EP1882013A1

EP1882013A1 - Highly filled colorant composition for colouring olefinic and non-olefinic plastics

Info

Publication number: EP1882013A1
Application number: EP06742783A
Authority: EP
Inventors: Reinholdn Kling; Uwe Bernhardt
Original assignee: Clariant Produkte Deutschland GmbH
Current assignee: Clariant Produkte Deutschland GmbH
Priority date: 2005-05-11
Filing date: 2006-05-03
Publication date: 2008-01-30
Also published as: US20090105373A1; WO2006119904A1; JP2008540744A; DE102005022652A1

Abstract

Colorant composition comprising finely divided colorants and two or more polyolefin waxes, the quantitatively greater fraction representing a metallocene wax, and the further waxes being polar or apolar non-metallocene-polyolefin waxes or copolymers of ethylene. All of the polyolefin waxes together make up at least 15% by weight of the formula, and melt between 70 and 15O0C. The colorant composition of the invention features reduced dust and is used for masterbatch production.

Description

description

Highly filled colorant composition for coloring olefinic and non-olefinic plastics

The present invention relates to a highly filled colorant composition which improves the uniform dispersion of pigments in plastics.

The invention also relates to the use of copolymeric low molecular weight waxes for the production of masterbatches, in which the waxes are produced to a large extent by means of metallocene catalysts, have a low dropping point, high transparency and low viscosity. By using these waxes, the dispersion of pigments is significantly improved, the pigment charge can be increased, there is a better compatibility with different polymers and can be dispensed with a polymeric support.

Plastics are usually dyed using pigment concentrates, so-called masterbatches. The pigment concentrates produced in the extrusion process, have pigment contents in the range of 10 to 75 wt .-% and contain a polymeric carrier and various other additives such as waxes and other dispersants that support the incorporation process and for a uniform distribution (= dispersion) of the pigments to care.

High demands are placed on such pigment concentrates: The pigments should be distributed optimally, since insufficient dispersion of the pigments can lead to pigment agglomerates and specks in the end product, which may be, for example, a film. Also, specks can easily lead to weakening of the mechanical properties of the final product, premature cracking of the final article occurs. The following single-stage or multi-stage processes are currently known for the preparation of dust-free, granular and pulverulent pigment and dye preparations:

The pigment carrier premixes can be made by cold or hot blending. Subsequently, a melt mixture can be carried out in a suitable extruder or in kneaders. This is followed by granulation, grinding or spraying.

A cold mixture consists of suitable polymer supports, such as polyethylene, polypropylene or ethylene vinyl acetate copolymer and similar and additionally dispersing aids such as waxes, fatty acid derivatives, stearates, etc. The disadvantage of these mixtures is the insufficient pre-wetting of the pigments by the mixing process, which manifests itself in a high dust formation ,

In the case of the hot mixing process, the mixing batch contains carrier materials as well as waxes, similar to cold mixing, but agglomeration of the mixture is achieved through the intense introduction of friction energy, thus achieving freedom from dust and a higher bulk density.

DE-A-15 44 830 discloses a pigment preparation in which the pigment particles are enveloped by an amorphous homopolymer or copolymer of propylene, butene-1 and hexene-1 or a propylene-ethylene block polymer. In the preparation of the pigment preparation, filtration and drying steps are required.

DE-A-12 39 093 describes support materials based on a mixture of an amorphous ethylene-propylene block copolymer and a crystalline polypropylene for the production of pigment concentrates.

DE-A-26 52 628 relates to the use of polypropylene waxes having a viscosity of 500 to 5000 mPa.s (170 ⁰ C) and an isotactic content of 40 to 90%. In DE-A-195 16 387 a highly effective dispersion is achieved by a dispersing agent which contains a mixture of different polyolefin components and more particularly polyacrylic acid esters.

In JP-A-88/88287 preparations are described which consist of pigment, lubricants, fillers and an amorphous polyolefin.

