DE102006046565A1 - Highly loaded antistatic masterbatches for the production of plastics with reduced electrostatic charge - Google Patents

Abstract

An active agent composition comprising a high proportion of liquid or easily flowing active substances such as antistatic agents and one or more polyolefin waxes, wherein the quantitatively greater proportion is a metallocene wax and wherein the further waxes are polar or non-polar non-metallocene polyolefin waxes. All polyolefin waxes together make up at least 15% by weight of the formulation and melt between 80 and 170 ° C. The antistatic masterbatch according to the invention is dust-reduced and is used for the masterbatch production.

Description

The The present invention relates to the manufacture and use of highly-charged ones Active ingredient masterbatches for the production of high-quality plastic parts Quality, which have a reduced electrostatic charge, resulting in leads to less pollution. By adding such antistatic agent batches, the cell structure becomes of foamed Plastic parts significantly improved, resulting in a higher load capacity leads the components And this at a reduced weight.

The The invention relates in particular to the use of copolymeric low molecular weight Grow for the Production of such masterbatches, wherein the waxes by means of metallocene catalysts be prepared, which has a low drop point, high transparency and low viscosity exhibit. By using these waxes, the incorporation the antistatics much easier, the process temperatures can be significantly be kept lower. Furthermore is a much higher one Loading as usual possible and on a polymeric carrier can be dispensed with.

At the Making the masterbatch, despite this high load, can be a Strand pelletizing can be used for many masterbatch producers the usual Procedure represents. But it can also be used in certain cases Underwater pelletizing can be used.

Around to reduce the high electrostatic charge of plastics, become common Antistatics in the form of masterbatches, this is the presentation of the active ingredient in a higher Concentration, added to the plastic. The in the extrusion process antistatic concentrates produced have antistatic contents in the Range of 5 to 20 wt .-% and occasionally included next a polymeric carrier a small proportion of polyolefin or amide waxes containing the Assisting process of incorporation of funds in the plastic matrix and improve the lubricity of the masterbatch and the final material. Likewise small amounts of fillers are added to the antistatic masterbatches, which improve the absorption of the low-melting or liquid products.

At Such concentrates are set high standards in the art: The incorporated antistatic products should be optimally distributed They should be present only limited on the surface, so that it is too small Clumping tendencies occurs, with the highest possible dosage the raw material costs as possible to keep low.

The production of dust-free, granulated and powdery highly charged antistatic masterbatches and preparations is currently carried out in the state of the art with single-stage or multi-stage processes:
For the antistatic masterbatches, all components are mixed cold and added via the main feed of the extruder. Or the waxy or polymeric formulation portions are fed through the main entrance of the extruder, the addition of the antistatic agents, which are powdery or liquid, via corresponding sidefeeder on the machine.

in the Following this, a melt mixture in a suitable extruder, be carried out in a kneader or compactor. This is followed a granulation, grinding or spraying on.

A Cold mix consists of suitable polymer supports such as polyethylene, polypropylene or Ethylenvinylazetatcopolymer and the like and may additionally dispersing agents like waxing, fatty acid derivatives, Stearates etc. included. The disadvantage of these polymer blends is that the polymer content is a higher addition of short chain components only conditionally allowed. If the saturation range is exceeded, and this can often already be below 10%, it happens a separation of polymer and the antistatic agents.

The JP 05098096 describes the use of an amorphous C ₃ H ₆ polymer having a melt viscosity of 500-3500 cP at 180 ° C into which 5-30% antistatic agent is incorporated.

The JP 63030546 describes the use of a mixture of amorphous and crystalline polypropylene and the addition of an antistatic agent of 5-25%.

The CN 1033063 describes the preparation of a PP masterbatch containing 10-30% of an antistatic product and produced at 130-230 ° C.

The JP 06322140 describes a mixture of thermoplastics, surfactants and powdery oxides.

The CN 1616531 describes a polyethylene compound with antistatic agents and flame retardants. The polyethylene content is 20-45%, the antistatic masterbatches of the polyethylene at 30-40% and a flame retardant masterbatch of 25-40%

The EP 1644432 describes a carrier for aqueous media which can be used as superabsorber for polymer additives. The product has a hydrophobic, open-pore structure.

Antistatic masterbatches which have a high active ingredient content, have a highly porous polyolefinic Carrier. In a special process step is in a temperature-controlled Vacuum chamber of the liquid Active substance sucked into the material. This special procedure is associated with high raw material and process costs.

