxygen supply should be adjusted so that the chloroform extraction amount, melt viscosity and melt viscosity ratio of the composition are within the scope of the present invention. Need to be adjusted. In this case, it is preferable to wash the PPS resin with an organic solvent and then crosslink with oxygen for the purpose of further reducing the amount of chloroform extracted. Such conditions differ depending on the type of filler to be blended with the PPS resin and the blending ratio thereof.

When an uncrosslinked PPS resin is used in the present invention, it is preferable to prepare a PPS resin composition by blending a silane compound as described later. In that case, the composition is extracted with chloroform. In order to keep the amount, the melt viscosity and the ratio of the melt viscosity within the ranges specified in the present invention, as the PPS resin, the PPS resin produced through the polymerization step represented by JP-B-52-12240 is washed with an organic solvent. It is preferable to remove it to obtain a low extractability and to subject it to acid treatment before use.

Further, the former, that is, the crosslinked PPS resin and the latter, that is, the uncrosslinked PPS resin can be used together and adjusted so as to be within the scope of the present invention.

The organic solvent used for washing the PPS resin in the present invention is not particularly limited as long as it has no action of decomposing the PPS resin, and examples thereof include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,
Nitrogen-containing polar solvents such as 3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone , Dimethyl ether, dipropyl ether,
Ether-based solvents such as dioxane and tetrahydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichlorethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, chlorobenzene, methanol, ethanol, propanol , Butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and other alcohol / phenol solvents, and benzene, toluene, xylene, and other aromatic hydrocarbon solvents. Among these organic solvents, N-methylpyrrolidone, acetone,
Particularly preferred is the use of dimethylformamide and chloroform and the like. Further, these organic solvents are used alone or as a mixture of two or more kinds.

As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent,
If necessary, it is possible to appropriately stir or heat.

The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and any temperature from room temperature to 300 ° C. can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be, but normally, the cleaning temperature of room temperature to 150 ° C. is sufficient to obtain the effect. It is also possible to wash under pressure at a temperature above the boiling point of the organic solvent in a pressure vessel.

There is no particular limitation on the cleaning time. Depending on the cleaning conditions, it is usually 5 for batch cleaning.
A sufficient effect can be obtained by washing for more than a minute. It is also possible to wash in a continuous manner.

When the PPS resin produced by polymerization is washed with an organic solvent, it is preferable to combine it with water washing or warm water washing in order to further exert the effects of the present invention. When a high-boiling-point water-soluble organic solvent such as N-methylpyrrolidone is used, it is preferable to wash the organic solvent and then wash with water or warm water to easily remove the residual organic solvent. Water used for these washings is preferably distilled water or deionized water.

The acid to be used for the acid treatment of the PPS resin in the present invention is not particularly limited as long as it has no action of decomposing the PPS resin, and acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl. Acids and the like can be mentioned, of which acetic acid and hydrochloric acid are more preferably used, but nitric acid and the like that decompose and deteriorate the PPS resin are not preferable.

The method of acid treatment is to add P to an acid or an aqueous solution of an acid.
There is a method of immersing the PS resin, and if necessary, it is possible to appropriately stir or heat. For example,
When acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous solution of PH4 heated to 80 to 90 ° C. and stirring for 30 minutes. The PPS resin that has been subjected to the acid treatment needs to be washed several times with water or warm water in order to physically remove the residual acid or salt.

The water used for washing is preferably distilled water or deionized water in the sense that the effect of preferable chemical modification of the PPS resin by acid treatment is not impaired.

As a preferred embodiment of the present invention, a silane compound may be blended, but a PPS resin having a relatively small molecular weight is used so that the melt viscosity of the PPS resin composition falls within the range specified in the present invention. Is preferable, and for example, the melt viscosity (320 ° C., shear rate 500 sec ⁻¹ ) of the PPS resin after washing with an organic solvent and acid treatment is 30 to 7
It is preferably 0 Pa · s.

Further, in the present invention, PP to be blended
The amount of S resin extracted by the Soxhlet extraction method in which it is subjected to total reflux extraction with chloroform for 5 hours is preferably 0.5% by weight or less, more preferably 0.3% by weight or less.

