JP3089810B2 - Polyphenylene sulfide composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide composition which gives a molded article having excellent wear resistance. More specifically, the present invention relates to a polyphenylene sulfide composition which is improved in slipperiness while maintaining surface smoothness and transparency when formed into a molded product such as fiber or film, and has excellent abrasion resistance with less shaving during processing.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter PPS)
Has a high melting point and a high second-order transition point, and has excellent mechanical properties and heat resistance, and can be melt-molded. Therefore, it can be used as a heat-resistant material for films, fibers and other molded products. Applications to the field are underway. For example, a biaxially oriented PPS film has further improved mechanical properties due to the biaxially oriented film.
It is expected to be used for electric insulating materials, base films of magnetic recording media, and the like.

However, PPS molded products generally have poor abrasion resistance. For example, in the case of a film, the surface of the film is shaved by a roller or the like which is in contact with the film during the film formation or the film processing step. There is a problem that a performance trouble occurs.

On the other hand, a biaxially oriented PPS film blended with inert fine particles and having improved slipperiness (Japanese Patent Laid-Open No.
No. 34968) and a biaxially oriented PPS film containing cross-linked polystyrene particles (Republished No. 2-80867)
7) has also been proposed, but was insufficient with respect to wear resistance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a PPS composition which solves the above-mentioned conventional disadvantages and satisfies abrasion resistance without impairing the excellent properties of PPS.

[0006]

In order to achieve the above object, the present invention provides a crosslinked poly (ethylvinylbenzene-divinyl) having an average particle diameter of 0.005 to 3.0 μm per 100 parts by weight of polyphenylene sulfide. The present invention is intended to provide a polyphenylene sulfide composition containing 0.01 to 30 parts by weight of (benzene) copolymer particles.

PPS referred to in the present invention is mainly composed of poly-p-phenylene sulfide, and preferably contains at least 70 mol% of p-phenylene sulfide units. More preferably, 90 mol% or more is a p-phenylene sulfide unit. If less than 30 mol%, for example,

Embedded image Although such a component may be contained as a copolymer component, the content of the copolymer component is more preferably 10 mol% or less. In particular,

Embedded image The content of the polyfunctional copolymer component having three or more functional units such as is preferably 2 mol% or less.

The PPS of the present invention has a melt viscosity of preferably 500,000 to 100,000 poise, more preferably 70,000 to 50,000 poise at a temperature of 300 ° C. and an apparent shear rate of 200 (sec) ⁻¹ .

The PPS of the present invention may contain additives other than PPS, such as polymers other than PPS, inorganic or organic lubricants, coloring agents, ultraviolet absorbers, antioxidants, heat stabilizers, and crystal nucleating agents. There is no problem as long as the purpose is not hindered.

The composition of the present invention must contain crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles. If the particles are not contained, both the slipperiness and the wear resistance of the molded product cannot be satisfied. The composition ratio of ethylvinylbenzene and divinylbenzene in the particles is 40:60 to 80:
When it is in the range of 20, preferably 50:50 to 70:30, it is particularly effective for further improving the abrasion resistance.
In addition, other components may be contained in the particles as long as the object of the present invention is not impaired, but it is preferable that other polymer components such as polystyrene are small, and 10% or less based on particles. And more preferably 5% or less.
Further, if a polymer containing a carbonyl group such as polyacrylic acid or polymethacrylic acid is contained in the particles, it becomes difficult to improve the abrasion resistance. Therefore, the case of 5% or less is particularly preferable. However, other polymer components such as polyacrylic acid and polymethacrylic acid can be present outside the particles.

The average particle size of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles in the present invention is 0.005 to 3 μm, preferably 0.01 to 2 μm. If it is less than 0.005 μm or more than 3.0 μm, the effect of improving wear resistance cannot be obtained, which is not preferable.

The particle size distribution coefficient of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles in the present invention is preferably from 1.15 to 5.0, particularly preferably from 1.2 to 3.

Further, the PPS composition of the present invention contains P
The crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles are contained in an amount of 0.01 to 3 with respect to 100 parts by weight of PS.
0 parts by weight must be contained. The preferred content is 0.05 to 10 parts by weight. If the amount is less than 0.01 part by weight, the slip property of the biaxially oriented film is poor, which is not preferable. If it exceeds 10 parts by weight, no improvement in wear resistance is observed, which is not preferable.

The crosslinked poly (ethylvinylbenzene-divinylbenzene) used in the PPS composition of the present invention
It is effective that the shape factor of the copolymer particles is between 0.75 and 1.0 to further improve the wear resistance.

