JPH10237254A - Method for mixing thermoplastic resin with fluoro resin and method for producing fluoro-resin-containing thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for mixing a thermoplastic resin with a fluoro resin while realizing improved productivity and reduction in white specks, which method comprises controlling the temperature at which the both components are mixed with each other in a specified ratio at highest the softening point (glass transition point) of the fluoro resin. SOLUTION: Thermoplastic resin powder of 100 pts.wt. is mixed with 0.1-100 pts.wt. fluoro resin powder. It is desirable that the temperature control is performed by introducing dry ice into the mixer. It is desirable that the thermoplastic resin is selected from among thermoplastic polyester resins, polyacetal resins and polyarylene sulfide resins, and the fluoro resin is polytetrafluoroethylene. It is desirable that 100 pts.wt. powdery mixture is mixed with 100-2,000 pts.wt. particulate or powdery thermoplastic resin, and the obtained mixture is melt-kneaded with an extruder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a fluororesin-containing thermoplastic resin composition, and a method for mixing a mixture of a thermoplastic resin powder and a fluororesin powder, which is suitably used in producing such a composition. . More specifically, the present invention relates to a method for producing a fluororesin-containing thermoplastic resin composition capable of significantly reducing white specifications after molding, and a mixing method therefor.

[0002]

2. Description of the Related Art Conventionally, for the purpose of improving friction and wear characteristics of a thermoplastic resin.
Alternatively, a fluororesin powder such as polytetrafluoroethylene is mixed with a thermoplastic resin for the purpose of improving whiteness. In this case, if the fluororesin powder is not uniformly dispersed in the thermoplastic resin, when this is molded, the occurrence of microaggregates of the fluororesin referred to as white specifications on the surface of the molded product is observed, which is not preferable in appearance. Product. Conventionally, a thermoplastic resin composition containing a fluororesin powder has been produced by blending a thermoplastic resin powder and a fluororesin powder in a container, followed by melt-kneading and extruding with a twin-screw extruder. However, there is a problem in that the dispersion of the fluororesin powder is insufficient only by blending with a container and melt-kneading with an extruder to obtain only a composition that generates a large number of the above-mentioned white specifications. to solve this problem,
It is conceivable to mix both by applying a shearing force with a mixer. That is, if mixing is performed for a long time with a mixer having a normal stirring blade (low-shear blade) (an example of a general low-shear blade is shown in FIG. 1), it is not possible to sufficiently disperse and mix to some extent. Yes, but it is too time consuming and not an economic method. Also, this method has a problem that the concentration of the fluororesin powder cannot be increased so much. On the other hand, such a problem can be solved by mixing with a mixer having high-shear blades (an example of a high-shear blade is shown in FIG. 2), but the temperature rises due to frictional heat generated by shearing during mixing, and fluorine There is a problem that the resin powder tends to aggregate instead. In addition, as described above, this problem easily occurs even when mixing is performed for a long time using a mixer having ordinary stirring blades (low-shear blades). As described above, in the production of a thermoplastic resin composition containing a fluororesin powder, a technique that achieves both improvement in productivity and reduction in occurrence of white specifications has not been proposed.

[0003]

The present inventors have made intensive studies to solve these problems, and as a result, it has been found that the temperature at which the thermoplastic resin powder and the fluororesin powder are mixed is properly controlled. They have found that they are effective and have completed the present invention. That is, the present invention relates to a fluororesin powder 0.1 to 100 parts by weight of a thermoplastic resin powder.
A mixing method of mixing the thermoplastic resin and the fluororesin, wherein the mixing is performed by controlling the temperature in the mixer to be equal to or lower than the softening point (glass transition point) of the fluororesin. A thermoplastic resin powder and a fluororesin powder are mixed together, and a method for producing a fluororesin-containing thermoplastic resin composition characterized by being melt-kneaded in an extruder, and a thermoplastic resin powder and a fluororesin powder by the mixing method. Mixing, further mixing 100 to 2000 parts by weight of the thermoplastic resin granules or powder with respect to 100 parts by weight of the powdery mixture, and melt-kneading with an extruder to obtain a fluororesin-containing thermoplastic resin composition. It is a manufacturing method.

