JPH11269384A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a carbon fiber-containing polyarylene sulfide (PAS) resin composition capable of providing a molded product scarcely causing surface roughness without deteriorating mechanical properties of the molded product. SOLUTION: This composition contains (A) 100 pts.wt. of a polyarylene sulfide having 150-20,000 P melt viscosity V6 and <=0.7 wt.% of an amount extracted with methylene chloride and (B1) 0.05-200 pts.wt. of carbon fibers containing 1.1-2.8 wt.% of a sizing agent having >=1 and <=15 wt.% percentage loss of weight at 270 deg.C and sticking thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyarylene sulfide resin composition, and more particularly to a carbon fiber-containing polyarylene sulfide resin composition.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as P
Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin represented by a resin (which may be abbreviated as PS) is excellent in heat resistance, chemical resistance, moldability, flame retardancy, and dimensional stability. It is widely used for electronic / electric parts and mechanical parts. Since the PAS itself is not so excellent in self-lubricating properties, it is used by adding a lubricant such as a tetrafluoroethylene resin or silicone oil to applications requiring lubrication and sliding properties. In particular, in addition to the above, in applications requiring mechanical strength, a formulation for adding carbon fiber (hereinafter sometimes abbreviated as CF) has been frequently used (for example, Japanese Patent Application Laid-Open No.
JP-A-5-7848, JP-A-1-40716).
However, when molded with the pellets of the sample prepared by adding the CF, the molded product is likely to be unfilled, causing gas burning on the product surface and surface roughness (cloudiness). Problems such as corrosion of the mold have occurred. Particularly, in a molded article having a smooth mirror surface with almost no surface roughness, the surface roughness is a fatal defect. It has been found that these problems are caused by gases generated at the time of melting, and most of them are generated by thermal decomposition of a sizing agent for converging CF.
Add a gas scavenger to suppress this gas, remove the gas by sufficiently pre-drying the pellets before molding, make the gas vent of the mold used for molding larger to make it easier for gas to escape, etc. Measures have been taken.

However, the addition of a gas scavenger degrades the mechanical properties of a molded article, requiring a great deal of time to remove gas before molding, and a method of enlarging a gas vent is not suitable for molding ultra-precision parts. It had the disadvantage that it could not be used. In addition, since any method requires considerable labor, a fundamental solution for reducing the amount of gas generated has been desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a carbon fiber-containing PAS resin composition which can provide a molded article without deteriorating the mechanical properties of the molded article and having almost no surface roughness. .

[0005]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems. As a result, a carbon fiber-containing PAS resin composition that gives a molded article without deteriorating the mechanical properties of the molded article and has almost no surface roughness can be obtained by including the prescribed carbon fiber in the prescribed PAS below in a prescribed amount. And found that the present invention was completed.

That is, the present invention relates to (1) (A) melt viscosity V
₆ is 150 to 20,000, and 100 parts by weight of a polyarylene sulfide having an extraction amount with methylene chloride of 0.7% by weight or less, and (B1) a weight reduction rate at 270 ° C. of 1% by weight to 15% by weight. Carbon fiber to which 1.1 to 2.8% by weight of the following sizing agent is attached
A polyarylene sulfide resin composition containing 0.05 to 200 parts by weight.

[0007] JP-A-64-29458 discloses a PA.
A PAS resin composition comprising S, CF, and an inorganic filler other than CF, wherein the CF is obtained by adhering 0.1 to 15% by weight of a polyurethane resin to CF. ing. In Examples 1 to 4 of the publication, CF to which 3% by weight or 5% by weight of a polyurethane resin is adhered is used. The effect of the invention described in the publication is that a PAS that is easier to prepare and process than conventional products, has improved physical properties such as mechanical strength, and has good heat resistance can be obtained.

The present inventors have limited the amount of the sizing agent to CF to 1.1 to 2.8% by weight, which is not specifically disclosed in the above publication, V
₆ is 150 to 20,000 and the amount of extraction with methylene chloride is 0.7% by weight or less. If PAS is used, the effects described in the above publication can be obtained without deteriorating the mechanical properties of the molded article. Have found that a different effect can be obtained, that is, the surface roughness of the molded article can be significantly reduced.