Usual antistatic masterbatches have a charge of around 10-20%, as higher charges lead to large viscosity differences to lead, the incorporation no longer even and the strand strength the masterbatch produced is low. Strand granulation is At masterbatch companies prior art, this equipment can be uploaded for Antistatic masterbatches are used.

A possibility To increase the active ingredient content in the masterbatch would theoretically be the use special polymers that flow easily, a higher antistatic content allow to work well at lower temperatures and to be well tolerated too different polymers are. Polymers that have this property profile, have higher ones Purchase costs, which in turn makes their use uneconomical.

The Object of the present invention was antistatic masterbatches for the Polymer processing with one possible high proportion of liquid, loaded low-melting or low-viscosity antistatic agents to can, Thus, the production of plastic parts with low electrostatic Charging and or fine cell structure economical and ecological can be accomplished advantageously and so products of high quality quality can be generated.

On a polymeric carrier should be largely dispensed with, which on the one hand anti-static masterbatches with a much higher one Active substance content possible and on the other hand, the manufactured masterbatches in much more different polymers, with different chemical composition than so far, can be used because less compatibility problems due to the high loading. The watchman should also easier incorporation and dispersion in the polymers enable, which results in a finer cell structure.

These Task is inventively characterized solved, by placing the antistatic components in a metallocene wax, in a Mixture of metallocene waxes, in a metallocene Ziegler wax mixture or incorporated into a wax-polymer blend. Main component of the wax carrier is a metallocene wax. Metallocene waxes are waxes that are present were prepared by metallocenes as a catalyst. The so produced Antistatic composition becomes an antistatic by extrusion Compounded masterbatch.

• i) ein oder mehrere fein verteilte Antistatika
• ii) ein oder mehrere Metallocen-Polyolefinwachse
• iii) ein oder mehrere Wachse ausgewählt aus polaren und unpolaren Nicht-Metallocen-Polyolefinwachsen und
• iv) ggf. ein oder mehrere Copolymere des Ethylens

deren kennzeichnendes Merkmal darin zu sehen ist, dass das Antistatika in einer Menge von 10-80% und mindestens 20 Gew.-% Wachs enthält, bezogen jeweils auf das Gesamtgewicht des Masterbatches, wobei das Wachs zu mindestens 50 Gew.-% Polypropylen-Metallocenwachs enthält, bezogen auf das Gesamtgewicht des Wachsanteils.The present invention is an antistatic masterbatch of the type mentioned, containing

• i) one or more finely divided antistatic agents
• ii) one or more metallocene polyolefin waxes
• iii) one or more waxes selected from polar and nonpolar non-metallocene polyolefin waxes and
• iv) optionally one or more copolymers of ethylene

their characteristic feature is that the antistatic agent contains in an amount of 10-80% and at least 20 wt .-% wax, based in each case on the total weight of the masterbatch, wherein the wax to at least 50 wt .-% polypropylene metallocene wax contains, based on the total weight of the wax portion.

The inventive masterbatch has a particularly high anti-static and filler content, it has a very good compatibility with the use of polymers and largely excludes negative effects of mechanical properties.

The Metallocene waxes ii.) And iii.) Or the copolymer of ethylene iv) melting at a temperature in the range of 50 to 170 ° C. The metallocene polyolefin wax has a dropping point between 80 and 170 ° C and a melt viscosity, measured at a temperature of 170 ° C, in the range of 40 to 80,000 mPa · s, preferably 45 to 35,000 mPa.s, particularly preferably from 50 to 10,000 mPa · s.

According to the invention preferred Antistatikamasterbatche contain 10 to 80 wt .-%, preferably 15 to 75 wt .-%, of one or more antistatic agents, in particular selected from organic or inorganic products, e.g. Alkyl amines Glycerol Monostearats, polyglycerols, alkyl sulfonates or any other Antistatic agent and 20 to 90% by weight, preferably 25 to 85% by weight, of the metallocene polyolefin wax, 0.1 to 30% by weight, preferably From 0.5% to 25% by weight of one or more non-metallocene waxes and / or Copolymers of ethylene. additionally may be the preferred according to the invention Masterbatch still small amounts of fillers or additives in one Amount between 0 to 15 wt .-%, based on the total weight of the masterbatch.

The waxes prepared in the presence of metallocene as a catalyst are copolymer waxes of propylene and 0.1 to 50% of ethylene and / or 0.1 to 50% of at least one branched or unbranched 1-alkene with 4 to 20 carbon atoms with a drop point (ring / ball) between 80 and 170 ° C.

The metallocene waxes prepared in the presence of metallocene as a catalyst are largely or completely amorphous and may additionally be polar modified as needed be.

The Non-metallocene polyolefin waxes are selected according to the invention from non-polar or oxidized waxes which have a dropping point below 135 ° C and a viscosity of less than 30,000 mPa · s (measured at 140 ° C) have.

When Non-metallocene polyolefin waxes are homopolymers of ethylene or higher 1-olefins having 3 to 10 carbon atoms or copolymers thereof with one another in question. Preferably, the non-metallocene polyolefin waxes a weight average molecular weight Mw between 1000 and 20,000 g / mol and a number average molecular weight Mn of between 500 and 15,000 g / mol on.

For the production the invention used Metallocene polyolefin waxes become metallocene compounds of the formula I used.

der Formel Ib

und der Formel Ic

This formula also includes compounds of the formula Ia,

the formula Ib

and the formula Ic

In formulas I, Ia and Ib, M ^{1 is} a Group IVb, Vb or VIb metal of the Periodic Table, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, preferably titanium, zirconium, hafnium.

R ¹ and R ² are identical or different and denote a hydrogen atom, a C ₁ -C ₁₀ , preferably C ₁ -C ₃ -alkyl group, in particular methyl, a C ₁ -C ₁₀ -, preferably C ₁ -C ₃ -alkoxy group, a C ₆ -C ₁₀ , preferably C ₆ -C _8, aryl group, a C ₆ -C ₁₀ , preferably C ₆ -C _8, aryloxy group, a C ₂ -C ₁₀ , preferably C ₂ -C ₄ alkenyl group, one C ₇ -C ₄₀ -, preferably C ₇ -C ₁₀ arylalkyl group, a C ₇ -C ₄₀ -, preferably C ₇ -C ₁₂ -alkylaryl group, a C ₈ -C ₄₀ -, preferably C ₈ -C ₁₂ -aryl-alkenyl group or a halogen, preferably chlorine atom.

R ³ and R ⁴ are identical or different and denote a mononuclear or polynuclear hydrocarbon radical which can form a sandwich structure with the central atom M ¹ . R ³ and R ⁴ are preferably cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, it being possible for the basic units to carry additional substituents or to bridge them with one another. In addition, one of the radicals R ³ and R ^{4 may be} a substituted nitrogen atom, wherein R ^{24 has} the meaning of R ¹⁷ and is preferably methyl, tert-butyl or cyclohexyl.

R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are identical or different and denote a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C ₁ -C ₁₀ -, preferably C ₁ C ₄ alkyl group, a C ₆ -C ₁₀ , preferably C ₆ -C ₈ aryl group, a C ₁ -C ₁₀ , preferably C ₁ -C ₃ alkoxy group, an -NR ¹⁶ ₂ -, -SR ¹⁶ -, -OSiR ¹⁶ ₃ -, -SiR ¹⁶ ₃ - or -PR ¹⁶ ₂ radical, wherein R ^{16 is} a C ₁ -C ₁₀ -, preferably C ₁ -C ₃ alkyl group or C ₆ -C ₁₀ -, preferably C ₆ -C ₈ -aryl or in the case of Si or P-containing radicals is also a halogen atom, preferably chlorine atom or two adjacent radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ form a ring with the carbon atoms connecting them. Particularly preferred ligands are the substituted compounds of the parent compounds cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl.

=BR¹⁷, =AlR¹⁷, -Ge-, -Sn-, -O-, -S-, =SO, =SO₂, =NR¹⁷, =CO, =PR¹⁷ oder =P(O)R¹⁷, wobei R¹⁷, R¹⁸ und R¹⁹ gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom, vorzugsweise ein Fluor-, Chlor- oder Bromatom, eine C₁-C₃₀-, vorzugsweise C₁-C₄-Alkyl-, insbesondere Methyigruppe, eine C₁-C₁₀-Fluoralkyl-, vorzugsweise CF₃-Gruppe, eine C₆-C₁₀-Fluoraryl-, vorzugsweise Pentafluorphenylgruppe, eine C₆-C₁₀-, vorzugsweise C₆-C₈-Arylgruppe, eine C₁-C₁₀-, vorzugsweise C₁-C₄-Alkoxy-, insbesondere Methoxygruppe, eine C₂-C₁₀, vorzugsweise C₂-C₄-Alkenylgruppe, eine C₇-C₄₀-, vorzugsweise C₇-C₁₀-Aralkylgruppe, eine C₈-C₄₀-, vorzugsweise C₈-C₁₂-Arylalkenylgruppe oder eine C₇-C₄₀, vorzugsweise C₇-C₁₂-Alkylarylgruppe bedeuten, oder R¹⁷ und R¹⁸ oder R¹⁷ und R¹⁹ bilden jeweils zusammen mit den sie verbindenden Atomen einen Ring.R is ¹³

