DD297920A5 - HIGHLY CONCENTRATED WAFER SOFT SUSPENSION OF MINERALS AND / OR FUELS AND / OR PIGMENTS - Google Patents

Abstract

Aqueous suspension of minerals and / or fillers and / or pigments having a solids content of 60 *, the mineral or the filler or pigment being dispersed with one or more dispersants, characterized in that the dispersant contains one or more amphoteric polyelectrolytes and / or or cationic polyelectrolytes and / or amphoteric cationic polyelectrolytes and / or amphoteric anionic polyelectrolytes and / or partially neutralized anionic polyelectrolytes and / or partially neutralized amphoteric anionic polyelectrolytes, wherein the filler and / or the pigment and / or the mineral particles are neutral or neutral carry positive charge. Furthermore, a method is disclosed wherein a part of the polyelectrolytes according to the invention are added before grinding, a part during grinding and a part after grinding. According to the invention, milling and dispersion can be carried out in a single operation.

Description

The present invention relates to an aqueous suspension of minerals and / or fillers and / or pigments having a solids content of> 60% by weight, based on the dry mineral or the dry filler or the dry pigment, wherein the mineral or the filler or the pigment is dispersed with one or more dispersants. The term "positive charges" is understood below to mean that the particles have a positive zeta potential on their surface (compare P. Ney "Zeta Potentials and Floatability of Minerals", Applied Mineralogy 6, Springer Verlag, Vienna, New York 1973, especially page 22ff.). The same applies to the "negative charges", as occurs, for example, with the cellulose fiber and anionically stabilized suspensions.For the neutral "charges", based on the particles, the negative and positive charges cancel each other out towards the outside. The isoelectric point need not be at pH = 7. The isoelectric point of particle surfaces and amphoteric polyelectrolytes and / or their salts, partial salts and / or full salts is at the pH at which the positive and negative external charges neutralize each other.

In the context of the invention, neutral monomer units are to be understood as meaning monomer units which contain no dissociable groups (such as, for example, the -COOH group), eg. B. ethylene groups.

The externally charged and outwardly neutral polyelectrolytes of the invention are defined in the above application by the number of positive and negative groups in the polymer, respectively. Accordingly, in the case of the amphoteric, externally neutral polyelectrolytes, the number of positive charges in the cationic monomer units is equal to the number of negative charges in the anionic monomer units. In the case of the amphoteric cationic polyelectrolytes, the non-neutral monomer units carry predominantly positive charges. In the case of the amphoteric anionic polyelectrolytes, the non-neutral monomer units carry predominantly negative charges.

However, this does not mean that, for example, with an excess of positive charges of the polyelectrolyte is automatically electrically positive. This is because the "acidity" and the "base strength" can each be different. So z. As an amphoteric polyelectrolyte with the same number of positive and negative groups are electrically either positive or negative or neutral. This also applies accordingly to the amphoteric cationic polyelectrolytes and the amphoteric anionic polyelectrolytes. The dissociation of the "acid or base groups" can be influenced by shifting the pH, in particular at pH values between 5 and 10, the polyelectrolytes according to the invention can have the following charge states to the outside:

pH 5-10 amphoteric cationic amph. easy a; nph. light

Polyelektr. Polyelektr. kati. Polyele. ariio.Polyel

neutral neutral neutral

something outweighs something

or neutral or neutral

A = possibility of electric charge to the outside B = number of charged monomer units C = charge of the particles

The neutralization of the negative groups with mono- and / or divalent and / or trivalent cations also influences their degree of dissociation and thus the state of charge to the outside.

Anionically stabilized, calcium-containing minerals such as calcium carbonate, dolomite, etc. are usually prepared by grinding with anionic polyacrylates, such as e.g. in patents EP 0100947 or FR 820806. In this patent it is disclosed that in anionically stabilized suspensions partially neutralized polyacrylic acids give better viscosity stabilities than fully neutralized. The disclosed range of neutralization is between 40 and 96% neutralization, this does not lead to satisfactory results in the cationic suspension according to the invention.

From the disclosed examples in FR 820806 it can be seen that a neutralization of <50% does not lead to the goal but that 60-70% degree of neutralization is the optimum. The minerals can also, as described in EP 0256312, be suspended in suspension with amphoteric dispersants. In the amphoteric polyelectrolytes disclosed in this prior publication, the isoelectric point is highly acidic in pH, so that they are not suitable for the pigment and / or filler and / or mineral suspensions according to the invention. In addition, only amphoteric polyelectrolytes are mentioned which contain predominantly anionic monomers in their molar monomer composition. The particles according to this prior art have a negative charge on their surface.

For some applications, however, anionic stabilization is undesirable. It would be useful to use a slurry with neutral or positively charged particles. When calcium carbonate coated with the anionic dispersant is used as a filler in the paper industry, it is necessary to bind the negatively charged filler with cationic retention aids to the paper fiber negatively charged by carboxyl groups by nature.

In the neutralization and flocculation of the negatively charged mineral and / or filler and / or pigment particles with the aim of achieving the highest possible fill levels and good filler retention in the paper, at the same time the negatively charged paper fiber can also be flocculated, resulting in a poorer paper formation and thereby lead to a more irregular review of the paper. In the current state of the art, this negative effect can hardly be avoided. For this reason, pulverized products that are mostly dry-ground today are still used in papermaking, which have only slightly negative or externally neutral or weakly positive surface charges.

In dry-ground products, however, the necessary finenesses are very difficult to produce. In addition, powders give rise to the problem of dust formation.

Cationically stabilized mineral and / or filler and / or pigment suspensions prepared by dispersion:

Cationically stabilized, d. H. on the surface positively charged, partially calcium-containing minerals such as calcium carbonate, dolomite, etc. are usually by dispersing in water with neutral and / or cationic protective colloids and / or cationic dispersants (see the published patent DE 3707221 and DE 3730833) or by dispersing with a combination from a fully neutralized anionic and a cationic dispersant, as described in European Patent 0278602 A1, the latter using so much cationic polymer that the particles in the suspension have a positive charge.

In EP 0278602 also polyacrylic acid is disclosed. Pure, not neutralized polyacrylic acid is unsuitable because it begins to crystallize at + 2O ⁰ C and thus is no longer dosed.

Once crystallization has occurred, the polymer solution must be heated to 100 ° C to re-dissolve the crystals.

In winter and in colder regions, production with non-neutralized polyacrylic acids is unthinkable.

These processes have the disadvantage that the comminution process, ie grinding, and the dispersion must be carried out in separate steps. According to the prior art, the following possibilities exist:

a) the calcium-containing rock is crushed dry way to get to the necessary fineness. The fineness that can be achieved in this way is limited. Reagglomeration by van der Waals forces largely prevent grinding to high levels of detail. In a separate step, the mixture is then dispersed with the dispersants mentioned above.

b) the calcium-containing rock is ground wet at low solids content (about 30 wt .-%) without grinding and dispersing and must be brought to the desired concentration via filter presses, by addition of flocculants or centrifuges. In a separate step, the mixture is then dispersed with the dispersants mentioned above.

c) the calcium-containing mineral is wet-milled with anionic dispersants to the desired fineness, dried and then redispersed with the aforementioned canonical polyelectrolytes and / or shear colloids. Drying produces aggregates which can not be fully disaggregated again, ie. h., it results in a lower fineness than originally. In addition, the anionic dispersant which is not destroyed during drying can interfere with the subsequent dispersion process and cause an excess consumption of cationic polyelectrolyte.

The viscosity stability over a long period of time is not given in the abovementioned production processes a-c. The preparation of the mineral and / or filler and / or pigment suspension must therefore inevitably take place at the consumer or in the immediate vicinity of the consumer and spoils in a short time by a strong increase in viscosity or sedimentation. A viscosity reduction by dilution is not possible in many cases, since the high concentration for further processing, e.g. in coating colors in the paper industry, is of crucial importance.

Cationically stabilized mineral and / or filler and / or pigment suspensions produced by milling:

Efforts have recently been made to prepare cationically stabilized, partially calcium-containing fillers by milling at low solids levels, as discussed in the Loreen Goodwin, Columbia River Carbonates lecture held at TAPPI Papermaker, April '89, Washington DC.

This process has the disadvantage that the solids content is limited to 45-50 wt .-%. At higher concentrations, the viscosities are so high that the suspensions are no longer processable.

The viscosity stability over a long time is not given.

Due to the low solids content, the suspension has a strong tendency to settle, and it is therefore not storage-stable. The transport costs, based on the dry product, are about 60% more expensive with 45% by weight suspensions than with 70% by weight suspensions. In addition, producers and consumers each need about 50% more storage capacity.

EP 0104904 describes an aqueous slurry of mineral particles having a solids content of at least 40% by weight. This slurry contains cationic and amphoteric polyelectrolytes with nitrogen-containing.

For example, those skilled in the art are not aware of what is meant by "amphoteric polyelectrolyte." Rather, the only amphoteric compound is misleading, since it has no apparent amphoteric character The copolymer referred to as amphoteric is exclusively cationic in structure.

In the aqueous slurries, a sedimentation of the dispersed mineral particles over 3-7 days is accepted, which in a ship transport of z. B. Scandinavia to England over 4-7 days is unthinkable, and emptying large ships, as they are used today for transports of this kind would make impossible.

Stirring such large shiploads is virtually impossible. A rail transport of 4-7 days in the 56-ton tanker wagon from Austria in northern Germany is also excluded for the same reasons.

Both rail and sea transport are very useful today for ecological reasons.

The following requirements (properties) on a suspension are desirable from the consumer point of view:

- good storage stability over weeks at low viscosities.

- To the necessary properties, such. B. to obtain a low abrasion of the paper machine wires in paper production and the doctor blade in the coating, it is necessary to produce very finely divided fillers. Also, coarse fillers in the pulp tend to dust in photocopiers, etc.

Paper opacity, paper gloss and paper whiteness are highly dependent on the fineness and filling levels of the fillers in and on the paper. Opacity and whiteness are of crucial importance to the paper industry today.

- For the pulp today usually minerals and / or fillers and / or pigments with an equivalent spherical diameter of the particles of 50-90Gew .-% <2 \ im (measured with the Sedigraph 5100) are necessary.

For coating formulations today, minerals and / or fillers and / or pigments with an equivalent spherical diameter of the particles up to 99% by weight (measured on the Sedigraph 5100) are usually used today.

- Viscosity stability over a few weeks must be guaranteed so that during transport and storage no spoilage of the suspension by Sedimentatir η or viscosity increase occurs and no unnecessarily high stirring costs. To ensure production reliability in the paper industry today, storage capacities of thousands of cubic meters of such suspensions are necessary.

The mineral and / or filler and / or pigment particles should be able to be retained in papermaking without the use of high amounts of retention aid. The strength values of the finished paper should not be greatly impaired by high degrees of filling of minerals and / or pigments and / or fillers.

- By filling high levels of cellulose can be saved, which means a huge economic advantage for the paper industry.

- Pigment and / or filler and / or mineral paints should as little as possible penetrate into the paper when applied to the paper, but remain on the paper surface and thus cause optimal fiber coverage. A cationic coating on anionic cellulose remains much better on the surface.

- The highest possible solids concentrations should be achieved.

An object of this invention is to provide storage stable filler and / or mineral and / or pigment suspensions with high solids content at low viscosities.

This object is achieved in accordance with the invention by providing an aqueous suspension according to the preamble of claim 1, wherein the dispersant comprises one or more amphoteric polyelectrolytes in which the number of negative charges in the anionic monomer units equals the number of positive charges in the cationic monomer units, and which may optionally contain additional neutral monomer units, and / or one or more cationic polyelectrolytes and / or one or more amphoteric cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges, and / or one or more amphoteric anionic ones Polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges and / or one or more partially neutralized anionic polyelectrolytes and / or several partially neutralized amphoteric anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges, wherein the filler and / or pigment and / or mineral particles carry an externally neutral or positive charge.

Surprising and unpredictable was the fact that the amphoteric polyelectrolytes according to the invention, in contrast to the prior art, in which the filler and / or pigment and / or mineral particles also bear neutral or positive charges against outside, a very good viscosity stability over a long time at low viscosities and yet no sedimentation of the mineral particles occurs, even when not stirred.

The following are the amphoteric polyelectrolytes in which the number of negative charges in the anionic monomer units is equal to the number of positive charges in the cationic monomer units and the amphoteric ones

cationic polyelectrolytes and the amphoteric anionic polyelectrolytes briefly ak invention amphoteric

Polyelectrolyte called. The amphoteric polyelectrolytes in which the number of negative charges in the anionic Monomer units equal to the number of positive charges in the cationic monomer units are abbreviated as

"Amphoteric".

Within the scope of the invention, it may be advantageous if some or more of the amphoteric polyelectrolytes are partially neutralized Advantageously, the amphoteric anionic and the amphoteric cationic polyelectrolyte and the amphoteric Polyelectrolyte in which the number of negative charges in the anionic monomer units is equal to the number of

is positive charges in the cationic monomer units, which is the positive charge generating functional group in a substituent of the ethylenic backbone.

It is also advantageous that the substituent carrying the cationic charge over

O H

Il

-C-N-

or

O Il -C-O-

is bound to the main chain. Excellently suitable is the former group.

It is furthermore advantageous if the amphoteric polyelectrolytes according to the invention comprise quaternary ammonium groups, carboxyl groups and / or sulfonic acid groups and / or acid groups containing phosphoric acid esters. Advantageously, the amphoteric polyelectrolyte according to the invention are one or more compounds from the group of the following compounds according to the following general formula

R _:

Ϊ I C-C

C =

C-C

i ί

R ₉ Z

- 'a

and (An) "= chloride and / or bromide and / or iodide and / or HSO ₄ " and / or CH ₃ SO ₄ "and / or nitrite, where R ₁ , R ₆ , R ₆ and R _{7 are} preferably H and or

R) to R ₇ alkyl, preferably a C 1 -C ₈ -alkyl, particularly preferably C) -C ₆ , optimally -CH ₃ and / or

- Aryl, preferably a 6-ring, in particular a non-substituted 6-ring may be, R ₈ and R ₉ =

- Dog / or

- alkyl, preferably a C, -C ₁₈ alkyl, particularly preferably C ₁ -C ₆ , optimally -CH ₃ or H and / or

- Aryl, preferably a 6-membered ring, in particular a non-substituted 6-membered ring, R ₈ or R ₉ also

-C

OH

can be, if

- C

OH

X = O and / or N-H

Y = -CH ₂ - to -

.0

Z = - C

OH

and or

- C

OH

and or

0 // S = O

\) Η

and or

and or

may be an acidic phosphoric acid ester group and η = 1-18.

Z may be partially neutralized by 1-, 2- and / or 3-valent cations.

Alkali and / or alkaline earth and / or earth metal cations are advantageously usable according to the invention, with alkaline earth metal cations being preferred. Particularly preferred are Ca ⁺⁺ and / or Mg ⁺ * and / or Sr ⁺⁺ , particularly preferably Ca ⁺⁺ and / or

The degree of neutralization of Z is 1 to 99 mol%, advantageously 50 to 98 mol%, preferably 70 to 97 mol% and

more preferably, each based on 95MoI- ⁰ Zo to Z in b.

In the neutralization with monovalent cations such as K ⁺ and / or Na ⁺ and / or Li ⁺ , the degree of neutralization of Z1 is up to 99 mol%, advantageously 1 to 50 mol%, preferably 1 to 25 mol% and particularly preferably <5 mol% depending on Z in b.

Z can also be fully neutralized if the cation is 2- and / or 3-valent or if it is NlV, prim., Sec, tert. Amines and / or quart. Ammonium ions is, with NH ₄ ⁺ leads to very unpleasant odor and harmful to health

Z can also be unneutralized.

If R ₅ or R, not

- C

is, and if that

-OH

amphoteric anionic polyelectrolytes are used in combination with the amphoteric kaiionischen polyelectrolytes and the particles are thus neutral or positive surface charges have, a and b in the following ratios:

amphoteric anionic a = 5-49 mol% b = 51-95 mol%

amphoteric

a = 50 mol% b = 50 mol%

amphoteric cationic a = 51-99 mol% b = 49-1 mol%

where η = 1-18

and (An) "may be chloride and / or ethylene and / or iodide and / or HSO ₄ " and / or CH ₃ SO ₄ "and / or nitrite.

amphoteric

amphoteric anionic a = 47-49 mol% b = 51-53 mol%

a = 50 mol% b = 50 mol%

amphoteric cationic a = 51-80 mol% b = 49-20 mol%

wobein = 1-18

can be and / or nitrite ^- and (An) ^- = »chloride and / or bromide and / or iodide and / or HSO ₄ ^- and / or CH ₃ SO _4.

If R ₈ or R ₉ = - C, and if the

OH

amphoteric anionic polyoxygenates are used in combination with the amphoteric cationic polyoxyethylene, and thus the particles are nondrural or have positive surface charges, a and b are present in the following proportions:

amphoteric amphoteric amphoteric

anionic cationic

a = 10-66 mol% a = 66.66 mol% a = 67-99 mol%

b = 34-90 mol% b = 33.33 mol% b = 1-33 mol%

where η = 1-18

and (An) "= chloride and / or bromide and / or iodide and / or HSO ₄ " and / or CHaSO ₄ "and / or nitrite may be.

Also advantageous are the following mixtures:

amphoteric amphoteric amphoteric

anionic cationic

a = 64-66 mole% a = 63.66 mole% a = 67-90 mole%

b = 34-36 mol% b = 33.33 mol% b = 10-33 mol%

wobein = 1-18

and (An) "= chloride and / or bromide and / or iodide and / or HSO ₄ " and / or CH ₃ SO ₄ "and / or nitrite.

It is particularly advantageous that the amphoteric polyoxyethylene according to the invention are a compound according to this general formula, wherein

R ₁ = H or -CH ₃

R ₂ = -CH ₃ or-C ₂ H ₆

R ₃ = -CH ₃ or-C ₂ H ₅

R ₄ = -CH ₃ bis-C ₄ H ₉ and isomers

X = O or N-H

Y = -CH ₂ -to-C ₆ H ₁₀ -

R ₆ and R ₈ = H

R ₇ = H or -CH ₃

R ₈ and R ₉ = H.