In a preferred embodiment, (2) and (B1) are
Weight loss rate at 270 ° C is 1% by weight or more and 15% by weight
The resin composition according to the above (1), which is carbon fiber to which the following sizing agent is attached in an amount of 1.5 to 2.5% by weight,
(3) The resin composition according to the above (1) or (2), wherein the sizing agent is selected from a polyurethane resin and an epoxy resin.
(4) A molded article comprising the resin composition described in any one of (1) to (3) above can be given.

Further, the present invention relates to (5) (A)
₆ is 150 to 20,000, and 100 parts by weight of a polyarylene sulfide having an extraction amount with methylene chloride of 0.7% by weight or less, and (B2) a weight reduction rate at 270 ° C. of 0.01% by weight or more and 1% by weight. Carbon fiber having less than 0.5% by weight of sizing agent attached thereto
A polyarylene sulfide resin composition containing 0.05 to 200 parts by weight.

The present inventors have found that the melt viscosity V ₆ is 150 to 2
If the above-mentioned predetermined CF (B2) is mixed with PAS having a molecular weight of 000 and an extraction amount of methylene chloride of 0.7% by weight or less, the mechanical properties of the molded article are reduced. It has been found that a carbon fiber-containing PAS resin composition that gives a molded article without any surface roughness and almost no surface roughness can be obtained.

In a preferred embodiment, (6) and (B2) are
The resin composition according to the above (5), wherein the resin composition is a carbon fiber to which 1 to 5% by weight of a sizing agent having a weight reduction rate at 270 ° C. of 0.01% by weight or more and less than 1% by weight is adhered, The resin composition according to the above (5) or (6), which is an etherimide resin, and (8) a molded article comprising the resin composition according to any one of the above (5) to (7) can be exemplified. .

[0013]

Component (A) PAS of the embodiment of the present invention, the melt viscosity V ₆ is 150～20,000 poise, preferably 200 to 10,000 poise, particularly preferably 300
~ 3,000 poise. Below the lower limit, the fluidity is too high to allow sufficient degassing from within the mold during molding, resulting in gas burning on the surface of the molded article. In addition, characteristics inherent in PAS such as mechanical strength cannot be obtained. Exceeding the above upper limit is not preferred because the moldability decreases. Here, the melt viscosity V ₆ was measured using a flow tester at 300 ° C., a load of 20 kgf / cm ² , and L / D = 10.
This is a value measured after holding at / 1 for 6 minutes.

(A) PAS has an extraction amount with methylene chloride of 0.7% by weight or less, preferably 0.6% by weight or less,
Particularly preferably, it is 0.5% by weight or less. The above range is preferable because there is no oligomer having a relatively low molecular weight in the PAS. If the amount of extraction exceeds the above upper limit, the amount of gas generated during molding will increase significantly, and the surface roughness of the molded product will become significant. Here, the amount of extraction with methylene chloride is a value determined as follows. 4 g of the PAS powder is added to 80 g of methylene chloride, soxhlet extraction is performed for 4 hours, the mixture is cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Further, the container used for the above-mentioned extraction is washed three times with a total of 60 g of methylene chloride, and after collecting the washing liquid, it is put in the weighing bottle. Next, the mixture is heated to about 80 ° C., the methylene chloride in the weighing bottle is removed by evaporation, and the residue is determined by weighing.

The method for producing the (A) PAS of the present invention is not particularly limited, and a known method can be used. The present invention is used in melt viscosity V ₆ is 150-2
000, and the extraction amount with methylene chloride is 0.7
By weight, the PAS is used to react an alkali metal sulfide with a dihaloaromatic compound in an organic amide-based solvent, and to cool the gas phase of the reactor during the reaction, thereby reducing the gas in the reactor. PAS (a) produced by condensing a part of the phase and refluxing the liquid phase to obtain a liquid phase can be obtained by washing with an organic solvent and then with water (Japanese Patent Application Laid-Open No. Hei 8-
253587). Further, the PAS obtained by the above method can be obtained by further performing a heat treatment in a gas phase oxidizing atmosphere (Japanese Patent Application Laid-Open No. 8-12781).