= BR ¹⁷ , = AlR ¹⁷ , -Ge, -Sn, -O-, -S-, = SO, = SO ₂ , = NR ¹⁷ , = CO, = PR ¹⁷ or = P (O) R ¹⁷ , wherein R ¹⁷ , R ¹⁸ and R ^{19 are the} same or different and a hydrogen atom, a halogen atom, preferably a fluorine, chlorine or bromine atom, a C ₁ -C ₃₀ , preferably C ₁ -C ₄ alkyl, in particular methyl group , a C ₁ -C ₁₀ fluoroalkyl, preferably CF ₃ , C ₆ -C ₁₀ fluoroaryl, preferably pentafluorophenyl, C ₆ -C ₁₀ , preferably C ₆ -C ₈ aryl, C ₁ -C ₁₀ -, preferably C ₁ -C ₄ alkoxy, especially methoxy, a C ₂ -C ₁₀ , preferably C ₂ -C ₄ alkenyl, a C ₇ -C ₄₀ -, preferably C ₇ -C ₁₀ aralkyl group , a C ₈ -C ₄₀ -, preferably C ₈ -C ₁₂ -aryl-alkenyl group or a C ₇ -C ₄₀ , preferably C ₇ -C ₁₂ -alkylaryl group, or R ¹⁷ and R ¹⁸ or R ¹⁷ and R ¹⁹ each form together with the atoms connecting them a ring.

M ² is silicon, germanium or tin, preferably silicon and germanium. R ¹³ is preferably = CR ¹⁷ R ^18, = SiR ¹⁷ R ^18, = GeR ¹⁷ R ^18, -O-, -S-, = SO, = PR ¹⁷ or = P (O) R ^17th

R ¹¹ and R ¹² are the same or different and have the meaning given for R ¹⁷ . m and n are the same or different and are zero, 1 or 2, preferably zero or 1, where m plus n is zero, 1 or 2, preferably zero or 1.

R ¹⁴ and R ¹⁵ have the meaning of R ¹⁷ and R ¹⁸ .