The degree of crosslinking of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles used in the PPS composition of the present invention is determined by the copolymerization ratio of divinylbenzene, but is at least 40%, preferably 45%. % Or more is preferable because the wear resistance is further improved.

Further, a cross-linked poly (ethylvinylbenzene-
Divinylbenzene) copolymer particles have a heat resistance temperature of 360 ° C.
The temperature is preferably at least 400 ° C.

The PPS composition of the present invention may contain particles other than the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles as long as the object of the present invention is not impaired. I don't care.

The PPS composition of the present invention may be in any form, but is preferably a film or a fiber, particularly preferably a biaxially oriented film. The biaxially oriented film has a degree of orientation OF determined for a crystal peak at 2θ = 20 to 21 ° in wide angle X-ray diffraction of 0.07 to less than 0.07 in the End direction and the Edge direction.
0.50, in the range of 0.6 to 1.00 in the Through direction.

The average surface roughness of the film is preferably such that at least one surface has an average surface roughness in the range of 0.003 to 0.1 μm. The coefficient of static friction is 0.2 to 3.
A range of 0 is preferred.

Next, a method for producing the polyphenylene sulfide composition of the present invention will be described.

First, as a method for producing crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles, an emulsion polymerization method, a suspension polymerization method and the like are preferably used (Japanese Patent Application Laid-Open No.
1-181837). In particular, the use of an emulsion polymerization method called a seed method is particularly suitable for controlling the particle size distribution coefficient within a preferable range of the present invention. At this time, it is preferable to sufficiently purify in advance so that other components and polymers are not mixed. In producing the particles, it is preferable that the particles are made as close as possible to the average particle diameter in the film at the time of production. There is also a method of pulverizing and classifying once produced large particles, but it is extremely difficult to improve the abrasion resistance.

Next, a method for producing the polyphenylene sulfide polymer itself is well known in this field, and any method can be adopted. Alkali sulfide and p-
A method of reacting dihalobenzene in a polar solvent under high temperature and high pressure is preferable. In particular, it is preferable to react sodium sulfide with p-dichlorobenzene in an amide polar solvent such as N-methyl-2-pyrrolidone. In this case, in order to adjust the degree of polymerization, a so-called polymerization aid such as an alkali metal hydroxide or an alkali metal salt of a carboxylic acid is added to the mixture.
Most preferably, the reaction is carried out at 0 ° C to 280 ° C.
The pressure and the polymerization time in the polymerization system are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like.

After completion of the polymerization, the system is gradually cooled to precipitate a polymer, and a slurry formed by throwing into water is filtered off with a filter, washed with water and dried to obtain a PPS powder.

Next, a slurry of crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles dispersed in a liquid was added to the above-mentioned PPS powder and uniformly mixed by a high-speed stirring means such as a Henschel mixer. Thereafter, the obtained mixture is fed to an extruder having at least one vent hole, the melt component is first kneaded in the extruder, the liquid component is removed from the vent holes, and the mixture is extruded from an appropriate die to form a crosslink. A PPS composition in which poly (ethylvinylbenzene-divinylbenzene) copolymer particles are finely dispersed is obtained.

Here, in the present invention, the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles have a boiling point of 180 ° C. to 290 ° C., preferably 180 ° C.
The slurry is dispersed in a liquid at a temperature of from 250C to 250C.
If the boiling point of the liquid is lower than the above range, secondary aggregation of fine particles is likely to occur when melt-kneading the PPS containing the slurry. Conversely, if the boiling point of the liquid is higher than the above range, the PPS containing the slurry will be used. After melt-kneading, it becomes difficult to remove the liquid from the system at the vent. Examples of the liquid include ethylene glycol, triethylene glycol, N
Examples thereof include -methyl-2-pyrrolidone and diphenyl ether, but those which do not dissolve PPS at a temperature equal to or higher than the boiling point as in the former two are preferable. Here, the average particle diameter of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles in this slurry state is 3 μm or less, preferably 2 μm or less. Although the method for preparing such a slurry is not particularly limited, a cross-linked poly (ethylvinylbenzene-
There is a method in which divinylbenzene) copolymer particles are added, dispersed by a dispersing means such as a ball mill or a vibration mill, and, if necessary, filtered to remove coarse particles. Crosslinked poly (ethylvinylbenzene-divinylbenzene) in slurry
The concentration of the copolymer particles is preferably in the range of 5% by weight to 50% by weight.

