EP3116958A2

EP3116958A2 - Method for treating the surface of particles, the thus obtained particles and use thereof

Info

Publication number: EP3116958A2
Application number: EP15716724.8A
Authority: EP
Inventors: Bernd Rohe; Petra Fritzen; Jörg HOCKEN
Original assignee: Huntsman P&A Germany GmbH
Current assignee: Venator Germany GmbH
Priority date: 2014-03-14
Filing date: 2015-03-13
Publication date: 2017-01-18
Also published as: WO2015135536A2; DE102015103697A1; JP2017519875A; US20170066924A1; TWI558774B; WO2015135536A3; CN106255729B; CN106255729A; US10131792B2; TW201536874A

Abstract

The invention relates to a surface-treated particles, to a method for producing surface-treated particles and use thereof, in particular the surface treatment of titanium dioxide, barium sulfate, zinc sulfide or lithopone particles, and to mixtures of said particles with special alkoxylated siloxanes and phthalate-free plasticizers for improving dispersion in plastics.

Description

, ,

Process for the surface treatment of particles, the particles thus obtained and their use

The present invention relates to surface-treated particles, processes for

Preparation of the surface-treated particles and their use, in particular the surface treatment of titanium dioxide, barium sulfate, zinc sulfide or lithopone particles, and mixtures of these particles with special alkoxylated siloxanes and phthalate-free plasticizers to improve the dispersion in plastics, which are formulated into corresponding polymer compositions divided into the main groups of thermoplastics and thermosets.

This refers to those polymers which have a flow transition region above the service temperature as thermoplastics. Thermoplastics are linear or branched polymers which, in the case of amorphous thermoplastics, above the glass transition temperature (Tg), in the case of (partly) crystalline thermoplastics above the melting temperature (Tm), in principle become flowable. They can be processed in the softened state by molding, extrusion, injection molding or other molding processes to form parts. The chain mobility is so great that the polymer molecules easily slide off each other and the material reaches the molten state (flow area, polymer melt). The thermoplastics also include thermoplastically processable plastics with pronounced entropy-elastic properties, the so-called thermoplastic elastomers. The thermoplastics include all plastics consisting of linear or thermolabelled crosslinked polymer molecules, for example polyolefins, vinyl polymers, polyesters, polyacetals, polyacetates, polycarbonates, in some cases also polyurethanes and ionomers but also TPEs-thermoplastic elastomers (RÖMPP ONLINE, Vers. 3.7, Carlowitz et al Werer, Kunststoffe (Merkblätter), 1st chapter thermoplastics, Berlin: Springer Verlag (1987), Domininghaus, p. 95 ff).

Duromers are plastics which are formed by irreversible and close-meshed crosslinking via covalent bonds of oligomers (technically: prepolymers), more rarely of monomers or polymers. The term "duromer" is used both for the raw materials before crosslinking (see reaction resins) and as a collective term for the cured, mostly completely amorphous resins Duromeres are steel elastic at low temperatures, and they can also be used at higher temperatures , - do not flow viscously, but behave elastically with very limited deformability. The thermosets include, inter alia, the technically important substance groups of diallyl phthalate resins (DAP), epoxy resins (EP), urea-formaldehyde resins (UF), melamine-formaldehyde resins (MF), melamine-phenol-formaldehyde resins (MPF ), Phenol-Formaldehyde Resins and Unsaturated Polyester Resins (UPES) (RÖMPP ONLINE, Vers 3.7, Becker, GW, Braun, D .; Woebcken, W., Kunststoff-Handbuch, Volume 10: Duroplaste, 2nd Edition, Hanser : Munich, (1988); Elias (6.) 1, 7, 476 ff.).

The properties of such plastics can be improved by additives. For example, plasticizers may be added as additives to make the plastics softer, more flexible, smoother and more elastic in use or for further processing. Plasticizers may be low-volatile esters, fatty oils, or soft resins. Furthermore, the plastics pigments can be added, which are composed of organic or inorganic constituents. For better compatibility, in particular of the inorganic particles, these can be surface-modified.

Such surface-modified particles may for example consist of an inorganic oxide, which is optionally provided with a further inorganic coating. As inorganic coating, for example a titanium dioxide pigment, silicon oxide and aluminum oxide can serve. In addition, the inorganic-coated pigment may have an organic coating for influencing the hydrophobicity. Examples of suitable organic coating compositions include PDMS (polydimethylsiloxanes) or polyalcohols, such as TMP, or substituted siloxanes, such as polydimethylsiloxane alkyl esters, or reactive coupling agents, such as silanes, zirconates or titanates, or phosphorus-containing organic compounds, or steric acid, Ca, Zn, Mg stearates known. For example, Gilbert (Gilbert, Varshney, van Soom and Schiller, "Plate-out in PVC Extrusion - I. Analysis of Plate-out", Journal of Vinyl and Additive Technology, (14) 1, 2008, 3-9) describes the Use of Ca-stearate or other soaps or the corresponding carboxylic acids such as stearic acid to surface treatment of titanium dioxide or barium sulfate or its mixtures may result in undesirable side effects as such products are often not readily available in large-scale pigment production processes are used or even lead to so-called plate out in the production of highly filled masterbatches, ie concentrates of the pigments in a thermoplastic matrix , , including the firing of the thermoplastic pigment mixture on the screw or the inside of the housing of the extrusion line. This causes costly cleaning, especially when changing color. In addition, such stratified layers can dissolve at any time and lead to specks in the masterbatch and later also in the final application, for example, to specks in thin-layered films.

Furthermore, the use of silicone oils of different chain length / viscosity is known from GB 1 288 581, which can be sprayed on either when grinding the pigment or as an emulsion in a pigment slurry. Although silicone oil surface treatment pigments have good hydrophobicity and, because of their low surface energy, are generally known to be readily incorporated into a low energy plastic environment. Such treated pigments have several disadvantages: · Silicone oil-treated particles have a strong dusting tendency. For example, although titanium dioxide having a relatively high density of 3.9 g / cm ³ should not necessarily tend thereto, the strong dusting tendency after silicone oil treatment is known from US 3,649,321. The tendency to dust is very problematic during further processing and possibly even relevant to safety.

• A low bulk density of the silicone-treated pigments leads to problems when packing the pigment in bagged goods, big bags or silos. A high amount of air requires filling with a lower mass per unit pack. If the bagged goods can not be stacked flat on a pallet, the strapping effort or expense increases when the pallets are re-wrapped. Automatic packaging with air delivery, which are to be regarded as standard with high performance, has this problem in particular.