Here, the above PAS (a) can be preferably manufactured by the method described in Japanese Patent Application Laid-Open No. 5-222196.

In this polymerization method, the refluxed liquid has a higher water content than the liquid bulk due to the vapor pressure difference between water and the amide solvent. The reflux liquid having a high water content forms a layer having a high water content at the upper portion of the reaction solution. As a result, residual alkali metal sulfide (eg, Na ₂ S),
Alkali metal halides (eg, NaCl), oligomers, and the like are included in the layer in large amounts. In the conventional method, PAS and N
In a state where the raw materials such as a ₂ S and by-products are uniformly mixed, not only a high molecular weight PAS cannot be obtained, but also
Depolymerization of the produced PAS also occurs, and by-products of thiophenol are observed. However, in the present invention, the above disadvantageous phenomenon can be avoided by actively cooling the gas phase portion of the reaction vessel and returning a large amount of the water-rich reflux liquid to the upper part of the liquid phase so as to inhibit the reaction. It can be considered that such factors can be effectively eliminated and a high molecular weight PAS can be obtained. However, the present invention is not limited only by the effect of the above phenomenon, but by various effects caused by cooling the gas phase part, high molecular weight PAS
Is obtained.

In this polymerization method, it is not necessary to add water during the reaction as in the conventional method. However, this does not preclude the addition of water at all. However, if the operation of adding water is performed, some of the advantages of the present invention are lost. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The gas phase portion of the reaction vessel can be cooled by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a cooling medium through an internal coil installed at an upper part in a reaction can, a method of flowing a cooling medium through an external coil or a jacket wrapped around the upper part of the reaction can, and using a reflux condenser installed at the upper part of the reaction can A method such as spraying water or blowing a gas (air, nitrogen, etc.) on the upper portion of the outside of the reaction vessel is conceivable, but any method can be used as long as it has the effect of increasing the amount of reflux in the vessel as a result. May be used. If the outside air temperature is relatively low (for example, normal temperature), appropriate cooling can be performed by removing a heat insulating material conventionally provided on the upper part of the reaction vessel. In the case of external cooling, water condensed on the reactor wall
The amide-based solvent mixture enters the liquid phase along the reaction vessel wall. Thus, the water-rich mixture pools on top of the liquid phase,
Keep the water content there relatively high. For internal cooling,
The mixture condensed on the cooling surface likewise travels down the cooling device surface or the reactor wall and into the liquid phase.

On the other hand, the temperature of the liquid phase bulk is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230-275 for constant temperature
It is preferred to carry out the reaction at a temperature of ° C for 0.1 to 20 hours. More preferably, the temperature is 240 to 265 ° C for 1 to 6 hours. In order to obtain a higher molecular weight PAS, it is preferable to use two or more reaction temperature profiles. This 2
When performing a step operation, the first step is preferably performed at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too low, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too high, so that not only a sufficiently high molecular weight PAS cannot be obtained, but also the side reaction rate is significantly increased. The end of the first phase,
The residual ratio of the dihalo aromatic compound in the polymerization reaction system is 1 mol% to 40 mol%.
It is preferable to carry out the reaction at a time point when the molar% is within the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo aromatic compound in the polymerization reaction system is in the range of 2 mol% to 15 mol%, and the molecular weight is in the range of 5,000 to 15,000. Residual rate is 40 mol%
If it exceeds 2,000, side reactions such as depolymerization are likely to occur in the second stage reaction, while if it is less than 1 mol%, high molecular weight P
It is hard to get AS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. PAS with sufficiently high molecular weight at low temperature
When the temperature is higher than 270 ° C., side reactions such as depolymerization are liable to occur, making it difficult to stably obtain a high molecular weight product.

As an actual operation, first, under an inert gas atmosphere, dehydration or water addition is performed as necessary so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount. The water content is preferably the alkali metal sulfide 1
It is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol, per mol. If it exceeds 2.5 moles, the reaction rate will be low, and the amount of by-products such as phenol will increase in the filtrate after the reaction, and the degree of polymerization will not increase. If the amount is less than 0.5 mol, the reaction rate is too high to obtain a product having a sufficient high molecular weight, and undesirable reactions such as side reactions occur.