In the present invention, it is necessary to blend (b) the fibrous inorganic filler for the purpose of improving the heat resistance and strength of the PPS resin. As the fibrous inorganic filler,
Examples include glass fiber, carbon fiber, and metal fiber,
Of these, glass fiber is preferable. The fibrous inorganic filler is
If necessary, it can be used after being pretreated with a silane coupling agent and a titanium coupling agent.

(B) The compounding amount of the fibrous inorganic filler is
(A) Usually, 10 to 10 parts by weight of PPS resin is used.
Although it is in the range of 100 parts by weight, a blending amount of 40 to 100 parts by weight is preferable from the viewpoint of the balance between heat resistance and mechanical strength of the resulting composition. If the blending amount of the fibrous inorganic filler is too large, the fluidity of the composition tends to be impaired.

A preferred embodiment of the present invention can be obtained by further adding a silane compound (c) to the above components (a) and (b). By this, the chloroform extraction amount, melt viscosity and melt viscosity ratio of the PPS resin composition can be controlled within the range of the present invention.

In particular, the uncrosslinked PPS that has been subjected to acid treatment by removing the oligomer component contained in the PPS resin by washing with an organic solvent to have low extractability has activated the reactivity with the silane compound. Not only can the melt viscosity ratio be controlled within the preferred range, but the amount of chloroform extracted can also be reduced. In addition to the above, uncrosslinked P having a relatively small molecular weight, for example, a melt viscosity (320 ° C., shear rate 500 sec ⁻¹ ) of 30 to 70 Pa · s.
When a PS resin is used, the number of terminal groups whose reactivity with a silane compound is activated by acid treatment is appropriately increased, so that not only the melt viscosity can be controlled within the range specified in the present invention, The amount of chloroform extracted and the melt viscosity ratio can be easily controlled within the preferred ranges in the present invention.

The amount of the silane compound blended is not particularly limited as long as it satisfies the requirements specified in the present invention and does not impair the effect, but (a) uncrosslinked PPS resin 100.
It is usually blended in a proportion of 0.001 to 0.025 parts by weight, preferably 0.005 to 0.015 parts by weight.

As the silane compound, various compounds such as an epoxysilane compound, an aminosilane compound, a ureidosilane compound and an isocyanatesilane compound can be used.

Specific examples of such compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. Containing alkoxysilane compound, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compound such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ
An ureido group-containing alkoxysilane compound such as-(2-ureidoethyl) aminopropyltrimethoxysilane,
γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanato Propylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Amino group-containing alkoxysilane compounds such as γ-aminopropyltrimethoxysilane and hydroxyl group-containing alkyl groups such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Kishishiran compounds and the like.

To the PPS resin composition of the present invention, usual additives such as a release agent, an anticorrosive agent and a crystal nucleating agent and a small amount of another kind of polymer may be added to the extent that the effects of the present invention are not impaired. it can.

For example, as the release agent, a polyolefin such as polyethylene or polypropylene, or a wax of montanic acid, a metal soap such as lithium stearate or aluminum stearate, or a fatty acid amide polycondensate such as ethylenediamine stearic acid. Examples thereof include polycondensates and ethylenediamine / stearic acid / sebacic acid polycondensates.

Examples of the anticorrosive agent include metal carbonates such as lithium carbonate and calcium carbonate, and metal oxides such as zinc oxide and calcium oxide.

Examples of the crystal nucleating agent include polyether ether ketone resin, nylon resin, talc and kaolin.

Further, a coloring inhibitor such as hypophosphite, a plasticizer such as an ester compound, or an antioxidant, a heat stabilizer, a depleting agent, an ultraviolet absorber, a coloring agent, a flame retardant, an antistatic agent, Conventional additives such as foaming agents can be added.

The method for producing the PPS resin composition of the present invention is not particularly limited, but the mixture of raw materials is fed to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. 280-3
A typical example is a method of melt-kneading at a temperature of 80 ° C. There is no particular limitation on the order of mixing the raw materials.
Further, as for the small amount additive component, it is also possible to add the other components after kneading and pelletizing the other components by the above method or the like before molding.