Examples of suitable metallocenes are:
Bis (1,2,3-trimethyl) zirconium,
Bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride,
Bis (1,2-dimethylcyclopentadienyl) zirconium dichloride,
Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,
Bis (1-methylindenyl) zirconium dichloride,
Bis (1-n-butyl-3-methyl-cyclopentadienyl) zirconium dichloride,
Bis (2-methyl-4,6-di-i.propyl-indenyl) zirconium dichloride,
Bis (2-methylindenyl) zirconium dichloride,
Bis (4-methylindenyl) zirconium dichloride,
Bis (5-methylindenyl) zirconium dichloride,
Bis (alkylcyclopentadienyl) zirconium,
Bis (alkylindenyl) zirconium,
Bis (cyclopentadienyl) zirconium,
(Indenyl) zirconium,
Bis (methylcyclopentadienyl) zirconium,
Bis (n-butylcyclopentadienyl) zirconium dichloride,
To (octadecylcyclopentadienyl) zirconium,
Bis (pentamethylcyclopentadienyl) zirconium,
Bis (trimethylsilyl) zirconium,
Biscyclopentadienylzirkoniumdibenzyl,
Biscyclopentadienylzirkoniumdimethyl,
Bistetrahydroindenylzirkoniumdichlorid,
Dimethylsilyl-9 fluorenylcyclopentadienylzirkoniumdichlorid,
Dimethylsilyl-bis-1- (2,3,5-trimethylcyclopentadienyl) zirconium dichloride,
Dimethylsilyl-bis-1- (2,4-dimethyl-cyclopentadienyl) zirconium dichloride,
Dimethylsilyl-bis-1- zirconium dichloride (2-methyl-4,5-benzoindenyl)
Dimethylsilyl-bis-1- (2-methyl-4-ethylindenyl) zirconium dichloride,
Dimethylsilyl-bis-1- (2-methyl-4-i-propylindenyl) zirconium dichloride,
Dimethylsilyl-bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride,
(2-methyl-indenyl) zirconium dichloride dimethylsilyl-bis-1,
Dimethylsilyl-bis-1- (2-methyltetrahydroindenyl) zirconium dichloride,
Dimethylsilyl-bis-1-indenylzirkoniumdichlorid,
Dimethylsilyl-bis-1-indenylzirkoniumdimethyl,
Dimethylsilyl-bis-1-tetrahydroindenylzirkoniumdichlorid,
Diphenylmethylene-9-fluorenylcyclopentadienylzirkoniumdichlorid,
Diphenylsilyl-bis-1-indenylzirkoniumdichlorid,
Ethylene-bis-1- zirconium dichloride (2-methyl-4,5-benzoindenyl)
Ethylene-bis-1- (2-methyl-4-phenylindenyl) zirconium dichloride,
Ethylene-bis-1- (2-methyl-tetrahydroindenyl) zirconium dichloride,
Ethylene-bis-1- (4,7-dimethyl-indenyl) zirconium dichloride,
Ethylene-bis-1-indenylzirkoniumdichlorid,
Ethylene-bis-1-tetrahydroindenylzirkoniumdichlorid,
Indenyl-cyclopentadienyl zirconium
Isopropylidene (1-indenyl) (cyclopentadienyl) zirconium dichloride,
Isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride,
(2-methyl-indenyl) zirconium dichloride phenylmethylsilyl-bis-1-,
and in each case the alkyl or aryl derivatives of these metallocene dichlorides.

To activate the single-center catalyst systems suitable cocatalysts are used. Suitable cocatalysts for metallocenes of the formula I are organoaluminum compounds, in particular alumoxanes or else aluminum-free systems such as R ²⁰ _x NH ₄ -x BR ²¹ ₄ , R ²⁰ _x PH _4-x BR ²¹ ₄ , R ²⁰ ₃ CBR ²¹ ₄ or BR ²¹ ₃ , In these formulas, x is a number from 1 to 4, the radicals R ²⁰ are identical or different, preferably identical, and are C ₁ -C ₁₀ -alkyl or C ₆ -C ₁₈ -aryl or two radicals R ²⁰ form together with the they join a ring and the radicals R ²¹ are the same or different, preferably the same, and are C ₆ -C ₁₈ -aryl which may be substituted by alkyl, haloalkyl or fluorine. In particular, R ^{20 is} ethyl, propyl, butyl or phenyl and R ^{21 is} phenyl, pentafluorophenyl, 3,5-bistrifluoromethylphenyl, mesityl, xylyl or tolyl.

In addition is often a third component is required to provide protection from polar Maintain catalyst poisons upright. These are organoaluminum Compound such as e.g. Triethylaluminum, tributylaluminum and others as well as mixtures.

ever according to procedures also carried Single-center catalysts are used. Preference is given to catalyst systems, in which the residual contents of support material and cocatalyst do not exceed a concentration of 100 ppm in the product.

in this connection became the melt viscosities according to DIN 53019 with a rotational viscometer, the dropping points according to DIN 51801/2, the softening points ring / ball according to DIN EN 1427 certainly. The drop point determination is carried out with a drop point device according to Ubbelohde according to DIN 51801/2, the softening point ring / ball according to DIN EN 1427.

The antistatic masterbatches according to the invention can as previously mentioned additionally still fillers such as silica; Zeolites, silicates, such as aluminum silicates, sodium silicate, calcium silicates, Chalk, talcum or even aids such as stearates, propellants, Peroxides, Antioxidants, UV Absorbers and HALS Products, Slip-, Antifogging, anticondensation and / or suspension stabilizers, contain.

Antistatic agents include glycerol stearates, glycerol monostearates, alkyl amines, alkoxylated fatty acids use is made of regimens, ethoxylated amines, alkyl sulfonates, glycerol esters or blends thereof.

Of the required proportion of metallocene waxes and their composition depends on from the additive-matrix exchange reaction, from the surface structure of the antistatic, of the surface structure of finished product, from the desired Cell structure, of the desired optical properties, the migration of antistatic from the Granules and of the desired End-use amount.