Silicone surface treatment oils can lead to further problems in the production of commodities, e.g. lack of recoatability,

Printability and / or weldability of films, in particular multi-layer films may lead to delamination of layers and loss of function (Plastics Additives: Advanced Industrial Analysis, 2006, Jan CJ Bart. Pp. 419-420, IOC Press, Netherlands, ISBN 1-58603 -533-9; brochure Trouble Shouting Guide-Siegwerk, March 2013). , ,

It is known from DE 41 40 793, EP 0 546 407, EP 0 546 406 that silicone oils or silane-based structures, such as methacryloxypropyltrimethoxysilane, are suitable for covering also oxidic surfaces, in order to achieve a hydrophobization or functionalization of the surface and a reduction of the viscosity to allow greater compatibility with the surrounding organic medium and thus a higher efficiency of the pigments used. Silanes are sensitive to hydrolysis and generally require an elevated temperature of about 80 ° C to activate the silyl functionality on the pigment or filler surface and to form a polymeric structure on the surface. Many processes in pigment production are aqueous slurry processes or the pigments such as titanium dioxide are formed by precipitation reactions in water, so that there is a need to be able to introduce surface treatment agents in aqueous form, for example emulsified, in a simple form into the process. On the other hand, there is a need in processes involving the surface treatment of dry pigments or fillers, that there is no automatic possibility or additional cost in these processes of raising the temperature significantly above ambient temperature there, which is for the attachment of silanes a process disadvantage is because it requires temperatures above 80 ° C for the elimination of the alcohol. Therefore, there was a need to provide a surface treatment for dry mulling or mixing processes which, if necessary, guarantees surface modification even without increasing the temperature. Furthermore, it would be advantageous to use a method in which no alcohol is eliminated in order to avoid expensive explosion protection in the Vermähl- and / or drying process. The dispersion of hydrophilic inorganic pigments such as titanium dioxide, barium sulfate, zinc sulfide and / or lithopone having a plurality of hydroxy groups (HO-) and / or thiol groups (HS-) on the surface, is a problem. Either great effort by long Dispergierzeiten be accepted or it results in an insufficient dispersion with an unacceptable error image of the final good. Such defects may be: specks in plastic films that are not only aesthetic nature, but can lead to the formation of holes and leaks in the packaging, specks in the injected plastic part can lead to mechanical defects so cause significantly lower tensile strength or impact resistance and Thus, a high reject rate in the injection molding production or even failure of safety-related components made of plastic in the automotive or electronics sector. , ,

As already mentioned above, other additives such as plasticizers can be added to plastics in addition to pigments. Plasticizers are substances that are added to thermoplastic polymers to make them softer, more flexible and / or more elastic. For example, unlike rigid PVC, plasticized PVC contains larger amounts of plasticizers and can be easily processed by calendering or extruding. By varying the plasticizer content, the flexibility of the plastic, for example a PVC film, can be adjusted in a targeted manner. Such films are oxygen and carbon dioxide permeable and have been used for food packaging. However, the phthalate plasticizers used for this use are sometimes said to have teratogenic and fertility-disturbing effects. In order to use plasticizers in food contact packaging, softeners with reduced migration tendency are required. Such plasticizers can then be used for food packaging as well as for medical equipment and children's toys.

Indispensable requirements for pigments for use in polymers are good flowability and low dusting, good dispersibility and fineness (eg later use in very thin films), fast wettability (to increase throughput in paste production), high possible fill levels (for reduction the storage volume of the stock pastes) and absolute flocculation and settling stability over the period of storage time. In addition, of course, an approval for the potential indirect contact with food and / or medical compatibility is required. Surface treated particles to be used in food grade plastic packaging are subject to European standard EC 10/201 1 and / or US FDA standards.

There are many requirements for pigments. On the one hand, they have to be optimized with regard to the end use for processing in plastics, on the other hand, the incorporation process into a plasticizer (eg with a dissolver) and its subsequent storage as a paste or liquid as a masterbatch requires a pigment which is suitable for Paints and colors must be optimized. Both requirements can be met in the context of an optimized organic coating. - -

In the known state of the art, however, no particles which fulfill both the aforementioned requirements and additionally avoid the aforementioned disadvantages are known. The object of the invention is therefore to provide particles for plastic products, which meet the aforementioned requirements, especially with regard to the approval of food packaging, and beyond, eliminate the known disadvantages of the prior art. Surprisingly, it has been found that the particles according to the invention having the features according to the main claim solve the problem.

Such particles, which have been post-treated with plasticizers and thus have a coating of plasticizers, are not known in the prior art. The invention is therefore directed to particles of Ti0 ₂ , BaS0 ₄ , ZnS or lithopone primary particles having a coating with at least one polyether siloxane of the formula (I)

in which

R ^{1 is} methyl or hydroxy;

a polyether radical of the formula (II):

-Z- (0-C _m H _2m . _(N. ₁₎ ) ₀ - [0- (EO _x , PO _y , BO _z ) -R ³ ] _n (II)

is, where

Z is a branched or unbranched alkylene radical having 2 to 4

Carbon atoms, preferably 3 carbon atoms, m is 2 to 4, preferably 3,

n is 1 to 3, preferably 1 or 2, particularly preferably 1,

o is 0 or 1, preferably 0, , ,

(EO _x , PO _y , BO _z ) an oxyalkylene radical containing oxyethylene (EO), oxypropylene (PO) and / or oxybutylene units (BO), wherein x, y and z are> 0 and at least one of x , y and z are not equal to 0,

R ^{3 is} hydrogen, when n is 1, or a hydrocarbon radical having 1 to 4 carbon atoms,

and with the proviso that in R the sum of carbon and oxygen atoms is at least 70,

a is from 20 to 200, preferably from 30, from 40, from 50, from 60 to 170, to 160, to 150, to 140, to 130, to 120, to 110 and in particular to 70 to 100,

b is from 1 to 50, preferably from 2, from 3, from 4 to 30, to 25, to 20 and particularly preferably from 5 to 15, with the proviso that when none of the radicals R is R, b is at least 3,

and with at least one phthalate-free plasticizer,

wherein the at least one compound of formula (I) in a proportion of 0.01 to 2 wt .-%, preferably 0.05 to 1 wt .-%, more preferably 0, 1 to 0.8 wt .-%, further more preferably 0.2 to 0.6 wt .-% and particularly preferably 0.3 to 0.5 wt .-% is present, and

wherein the at least one phthalate-free plasticizer is present in a proportion of 0.01 to 4.0 wt .-%, preferably 0.05 to 2.0 wt .-%, more preferably 0, 1 to 1, 6 wt .-% .

the data in% by weight being based on the weight of the dried primary particles used. In the context of the present invention, including the preferred embodiments, the radicals R and R in the formula (I) or R ³ in the formula (II) may each have different meanings if a plurality of radicals R, R and R ³ in a polyethersiloxane of the formula (I) are present. For example, R at one end of the molecular chain may have the meaning of methyl and R at the other end of the molecular chain, for example, the meaning of R ¹ , which in turn may have a meaning other than one or more R in the side chain when b is a number from 1 to 50 stands. Likewise, R ³ in the polyether radical of the formula (II) in the case of several radicals R in a polyethersiloxane of the formula (I) in each radical R may each have a different meaning. - -

All figures by weight are based on the weight of the dried primary particles used, drying being understood to mean heating the particles to a temperature of up to 250 ° C. for a period of a few seconds to eight hours to constant weight.

Thus, the particles of the invention from Ti0 ₂ , BaS0 ₄ , ZnS or lithopone primary particles are prepared, which after drying with the polysiloxane compound of formula (I) as above, which are described in DE 102013226800 first described, and the phthalate-free plasticizer be, wherein the coating is formed. A coating according to the invention may consist of at least one layer applied to a particle, for example also of two layers. Within a layer, the layer thickness can vary. A layer can consist of several components which are regularly or irregularly distributed within the layer, or the components can also be distributed over different layers. The at least one layer can cover the surface of a particle in whole or in part.

The coating according to the invention may preferably comprise a layer which comprises at least one polysiloxane compound of the formula (I) and at least one phthalate-free plasticizer, the two components being randomly distributed within the layer. More preferably, the layer covers the entire particle surface.

In the polysiloxane compound of the formula (I), the oxyalkylene group (EO _x , PO _y , BO _z ) may preferably be from 0 to 50% by weight, preferably from 5 to 35% by weight, more preferably from 15 to 30 Wt .-% oxyethylene groups based on the total mass of the radical R have. Among the alkylene radical is a radical according to the invention - (CH ₂₎ 2 ₄ oxyalkylene group and a radical -0- _(CH2) 2- ₄ - understood.