In the method for producing a PPS composition of the present invention, P
The above-mentioned slurry of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles is added to the PS powder, mixed uniformly, and then supplied to an extruder. As a method of uniformly mixing the PPS powder and the slurry of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles, it is preferable to use a high-speed stirring means such as a Henschel mixer. In addition, during such mixing, it is preferable to keep the temperature of the material lower than the boiling point of the liquid as a dispersion medium of the slurry by 50 ° C. or more to prevent the liquid from volatilizing. The amount of the slurry of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles added to the PPS powder was PPS10.
The weight ratio of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles to 0 parts by weight is adjusted to 1 to 100 parts by weight. PPS powder 1
The weight ratio of the liquid component to 00 parts by weight is preferably 1 part by weight to 80 parts by weight. The mixture obtained in this manner is supplied to an extruder having at least one vent hole, and is first melt-kneaded in the extruder, then the liquid component is removed from the vent hole, and extruded from an appropriate die. Obtain the composition. Even when using an extruder having two or more vent holes, the final vent should be performed with the polymer in a molten state, and some of the liquid components in the unmelted mixture are passed through some of the vent holes. Even in the case of removal, it is preferable that the weight ratio of the liquid component to 100 parts by weight of PPS be 50 parts by weight or less. In any case, in the cylinder of the extruder, at least a state in which a liquid as a dispersion medium, crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles, and a polymer in a molten state coexist at least exists. is necessary. In this way, the liquid component in the polymer is finally removed to such an extent that no drawbacks associated with the vaporization of the liquid due to foaming or the like occur.

In the above method, the PPS powder and the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles are mixed before being supplied to the extruder.
The PS powder is supplied, and the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particle slurry is forcibly injected from an opening provided in the extruder before or after the polymer is melted in a cylinder portion of the extruder. It is also possible. This injection can be performed continuously while performing extrusion molding. Other manufacturing conditions are the same as in the above-described method.

In any of the above methods, PPS in which crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles are dispersed from a suitable die attached to an extruder.
The composition can be extruded and pelletized once or in the form of a film as it is, but is preferably pelletized once. The obtained pellet can be formed into a molded product such as a biaxially oriented film as it is or by mixing it with, for example, a plain pellet of PPS containing no particles.

For the biaxial stretching, a well-known method (for example,
No. 5-111235). That is, pellets in which the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles are dispersed as they are or mixed with PPS plain pellets, supplied to an extruder, melted, and placed on a cooling drum from a T-die. It is cast into an unstretched sheet, and the sheet is heated at 80 ° C. to 12
The film is stretched at a temperature of 0 ° C. vertically or horizontally simultaneously or sequentially, preferably at least 4 times in area magnification, and further heat-treated under tension at a temperature of 180 ° C. or more and a melting point or less to obtain a biaxially oriented film of the present invention. be able to.

[0030]

The present invention will be described below in more detail with reference to examples. Evaluation and analysis were performed as follows.

(1) Average particle diameter of particles, particle size distribution coefficient,
Shape Factor The film containing the particles is formed into an ultra-thin section of about 1000 Å to 10,000 Å in the thickness direction, and is measured with a transmission electron microscope (JEM-1200 manufactured by JEOL Ltd.).
EX) at a magnification of about 2000 to 200,000. Below for 1000 particles,
From the circle equivalent diameter to the number average particle diameter (Dn),
The volume average particle diameter (Dw) is measured respectively. The average particle diameter of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles is defined as the number average particle diameter (Dn). The particle size distribution coefficient was defined as the ratio of the number average particle diameter to the volume average particle diameter (Dn / Dw) as the particle size distribution coefficient. Dn = ΣDi / 1000 ... (i = 1~1000) Dw = (ΣDi 3/1000) (1/3) also ... (i = 1~1000), when observing the particles in the manner described above, the maximum of the particle The value obtained by averaging the ratio of the diameter to the equivalent circle diameter for 1000 particles was defined as the shape factor of the particles.

(2) Content of Particles The film is dissolved in α-chloronaphthalene and filtered while hot to separate the particles, and the particle content is defined as a ratio (% by weight) to the total weight of the film. In addition, quantification can be performed using infrared spectroscopy or SEM-XMA, if necessary.

(3) Heat resistance temperature of particles Using TG-30M manufactured by Shimadzu Corporation, the temperature rising rate was 10
Differential thermogravimetric analysis was performed at 50 ° C./min under a nitrogen stream (50 ml / min), and the maximum differential heat loss peak was taken as the heat resistant temperature of the particles.

(4) Surface roughness Measured according to JIS R-0601.

(5) Slip property Measured according to ASTM 1894-63.