The PPS resin composition of the present invention has an extraction amount of 0.3 wt% or less by the Soxhlet extraction method in which it is subjected to a total reflux extraction with chloroform for 5 hours, at 320 ° C. and a shear rate of 5
Melt viscosity of 150P measured under the condition of 000sec ^-1
a · s or less and a shear rate of 50 at 320 ° C.
The melt viscosity ratio between 0 sec ^-1 and 5000 sec ^-1 is 2.3.
It is necessary to be above.

The relationship between the amount of chloroform extracted, the melt viscosity and the melt viscosity ratio of the resin composition and the low extractability and low burr property is described below.

The amount of chloroform extracted from the resin composition was 0.3.
When the content is more than 10% by weight, the clogging of the capillaries in the refrigerant compressor is likely to occur. Therefore, the chloroform extraction amount of the resin composition of the present invention needs to be 0.3% by weight or less, and 0.15% by weight or less. Preferably there is.

Generally, burrs are generated in a gap of about several tens of μm such as a parting line surface of a mold and a gas vent.
Shear rate 5 which is the velocity range of resin flowing through several tens of μm thick
At 00 sec ^-1 , the larger the melt viscosity is, the more the resin flow is blocked and the burr is less likely to occur. However, if the melt viscosity until reaching the burr portion, that is, the melt viscosity at a shear rate of 5000 sec ^-1 , which is the injection speed region, becomes large, the injection pressure for filling the molded product also becomes high. Can be a cause of increase. Therefore, the melt viscosity ratio of the resin composition of the shear rate 500 sec ^-1 and 5000sec ^-1 at 320 ° C. (320 ° C.
Viscosity at a shear rate of 500 sec ^-1 / 320 ° C
Melt viscosity at a shear rate of 5000 sec ^-1 ) of 2.
If it is less than 3, the occurrence of burrs increases, and the melt viscosity (320 ° C., 5000 sec ⁻¹ ) of the resin composition is 150 Pa.
・ Even if it is larger than s, burrs are likely to occur. Therefore, in the resin composition of the present invention, the ratio of the melt viscosity shear rate 500 sec ^-1 and 5000sec ^-1 at 320 ° C. is not less than 2.3, and a melt viscosity (320 ° C., 5
000 sec ⁻¹ ) needs to be 150 Pa · s or less. Above all, shear rate at 320 ° C: 500s
The ratio of the melt viscosity of ec ^-1 to 5000 sec ^-1 is preferably 2.5 or more. The upper limit of this ratio is not particularly limited, but is preferably 3.0 or less. Melt viscosity (320 ° C, 5000sec ^-1 ) 140Pa ・ s
The following is preferable. The lower limit of the melt viscosity is not particularly limited, but is preferably 100 or more.

To control the PPS resin composition within the above range, the above-mentioned methods are adopted, but the fine adjustment of the melt viscosity, the melt viscosity ratio and the like can be carried out by the following method. That is, in order to reduce the melt viscosity of the PPS resin composition, it is possible to reduce the amount of the fibrous inorganic filler used, the amount of the silane compound used, or to use a lower viscosity PPS resin. In order to increase the melt viscosity ratio, when the PPS resin is used after being oxidatively crosslinked, a method such as increasing the oxidative crosslinking temperature, time and oxygen supply amount, and when adding a silane compound, It is possible to lower the cleaning pH at the time of acid treatment of PPS, or to strengthen the acid treatment by a method such as increasing the number of acid treatments, or increase the amount of the silane compound.

The resin composition of the present invention is molded by a known molding method of a thermoplastic resin, such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, transfer molding and vacuum molding. Injection molding is preferred.

The PPS resin composition obtained by the present invention is a resin composition in which the generation of effluents of oligomer components and the like in the refrigerant and burrs of the molded product are greatly reduced, and by utilizing such characteristics, electric lighting It is useful for automotive parts, electronic parts, machine related parts, optical equipment / precision machine related parts, automobile / vehicle related parts, and various other applications. Among them, it is suitable for applications requiring low extractability and low burr properties, and specific examples thereof include parts for refrigerant compressors.

[0055]

The present invention will be described in more detail with reference to the following examples. In addition, the chloroform extraction amount, melt viscosity, melt viscosity ratio, and burr value described in Examples and Comparative Examples were measured according to the following methods.