In the presence of oxybutylene groups, the molar fraction of oxybutylene groups based on the sum of oxypropylene and oxybutylene groups is preferably not more than 50%, preferably up to 45, 40, 35, 30, 25, 20, 15, 10 and in particular up to 5%.

The numerical proportion of unmodified siloxane fragments with the index a is preferably up to 20 times greater than the proportion of polyether-modified siloxane fragments with the index b, preferably up to 20 times, up to 19, up to 18, up to 17, up to 16 , up to 15, up to 14, up to 13, up to 12, up to 11, up to 10, up to 9, and most preferably up to - - to 8 times. Preferably, the index a is at least 7 times the index b, more preferably at least 8 times, 9 times, 10 times, 1 times, and especially at least 12 times the index b. The numerical ratio of index a to index b is preferably 8 to 18, preferably 9 to 15 and particularly preferably 10 to 12.

Preferably, the index o is equal to zero. The fragment with the index o is preferably an unbranched radical, more preferably an unbranched radical with 3 carbon atoms. The fragment with the index o is particularly preferably a glyceryl radical, particularly preferably an n-glyceryl radical, which terminally carries the group -O-Z. The radical Z is preferably a linear propylene radical.

The radical R ³ is preferably a hydrogen.

Particular preference is given to particles according to the invention having a coating with at least one compound of the formula (I) where in formula (I):

R is a polyether radical of formula (II), wherein

Z is an unbranched alkylene radical having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms,

o is 0,

x is 0 to 20, preferably 3 to 15, particularly preferably 4 to 10,

y is 5 to 100, preferably 8 to 50, particularly preferably 10 to 30,

z is 0 to 20,

R and R ³ and the remaining definitions are given in claim 1. The numerical ratio of index a to index b is preferably 8 to 18, preferably 9 to 15 and particularly preferably 10 to 12.

Preferably, the index x is less than or equal to 1, 2 preferably less than 1, 1, more preferably less than 1, less than 0.9, less than 0.8, less than 0.7, less than 0.6, less than 0.5, less than 0, 4; less than 0.3 and in particular less than 0.2. - -

The index x is preferably between 0.05 and 1.2 times the sum of the indices (y + z), preferably between 0.07 and 0.8 times, in particular between 0.1 and 0.5 times.

It is further preferred that the index z is less than or equal to the index y, preferably less than or equal to the half, the third, the quarter, the fifth, the sixth, the seventh, the eighth, the ninth and in particular less than or equal to one tenth of Indexes y is.

Preferably, an oxybutylene group is linear, ie- (CH ₂ ) 4-O- and / or branched, ie CH (CH ₂ CH ₃ ) CH ₂ -O-.

R is methyl,

a 80 to 95,

b 5 to 8,

R ^{3 is} hydrogen

x 3 to 5,

y 10 to 25,

z o are.

More preferably, the particles according to the invention consist of titanium dioxide.

Polyether siloxanes in the context of the invention are compounds of the formula (I).

The siloxane fragments of the formulas (I) and (II), as well as the siloxane fragments (EO _x , PO _y , BO _z ) and R can be constructed statistically. Statistical distributions are blockwise constructed with an arbitrary number of blocks and an arbitrary sequence or a randomized distribution, they can also be constructed alternately or form a gradient over the chain, in particular they can also form all mixed forms in which optionally groups of different Distributions can follow one another. Special designs may cause statistical distributions to be constrained by execution. For all areas that are not affected by the restriction, the statistical distribution does not change. _ _

The surface-treated particles according to the invention comprise phthalate-free plasticizers. Phthalate-free means that the plasticizers according to the invention do not comprise 1, 2-phthalic acid esters. Plasticizers which are used to treat the primary particles of TiO ₂ , BaSO ₄ , ZnS or lithopone for the preparation of the particles according to the invention therefore comprise phthalate-free plasticizers from the group consisting of esters of aliphatic hydrocarbons having 6 to 21 carbon atoms with at least one acid group selected from a carboxyl group -C0 ₂ H, sulfonyl group -S0 ₃ H, or sulfinyl group -S0 ₂ H, with a mono- or polyhydric aliphatic alcohol preferably having six to twenty carbon atoms or a mono- or dihydric aromatic alcohol or mixtures thereof, and esters of aromatic 1,4-para-dicarboxylic acids, preferably 1,4-benzenedicarboxylic acid, or aromatic tricarboxylic acids with a monohydric or polyhydric aliphatic alcohol preferably having six to twenty carbon atoms or mixtures thereof.

By way of example, the phthalate-free plasticizers are named:

Esters of aliphatic hydrocarbons having 6 to 21 carbon atoms with at least one acid group selected from a carboxyl group, such as esters of polybasic aliphatic carboxylic acids, for example Alkylcarbonsäurealkylester or Alkyldicarbonsäuredialkylester, Polyethylenglcoldialkylcarbonsäureester, especially esters of polyhydric cycloaliphatic carboxylic acids, such as esters of cyclohexanedicarboxylic acid, especially esters of 1, 2 cyclohexanedicarboxylic acid; with a monohydric or polyhydric aliphatic alcohol or mixtures thereof;

- esters of aliphatic hydrocarbons having 6 to 21 carbons with

at least one acid group selected from a sulfonyl group -SO ₃ H, or sulfinyl group -S0 ₂ H, with a mono- or polyhydric aliphatic or aromatic alcohol or mixtures thereof I; for example

Alkanesulfonic acid alkyl ester or alkanedisulfonic acid dialkyl ester,

Polyethylenglycoldialkylsulfonsäureester, alkanesulfonyl or

Alkandisulfonsäurediarylester;

Esters of aromatic 1,4-dicarboxylic acids or aromatic tricarboxylic acids with a monohydric or polyhydric aliphatic alcohol or mixtures thereof. - -

Aliphatic hydrocarbon having 6 to 21 carbons with at least one

Acid group in the context of the invention comprises straight-chain, branched or cyclic aliphatic hydrocarbons which may also have one or more substituents. Aromatic hydrocarbon such as aromatic 1, 4-dicarboxylic acids or aromatic tricarboxylic acids for the purposes of the invention comprises aromatic C ₆ to d ₄

Hydrocarbons which may also have one or more substituents.

By monohydric or polyhydric aliphatic alcohols are meant according to the invention those having six to twenty carbon atoms with one or more hydroxy groups which, as mentioned above, straight-chain, branched or cyclic aliphatic

Hydrocarbons, which may also contain one or more functional groups as mentioned above, may be. These also include oligomers of glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, etc.

According to the invention, phthalate-free plasticizers 1, 2-dicisononyl cyclohexanedicarboxylate (hexamold dinch-BASF, Elatur CH-Evonik), alkanesulfonic acid phenyl ester, alkanesulfonic acid diphenyl ester (Mesamoll-Lanxess), bis (2-ethylhexyl) 1,4-benzene dicarboxylate (Oxosoft GPO-Oxea) are preferred. , Triethylene glycol bis (2-ethylhexanoate) (Oxosoft 3G8 - Oxea), trioctyl trimellitate (Oxea).

An advantage of the surface-treated particles according to the invention is the improved dusting tendency compared to prior art pigments, e.g. treated with silicone oil is significantly reduced. This reduces emissions of dust during further processing. Furthermore, possible dust explosions are prevented.

A further advantage of the particles according to the invention is that they are not subject to any restrictions under current regulations, such as the European standard EC 10/2011 and / or standards of the American FDA, with respect to their use in food packaging.

A further advantage of the particles and compositions according to the invention is that the pressure filter values are lowered compared to the prior art. This increases the service life of the processing equipment, especially the extruder and reduces their cleaning cycles. - -

Also advantageous is a good dispersion to avoid fiber breaks and / or specks of the products. Also advantageous is the high temperature resistance of the particles according to the invention and of the compositions according to the invention.