(6) Abrasion Resistance One edge of the film is vertically pressed into a tape or a film obtained by slitting the film into a tape with a width of 1/2 inch, and the film is further pushed in by 2 mm and run for 200 m (film running tension: 150 g, filament) Running tension: 30 g,
Running speed: 400 m / min). At this time, the height of the shaved object adhering to the tip of the single blade was read with a microscope, and the shaved amount was used (unit: μm). When the amount of scraping was 100 μm or less, the abrasion resistance was determined to be good, and when the amount exceeded 100 μm, the abrasion resistance was determined to be poor.

Example 1 (1) Polymerization of PPS Sodium sulfide 32.6 in a stainless steel autoclave
kg (250 mol, including 40 wt% of water of crystallization), 100 g of sodium hydroxide, 36.1 kg of sodium benzoate
(250 mol) and 79.2 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), and after dehydration at 205 ° C., 37.5 kg of 1,4-dichlorobenzene
(255 moles) and 20.0 kg of NMP.
The reaction was performed at 4 ° C. for 4 hours. The reaction product was washed with water and dried to obtain 21 kg of PPS powder having a melt viscosity of 3300 poise.

(2) Preparation of PPS Composition Crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles (particle A) having the composition shown in Table 1 were synthesized by an emulsion polymerization method (seed method). P obtained above
10 parts by weight of a 10% by weight ethylene glycol slurry containing these particles in an emulsified state was added to 100 parts by weight of PS powder, and the mixture was stirred at a high speed at 50 ° C. using a Henschel mixer.

This mixture was fed to a different direction rotary twin-screw extruder having a single-stage vent hole and melted at 310 ° C., and ethylene glycol was removed from the molten resin at the vent portion. Thereafter, the molten polymer is extruded from a 3 mmφ die, quenched, cut into pellets, and the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles 0.1.
A PPS composition containing 4 parts by weight was obtained.

(3) Film Formation The obtained PPS composition was melted at 310 ° C. with an extruder having a diameter of 40 mm, filtered with a filter having a 95% cut pore diameter of 10 μm using metal fibers, and then 400 m in length.
m, and extruded from a T-die having a linear lip with a gap of 1.5 mm, cast on a metal drum whose surface was kept at 25 ° C., and cooled and solidified to obtain an unstretched film having a thickness of 25 μm. The film is stretched 3.7 times at a film temperature of 100 ° C. and a stretching speed of 30000% / min by a longitudinal stretching apparatus composed of rolls.
The film is stretched 3.4 times at 1000 ° C. and a stretching speed of 1000% / min, and further heat-treated under tension at 270 ° C. for 10 seconds in a subsequent heat treatment chamber in the same tenter to obtain a biaxially oriented PPS film having a thickness of 2 μm. Was. Table 2 shows the evaluation results of this film.

Example 2 Only the PPS powder used in Example 1 was supplied to the extruder used in Example 1, and was melt-extruded at a discharge rate of 20 kg / h at 310 ° C. while being opened at the feed section of the extruder. The ethylene glycol slurry of the crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles used in Example 1 was injected at a rate of 1 kg / hour from the injection hole. Example 1
As in the above, ethylene glycol was removed from the molten resin at the vent. Thereafter, the molten polymer was extruded from a die having a diameter of 3 mm, rapidly cooled, and cut into pellets to obtain a PPS composition containing 0.4 parts by weight of crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles.

Using this resin, a biaxially oriented PPS film having a thickness of 2 μm was obtained in the same manner as in Example 1. Tables 1 and 2 show the evaluation results of this film.

Examples 3 to 6, Comparative Examples 1 to 4 As shown in Table 1, PPS compositions and biaxially oriented PPS films were obtained in the same manner as in Example 1 except that the kind and content of the particles contained were variously changed. Tables 1 and 2 show the evaluation results of this film.

[0044]

[Table 1]

[Table 2] Example 7 The PPS composition of Example 1 was melted at 330 ° C., discharged from a die having 18 pores having a diameter of 0.3 mm, cooled, solidified, and then heated to 95 ° C. It was drawn three times to obtain a PPS filament. The abrasion resistance of the obtained filament was good.

[0045]

The PPS composition of the present invention contains a specific amount of crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles having a specific average particle size, thereby improving the slipperiness of a molded article and at the same time. Excellent wear resistance.

Therefore, the PPS composition of the present invention is preferably used not only in the field of films such as dielectrics for capacitors, electric insulating materials, base films for magnetic recording media, but also as fibers and other molded products.

Continuation of front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 81/00-81/02 C08L 25/00-25/16

Claims (1)

(57) [Claims] (1) 100 to 100 parts by weight of polyphenylene sulfide, containing 0.01 to 30 parts by weight of crosslinked poly (ethylvinylbenzene-divinylbenzene) copolymer particles having an average particle diameter of 0.005 to 3.0 μm. Polyphenylene sulfide composition comprising: