JPH06889B2 - Polyphenylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyphenylene sulfide resin (hereinafter referred to as PPS).
The above) relates to the improvement of a conductive or antistatic composition in which carbon black is dispersed.

<Prior Art> An injection-moldable resin composition in which a conductive powder, for example, a conductive carbon black, is dispersed in PPS has been conventionally known (JP-A-60-8335). in this case,
As the PPS, use a melt indexer (Olyphis diameter 0.0825 inch, length 0.315 inch) specified by ASTM-D1238-70T, and set it to 50 at 315 ° C and a load of 5 kg.
Those having a melt flow rate in the range of up to 800 g / 10 minutes are of interest.

On the other hand, as the conductive carbon black used in the past, acetylene black, thermal black, fannes black, ketchen black, etc. were generally used.

<Problems to be Solved by the Invention> However, when a general conductive carbon black is added to the above-mentioned high-viscosity PPS, a PPS composition having a conductive property or an antistatic property depending on the added amount is provided. However, in each case, there is a drawback that the properties such as excellent moldability and high mechanical strength of PPS are considerably or decisively impaired depending on the amount of carbon black added. This problem is due to insufficient uniform dispersibility of the carbon black in the high-viscosity PPS. Also, due to the low conductivity of carbon black,
Depending on the use, it is also a factor that a large amount must be added.

The present invention is different from the conventional carbon black-dispersed PPS composition in that it has high conductivity or high antistatic property, but the mechanical strength of PPS is not significantly lowered, and the processability of injection molding or extrusion molding is high. It is an object of the present invention to provide an easy PPS composition.

<Means for Solving Problems> In the present invention, as a first step, ASTM-D1238
With a melt indexer specified at -70T, 315 ° C,
Under a load of 5 kg, D is added to 100 parts by weight of PPS (A) having a melt flow rate of 2.5 to 10 kg / 10 minutes.
A resin composition (B) is obtained in which 4 to 45 parts by weight of a conductive carbon black having a BP oil absorption of 400 ml / 100 g or more and a total content of nickel and vanadium is 200 ppm or less are dispersed. Next, as a second step, the melt flow rate measured under the above conditions is 10 to 1500 g.
The weight ratio of PPS (C) and (B) within the range of 10 minutes B /
By blending C in the range of 0.1 to 4, a conductive or highly antistatic PPS composition is provided.

The PPS used in the first step of the present invention is ASTM-D1.
Melt indexer defined by 238-70T (diameter 0.
0825 inches, with 0.315 inches long orifice
At 315 ℃, under load of 5kg, melt flow rate
Range of 2.5 to 10 kg / 10 minutes, preferably 3 to 8 kg / 1
It must be in the 0 minute range. If the melt flow rate is less than 2.5 kg / 10 minutes, in the case of high concentration carbon black, the fluidity during kneading becomes poor,
A uniform dispersion cannot be obtained, which is not preferable. Also, 10kg / 10
When it is larger than the amount, the mechanical strength of the final PPS composition is impaired, which is not preferable.

Next, as a carbon black used in the present invention, DB
A conductive carbon black with a P oil absorption of 400 ml / 100 g or more and a total content of nickel and vanadium of 200 ppm or less is required, but when such a carbon black is kneaded into a PPS composition, it is more than a conventional carbon black. Provides high conductivity or high antistatic properties.
The DBP oil absorption amount means the oil absorption amount defined in ASTM-D2414-79. When the DBP oil absorption of this carbon black is less than 400 ml / 100g,
To obtain a highly conductive PPS composition, a large amount must be added, and the moldability and mechanical strength of the final composition are impaired accordingly, which is not preferable. The upper limit of the DBP oil absorption amount of the carbon black targeted by the present invention is not limited, but it is actually 750 ml / 10 for the convenience of production.
An amount of 0 g or less is suitable.