Another advantage of the particles according to the invention is their powder flowability, which is particularly in the discharge of big bags and silo vehicles in the further processing of the particles or in the direct use of the particles in the metering via pneumatic systems and powder screws in the processing unit (eg extruder or kneader) reflected.

Another advantage of the particles of the invention is that compositions can be formulated in many ways. This manifests itself in that the compositions can be formulated on the basis of thermoplastics, thermosets and plasticizers. This means for the processing industry, such as Paste manufacturers, compounders and masterbatchers have the advantage that the particles according to the invention can be used without further adjustments. This generates a financial advantage and formulation flexibility.

Another advantage of the particles according to the invention is the low agglomeration tendency due to the coating according to the method of the invention.

To produce the particles according to the invention, all crystal forms of titanium dioxide, barium sulfate and zinc sulfide are suitable as primary particles.

For the purposes of the invention, primary particles are to be understood as meaning particles which are obtained as end products from their respective production processes and are thus present as particles of TiO ₂ , BaSO ₄ , ZnS or lithopone composed of crystallites and / or amorphous units. The primary particles, for example of TiO ₂ , can be subjected to an inorganic pretreatment. These particles can then be treated with the polysiloxanes of formula (I) and plasticizers and subsequently ground. In the milling process and then migrate to the surface of the - -

Particles existing polysiloxanes of the formula (I) and plasticizer, so that the entire particle surface is coated therewith.

In the case of titanium dioxide, these are, for example, polymorphic forms, rutile, anatase or brookite. The titanium dioxide can be prepared by various methods known in the art. Various hydrated forms of titanium dioxide can also be used according to the invention. As a white pigment, titanium dioxide is approved under the name E171 according to food additive regulation 231/2012 / EC, and under the name Cl 77891 according to the cosmetic regulation EC 1223/2009. Barium sulfate is used according to the invention under the names barite, baryte, barite white and blanc fixe. According to the invention, the different crystal forms of zinc sulfide are used, the alpha-zinc sulfide, known in nature as wurtzite and / or the beta-zinc sulfide, known in nature as zinc blende and sphalerite. If desired, mixtures of said pigments can also be surface-treated according to the invention. The mixtures can be made by mixing the pigments previously prepared in pure form or by co-precipitation, in particular in the form of lithopone. For the purposes of the invention, these mixtures are primary particles. In a preferred embodiment, unmodified or inorganically modified titanium dioxide is used. To treat the surface of the Ti0 ₂ - base body is ground and then covered with one or more layers of inorganic substances. The substance to be precipitated is first added in dissolved form. For this purpose, it is necessary to set a pH in the suspension at which the inorganic substance does not precipitate as a solid. From this suspension is then precipitated by a pH change to the neutral point, the inorganic substance. The oxides or hydroxides of aluminum, of silicon, of zirconium and also of titanium are used in this treatment (J. Winkler, Titandioxid, (2003), Chapter 3.4, pp. 38-41, ISBN 3-87870-738-X ). After this treatment, the surface of the titanium dioxide particles is modified accordingly, so that the particles consist of at most 99 wt .-% of titanium dioxide, preferably at most 95 wt .-%, more preferably at most 85 wt .-% based on the total mass of the particle. Further preferably, the particles are at least 80 wt .-%, preferably at least 85 wt .-%, more preferably at least 90 wt .-% of titanium dioxide based on the total mass of the particles. The inorganic titanium dioxide particles are primary particles in the sense of the invention. - -

Preferred particles are titanium dioxide particles, optionally inorganic modified.

The surface treatment according to the invention preferably increases the packing density of the particles, which then becomes apparent in a reduced bulk density and also in improved flowability.

The surface-treated particles according to the invention preferably have a reduced dust tendency. The dust tendency can be determined in a so-called dust chamber. Here, a defined amount of particles, e.g. 100g, exposed in a downpipe to the free fall in the atmosphere of the environment. The particles sediment in the atmosphere at the bottom of a cylinder and a part remains as dust in the gas phase of the drop volume. The volume above the sediment is sucked off and the dust collected is filtered off. By weighing the filter, the amount of dust is determined. The particles according to the invention preferably have a dust mass of less than 30 mg / 100 g of surface-treated particles, preferably of less than 10 mg / 100 g of surface-treated particles.

The powder flowability can with a z. B. Ring shear device RST -XS (Schulze, Powder and Bulk Solids, Springer, 2006, Chapter 3.1 .4, page 42). The bulk material sample is loaded in a measuring cell from above with a force (normal force) of 3.5 kPa. During the measurement, the shear cell rotates slowly (ω). This results in a shear deformation of the bulk material sample. The required force (Fi and F ₂ ) is measured. From the ratio of solidification stress σ ^ to bulk material strength o _c , the flowability ff _{c of} the bulk material is determined. The greater the flowability ff _c , the better the bulk material flows.

The particles according to the invention preferably have a powder flowability of greater than 2.1. The determination of the powder flowability can be determined analogously to ASTM D6773-08.

The dispersibility of the surface-treated particles according to the invention can be determined and evaluated on the basis of the pressure increase in front of a filter (with mesh size to be specified) which is produced when extruding a polymer melt through a sieve packet (pressure filter value). The test can z. For example, in accordance with DI N EN 13900-5: 2005. - -

Preferably, the compositions according to the invention in the form of masterbatches have a pressure filter value (14μηι) of up to 10 bar * cm ² / g, more preferably of up to 5 bar * cm ² / g and in particular of up to 3 bar * cm ² / g , The pressure filter values can be determined as described in the examples.

Another way of assessing dispersibility is to determine and evaluate the number of agglomerates in a flat film. Agglomerates are recognizable as specks. The number of specks should be as low as possible.

Another way of assessing dispersibility is to determine the fineness of the particles of the invention, e.g. in a white paste under defined dispersing conditions. For example, a grindometer according to Hegman is suitable for this purpose. The determination may e.g. according to DIN EN 21524 (according to ISO 1525). The particles of the invention should be as fine as possible, preferably less than 20 μηι, more preferably less than 18 μηι, especially less than 16 μηι.

Another object of the invention is the use of the particles according to the invention for the preparation of polymer compositions.

The particles according to the invention are preferably used for the production of compositions, in particular polymer compositions, containing the particles according to the invention, for processing into plastic moldings or films. A further subject of the invention are thus compositions comprising at least one polymer and at least particles according to the invention.

The compositions according to the invention contain, in addition to the particles according to the invention, at least one polymer.

Preferred polymers of the compositions of the invention are thermosets or thermoplastics. Examples of suitable thermosets are unsaturated polyester resins (UP), phenolic resins, melamine resins, formaldehyde molding compounds, vinyl ester resins, diallyl phthalate resins, silicone resins or urea resins. As thermoplastic materials are, for example, polyethylene, polypropylene, polyester, polyamide, PET, - -

Polystyrene, its copolymers and blends, polycarbonate, PMMA, or polyvinyl chloride suitable.

The thermoplastic compositions according to the invention are preferably processed into masterbatches and / or plastic films.

The compositions are preferably processed into masterbatches, plastic moldings and / or plastic films. With further preference the duromer-containing compositions according to the invention are processed to form plastic molded articles.

In principle, the particles according to the invention can be prepared according to processes of the prior art, but they are preferably prepared by the process described below.

Another object of the invention is thus a process for the surface treatment of Ti0 ₂ , BaS0 ₄ , ZnS or lithopone primary particles, wherein the primary particles with at least one polyether siloxane of the formula (I)

in which

RR ^{1 is} methyl or hydroxy;

R is a polyether radical of the formula (II):

-Z- (O-C _m H _2m . _(N. ₁₎ ) ₀ - [O- (EO _x , PO _y , BO _z ) -R ³ ] _n (II) where

Z is a branched or unbranched alkylene radical having 2 to 4 carbon atoms, preferably 3 carbon atoms, - m is 2 to 4, preferably 3,

n is 1 to 3, preferably 1 or 2, particularly preferably 1,

o is 0 or 1, preferably 0,

R ^{3 is the} same or different hydrogen, when n is 1, and one

Hydrocarbon radical having 1 to 4 carbon atoms, and with the proviso that in R the sum of carbon and oxygen atoms is at least 70,

a is from 20 to 200, preferably from 30, from 40, from 50, from 60 to 170, to 160, to 150, to 140, to 130, to 120, to 110 and in particular to 70 to 100, b 1 to 50, preferably from 2, from 3, from 4 to 30, to 25, to 20 and particularly preferably 5 to 15, with the proviso that when none of the radicals R is R, b is at least 3,

and contacted with at least one phthalate-free plasticizer or mixtures thereof simultaneously or sequentially,

wherein the at least one compound of formula (I) in a proportion of 0.01 to 2 wt .-%, preferably 0.05 to 1 wt .-%, more preferably 0, 1 to 0.8 wt .-%, further more preferably 0.2 to 0.6 wt .-% and particularly preferably 0.3 to 0.5 wt .-% is used, and

wherein the at least one phthalate-free plasticizer in a proportion of 0.01 to 4, 0 wt .-%, preferably 0.05 to 2.0 wt .-%, more preferably 0, 1 to 1, 6 wt .-% is used .

the data in% by weight being based on the weight of the dried primary particles used.

It is thus possible to use compounds of the formula (I) individually or in mixtures of several compounds thereof with a phthalate-free plasticizer, individually or in mixtures of several thereof, for the surface treatment of TiO ₂ , BaSO ₄ , ZnS or lithopone primary particles. Preferred embodiments of the surface-treating agents of the formula (I) and the phthalate-free plasticizers are already described above and also apply to the process for the surface treatment of ΤΊO 2, BaSO 4, ZnS and lithopone particles. - -

The surface treatment of the primary particles can be done dry or wet, in the case of wet execution, this is preferably carried out in emulsion. If the surface treatment is carried out with an emulsified polyethersiloxane of the formula (I), this can be done with the addition of emulsifiers.

In the preparation of the polyethersiloxanes of the formula (I) as emulsions, oil-in-water emulsions comprising 5 to 70% by weight of polyethersiloxanes, 1 to 20% by weight of emulsifiers and 20 to 94% by weight of water are preferred. Processes for the preparation of silicone emulsions are known to the person skilled in the art. The preparation is usually carried out by stirring all constituents and optionally subsequent homogenization with jet dispersants, rotor-stator or rotor-rotor homogenizers, colloid mills or high-pressure homogenizers. Methods of emulsion preparation are described e.g. in EP0093310, DE2555048, EP1132417. All emulsifiers known to those skilled in the art for preparing polysiloxane emulsions, e.g. anionic, cationic, amphoteric or nonionic emulsifiers.

Exemplary, but not limited, anionic emulsifiers are: alkyl sulfates, especially having 8 to 22 carbon atoms in the alkyl group, alkyl and alkylaryl ether sulfates having 8 to 22 carbon atoms in the alkyl group and 1 to 40 oxyethylene or oxypropylene units. Sulfonates, in particular alkylsulfonates having 8 to 22 carbon atoms, alkylarylsulfonates having 8 to 22 carbon atoms, mono- and diesters of sulfosuccinates, salts of carboxylic acids having 8 to 22 carbon atoms in the alkyl, aryl, alkaryl or arylalkyl unit. Phosphoric acid monoesters and diesters and their salts, in particular alkyl and alkaryl phosphates having 8 to 22 carbon atoms in the organic moiety, alkyl ether and alkaryl ether phosphates having 8 to 22 carbon atoms in the alkyl or alkaryl moiety and 1 to 40 oxyethylene moieties. As is well known in the field of emulsifiers, in the case of anionic emulsifiers, the counterions may be alkali metal cations, ammonium or protonated substituted amines such as trimethylamine or triethanolamine. Normally, ammonium, sodium and potassium ions are preferred.

Exemplary, but not limited, cationic emulsifiers are: salts of primary, secondary and tertiary fatty amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrogen chloride and phosphoric acids. Quaternary alkyl , and alkylphenylammonium salts, especially those having from 6 to 24 carbon atoms, especially their halides, sulfates, phosphates and acetates. Alkylpyridinium, alkylimidazolinium and Alkyloxazoliniumsalze, especially those having an alkyl chain of up to 18 carbon atoms, especially their halides, sulfates, phosphates and acetates.

Suitable amphoteric emulsifiers are: amino acids with long-chain substituents, e.g. N-alkyldi (aminoethyl) glycine or N-alkyl-2-aminopropionic acid salts. Betaines, such as e.g. N- (3-acylamidopropyl) -N, N-dimethylammonium salts with an acyl radical of 8 to 20 carbon atoms.

Exemplary, but not limited, nonionic emulsifiers are: polyoxyethylene condensates of fatty acids or fatty alcohols having 8 to 22 carbon atoms with up to 95 wt .-% oxyethylene content based on the molecular weight of the emulsifier; Polyoxyethylene derivatives of phenols having 6 to 20 carbon atoms on the aromatic and up to 95 percent oxyethylene content; Oxyethylene condensates of fatty acid monoesters of glycerol having from 10 to 22 carbon atoms and up to 95 percent oxyethylene; Sorbitan esters of fatty acids having from 10 to 22 carbon atoms; Polyoxyethylene sorbitan esters of fatty acids having 10 to 22 carbon atoms; ethoxylated amides, exoxylated amines, alkoxylated polysiloxanes, block copolymers of propylene, ethylene oxide and / or other epoxides.

The abovementioned fatty structures usually represent the lipophilic part of the emulsifiers. A common fatty group is an alkyl group of natural or synthetic origin. Known unsaturated groups are the oleyl, linoleyl, decenyl, hexadecenyl and dodecenyl radicals. Known saturated groups are lauryl, stearyl, myristyl, palmityl residues. Alkyl groups may be cyclic, linear or branched. When emulsifying an emulsifier or a mixture of several different emulsifiers can be used, wherein preferably at least one nonionic emulsifier, such as ethoxylated fatty acids, ethoxylated linear or branched fatty alcohols, sorbitan fatty acid esters or ethoxylated sorbitan fatty acid esters should be included. - -

Furthermore, known compounds such as polyacrylic acid, polyacrylates, cellulose ethers such as carboxymethylcellulose and hydroxyethylcellulose, natural gums such as xanthan gum, and polyurethanes as well as preservatives and other conventional additives known to those skilled in the art may be added to the emulsions as thickeners.

In the process according to the invention, the particles can be surface-treated in a one-step or two-step process.

In the one-step process, the mixing and grinding takes place simultaneously.

In the two-stage process, the primary particles may be admixed with the polyethersiloxanes of the formula (I) and the phthalate-free plasticizers in the first stage. However, it is also possible to add any two of the three components successively or simultaneously to the third component and to mix with it.

The primary particles are preferably subsequently or simultaneously mixed and mixed with at least one of the polyethersiloxanes of the formula (I) and at least one phthalate-free plasticizer according to the invention. Particularly preferably, the polyethersiloxanes of the formula (I) and the phthalate-free plasticizers according to the invention are added to the primary particles in succession.

Preferably, a ploughshare mixer is used for mixing. The first stage is preferably carried out at room temperature or temperatures up to 60 ° C.

In the second stage, the particles of the first stage are ground. Preferred mills are steam jet mills, pin mills, air jet mills, roll mills or ball mill mills, particularly preferred is a steam jet mill.

The grinding can be carried out at atmospheric pressure or at elevated pressure up to 20 bar, preferably up to 19 bar, 18 bar, 17 bar, 16 bar, 15 bar, 14 bar, 13 bar, 12 bar, 1 1 bar, 10 bar, 9 bar, 8 bar, 7 bar, 6 bar, 5 bar, 4 bar, 3 bar or up to 2 bar. - -

In the second step of the process according to the invention, the particles are preferably ground in a steam jet mill at a pressure of 8 to 20 bar, preferably 10 to 19 bar, more preferably 12 to 18 bar. The particles are preferably surface-treated in a one- or two-stage process.

Reference is made to the patent application DE 102013226800, the content of which is incorporated herein by reference to the preparation of the polyether siloxanes used according to the invention. Accordingly, the polyethersiloxanes used according to the invention can be prepared by noble metal-catalyzed hydrosilylation of the linear or branched siloxanes of the formula (Ia)

wherein: RR ¹ , methyl or hydroxy and R is hydrogen, with the abovementioned definitions of the radicals and indices, with terminally unsaturated polyethers, as described for example in EP1520870. The hydrosilylating polyethers correspond to the formula (IIa)

-Y- (O-C _m H _2m . _(N. ₁₎ ) ₀ - [0- (EO _x , PO _y , BO _z ) -R ³ ] _n (IIa) with the above definitions and preferences of the radicals and indices where the radical Y is terminally unsaturated, preferably with a C =C double bond, more preferably with respect to the oxygen, allylic unsaturated, in particular an allyl ether.

In a particular embodiment, starting alcohols which lead to branched polyethers, which then have two or more oxyalkylene chains, can be used for the preparation of these polyethers. Starting alcohols are exemplary, , -

Trimethylolpropane monoallyl ether or the glycerol monoallyl ethers. Preferred according to the invention are glycerol monoallyl ethers, in particular the terminal allylic substituted glycerol monoallyl ether. The hydrogen siloxanes used in the preparation of the polyether siloxanes can be prepared as described in the prior art, for example in EP1439200. The unsaturated polyethers used can be prepared starting from unsaturated starting alcohols by the methods known in the literature of alkaline alkoxylation or using DMC catalysts as in the prior art, as described for example in DE102007057145.

The particles according to the invention, the compositions according to the invention comprising the particles according to the invention and the use according to the invention of the particles and their compositions, and furthermore the method according to the invention for the production of the particles are described below by way of example, without the invention being restricted to these exemplary embodiments. Given below, ranges, general formulas, or compound classes are intended to encompass not only the corresponding regions or groups of compounds explicitly mentioned, but also all sub-regions and sub-groups of compounds obtained by taking out individual values (ranges) or compounds can be. If documents are cited in the context of the present description, their contents are intended to form part of the disclosure content of the present invention. If% data is given below, it is by weight unless stated otherwise. In the case of compositions, the percentages, unless stated otherwise, refer to the total composition. If mean values are given below, these are, unless stated otherwise, weight average (weight average). If measured values are given below, these values were determined at a pressure of 101325 Pa and a temperature of 25 ° C, unless stated otherwise.

Brief description of the illustrations

Figure 1: The figure shows the principle of the dust chamber, whose operation is described in detail in Example 2 in V1. The digits mean: 1) case box, 2) release lever, 3) glass cylinder, 4) slider, 5) rubber seal, 6) test tube (filled with quartz cotton), 7) +9) wash bottle (filled with quartz cotton), 8) vacuum pump, - -

10) Gas meter, the letter G at the output of the gas meter indicates the outlet for the extracted gas.

Figure 2: The figure shows the principle of the measuring cell of the ring shear device RST-XS, whose operation is described in detail in Example 2 V2. ω: rotation of the measuring cell, Fi and F ₂ : forces to hold back the lid of the measuring cell, F _N normal force of the lid on the measuring cell.

Examples:

Example 1: Surface treatment of particles

V1: Treatment of TiO 2 particles in dry phase

The starting material for the dry surface treatment of titanium dioxide was a TiO ₂ in rutile modification with an inorganic modification of silica and alumina directly from the spray dryer. This powder was added to the components indicated in Table 1 attached to the end of the description in amounts as indicated and homogenized in a Lödige mixer for 60 seconds. Thereafter, the surface-treated Ti0 _{2 was} ground dry in a steam jet mill with 18 bar steam. Alternatively, the grinding can be done by means of pin mill, air jet mill, roller mill or ball mill. In the following Examples 2-4, investigations were conducted on the samples thus prepared.

V2: Treatment of TiO? Particles in wet phase

The starting material for the wet surface treatment of Ti0 ₂ with polyethersiloxanes and phthalate-free plasticizers was a Ti0 ₂ filter cake after the inorganic modification, wherein the Ti0 _{2 was present} in the rutile modification and the inorganic modification consisted of silica and alumina. This filter cake was redispersed in water by means of a dissolver and to the suspension a polyethersiloxane emulsion and phthalate-free plasticizer were added. This suspension obtained was spray dried and then the spray grain was ground dry with a steam jet mill with 18 bar steam.

V3: Treatment of BaSO * - Parti no in dry phase

Starting material for the dry surface treatment of barium sulfate with polyether siloxanes and phthalate-free plasticizers was a wet-chemically precipitated barium sulfate (so-called blanc fixe), which does not dry-mill, ie, for example. , - steam jet ground, was. This powder was added to polyethersiloxane and phthalate-free plasticizers and homogenized in a Lödige mixer for 60 seconds. Thereafter, the wetted with polyethersiloxane and phthalate-free plasticizer BaS0 _{4 was} ground dry in a steam jet mill with 10 bar steam. Alternatively, the grinding can be done by means of pin mill, air jet mill, roller mill or ball mill.

V4: Treatment of ZnS particles in dry phase

Starting material for the dry surface treatment of zinc sulfide with polyethersiloxanes was a wet-chemically precipitated zinc sulfide (so-called sachtolith), which does not dry mill, i. z. B. steam jet milled was. This powder was mixed with polyethersiloxane and phthalate-free plasticizers and homogenized in a Lödige mixer for 60 seconds. Thereafter, the wetted with polyether siloxane and phthalate-free plasticizer ZnS was ground dry in a steam jet mill with 10 bar steam. Alternatively, the grinding can be done by means of pin mill, air jet mill, roller mill or ball mill.

V5: Treatment of Lithopone particles in dry phase

The starting material for the dry surface treatment of lithopone with polyethersiloxanes was lithopone, which had been produced in a wet-chemical co-precipitation of BaS0 ₄ and ZnS and which had not yet been dry-ground, ie steam jet-milled. This powder was mixed with polyethersiloxane and phthalate-free plasticizers and homogenized in a Lödige mixer for 60 seconds. Thereafter, the lithopone wetted with polyethersiloxane and phthalate-free plasticizers was ground dry in a steam jet mill with 10 bar of steam. Alternatively, the grinding can be done by means of pin mill, air jet mill, roller mill or ball mill.