It is particularly advantageous if (An) "= ΠΓ and Y = - (CH ₂ J ₃ -.

According to the invention, amphoteric anionic means that the anionic charges in the amphoteric polyoxygenes predominate over the cationic charges.

Amphoteric cationic means that the cationic charges in the amphoteric polyoxygenes predominate over the anionic charges.

Amphoteric weakly anionic or cationic means according to the invention that the corresponding negative or positive excess charges in the amphoteric Poiyeiektroiyten are nurgering. Amphoteric weakly anionic means that the ratio of anionic charge to cationic charge ranges from 55:45 to 51:49 mole%.

Amphoteric weakly cationic means that the ratio of anionic to cationic charges ranges from 45:55 to 49:51 mol%.

It should be noted that the terms "weak" and "light" are used synonymously in this application.

Poiyeiektroiyten according to the following formula are particularly favorable according to the invention

C -

C = O

4 c - c

C = O

ι C

- C

ζ (cat)

H ₃ CS ⁺ -CH ₃

CH ₃

(On)*

Valence of (Kat) * If c = 0, then ζ =

(KaD ⁺ = alkali and / or

Alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or quaternaries

Ammonium cations (An) "= chloride, bromide.iodide, HSO ₄ ", CH ₃ SO ₄ "and / or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric

amphoteric slightly anionic

a = 49-47 mol% a = 50 mol%

= 51-53 mol% b + c = 50 mol%

amphoteric cationic a = 51-80 mol%

49-20Mol-%

where η = 1-18

Particularly advantageous are polyelectrolytes according to this a. my formula, where

(Cat) ⁺ = alkali and / or alkaline earth cations (An) "= chloride, bromide, iodide, HSO ₄ ", CH ₃ SO ₄ "and / or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric slightly anionic a = 49-48 mol% = 51-52 mol%

amphoteric

a = 50 mol% b -: - c = 50 mol%

amphoteric cationic a = 51-70 mol% = 49-30 mol%

and where ζ =

Valence (cat) 'In the polyelectrolytes according to the invention a and b and c are furthermore advantageously present in the following ratios:

amphoteric slightly anionic a = 49-47 mol%

amphoteric

a = 50 mol% b = 0-50 mol% c = 50-0 mol%

amphoteric cationic a = 51-80 mol%

51-53 mol% c = 50-0 mol% b + c = 49-20 mol%

Particularly advantageous are polyelectrolytes according to this general formula, wherein

(KaD ⁺ = alkaline earth cations

(An) "=" chloride, bromide, iodide, HSO ₄ ", CH ₃ SO ₄ " and / or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric amphoteric amphoteric

slightly anionic cationic

a = 49-40 mol% a = B0 mol% a = 51-70 mol%

b = 0-25mol%

51-52 mol% c = 25-50 mol% b + c = 49-30 mol%

and where ζ =

Valence (cat) * Also advantageous are polyelectrolytes according to this general formula, wherein

(KaI) ⁺ = Na ⁺ , K ⁺ , Li ⁺ , Ca ²⁺ , Mg ² ",

(An) "= chloride, bromide, JOdId ₁ HSOr ₁ CH ₃ SO ₄ " and / or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric amphoteric amphoteric

slightly anionic cationic

a = 49-48.5 mol% a = 50 mol% a = 51-60 mol%

b + c = 51-51.5 mole% b + c = 50 mole% b + c = 49-40 mole% and where

Valence (cat) ⁴

Very particularly favorable results are achieved if in the polyelectrolyte according to the invention according to these general formulas

(KaD ⁺ = Alkali cations (An) "= Haiogenidionen

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric amphoteric amphoteric

slightly anionic cationic

a = 49 mol% a = 50 mol% a = 51 mol%

b = 51 mol% b = 50 mol% b = 49 mol%

c = <1 mol% c = <1 mol% c = <1 mol%

Valence (Cat) 'Also advantageous are polyelectrolytes according to this general formula, wherein

amphoteric amphoteric amphoteric

slightly anionic cationic

a = 49-48.5 mol% a = 50 mol% a = 51-60 mol%

b = 0-10 mol%

b + c = 51-51.5 mol% C = 40-50 mol% b + c = 49-40 mol%

and where

Valence (cat) * Very favorable results are achieved with the polyelectrolytes according to these general formulas

(Cat) ⁺ = alkaline earth cations (An) "= halide ions

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric C amphoteric amphoteric slightly anionic cationic a = 49mol% a = 50mol% a = 51 MoM b = 2mol% b = 2 mol% b = 2mol% c = 49mol% c = 48mol% c = 47 MoI- ⁰ / ζ =

Valence (cat) '

Also advantageous are mixtures of amphoteric cationic polyelectrolytes and amphoteric polyelectrolytes in which the number of cationic monomer units is equal to the number of anionic monomer units, according to the general formula given above, wherein

Cat) + = alkali and / or alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or

quaternary ammonium cations (An) "= chloride, bromide, iodide, HSO ₄ ", CH ₃ SO ₄ "and or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric amphoteric

cationic

a = 50 mol% a = 70-99 mol%

b + c - = 50 mol% b + c = 30-1 mol%

Also advantageous in the mixture according to the invention are the following ratios of the polyelectrolytes a and b and c according to the general formula given above:

amphoteric a = 50 mol% b + c = 50 mol% amphoteric cationic a = 75-98 mol% b + c = 25-2 mol% prefers: amphoteric a = 50 mol% b + c = 50 mol% amphoteric cationic a = 80-97 mol% b + c = 20-3 mol% furthermore preferred: amphoteric a = 50 mol% b + c = 50 mol% amphoteric cationic a = 90-96 mol% b + c = 10-4 mol% especially preferred: amphoteric a = 50 mol% b + c = 50 mol% amphoteric cationic a = 95 mol% b + c = 5 mol%

Also advantageous are mixtures of amphoteric slightly anionic and amphoteric cationic polyelectrolyte according to the general formula given above, wherein

(Cat) + = alkali and / or alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or

quaternary ammonium cations (An) "= chloride, bromide.iodide, HSO ₄ ", CH ₃ SO ₄ "and / or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric amphoteric

slightly anionic cationic

a = 47-49 mole% a = 70-99 mole%

= 51-53 mol% b + c = 30-1 mol%

better:

amphoteric slightly anionic a = 48-49 mol% = 51-52 mol%

amphoteric

cationic

a = 75-98 mol%

b + c = 25-2 mol%

amphoteric cationic a = 80-97 mol% = 20-3 mol%

prefers:

amphoteric slightly anionic a = 48.5-49 mol% b + c = 51-51.5 mol%

especially preferred:

amphoteric slightly anionic a = 49 mol% b + c = 51 mol%

Also advantageous are mixtures of amphoteric cationic and amphoteric cationic cationic polyelectrolytes according to the general formula given above, wherein

(Cat) ⁺ = alkali and / or alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or quaternaries

Ammonium cations (An) "= chloride, bromide, iodide, HSO ₄ ", CH ₃ SO ₄ "and / or nitrite

and wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios:

amphoteric cationic a = 95 mol% 5 mol%

amphoteric

cationic

a = 80-97 mol%

b + c = 20-3 mol%

amphoteric

cationic

a = 90-96 mol%

bra C = 10-4 mol%

amphoteric light anionic a = 51-53 mol% b + c = 49- ^ 7 mol%

prefers:

amphoteric slightly cationic a = 51-52 mol% b + c = 49-48 mol%

especially preferred:

amphoteric amphoteric

slightly cationic cationic

a = 51 mol% a = 95 mol%

b + c = 49mol% b + c = 5mol%

Advantageously, the degree of neutralization of the anionic component in the amphoteric cationic and amphoteric weakly anionic and amphoteric weakly cationic and amphoteric polyelectrolyte with alkaline earth cations, especially with Ca ⁺⁺ and / or Mg ⁺⁺ , 0.1-100mol%, better 50-100mol% and preferably 70 ~ 99 mol%, most preferably 98 mol%, or the anionic component is unneutralized.

Advantageously, the degree of neutralization of the anionic component in the amphoteric cationic and amphoteric weakly anionic and amphoteric weakly cationic and amphoteric polyelectrolytes with monovalent cations is 0.1-100 mol%, more preferably 0.1-50 mol% and preferably 0.1-39 mol% or 0.1-30 mol%, more preferably 0.1-35 mol% or 0.1-25 mol% or 0.1-15 mol%, most preferably <1 mol%, or the anionic component is not neutralized. When divalent cations such as Ca ⁺⁺ and Mg ⁺⁺ are used, a degree of neutralization of> 90% is preferred. A degree of neutralization of> 90% with Ca ⁺⁺ is better according to the invention than a degree of neutralization <1% with Na ⁺ . It is advantageous that the degree of polymerization of the polyelectrolytes according to the invention, measured by their viscosity in an aqueous solution at 32% concentration, is in the range from 6 mPa s to 150 mPa · s. Very particularly advantageous is the viscosity in the range of 15 mPa · s to 10OmPa s, with a range of 25 mPa s to 7OmPa s is particularly preferred. Further advantageous in the case of the mixture of amphoteric cationic polyelectrolytes and amphoteric slightly cationic polyelectrolytes and / or amphoteric polyelectrolytes and / or amphoteric slightly anionic polyelectrolytes is that the degree of polymerization of the amorphous cationic polyelectrolytes, measured via the intrinsic viscosity, in the range from 5 ml / g to 50 ml / g, preferably in the range of 15 ml / g to 40 ml / g, particularly preferably from 25 ml / g to 35 ml / g, and the degree of polymerization of the amphoteric slightly cationic polyelectrolytes and the amphoteric polyelectrolytes and the amphoteric slightly anionic polyelectrolytes, measured in terms of their viscosity in an aqueous solution at 32 wt .-% Conc. In the range of 5 to 150ml / g, preferably from 15 to 100ml / g, more preferably from 25 to 70ml / g. Further advantageously, the dispersant contains one or more amphoteric polyelectrolytes in which the number of

negative charges in the anionic monomer units equal to the number of positive charges in the cationic

Is monomer units. Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric, light cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges and one or more amphoteric anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric, lightly cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges and one or more amphoteric anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric polyelectrolytes in which the non-neutral monomer units are predominantly positive

Carry charges and one or more amphoteric, slightly anionic polyelectrolytes in which the non-neutral Monomer units carry predominantly negative charges. Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric, slightly cationic polyelectrolyte in which the non-neutral monomer units carry predominantly positive charges and one oc '> several amphoteric, slightly anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains one or more amphoteric cationic polyelectrolytes in which the

non-neutral monomer units carry predominantly positive charges.

Further advantageously, the dispersant contains one or more amphoteric cationic polyelectrolytes and one or more

several amphoteric, slightly cationic polyelectrolytes, which the non-neutral monomer units carry predominantly positive charges.

Further advantageously, the dispersant contains one or more amphoteric, slightly cationic polyelectrolytes, at

which the non-neutral monomer units carry predominantly positive charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric cationic Polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges and one or

several amphoteric anionic polyelectrolytes in which the non-neutral monomer units predominantly negative

Carry loads. Further advantageously, the dispersant contains a mixture of one or more amphoteric, slightly cationic Polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges and one or

several amphoteric anionic polyelectrolytes in which the non-neutral monomer units predominantly negative

Carry loads. Further advantageously, the dispersant contains a mixture of one or more amphoteric cationic Polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges and one or

several amphoteric, slightly anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric, slightly cationic Polyeleklrclyten, in which the non-neutral monomer units carry predominantly positive charges and one or

several amphoteric, slightly anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric, slightly cationic Polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges and one or

several amphoteric, slightly anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains a mixture of one or more amphoteric polyelectrolytes, and

one or more amphoteric, slightly anionic polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges.

Further advantageously, the dispersant contains one or more amphoteric, slightly anionic polyelectrolytes in which

the non-neutral monomer units carry predominantly negative charges.

The filler particles exhibit the use of the amphoteric, slightly anionic polyelectrolytes despite the slight Excess negative charge (carboxyl groups) on neutral or slightly positive surface charge. This is touching

probably because some of the carboxyl groups are so strongly neutralized by Ca ⁺ ions that they are not dissociated and therefore neutral to the outside. As a result, the dissociated cationic groups predominate, and the filler particles have no negative charge despite excess carboxyl group in the actual dispersant.

This is especially the case with a ratio of 51-53 mole% carboxyl groups to 47-49 mole% quaternary Ammonium groups in the polymer molecule. Further preferred is a ratio of 51 to 52 mole% carboxyl groups to 49-48 mole% quaternary ammonium groups

in the polymer molecule. Especially preferred is a ratio of 51 mole% carboxyl groups to 49 mole% quaternary

Ammonium groups in the polymer molecule. Preferably, the dispersant contains 0 to 100% by weight of a first amphoteric polyol electrolyte and 100% by weight of a

second amphoteric polyelectrolyte.

Further preferably, the dispersant contains a mixture of 0.1 to 99.9 wt .-% of one or more amphoteric Polyelectrolytes and 99.9 to 0.1 wt .-% of one or more amphoteric cationic polyelectrolyte. Particularly preferably, the dispersant contains a mixture of 50-99.9Gew .-% or 80 to 99.9Gew .-% or

10-50 wt.% Or 10-30 wt.% Of one odar of several amphoteric polyelectrolytes and 0.1 to 50 wt.% Or 0.1 to 20 wt.% And 50 to 90 wt. 90% by weight of one or more amphoteric cationic polyelectrolytes.

Further preferably, the dispersant contains from 0.1 to 99.9% by weight of one or more amphoteric polyelectrolytes and 99.9

to 0.1% by weight of one or more amphoteric cationic polyelectrolytes.

Further preferably, the dispersant contains a mixture of 0.1 to 99.8Gew .-% of one or more amphoteric Polyelectrolytes and 0.1 to 99.8Gew .-%, preferably 0.1 to 49.8Gew .-% of one or more amphoteric cationic Polyelectrolytes and 0.1 to 99.8Gew .-%, preferably 0.1 to 49.8Gew .-% of one or more amphoteric anionic Polyelectrolyte. Further preferably, the dispersant contains a mixture of 0.1 to 20 wt .-% of one or more amphoteric Polyelectrolytes and 60 to 79.9% by weight of one or more amphoteric cationic polyelectrolytes and 0.1 to 20% by weight

one or more amphoteric anionic polyelectrolytes.

Further preferably, the dispersant contains a mixture of 0.1 to 99.8 wt .-% of one or more amphoteric Polyelectrolytes and 0.1 to 99.8Gew .-%, preferably 0.1 to 49.8 wt .-% of one or more amphoteric slightly cationic Polyelectrolytes and 0.1 to 99.8 wt .-%, preferably 0.1 to 49.8 wt .-% of one or more amphoteric anionic Polyelectrolyte. Further preferably, the dispersant contains a mixture of 0.1 to 99.8Gew .-% of one or more amphoteric Polyelectrolytes and 0.1 to 99.8 wt .-%, preferably 0.1 to 49.8Gew .-% of one or more amphoteric cationic Polyelectrolytes and 0, 'to 99.8 wt .-%, preferably 0.1 to 49.8 wt .-% of one or more amphoteric slightly anionic Polyelectrolyte. Further preferably, the dispersant contains a mixture of 0.1 to 99.8Gew .-% of one or more amphoteric Polyelectrolytes and 0.1 to 99.8% by weight of one or more amphoteric cationic polyelectrolytes and 0.1 to

99.8% by weight of one or more amphoteric, slightly anionic polyelectrolytes.

Further preferably, the dispersant contains 0 to 100% by weight of a first amphoteric cationic polyelectrolyte and 0

to 100% by weight of a second amphoteric canonical polyelectrolyte.

Further preferably, the dispersant contains 0.1 to 99.9% by weight of a first, amphoteric slightly cationic Polyelectrolytes and 0.1 to 99.9 wt .-% of a second amphoteric slightly cationic polyelectrolyte. Further preferably, the dispersant contains 50 to 99.9% by weight or 70 to 99.9% by weight of one or more amphoteric agents

cationic polyelectrolyte and 0.1 to 50% by weight or 0.1 to 30% by weight of one or more amphoteric anionic

Polyelectrolyte. Further preferably, the dispersant contains a mixture of 90 to 99.9% by weight or 75 to 90% by weight and 80% by weight, respectively.

of one or more amphoteric cationic polyelectrolytes and 0.1 to 10% by weight or 25 to 10% by weight or 20% by weight of one or more amphoteric anionic polyelectrolytes.

Further preferably, the dispersant contains a mixture of 80 to 99.9 wt .-% of one or more amphoteric easily

cationic polyelectrolyte and from 0.1 to 20% by weight of one or more amphoteric anionic polyelectrolytes.

Further preferably, the dispersant contains a mixture of 0.1 to 99.9 wt .-% of one or more amphoteric

cationic polyelectrolyte and 99.9 to 0.1% by weight of one or more amphoteric, slightly anionic polyelectrolytes.

Further preferably, the dispersant contains 50 to 99.9% by weight or 70 to 90% by weight or 75% by weight of one or more

amphoteric cationic polyelectrolyte and 0.1 to 50% by weight or 10 to 30% by weight or 25% by weight of one or more amphoteric light anionic polyelectrolytes.

Further preferably, the dispersant contains from 0.1 to 99.9% by weight of one or more amphoteric slightly cationic Polyelectrolytes and 99.9 to 0.1 wt .-% of one or more amphoteric slightly anionic polyelectrolyte. Further preferably, the dispersant contains a mixture of 0.1 to 99.9 wt .-% and 50 to 99.9 wt .-% of one or

several amphoteric polyelectrolytes and 0.1 to 99.9 wt .-% and 0.1 to 50Gew .-% of one or more amphoteric light anionic polyelectrolyte.

Further preferably, the dispersant comprises -M to 0 to 100 wt .-% of a first and 0 to 100 wt .-% of a second amphoteric

slightly anionic polyelectrolytes.