[0004]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. In the present invention, as described above, in producing a fluororesin-containing thermoplastic resin composition, the temperature of the mixture of the thermoplastic resin powder and the fluororesin powder is controlled to be equal to or lower than the softening point (glass transition point) of the fluororesin. It is characterized by performing. There is no particular limitation on the temperature control method, a method using a cooling medium from outside the mixer, a cooling medium inside the mixer,
For example, a method of introducing a cooling gas such as air, nitrogen, or helium, or a method of introducing a substance that evaporates or sublimates at a low temperature into a mixer is used. In the present invention, the temperature controlled by such a method is basically sufficient if it is equal to or lower than the softening point (glass transition point) of the fluororesin used.
More preferably, the softening point (glass transition point) of the fluororesin
And mixing at a temperature lower than 10 ° C. Specifically, since the softening point (glass transition point) of polytetrafluoroethylene, which is the most common fluororesin, is about 28 ° C, in this case, the temperature should be controlled so that it does not reach about 18 ° C or more. Preferably, mixing is performed. The lower limit of the temperature to be controlled is not particularly limited.
C. or more is preferable, and a sufficient effect can be obtained. From such a viewpoint, as a particularly preferable temperature control method in the present invention, a method of putting dry ice into a mixer is exemplified. Dry ice sublimes and is emitted as carbon dioxide gas and does not remain in the mixer, so there is no effect on the quality of the mixture.In addition, since the dry ice is injected into the mixer, the temperature control efficiency is high, making it extremely convenient. is there.
The amount of dry ice to be used can be easily determined empirically and experimentally in consideration of the heat generation during mixing and the temperature to be controlled.

In the present invention, examples of the mixer include a container rotary mixer (a cylindrical mixer (a rotary blender, a container drum mixer, and a turbula mixer)).
V-shaped container mixer, double cone mixer], fixed container mixer (ribbon type, horizontal screw type, paddle type, vertical ribbon type, vertical screw type, planetary motion type, muller type), air flow stirring A type mixer (jet pump type) can be used.
Preferred mixers are those having functions such as impact by high-speed rotation of a stirring blade, shearing, fluidization, and dispersion by a rotating disk, and a high mixing speed due to shearing action. Specifically, a Henschel mixer, Examples thereof include a super mixer, a micro speed mixer, and a mixer in which a double conical rotary container and a high-speed stirring blade are combined.

The thermoplastic resin used in the present invention is not particularly limited. Polyacetal resin, thermoplastic polyester resin (eg, polyethylene terephthalate, polybutylene terephthalate, etc.), polyarylene sulfide resin, polyamide resin, liquid crystalline polyester resin , Polyolefin resin, polystyrene, ABS
And the like, styrene resins, polycarbonate resins, polyphenylene oxide resins, polyalkyl acrylate resins, polysulfone resins, polyethersulfone resins, polyetherimide resins, polyetherketone resins, and the like. Among them, when a fluororesin-containing resin composition, the effect is remarkable when the present invention is applied to a thermoplastic polyester resin, polyacetal resin, and polyarylene sulfide resin, which are considered to be difficult to disperse well in the fluororesin. In particular, the effect on polybutylene terephthalate resin is remarkable. These thermoplastic resins generally have an average particle diameter of 0.1 to 1 mm.
Is used.

The fluororesin used in the present invention includes tetrafluororesin (polytetrafluoroethylene),
Various materials such as a tetra-hexafluoride resin, ethylene trifluoride, and vinylidene fluoride resin are exemplified. The softening point (glass transition point) of these fluororesins is about 10 to 40 ° C. Among them, the effect of the present invention is remarkable for polytetrafluoroethylene powder, which has high versatility and is considered to be easily aggregated. The average particle size of the fluororesin powder is generally 1 to 500 μm.

In mixing the thermoplastic resin powder and the fluororesin powder as described above, the amount of the fluororesin powder is 0.1 to 100 parts by weight of the thermoplastic resin powder.
100 parts by weight. If the amount of the fluororesin powder is less than 0.1 part by weight, the effect of improving the friction and abrasion characteristics of the thermoplastic resin does not occur, and it is meaningless to apply the present invention as a mixing method. On the other hand, when the amount of fluororesin powder is 10
If the amount is more than 0 parts by weight, flocculation of the fluororesin powder occurs even in the present invention, and uniform dispersion becomes difficult. More effective mixing ratio is 100% thermoplastic resin powder
1 to 20 parts by weight of fluororesin powder, especially 1 part by weight
~ 10 parts by weight.

In the present invention, in the above-mentioned mixing step, it is possible to add an optional component according to the purpose within a range that does not greatly impair the mixing performance. For example,
In the production of the fluororesin-containing thermoplastic resin composition to be described later, various substances including a stabilizer are often blended, but some or all of such components can be added at this mixing stage. .

In the present invention, a mixture of the thermoplastic resin powder and the fluororesin powder mixed and prepared as described above is used to produce a fluororesin-containing thermoplastic resin composition. A method in which the mixture is directly supplied to an extruder for melt-kneading, or a method in which a thermoplastic resin particle or powder is added to the above mixture to adjust the concentration of the fluororesin and then supplied to the extruder for melt-kneading, can be used. In the latter case, the ratio of the thermoplastic resin particles or powder to the mixture is
100 parts by weight of thermoplastic resin granules or powder 10
0 to 2000 parts by weight. If the proportion of the thermoplastic resin particles or powder is excessive, uniform dispersion of the fluororesin becomes difficult.