Furthermore, the total amount of nickel and vanadium contained in the carbon black of the present invention is 200 pp.
m or less, more preferably vanadium content of 80 ppm or less and nickel content of 40 ppm or less are required.

Usually, heavy metals contained in carbon black are nickel, vanadium, iron, manganese, chromium, copper,
Although there are cobalt and the like, the content of other heavy metals is also practically limited by defining nickel and vanadium, so in the present invention, the total amount of nickel and vanadium is defined as an index. If this total amount exceeds 200 ppm, the heavy metals of PPS are affected by the ions, the dispersibility of the carbon black deteriorates, and the moldability of the composition remarkably decreases. In the present invention, the carbon black is kneaded in an amount of 4 to 45 parts by weight with respect to 100 parts by weight of the PPS resin (A) and dispersed to obtain a composition (B). When the amount of the carbon black added is less than 4 parts by weight, it is difficult to maintain not only the conductivity but also the antistatic property of the final PPS composition, which is not preferable. On the other hand, when the amount is more than 45 parts by weight, the kneading workability in the first step and the carbon black dispersibility are deteriorated, and the compounding conditions (B / C weight ratio, equipment) for maintaining the mechanical strength of the final PPS composition are used. Conditions, etc.) becomes narrower, making uniform dispersion difficult and B
If / C ratio is close to 4, conductivity-imparting effect of the carbon black also becomes 10 ⁰ Ω · cm level close to saturation, increasing effect is small in spite of the multiple addition.

Next, the PPS (C) used in the second step of the present invention is required to have a melt flow rate of 10 to 1500 g / 10 min under the melt flow rate measurement conditions described above. Particularly preferably, it is in the range of 30 to 1000 g / 10 minutes. If the melt flow rate of C is less than 10 g / 10 minutes, the flowability of the composition during molding will be poor and the dispersibility of the carbon black will be poor at high carbon black concentrations, which is not preferable. On the other hand, 150
When it exceeds 0 g / 10 minutes, it is not preferable in terms of mechanical strength of the final composition.

PPS of PPS (A) and PPS (C) to which the present invention is applied
What is poly (paraffinenylene sulphide), poly (metamorphenylene sulphide) and poly (paraffinenylene sulphide) + metamorphenylene sulphide)
Etc. are included. These PPS per se are well known,
It can be easily obtained from the market. Also, these P
PS as the main component and other minor components such as polysulfone, polyether sulfone, polyallyl sulfone, polyarylate, polyamide imide, polyether imide,
Known thermoplastic polymers such as aromatic polyester resins and polyether ether ketone can be used in combination.
Further, as a matter of course, as long as A and C are kept within the range of the melt flow rate specified in the present invention, suitable fillers are added to strengthen, suppress thermal expansion, impart slidability, improve heat resistance, Effects such as dimensional stabilization can also be given. These effects are exhibited especially by adding to C. In addition to these, heat stabilizers such as lithium carbonate and commonly used colorants can also be appropriately used. The filler is not particularly limited, but a fiber material or solid fine powder having excellent heat resistance is effective. The fiber material is glass fiber,
Carbon fibers, steel fibers, brass fibers, potassium titanate whiskers, etc. having excellent heat resistance and durability are used. Further, as the fine solid powder, graphite powder, talc powder, calcium carbonate powder, colloidal silica, quartz powder, tungsten disulfide, molybdenum disulfide, boron nitride, ferrite powder, magnetite powder and the like are preferably used. Among these fillers, carbon fiber, steel fiber, brass fiber, graphite powder, talc powder, calcium carbonate powder, when used in combination with the carbon black of the present invention, in terms of conductivity or antistatic properties, the amount of carbon black added There is an effect that can reduce. In order to exert such an effect, PPS (C) is dispersed with the conductivity increasing filler in an amount of 0.3 to 5 times the weight of the carbon black contained in the composition (B).
It is preferable to add it at the time of kneading. If the amount added is less than 0.3 times the weight of the carbon black, a contribution in terms of conductivity can hardly be expected. In addition, if the weight is more than 5 times, in many cases, the negative effects (reduction of kneading property, reduction of moldability, cost increase, etc.) due to these fillers become large, which is not preferable.

In the second step of the present invention, B and C are added in a B / C weight ratio of 0.1.
By kneading in the range of 4 to 4, a desired conductive or antistatic PPS composition is formed. B / C
If the weight ratio is smaller than 0.1, the antistatic property of the molded product (the volume resistivity value is in the range of 10 ³ to 10 ⁹ Ω · cm) varies in many cases, which is not preferable. On the other hand, when the B / C weight ratio is more than 4, the conductivity (volume specific resistance value is 10 ³ Ω · cm or less) is easily satisfied, but in many cases the mechanical strength of the molded product is insufficient for practical use. Become. Here, B is a composition containing at least a PPS resin and carbon black, while C is a composition containing the PPS resin itself or a composition containing another substance.

In the present invention, the term "weight of C" means that C is PP.
When S alone, it refers to the weight of the PPS, and when C is the composition, it refers to the weight of the composition.

In the kneading in the first step and the second step of the present invention, a conventional method, for example, kneading in a batch type kneader such as a Banbury mixer and then pulverizing, or after dry blending in a Hensiel mixer, in an extruder A method of continuously kneading and extruding to form pellets, or pulverizing to obtain amorphous particles can be employed.

<Example> Next, an example will be described in detail.

The methods for measuring melt flow rate, volume resistivity and Izod impact strength described in Examples and Comparative Examples are as follows.

(1) Melt flow rate Measured under a load of 315 ° C. and 5 kg with a melt indexer specified by ASTM-D1238-70T.

(2) Volume resistivity Using Takeda Riken TR 6877 computerizing digital multimeter, a disk sample with a shape of 40 mm in diameter and a thickness of 3 mm was subjected to a surface load of 5 kg / cm ² and an atmosphere of 18 ° C. and 40% RH. Measurement.

(3) Izod impact strength With ASTM-D256 Method A, shape: 12.7 × 12.
Measure a sample of 7 x 62.5 mm (with notch) at 23 ° C.

Examples 1, 2 and 3 Melt flow rates of 2.5, 5.0 and 10 kg / 10, respectively.
Separated PPS (Ryton, manufactured by Phillips) 10 kg each
(Plastic A), DBP oil absorption 480ml / 100g,
Nickel content 15ppm, vanadium content 50ppm conductive carbon black (Lion Akzo, EC-DJ60
0) for each 1 kg (10 parts by weight for 100 parts by weight of resin A)
Was mixed with a Henschel mixer, heated and kneaded with a 40 mm extruder, extruded into a strand, cooled with water, passed through a cutter, and pelletized to obtain a resin composition B (3 types). The kneading and pelletizing property at this time was low, but both were stable without surging and cracking, and the workability was good. Subsequently, a PPS composition (C) comprising 60 parts by weight of PPS having a melt flow rate of 100 g / 10 minutes and 40 parts by weight of glass fiber (Ryton R-
4, manufactured by Phillipps Co., Ltd.) with each composition B by weight ratio B
After mixing with a Henschel mixer so that / C becomes 0.3, pelletize with a 40 mm extruder as above,
Three PPS compositions corresponding to the above B (Examples 1, 2,
3) was obtained. At this time, the pelletizing properties were almost all stable, and the flow stability during kneading was good or good. The volume resistivity, tensile strength and Izod impact strength of the obtained PPS composition are shown in Table 1 and show physical properties useful as an antistatic PPS resin composition.