In the case of a one-stage reaction at a constant temperature, the cooling of the gas phase during the reaction is preferably carried out from the start of the reaction, but must be carried out at least in the course of raising the temperature to 250 ° C. or lower. In the multi-stage reaction, it is preferable to perform cooling from the first-stage reaction, but it is preferable to perform cooling at the latest after the completion of the first-stage reaction. The degree of the cooling effect is usually the most suitable index of the pressure in the reactor. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the amount of water in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, when the pressure in the reaction vessel is reduced as compared with the case where the reaction vessel is not cooled under the same reaction conditions, the amount of the reflux liquid increases, which means that the temperature at the gas-liquid interface of the reaction solution decreases. It is considered that the relative degree of decrease indicates the degree of separation between a layer having a high water content and a layer having no water content. Therefore, it is preferable to perform cooling to such an extent that the internal pressure of the reaction vessel is lower than that in the case where no cooling is performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment used, operating conditions, and the like.

The organic amide solvent used here is PA
Known for S polymerization, such as N-methylpyrrolidone (NMP), N, N-dimethylformamide,
N, N-dimethylacetamide, N-methylcaprolactam, and the like, and mixtures thereof can be used, with NMP being preferred. They all have a lower vapor pressure than water.

Alkali metal sulfides are also known, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof. These hydrates and aqueous solutions may be used. Hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides.
Inexpensive sodium sulfide is preferred.

Dihaloaromatic compounds are described in, for example,
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using one or more kinds of para-, meta- or ortho-dihalides of diphenyl ether, diphenyl sulfone or biphenyl in a small amount (20 mol% or less). For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenylether, m, p'-dichlorodiphenylether, m, m'-dichlorodiphenylether, p, p'-dichlorodiphenylsulfone, m, p'-dichlorodiphenylsulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
Dichlorobiphenyl.

In order to increase the molecular weight of PAS,
For example, 1,3,5-trichlorobenzene, 1,2,4-
Polyhalo compounds such as trichlorobenzene can also be used, preferably in a concentration of 5 mol% or less, based on the total amount of the para and metadihalo aromatic compounds.

As other small additives, a terminal stopper and a monohalide as a modifier can be used in combination.

Next, the washing of the PAS with an organic solvent is preferably carried out by the following method. That is, after filtering the slurry of PAS (a) produced in the above step, the obtained filter cake is dispersed in an organic solvent. The washing is preferable because the oligomer component having a relatively low molecular weight present in the PAS (a) can be satisfactorily removed.

In one embodiment of the washing, the slurry of PAS (a) produced in the above step is filtered to obtain a PAS cake. Next, the PAS cake is put into an organic solvent, preferably 0.5 to 10 times by weight, and the mixture is stirred and mixed at room temperature to 180 ° C., preferably for 10 minutes to 10 hours, and then filtered. The stirring, mixing and filtration operations are preferably repeated 1 to 10 times. Examples of the organic solvent used for the washing include the organic amide solvents described in the description of the process for producing the PAS (a), xylene, and the like. Preferably, an organic amide solvent is used. The organic amide solvent may be the same as or different from the one used in the production process of PAS (a). As the organic amide solvent, N-methylpyrrolidone is particularly preferably used.

The subsequent washing with water can be performed according to a known method. However, it is preferably carried out by dispersing the filter cake obtained after washing with the above organic solvent in water. For example, the above-mentioned filter cake is poured into water, preferably 1 to 5 times in weight, and is preferably mixed at room temperature to 90 ° C., preferably for 5 minutes to 10 hours, and then filtered. The stirring, mixing and filtering operations are preferably performed for 2 hours.
By repeating 〜１０10 times, the solvent and by-product salts attached to the PAS are removed, and the water washing is completed. By performing water washing as described above, efficient washing can be performed with a smaller amount of water than in a washing method in which water is poured into a filter cake.