DE-A 26 08 600 relates to pigment concentrates for coloring thermoplastics containing pigment, polyolefin wax, an ethylene-vinyl acetate copolymer and colloidal silica.

All previously used in practice pigment preparations for polymer coloration preferably contain the polymer to be colored, and partially incompatible ingredients. When used in other polymers, the known pigment preparations due to the less favorable carrier material with the same pigment content are weaker in color and cloudy. Special masterbatches are more complex and can not be prepared with the same high colorant concentrations as the property profile described below.

Usually, in the production of organic pigment masterbatches in a two-stage process with a pigment content of 40 wt .-% and less, since the strand strength of the produced masterbatches is low due to the high pigment content. Strand granulation is state of the art in masterbatch production. One way to improve this would be to use polymers with a lower MFR, which translates into higher melt strength and therefore less strand breakage. However, polymers that have a lower MFR are more poorly distributed in the end product, with the result that color differences in the form of color streaks in the end product become apparent.

The object of the present invention was to provide dust-free colorant preparations for masterbatch production and polymer coloration To load with the highest possible proportion of organic and inorganic pigments, so that the production of compounds and the direct coloring of plastomers and elastomers can be economically and ecologically advantageous with a uniform support system and thus delivers products of high quality. On a conventional polymeric support is to be dispensed with, which are on the one masterbatches with a significantly higher pigment content possible and on the other masterbatches can be used in significantly more polymers with different chemical composition than before, because the compatibility increases.

This object is achieved by a

Colorant composition of a mixture of wax and polymer, which contains a large part of a metallocene wax, which is a wax which is prepared in the presence of metallocenes as a catalyst. The so produced

Colorant composition is compounded in a special extrusion process to color masterbatches, but the mixture can alternatively be used directly for the plastic coloring.

The present invention relates to a colorant composition comprising i) one or more metallocene polyolefin waxes, ii) one or more waxes selected from polar and nonpolar non-polar waxes.

Metallocene polyolefin waxes and iii) optionally one or more copolymers of ethylene iv) one or more finely divided colorants, the characteristic of which is that they contain at least 15% by weight, based on the total weight of the colorant composition, wax and / or Contains copolymers of ethylene and that contained in the colorant composition waxes or copolymers at least

Contain 50 wt .-% polypropylene metallocene wax. All waxy or polymeric constituents of the carrier melt between 50 and 150 ⁰ C.

Colorant compositions preferred according to the invention contain from 30 to 85% by weight, preferably from 35 to 80% by weight, of an organic or inorganic pigment and from 7.5 to 42.5% by weight, preferably from 8.5 to 40% by weight, of the metallocene polyolefin wax. In addition, the colorant composition preferred according to the invention may contain from 0.1 to 30% by weight, preferably from 0.5 to 25% by weight, of functional constituents for improving wetting and compatibility in the form of non-metallocene polyolefin waxes or copolymers of ethylene and 0 to 15 wt .-% of conventional fillers or additives.

The waxes prepared as catalyst in the presence of metallocene are preferred. Copolymer waxes of propylene and 0.1 to 50% ethylene and / or 0.1 to 50% of at least one branched or unbranched 1-alkene having 4 to 20 carbon atoms with a dropping point (ring / ball) between 80 and 150 ⁰ C and a melt viscosity, measured at a temperature 170 ⁰ C, from 30 to 3000 mPa-s. The waxes prepared in the presence of metallocene as a catalyst are largely or completely amorphous and can additionally be polar modified if necessary.

As non-metallocene polyolefin waxes are on the one hand ethylene vinyl acetate waxes with a dropping point between 90 and 120 ⁰ C, a vinyl acetate content of 1 to 30% and a viscosity of 50 to 1500 mPa-s at 140 ⁰ C, as well as nonpolar, but also polar non-metallocene waxes having a dropping point in the range of 90 to 120 ⁰ C and a viscosity of less than 1500 mPa-s at 14O ⁰ C.

Suitable non-metallocene polyolefin waxes are homopolymers of ethylene or higher 1-olefins having 3 to 10 carbon atoms or copolymers thereof with one another. Preferably, the polyolefin waxes have a weight average molecular weight M _w between 1000 and 10 000 g / mol and a number average molecular weight M _n between 500 and 5000 g / mol. Furthermore, copolymers of ethylene can be advantageously used as a compatibilizer in the novel Frabmittelzusammensetzung. Ethylene-methyl-acrylate copolymers, ethylene-ethyl-acrylate copolymers, ethylene-butyl-acrylate copolymers or ethylene-vinyl-acetate copolymers are suitable as copolymers of ethylene. These products typically have a softening point of less than 40 ⁰ C, a melting temperature of less than 100 ⁰ C, a comonomer content of 10 to 20%, and a melt index at 190 ° and 2.16 kg from 1 to 10 g / 10 min. In the further course of the description, they are referred to as "copolymers of ethylene".

Metallocene compounds of the formula I are used for the preparation of the metallocene polyolefin waxes used according to the invention.

This formula also includes compounds of the formula Ia,

there)

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 the same or different and represent a hydrogen atom, a C ₁ -C _10, preferably CiC ₃ alkyl group, in particular methyl, a C ₁ -C ₁₀ -, preferably -C ₃ alkoxy group, a C ₆ -C _0, preferably Cβ-Cβ-Arvigruppe, a C ₆ -C ₁₀ - , preferably Cβ-Cβ-aryloxy group, a C2-C1 _0, preferably C ₂ - C ₄ alkenyl group, a C7-C4 ₀ -, preferably C7-Cio-arylalkyl group, a C ₇ -C ₄₀ -, preferably C ₇ -C _2- alkylaryl group, a C ₈ -C40, preferably Ce-Ci ₂ - arylalkenyl 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 . Preferably, R ³ and R ^{4 are} cyclopentadienyl,

Indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl, wherein the main body may carry additional substituents or may be bridged with each other. 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 -C ₄ - Alkyl group, a Ce-Ci ₀ , preferably Cβ-Cβ-aryl group, a Ci-Ci ₀ , preferably Ci-C ₃ alkoxy group, a -NR ¹ V, -SR ¹⁶ -, -OSiR ¹ V, -SiR ¹ V or -PR ¹⁶ ₂ radical in which R ^{16 is} a Ci-Ci ₀ -, preferably CrC ₃ alkyl group or Cβ-Cio, preferably Cβ-Cβ- aryl group or in the case of Si or P-containing radicals also a halogen atom, preferably chlorine atom or each two adjacent radicals R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ or R ¹⁰ form a ring with the C atoms connecting them. Particularly preferred ligands are the substituted compounds of the parent compounds cyclopentadienyl, indenyl, tetrahydroindenyl, benzoindenyl or fluorenyl. R is ¹³

O

17, 17, 17, 17

O- M 'M' M '

, 18 R 18> 18 R 18

= BR ¹⁷ , = AIR 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 CTC ₃ O, preferably Ci-C ₄ alkyl, especially methyl group, a Ci -Cio-fluoroalkyl, preferably CF ₃ group, a C ₆ -Cio-fluoroaryl, preferably pentafluorophenyl, a Cβ-C-io, preferably Cβ-Cβ-aryl group, a C ₁ -C ₁ -, preferably C C ₄ alkoxy, especially methoxy, C ₂ -C 10, preferably C ₂ -C ₄ alkenyl, C ₇ -C 40, preferably C ₇ -C 10 aralkyl, C 8 -C 40, preferably C 8 -C 12 aryl alkenyl, or C ₇ -C _4O, preferably C ₇ -Ci2-alkylaryl group, or R ¹⁷ and R ¹⁸ or R ¹⁷ and R ¹⁹ in each case 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 ¹⁷ .

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 (1,1'-trimethylcyclopentadienyl] zirconium dichloride,

Bis (1,2 ₎ 4-trimethylcyclopentadienyl) zirconium dichloride _I

Bis (1, 2-dimethylcyclopentadienyl) zirconium dichloride,

Bis (1,3-dimethylcyclopentadienyl) zirconium dichloride,

Bis (1-methylindenyl) zirconium dichloride, bis (1-n-butyl-S-methylcyclopentadienyl) 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 _I bis (alkylcyclopentadienyl) zirconium dichloride,

Bis (alkylindenyl) zirconium,

Bis (cyclopentadienyl) zirconium,

(Indenyl) zirconium,

Bis (methylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride,

To (octadecylcyclopentadienyl) zirconium,

Bis (pentamethylcyclopentadienyl) zirconium,

Up ^ rimethylsilylcyclopentadienyOzirkoniumdichlorid,

Biscyclopentadienylzirconiumdibenzyl, biscyclopentadienylzirconiumdimethyl,

Bistetrahydroindenylzirkoniumdichlorid,

Dimethylsilyl-θ-fluorenylcyclopentadienylzirkoniumdichlorid,

Dimethylsilyl-bis-1- _(2,3) 5-trimethylcyclopentadienyl) zirconium dichloride,

Dimethylsilyl-bis-1- (2,4-dimethyl-cyclopentadienyl) zirconium dichloride, dimethylsilyl-bis-1- (2-methyl-4,5-benzoindenyl) zirconium dichloride,

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, Dimethylsilyl-bis-1- (2-methyl-indenyl) zirconium dichloride,

Dimethylsilyl-bis-1- (2-methyltetrahydroindenyl) zirconium dichloride,

Dimethylsilyl-bis-1-indenylzirkoniumdichlorid,

Dimethylsilylbis-1-indenylzirconiumdimethyl, dimethylsilylbis-1-tetrahydroindenylzirconium dichloride,

Diphenylmethylene-θ-fluorenylcyclopentadienylzirkoniumdichlorid,

Diphenylsilyl-bis-1-indenylzirkoniumdichlorid,

Ethylene-bis-1- (2-methyl-4,5-benzoindenyl) zirconium dichloride,

Ethylene-bis-1- (2-methyl-4-phenyl-indenyl) zirconium dichloride, ethylene-bis-1- (2-methyltetrahydroindenyl) zirconium dichloride,

Ethylene-bis-1- (4,7-dimethyl-indenyl) zirconium dichloride,

Ethylene-bis-1-indenylzirconium dichloride,

Ethylene-bis-1-tetrahydroindenylzirconium dichloride,

Indenyl-cyclopentadienyl-zirconium dichloride isopropylidene (1-indenyl) (cyclopentadienyl) zirconium dichloride, isopropylidene (9-fluorenyl) (cyclopentadienyl) zirconium dichloride,

Phenylmethylsilyl-bis-1- (2-methyl-indenyl) zirconium dichloride, and in each case the alkyl or aryl derivatives of these metallocene dichlorides.

To activate the single-center catalyst systems are suitable

Cocatalysts used. Suitable cocatalysts for metallocenes of the formula I are organoaluminum compounds, in particular alumoxanes or else aluminum-free systems such as R ²⁰ _× NH ₄ -x BR ²¹ ₄ , R ²⁰ _× PH 4-21BR 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 Ci-C-io-alkyl or Cβ-Ciβ-aryl or two radicals R ²⁰ form together with the connecting them Atom is a ring, and the radicals R ²¹ are the same or different, preferably the same, and are C ₆ -C ₈ -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-bis-trifluoromethylphenyl, mesityl, xylyl or ToIyI.

In addition, a third component is often required to maintain protection of polar catalyst poisons. These are organoaluminum Compound such as triethylaluminum, tributylaluminum and others and mixtures suitable.

Depending on the process, supported single-center catalysts can also be 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.

Here, the melt viscosities were determined according to DIN 53019 with a rotary viscometer, the dropping points according to DIN 51801/2, the softening points ring / ball according to DIN EN 1427. 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 pigment concentrates may additionally contain fillers or auxiliaries such as antistatic agents, oleic acid amide, glycerol fatty acid partial esters, stearates and antioxidants. It is likewise possible to use silicic acid, silicates, such as aluminum silicates, sodium silicate, calcium silicates.

Suitable colorants are organic and inorganic dyes and pigments. The organic pigments used are preferably azo or disazo pigments, laked azo or disazo pigments or polycyclic pigments, preferably phthalocyanine, quinacridone, perylene, dioxazine, anthraquinone, thioindigo, diaryl or quinophthalone pigments.

Suitable inorganic pigments are metal oxides suitable for pigmentation, mixed oxides, aluminum sulfates, chromates, metal powders, pearlescent pigments (mica), luminous colors, titanium oxides, cadmium-lead pigments, preferably iron oxides, carbon black, silicates, nickel titanates, cobalt pigments or chromium oxides.

The required proportion of metallocene waxes and other polyolefin waxes or copolymers of ethylene depends on the surface structure and Particle size of the colorants used and should preferably be adjusted to it.

When using organic pigments, a colorant composition containing 30 to 75% by weight of organic pigment, 7.5 to 42.5% by weight of the amorphous metallocene wax, 0.1 to 20% by weight of ethylene vinyl acetate wax, 0, 5 to 20 wt .-% of oxidized wax or 0.5 to 20 wt .-% of copolymers of ethylene and other fillers or additives in amounts of 0 to 4 wt .-% particularly advantageous.

When using inorganic pigments is a colorant composition containing 60 to 85 wt .-% of inorganic pigment, 7.5 to 30 wt .-% of metallocene wax and 7.5 to 20 wt .-% of other olefin waxes or copolymers of ethylene and 0 to 2 wt .-% additives particularly advantageous.

Carbon blacks are conveniently formulated as organic formulations to obtain dispersed dispersions.

The colorant compositions of the invention may additionally contain other additives, such as fillers, for example lubricants, antistatics,

Anti-blocking agents, anti-slip agents and / or suspension stabilizers.

The premixing of the individual components is an important prerequisite in the production of the product and can be carried out at room temperature in a suitable mixing apparatus. If the formulation is to be used as a dust-free powder mixture, a mixing phase with higher mixing energy follows, it being expedient to heat in a first phase to about 15 K below the softening point of the metallocene wax and in a second phase to about 5 K below the softening point of the metallocene wax. The first phase lasts about 3 to 10 minutes, preferably 5 to 7 minutes, the second phase lasts about 1 to 5 minutes, preferably 2 to 3 minutes. The last mixing phase is followed by a cooling mixture, wherein the colorant composition on is cooled to about 30 ° C. This process usually takes 3 to 15 minutes, preferably 5 to 10 minutes.

In the case of mixing, the heat energy can be introduced via friction, via separate heating of the mixing trough or via both types. A pre-tempering to about 25 ° C is considered advantageous. Higher starting temperatures in the hot mix lead to clumping of the carrier and formation of bottom deposits. Cooling of the mixing trough after the last mixing phase to the pre-treatment temperature is also advantageous.

In order to improve the flowability, up to 0.5% by weight of free-flow improvers, based on the total mixture, can additionally be added to the subsequent cooling mixture in order to achieve a granulation of 0.05 to 3 mm of a dust-poor powder mixture. Does the handling form play a special role in subsequent processes, e.g. When using the mixture in a further intensive mixing process, the masterbatch production can be dispensed with.

When batching on a co-rotating twin screw is appropriate with a matched to the high wax content

Worm construction worked. The temperature image is preferably lower than previously indicated in the prior art. For the production of masterbatches an underwater granulation is advantageously used.

The use of these preparations significantly improves the granulation ability in such pigment loadings, in Kopfgranulierungen as well as in the strand granulation.

The colorant compositions according to the invention are used in particular for the preparation of masterbatches. In the production, it is also expedient to work with an initial mixing process. First, a mixture of the colorant composition of the invention is prepared. The mixture is made with appropriate Mixed media. The preparation of mixtures can be omitted, however, by feeding the individual components of a recipe directly to the extrusion plant. In most cases, however, this means a loss of quality of the final product and is therefore carried out in practice only with suitable pigments. The said mixture is then fed by means of a suitable metering device to an extrusion plant. In general, these are single or twin-screw extruder, but there are also continuous and discontinuous kneaders use. The subsequent granulation takes place via strand and Kopfgranulierung, but also spraying is possible.

In order to create certain special colors, mono-preparations are blended with each other or only with plastic in a second extrusion pass. So far, the high consumption of mono-batches has had a detrimental effect on the development of special colors. Another cost-increasing factor in production was the second extrusion process, in some cases even a third extrusion process. These disadvantages could be eliminated by using the colorant compositions of the invention.

The colorant compositions according to the invention can also be used for compounds and for the direct coloring of plastics. Compounds are mixtures of polymers with the abovementioned additives, fillers and / or colorants.

With the inventive colorant composition polyolefins, polyvinyl chloride (PVC), ethylene-vinyl acetate copolymers (EVA), for example ₁ styrene-acrylonitrile copolymers (SAN), poly-ethyleneglycol-terephthalate (PET), poly butylene terephthalate (PBT) and their Copolyesters, acrylonitrile-butadiene-styrene copolymers (ABS), polycarbonate (PC), polyethylene waxes, polypropylene waxes, amide waxes, hydrocarbon resins, montan waxes, aliphatic waxes, rubber, butyl rubber, paraffin and bitumen and some special polymers dyed. In the applications in plastics, especially in masterbatch production, the preparation of the invention is used as previous mixtures and masterbatches. The customary in organic pigments hot mixture of the total formulation for a better wetting of the pigments can be omitted.

In the following embodiments, in each case a metallocene wax mixture prepared from the waxes metallocene-PP wax, ethylene vinyl acetate wax and polar or non-polar non-metallocene PE waxes and copolymers of ethylene with the following material parameters was used (see below). The use of the products takes place in a fine-grained state.

PP waxes prepared as catalyst with metallocene a) and b):

Drop point viscosity at 17O ⁰ C molecular weight density

[° C] [mPa.s] (M _n) [Dalton] [g / cm ^3] a) 88 200 3.000 0.88 b) 90 1800 7,000 0.88

VA - wax:

Drip point viscosity at 140 ° C Acid number Density

[ ⁰ C] [m Pa-s] [mg KOH / g] [g / cm ³ ] about 97 about 350 10 - 12% vinyl acetate 0.92

Oxidized PE wax a) or non-polar PE wax b):

Drop point viscosity at 120 ° C acid number density

[° C] [m Pa-s] [mg KOH / g] [g / cm ³ ]

a) approx. 105 approx. 300 17 0.92 b) approx. 118 approx. 650 0 0.92 Copolymer of ethylene:

Softening point melting point viscosity MFR comonomer density

Et-acrylate

[ ⁰ C] [ ⁰ C] 190 ° C / 2.16kg% [g / cm ³ ] approx. 50-60 approx. 85-98 approx. 5-10 g / 10min approx. 15-20 approx. 0.94

The application takes place in the fine-grained state (sprayed or ground). The dye compositions according to the invention were prepared as described below:

As a mixture for the extrusion: Mixer: Hentschel mixer, content 5 liters Preparation: according to the examples given below Premixing: batch approx. 4 to 6 min. at U = 700 / min

Subsequently, the extrusion was carried out on a co-rotating twin screw with downstream underwater head granulation. Granule size in diameter 0.8 to 2 mm.