Comparative Examples 1 and 2 In contrast to the above Examples, PPS (manufactured by Phillips Co.) having a melt flow rate of 2.3 and 12 kg / 10 min, which is outside the scope of the present invention, was used as Resin A, and the same conditions as those of the above Examples were used. The results obtained by kneading composition C with composition B to obtain the final composition are shown in Table 1. In the case of Comparative Example 1 (melt flow rate 2.3 kg / 10 min), the workability of carbon black kneading was poor, a sufficiently uniform product made of carbon black was not obtained, and tensile strength and buffer strength were insufficient. It was On the other hand, in the case of Comparative Example 2 (melt flow rate 1
2 kg / 10 minutes), the carbon black dispersibility was sufficient, but the strength was not satisfactory.

Examples 4 and 5 As Resin A, 10 kg of PPS (Ryton V-1) having a melt flow rate of 5.0 kg / 10 min was prepared, and 3 kg of the same conductive carbon black as in Examples 1 to 3 was mixed with the Henschel mixer. Then, the mixture was kneaded by heating with a 40 mm extruder and hot-cut to obtain a granular composition B. on the other hand,
Melt flow rate 10g / 10min and 1000g / 10
Separate two types of PPS (manufactured by Phillipps Co., Ltd.) are prepared, and the ratio of PPS is 60 parts by weight and glass fiber (Glasslon Chiyodo Strand CS-06-MA-497, manufactured by Asahi Fiber Glass Co., Ltd.) 40 parts by weight. Both were blended with a Henschel mixer and pelletized with a 40 mm extruder to prepare two types of composition C (5 kg each). 2.5 kg of each of composition B and 5 kg of composition C (B / C
The ratio was 0.5), and the final compositions (Examples 4 and 5) were obtained in the same manner as in Examples 1 to 3 below. As shown in Table 1, the evaluation results are excellent as a conductive PPS resin composition.

Comparative Example 3 In contrast to Examples 4 and 5, an example in which the melt flow rate of PPS of the composition C was 7 g / 10 min was produced as a trial with a conductive resin composition under the same conditions as in Examples 4 and 5. Since the flow stability of B and C during kneading was poor, the carbon black was not uniformly dispersed and only low strength was obtained.

Example 6 As Resin A, a composition B was prepared in the same manner as in Examples 1 to 3 except that 1.5 kg of the same conductive carbon black as in Examples 1 to 3 was used for 3.5 kg of PPS having a melt flow rate of 2.5 kg / 10 minutes.
Got On the other hand, 40 parts by weight of glass fiber was mixed and pelletized with 60 parts by weight of PPS having a melt flow rate of 1500 g / 10 minutes, and pelletized to obtain 5 kg of a composition C. 2.5 kg of the above composition B was added to this (B / C ratio: 0.
5) Then, in the same manner as in Examples 1 to 3 below, final compositions were obtained. The results are shown in Table-1, and the volume resistivity 10 ¹
It reached the level of Ω · cm, the strength level was also highly practical, and it was an excellent conductive PPS composition.

Comparative Example 4 In Example 6, a trial was made in which only the melt flow rate of PPS in the composition C was changed to 1800 g / 10 minutes. As a result, the tensile strength and impact strength of the final composition were much lower than those in the range of the present invention.

Example 7 The conductive carbon black used in Example 2 was
DBP oil absorption 420ml / 100g, nickel 40pp
A prototype composition was obtained in the same manner except that the composition was changed to one having characteristics of m and vanadium content of 140 ppm. As shown in Table-1, the composition had excellent strength levels as an antistatic PPS composition.

Comparative Example 5 A trial production was carried out in the same manner as in Example 2, except that the conductive carbon black was changed to one having the physical properties of 350 ml / 100 g of DBP oil absorption, 40 ppm of nickel content and 140 ppm of vanadium content. As shown in Table 1, the result is that the volume resistivity is considerably lower than that of the examples of the present invention.