In the present invention, the PAS obtained as described above can be further subjected to an acid treatment. The acid treatment is carried out at a temperature of 100 ° C or lower, preferably at a temperature of 40 to 80 ° C. If the temperature exceeds the above upper limit, the PAS molecular weight after the acid treatment decreases, which is not preferable. On the other hand, when the temperature is lower than 40 ° C., the remaining inorganic salt precipitates out and lowers the fluidity of the slurry, which hinders the continuous treatment process, which is not preferable. The concentration of the acid solution used for the acid treatment is preferably 0.01 to 5.0% by weight. Further, the pH of the acid solution after the acid treatment is preferably 4.0 to 5.0. By adopting the above concentration and pH, most of -SY (Y represents an alkali metal) terminal in PAS to be treated can be converted to -SH terminal, and corrosion of plant equipment and the like can be achieved. This is preferable because it can prevent The time required for the acid treatment depends on the temperature of the acid treatment and the concentration of the acid solution.
Minutes or more, particularly preferably 10 minutes or more. If it is less than the above, -SY terminal in PAS cannot be sufficiently converted to -SH terminal, which is not preferable. In the acid treatment, for example, acetic acid,
Formic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, boric acid, carbonic acid and the like are used, and acetic acid is particularly preferred. By performing the treatment, an alkali metal such as sodium which is an impurity in the PAS can be reduced. Therefore, elution of alkali metal such as sodium during use of the product and deterioration of electrical insulation can be suppressed.

In the component (B1) carbon fiber used in the first embodiment of the present invention, the sizing agent having a weight loss rate of 1% by weight or more and 15% by weight or less at 270 ° C. is 1.1.
To 2.8% by weight, preferably 1.5 to 2.5% by weight. If the amount of the sizing agent exceeds the above upper limit, the surface roughness of the molded article becomes remarkable, and if it is less than the above lower limit, the mechanical properties deteriorate, which is not preferable. As the sizing agent having a weight reduction ratio at 270 ° C. of 1% by weight or more and 15% by weight or less, a known one can be used, and a polyurethane resin, an epoxy resin, a nylon resin, a polyester resin and the like are preferable. Here, the weight loss rate is a value calculated from the weight loss after holding at 270 ° C. for 30 minutes in a nitrogen atmosphere.

The component (B2) carbon fiber used in the second embodiment of the present invention contains 0.5 to 8% by weight of a sizing agent whose weight loss rate at 270 ° C. is 0.01% by weight or more and less than 1% by weight. %, Preferably 1 to 5% by weight. If the amount of the sizing agent exceeds the above upper limit, the surface roughness of the molded article becomes remarkable, and the mechanical properties are lowered. If it is less than the above lower limit, the mechanical properties are undesirably reduced. As the sizing agent having a weight loss rate of not less than 0.01% by weight and less than 1% by weight at 270 ° C., known substances can be used. Preferably, a sizing agent having a weight loss rate of 0.05 to 0.1% by weight at 270 ° C, particularly preferably a polyetherimide resin, polyarylene sulfone polyetherimide, polyimide or the like is used. Here, the weight reduction rate is a value calculated in the same manner as above.

Various known carbon fibers can be used. For example, fired acrylic fibers, rayon fibers, lignin fibers, petroleum-based or coal-based pitch fibers, and the like are preferable, and polyacrylonitrile-based carbon fibers are particularly preferable. When attaching the sizing agent to the carbon fiber, the surface of the carbon fiber can be oxidized in advance, or the surface can be treated in advance with a silane coupling agent or the like. To attach a sizing agent to carbon fiber, for example,
After dissolving the sizing agent in a solvent such as acetone and tetrahydrofuran, immersing the carbon fiber bundle in the solution,
The solvent is removed or the sizing agent is emulsified, and the carbon fiber bundle is immersed in the sizing agent and then dried. The carbon fiber thus obtained can be used as a long fiber, but is preferably 50 to 200.
It can be used as a chopped strand having a length of 1 to 10 mm with zero converging.