Example 2: Property Determinations of the Surface-Treated Particles

V1: Dust determination

100 g of the substance to be tested were weighed into the case box (1). The case box was locked with the lever (2) and hooked into the glass cylinder (3). The sample tube (6) was filled with quartz cotton, weighed and inserted into the glass cylinder (3). One end of the sample tube (6) was passed over the slide (4) , - locked. The other end was connected via a quartz-wadded wash bottle (7) through a vacuum hose to a vacuum pump (8). After 5 sec the case box (1) was unlocked. The pigment fell into the glass cylinder and dust developed. After 10 sec., The slider (4) was raised. After 20 sec., The vacuum pump was put into operation and sucked exactly 20 l of air through the glass cylinder. The power of the vacuum pump was 10 l / min. After switching off the vacuum pump, the previously balanced sample tube was removed and weighed again. The weight difference was given as a measure of the dust. The determination was carried out as a duplicate determination. The mean values of these measurements of the samples are given in Table 1 (unit: mg / 100 g of material).

V2: powder flowability

The powder flowability is determined with the RST -XS ring shear device. The bulk material sample is filled into the measuring cell and loaded from above via a lid with a force (normal force) of 3.5 kPa. During the measurement, the shear cell rotates slowly (ω). The lid is prevented from rotating by means of two tie rods. This results in a shear deformation of the bulk material sample. The required force (Fi and F ₂ ) is measured. From the ratio of solidification stress σ ^ to bulk material strength o _c , the flowability ff _{c of} the bulk material is determined. The measurement results are shown in Table 1.

The greater the flowability ff _c , the better the bulk material flows. The following areas of different flowability are defined (D. Schulze, Pulver und Schüttgüter, Springer, 2006, Chapter 3.1.4, page 42):

ff _c less than or equal to 1, not flowing, hardened

ff _c from greater than 1 to equal to 2, very cohesive (to non-fluent)

ff _c from greater than 2 to equal to 4, cohesive

ff _c from greater than 4 to equal to 10, slightly flowing

ff _c greater than 10, free-flowing.

Example 3: Compositions

V1: Masterbatches

The thermoplastic compositions are also referred to as masterbatches. These masterbatches can be prepared according to the following instructions. - -

First, a dry blend of the surface-treated pigments (TiO ₂ ) to be investigated and polyethylene as an example of a thermoplastic (LDPE: Lupolen Pureil 1800 SP 15) in a concentration of 50% by weight was prepared by weighing both components in a plastic bottle and then 15 min were mixed on a potholder. The resulting dryblend was then added to the Brabender dosing unit and fed via a screw conveyor to the Leistritz DS ZSE 18HP twin-screw extruder for processing. With a speed of 150 revolutions per minute (rpm) and a temperature setting of 150 ° C in all zones, the processing was carried out to masterbatch. The polymer strand was granulated.

Following this procedure, the compositions containing samples 1-5 were prepared according to Table 1. V2: white paste

As an example of compositions, white pastes were prepared.

90 g of dioctyl phthalate (DOP) were weighed into a 250 ml dissolver pot. With gentle stirring, 167 g of the surface-treated particles were incorporated in portions within 3 min using a 3 cm dissolver disk (about 5 m / sec). The dissolver was ramped up to 12500 rpm and dispersed for five minutes.

Following this procedure, the compositions containing samples 1-5 were prepared according to Table 1.

Example 4: Testing of the dispersibility of surface-treated particles

V1: Checking the masterbatches in the pressure filter test

The dispersibility was evaluated in a pressure filter test on the basis of the pressure increase in front of the filter, which is produced by extruding a polymer melt through a sieve packet.

The determination of the pressure filter value was carried out with the single-screw extruder Brabender Plasti-Corder LAB Station (screw diameter: 30 mm / 25D). It was a Siebpaket the Fa. GKD with a PZ-Microdur 14 (filter fineness nominally 14 μηι) and a supporting fabric with 315 μηι mesh size used. , -

The extruder was heated to a temperature of 200 ° C. The temperature of the filter equipment was set at 230 ° C. After thoroughly rinsing the extruder with LDPE, the filter receiver was installed with the sieve pack. After application of the Ti0 ₂ / LDPE masterbatch granules to be tested and exit of the pigmented material at the bypass, the melt stream was passed over the sieve packet and the computer-aided measurement data acquisition was started. The measured data were recorded up to a maximum pressure of 150 bar or with a slight increase in pressure up to a duration of 60 minutes. The throughput was 40 g / min. The measurement results are shown in Table 1 below.

The measure of the dispersion quality is the pressure filter value (DF), which is calculated according to the following formula:

DF ~ [bar x cm ^£: / g]

(t x K x G)

Pmax: final pressure [bar]

Bottom: initial pressure [bar]

F: Filter area = 6.16 cm ²

t: measuring time [min]

K: Concentration [% by weight] of pigment based on total composition

G throughput [g / min]

The lower the pressure filter value, the better the dispersion of the pigment in the polymer. The samples according to the invention have good dispersibility.

V2: Testing of masterbatches in polymer flat films:

The examination of the dispersing behavior of pigments in polymers is based on the number of agglomerates in a flat film. The masterbatches according to Example 3 (V1) were extruded into films according to the following procedure. For this purpose, the masterbatches were diluted with LDPE granules (Pureil PE 3020H) to a concentration of 10% by weight of pigment (TiO ₂ ). For this purpose, masterbatch and polymer granules were placed in a plastic bottle and shaken by hand Vz min. - -

Thereafter, the sample was extruded on the single screw extruder Brabender Plasti-Corder LAB Station (screw diameter length: 30 mm / 25D) at 15 rpm and at a temperature of 190 ° C. About a slot die an approximately 8 cm wide film was discharged. The film strand was pulled off via a conveyor belt, cooled and rolled up.

From the film strand 5 pieces about 50 cm long were examined. The evaluation was carried out in transmitted light with respect to the number of undispersed agglomerates at two different magnifications (0 times: no magnification, 30 times: at 30 times magnification). The size of the specks, which consist of incompletely dispersed agglomerates, had no influence on the grading.

The results were graded in a five-step system, with grade 1 no specks, grade 2 scattered specks (there were test areas with 1 to 2 specks but also test areas without specks), grade 3 moderate number of specks (all test areas had specks, average these at less than 5 per test area), Grade 4 many specks (all test areas had 5 to 10 specks) and Grade 5 very many specks (on average, all test areas had at least 10 specks). The values in Table 1 below are given as a score of the count of 5 test areas. From Grade 3, the masterbatches are unsuitable for the production of foils. The samples according to the invention have good dispersibility.

V3: testing in plasticizers

For this purpose, the granularity of pigments in a white paste is to be determined under defined dispersing conditions. For this purpose, 3 g of the prepared white pastes according to Example 3 (V2) were stirred well in a plastic cup with the same amount of DOP with the spatula. To determine the fineness, the diluted paste was first applied to the Hegman wedge (Grindometer) on the Hegmann wedge from 0 to 100 μm, and then the correspondingly fine samples were applied to the Hegmann wedge from 0 to 25 μm (Erichsen). The visually determined fineness values in μηι were noted and are shown in Table 1 below. A fineness of greater than 20 μηι shows a poor dispersion. Table 1

Polyethersiloxane PE film grade

Food filter pressure value

according to formula I dust mass (example 4 v.2) ffc values with approval [bar * cm ² / g] fineness

Sample (x) or not plasticizer mg / 100g Ringscherger

(Indirect Food Contact (Example 4 without 30x [pm]

according to formula I (example 2) RST-XS according to EU 10/2011) V.1) Enlargement Enlargement

(O)

without

1 x (0.45%) Yes 40 0.9 1- 1-2 1.5 1.5

softener

0.2%

Hexamoll

2 x (0.45%) yes 8 1.09 1-2 1-2 2.2 2.2

DINCH (Fa.

BASF)

without

3 o (0.45%) No 37 0.9 1 1-2 1.4 1.4

softener

0.2%

Hexamoll

4 o (0.45%) No 8 2.5 2 2-3 1.8 1.8

DINCH (Fa.