[Chloroform Extraction Amount] The ground sample was washed 5 times with 30 ml of methanol to remove the deposits on the surface and then subjected to total reflux extraction (Soxhlet extraction) for 5 hours using chloroform and a Soxhlet extractor. The value obtained by dividing the weight after drying to the weight before extraction is the chloroform extraction amount.

[Melt viscosity] Diameter 0.1 mm × length 10 mm
320 with a capillograph using an orifice
℃, shear rate 500sec ^-1 and shear rate 5000s
The melt viscosity at ec ^-1 was measured.

[Melt Viscosity Ratio] From the measured values obtained by the above-mentioned measurement of melt viscosity, the ratio (shear rate 500 at 320 ° C. 500
Melt viscosity of sec ^-1 / 5000 sec at 320 ° C
^-1 melt viscosity) was calculated.

[Burr] Around the circumference (a) width 4 mm x length 20
mm x depth 500 μm, (b) width 4 mm x length 20 mm x
Injection molding is performed using a disk-shaped mold having two protrusions with a depth of 50 μm, and the filling length of the protrusion of (b) when the protrusion of (a) is just filled is measured. Is the burr length. The smaller the burr length, the better the burr resistance.

[Reference Example (Production of PPS)] Production of PPS-1 Sodium sulfide nonahydrate was added to an autoclave equipped with a stirrer.
005 kg (25 mol), sodium acetate 0.183 k
g (2.23 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 3.815 kg (25.95 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, and the mixture was sealed under nitrogen and sealed at 270
After the temperature was raised to ℃, it was reacted at 270 ℃ for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water of 40 to 60 ° C.
Then, the mixture was put into 10 kg of NMP heated to 100 ° C., and the mixture was continuously stirred for about 1 hour and then filtered, and further 60 to 8
It was washed 3 times with hot water at 0 ° C. This was put into 25 liters of an acetic acid aqueous solution having a pH of 4 and heated at 90 ° C., and after stirring for about 1 hour, it was filtered and washed with ion-exchanged water at a temperature of about 90 ° C. until the pH of the filtrate became 7, After drying under reduced pressure at 80 ° C. for 24 hours, melt viscosity 35 Pa · s (320 ° C., shear rate 500 sec ⁻¹ ) and chloroform extraction amount 0.20% by weight.
PPS-1 was obtained.

Preparation of PPS-2 Sodium sulfide nonahydrate 6.
005 kg (25 mol), sodium acetate 0.205 k
g (2.5 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 3.719 kg (25.3 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, and the mixture was sealed under nitrogen and sealed at 270 ° C.
After the temperature was raised to 270 ° C., the reaction was performed for 2.5 hours. After cooling
The reaction product was washed 5 times with warm water of 40 to 60 ° C. Then 1
Approximately 1 when put into 10 kg of NMP heated to 00 ° C.
After continuing stirring for an hour, it was filtered and washed with hot water at 60 to 80 ° C. three times. This was put into 25 liters of an acetic acid aqueous solution having a pH of 4 and heated at 90 ° C., and after stirring for about 1 hour, it was filtered and washed with ion-exchanged water at a temperature of about 90 ° C. until the pH of the filtrate became 7, It is dried under reduced pressure at 80 ° C. for 24 hours and melt viscosity 65 Pa · s (320 ° C., shear rate 500
sec ^-1 ), chloroform 0.20 wt% PP
S-2 was obtained.

Preparation of PPS-3 Sodium sulfide nonahydrate was added to an autoclave equipped with a stirrer.
005 kg (25 mol), sodium acetate 0.656 k
g (8 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled.
Then, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and NM
After adding 3.7 kg of P, the mixture was sealed under nitrogen, heated to 270 ° C., and reacted at 270 ° C. for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water of 40 to 60 ° C. Then 100
The mixture was put into 10 kg of NMP heated to 0 ° C., continuously stirred for about 1 hour, filtered, and further washed with hot water at 60 to 80 ° C. three times. This was put into 25 liters of an acetic acid aqueous solution having a pH of 4 and heated at 90 ° C., and after stirring for about 1 hour, it was filtered and washed with ion-exchanged water at a temperature of about 90 ° C. until the pH of the filtrate became 7, After drying under reduced pressure at 80 ° C. for 24 hours, melt viscosity 100 Pa · s (320 ° C., shear rate 500 se
c ⁻¹ ), chloroform extracted 0.20 wt% PPS-
Got 3.