In the resin composition of the present invention, (A) PA
The upper limit of (B1) or (B2) carbon fiber is 200 parts by weight, preferably 150 parts by weight, particularly preferably 100 parts by weight of (A) PAS, with respect to S and (B1) or (B2) carbon fiber. Is 100 parts by weight, and the lower limit is 0.05 parts by weight, preferably 1 part by weight, particularly preferably 10 parts by weight. If the upper limit is exceeded, the moldability will deteriorate, and if it is less than the lower limit, the mechanical properties will decrease.

[0036] In the present invention, an inorganic filler other than carbon fiber can be blended as an optional component.
The inorganic filler is not particularly limited, and for example, a powdery / flaky filler, a fibrous filler, and the like can be used.
As the powdery / flaky filler, for example, alumina,
Talc, mica, kaolin, clay, titanium oxide, calcium carbonate, calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite, zirconium oxide, glass beads, carbon black, etc. Can be Examples of the fibrous filler include glass fiber, asbestos fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition, a filler such as a ZnO tetrapot, a metal salt (eg, zinc chloride, lead sulfate, etc.), an oxide (eg, iron oxide, molybdenum dioxide, etc.), and a metal (eg, aluminum, stainless steel, etc.) may be used. it can. These can be used alone or in combination of two or more.

The amount of the inorganic filler is (A) PAS1
The upper limit is preferably 400 parts by weight, particularly preferably 200 parts by weight, and more preferably 100 parts by weight, based on the total weight of (B1) or (B2) carbon fiber with respect to 00 parts by weight. If the amount of the inorganic filler exceeds the above upper limit, the moldability deteriorates, which is not preferable.

The resin composition of the present invention is prepared by mixing the above components. Preferably, after the components are preliminarily mixed by dry blending, the mixture is heated to a temperature higher than the melting temperature of the resin and melt-kneaded. Further, the carbon fiber can be side-fed and melt-kneaded with the resin. The melt-kneaded material is once formed into pellets, which can be used for molding, or can be directly used for molding. These methods themselves are known for the preparation and molding of resin compositions.

The CF-containing PAS resin composition of the present invention is widely used as a material for electric and electronic equipment parts, a material for automobile parts, a material for chemical parts and the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0041]

【Example】

[0042]

Examples 1 to 9 and Comparative Examples 1 to 13 In the examples and comparative examples, the following substances were used. <(A) PAS> A PAS produced as described below was used.

Synthesis Example 1 In a 150-liter autoclave, 19.285 kg of flaky sodium sulfide (60.7% by weight Na ₂ S) and N
45.0 kg of -methyl-2-pyrrolidone (hereinafter abbreviated as NMP) was charged. The temperature was raised to 204 ° C. while stirring under a nitrogen stream to distill 4.752 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and 21.940 kg of paradichlorobenzene (hereinafter sometimes abbreviated as p-DCB) and 18.0 k of NMP were used.
g. 1 kg using nitrogen gas at a liquid temperature of 150 ° C
/ Cm ² G and the temperature was raised. Liquid temperature 220 ° C
While stirring for 5 hours, water was sprinkled with a sprinkler attached to the outside of the upper part of the autoclave to cool the upper part of the autoclave. Then, the temperature was raised to 260 ° C.,
Then, the mixture was stirred at the same temperature for 3 hours to proceed with the reaction. Next, the temperature was lowered and the cooling at the top of the autoclave was stopped. During the cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop.

After filtering the obtained polymerization slurry, the obtained filter cake was slurried in unused NMP (slurry concentration: 15% by weight). Then at 120 ° C. for 30
Stirred for minutes and filtered to remove NMP. The NMP washing was performed twice. Next, the filter cake was put into warm water of about 80 ° C. (about twice the weight of the filter cake by weight), sufficiently stirred for about 30 minutes, and then filtered. This operation of water washing and filtration was repeated seven times. After that, the obtained filter cake is
The powder was dried in a circulating hot air dryer at about 5 ° C. for about 5 hours to obtain a white powdery PPS. V ₆ of the obtained PPS (P-1) 17
The content was 60 poise, and the amount of methylene chloride extracted was 0.48% by weight.