BASF)

0.3%

without Mesamoll TP

5 Yes 8 18.5 3 3-4 1.3 1.3 Polyethersiloxane LXS 51067

(Lanxess)

- -

When looking at the measured values in Table 1, it can be stated that only the particles according to the invention and the corresponding compositions have good results in the measurement results of the example experiments. No comparison particles or comparative compositions according to Samples 1, 3, 4, 5 can achieve such good measurement values in terms of dust mass, pressure filter value, PE film grade and fineness in plasticizer paste. The particles of the invention are approved for indirect food contact according to EU 10/2011 and have a low tendency to dust and a good dispersibility.

Claims

P tentanspruches

1. particles of Ti0 ₂ , BaSö «, ZnS or üthopone with a Besch! sg from at least one compound of the formula (I)

where egg

RR ^{1 is} methyl or hydroxy;

R ^f a FoSyetherrest of the forms! (II):

CHEO "PO _y , 80 R ³ 1" 01)

is, where

Z is a branched or unimpaired Älkylenresi with 2 to 4

Carbon atoms, preferably 3 Könlensioffafomen is,

m is 2 to 4, preferably 3 is,

n! is up to 3, preferably 1 or 2, particularly preferably 1, o is 0 or 1, 0 is 0,

{EO _x , POy, B0 ₂ } an oxyalkylene radical containing oxyethyfene (EO),

Oxypropylene (PO) and / or obutlylene units (SO), where x, y and z are each a 0 and at least one of x, y and z is not 0,

R ^{3 is} hydrogen, when n is 1, or an oxygen radical with 1 to 4 oxygen atoms,

and with the proviso that R in R ^{1 is} the sum of carbon and carbon

Oxygen atoms is at least 70,

a is from 20 to 200, preferably from 30, from 40, from 50, from 60 to 170, to 160, to 150, to 140, to 130, to 120, to 110 and in particular to 70 to 100, b is 1 to 50, preferably from 2, from 3, from 4 to 30, to 25, to 20, and in particular from 5 to 15, with the suggestion that none of the radicals R is R ¹ , b is at least 3, and at least one non-phthalate plasticizer,

wherein the at least one compound of Formet (i) in a proportion of 0.01 to 2 wt .-%, preferably 0.05 to 1 wt .-%, more preferably 0.1 to 0.8 wt .-%, W8 more preferably 0.2 to 0.8% by weight, and more preferably 0.3 to 0.5% by weight, and%

wherein the at least one phthalate-free plasticizer is present at a level of 0.01 to 4.0% by weight, preferably 0.05 to 2.0% by weight, more preferably 0.1 to 1.6% by weight is

where the data in% by weight are based on the weight of the dried primary particles used.

Particles according to claim 1, characterized in that in forms! (I):

R and R ^{3 are} defined in claim 1,

R is a polyether radical of the formula (Ii), -Ist, where

2 is an unsubstituted alkylene radical having from 2 to 4 oxygen atoms, preferably 2 or 3 carbon atoms,

8 is 0,

x is 0 to 20, preferably 3 to 1§, particularly preferably 4 to 10, y is 5 to 100, preferably S to 50, particularly preferably 10 to 30, z is 0 to 2ö

Particles according to one of claims 1 or 2 _» characterized _» that the numerical ratio of index a to index b in formula (1) is equal to S to 10, preferably 9 to 15 and in particular 10 to 12

Particles according to one of claims 2 or 3, characterized in that the index x is between 0.05 and 1.2 times the sum of the Irtdices (y + ^■ z), preferably between 0.07 and 0.8 a, in particular between 0 ₍ 1 and 0.5 ma!

Particles according to claim 2, characterized in that

R is a & yl,

R ^{3 is} hydrogen x 3 to §,

y tO to 2S,

z 0, and

Z and o as defined in claim 2

Particles according to one of claims 1 to 5, characterized in that the particles are TsOj.

0

7. Particles according to one of claims 1 to 6, characterized in that they have a dust value of at most 30 mg, preferably of at most 10 mg per 100 g oberflächenbshsndeite particles.

Particles according to any one of Claims 1 to 7, characterized in that the at least one plasticizer is selected from the group consisting of aliphatic hydrocarbons having preferably 6 to 21 carbon atoms and having at least one acid group selected from a carboxy group, sulfenyl group, -SO _s H, or Sutfinylgruppe -S0 ₂ H, with a ^'eirs- or polyhydric aliphatic alcohol having preferably six to twenty carbon atoms or a "or such eäwertigen aromatic alcohol and esters of aromatic 1,4- {para) -DicarbQnsäuren _t preferably 1 , 4-Senzotdicarbons & ure, or aromatic tricarboxylic acids with a mono- or polyhydric aliphatic alcohol having preferably six to twenty Kohienstoffatomen.

Process for the preparation of o & TiOj treated particles, BaSÖ ^, ZnS or Lithopone, characterized in that Prim & partike! made of Ti0 ₂ , BaSO <, ZnS or LÜhopone with at least one compound of the forms! (I)

D

(!) where R, a and b have the meanings given above and are simultaneously and successively brought into contact with at least one phthalate-free plasticizer or mixtures thereof.

wherein the at least ee compound of Formet (I) in a proportion of 0.01 to 2 wt .-%, preferably 0.05 to 1 G © w .-%, more preferably 0.1 to 0.8% by weight , weiisr more preferably especially preferably 0.3 to 0.5 wt .-% 0.2 to 0.6 percent by and. ^"% is used, and

wherein the at least ein® phthalate plasticizer in a proportion of 0.01 to 4, 0 wt .-%, preferably 0.05 to 2.0 percent, ^"%, more preferably 0.1 to 1.6 Ge used .-% becomes,

the data in% by weight being based on the weight of the dried primary component used.

Process for the production of surface-treated particles of TiO ₃ , SaSO 2, ZnS or Uthopone according to Claim 9, characterized in that at least one compound of the formula (I)

used in Formet (I):

I (II) is, \ being

o is 0.

x is 0 to 20, preferably 3 to 15, particularly preferably 4 to 10, y is 5 to 100, preferably 8 to SO, particularly preferably 10 to 30, z is 0 to 20,

R and R ^{3 are} as defined in claim 1.

A process for the production of over-coated particles of TiOz, 8aSO 2, ZnS and othopone according to claim 9 or 10, wherein the at least one phihatet-free plasticizers selected from the group consisting of esters of aliphatic hydrocarbons having 6 to 21 carbon atoms with at least one acid group selected from a Csr oxytgnjpp®, suifonyi group -SQ _s H _t or suifinyl group -SO _a H, with an eirs- or polyhydric aliphatic Aäko oi § having preferably six to twenty ohSensioffaiomen or © domestic or divalent aromatic alcohol and esters of aromatic) 1,4- (para) - Di ar ensauren, preferably 1,4-Benzoidicarbonsäure _t or aromatic Tficar onsiuren with a monovalent or polyhydric aliphatic alcohol having preferably six to ten carbon atoms

0

2. Particles on Ti0 ₂ , Sa80 ₄ , ZrtS or Uthspone, obtained according to the method of claim 9, 10 or 11,

13. Use of the Partiks! according to one of claims 1 to 8 or 12 in the preparation of polymer aggregates, in particular for

Kunststo ormkorper or -foiien, or a Masteröaich.

14, composition comprising a polymer and / or a plasticizer, characterized in that it contains particles according to one of claims 1 to 8 or 120.

15. Composition according to claim 14, characterized in that the polymer is a thermoset or thermoplastic. Claims 14 or 15, characterized in that the composition is a masterbatch

Kunststoffformkorper or a plastic film is.