According to the invention, the minerals or fillers or pigments in particular comprise elements from the second and / or

third main group and / or from the fourth subgroup of the Periodic Table of the Elements. Conveniently, calcium and / or silicon-containing and / or aluminum-containing and / or titanium-containing minerals and / or fillers and / or

Pigments used, with calcium carbonate minerals and / or fillers and / or pigments are preferred. All

particularly preferred are natural calcium carbonate and / or precipitated calcium carbonate and / or marble and / or

Chalk and / or dolomite and / or dolomite-containing calcium carbonate. The aqueous suspension preferably consists of 97.0% by weight to 99.97% by weight of minerals and / or fillers and / or Pigments and water and 0.03Gew .-% - 3.0Gew .-% of the amphoteric polyelectrolyte according to the invention in a Fistis content of 60-80Gew .-%, based on the dry mineral or the dry filler or the dry pigment. It is furthermore advantageous for the aqueous suspension to consist of 98.5% by weight to 99.95% by weight of minerals and / or fillers and / or

or pigments and water and from 0.05% to 1.5% by weight of the amphoteric polyelectrolyte of the present invention

Solids content of 65-77 wt .-%, based on the dry mineral or the dry filler or the dry pigment,

consists.

Good results continue to be achieved when the aqueous suspension of 98.8Gew .-% to 99.90Gew .-% minerals and / or Fillers and / or pigments and water and 0.1 wt .-% to 1.2 wt .-% of the amphoteric invention Polyelectrolytes at a solids content of 67-76Gew .-%, based on the dry mineral or the dry filler

or the dry pigment exists.

Excellent results are achieved if the aqueous suspension consists of 93.5% by weight or 98.8% by weight or

99.6% by weight minerals and / or fillers and / or pigments and water and O, 5% by weight, 1.2% by weight and 0.4% by weight, respectively, of an amphoteric, externally neutral polyelectrolyte having a viscosity of 37mPa · s at a solids content of 72% by weight and 72% by weight and 67% by weight, respectively, based on the dry mineral or the dry filler or the dry one

Pigment, with a grain distribution such that 70% by weight, 90% by weight and 6% by weight, respectively, of the particles are equivalent spherical Have diameter <2μπι. Furthermore, it is advantageous if the aqueous suspension from 97 to 99.89 wt .-%, better 98.5 bin 39.8Gew .-%, better 99.2 to

99.65% by weight minerals and / or fillers and / or pigments and water and a dispersant mixture

amphoteric cationic and amphoteric slightly anionic and / or smphoteren and / or amphoteric light cationic

Polyelectrolyte in the range of 0.11 to 3.00 wt .-%, better 0.2 to 1.5 wt .-%, better 0.35 to 0.8 wt .-%, depending

to a solids content in the range of 60-80 wt .-%, preferably 62-75 wt .-%, in particular 65-72 wt .-% based on the dry mineral or the dry filler or the dry pigment.

Excellent results are achieved when the aqueous suspension of 99.6Gew .-% minerals and / or fillers

and / or pigments and water and 0.4% by weight of the dispersant mixture of the invention set forth above.

In particular, good results are achieved when the aqueous suspension consists of 99.6Gew .-% minerals and / or Fillers and / or pigments and water and 0.4 oew .-% of a dispersant mixture consisting of 0.35 wt .-% of a

amphoteric cationic polyelectrolyte according to the general formula of page 17, wherein a = 95 mol% and b = 5 mol% and c = OMol% at an intrinsic viscosity of 27.3 ml / g and 0.1 wt% of an amphoteric polyelectrolyte according to the general Formula of page 17, where a = 50 mol% and c = 0 mol%, with a viscosity measured in an aqueous

Solution of 32% by weight, of 37mPa.s at a solids content of 67% by weight, with 60% by weight of the particles being equivalent

have spherical diameter <2μπι.

A further object of this invention is to provide a process with which a storage-stable, highly concentrated mineral

and / or filler and / or pigment suspension can be prepared by grinding at high solids contents, wherein

Grinding and dispersing are carried out at high solids contents in one operation. This object is achieved in that a method for producing an aqueous suspension

is provided, which is characterized by the following method steps

a) an aqueous suspension of minerals and / or fillers and / or pigments is wet-ground together with the dispersing and Mahlhilfsmittelmischung invention, wherein

b) the amphoteric polyelectrolytes according to the invention completely before the grinding or

c) a part of the amphoteric polyelectrolytes according to the invention before the grinding and

d) a part of the amphoteric polyelectrolyte according to the invention during the milling and / or

e) a part of the amphoteric polyelectrolyte according to the invention are added after the grinding.

Particularly advantageous is a method, wherein

a) the amphoteric, slightly anionic and / or amphoteric polyelectrolytes completely before grinding or

b) a part of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes before grinding and

c) a part of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes during the milling and / or

d) a part of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes are added after the grinding.

Also advantageous is a method in which

a) the amphoteric and / or amphoteric cationic polyelectrolytes completely before grinding or

b) a part of the amphoteric and / or the amphoteric cationic polyelectrolytes before grinding and

c) a part of the amphoteric and / or the amphoteric cationic polyelectrolytes during the milling and / or

d) a part of the amphoteric and / or the amphoteric cationic polyelectrolytes are added after the grinding.

Particularly advantageous is a method in which

a) 50-100Gew .-% of amphoteric, slightly anionic and / or amphoteric polyelectrolytes before grinding and

b) 0-50% by weight of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes during the milling and / or

c) 0-50 wt .-% of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes are added after grinding.

Also advantageous is a method in which

e.) 50-100Gew .-% of amphoteric and / or amphoteric cationic polyelectrolytes before grinding and

b) 0-50% by weight of the amphoteric and / or amphoteric cationic polyelectrolytes during milling and / or

c) 0-50Gow .-% of amphoteric and / or amphoteric cationic polyelectrolytes are added after grinding.

Very good results are achieved when a method is used in which

a) 70-100Gew .-% of amphoteric, slightly anionic and / or amphoteric polyelectrolytes before grinding and / or

b) 0-30% by weight of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes during milling and / or

c) 0-30% by weight of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes are added after the milling.

Also advantageous is a method in which

a) 70-100Gew .-% of amphoteric and / or amphoteric cationic polyelectrolytes completely before grinding and

b) 0-30% by weight of the amphoteric and / or amphoteric cationic polyelectrolytes during the milling and / or

c) 0-30% by weight of the amphoteric and / or the amphoteric cationic polyelectrolytes are added after the milling.

Also advantageous is a method in which

a) a part of the amphoteric, slightly kaiionischen and / or amphoteric, slightly anionic polyelectrolytes before grinding and

b) a part of amphoteric, slightly cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes during milling and / or

c) a portion of the amphoteric, light cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes after milling

be added.

Also advantageous is a method in which

a) the amphoteric cationic polyelectrolytes completely before grinding or

b) a part of the amphoteric cationic polyelectrolytes before grinding and

c) a part of the amphoteric cationic polyelectrolytes during the milling and / or

d) adding a portion of the amphoteric cationic polyelectrolytes after milling.

Particularly advantageous is a method in which

a) 10-90 wt .-% or 20-40Gew .-% or 30Gew .-% of the amphoteric, easily katio hen and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes before grinding and

b) 10-90% by weight or 60-60% by weight or 70% by weight of the amphoteric, slightly cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes during the milling and / or

c) 0-80% by weight or 0-20% by weight of the amphoteric, slightly cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes after the milling

be added.

Particularly preferred is a method in which

a) 50-100Gew .-% and 70-100Gew .-% of amphoteric cationic polyelectrolytes before grinding and

b) 0-50 wt .-% and 0-30Gew .-% of the amphoteric cationic polyelectrolytes during the milling and / or

c) 0-50 wt .-% and 0-30Gew .-% of the amphoteric cationic polyelectrolytes are added after grinding.

Excellent results are achieved in the process in which, on the one hand, 100% by weight of the amphoteric, light

anionic and / or amphoteric polyelectrolytes or else 100% by weight of the amphoteric and / or amphoteric cationic polyelectrolytes are added prior to milling when the desired final fineness in a

Mill passage should be achieved. With several mill passes to reach the final fineness results excellent results when the

necessary amount of dispersant is divided according to the achieved intermediate fineness.

According to the invention, the use of the aqueous suspension of minerals and / or fillers and / or pigments

in papermaking or in papermaking. Further uses relate to the surface treatment (pigmentation) of the paper surface in the size press of the paper machine, the use in paper coating, in

Primer or in the top coat in the Papierstreicherei, in groundwood for Störstoffbekämpfung, in the Streichereiausschuß to Störstoffbekämpfung (pitch control), in the circulation water of the paper machine for COD reduction (chemical Oxygen demand reduction), in the sewage treatment plant for wastewater treatment, for preflocculation of anionically stabilized pigment

and / or mineral and / or filler suspensions in papermaking or for pre-flocculation (immobilization) of

Paints in the stringing. It is inventively, a mineral and / or filler and / or pigment suspension by grinding at high To produce solids contents of a 60% by weight, in which the mineral and / or filler and / or pigment particles

presumably both electrostatically positive and sterically stabilized and the suspension remains stable enough viscosity over weeks, is very well transportable over long distances, does not settle and z. B. the retention in the

Papermaking is excellent. Surprising and unpredictable was the fact that in the appropriate combination of one or more cationic Monomers and one or more anionic monomers and the appropriate addition point of polymerized therefrom

amphoteric polyelectrolytes before, and / or during and / or after the milling process at high shear forces and

Temperatures, as they occur in wet grinding, no mutual neutralization of the oppositely charged Monomer units and thus coagulation of the polymers occurs. In contrast, optimal grinding and Stabilization over a longer period of suspension achieved. Di) zeta potentials of the filler and / or pigment and / or mineral particles have positive signs or are against

neutral on the outside, d. H. in the case of the neutral filler and / or pigment and / or mineral particles, the sum of the positive and negative charges on the surface of the particles to each other cancel each other out.

A good storage stability in terms of viscosity and settling behavior is especially in transport and large Storage tanks of crucial importance to prevent spoilage of the goods. With the orf according manufactured Mineral and / or filler and / or pigment suspension, it is possible to determine the place of production (production location of the mineral

and / or filler and / or pigment suspension) as well as the consumer location (eg paper mill). The

Production location can thus the geological occurrence of mineral and / or filler and / or pigment deposits

be adapted and it must not be taken into account for logistical reasons, the location of the customer. It is therefore also completely free in the choice of means of transport and can choose the ecologically most sensible option.

An aqueous suspension of minerals and / or fillers and / or pigments having a solids content> 60% by weight,

based on the dry minerals and / or fillers and / or pigments is prepared according to the invention by grinding a coarse crushed rock, wherein the amphoteric polyelectrolytes according to the invention are added at the beginning of grinding and / or other parts of the amphoteric polyelectrolyte according to the invention during grinding and / or after grinding be added in the composition according to the invention for reducing viscosity.

The ideal grain distribution, concentration and storage stability for users, especially the paper industry, at a lower level Viscosity of the mineral and / or filler and / or pigment suspensions can according to the inventive method in

a process, which represents a huge economic and qualitative progress.

Preferably, the concentration of the aqueous slurry is 60-78% by weight based on the dry mineral.

Preferably, the raw material before the grinding process according to the invention has a mean equivalent spherical particle diameter of 10-50 μm (measured on the Sedigraph 5100).

Preliminary remarks on the examples:

a) Viscosity measurement of amphoteric polyelectrolytes

The viscosity was measured on a Brookfield viscometer type PVF-100 at 100 rpm. Spindle 1 was used for the individual measurements:

The concentration for all samples was 32% by weight polymer in water. The pH word at which the viscosity was measured corresponds to the stated value in the corresponding examples. The anionic groups were not neutralized

The measurement was carried out in a 400 ml beaker of low form.

The temperature during the measurement was 20 ° C. The measurement ei followed after 1 min stirring time.

This type of viscosity measurement was used for all of the following examples, except for the amphoteric cationic polyelectrolytes in admixture with the amphoteric, light cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes.

b) Fineness of the mineral and / or filler and / or pigment suspension:

The fineness characteristics of the suspensions prepared according to the invention were determined by sedimentation analysis in the gravitational field using the SEDIGRAPH 5100 from Micromeritics, U.S.A.

The measurement of the cationically stabilized suspensions was carried out in distilled water. The dispersion of the samples was carried out by means of a high-speed stirrer and ultrasound.

The measurement of the powder was carried out in 0.1% Na ₄ P ₂ O ₇ solution.

The measured particle distribution was shown on a XY recorder as a transit cumulative curve (see, for example, Beiger P., Swiss Association of Varnish and Color Chemists, XVIIth FATIPEC Congress, Lugano, September 23-28, 1984) , wherein on the X-axis, the particle diameter of a corresponding spherical diameter and on the Y-axis, the proportion of particles in wt .-% was applied.

e) Viscosity measurement of the mineral and / or filler and / or pigment suspensions:

The viscosity was measured on a Brookfield viscometer type PVF-100 at 100 rpm. The following spindles were used for the individual measurements:

Spindle RV2 40-320mPas RV3 320-800mPas RV4 800-1600mPas RV5 1600-3200mPas RV6 3200-8000mPas

The measurement was carried out in a 400 ml area of low form.

The temperature during the measurement was 20 ° C. The measurement was carried out after 1 min stirring time.

Before the actual measurements, all samples were intensively stirred for 2 minutes (5000 rpm, stirring disc diameter 50 mm).

This type of viscosity measurement was used for all the following examples.

d) The specific viscosity for the anionic dispersants in the application examples, which has the Greek letter "Eta" as a symbol, was determined as follows:

A solution of the polymer / copolymer, for the measurement 100% neutralized with sodium hydroxide solution (pH 9), is prepared by dissolving 50 g, based on dry polymer / copolymer, in 1160 g of NaCl-containing, distilled water.

Thereafter, the time required for a well-defined volume of the alkaline polymer / copolymer solution to flow through the capillary is measured with a capillary viscosimeter with a tree constant of 0.000105 in a 25 ° C thermostabilized bath, and compares over time to the same volume of blank solution with 60g NaCl / l to flow through the capillary needs.

It is thus possible to define the specific viscosity "Eta" as follows:

_ Time of flow through the polymer solution - time of passage of the NaCl solution

Time of passage of the NaCl solution

The best results are achieved when the capillary diameter is chosen such that the time required for the polymer / copolymer-containing NaCl solution is between 90 and 100 seconds.

e) The intrinsic viscosity of the amphoteric cationic polyelectrolytes in the mixture with the amphoteric, slightly cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes and poly-DADMAC of Examples 1 a) to 1 c) was determined according to the following literature:

B. Fullmüller "Grundriß der Makromolekularen Chemie" Volume III E.Vollmert-Verlag, Karlsruhe 1985.

f) Charge measurement of the pigment, filler and mineral suspension with SCD

To determine the surface charges, the "Streaming Current Detector" from Mütek, Hersching b.Munich, was used (type PCD-02).

The titrations were carried out according to the statements in the dissertation "Investigations on the Application of Polyelectrolyte Titration in the Field of Paper Production" by Pater Hess, Darmstadt, 1983, in particular according to pages 33ff of this dissertation.

-32- 297 920 The titration solution used was 0.01 M potassium polyvinyl sulfate solution (KPVS) from SERVA.

Herstellungsbelsplele

I. Examples of the prior art

Example 1a

A 60% by weight aqueous slurry of natural marble having a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100) was blended with 0.1% by weight of a poly (diallyldimethylammonium chloride), limiting viscosity 25 ml / g, and 0.02 wt .-% einet. Sodium polyacrylate (specific viscosity 0.35, 100% of the carboxyl groups neutralized with NaOH), based on the dry marble, with high shear forces dispersed (8 000 U / min, stirring discs 050mm).

Viscosity in mPas after hours. 2 days 6 days 12 days

204 420 640 1560

Example 1 a shows that the viscosity in the prior art is not stable and that the suspension is already useless after two weeks.

Example 1b

An attempt was made to obtain a 67% by weight aqueous slurry of natural marble having an equivalent spherical mean particle diameter of 12 pm (as measured on the Sedigraph 5100) according to the following recipe on a Dynomill (0.6 l milling container) using grinding media of glass (01mm) on a grain distribution curve so that 60% by weight of the particles have an equivalent spherical diameter <2μm (as measured on the Sedigraph 5100).

ReLaptur: 5000g marble

15 g poly (diallyldimethylammonium chloride) limiting viscosity 25 ml / g

4.5 g of sodium polyacrylate (specific viscosity 0.35.100% of the carboxyl groups neutralized with NaOH) 2472 g of water

The grinding had to be stopped because the increase in viscosity was so high that a further milling was no longer possible because the mill blocked. The desired final fineness could not be achieved.

Example 1c

A 60% by weight aqueous slurry of natural marble having an equivalent spherical mean particle diameter of 12 μm (measured on the Sedigraph 5100) was prepared in the following formulation on a Dynomill (0.6 liter grinding container) using grinding media Glass (01 mm) on a grain distribution curve so that 60% by weight of the particles had an equivalent spherical diameter <2μ <η (measured on the Sedigraph 5100).

Recipe 5000 g of marble

15 g poly (diallyldimethylammonium chloride) limiting viscosity 25 ml / g

4.5 g of sodium polyacrylate (specific viscosity 0.35, 100% of the carboxyl groups neutralized with NaOH) 3346 g of water

Even at a concentration of 60% by weight, there was no improvement in the milling properties with a poly (diallyldimethylammonium chloride) compared with experiment 1 b

 Milling to the desired fineness at viscosities <2000 mPas was not possible with the prior art.

II. Examples according to the invention

Example 2

A 67% by weight aqueous slurry of natural marble having a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100) was coated at different amounts relative to the dry marble. the following copolymer was prepared,

-C

C = O

NH iCH ₂ I ₃ -S + -CH

CK ₃

c:

j C

C = O i

a = 50 mol ^.: b = 50 mol.