Or for use as dust-free mixtures:

Mixer: heating / cooling mix combination, content 5 liters Preparation: according to the examples given below Premixing: batch approx. 2 min. at U = 350 / min

Mixing stage 1) and 2) and cooling phase

I. Phase: U = 3100 min ^-1 T = 50 ° C - 60 ° C.

Mixing time: approx. 5 min to 7 min

2nd phase: U = 1500 min ^'1 T = 65 ° C - 85 ° C

Mixing time: approx. 2 min to 3 min Cooling mixture: to 20 - 3O ⁰ C mixing time: 5 min to 10 min at U = 360 min ^"1

The energy input was exclusively via friction. The resulting mixture had an average grain size of less than 1 mm.

Preparation Examples:

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

1) 50% by weight of Cl. Pigment Blue 15: 1 (Cl.No. 74 160 Heucoblau 515303), 15% by weight non-polar PE wax and 35% by weight metallocene wax

2) 50% by weight of Cl. Pigment Blue 15: 1 (Cl.No. 74 160 Heucoblau 515303), 15% by weight of EVA wax and

35% by weight of metallocene wax

3) 55% by weight of Cl. Pigment Blue 15: 1 (Cl.No. 74 160 Heucoblau 515303), 7.5% by weight EVA wax and 7.5% by weight oxide. PE wax and

30% by weight of metallocene wax

4) 50% by weight of Cl. Pigment Red 122 (Cl.No. 73 915) 7.5% by weight of EVA wax and 7.5% by weight of oxide. PE wax and

35% by weight of metallocene wax

5) 50% by weight of Cl. Pigment Red 122 (Cl.No. 73 915 12.5 wt .-% EVA wax and 2.5 wt .-% oxide. PE wax and 35 wt .-% metallocene wax

6) 50% by weight of Cl. Pigment Red 101 (Cl.No. 77491), 15% by weight EVA wax and 35% by weight metallocene wax

7) 60% by weight Pigment Yellow 191 15% by weight Copolymer of ethylene

25% by weight of metallocene wax

8) 50% by weight Pigment Red 48: 3

20% by weight copolymer of ethylene 30% by weight metallocene wax

Application examples:

The colorant compositions according to Preparation Examples 1 to 8 were added or used directly as a powder for coloring plastics. They can be further manufactured in a co-rotating twin screw with a special screw design and with a low temperature image to masterbatches, which are used in different polymers for their coloring.

The following plastics were used:

1 ) . Acrylonitrile-butadiene-styrene copolymer (ABS);

2) ethylene-vinyl acetate copolymer (EVA); 3) polyesters: polyethylene terephthalate (PET), polybutylene terephthalate (PBT);

4) polyethylene (HDPE);

5) polypropylene (PP);

6) styrene-acrylonitrile copolymers (SAN); 7) polystyrene (PS)

8) polycarbonate (PC).

Color strength tests (ST 1/3), filter value, film quality and 5 basic mechanical data.

In the dispersion, very good qualities were achieved, and the film quality, which is characteristic of a good statistical pigment distribution, can be estimated as good. 0 The effects on the mechanical properties of the colored polymers did not cause any significant adverse effects. In places, even improvements have been noted.

Tensile strength, tensile elongation, tear strength and elongation at break were tested with batch concentrations of 1, 5% and 0.5%. Comparative values were the pure polymer tests.

K) κ>

Claims

claims:

1. colorant composition comprising i) one or more metallocene polyolefin waxes, ii) one or more waxes selected from polar and nonpolar non-aqueous

Metallocene polyolefin waxes and iii) optionally one or more copolymers of ethylene iv) and one or more finely divided colorants, characterized in that they contain at least 15 wt .-%, based on the total weight of the colorant composition, wax and / or copolymers of ethylene and that the waxes or copolymers contained in the colorant composition contain at least 50 wt .-% polypropylene metallocene wax.

2. colorant composition according to claim 1, characterized in that the waxes or copolymers of ethylene of the components i), ii) and iii) at temperatures in the range of 50 to 150 ⁰ C melt.

3. dye composition according to claim 1 or 2, characterized in that the polypropylene metallocene wax has a dropping point between 80 and 15O ⁰ C and a melt viscosity at 170 ° C between 30 and 3000 mPa-s.