Production of PPS-4 Sodium sulfide nonahydrate 6.
005 kg (25 mol), sodium acetate 0.090 k
g (1.11 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 3.815 kg (25.95 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, and the mixture was sealed under nitrogen and sealed at 270
After the temperature was raised to ℃, it was reacted at 270 ℃ for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water of 40 to 60 ° C.
Then, the mixture was put into 10 kg of NMP heated to 100 ° C., and the mixture was continuously stirred for about 1 hour and then filtered, and further 60 to 8
It was washed 3 times with hot water at 0 ° C. This was put into 25 liters of an aqueous solution of 10 g of calcium acetate heated to 90 ° C., and the mixture was stirred for about 1 hour and then filtered, and the pH of the filtrate was adjusted to 7
After being washed with ion-exchanged water at about 90 ° C, it is dried under reduced pressure at 80 ° C for 24 hours to obtain a melt viscosity of 35 Pa · s (320
C., a shear rate of 500 sec ⁻¹ ) and a chloroform extraction amount of 0.20% by weight to obtain PPS-4.

Production of PPS-5 Into an autoclave equipped with a stirrer, sodium sulfide nonahydrate 6.
005 kg (25 mol) and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were charged, the temperature was gradually raised to 205 ° C. while passing nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 1,4-
Add 3.749 kg (25.50 mol) of dichlorobenzene and 3.0 kg of NMP, seal under nitrogen and
After the temperature was raised to 74 ° C, the reaction was carried out at 274 ° C for 0.8 hours. Two
NMP under high temperature and high pressure of 30 to 250 ° C and 5 to 10 kPa
After removing the water, it was washed with hot water at 50 to 70 ° C. This was filtered, put into 25 liters of an aqueous solution of 50 g of calcium acetate, sealed under nitrogen, heated to 192 ° C., then washed with about 1
After continuously stirring for an hour, the mixture was cooled and filtered, washed with ion-exchanged water at about 90 ° C until the pH of the filtrate became 7, and then at 24 ° C at 24 ° C.
After drying under reduced pressure for 35 hours, the melt viscosity is 35 Pa · s (320 ° C,
Shear rate 500 sec ^-1 ), Chloroform extraction 1.8
7% by weight of PPS-5 was obtained.

[Compounding material used in Examples and Comparative Examples] (a) PPS resin: PPS-1, PPS-2, PPS-
3, PPS-4, PPS-5 (b) Glass fiber: Asahi Fiber Glass Co., Ltd. J
A523 (c1) Silane compound-1: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd. KBM303 (c2) Silane compound-2: γ-isocyanatopropyltriethoxysilane, Shin-Etsu Chemical KB manufactured by Kogyo Co., Ltd.
E-9007

Examples 1 to 8 PPS, glass fiber, and silane compound prepared as described above were dry-blended in the ratio shown in Table 1, and then 32
The mixture was melt-kneaded and pelletized by a screw type extruder set to an extrusion condition of 0 ° C. After drying the obtained pellets,
Using an injection molding machine, injection molding was performed under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. to obtain a predetermined test piece for property evaluation. With respect to the obtained test pieces and pellets, the chloroform extraction amount, melt viscosity, melt viscosity ratio, and burr were measured by the methods described above. The results are shown in Table 1.

The resin composition and molded product obtained here were excellent in both low extractability and low burr property, and were of high practical value.

Comparative Example 1 In the same manner as in Example 1, melt kneading, pelletizing, molding and evaluation were carried out in the proportions shown in Table 1. The results are shown in Table 1.

Comparative Example 2 In the same manner as in Example 1, dry blending, melt kneading, pelletizing, molding and evaluation were carried out in the proportions shown in Table 1. The results are shown in Table 1. When compounding a silane compound, PP
Since S resin having too high melt viscosity was used, P
The melt viscosity of the PS resin composition exceeded the range of the present invention, and only those having low burr resistance were obtained.