- o

wherein the copolymer in addition rosp in molecular weight. Intrinsic viscosity of the 32 wt .-% aqueous solution was varied. It was dispersed with vigorous stirring (8000 rpm, 50 mm stirring disc diameter). The aim of this series of experiments was to determine the optimum viscosity or molecular weight of the amphoteric polyelectrolytes and the optimum amount of dispersant.

Table 1

Viscosity and pH-Wt. t of the amphoteric polyelectrolyte (32% by weight in H ₂ O)

Viscosity pH

Addition amount in% by weight viscosity to bez. on dry marble 20TG the suspension 0.1 immediately 0.15 1440 0.2 840 0.25 610 0.3 420 0.35 340 155 0.4 275 0.5 215 0.1 165 0.2 1430 180 0.3 420 0.4 265 0.1 190 230 0.2 950 0.3 250 0.1 145 0.2 1910 0.3 1180 0.4 670 0.5 455 280 0.6 360 0.7 275 200

The optimum viscosity of the amphoteric polyelectrolytes is 30-50mPas.

Example 3

A 67% by weight aqueous slurry of natural marble having a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2μm (as measured on the Sedigraph 5100) was coated at different amounts relative to the dry marble. the following copolymer,

C-C

ti V-U

i S-H

(CH ₂ ) ₃

K ₃ CN "* - CH:

j CH ₃

Cl

C-C

H C:

OH

- ¹ D

a = 70 MoI.% b = 30 MoI.%

wherein the copolymer additionally in the molecular weight resp. Intrinsic viscosity of the 32 wt .-% aqueous solution was varied. It was dispersed with vigorous stirring (8000 rpm beater diameter 50 mm).

The aim of this series of experiments was to determine the optimum viscosity or molecular weight of the amphoteric cationic polyelectrolytes and to determine the optimum amount of dispersant.

Table 2

Viscosity and pH of the amphoteric cationic polyelectrolyte (32 wt% iginH ₂ O)

Viscosity pH

106mPas3,7

44 m pas 3.7

33mPas3,7

Addition amount in% by weight viscosity to bez. on dry marble 10Tg the suspension 0.1 immediately 345 0.2 465 0.3 260 0.1 200 375 0.2 535 0.3 220 0.1 140 0.2 1090 0.3 750 0.4 570 530 0.5 430 0.6 290 200

Example 4

A 67% by weight aqueous slurry ¹ of natural marble having a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100) was used in different amounts, based on the dry marble, of the following copolymer.

- C

π C = O

N '-H (CH ₂ J ₃ H ₃ CN - CH ₃

CH ₃

Cl

C-C

C = O

OH

- 'b

a = 47 mol% b = 53 mol%

wherein the copolymer additionally in Mo 'kulargewicht resp. Intrinsic viscosity of the 32 wt .-% aqueous solution was varriert. It was dispersed with vigorous stirring (8000 rpm beater diameter 50 mm).

The aim of this series of experiments was Θ3 to determine the optimum viscosity or the molecular weight of the amphoteric, slightly anionic polyelectrolytes, and to determine the optimum amount of dispersant.

Table 3

Viscosity and pH of the amphoteric, slightly anionic polyelectrolyte (32% by weight of iginH ₂ O)

Viscosity pH

Amount added in Gow% viscosity to bez. aufi ackerten marble 10Tg the suspension 0.1 immediately 0.2 1500 0.3 840 16fi 0.4 420 0.5 275 0.1 185 190 0.2 1180 0.3 265 165

Example 5

A 72 weight percent aqueous slurry of natural marble having an equivalent spherical mean particle diameter of 12 microns (as measured on the Sedigraph 5100) was made with the following recipe in a Dynomill (0.6-liter mill container) using media Glass (01mm) on a grain distribution curve so that 70% by weight of the particles had an equivalent spherical diameter <2μηη (as measured on the Sedigraph 5100).

Recipe 5000g marble

25 g of amphoteric copolymer according to the formula of Example 2 (viscosity 37mPas) 1925g of water

1 day 255

5days 8days 16days 300 365

Viscosity: after 2h

After 30 days

515 mPas

Surface charge after 7 days + 7 ^ Val / g solid

In Example 5 it can be clearly seen that when using the amphoteric polyelectrolytes according to the invention at high concentrations, a very deep and sufficiently stable viscosity over weeks is also to be produced in the case of finely divided mineral and / or filler and / or pigment suspensions produced by grinding.

Example 6 A 72% by weight aqueous slurry of champagne chalk with an equivalent spherical middle one Teichiel diameter of 12 pm (measured on the Sedigraph 5100) was with the following formulation in a Dynomill

(0.6 liter grinding container) using glass grinding media (01 mm) on a particle size distribution curve so that 90% by weight of the particles had an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100).

Recipe 5000g Champagne Crayon

60 g of amphoteric copolymer from Example 2 (viscosity 37 mPas) 1715 g of water

Viscosity in mPas:

nachiStd. 1 day 10days 20days 600 650 710

Example 7 A 72% by weight aqueous slurry of natural marble with an equivalent spherical middle Teiichendurchmesser of 12μπι (measured on the Sedigraph 5100) was with the following recipe in a Dynomill

(0.6 liter grinding container) with milling glass bodies (01 mm) on a particle size distribution curve, so that 90% by weight of the particles had an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100).

Recipe 5000g marble

Add 55 g amphoteric polymer from Example 2 1418 g of water

Viscosity in mPas: after-hours. 1 day 10days 20 days

740 780 870

Surface charge after 7 days + 10.1 μVal / g solid

297

Example 7 a

In the Pilct-plant scale, the marble used in Example 7 was placed in a vertically arranged permill (180 liters content) with glass frits (01-2 mm) on a grain distribution curve so that 90% by weight of the particles would be an equivalent spherical one Diameter <2 μητι (measured on the Sedigraph 5100) had, at a concentration of 74.5Gew .-% milled. About 2 tons of this slurry were produced.

recipe

1480kg of marble

10.4 kg a lter polymer from Example 2 ö1Okg add water

Viscosity in mPas: after-hours. 1 day 10days 20 days

600 560 680

Surface charge after 7 days + 11.9 pVal / g solid

Examples 6 and 7 and 7a show that even very high finenesses, such as those used in coating formulations, can be produced without problem by grinding coarsely crushed raw rock at high concentrations.

Example 8

A G7 wt .-% aqueous slurry of natural marble with an equivalent spherical average particle diameter of 12μπι (measured on the Sedigraph 5100) were with the following recipe Γη a Dynomill (0.6-liter grinding container) using grinding media made of glass ( 01 mm) on a particle size distribution curve, so that 60% by weight of the particles had an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100).

Recipe 5000g marble

20 g of amphoteric copolymer according to the formula of Example 2 (viscosity 37mPas) 2 472 g Wassor

Viscosity in mPas: after 2S «d. 1day 5days 8days 16days

120 130 140 212 200

after 30 *> agen

520 surface charge after 7 days + 4.8 pVal / g solid.

In Example 8 it can be clearly seen that in the inventive use of amphoteric, against neutral neutral Poiyelektrolyten at high concentrations, a very deep and stable enough for weeks to produce viscosity even when produced by milling finely divided mineral and / or filler and / or pigment suspensions as used as filler for paper production.

Example 9

A 72 wt% aqueous slurry of natural marble with an equivalent spherical mean particle diameter of 12 μσι (as measured on the Sedigraph 5100) was coated with the following formulation in a Dynomill (0.6 liter milling vessel) using glass frit (01 mm) on a particle size distribution curve so that 60% by weight of the particles had an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100).

recipe

6000 g of marble

25 g of amphoteric polymer from Example 5, wherein in a) 95 mol% of the carboxyl groups are neutralized with Ca (OH) ₂ and b)

95 mol% were neutralized with Mg (OH) ₂

 Add 2460g of water

Viscosity in mPas: after 1 hour 1 day 4 days 8 days 16Tagen a) 96 110 130 140 160 b) 104 155

Example 9 shows that the calcium and / or magnesium neutralization of the carboxyl groups according to the invention in the amphoteric polyelectrolyte, despite a significantly higher solids content and only slightly more dispersants, compared to Example 8 again brings better viscosity than the same non-neutralized amphoteric polyelectrolyte.

Example 10

A 67% by weight aqueous marble slurry having an equivalent spherical mean particle diameter of 12μηι (as measured on the Sedigraph 5100) was coated with the following formulation in a Dynomill (0.6 liter millbase) using glass frit media ( 01mm) to a grain distribution curve so that 60% by weight of the particles had an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100).

recipe

marble

aphoteres cationic copolymer of the following compound

C-C

H-c-c

C = O N-H

(CH ₂ J ₃

CH ₃

C = O ι

OH

a = 9 5 mol% b = 5 mol%

jb

^cl intrinsic viscosity 27.3 ml / g

Viscosity:

amphoteric copolymer, wherein <* inionischen and cationic groups in the ratio 1: 1 are analogous to Example 2 with a viscosity voi ι ^ ,. lPas added before grinding "like the first 2.5g" added during the grinding of water

nach2Std

 45OcP 30 days 83OcP

1 day 4 days 8 days 16 days 45OcP 52OcP 615cP 73OcP

Example 10 shows that with the combination according to the invention of the amphoteric polyelectrolytes according to the invention, a transportable, non-sedimenting slurry of calcium carbonate by grinding coarsely crushed stone is possible. The viscosity at high concentration is good.

The marble slurries prepared in Preparation Examples 5 + 8 were tested for their retention in papermaking compared to a marble slurry commonly prepared today with anionic dispersants.

test conditions

Fabric: 80% birch sulphate freeness 23 ° SR

20% pine sulfate retention aid: 0.05% polyacrylamide (intrinsic viscosity 700ml / g)

Carrying out retention test according to Britt-Jar Company Paper Research Material, SYRACUSE, U.S.A.

1. 275ml 2% fiber suspension (atro 3.63g fibers) and 275ml dist. Put the warrior in the Britt Jar jar;

2. Britt-Jar stirrer at 700 rpm;

3. Add 25.4 ml of 5% mineral and / or filler and / or pigment suspension;

4. after 20 seconds, add the appropriate amount of retentilizing agent;

5. after another 25sec drain tap open and drain 100ml white water.

6. In the white water the CaCO ₃ -AnIeH is determined complexometrically after digestion with K Ί or with flame AAS. For other minerals and / or fillers and / or pigments, the white water - filtered through membrane filter, ashed at 600 ⁰ C, via an alkaline melt digestion, z. B. with NaOH / KOH in Zirkontiec, al, brought into a water-soluble form and determined in the acidified state by means of AAS. Taking into account the corresponding conversion factors, it is possible to deduce the respective mineral ores and / or fillers and / or pigments.

7. The filler retention can be calculated via the registered proportion of mineral oils and / or fillers and / or pigments per 100 ml and the proportion of minerals and / or fillers and / or pigments per 100 ml determined in the white water.

results:

Products:

Filler First Pass Retention

Anionically stabilized CaCO ₃ suspension 41.1%

with 60% <2 pm (0.15% sodium polyacrylate spec.

Anionically stabilized CaCO ₃ suspension with 70% 35.3%

<2 pm (0.3% sodium polyacrylate lat. Visc. 0.54)

CaCO ₃ suspension from Preparation Example 8 62.4%

CaCO ₃ suspension of Preparation Example 5 65.8%

By using a marble suspension produced by the novel production process according to the invention, it is possible to increase the filler retention without adversely affecting paper formation and paper strength, which represents a huge leap in development.

The aqueous suspensions according to the invention and the process according to the invention for their preparation have u.a. following advantages:

In contrast to the processes known to date, it is possible to produce highly concentrated (> 60% by weight) mineral and / or filler and / or pigment suspension by wet milling from coarsely crushed rough stone.

- An increase in Füllstoff without significant drop in the tensile strength of the paper is possible, resulting in a huge economic advantage in paper production. Furthermore, it was found with the composition of the invention that a Füllgraderhöhung of 15Gew .-% to 17Gew .-% without significant loss of paper strength, especially tensile strength, is possible.

Recent field trials have shown that a filler increase from 164 to 26% can be achieved without negatively affecting the paper properties.

The suspensions have excellent storage stability at low viscosities without sedimentation problem.

- In the application arise z. B. great advantages in terms of filler retention in paper production.

- The grinding and dispersion is possible under high grinding and at boiling temperature of the water.

- The most environmentally friendly transport option can be chosen.

A preferred embodiment of the invention is characterized in that the dispersant comprises a mixture of one or more cationic polyelectrolytes and / or one or more amphoteric cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges, and one or more partially neutralized anionic polyelectrolytes and / or one or more partially neutralized amphoteric anionic polyelectrolytes to which the non-neutral monomer units carry predominantly negative charges. In the following, the partially neutralized anionic or cationic polyelectrolytes and the partially neutralized amphoteric anionic or cationic polyelectrolytes are referred to briefly as anionic or novel cationic polyelectrolytes according to the invention.

Advantageously, the dispersant is a mixture of one or more homopolymeric cationic polyelectrolytes and / or one or more copolymeric amphoteric cationic polyelectrolytes in which the nonneutral monomer units carry predominantly positive charges, and one or more homo- and / or copolymer partially neutralized anionic polyelectrolytes and / or one or more amphoteric anionic partially neutralized polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges. Advantageously, the cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte in which the non-neutral monomer units carry predominantly positive charges carry the positive charge-generating functional group in a substituent of the main ethylenic chain

 It is further advantageous that the substituent on

O H

U I

-C-N-

or

O Il -CO-

is bound to the main chain.

It is furthermore advantageous that the cationic polyelectrolyte contains quaternary ammonium groups and that the amphoteric

cationic polyelectrolyte in which the non-neutral monomer units carry predominantly positive charges, quaternary ammonium groups and carboxyl groups and / or sulfonic acid groups and / or acid phosphoric acid ester-containing groups.

It is particularly advantageous that the cationic polyelectrolyte M comprises one or more compounds from the group of the following Compounds according to the following general formula

C-C

Ro C = O

! χ

R:

(Ap.) -

where Ri, R ₆ and R ₈ =

- and / or R) to R ₈

Alkyl and / or aromatic aryl,

where Rs too

C = O

R ₃ - S + -

X = O and / or N-H

Y = -CH ₂ -Ws-C ₆ H ₁₀ -n = 20 to 3,000

and (An) ^- = chloride and / or bromide and / or iodide and / or HSO ₄ "and / or CH ₃ SO ₄ " and / or nitrite.

It is particularly advantageous if according to this general formula

Ri = Hoder-CH ₃ R ₂ = -CH ₃ or-C ₂ H ₆ R ₃ = -CH ₃ OdOr-C ₂ H ₅

R ₄ = -CH ₃ Ws-C ₄ Hg and isomers

X = O or N-H

Y = -CH ₂ -Ms-C ₆ H ₁₀ -R ₆ and R ₆ = H, especially when Y = - (CH ₂ I ₃ - and X = -NH.

Advantageously, the amphoteric cationic polyelectrolyte, in which the non-neutral monomer units carry predominantly positive charges, is one or more compounds from the group of the following compounds according to the following general formula

R ₅ R * CC-Re C = A

Ra R ₇

j I

C-C-

i

3 ,. • 'S - ¹

 "2

(On)

wherein R ₁ , R ₆ , R ₆ and R ₇ = H

- and / or R ₁ to R ₇

- alkyl and / or

- Aryl, where Rs too

C =

ν 1 R-, - N ⁺ -

Λ

can be, Re and Rg =

- Dog / or

- alkyl and / or

- Aryl can be; Rg or Re too

OH

can be, if

- C

.0

OH

X = O and / or N-H

Y = -CH ₂ -to-C ₆ H ₁₀ -

Z = - C

OH

and or

- C

OH

and or

- (CH ₂ )., -

O ff

S = O

and or

and or

may be an acidic phosphoric acid ester group, a = 70-99 mole% b = 1-30 mole% η * = 1-18

and (An) ^- = chloride and / or bromide and / or iodide and / or HSU ₄ "and / or CH ₃ SO ₄ ^- and / or nitrite.

It is particularly advantageous that the amphoteric cationic Polyeiektroiyt a compound according to this general formula

is, where

R, = Hoder-CH ₃ R ₂ = -CH ₃ OdOr-C ₂ H ₆ R ₃ = -CH ₃ or-C ₂ H ₆

R ₄ = -CH ₃ DiS-C ₄ H ₉ and isomers

X = 0 or N-H

Y = -CH ₂ - to-CsHur-

R ₆ and R ₈ = HR, = Hoder-CH ₃ R ₈ and R ₃ = H.

It is particularly advantageous if (An) "= Cl" and Y = - (CHj) ₃ -.

It is furthermore advantageous if the anionic partially neutralized polyelectrolyte is one or more compounds from the group of the following compounds according to the following general formula

-i

C - C! - | Ka

ft ₃ z

r j

O

J ₁ -.

^z = - C or - (CHJ _n - C ^

^{X 0H} ^ OH

and or

O 1-0

and or

"\ ί ¹ O / - ^{s = 0} and / or

an acid phosphoric ester group R ₁ = -H or -CH ₃

R ₂ and R ₃ = -H and / or alkyl and / or aryl wherein R ₂ or R _{3 may} also be Z, if

^N 0H

u = +1 and / or +11 and / or +111

Ka - alkali and / or alkaline earth and / or Erdmetallion

w = 59 to 95 mol% per number Z in the monomer

ν = 5 to 41 mol% divided by u

η = ·· 1-12.

Furthermore, it is advantageous that the partially neutralized anionic polyelectrolyte is a mixture of one or more of the homopolymers and / or copolymers of compounds according to this general formula.