• a) die Einzelkomponenten kalt gemischt oder
• b) es kann auf eine Mischung der Komponenten verzichtet werden, wenn an der Maschine eine direkte Einarbeitung des Wirkstoffes möglich ist

und das anschließend die Homogenisierung der Einzelbestandteile in einem Extruder erfolgt.In the preparation of the antistatic masterbatches according to the invention

• a) the individual components cold mixed or
• b) it can be dispensed with a mixture of components, if a direct incorporation of the active ingredient is possible on the machine

and then the homogenization of the individual components takes place in an extruder.

The Premixing the individual components is an important prerequisite in product manufacture and may be in a room temperature at room temperature suitable mixing apparatus. The first phase lasts about 3 to 10 minutes, preferably 5 to 7 mm.

at batch production on a co-rotating twin screw appropriate with a worm structure adapted to the high antistatic content worked. The temperature image is preferably lower than before indicated in the prior art. For the production of masterbatches Advantageously, a strand granulation is used, an underwater granulation but can in special cases but also used.

Of the antistatic masterbatch according to the invention becomes convenient way also worked with an initial mixing process. First is a mixture of the active ingredient composition according to the invention produced. The mixture is done with appropriate mixing technique. However, the preparation of mixtures can be omitted if the Single components of a recipe feeds directly to the extrusion plant. The said mixture is then removed by means of a suitable metering device fed to an extrusion plant.

In Usually these are single or twin screw extruders, but they can also continuous and discontinuous kneaders or compactors Find use. The subsequent Granulation takes place via strand and Kopfgranulierung, but also spraying is possible.

Around To make certain special types, you can also make preparations in a second extrusion cycle with each other or with plastic be blended.

Of the antistatic masterbatch according to the invention has a very good compatibility with many polymers, such as polyolefins, polyvinyl chloride (PVC), ethylene-vinyl acetate copolymers (EVA), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyamide (PA) and some special polymers

Examples:

The polyolefins a) -c), which are used according to the invention and have been listed in Table 1, were prepared by copolymerization of propylene with ethylene with the metallocene catalyst dimethylsilylbisindenylzirconium dichloride according to the method described in US Pat EP A 0 384 264 specified method (general rule Ex. 1-16). The different dropping points and viscosities were adjusted by varying the ethylene input and the polymerization temperature. The use of the products takes place in feinkörnigem Zusatnd or in granular form. Table 1: Polyolefins used Metallocene waxes Polyolefin b) Polyolefin c) Dropping point (° C) 93 102 Viscosity at 170 ° C (mPa · s) 7900 9800

The product characteristics are determined by the following methods:
Drop point ISO 2176 // ASTM D 3954 (° C)
Viscosity DIN 53018 (mPa · s)
Density ISO 1183 (g / cccm)
Molecular weight is determined by GPZ method Oxidized PE wax a) or non-polar PE wax b): Dropping point viscosity acid number density [° C] at 120 ° C [mg KOH / g] [g / cm ³ ] [MPa.s] a) Approximately 120 Approximately 3000 17 0.92 b) Approximately 118 Approximately 650 0 0.92 Copolymer of ethylene softening melting point Viscosity MFR comonomer density Et-acrylate [° C] [° C] 190 ° C / 2, 16kg % [g / cm ³ ] about 50-60 about 85-98 about 5-10 about 15-20 about 0.94 g / 10 min

The use takes place in the fine-grained state (sprayed or ground), or else in granular form. The antistatic masterbatch according to the invention was prepared as described below:
As a mixture for the extrusion:
Mixer: Hentschel mixer, content 5 liters
Approach: according to the examples given below
Premixing: approx. 2 to 4 min. at U = 600 / min

following the extrusion took place on a co-rotating twin screw with downstream strand granulation.

Partially the antistatic product was added directly to the extruder via sidefeeder, the premix could be dispensed with (Example 1, 3 and 7).

Granule size in diameter 0.8 to 3 mm.