Synthesis Example 2 Except that the charged amount of p-DCB was 22.600 kg,
A white powdery PPS was obtained in the same manner as in Synthesis Example 1. The resulting V ₆ of PPS (P-2) was is 380 poise, the amount of methylene chloride extract was 0.59 wt%.

Synthesis Example 3 The PPS (P-2) obtained in Synthesis Example 2 was subjected to a heat treatment in an oven at 230 ° C. for 36 hours in an air stream to obtain a black-brown powdered PPS. V of the obtained PPS (P-3)
₆ was 10350 poise and the amount of methylene chloride extracted was 0.44% by weight. <Comparative PAS> The one manufactured as follows was used.

Synthesis Example 4 A white powdery PPS was obtained in the same manner as in Synthesis Example 1 except that NMP washing after the reaction was not performed. PPS obtained
(P-4) V ₆ of a 1670 poise, the amount of methylene chloride extract was 1.21 wt%.

Synthesis Example 5 The PPS (P-4) obtained in Synthesis Example 4 was heat-treated in an oven at 230 ° C. for 36 hours under an air stream to obtain a black-brown powder PPS. V of the obtained PPS (P-5)
₆ was 11220 poise, and the methylene chloride extraction amount was 0.95% by weight.

Synthesis Example 6 Except that the charged amount of p-DCB was 23.200 kg,
A white powdery PPS was obtained in the same manner as in Synthesis Example 1. The resulting V ₆ of PPS (P-6) was is 110 poise, the amount of methylene chloride extract was 0.63 wt%.

Here, the melt viscosity V ₆ is a value measured using a flow tester CFT-500C manufactured by Shimadzu Corporation. <(B1) CF> CF-1 thermoplastic polyurethane resin sizing agent (adhesion amount 2.0% by weight) CF-2 thermoplastic polyurethane resin sizing agent (adhesion amount 2.5% by weight) CF-3 epoxy resin sizing agent ( <(B2) CF> CF-4 polyetherimide resin sizing agent (adhesion amount: 2.5% by weight)
0% by weight) CF-5 polyetherimide resin sizing agent (adhesion amount: 3.
<Comparative CF> CF-6 thermoplastic polyurethane resin sizing agent (adhesion amount: 1.0% by weight) CF-7 thermoplastic polyurethane resin sizing agent (adhesion amount: 3.0% by weight) CF-8 thermoplastic polyurethane Resin sizing agent (adhesion amount: 4.0% by weight) CF-9 polyetherimide resin sizing agent (adhesion amount: 0.4% by weight)
1% by weight) CF-10 polyetherimide resin sizing agent (adhesion amount: 1
0% by weight) The weight reduction rate of the thermoplastic polyurethane resin sizing agent is 1 to 3
% By weight, and the weight loss rate of the epoxy resin sizing agent is 5 to 5%.
The weight reduction rate of the polyetherimide resin sizing agent was 0.05 to 0.1% by weight. Here, the weight loss rate is a value calculated by measuring the weight loss after holding at 270 ° C. for 30 minutes in a nitrogen atmosphere using a thermogravimetric analyzer TG-50 manufactured by Shimadzu Corporation.

Each measurement in the examples and comparative examples was performed as follows. (1) Preparation of Test Specimens (A) PPS and (B1) or (B2) CF having the compounding amounts (parts by weight) shown in Tables 1 and 2 were brought to 310 ° C. using a biaxial kneader (screw diameter: 20 mm). And melt-kneaded. At this time, CF was side-fed using an auto feeder. Using the pellets obtained, cylinder temperature 32
Each test piece was manufactured by injection molding at 0 ° C. and a mold temperature of 130 ° C. (2) Flexural strength and flexural modulus Measured according to ASTM D790. (3) Dynamic friction coefficient (to steel) Measured according to ASTM D1894. (4) Amount of gas generated After holding one pellet (about 0.02 g) prepared above at 350 ° C. for 10 minutes in a nitrogen atmosphere, the weight loss was measured using a thermogravimetric analyzer TG-50 manufactured by Shimadzu Corporation. It was used and measured and calculated. (5) Surface Roughness In conformity with JIS K7104, a flat plate having an MR-2 surface roughness of 80 mm in length x 80 mm in width x 3 mm in thickness is injection-molded, and a region with a higher surface roughness (cloudy region)
Was determined as a ratio (%) to the entire surface.