It is also advantageous that the amphoteric anionic partially neutralized polyelectrolyte in which the non-neutral monomer units carry predominantly negative charges, ^e: is ne or more compounds from the group of compounds represented by the following general formula:

C-

S ₃

wherein R ₁ , R ₆ , R ₆ and R ₇ = H

- and / or Ri to R ₇

- alkyl and / or

- Aryl, where R ₆ also

C =

I Λ

R ₂ - A + - R.

can be, R ₈ and R ₉ =

- H and / or

- alkyl and / or

- Aryl can be; R ₈ or R ₉ too

OH

can be, if

- C

OH

X = O and / or NH Y = -CHr-bis-C ₆ H ₁₀ -

Z = - C

OH

(On)" L. Α. «Ι χ t j i ι

R-

C-C

and or

- (CH ₂ J _n -C

OH

and or

O // S = O

OH

and or

and or

may be an acidic phosphoric ester group.

a = 1-30ΜοΙ-% b = 70-99 mole% η = 1-18

and (on) "= chloride and / or bromide and / or iodide and / or HSO ₄ "

and / or CH ₃ SO ₄ "and / or nitrite.

It is particularly advantageous that the amphoteric anionic teilneutraüsierte polyelectrolyte one or more compounds

according to this general formol, wherein R, = Hoder-CH ₃ R ₂ = -CH ₃ or -C ₂ H ₆ R ₃ = -CH ₃ or-C ₂ H ₆ R ₄ = -CH ₃ to -C ₄ K ₉ and isomers X = O or NH Y = ^ H ₂ -Ws-C ₆ H ₁₀ -R ₆ and R ₆ = HR ₇ = H or -CH ₃ R ₈ and R ₉ = H,

It is particularly advantageous if (An) "= Cl" and Y = - (CH ₂ ); -.

A further favorable embodiment of the invention is that the anionic partially neutralized polyelectrolyte is a homopolymeric copolymer and that the amphoteric anionic partially neutralized polyelectrolyte in which the nonneutral monomer units carry predominantly negative charges has one carboxyl group and / or sulphonic acid group and / or acidic phosphoric acid ester group-containing partially neutralized anionic polyelectrolyte.

In particular, it is favorable that the partially neutralized anionic polyelectrolyte is a teueneutralized polyacrylic acid and / or a partially neutralized polymethacrylic acid and / or a partially neutralized copolymer thereof.

Advantageously, in the anionic partially neutralized polyelectrolyte and the amphoteric anionic partially neutralized polyelectrolyte, only a statistical portion of the acid groups are neutralized with a monovalent and / or polyvalent cation.

Conveniently, as cations alkali and / or alkaline earth and / or Erdmetallkationen and / or amines and / or alkanolamines and / or quaternary ammonium cations are used, in particular advantageous as cations Na ⁺ and / or K ⁺ and / or Li ⁺ and or NH ₄ ⁺ and / or Ca ²⁺ and / or Mg ²⁺ and / or Sr ²⁺ . Very particularly good results are obtained when alkali cations and / or alkaline earth cations are used as cations, in particular alkali cations and in particular Na ⁺ . NH ₄ ⁺ is particularly unsuitable because it causes excessive odor nuisance and

Health harm leads.

Dispersants which are particularly suitable according to the invention are mixtures according to the general formulas of claim 14 and / or the amphoteric cationic polyelectrolytes of claim 15 and of claim 16 and / or

amphoteric anionic partially neutralized polyelectrolytes of claim 15.

Particularly favorable is a dispersant mixture according to the following general formula

** Γ *. (Απ "} t j I i I i ι η · · \\ ν. Γ. 2/3 ~ ί 3 C - Λ · - C H 2

r -

C -

C: ·

:! j ill

C-C i ρ C-C r-

! I ι! ! i

H C = O j F. C = O ί

ι ι

! ι Λ ·

ζ (cat)

(Cat) ⁺ = alkali and / or alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or

quaternary ammonium cations (An) "= chloride, bromide.iodide, HSO ₄ ", CH ₃ SO ₄ "and / or nitrite

a = 60-99 mol%

b = 1-40 mol%

ζ = 1-70 mol%

w = 30-99 mol%.

Particularly advantageous dispersant mixtures according to this general formula, wherein (KaO ⁺ = alkali and / or Eidalkalikationen (An) "= chloride, Bromid.Jodid, HSO ₄ ", CH ₃ SO ₄ "and / or nitrite

a = 80-98 mol%

b = 2-20 mol%

ζ = 2-50 mol%

w = 50-98 mole%.

Also advantageous are dispersant mixtures according to this general formula, where (Kat) ⁺ = Na ⁺ , K ⁺ , Li ⁺ , Ca ²⁺ , Mg ²⁺ , and / or Sr ²⁺ (An) "= chloride, bromide, iodide, HSO ₄ ", CH ₃ SO ₄ " and / or nitrite

a = 85-97 mol%

b = 3-15 mol%

ζ = 3-30 mol%

w = 70-97 mol%.

Very particularly favorable results are achieved when the dispersant mixture is a mixture of this general formula, wherein

(KaD ⁺ = alkali ion (An) "= halogen ion

a = 90-96 mol%

b = 4-10 mol%

ζ = 4-20 mol%

w = 80-96 mol%.

Excellent results are achieved when the dispersant mixture is a mixture according to this general formula, wherein

(KaD ⁺ = Na ⁺ (An) "= Cl"

a = 95 mol%

b = 5 mol%

z = 5 mol%

w = 95 mol%.

Advantageously, the anionic polyelectrolyte and / or the amphoteric anionic polyelectrolyte with alkali, and / or alkaline earth and / or earth metal cations and / or amines and / or Aikanolaminen and / or quaternary ammonium cations are partially neutralized, in particular alkali and / or Alkaline earth cations, especially alkali cations and in particular Na ⁺ cations are suitable.

Conveniently, the anionic polyelectrolyte and / or the amphoteric anionic polyelectrolyte 1 to 70 mol% of the acid groups are neutralized. Particularly favorable results are achieved when 2 to 60 mol%, especially when 3 to 30 mol% of the acid groups are neutralized, with a degree of neutralization of 5MoI-% to 10 mol% achieved best results.

Non-neutralized polyacrylic acid is unsuitable because it begins to crystallize at + 2O ⁰ C and thus is no longer dosed.

Once the crystallization has occurred, the polymer solution must be heated to 100 ⁰ C, so that the crystals are redissolved.

In winter and in colder regions, production with non-neutralized polyacrylic acids is unthinkable.

It is advantageous that the specific viscosity "Eta" of the partially neutralized anionic polyelectrolyte and / or the

amphoteric anionic polyelectrolytes in the mixture with the cationic and / or the amphoteric cationic

Polyelectrolyte, measured in the full salt form, is between 0.2 and 1.0. It is particularly advantageous that "Etd" is between 0.35 and 0.6 and it is particularly favorable if "Eta" is 0.55.

It is advantageous that the degree of polymerization of the cationic polyelectrolyte and / or the amphoteric cationic

Poiyelektrolyten in the mixture with the partially neutralized anionic polyelectrolyte and / or the amphoteric

anionic partially neutralized polyelectrolytes, measured over the intrinsic viscosity, in the range of 5 ml / g to 50 ml / g.

Very particularly advantageous is a degree of polymerization in the range of 15 ml / g to 40 ml / g, with a range of i5 ml / g to 35 ml / g being particularly preferred.

Advantageously, the dispersant mixture consists of

70-98% by weight of cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte and 2-30% by weight of anionic partially neutralized polyelectrolyte and / or amphoteric partially neutralized anionic polyelectrolyte.

Further advantageous may be a dispersant mixture

75-95 wt .-% of the cationic polyelectrolyte according to the invention and 5-25 wt .-% of the anionic polyelectrolyte according to the invention can be used. Also suitable are dispersant mixtures comprising 80-90% by weight of the cationic polyelectrolytes according to the invention and 10% to 20% of the anionic polyelectrolytes according to the invention. Dispersing agent mixtures of 80 or 90% by weight of the cationic polyelectrolytes according to the invention and 20 or 10% by weight of the anionic polyelectrolytes according to the invention are very particularly advantageously suitable.

Advantageously, the mixing ratio of cationic polyelectrolyte to amphoteric cationic polyelectrolyte in admixture with the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte is 0-100 wt% cationic polyelectrolyte and 100-0G6w% amphoteric cationic polyelectrolyte. Further preferred is a mixing ratio of 0 to 30% by weight of cationic polyelectrolyte and 70 to 100% by weight of amphoteric cationic polyelectrolyte, in particular a mixing ratio of 0 to 20% by weight of cationic polyelectrolyte and 80 to 100% by weight of amphoteric cationic polyelectrolyte.

Preferably, the molar composition of the individual components in the partially neutralized anionic polyelectrolyte in the mixture with the cationic and / or amphoteric cationic polyelectrolyte is between 100% by mole acrylic acid and 100% by mole to 0% by mole of other monomers. The other monomers are advantageously carboxyl group-containing and / or containing sulfonic acid groups and / or acidic phosphoric ester groups.

It is particularly favorable that the molar composition of the individual components in the partially neutralized anionic amphoteric polyelectrolyte in the mixture with the cationic and / or amphoteric cationic polyelectrolytes is between 0 mol% to 99 mol% acrylic acid and 100% to 1 mol% of other monomers.

Very particularly favorable results are achieved if the other monomers contain carboxyl groups and / or containing sulfonic acid groups and / or acidic phosphoric ester groups and / or one or more compounds from the group of compounds according to the general formula of claim 6.

It is particularly advantageous that the anionic polyelectrolyte is partially neutralized acrylic acid. Advantageously, 2-80 mol% of the acid groups of the anionic glycolysis electrolyte are neutralized, more preferably 3 to 70 mol%, and most preferably 3 to 10 mol% of the acid groups.

According to the invention, the minerals or fillers or pigments in particular contain elements from the second and / or third main group and / or from the fourth subgroup of the periodic table of the elements. Conveniently, calcium- and / or siliceous and / or alumium-containing and / or titanium-containing minerals and / or fillers and / or pigments are used, calcium carbonate salts and / or fillers and / or pigments being preferred. Very particular preference is given to natural calcium carbonate and / or precipitated calcium carbonate and / or marble and / or circles and / or dolomite and / or dolomite-containing calcium carbonate.

The aqueous suspension preferably consists of 97.0 wt .-% to 93.89 wt .-% minerals and / or fillers and / or pigments and water and 0.11 wt .-% - 3.0Gew .-% of a mixture of cationic and or amphoteric cationic and partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte, at a solids content of 60-80Gew .-%, based on the dry mineral or the dry filler or the dry pigment.

It is further favorable that the aqueous suspension of 98.5 wt .-% to 99.8Gew .-% minerals and / or fillers and / or pigments and water and 0.2Gew .-% - 1, üGow .-% of a Mixture of cationic and / or amphoteric cationic and partially neutralized and / or amphoteric cationic and partially neutralized amphoteric anionic Pclyelektrolyt, at a Feststoffgehali of 60-75Gew .-%, based on dry mineral or the dry filler or the dry pigment exists.

Furthermore, good results are achieved when the aqueous suspension of 99.2% by weight to 99.65% by weight of minerals and / or fillers and / or pigments and water and 0.35% by weight of O, 8% by weight a mixture of cationic and / or amphoteric cationic and partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte, at a solids content of 60-70 wt .-%, based on that dry mineral or the dry filler or

the dry pigment exists.

Excellent results are obtained when the aqueous suspension consists of 99.6Gew .-% and 99.05Gew .-% or

99.1 wt .-% minerals and / or fillers and / or pigments and water and 0.4 wt .-% or 0.95 wt .-% or 0.9Gew .-% of a mixture of cationic and / or amphoteric cationic and partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte, at a solids content of 67% by weight and 67% by weight, respectively

-46-? 97 920

60 wt .-%, based on that dry mineral or the dry filler or the dry pigment, in a Koniveriöilung, so that 60 wt .-% or 70 wt .-% and 90 wt .-% of the particles an equivalent spherical diameter 2pm. Advantageously, the anionic polyelectrolyte and / or amphoteric anionic polyelectrolyte is partially neutralized in the mixture with the cationic and / or amphoteric cationic polyelectrolyte with a mono- and / or polyvalent cation. Particularly good results are achieved when the anionic polyelectrolyte and / or amphoteric anionic polyelectrolyte in the mixture with the cationic and / or amphoteric cationic polyelectrolyte with alkali metal cations and / or amines and / or alkanolamines and / or quaternary ammonium compounds, in particular abar is partially neutralized with Na ⁺ and / or Ca ²⁺ and / or Mg ²⁺ .

The intrinsic viscosity of the cationic and / or amphoteric cationic polyelectrolytes used in the aqueous suspension is preferably in the range between 9.2 ml / g and 48.5 rH / g, but more preferably in the range between 16.2 ml / g and 31.2 ml / g.

Another preferred embodiment of the method according to the invention is characterized by the following method steps:

a) an aqueous suspension of minerals and / or fillers and / or pigments is wet-ground together with the dispersing and Mahlhilfsmittelmischung invention, wherein

b) a part of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte before grinding and

c) a part of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte during the milling and / or

d) a part of the partially neutralized anionic and / or toileutraüsierten amphoteric anionic polyelectrolyte after milling,

e) and the cationic and / or amphoteric cationic polyelectrolyte completely before grinding or only

f) a part of the cationic and / or amphoteric cationic polyelectrolyte before grinding and

g) adding a portion of the cationic and / or amphoteric cationic polyelectrolyte during milling and / or h) a portion of the cationic and / or amphoteric cationic polyelectrolyte after milling.

Particularly advantageous is a method in which

a) 10-90% by weight of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte before milling and

b) 10-90% by weight of the partially neutralized anionic and / or partially amitrified amphoteric anionic polyelectrolyte during milling and / or

c) 0-80% by weight of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte after milling,

d) 50-100Gew .-% of the cationic and / or cationic amphoteric polyelectrolyte before grinding and

e) 0-50% by weight of the cationic and / or cationic amphoteric polyelectrolyte during milling and / or

f) 0-50 wt .-% of the cationic and / or amphoteric cationic polyelectrolyte are added after grinding.

Good results are achieved when a method is used in which

a) 20-40Gew .-% of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte before grinding and

b) 60-80 wt .-% of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte during the milling and / or

c) 0-20% by weight of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte after milling,

d) 50-100Gew .-% of the cationic and / or cationic amphoteric polyelectrolyte before grinding and

e) 0-50% by weight of the cationic and / or cationic amphoteric polyelectrolyte during milling and / or

f) 0-50% by weight of the cationic and / or amphoteric cationic polyelectrolyte are added after the milling.

Very good results are achieved when a method is used in which

a) 25-35 wt .-% of teilneutrdlisierten anionic and / or partially neutralized amphoteric anionic polyelectrolyte before grinding and

b) 65-75% by weight of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte during milling and / or

c) 0-10 wt .-% of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte after milling, and

d) 70-100Gew .-% of the cationic and / or cationic amphoteric polyelectrolyte before grinding and

e) 0-30% by weight of the cationic and / or cationic amphoteric polyelectrolyte during milling and / or

f) 0-30% by weight of the cationic and / or amphoteric cationic polyelectrolyte are added after the milling.

Excellent results are achieved in an ancestor, wherein

a) 30 wt .-% of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte before grinding and

b) 70% by weight of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte during milling and

c) 100% by weight of the cationic and / or cationic amphoteric polyelectrolyte are added before the premilling.

According to the invention, the use of the aqueous suspension of minerals and / or fillers and / or pigments in papermaking or in paper production. Further uses relate to the surface treatment (pigmentation of the paper surface in the size press of the paper machine, the use in the Papierstreicherei, in the pre-coat or top coat in Papierstreicherei, in groundwood for Störstoffbekämpfung, in the Streichereiausschuß for Störstoffbekämpfung (pitch control), in the circulation water of the paper machine for COD -Reduction (reduction of chemical oxygen demand), in the sewage treatment plant for wastewater treatment, for pre-flocculation of anionically stabilized pigment and / or mineral and / or filler suspensions in paper production or for preflocculation (immobilization) of coating colors in the coating.

According to the invention, it has been possible to produce a mineral and / or filler and / or pigment suspension by grinding at high solids contents of 60% by weight, at which the mineral and / or filler and / or pigment particles are both electrostatically positive and likely are sterically stabilized and the suspension remains viscous stable for weeks and z. B. the retention in papermaking is excellent.

Surprisingly and not foreseeable is the fact that in the appropriate combination of one or more cationic polyelectrolytes and / or one or more amphoteric cationic polyelectrolytes and one or more partially neutralized anionic polyelectrolytes and / or one or more amphoteric anionic partially neutralized polyelectrolytes and the appropriate addition site of the polyelectrolytes before, during and / or after the grinding process, at the high shear forces and temperatures, as they occur in wet milling, no mutual neutralization of the oppositely charged polymers and thus coagulation of the polymers occurs. In contrast, optimal grinding and stabilization of the suspension is effected by the anionic polyelectrolytes of the invention

a) presumably act as a bridging agent between the mineral and / or filler and / or pigment particles and the cationic and / or amphoteric cationic polyelectrolytes according to the invention, the cationic and / or pigmentary surface thus fixed on the mineral and / or filler surface and / or or amphoteric cationic polyelectrolyte gives a positive charge to the mineral and / or filler and / or pigment particles and thereby leads to an electrostatically positive stabilization of the system, and

b) According to the invention, by further additions of the anionic polyelectrolytes according to the invention during and / or after milling, these presumably act as bridging agents between the cationic polymer chains of the cationic and / or amphoteric cationic polyelectrolyte, presumably resulting in a superstructure containing the mineral and / or filler and / or pigment particles sterically stabilized, which leads to a much lower, stable viscosity at hc concentration, as if the entire amount of inventive anionic polyelectrolyte is added at the beginning of grinding.