In the present invention, various additives, fillers and the like can be blended according to the purpose at the stage of producing the fluororesin-containing thermoplastic resin composition. Specific examples include antioxidants, lubricants, flame retardants, coloring agents, organic and inorganic fillers, and the like.

In the production of the fluororesin-containing thermoplastic resin composition as described above, the extruder to be used is not particularly limited, and includes a single-screw extruder, a twin-screw extruder, and an extruder in which these are combined in two stages. Can be used.

[0013]

Next, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited by these examples. Experimental Example A (Examples 1 and 2, Comparative Examples 1 and 2) (1) Mixed 3 kg of polytetrafluoroethylene (trade name: Hostaflon) powder (average particle size: 20 μm) and polybutylene terephthalate resin powder (average particle size) 0.2 μm) was blended in a Henschel mixer for the time shown in Table 1. Table 1 shows the amount of dry ice added and the temperature in the mixer.
The Henschel mixer used was as follows. Capacity: 1000 liters Henschel water cooling; 10 liters / min blade; high shear type shown in FIG. 2 Rotational speed: 300 rpm The powder of the remaining polytetrafluoroethylene was observed with an optical microscope, and the state of dispersion was evaluated according to the following three grades.
Table 1 shows the results. [Evaluation of dispersion state] ；: Not fiberized, dispersed in particles of 100 μm or less ○: Fiberized, but particleization progressed to 100 to 150 μm ×: Fiberization progressed, 400 μm or more (2) Melt kneading Next, 63 kg of the powdery mixture obtained as described above, 800 kg of polybutylene terephthalate resin chips, and 30 kg of various additives were mixed by a container drum mixer, and this was mixed with an extruder. The mixture was melt-kneaded and granulated. The obtained fluororesin-containing polybutylene terephthalate resin composition was applied to a molding machine and molded into a plate having a thickness of 30 mm × 40 mm and a thickness of 3 mm, and the number of white specs of polytetrafluoroethylene on the surface of the molded plate was measured. Table 1 shows the results.

[0014]

[Table 1]

Experimental Example B (Examples 3 to 8, Comparative Examples 3 to 5) The same polytetrafluoroethylene powder as in Experimental Example A above.
10 kg and polybutylene terephthalate resin powder 100
Using kg, the mixing time and the amount of dry ice added were changed as shown in Table 2, and the same evaluation was performed. Table 2 shows the results.

[0016]

[Table 2]

[0017]

As is apparent from the above description and Examples, according to the method of the present invention, in the production of a thermoplastic resin composition containing a fluororesin powder, the productivity is improved and the generation of white specs is reduced. Could be compatible.

[Brief description of the drawings]

FIG. 1 is a view showing an example of a general low-shear stirring blade of a Henschel mixer, wherein (a) is a front view and (b) is a side view.

FIG. 2 is a diagram showing an example of a high shear stirring blade of a Henschel mixer, wherein (a) is a front view and (b) is a side view.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 101/00 C08L 101/00

Claims (7)

[Claims] When mixing 0.1 to 100 parts by weight of a fluororesin powder with respect to 100 parts by weight of a thermoplastic resin powder, the inside of the mixer is mixed by controlling the temperature below the softening point (glass transition point) of the fluororesin. A method of mixing a thermoplastic resin with a fluororesin. 2. The mixing method according to claim 1, wherein the temperature control is performed by introducing dry ice into the mixer. 3. The mixing method according to claim 1, wherein the thermoplastic resin is selected from a thermoplastic polyester resin, a polyacetal resin, and a polyarylene sulfide resin. 4. The mixing method according to claim 3, wherein the thermoplastic resin is a polybutylene terephthalate resin. 5. The mixing method according to claim 1, wherein the fluororesin is polytetrafluoroethylene. 6. A fluororesin-containing thermoplastic resin composition, comprising mixing a thermoplastic resin powder and a fluororesin powder by the mixing method according to claim 1 and melt-kneading the mixture with an extruder. Method of manufacturing a product. 7. A thermoplastic resin powder and a fluororesin powder are mixed by the mixing method according to any one of claims 1 to 5, and a thermoplastic resin granule or powder is further added to 100 parts by weight of the powdery mixture. A method for producing a fluororesin-containing thermoplastic resin composition, comprising mixing 100 to 2000 parts by weight and melt-kneading with an extruder.