JPH06322140A - Thermoplastic resin-based masterbatch containing antistatic agent and its production - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a surfactant at a high concentration without inhibiting physical properties of a resin and mutually fusing masterbatches by kneading the thermoplastic resin with the surfactant and a fine powdery oxide. CONSTITUTION:The objective composition is obtained by continuously kneading (A) 30-70 pts.wt. thermoplastic resin with (B) 25-65 pts.wt. surfactant and (C) 0.2-15 pts.wt. fine powdery oxide in an extruder. Furthermore, the particle diameter of the component (C) is 5-50nm and silicon oxide is especially used. The viscosity of the premixed components (B) with (C) is preferably >=100cp.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a masterbatch and a method for producing the same. More specifically, it relates to an antistatic agent-containing thermoplastic resin masterbatch containing a surfactant in a high concentration and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a surfactant is kneaded in two steps of producing a masterbatch in which a resin is kneaded with a surfactant at a high concentration, and kneading this with a resin used for molding or the like. There is. And the improvement of the handling property,
From the viewpoint of cost reduction, it is desired to increase the concentration of the masterbatch. However, when trying to knead the surfactant in a high concentration, a surging occurs due to a large difference in viscosity between the resin and the surfactant. Generally, when the surfactant is solid, about 20% by weight of liquid In this case, a concentration of about 10% by weight was the maximum production limit of the masterbatch. Therefore, it has been attempted to produce a masterbatch containing a surfactant in a higher concentration. For example, JP-A-5
JP-A-7-30746 discloses a technique in which a resin having a very high fluidity is used as a resin to be kneaded with the surfactant so that the surfactant is contained in a higher concentration. However, this technique has a drawback in that the resin used for producing the masterbatch has much higher fluidity than the resin used for molding and the like, which hinders the physical properties of the resin in the molded product. Further, Japanese Patent Application Laid-Open No. 62-109854 discloses a technique in which both a resin and a surfactant are melt-mixed in advance and then charged into an extruder so that the surfactant is contained in a higher concentration. . However, in this technique, since the surfactant is exposed to a high temperature at which it is melt-mixed for a long time, problems such as heat deterioration and coloring occur, and an apparatus for melt-mixing both the resin and the surfactant is required in addition to the extruder. In addition, it is not suitable for continuous production and has a drawback that productivity is deteriorated. Furthermore, the masterbatch produced by this technology is
There is a drawback that the master batches are easily fused to each other due to the surfactant contained therein bleeding out during storage.

[0003]

The present invention has been made as a background to solve the above-mentioned problems of the prior art, and does not impair the resin physical properties of the molded product, and the produced master batches are fused with each other. It is an object of the present invention to provide an antistatic agent-containing thermoplastic resin masterbatch containing a high concentration of a surfactant, which does not adhere, and a method for producing the same.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the combined use of finely divided oxides reduces the viscosity difference between the resin and the surfactant, It is possible to make a high-concentration masterbatch, and
The present invention has been accomplished by finding that the manufactured master batches do not fuse with each other.

That is, the present invention relates to a thermoplastic resin (A),
Consisting of a surfactant (B) and a finely divided oxide (C),
The content of each of (A), (B) and (C) is 30 to 70% by weight of (A) and 25 to 65 of (B).
%, (C) is 0.2 to 15% by weight, and an antistatic agent-containing thermoplastic resin-based masterbatch;
In addition, 30 to 70 parts by weight of the thermoplastic resin (A), 25 to 65 parts by weight of the surfactant (B) and 0.
A method for producing an antistatic agent-containing thermoplastic resin masterbatch, which comprises continuously kneading 2 to 15 parts by weight in an extruder.

The thermoplastic resin (A) of the present invention includes polyethylene resins (polyethylene, ethylene-α-olefin copolymers, ethylene-vinyl acetate copolymers, etc.),
Polypropylene resin (polypropylene, propylene-
α-olefin copolymer, etc.), styrene resin (polystyrene, AS resin, ABS resin, styrene-butadiene resin, styrene-maleic anhydride resin, HIPS, etc.),
Polyamide resin (6 nylon, 6,6 nylon, 11 nylon, 12 nylon, etc.), (meth) acrylic resin,
Thermoplastic polyester resin (polyethylene terephthalate
, Polybutylene terephthalate, polycarbonate, etc.), thermoplastic polyurethane, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, elastomers (ethylene-propylene rubber, EPDM, butadiene rubber, polyester elastomer) Etc.) and the like.

In the present invention, the melt flow rate of the thermoplastic resin (A) is usually 100 g / 10 minutes or less (JI
SK7210A method). The conditions for measuring the melt flow rate are 190 ° C. and a load of 2.16 kg in the case of polyethylene resin, thermoplastic polyurethane, polyvinyl chloride, polyvinylidene chloride, and polyvinyl acetate, and 200 ° C. and a load of 5. in the case of styrene resin. 00 kg, polypropylene resin, (meth) acrylic resin, elastomers, 230 ° C, load 2.16 kg, polyamide resin (6 nylon, 11 nylon, 12 nylon, etc.) 235 ° C, load 2.16 kg, In the case of thermoplastic polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), 250 ° C, load 2.16k
280 g, polyamide resin (6,6 nylon, etc.), thermoplastic polyester resin (polycarbonate, etc.)
C., load 2.16 kg.

The surfactant (B) is a nonionic surfactant (polyethylene glycol type such as higher alcohol ethylene oxide adduct, fatty acid ethylene oxide adduct, higher alkylamine ethylene oxide adduct, polypropylene glycol ethylene oxide adduct, etc.). Nonionic surfactant, polyethylene oxide, fatty acid ester of glycerin, fatty acid ester of pentaerythritol, fatty acid ester of sorbit and sorbitan, alkyl ether of polyhydric alcohol, polyhydric alcohol type nonionic such as aliphatic amide of alkanolamines Surfactants), anionic surfactants (carboxylic acid salts such as alkali metal salts of higher fatty acids, sulfuric acid ester salts such as higher alcohol sulfuric acid ester salts and higher alkyl ether sulfuric acid ester salts, Sulfonates such as killbenzene sulfonate and paraffin sulfonate, phosphate ester salts such as higher alcohol phosphate ester salts), cationic surfactants (quaternary ammonium salts such as alkyl trimethyl ammonium salts), amphoteric interfaces Activators (amino acid-type amphoteric surfactants such as higher alkylaminopropionate, betaine-type amphoteric surfactants such as higher alkyldimethyl betaine and higher alkyldihydroxyethyl betaine) are listed, and one or more of these may be used. it can.

The fine powder oxide (C) usually has a particle size of 5
Silicon oxide, aluminum oxide, titanium oxide and the like having a thickness of up to 50 nm can be used, and one or more of them can be used, but it is preferable to use silicon oxide.

In the present invention, the content of the thermoplastic resin (A), the surfactant (B) and the fine powder oxide (C) in the masterbatch is 3 when the content of the masterbatch is (A).
0-70% by weight, (B) 25-65% by weight, (C) 0.2-15% by weight, preferably (A) 45-70%.
% By weight, (B) 25 to 50% by weight, and (C) 1 to 5% by weight. When the content of the surfactant (B) is small, the meaning of obtaining a high-concentration masterbatch is diminished, and it can be produced by a known method without using a fine powder oxide having a particle diameter of 5 to 30 nm together. . In the masterbatch produced by the production method of the present invention, (B) may exceed 65% by weight, but in many cases, the surfactant bleeds out on the surface of the masterbatch, and thus the resin used for molding or the like is often used. On the contrary, when kneading, the handling property becomes worse. Further, if the content of the fine powder oxide (C) exceeds 15% by weight, the surface of the masterbatch may be roughened or the fluidity of the masterbatch itself may be deteriorated due to its thickening effect.

The masterbatch of the present invention can be continuously produced by a known extruder (single screw or twin screw extruder). It is preferable to use a twin-screw extruder from the viewpoint of kneadability.

The temperature for kneading the masterbatch of the present invention may be set at an appropriate temperature depending on the type of the thermoplastic resin (A), but it is usually 90 to 280 ° C.

As a method of charging (A), (B) and (C) into the extruder, (A), (B) and (C) are separately charged, and (A) and (B) are used. A method in which (C) is pre-blended with a tumbler, a Henschel mixer, etc. and then added,
(B) and (C) are mixed in advance and then added separately from (A), or (B) and (C) are mixed in advance, and (A) is pre-blended with a tumbler or a Henschel mixer. There is a method of inputting from
(B) and (C) are mixed in advance and then added separately from (A), or (B) and (C) are mixed in advance, and (A) is pre-blended with a tumbler or a Henschel mixer. The method of charging from the above is preferable. this is,
By pre-mixing (B) and (C), the thickening effect of the surfactant appears more significantly, the difference in melt viscosity between the resin and the surfactant can be reduced, and a masterbatch having a higher concentration can be produced. is there. As a method of previously mixing (B) and (C), a method of mixing (B) and (C) in an ordinary mixing tank, a tumbler of (B) and (C),
A method of pre-blending with a Henschel mixer or the like can be mentioned, but a method of mixing (B) and (C) in an ordinary mixing tank is preferable because the thickening effect of the surfactant is more significantly exhibited. In addition, when (B) and (C) are mixed in a mixing tank in advance, it is sufficient that the masterbatch is thickened to the point where it can be continuously produced, and its viscosity is not limited, but more stable production is possible. Its viscosity is 100c
ps or more (B type viscometer, rotor No. 3, 60 rpm,
It is preferably 130 ° C.). When (A), (B), and (C) are separately charged, and when the mixture of (B) and (C) and (A) are separately charged, even if all are charged, (B) ) And (C) may be partly or wholly fed from the side feed unit. In addition, when charging from a side feed unit, it may be heated and melted, or may be charged in a solid state. When (B) is liquid, a side liquid feed unit may be used.
When (A), (B) and (C) are pre-blended,
When pre-blending a mixture of (B) and (C) with (A), when (B) is liquid, it can be applied to such an extent that the pre-blend does not block.

In the masterbatch of the present invention, if necessary, a higher alcohol (having 12 to 18 carbon atoms), a colorant,
You may contain additives, such as an antioxidant, an ultraviolet absorber, an infrared absorber, a plasticizer, and a filler. These higher alcohols and additives may be used in combination of several kinds according to the purpose, and may be used in the required amounts, but usually, the higher alcohol is used in the same amount as the surfactant (B). The additive is up to the same amount as the fine powder oxide (C). As the method of charging into the extruder, in the case of higher alcohols, the same method as that of the surfactant (B) may be selected, and in the case of additives, the same method as that of the fine powder oxide (C) may be selected.

[0015]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In the following description,% means% by weight unless otherwise specified.

Examples 1 to 6 Thermoplastic resins, surfactants (and higher alcohols) and silicon oxides shown in Table 1 were melt-kneaded in the same ratio in a co-rotating twin-screw extruder to prepare thermoplastics containing antistatic agents. A resin masterbatch was obtained. Table 2 shows the feeding method, kneading property and the like when kneading.

Comparative Examples 1 to 3 The same operations as in Examples 1 to 6 were carried out except that silicon oxide was not used. The thermoplastic resin, the surfactant and the ratio thereof are shown in Table 1, and the feeding method, kneading property and the like when kneading are shown in Table 2.

Comparative Example 4 The same operations as in Examples 1 to 6 were carried out except that the thermoplastic resin and the surfactant were melt-mixed with a kneader and then processed with a single-screw extruder. The thermoplastic resin, the surfactant and their ratios are shown in Table 1, and the kneading properties are shown in Table 2.

[0019]

[Table 1]

Note) A-1: Polyethylene (MFR = 4
0) A-2: Polyethylene (MFR = 5) A-3: Polypropylene (MFR = 20) A-4: Vinyl chloride (MFR = 50) A-5: PBT (MFR = 1) B-1: Stearylamine EO Mixture of adduct (50%) and stearic acid monoglyceride (50%) B-2: stearic acid monoglyceride B-3: laurylamine EO adduct B-4: sodium stearyl sulfonate C-1: Nippon Aerosil Co., Ltd. Aerosil 200 C-2: Nippon Aerosil Co., Ltd. Aerosil R972 D-1: Stearyl alcohol

[0021]

[Table 2]

Note) Feeding method; (a): The surfactant and silicon oxide were melt-mixed in advance, and then preblended with the thermoplastic resin and tumbler, and then fed (b): The surfactant and silicon oxide were previously mixed. Melt-mixed and side-fed in liquid form (c): Surfactant and silicon oxide were pre-blended with tumbler, and side-fed (d): Surfactant was pre-blended with thermoplastic resin with tumbler and then fed (E): Surfactant was side-fed in liquid form (f): Surfactant was side-fed (g): Surfactant and thermoplastic resin were added to the kneader at room temperature Viscosity; pre-mixed surfactant However, in Comparative Example 4, the viscosity of the surfactant was measured (measurement conditions: B-type viscometer, rotor No. 3, 60 rp).
m, 130 ° C) Kneading property; visually determined ◎: good (no surfactant bleed-out to the surface) ○: good (surfactant bleed-out to the surface is slightly) ×: poor (extruder Inability to form due to unstable discharge from the pellet) Presence or absence of fusion of the granulated product; 25 kg of the granulated product was filled in a kraft bag made of an internal aluminum, and the granulated product was allowed to stand at room temperature for 1 month in four layers. The bottom craft bag was opened and the presence or absence of fusion was visually judged. In addition, since a granulated product was not obtained, a product having a poor kneading property was indicated by "-".

Application Example 1 Using the masterbatch obtained in Example 1, the resin was diluted with the same kind of resin so that the concentration of the surfactant was 0.5% to obtain a molded product. Table 3 shows the surface specific resistance values of the obtained molded products.
It was shown to.

[0024]

[Table 3] Note) Surface resistivity measurement conditions: 20 ° C 65RH%, measured 5 days after molding

[0025]

INDUSTRIAL APPLICABILITY The present invention is a thermoplastic resin-based masterbatch containing a surfactant in a high concentration and can be continuously produced by an extruder regardless of the melt viscosity of the thermoplastic resin. It is a thing. In the masterbatch of the present invention, the resin used for producing the masterbatch does not have extremely high fluidity as compared with the resin used for molding and the like, and therefore does not impair the resin physical properties of the molded product. In addition, since it can be continuously manufactured with an extruder, the surfactant is exposed to the high temperature at which it is melt-mixed for a long time as in the method in which both the resin and the surfactant are melt-mixed beforehand and then charged into the extruder. It has excellent productivity with no problems of deterioration and coloration. Further, since the fine powdered oxide is contained, the surfactant does not bleed out to the surface and the produced master batches are not fused to each other. Because of the above effects, the masterbatch of the present invention is useful as a material for imparting antistatic ability to thermoplastic resins for various molding materials that require antistatic properties.

Claims (8)

[Claims] 1. A thermoplastic resin (A) and a surfactant (B).
And finely divided oxide (C), and the content of each of (A), (B) and (C) is 3
0 to 70% by weight, (B) 25 to 65% by weight, (C) 0.2 to 15% by weight, an antistatic agent-containing thermoplastic resin masterbatch. 2. The masterbatch according to claim 1, wherein the particle size of (C) is 5 to 50 nm. 3. The masterbatch according to claim 1, wherein (C) is silicon oxide. 4. A thermoplastic resin (A) in an amount of 30 to 70 parts by weight, a surfactant (B) in an amount of 25 to 65 parts by weight, and a fine powdered oxide (C) in an amount of 0.2 to 15 parts by weight are continuously added in an extruder. A method for producing a thermoplastic resin-based masterbatch containing an antistatic agent, which comprises kneading with 5. The method for producing a masterbatch according to claim 4, wherein the particle size of (C) is 5 to 50 nm. 6. The method for producing a masterbatch according to claim 4, wherein (C) is silicon oxide. 7. The method for producing a masterbatch according to claim 4, wherein (B) and (C) are mixed in advance. 8. The viscosity of (B) and (C) premixed is 100 cps or more (B type viscometer, rotor No. 3,
The method for producing a masterbatch according to claim 7, wherein the rotation speed is 60 rpm and 130 ° C.