Surprising and unpredictable is also the fact that the degree of neutralization of the inventive

anionic polyelectrolytes with mono- and / or polyvalent cations has a decisive influence on the storage stability of the mineral and / or filler and / or pigment suspension, d. H. on the viscosity constant of the suspension over the

When using 100 mol% sodium neutralized anionic polyol electrolyte, as in the examples of the The viscosity increases strongly over time, so that the suspension becomes unusable. When using an inventively partially neutralized with monovalent and / or polyvalent cations anionic Polyelectrolytes and / or partially neutralized amphoteric anionic polyelectrolytes, however, the viscosity remains

stable for days to weeks in proportion to the degree of neutralization. The lower the degree of neutralization with monovalent cations, the better the storage stability. Most suitable are degrees of neutralization of 5-10 mol%. Multi-valued cations, like

Calcium and / or magnesium have a smaller negative influence on the storage stability. In non-neutralized anioric polyelectrolytes, especially in polyacrylic acid, the problem arises that a

usually 40 wt .-% aqueous polymer solution is very highly viscous and normally has a crystallization temperature above 0 ° C. Polyacrylic acid already crystallizes at 20 ° C. This leads to problems with the dosage, especially in cold

Seasons and especially in Scandinavia. This results in an irregular dosage that is too large Viscosity variations in the produced mineral and / or filler and / or pigment suspensions leads. However, this is not the case with the anionic polyelectrolytes according to the invention. A good storage stability in terms of viscosity and settling behavior is especially in transport and large Storage tanks of crucial importance to prevent spoilage of the goods. With the invention produced Mineral and / or filler and / or pigment suspension, it is possible to determine the place of production (production location of the mineral

and / or filler and / or pigment suspension) as well as the consumer location (eg paper mill). The

Production location can thus the geological occurrence of mineral and / or filler and / or pigment deposits

be adapted, and it must not be included for purely logistical reasons, the location of the customer.

An aqueous suspension of minerals and / or fillers and / or pigments having a solids content a 60% by weight,

based on the dry minerals and / or fillers and / or pigments, is prepared according to the invention by grinding a coarse crushed rock, wherein a combination of a teilneutralistarten anionic and / or teilneutralisierten amphoteric anionic polyelectrolyte and a cationic and / or amphoteric cationic

Polyelectrolyte is used in such a way that the whole or a part of the cationic and / or the amphoteric

cationic polyelectrolytes and only part of the partially neutralized anionic polyelectrolyte and / or neutral-neutralized amphoteric anionic polyelectrolyte are added at the beginning of the grinding and further parts of the anionic polyelectrolytes according to the invention are added during the grinding and / or after the grinding to reduce the viscosity.

Although the cationic and / or amphoteric cationic polyelectrolyte is present in excess and thereby a

positive charge on the mineral and / or filler and / or pigment particles, further addition of the anionic and / or amphoteric anionic polyelectrolyte of the present invention during grinding and / or after milling causes an unforeseen tremendous viscosity reduction.

In the partial neutralization according to the invention of the anionic and / or amphoteric anionic polyelectrolyte with a

and / or polyvalent cations results in 'a very stable viscosity over several weeks. This effect could be achieved with no prior art system.

In the Tochnik prior art examples, milling had to be stopped before the mill had reached its desired level Fineness to be canceled. The blocking of the mill came by a huge increase in viscosity during grinding

conditions.

The increase in viscosity presumably stems from the fact that normally cationic polymeric polyelectrolytes with polymeric

anionic polyelectrolytes under Ρλί:; ^ -ig react with each other and neutralize each other and fail. ! In of the inventive Po yelek. '!'. ^R H _v -iko ,, i :: in ".. i and the addition points invention this occurs surprisingly not, but one does not occur ' - .. "Jug explainable strong viscosity reduction. The anionic and / or amphoteric anionic polyelectrolyte according to the invention, which has been added without difficulty during the grinding and / or η, does not have a charge-neutralizing effect on cationic and / or amphoteric cationic polyelectrolytes, as might actually be expected

The ideal particle size distribution, concentration and low viscosity of the mineral water for the users, especially the paper industry.

and / or filler and / or pigment suspensions can be prepared by the process of the invention in one operation, which represents tremendous economic and qualitative progress.

Preferably, the concentration of the aqueous slurry is 60-70% by weight, based on the dry mineral.

Preferably, the raw material before the grinding process according to the invention has a mean equi-talient spherical particle diameter of 10-50 μm (measured on the Sedigraph 5100).

During grinding, therefore, it is believed that the anionic and / or amphoteric anionic polyelectrolyte of the present invention, which has a chemical property to the newly formed surface of the mineral and / or filler and / or pigment during milling, serves as a bridging agent between the mineral and / or filler and / or Pign int and the cationic and / or amphoteric cationic polyelectrolyte. The cationic and / or amphoteric cationic polyelectrolyte thus sufficiently fixed gives the mineral and / or filler and / or pigment a positive charge. In addition, the anionic and / or amphoteric anionic polyelectrolyte according to the invention having the chain length according to the invention which is added in further steps to the mineral and / or filler and / or pigment suspension probably acts as a bridging agent between the polymer chains of the cationic and / or amphoteric cationic polyelectrolyte. which leads to larger polymer chain assemblies, which presumably additionally sterically stabilize the mineral particles.

During the grinding serves the cationic and / or amphoteric cationic polyelectrolyte, which, supported by the anionic and / or amphoteric anio tables according to the invention polyelectrolytes, presumably raises to the mineral and / or filler and / or pigment surface, as a positive charge carrier and stabilized so the mineral and / or filler and / or pigment particles positive.

By suspected bridge formation between the anionic and / or amphoteric gnionic polyelectrolyte according to the invention and the cationic and / or amphoteric cationic polyelectrolyte, steric stabilization of the mineral and / or filler and / or pigment partchain is presumably effected.

Suitable mixtures of the anionic and / or amphoteric anionic polyelectrolyte according to the invention and the cationic and / or amphoteric cationic polyelectrolyte before milling are according to the invention: partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte to cationic and / or amphoteric cationic polyelectrolyte = 1:10 to 1: 40

preferably for marble 1:12

for Champagnerkrjide 1:30.

During and / or after grinding, depending on the concentration and the desired final viscosity, partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte are added again. Preferably about twice as much as before the grinding.

Other examples of the invention Example 11 As Example 1 a (prior art), but partially neutralized polyacrylic acid as Example 12.

Viscosity in mPas after hours. 1 day 16 days

144 152 280

Example 11 clearly shows that, in contrast to example 1a (prior art), a substantially better storage stability over several weeks is achieved with a partially neutralized polyacrylic acid.

Example 12

A 70% by weight aqueous slurry of natural marble having a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100) was 0.33% by weight on the dry marble, the following copolymer (amphoteric, cationic polymer),

,; i C - "" ί i i HC - j I ι I H ₃ C - ^ - T - CH ₃

i!

CH

'- = : · '. \ Zl ~ k Limit Vis: -: csität (27.3 -], 'c

and with 0.06Gew .-%, rel. on the dry marble, with sodium hydroxide partially neutralized polyacrylic acid (10 mol, the carboxyl groups neutralized) of various specific viscosities resp. Dispersed molecular weights with vigorous stirring (8000 U / min, Rührscheibedurchmosser 50 mm).

The aim of this series of experiments was to determine the optimum specific viscosity or the molecular weight of the teilneuiralisiefien anionic polyelectrolyte.

spec. Viscosity of Viscosity of partially neutralized polyacrlate suspension 0.20 2640mPas 0.35 370mPas 0.54 350mPas 0.71 1420mPas

The optimal spec. Viscosity of the partially neutralized polyacrylates is 0.35-0.54.

Example 13

A 67% by weight aqueous slurry of natural marble with a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100) was 0.33% by weight, reported , on the dry marble of the copolymer of Example 12, but with different intrinsic viscosities resp. Molecular weights, and 0.06Gew .-%, rel. on the dry marble, the partially neutralized polyacrylate of Example 12 with the spec. Viscosity of 0.35 with vigorous stirring dispersed (8000U / min, stirrer diameter 50mm).

Intrinsic viscosity of the viscosity of the suspension

cationic copolymer 1 hour after dispersing

9.2 ml / g 730mPas

12.8 ml / g 500mPas

15.5 ml / g 350mPas

16.2 ml / g 156mPas

31.2ml / g 112mPas

48.5 ml / g 840mPas

The optimum intrinsic viscosity of the cationic copolymer used is between 15 ml / g and 40 ml / g.

Example 14

A 70 wt .-% aqueous slurry of natural marble with a particle size distribution, so that 60Gew .-% of the particles have an equivalent spherical diameter <2μηι (measured on the Sedigraph 5100), were with 0.33Gew .-%, rel. on the dry marble, the copolymer of Example 12 and 0.06Gew .-%, rel. on the dry marble, polyacrylic acid (specific viscosity 0.35) with a different degree of neutralization of the carboxyl groups with sodium hydroxide, with vigorous stirring dispersed (8000 U / min, 50 mm stirring disc diameter).

Degree of neutralization to Viscosity of the suspension to to the carboxyl groups 1 H. to 12Tg. 18Tg. the polyacrylic acid 148mPas 6TG. 1560mPas > 3,000 m pas 100 mol% neuter. 128mPas 640mPas 1075mPas 1420mPas 70Mol-% neuter. 112mPas 350 mPas 720mPas 1075mPas 50 mol% neuter '. 112mPas 176mPas 460mPas 720mPas 3CMol-% neuter. i12mPas 172mPas 172mPas 156mPas 10 mol% neuter. 128mPas

The best long-term stability is achieved with a polyacrylic acid in which 5-10% by mole of the carboxyl groups are neutralized.

-50- 297 92D

Bet game 15

A 70% by weight aqueous slurry of natural marble having a grain distribution such that 60% by weight of the particles have an equivalent spherical diameter <2μσι (as measured on the Sedigraph 5100) was 0.33% by weight, reported , on dry marble, various percent molar compositions df «! Copolymers of Example 12 and 0.06Gew .-%, rel. on the dry marble, the partially neutralized polyacrylates (specific viscosity 0.35, from Example 12) with vigorous stirring dispersed (8000U / min, stirrer diameter 50mm).

Mol% cationic Mole% anionic Viscosity of the suspension monomer monomer after 1 hour 80 mol% 20 mol% 680mPas 87 mol% 13 mol% 580 mPas 95Mol -.% 5 mol% 172mPas 100 mol% 0 mole% 420mPas

The optimum monomer composition of the cationic polyelectrolyte is 95 mole percent cationic compound and 5 mole percent anionic compound.

Example 16

A 67 wt% aqueous slurry of natural marble having an equivalent spherical mean particle diameter of 12μπι (as measured on the Sedigraph 510C) was made with the following formulation in a Dynomill (0.61 grind container) using glass grindings (δ 1 mm ) to a grain distribution curve so that 60% by weight of the particles had an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100).

Recipe 5000g marble

15 g amphoteric, cationic polymer according to the formula of Example 12

1.35 g polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH, before the grinding added 3.15 g polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH while grinding added 2472g of water

Viscosity: after 2 hours 1 day 5 days 10 days 20 days 200 116 148 104 104 mPas

In Example 16, can be clearly seen that produced in the inventive type and combination of anionic and cationic polyelectrolyte a very deep ^one and stable for weeks viscosity even at by grinding! One-piece mineral and / or filler and / or produce pigment suspensions ,

Example 17

A 67% by weight aqueous slurry of champagne chalk having an equivalent spherical mean particle diameter of 12μιη (as measured on the Sedigraph 5100) was coated with the following formulation in a Dynomill (0.6 ℓ grinding bowl) using glass (01mm) grinding media a grain distribution curve so that 67% by weight of the particles had an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100).

recipe

5000g champagne chalk

25 g amphoteric, cationic polymer from Example 12

0.5 g of polyacrylic acid (specific viscosity 0.64) 5 mol% of the carboxyl groups neutral with NaOH, before the grinding added 2472 g of water

Viscosity in mPas

after 1 hour 1 day 5 days 10 days 20 days

2400 3900> 5000

2.5 g polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH, 5 min after grinding with intensive stirring added (8000U / min, stirring disc diameter 50 mm)

Viscosity in mPas

after 1 hour ITag 5days 10days 20 days

235 230 200 200 210

In Example 17 it can be clearly seen that a subsequent addition of the anionic polyelectrolyte according to the invention results in an enormous reduction in viscosity and that the viscosity remains stable for weeks.

Example 18

A 60 wt% aqueous slurry of natural marble having an equivalent spherical mean particle diameter of 12 μm (measured on the Sedigraph 5100) was coated with the following formulation in a Dynomill (0.61 grind container) using glass grindstones (01 mm ) to a grain distribution curve so that 88% by weight of the particles had an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100).

Rezoptur5000g marble 40g amphoteric, cationic polymer from example 1.35g polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH, added before the grinding.

2.65 g of polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH, during the grinding added 3363 g of water

Viscosity: after 1 hour 1 day 4 days 8 days 11 days 500 520 400 400 390 mPas

Even very high finenesses, such as those used in coating formulations, can easily be produced by grinding coarsely crushed raw rock at high concentrations.

Example 19

A 67% by weight aqueous campaign of natural Campagnekreide having an equivalent spherical mean particle diameter of Ιδμιη (measured on the Sedigraph 5100) was made with the following formulation in a Dynomill (0.61 grinding container) using glass (01mm) grinding media a grain distribution curve, so that 67 wt .-% of the particles have an equivalent spherical diameter <2μιη (measured on the Sedigraph 5100) ground.

recipe

5000 g chempagn chalk37.5 g amphoteric, cationic polymer from example 1.35 g polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH, before the grinding added 7.65 g polyacrylic acid (specific viscosity 0.54), 5 Mol% of the carboxyl groups neutral with NaOH during milling

added2486g of water

Viscosity: after 1 hour 1 day 4 days 7 days

212 170 132 124mPas

Belsplol 20

On the pilot plant scale, the natural marble used in Example 16 became a vertically arranged pearl millet

(Süßmeier with 1801 content) with grinding media of glass (0 1-2 mm) on a particle size distribution curve, so that 63 wt .-% of the particles an equivalent spherical diameter <2pm (measured on the Sedigraph 5100) at a concentration of 67.6Gew. -%

Have solid, ground. In batches of approx. 600kg 50 to this suspension was produced.

Recipe400 kg marble 1.4 kg amphoteric cationic polymer from example 0.12 kg polyacrylic acid (specific viscosity 0.54) 5 mol% of the carboxyl groups neutral with NaOH, before grinding added 0.24 kg polyacrylic acid (specific viscosity 0.54) 5 mol% of the carboxyl groups neutral with NaOH, added during the milling

197 kg of water

The hourly output of the pearl millet was 500 l slurry / hour.

Viscosity: after 1 hour 1 day 7 days 14Tsge 21 days cP 230 230 150 150 160

Example 21

On the pilot plant scale, the marble used in Example 16 was placed in a vertically arranged bead mill (1801 content sweetener) with glass frits (01-2 mm) on a grain distribution curve such that 70 wt% of the particles had an equivalent spherical diameter <2pm (measured on the Sedigraph 5100), milled at a concentration of 70.6 wt%. In Betches of about 600kg 4to this slurry were produced.

Recipe 400 kg marble 2.0 kg amphoteric cationic polymer from Example 0.12 kg polyacrylic acid (specific viscosity 0.54), 5 mol% of the carboxyl groups neutral with NaOH, before grinding added 0.36 kg polyacrylic acid (specific viscosity 0.54) , 5 mol% of the carboxyl groups neutral with NaOH, added during the milling

168kg of water

The hourly output was 500! Suspension / hour. Viscosity: after 1 hour 1 day 7 days 14 days 21 days

450 420 400 400

Example 22

A 70 wt .-% aqueous slurry of titanium dioxide with a particle size distribution, so that 94Gew .-% of the particles have an equivalent spherical diameter <2μηι (measured on the Sedigraph 5100) were dispersed under strong shear forces (8000U / min, stirring discs 0 50mm ).

Recipe 150Og TiO ₂

7g amphoteric, cationic polymer from Example 12 add 640g of water

Viscosity in mPas

nachiStd. 1 day 10days 20 days

275 - 300 290

Example 23

A 65% by weight aqueous slurry of titanium dioxide having a grain distribution such that 94% by weight of the particles have an equivalent spherical diameter <2 μm (as measured on the Sedigraph 5100) was dispersed under high shear forces (8000 rpm, stirrer discs 0 50mm).

Recipe 125OgTiO,

2g amphoteric cationic polymer from Example 2 add 675g of water

Viscosity in mPas

nachiStd. 1 day 10days 20days

350 370 400 420

Example 24

A 60% by weight aqueous slurry of natural CaSO ₄ with a grain distribution such that 23% by weight of the particles have an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100 anionic) was dispersed under high shear rate (8000 rpm). Stirring discs 0 50mm).

Recipe 100OgCaSO ₄

Add 3.6 g of amphoteric cationic polymer from Example 12 to 670 g of water

Viscosity in mPas

nachiStd. 1 day 10days 20days

350 390 400

Example 25

A 63% by weight aqueous slurry of CaCO ₃ (74.5% slurry from Example 7A) and dry TaCl, of which 47% by weight of the particles have an equivalent spherical diameter <2 μm (measured on the Sedigraph 5100) were dispersed under strong shearing forces (8000 rpm, stirring disks 0 50 mm), so that a 1: 1 mixture of Talc / CaCO ₃ is formed.

recipe

670 g of slurry 74.5% from Example 7 A

549g TaIc dry 91%

2.8 g of amphoteric cationic polymer from Example 12 add 594 g of water

Viscosity in mPas

nachiStd. 1 day 2 days

450 500

example

The marble slurries prepared in Preparation Examples 20 + 21 were tested for their retention in papermaking compared to a marble slurry commonly prepared today with anionic dispersants.

Test conditions:

Fabric: 80% birch suede Milled to 23 ° SR

20% pine sulfate retention aid: 0.05% polyacrylamide (intrinsic viscosity 700ml / g)

Carrying out retention test according to Britt-Jar Company Paper Research Material, SYRACUSE, U.S.A.

1. Add 275ml of 2% fiber suspension (atro 3.63g of fiber and 275ml of water to Britt-Jar jar;

2. Britt-Jar stirrer on 700U / m;

3. 25.4m? Add 5% of mineral and / or filler and / or pigment suspension;

4th to 20see. add the appropriate amount of retention agent;

5. after another 25ssc. Open the drainage path and drain 100 ml of white water.

6. In the screen water, the CaCOa content is determined complexometrically after digestion with HCl or with flame AAS. For other minerals and / or fillers and / or pigments, the white water is filtered through membrane filters, passes through an alkaline melt digestion, eg with NaOH / KOH in the zirconium crucible, into a water-soluble form and in the acidified form Condition determined by AAS Taking into account the respective conversion factors, it is possible to infer the respective minerals and / or fillers and / or pigments.