Preparation Examples:

• 1) 70 Gew.-% GMS, 30 Gew.-% Metallocenwachs B
• 2) 40 Gew.-% Alkyl-Sulfunat 60 Gew.-% Metallocenwachs B
• 3) 30 Gew.-% Sorbitanester 70 Gew.-% Metallocenwachs B
• 4) 30 Gew.-% Sorbitanester 60 Gew.-% Metallocenwachs B 10 Gew.% unpolares PE Wachs
• 5) 30 Gew.-% Alkylamine 70% Metallocenwachs C
• 6) 40 Gew.-% Alkylamine 60% Metallocenwachs B
• 7) 30 Gew.-% Alkylamine 55 Gew.-% Metallocenwachs C 15 Gew.-% Copolymer des Ethylens

In the following examples, the following antistatic compositions were prepared by the methods described above. As metallocene waxes, the above described wax was used in each case:

• 1) 70% by weight of GMS, 30% by weight of metallocene wax B
• 2) 40% by weight of alkyl sulphunate 60% by weight of metallocene wax B
• 3) 30% by weight of sorbitan ester 70% by weight of metallocene wax B
• 4) 30% by weight of sorbitan ester 60% by weight of metallocene wax B 10% by weight of nonpolar PE wax
• 5) 30% by weight of alkylamines 70% of metallocene wax C
• 6) 40% by weight of alkylamines 60% of metallocene wax B
• 7) 30% by weight of alkylamines 55% by weight of metallocene wax C 15% by weight of copolymer of ethylene

Application examples:

The Additive masterbatch compositions according to Preparation Examples 1 up to 7 were fitted and in a co-rotating twin screw with a special screw construction and with a low temperature image to masterbatches are made in different polymers to a quality improvement to lead, This can be a reduced electrostatic charge, a better Cell structure, or be a better sliding behavior.

Claims (10)

An uploaded antistatic masterbatch for use in the manufacture of plastics for reducing surface charge or cell regulation, comprising i) one or more finely divided antistatics ii) one or more metallocene polyolefin waxes, iii) one or more waxes selected from polar and nonpolar non-metallocene Polyolefin waxes and iv) optionally one or more copolymers of ethylene, characterized in that it contains antistatic agents in an amount of 10-80% and at least 20% by weight of waxes, based in each case on the total weight of the masterbatch, wherein the wax is at least Contains 50 wt .-% polypropylene metallocene wax, based on the total weight of the wax portion. Masterbatch according to Claim 1, characterized that the waxes or the copolymer of Etyhlens of the components ii) iii) and iv) at a temperature in the range of 50 to 170 ° C melt. Active agent composition according to claim 1 or 2, characterized in that the metallocene polyolefin wax has a Dropping point between 80 and 170 ° C has and has a melt viscosity, measured at a temperature of 170 ° C, between 40 and 80,000 mPa · s, preferably from 45 to 35,000 mPa · s, in particular from 50 to 10,000 mPa · s. Masterbatch according to one or more of claims 1 to 3, characterized in that it is 20 to 90 wt .-%, preferably From 25% to 85% by weight of the metallocene polyolefin wax, from 0.1% to 30% % By weight, preferably 0.5 to 25% by weight of one or more non-metallocene waxes and / or copolymers of ethylene, 10 to 80 wt .-%, preferably 15 to 75% by weight of one or more antistatic agents, and 0 to 15% by weight more commonly fillers or contains additives. Masterbatch according to one or more of claims 1 to 4, characterized in that the one or more antistatic agents selected from inorganic and organic products. Masterbatch according to one or more of claims 1 to 5 characterized in that it has one or more antistatic agents contains selected from the group comprising alkyl amines, glycerol monostearates, polyglycerols, Alkyl sulfonates or other antistatic agent and mixtures thereof. Masterbatch according to one or more of claims 1 to 6, characterized in that one or more non-metallocene polyolefin waxes selected are, from non-polar or oxidized waxes, which are a dropping point below 135 ° C and a viscosity of less than 30,000 mPa · s (measured at 140 ° C) have. Masterbatch according to one or more of claims 1 to 7, characterized in that they are next to the predominantly or completely amorphous Polyolefin metallocene waxes one or more metallocene copolymer waxes of propylene and 0.1 to 50% by weight of one or more others Monomers selected of ethylene and branched or unbranched 1-alkenes with 4 to Contains 20 carbon atoms. Masterbatch according to one or more of claims 1 to 8, characterized in that a very good compatibility with polymers, in particular with polyolefins, polyvinyl chloride (PVC), ethylene-vinyl acetate copolymers (EVA), polystyrene (PS), styrene-acrylonitrile copolymers (SAN), acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), Polyamide (PA) and some special polymers used. Using a masterbatch after or after several of the claims 1 to 9 for producing antistatic or foamed plastic parts.