Comparative Example 6 A composition was produced in the same manner as in Example 2, except that the conductive carbon black was changed to a DBP oil absorption amount of 410 ml / 100 g, a nickel content of 180 ppm, and a vanadium content of 620 ppm. Step of carbon black kneading workability and composition B of second step
And composition C have poor flow stability during kneading, resulting in surging,
Frequent cracking occurred, and the strength of the final composition obtained was not sufficient.

Example 8 In Example 2, the conductive carbon black was added in an amount of 0.4 kg (4 parts by weight based on 100 parts by weight of resin A) with respect to 10 kg of resin A, and the weight ratio between composition B and composition C. A composition was trial-produced in the same manner as in Example 2 except that B / C was changed to 4. As shown in Table 1 as a result, the antistatic resin composition has a low volume resistivity value and a preferable strength.

Example 9 In Example 5, the amount of conductive carbon black added was changed to 4.5 kg (45 parts by weight relative to 100 parts by weight of resin A) with respect to 10 kg of resin A, and the weight ratio B between composition B and composition C was changed. A PPS resin composition was produced in the same manner as in Example 5, except that / C was changed to 4. Table-
As shown in 1, the workability of kneading the carbon black was slow, but the strength level was also good because the dispersed state was almost uniform.

Comparative Example 7 A sample was manufactured in the same manner as in Example 8 except that the amount of conductive carbon black added was changed to 0.3 kg (10 parts by weight of resin A, 3 parts by weight based on 100 parts by weight of resin A). As shown in Table 1, the volume resistivity and strength levels were unsatisfactory.

Comparative Example 8 In the same manner as in Example 9, except that the amount of the conductive carbon black added was changed to 5.0 kg (50 parts by weight relative to 100 parts by weight of resin A) with respect to 10 kg of resin A. As shown in Table 1, the carbon black was poorly dispersed, so that the strength was low.

Comparative Example 9 In Example 9, the weight ratio of composition B and composition C B /
All prototypes were made in the same manner as in Example 9 except that C was changed to 0.08. As shown in Table 1, the volume resistivity values varied in the range of 10 ⁵ to 10 ¹⁰ Ω · cm, and the strength also varied. The result was large and inferior to the level of the present invention.

Comparative Example 10 In Example 8, the weight ratio of composition B and composition C B /
All prototypes were produced in the same manner as in Example 8 except that C was changed to 5. The results are shown in Table 1, which shows that the volume resistivity value varies in the range of 10 ⁴ to 10 ⁷ Ω · cm and the tensile strength also varies greatly at a low level, which is considerably inferior to the level of the present invention.

The present invention <Effects of the Invention>, molding flowability of the PPS and with less reduction in mechanical strength, and small amount with high conductive carbon black (volume resistivity 10 ⁰ Ω · cm level)
Or high antistatic property (volume resistivity 10 ³ Ω · cm
Since it is possible to obtain a PPS composition of a level), the mechanical strength and molding processability thereof are excellent, unlike the case of the conventional heat-resistant conductive resin composition. Therefore, the PPS resin composition of the present invention can be applied to various uses. For example, surface heating elements, conductive materials such as switches, packaging materials for electronic devices and ICs that need to avoid electromagnetic interference, molding materials for VTRs, video disks, mechanical parts for compact disks, antistatic materials, etc. It can be used in many fields such as application to

Claims (1)

[Claims] 1. A melt indexer defined by ASTM-D1238-70T at 315 ° C. under a load of 5 kg, 2.
With respect to 100 parts by weight of a polyphenylene sulfide resin (A) having a melt flow rate of 5 to 10 kg / 10 minutes,
Melt measured under the above conditions with a resin composition (B) obtained by dispersing 4 to 45 parts by weight of a conductive carbon black having a DBP oil absorption of 400 ml / 100 g or more and a total amount of nickel and vanadium of 200 ppm or less. Flow rate 1
A polyphenylene sulfide resin composition comprising a polyphenylene sulfide resin (C) of 0 to 1500 g / 10 min in a weight ratio of B / C 0.1 to 4.