7. On the registered portion of minerals and / or fillers and / or pigments per 100ml and the determined in the white water content of minerals and / or fillers and / or pigments per 100ml, the filler retention can be calculated.

results:

Products: Filler

First Pass Retention

Anionically stabilized slurry with 60% <2 pm 41.1%

(0.1 B% sodium polyacrylate

spez.Visk.0,35)

Anionically stabilized slurry with 70% <2 \ in 35.3%

(0.3% sodium polyacrylate

spec. Visc. 0.54)

Slurry from Production Example 19 61.9%

Slurry from Production Example 20 67.8%

By using a marble slurry produced by the novel production method according to the invention, a large increase in the filler content is possible without negatively affecting the paper formation, which represents a huge leap in development.

The aqueous suspensions according to the invention and the process according to the invention for their preparation have u. a. following advantages:

In contrast to the processes known to date, it is possible to produce highly concentrated (> 60% by weight) mineral and / or filler and / or pigment suspension by wet milling from coarsely crushed rough stone.

- The suspensions have excellent storage stability at low viscosities.

- In the application arise z. B. great advantages bezüg'xh the filler retention in paper production.

- The grinding and dispersion is possible under high grinding forces and boiling temperature of the water.

Claims (23)

1. Aqueous suspension of minerals and / or fillers and / or pigments having a solids content of 60% by weight, based on the dry mineral or the dry filler or the dry pigment, wherein the mineral or the filler or the pigment dispersant is dispersed with one or more dispersants, characterized in that the dispersant comprises one or more amphoteric polyelectrolytes in which the number of negative charges in the anionic monomer units is equal to the number of positive charges in the canonical monomer units, and which optionally additionally contain neutral monomer units can, and / or one or more cationic polyelectrolytes and / or one or more amphoteric cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges, and / or one or more amphoteric anionic polyelectrolytes in which the non-neutral monomer units predominantly ne carry and / or one or more partially neutralized anionic polyelectrolytes and / or one or more partially neutralized amphoteric anionic Pnlyelektrolyten in which the non-neutral monomer units carry predominantly negative charges, wherein the filler and / or pigment and / or mineral particles wear neutral or positive charge against outside. 2. Aqueous suspension according to claim 1, characterized in that the dispersant one or more amphoteric polyelectrolytes or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric cationic polyelectrolytes or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric, light cationic polyelectrolyte or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric cationic polyelectrolytes and one or more amphoteric anionic polyelectrolytes; or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric, lightly cationic polyelectrolytes and one or more amphoteric anionic ones Polyelectrolytes or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric cationic polyelectrolytes and one or more amphoteric, lei anionic polyelectrolyte or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric, slightly cationic polyelectrolytes and one or more amphoteric, slightly anionic polyelectrolytes or one or more amphoteric cationic polyelectrolytes or one or more amphoteric, slightly cationic polyelectrolytes or a mixture of one or more amphoteric cationic polyelectrolytes and one or more amphoteric anionic polyelectrolytes or a mixture of one or more amphoteric, slightly cationic polyelectrolyte and one or more amphoteric anionic polyelectrolytes or a mixture of one or more amphoteric cationic polyelectrolytes and one or more amphoteric, slightly anionic Polyelectrolyte or a mixture of one or more amphoteric, slightly cationic polyelectrolytes and one or more amphoteric, slightly anionic polyelectrolyte olyten or a mixture of one or more amphoteric polyelectrolytes and one or more amphoteric, slightly anionic polyelectrolytes or one or more amphoteric, slightly anionic polyelectrolytes or one or more cationic polyelectrolytes and one or more amphoteric light cationic polyelectrolytes, wherein one or more of Polyelectrolytes according to the invention are partially neutralized and wherein the filler and / or the pigment and / or mineral particles carry a neutral to the outside or positive charge. 3. Aqueous suspension according to one or more of the preceding claims, characterized in that the amphoteric anionic and the amphoteric and the amphoteric cationic polyelectrolyte carries the positive charge-generating functional group in a substituent of the ethylenic main chain, and quaternary ammonium groups, carboxyl groups and / or sulfonic acid groups and / or containing acid phosphoric acid ester-containing groups and the cationic charge bearing substituent over O H or O - C-N - C-O- is bound to the main chain. 4. Aqueous suspension according to one or more of the preceding claims, characterized in that the amphoteric anionic and the amphoteric and the amphoteric cationic polyelectrolyte one or more compounds from the group of the following compounds according to the following general formula: R ₃ Rx ! I C-C- ! I R ₀ C = O R ₇ I! C - j b R ₃ - Ν ¹ * · - R. (On)" I. - a wherein R ₁ , R ₅ , Re and R _{7 is} preferably H, and / or Ri to R ₇ = - alkyl, preferably a C ₁ -C ₁ B-AllCyI, more preferably C ₁ -C ₆ , optimally -CH ₃ or H and / or - Aryl, preferably a 6-ring, in particular a non-substituted 6-ring may be, R ₈ and Rg = - H and / or - Aryl, preferably a C ₁ -C ₁₈ alkyl, more preferably C ₁ -C ₆ , optimally -CH ₃ or H and / or - aryl, preferably a 6-membered ring, in particular a non-substituted 6-ring, preferably R ₁ = H or CH ₃ R ₂ = -CH ₃ or-C ₂ H ₅ R ₃ = -CH ₃ or-C ₂ H ₅ R ₄ = -CH ₃ to -C ₄ H ₉ and isomers X = O or NH Y = -CH ₂ - to-C ₅ H ₁₀ -R ₅ and R ₆ = HR ₇ = H or -CH ₃ R ₈ and R ₉ = H, R ₈ or Rg also OH can be, if ζ = X = O and / or NH Y = -CH ₂ -bis-C ₅ H ₁₀ - 0H Z = - C OH - (CH ₂ ) _n - and or , 0 and or OH O
_ (CH ₂ ) _n S = O and / or and or an acidic phosphoric acid ester group and η = 1-18, wherein the substituent Z by 1- and / or 2- and / or 3-valent cations, preferably by alkali metal and / or alkaline earth and / or Erd'metallkationen and in particular advantageous by Ca ⁺⁺ and / or Mg ⁺⁺ and / or Sr ⁺⁺ , wherein Ca ⁺⁺ and / or Mg ^{++ are} preferred, may be partially neutralized, wherein the degree of neutralization of Z in the case of polyvalent cations 1 to 99 mol%, advantageously at 50 to 98 mol%, preferably at 70 to 97 mol% and particularly preferably at 95 mol%, based on Z in b, wherein, in the neutralization with monovalent cations such as K ⁺ and / or Na ⁺ and / or Li ⁺ the degree of neutralization of Z1 to 99 mol%, preferably 1 to 50 mol%, preferably 1 to 25 MoI% and particularly preferably <5mol%, based on Z in b, is, or the -Z is fully neutralized when the cation is 2- and / or 3wertig or it is NH ₄ ⁺ , primary, secondary and / or tertiary amines and / or quaternary ammo or that the substituent Z is not neutralized, and where (An) "= chloride, bromide, iodide, HSO ₄ ", CHaSO ₄ "and / or nitrite may be, and wherein if R ₈ or R _{9 is} not - C, and if the amphoteric anionic polyelectrolytes are used in combination with the amphoteric cationic polyelectrolytes and the particles are thereby neutral or have positive surface charges, a and b in the following ratios: amphoteric amphoteric amphoteric anionic cationic a = 5-49 mol% a = 50 mol% a. = 51-99 mol% b = 51-95 mol% b = 50 mol% b = 49-1 mol% and wherein the following mixtures are also advantageous: amphoteric amphoteric amphoteric anionic cationic a = 47-49 mol% a = 50 mol% a = 51-80 mol% b = 51-53 mol% b = 50 mol% b = 49-20 mol% and where, if R ₈ or R ₉ = - C, and if the OH amphoteric anionic polyelectrolytes are used in combination with the amphoteric cationic polyelectrolytes and the particles are thereby neutral or have positive surface charges, a and b in the following ratios: amphoteric amphoteric amphoteric anionic cationic a = 10-66 mole% a = 66.66 mole% a = 67-99 mole% b = 34-90 mol% b = 33.33 mol% b = 1-33 mol% where η = 1-18 and (An) "may be chloride and / or bromide and / or iodide and / or HSO ₄ " and / or CH ₃ SO ₄ "and / or nitrite, and wherein the following mixtures are also advantageous: amphoteric anionic a = 64-66 mole% b = 34-36 mole% amphoteric a = 66.66 mol% b = 33.33 mol% amphoteric cationic a = 67-90 mol% b = 10-33 mol% and wherein the ratio of anionic charge to cationic charge is in the range of 55:45 to 51:49 mole%, preferably in the range of 45:55 to 49:51 mole%. 5. Aqueous suspension according to one or more of the preceding claims, characterized in that the polyelectrolyte according to the invention are compounds according to the following formula: c - NH <CK _a ) _a H ₃ CS ^ -CH ₃ i CH ₃ (On") Γ! K C - • i I C JOJ- z (cat) ⁺ Z = Valency (cat) j-, and if c = 0, then ζ = 0, and where (Kat) ⁺ = alkali and / or alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or quaternary ammonium cations, preferably Ca ²⁺ , Mg ²⁺ , Na ⁺ , K ⁺ , Li ⁺
(An) "= chloride, bromide, iodide, HSO ^ CHaSOr and / or nitrite, preferably the halide and wherein in the polyelectrolytes according to the invention a and b and c are present in the following proportions, in each case more preferably: amphoteric
slightly anionic a = 49-47 mol% b + c = 51-53 mol% or: amphoteric
slightly anionic a = 49-48 mol% b + c = 51-52 mol% or: amphoteric
light anionic a 49-47 mol% amphoteric a = 50 mol% b + c = 50 mol% amphoteric a = 50 mol% b + c = 50 mol% amphoteric a = 50 mol% b = 0-50 mol% = 51-53 mol% C = 50-0 mol% amphoteric cationic a = 51-80 mol% b + c = 49-20 mol% amphoteric cationic a = 51-70 mol% b + c = 49-30 mol% amphoteric cationic a = 51-80 mol% b + c = 49-20 mol% or: amphoteric
slightly anionic
a = 49-48 mol% b + c = 51-52 mol%
or: amphoteric
slightly anionic
a = 49-48.5 mol%
b + c = 51-51.5 MoI or: amphoteric
slightly anionic
a = 49 mol%
b «51 mol% or: amphoteric
leichtanionisch
a = 49 mol%
b = 51 mol%
c = <1 mol% or: amphoteric
leichtanionisch
a = 49 mol%
b = 2mol%
c = 49 mol% amphoteric a = 50 mol% b = 0-25 mol% c = 25-50 mol% amphoteric a = 50% by mole% b + c = 50% by mole amphoteric a = 50 mol% b = 50 mol% amphoteric a = 50 mol% b = 50 mol% c = <1 mol% amphoteric a = 50 mol% b = 2 mol% c = 48 mol% amphoteric cationic a = 51-70 mol% b + c = 49-30 mol% amphoteric cationic a = 51-60 mol% b + c = 49-40 mol% amphoteric cationic a = 51 mol% b = 49 mol% amphoteric cationic a = 51 mol% b = 49 mol% c = <1 mol% amphoteric cationic a = 51 mol% b = 2 mol% c = 47 mol% 6. Aqueous suspension according to one or more of the preceding claims, characterized in that the degree of neutralization of the anionic component of all polyelectrolytes except the purely cationic in neutralization with alkaline earth cations, especially with Ca ⁺⁺ and / or Mg ⁺⁺ , 0.1-100 Mol%, more preferably 50-100 mol%, and more preferably 70-99 mol%, most preferably 98 mol%, when neutralized with monovalent cations, is 0.1-100 mol%, more preferably 0.1-50 mol%, and preferably 0.1-39 mol% or 0.1-30 mol%, more preferably 0.1-35 mol% or 0.1-25 mol% or 0.1-15 mol%, most preferably <1 mol%, or that the anionic component is not neutralized, when neutralized with divalent cations, especially for Ca ⁺⁺ and Mg ⁺⁺ ,> 90%, and that the degree of polymerization of the amphoteric anionic and the amphoteric neutral and the amphoteric cationic polyelectrolyte, measured by viscosity, is in the range of 5 mPa · s to 15OmPa · s, w the viscosity is more preferably in the range of 15 mPa · s to 10OmPa · s, more preferably in the range of 25mPa · s to 7OmPa · s, and the ratio of the carboxyl groups to the quaternary ammonium groups in the polymer molecule of the amphoteric, lightly anionic polyelectrolytes is 51-53mol% 47-49mol%. 7. Aqueous suspension according to one or more of the preceding claims, characterized in that the aqueous suspension of 97.0Gew .-% to 99.97 wt .-% minerals and / or fillers and / or pigments and water and 0.03 wt .-% - 3.0 wt .-% of amphoteric polyelectrolyte according to the invention at a solids content of 60-80Gew .-%, based on the dry mineral or the dry filler or the dry pigment, or preferably from 98.5 wt .-% to 99.95 wt .-% of minerals and / or fillers and / or pigments and water and 0.05 wt .-% to 1.5 wt .-% of the amphoteric polyol according to the invention at a solids content of 6F-77 wt .-%, based on the dry mineral or the dry filler or the dry pigment, more preferably from 98.8% to 99.90% by weight minerals and / or fillers and / or pigments and water and 0.1% to 1.2% by weight of the invention amphoteric polyelectrolytes at a solids content of 67-76 wt .-%, based on the dry mineral or the dry filler or the dry pigment, and particularly preferably from 99.5 wt .-% or 98.8 wt .-% or 99.6% by weight of minerals and / or fillers and / or pigments and water and 0.5% by weight or 1.2% by weight wt .-% or 0.4Gew .-% of an amphoteric polyelectrolyte having a viscosity of 37 mPa.s at a solids content of 72 wt .-% and 72 wt .-% and 67Gew .-%, based on the dry mineral or the dry filler or the dry pigment, with a particle size distribution such that 70% by weight or 90% by weight or 60% by weight of the particles have an equivalent spherical diameter <2 μm, wherein the minerals or Fillers or pigments in particular comprise elements from the second and / or third main group and / or from the fourth subgroup of the Periodic Table of the Elements, where calcium- and / or siliceous and / or aluminum-containing and / or titanium-containing, but especially calcium carbonate-containing, minerals and / or or fillers and / or pigments are used and in this case natural calcium carbonate and / or precipitated calcium carbonate and / or marble and / or chalk and / or dolomite and / or dolomite-containing calcium carbonate are preferred. 8. Aqueous suspension according to one or more of the preceding claims, characterized in that the dispersant 0 to 100Gew .-% of a first amphoteric polyelectrolyte and 100-0 wt .-% of a second amphoteric polyelectrolyte or a mixture of 0.1 to 99, 9% by weight of one or more amphoteric polyelectrolytes and 99.9 to 0.1% by weight of one or more amphoteric cationic polyelectrolytes or of a mixture of 50% to 99.9% by weight and 80% to 0.9% by weight or 10-50% by weight or 10-30% by weight of one or more amphoteric polyelectrolytes and 0.1 to 50% by weight or 0.1 to 20% by weight or 50 to 90% by weight or 70-90 wt .-% of one or more amphoteric cationic polyelectrolyte or a mixture of 0.1 to 99.9 wt .-% of one or more amphoteric polyelectrolyte and 99.9 to 0.1 wt .-% of one or more amphoteric easily cationic polyelectrolyte or a mixture of 0.1 to 99.8% by weight of one or more amphoteric polyelectrolytes and 0.1 to 99.8% by weight , preferably 0.1 to 49.8% by weight of one or more amphoteric cationic polyelectrolytes and 0.1 to 99.8% by weight, preferably 0.1 to 49.8% by weight, of one or more amphoteric anionic polyelectrolytes or a mixture from 0.1 to 20% by weight of one or more amphoteric polyelectrolyte and from 60 to 79.8% by weight of one or more amphoteric cationic polyelectrolytes and from 0.1 to 20% by weight of one or more amphoteric anionic polyelectrolytes or a mixture thereof 0.1 to 99.8% by weight of one or more amphoteric polyelectrolytes and 0.1 to 99.8% by weight, preferably 0.1 to 49.8% by weight, of one or more amphoteric, lightly cationic polyelectrolytes and 0.1 to 99.8% by weight, preferably 0.1 to 49.8% by weight, of one or more amphoteric anionic polyelectrolytes or a mixture of 0.1 to 99.8% by weight of one or more amphoteric polyelectrolytes and 0.1 to 99.8% by weight, preferably 0.1 to 49.8% by weight, of one or more amphoteric cationic polyelectrolytes and 0.1 to 99.8% by weight, preferably 0.1 to 49.8% by weight, of one or more amphoteric, slightly anionic polyelectrolytes or a mixture of 0.1 to 99.8% by weight of one or more amphoteric polyelectrolytes and 0/1 to 99.8% by weight of one or more amphoteric light cationic polyelectrolytes and 0.1 to 99.8% by weight of one or more amphoteric slightly anionic polyelectrolytes or a mixture of 0 to 100% by weight of a first amphoteric cationic polyelectrolyte and 0 to 100% by weight of a second amphoteric cationic polyelectrolyte or a mixture of 0.1 to 99.9% by weight of a first amphoteric slightly cationic polyelectrolyte and 0.1 to 99.9% by weight of a second amphoteric slightly cationic polyelectrolyte or a mixture of 5C-99.9Gew .-% and 70 to 99.9Gew .-% of one or more amphoteric cationic polyelectrolyte and 0.1 to 50 wt .-% and 0.1 to 30 wt .-% of one or more amphoteric anionic polyelectrolyte or a mixture of 90 to 99.9Gew .-% or 75 to 90Gew .-% or 80Gew .-% of one or more amphoteric cationic polyelectrolyte and 0.1 to 10 wt% b.w. 25 to 10% by weight or 20% by weight of one or more amphoteric anionic electrolyte or a mixture of 80 to 99.9% by weight of one or more amphoteric slightly cationic polyelectrolytes and 0.1 to 20% by weight of one or more amphoteric anionic polyelectrolytes or a mixture of 0.1 to 99.9% by weight of one or more oteric cationic polyelectrolytes and 99.9 to 0.1% by weight of one or more amphoteric slightly anionic polyelectrolytes or a mixture of 50 to 99.9% by weight. % or 70 to 90% by weight or 75% by weight of one or more amphoteric cationic polyelectrolytes and 0.1 to 50% by weight or 10 to 30% by weight, respectively. 25% by weight of one or more amphoteric slightly anionic polyelectrolytes or a mixture of 0.1 to 99.9% by weight of one or more amphoteric light cationic polyelectrolytes and 99.9 to 0.1% by weight of one or more amphoteric slightly anionic ones Polyelectrolytes or a mixture of 0.1 to 99.9% by weight or 50 to 99.9% by weight of one or more amphoteric polyelectrolytes and 0.1 to 99.9% by weight or 0.1 to 50% by weight % of one or more amphoteric, lightly anionic polyelectrolytes, or 0 to 10 wt% of a first and 100 to 0 wt% of a second amphoteric, light, anionic polyelectrolyte. 9. Watery Suspei. Jion according to one or more of the preceding claims, characterized in that the dispersant is a mixture of amphoteric cationic polyelectrolytes and amphoteric polyelectrolytes according to the general formula of claim 5, wherein in the polyelectrolytes according to the invention a and b and c are present in the following proportions: amphoteric amphoteric cationic a = 50 mol% a = 70-99 mol% b + c = 50 mol% b + c = 30-1 mol% amphoteric amphoteric cationic a = 50 mol% a = 75-98 mol% b + c = 50 mol% b + c = 2F ^ 2 mol% prefers: amphoteric amphoteric cationic a = 50 mol% a = 80-97 mol% b + c = 50 mol% b + c = 20-3 mol% furthermore preferred: amphoteric amphoteric cationic a = 50Moi-% a = 9ö-S6Moi-% b + c = 50 mol% b + c = 10-4 mol% especially preferred: amphoteric amphoteric cationic a = 50 mol% a = 95 mol% b-fc = 50 mol% b + c = 5 mol% the dispersant is a mixture of amphoteric slightly anionic and amphoteric cationic polyelectrolytes according to the general formula of claim 5, wherein in the polyelectrolytes according to the invention a and b and c are present in the following proportions: amphoteric