Comparative Example 3 In the same manner as in Example 1, dry blending, melt kneading, pelletizing, molding and evaluation were carried out in the proportions shown in Table 1. The results are shown in Table 1. When compounding a silane compound, PP
When the S resin washed with an aqueous solution of calcium acetate is used instead of the acid washing, the melt viscosity ratio and the chloroform extraction amount of the PPS resin composition are out of the range of the present invention.
Only low extractability and low burr were obtained.

Comparative Example 4 In the same manner as in Example 1, dry blending, melt kneading, pelletizing, molding and evaluation were carried out in the proportions shown in Table 1. The results are shown in Table 1. When compounding a silane compound, PP
When the S resin which was not solvent-washed was used, the melt viscosity ratio of the PPS resin composition and the amount of chloroform extracted were out of the scope of the present invention, and only low extractability and low burrability were obtained.

[0072]

[Table 1]

The PPS resin composition of the present invention has a very high level of low extractability and low burrability of oligomer components and the like. Therefore, when it is used as a component for a refrigerant compressor, It is clear that practical performance can be obtained without causing capillary clogging.

[0074]

EFFECTS OF THE INVENTION The PPS resin of the present invention is excellent in balance of low extractability and low burr property, and is particularly useful for applications such as parts for refrigerant compressors.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) F04B 39/00 C08K 5/54 (72) Inventor Michiyoshi Matsumoto 9 Oe-cho, Minato-ku, Nagoya-shi, Aichi 1 Toray Co., Ltd. Nagoya business site F-term (reference) 3H003 AC03 AD03 4F071 AA62 AA88 AB03 AB06 AB28 AD01 AF05Y AG33 AH07 AH12 AH17 BB03 BB05 BB06 BB09 4F072 AA05 AA08 AA09 AB09 AB10 AB11 AC06 AD46 AK01 FA0 DA16J016 DA16 DA16 DA16 DA0 0 GN00 GQ01

Claims (5)

[Claims] 1. (a) Polyphenylene sulfide resin 10
(B) Fibrous inorganic fillers 10 to 10 relative to 0 parts by weight.
0 A parts by blending the polyphenylene sulfide resin composition, the amount extracted by Soxhlet extraction method to extract 5 hours total reflux with chloroform is not more than 0.3% by weight, melt viscosity (320 ° C., a shear rate 5000Sec ^{- 1} )
There is less 150 Pa · s, and, (melt viscosity of 5000Sec ^-1 in the melt viscosity / 320 ° C. in a shear rate of 500 sec ^-1 at 320 ° C.) ratio of melt viscosity shear rate 500 sec ^-1 and 5000sec ^-1 at 320 ° C.
A polyphenylene sulfide resin composition having a ratio of 2.3 or more. 2. The (a) polyphenylene sulfide resin comprises:
Organic solvent washing and acid treatment, and
Melt viscosity (320 ° C, shear rate 500sec ^-1) Is 30
~ 70 Pa · s uncrosslinked polyphenylene sulfide
Resin and polyphenylene sulfide resin composition
The composition according to claim 1, further comprising (c) a silane compound.
The listed polyphenylene sulfide resin composition. 3. An uncrosslinked polyphenylene sulfide resin having a melt viscosity of 30 to 70 Pa · s at 320 ° C. and a shear rate of 500 sec ⁻¹ which has been acid-treated after being washed with an organic solvent, and (b) a fibrous form. Inorganic filler 10-100
3 parts by weight and (c) a silane compound are blended, and the amount of extraction by Soxhlet extraction method in which total reflux extraction with chloroform is performed for 5 hours is 0.3% by weight or less, and 3
The melt viscosity at 20 ° C. and a shear rate of 5000 sec ⁻¹ is 150 Pa · s or less, and the melt viscosity ratio (3
Melt viscosity / 3 at a shear rate of 500 sec ^-1 at 20 ° C
Melt viscosity of 5000 sec ^-1 at 20 ° C) is 2.3
The method for producing a polyphenylene sulfide resin composition as described above. 4. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition is for refrigerant compressor parts. 5. A component for a refrigerant compressor comprising the polyphenylene sulfide resin composition according to claim 1 or 2.