4. Colorant composition according to one or more of claims 1 to 3, characterized in that it contains 7.5 to 42.5 wt .-%, preferably 8.5 to 40 wt .-%, of the polypropylene-metallocene wax, 0.1 to 30% by weight, preferably 0.5 to 25% by weight, of one or more non-metallocene waxes or copolymers of ethylene, 30 to 85% by weight, preferably 35 to 80% by weight, of one or more colorants and 0 to 15 wt .-% of conventional fillers or additives.

5. Colorant composition according to one or more of claims 1 to 4, characterized in that the one or more colorants are selected from inorganic and organic pigments.

6. colorant composition according to one or more of claims 1 to 5, characterized in that the one or more inorganic pigments are selected from suitable for pigmentation metal oxides, mixed oxides, aluminum sulfates, chromates, metal powders, pearlescent pigments (mica), luminous colors, titanium oxides, Cadmium lead pigments, iron oxides, carbon black, silicates, nickel titanates, cobalt pigments or chromium oxides.

7. Colorant composition according to claim 6, characterized in that it contains 7.5 to 30 wt .-%, preferably 12.5 to 20.5 wt .-%, of the polypropylene metallocene wax, 7.5 to 20 wt .-% of a or more non-metallocene waxes or copolymers of ethylene and 60 to 85 wt .-%, preferably 79 to 85 wt .-%, of one or more inorganic pigments and 0.1 to 2 wt .-% of conventional fillers or additives.

8. Colorant composition according to one or more of

Claims 1 to 5, characterized in that the one or more organic pigments are selected from azo or disazo pigments, laked azo or disazo pigments and polycyclic pigments, phthalocyanine, quinacridone, perylene, dioxazine, anthraquinone, thioindigo , Diaryl or quinophthalone pigments.

9. Colorant composition according to claim 8, characterized in that it contains 7.5 to 42.5 wt .-% of predominantly or completely amorphous polypropylene metallocene wax, 0.1 to 30 wt .-% of one or more non-metallocene waxes or copolymers of Ethylene, 30 to 75 wt .-% of one or more organic pigments and 0 to 4 wt .-% of conventional fillers or additives.

10. Colorant composition according to one or more of claims 1 to 9, characterized in that the one or more non-metallocene polyolefin waxes are selected from EVA waxes and oxidized waxes having a dropping point below 12O ⁰ C and a viscosity of less than 1000 mPa-s (measured at 140 ⁰ C) possess.

11. Colorant composition according to one or more of claims 1 to 10, characterized in that in addition to the predominantly or completely amorphous polypropylene metallocene wax one or more metallocene copolymer waxes of propylene and 0.1 to 50 wt .-% of one or more further Contains monomers selected from ethylene and branched or unbranched 1-alkenes having 4 to 20 carbon atoms.

12. Colorant composition according to one or more of claims 1 to 11, characterized in that in addition to the predominantly or completely amorphous polypropylene metallocene wax one or more metallocene copolymer waxes of propylene and 0.1 to 50 wt .-% of one or more further Contains copolymers of ethylene.

13. A method for producing a colorant composition according to one or more of claims 1 to 12, characterized in that a) the individual components are mixed cold or b) the mixture of dyes and wax by mechanical mixing to a temperature of 15 to 5 K below the softening point of the predominantly or completely amorphous polypropylene metallocene wax is heated and then cooled to a temperature of 10 to 30 ⁰ C.

14. Use of a colorant composition according to one or more of claims 1 to 12 for the preparation of a masterbatch.

15. Use according to claim 14, characterized in that the preparation takes place at a temperature in the range of 80 to 140 ⁰ C.

16. Use according to claim 14 or 15, characterized in that the preparation is carried out using a co-rotating twin screw.

17. Use according to claim 16, characterized in that the twin screw is operated with a screw profile, which is tuned to easily flowing masses.