The above results are shown in Tables 1 and 2.

[0053]

[Table 1]

[0054]

[Table 2] Table 1 shows the results for the resin composition of the first embodiment of the present invention. In Examples 1 and 2, the amount of the thermoplastic polyurethane resin sizing agent was changed within the scope of the present invention using a sizing agent. In each case, good surface roughness and mechanical properties were obtained. Example 3 uses an epoxy resin sizing agent. Good results were obtained almost in the same manner as in Example 2. Examples 4 and 5 vary the V ₆ and methylene chloride extractions of PPS within the scope of the present invention.
Good results were obtained almost as in Example 1 using the same CF.

In Comparative Examples 1 to 3, the added amount of the sizing agent was out of the range of the present invention. When the amount of the sizing agent was small (Comparative Example 1), the CF was defibrated and fell apart to form a floc, clogged in a kneader and could not be kneaded. When the amount of the sizing agent was too large [Comparative Examples 2 (corresponding to Example 1 in JP-A-64-29458) and 3], the surface roughness was very poor. In Comparative Examples 4 and 5, the amount of PPS extracted with methylene chloride exceeded the range of the present invention. In each case, the surface roughness was very poor. In Comparative Example 4, the bending strength was also significantly reduced. Comparative Example 6, V ₆ of PPS is of less than the scope of the present invention. Although the surface roughness was good, the mechanical properties were remarkably reduced, and it was not practical. In Comparative Example 7, the amount of CF exceeded the range of the present invention. CF was clogged in the kneader and could not be kneaded.

Table 2 shows the results for the resin composition according to the second embodiment of the present invention. Examples 6 and 7 use a polyetherimide resin sizing agent and vary the amount of adhesion within the scope of the present invention. In each case, good surface roughness and mechanical properties were obtained. Examples 8 and 9 are PP
The V _{6 of} S and the extraction amount of methylene chloride were changed within the scope of the present invention. Good results were obtained almost in the same manner as in Example 6 using the same CF.

In Comparative Examples 8 and 9, the added amount of the CF sizing agent was out of the range of the present invention. When the amount of the sizing agent was small (Comparative Example 8), the CF was defibrated and fell apart to form a floc, clogged in the kneading machine and could not be kneaded. When the amount of the sizing agent was too large (Comparative Example 9), the surface roughness was very poor. In Comparative Examples 10 and 11, the amount of PPS extracted with methylene chloride exceeded the range of the present invention. In each case, the surface roughness was very poor. Comparative Example 12, V ₆ of PPS is of less than the scope of the present invention. Although the surface roughness was good, the bending strength was significantly reduced. Comparative Example 1
In No. 3, the amount of CF exceeds the range of the present invention.
CF was clogged in the kneader and could not be kneaded.

[0058]

According to the present invention, there is provided a carbon fiber-containing PAS resin composition which provides a molded article without deteriorating the mechanical properties of the molded article and having almost no surface roughness.

Claims (2)

[Claims] (A) A melt viscosity V ₆ of 150 to 20,000.
0 and 100 parts by weight of a polyarylene sulfide having an extraction amount with methylene chloride of 0.7% by weight or less, and (B1) a sizing agent having a weight loss rate of 1 to 15% by weight at 270 ° C. .1 to 2.8% by weight
A polyarylene sulfide resin composition containing 0.05 to 200 parts by weight of the attached carbon fiber. (A) a melt viscosity V ₆ of 150 to 20,000;
0, and 100 parts by weight of a polyarylene sulfide having an extraction amount with methylene chloride of 0.7% by weight or less, and (B2) a weight loss rate at 270 ° C. of 0.0
0.5 to 8% by weight of 1% to less than 1% by weight of sizing agent
A polyarylene sulfide resin composition containing 0.05 to 200 parts by weight of the attached carbon fiber.