slightly anionic
a = 47 ~ 49mol%
= 51-53mol% better: amphoteric
slightly anionic
a = 48-40 mol%
b + c = 51-52 mol% prefers: amphoteric
leichtanionisch
a = 48.5-49 mol% amphoteric cationic a = 70-99 mol% b + c = 30-1 M oil .-% amphoteric cationic a = 75-98 mol% b + c = 25-2 mol% amphoteric cationic a = 80-97 mol% b + c = 51-51.5 mol% b + c = 20-3 mol%, especially preferred: amphoteric
leichtanionisch
a = 49 mol%
b + c = 51 mol% amphoteric cationic a = 95 mol% b + c = 5 mol% in that the dispersant mixture contains amphoteric cationic and amphoteric light cationic polyelectrolytes according to the formula of claim 5, wherein in the polyelectrolytes according to the invention a and b and c are present in the following ratios: amphoteric
slightly cationic
a = 51-53 mol%
b + c = 49-47 mol% prefers: amphoteric
slightly cationic
a = 51-52 mol%
= 49-48 mol% amphoteric cationic a = 80-97 mol% b + c = 20-3 mol% amphoteric cationic a = 90-96 mol% b + c = 10-4 mol% especially preferred: amphoteric
slightly cationic
a = 51 mol%
b + c = 49 mol% pmphoter cationic a = 95 mol% b + c = 5 mol% 10. Aqueous suspension according to one or more of the preceding claims, characterized in that the aqueous suspension of 97 to 99.89 wt .-% or 98.5 to 99.8 wt .-% or 99.2 to 99, 65 wt .-% and 99.6 wt .-% minerals and / or fillers and / or pigments and water and a dispersant mixture of amphoteric anionic and amphoteric slightly anionic and / or amphoteric and / or amphoteric light cationic polyelectrolyte in the range of 0 , 11 to 3.00 wt .-% or 0.2 to 1.5 wt .-% or 0.35 to 0.8 wt .-% or 0.4 wt .-%, depending on a solids content in the range of 60-80 wt .-%, based on the dry mineral or the dry filler or the dry pigment, the aqueous suspension preferably consisting of 99.6% by weight of minerals and / or fillers and / or pigments and water and 0.4% by weight of a dispersant mixture consisting of 0.35% by weight of an amphoteric cationic polyelectrolyte according to the general formula of claim 5, wherein a = 95 mol% and b = o mol% and c = 0 mol% at an intrinsic viscosity of 27.3 ml / g and 0.1 wt% of an amphoteric polyelectrolyte according to the general formula of claim 5, wherein a = 50 mol% and b = 50 mol% and c = 0 mol%, at a viscosity in aqueous 32% solution of 37 mPas at a solids content of 67% by weight, with 60% by weight of the particles having an equivalent spherical diameter <2 μm. 11. A process for producing an aqueous suspension (slurry), in particular according to one or more of the preceding claims, characterized by the following process steps: a) an aqueous suspension of minerals and / or fillers and / or pigments is wet-ground together with a dispersing and Mahlhilfsmittelmischung in particular according to one or more of claims 1-10, wherein b) the amphoteric polyelectrolytes according to the invention completely before the grinding or c) a part of the amphoteric polyelectrolytes according to the invention before the grinding and d) a part of the amphoteric polyelectrolyte according to the invention during the milling and / or e) a part of the ampholytic polyelectrolytes according to the invention are added after the grinding, or a) the amphoteric, slightly anionic and / or amphoteric polyelectrolytes completely before grinding or b) a part of the amphoteric, not anionic and / or amphoteric polyelectrolytes, preferably 50-100% by weight, particularly preferably 70-100% by weight, before grinding and c) a portion of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes, preferably 0-50 wt .-%, particularly preferably 0-30Gew .-%, during the grinding and / or d) a portion of the amphoteric, slightly anionic and / or amphoteric polyelectrolytes, preferably 0-50 wt .-%, particularly preferably 0-30 wt .-%, after milling be added, or a) the amphoteric and / or amphoteric cationic polyelectrolytes completely before grinding or b) a portion of the amphoteric and / or the amphoteric cationic polyelectrolytes, preferably 50-100Gew .-%, more preferably 70-100Gew .-%, before the grinding and c) a portion of the amphoteric and / or the amphoteric cationic polyelectrolytes, preferably 0-50Gew, -%, in particular 0-30Gew .-%, during the grinding and / or d) a part of the amp'ioteren and / or the amphoteric cationic polyelectrolytes, preferably 0-50 wt .-%, particularly preferably 0-30Gew .-%, after the grinding be added, or a) the amphoteric cationic polyelectrolytes completely before grinding or b) a portion of the amphoteric cationic Poiyelektrolyten, preferably 50-100Gew .-%, particularly preferably 70-100Gew .-%, before the grinding and c) a portion of the amphoteric canonical polyelectrolytes, preferably 0-50 wt .-%, particularly preferably 0-30Gevv .-%, during the grinding and / or d) a portion of the amphoteric cationic polyelectrolytes, preferably 0-50% by weight, particularly preferably 0-30% by weight, after the milling be added, or a) a portion of the amphoteric, slightly cationic and / or amphoteric and / or amphoteric, slightly anionic Polyelektroiyten, preferably 10-90Gew .-% or 2CM0 wt .-% or 30 wt .-%, before the grinding and b) a portion of the amphoteric, light cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes, preferably 10-90 wt .-% or 60-80Gew .-% or 70Gew .-%, during the grinding and /or c) a portion of the amphoteric, light cationic and / or amphoteric and / or amphoteric, slightly anionic polyelectrolytes, preferably 0-80 wt .-% or 0-20 wt .-%, after the milling be added, where - if the desired final fineness is to be achieved in one mill run - 100% by weight of the amphoteric light anionic and / or amphoteric neutral to neutral Polyelectrolytes or 100 wt .-% of amphoteric against outside neutral and / or amphoteric cationic polyelectrolytes are added before grinding, or the necessary amount of dispersant is divided according to the achieved final fineness. 12. Aqueous suspension in particular according to one or more of the preceding claims, characterized in that the dispersant is a mixture of one or more cationic polyelectrolytes and / or one or more amphoteric cationic polyelectrolytes, in which the non-neutral monomer units carry predominantly positive charges, and one or a plurality of partially neutralized anionic polyelectrolytes and / or one or more partially neutralized amphoteric anionic polyelectrolytes in which the nonneutral monomer units carry predominantly negative charges, wherein the cationic polyelectrolyte and / or the amphoteric cationic polyelectrolyte is present in an amount such that the dispersed mineral or Filler or pigment particles carry positive charges. 13. Aqueous suspension according to one or more of the preceding claims, characterized in that the dispersant is a mixture of one or more homopolymeric cationic polyelectrolytes and / or one or more copolymeric amphoteric cationic polyelectrolytes in which the non-neutral monomer units carry predominantly positive charges, and a or a plurality of homo- and / or copolymer partially neutralized anionic polyelectrolytes and / or one or more amphoteric anionic partially neutralized polyelectrolytes in which the non-neutral monomer units carry predominantly negative charges, and the cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte in which the non-neutral monomer units carry predominantly positive charges carrying the positive charge-generating functional group in a substituent of the ethylenic main chain, wherein the substituent on Main chain is bound, and the cationic polyelectrolyte quaternary ammonium groups and the amphoteric cationic polyelectrolyte in which the non-neutral monomer units carry predominantly positive charges, quaternary ammonium groups and carboxyl groups and / or sulfonic acid groups and / or acid phosphoric acid ester-containing groups, and the anionic teilneutralisierte and the amphoteric anionic partially neutralized polyelectrolyte per carboxyl groups and the anionic partially neutralized polyelectrolyte is a homo- and / or copolymeric polyelectrolyte. 14. Aqueous suspension according to one or more of the preceding claims, characterized in that the cationic polyelectrolyte is one or more compounds from the group of the following compounds according to the following general formula IH ₃ R ₃ . C-C R ₆ C = O (On)" - η wherein R ₁ , R ₅ and R ₆ = -H and / or R ₁ to R ₆ = alkyl and / or aryl, wherein R ₅ also R ₃ - N ⁺ - R < R ₃ O and / or NH-CH ₂ -Ws-C ₆ H ₁₀ -20 to 3,000 and (on) chloride and / or bromide and / or iodide and / or HSO4 and / or CH3SO4 and / or nitrite, preferably chloride, preferably R ₁ = Hoder-CHa R ₂ = -CH ₃ or-C ₂ H ₅ R ₃ = -CH ₃ or-C ₂ H ₅ R 4 = -CH ₃ Ws-C ₄ H ₉ and isomers X = O or NH Y = -CH _r preferably bis-C ₅ H ₁₀ -, preferably-( CH ₂ ) ₃ -, R ₅ and R ₆ = H
can be. 15. Aqueous suspension according to one or more of the preceding claims, characterized in that the amphoteric cationic polyelectrolyte in which the non-neutral monomer units carry predominantly positive charges, one or more of the compounds from the group of the following compounds according to the following general formula I I C-C 1 R C = ta - Ν ' ¹ "" rU Re R YES (On)" R ₃ where R ₁ , R ₆ , R ₈ and R ₇ = H and / or R ₁ to R ₇ = alkyl and / or - aryl,
wherein R ₅ and C = O R ₂ - ^ f- R. R ₃ can be,
R ₈ and R ₉ =
-H and / or
Alkyl and / or aryl; R ₈ and R ₉ also -C can be,
if Z = _ _c '/ ^ OH X = O and / or NH Y = -CH ₂ -bis-C ₅ H ₁₀ ~? and or OH - (CH ₂ ) _n - C and / or OH - ( ^CH 2) n - ^{s = 0} and / or OH and or an acid phosphoric ester group, a = 70-99 mol% b = 1-30 mol% η = 1-18 and (An) "= chloride and / or bromide and / or iodide and / or HSO ₄ " and / or CH ₃ SO ₄ "and / or nitrite, with preference R ₁ = Hoder-CH ₃ R ₂ = -CH ₃ or-C ₂ H ₅ R ₃ = -CH ₃ or-C ₂ H ₅ R ₄ = -CH ₃ to-C ₄ Hg and isomers X = 0 or preferably NH Y = -CH ₂ -Ns-CbH ₁₀ -, preferably - (CH ₂ ) 3, R ₅ and R ₆ = H R ₇ = H or -CH ₃ R ₈ and R ₉ = H, and the amphoteric anionic partially neutralized polyelectrolyte, in which the non-neutral Monomer units carry predominantly negative charges, one or more of the compounds from the group of compounds according to the above general formula, wherein a = 1-30 mol% and
b = 70-99 mol%
are. 16. Aqueous suspension according to one or more of the preceding claims, characterized in that the anionic partially neutralized polyelectrolyte is one or more of the compounds from the group of the following compounds according to the following general formula Z = K ₃ K; A-A I i R ₃ Z H. - C OH · - w and / or - (CH ₂ J _n -C and or - (CH ₂ ) _n ι - S = O and or I / S = O I OH and or an acidic phosphoric ester group R ₁ = -H or -CH ₃ R ₂ and R ₃ = -H and / or -alkyl and / or -aryl where R ₂ and R _{3 may} also be 2, if , 0 Z = C
\ OH u = + I and / or + II and / or + III Ka = alkali and / or alkaline earth and / or earth metal ion w = 59 to 95 mol% per number Z in the monomer ν = 5 to 41 mol% divided by u η = 1-12, and preferred is a mixture of one or more of the homopolymers and / or copolymers of compounds according to the above formula. 17. Aqueous suspension according to one or more of the preceding claims, characterized in that the anionic teilneutralisierte Poiyelektrolyt a homo- and / or copolymeric and the amphoteric anionic teilneutralisierte polyelectrolyte, in which the non-neutral monomer units carry predominantly negative charges, depending on a carboxyl group and / or polyols containing sulfonic acid groups and / or acidic phosphoric acid ester groups, the partially neutralized anionic polyelectrolyte being a partially neutralized polyacrylic acid and / or a partially neutralized polymethacrylic acid and / or partially neutralized copolymer thereof, and preferably only one for the anionic partially neutralized polyelectrolyte and the amphoteric anionic partially neutralized polyelectrolyte is neutralized statistical part of the acid groups with a monovalent and / or polyvalent cation, where as cations alkali and / or alkaline earth and / or Erdmetallkationen and / or amines and / or alkanolamines and / or quaternary ammonium cations are used, preferably Na ⁺ and / or K ⁺ and / or Li ⁺ and / or Ca ²⁺ and / or Mg ²⁺ and / or Sr ²⁺ . 18. Aqueous suspension according to one or more of the preceding claims, characterized in that the dispersant is a mixture according to the general formulas of claim M and / or claim 15 and claim 16 or that the dispersant is a mixture according to the following general formula C-C ί ν. j J I
B C - C = OH ~ C - C C-C C - 0 ioi- C = OH in which
(KaO ⁺ = Alkali and / or alkaline earth and / or Ercmetallkationen and / or amines and / or Alkanolamines and / or quaternary ammonium cations = chloride and / or bromide and / or iodide and / or HSOi and / or CH ₃ SO ₄ "and / or nitrite may be and a = 60-99 mol% b = 1-40 mol% ζ = 1-70 mol% w = 30-99 mol%, or (Cat) ⁺ = alkali and / or alkaline earth (An) "= chloride and / or bromide and / or iodide and / or HSO ₄ and / or CH ₃ SO ₄ " and / or nitrite may be and a = 80-98 mol% b = 2-20 mol% ζ = 2-50 mol% w = 50-98 mole%, or (KaO ⁺ = Na ⁺ and / or K ⁺ and / or Li ⁺ and / or NHJ and / or Ca ²⁺ and / or Mg ²⁺ and / or Sr ² + (An) "= chloride and / or bromide and / or iodide and / or HSOi and / or CH ₃ SOJ and / or nitrite, and a = 85-97 mol% b = 3-15 mol% ζ = 3-30 mol% w = 70-97 mol%, or (KaO ⁺ = alkali ion
(An) "= halides a = 90-96 mol% b = 4-10 mol% ζ = 4-20 mol% w = 80-96 mol%, or (KaI) ⁺ = Na ⁺
(An) "= Cr a = 95 mol% b = 5 mol% ζ = 5 mol% w = 95 mol% the anionic polyelectrolyte and / or the amphoteric anionic polyelectrolyte with alkali, and / or alkaline earth and / or earth metal cations and / or amines and / or alkanolamines and / or quaternary ammonium cations, in particular with Na ⁺ , partially neutralized. 19. An aqueous suspension according to one or more of the preceding claims, characterized in that the anionic polyelectrolyte and / or the amphoteric anionic polyelectrolyte, in each case more preferably, 1 to 70 mol% or 2-60 mol% or 3-30 mol % or 5 mol% of the acid groups are neutralized, wherein the specific viscosity "Eta" of the partially neutralized anionic polyelectrolyte and / or the amphoteric anionic polyelectrolyte in the mixture with the cationic and / or the amphoteric cationic polyelectrolyte, measured in the full salt form, between 0.2 and 1.0, or between 0.35 and 0.6 or 0.55 and the degree of polymerization of the cationic polyelectrolyte and / or the amphoteric cationic polyelectrolyte in the mixture with the partially neutralized anionic polyelectrolyte and / or the amphoteric anionic teilneutralisierten Polyelectrolytes, measured over the intrinsic viscosity, in the range of 5ml / g to 50ml / g, or in the range of 15 ml / g to 40 ml / g or in the range of 25 ml / g to 35 ml / g, and the intrinsic viscosity of the cationic and / or amphoteric cationic polyelectrolytes used in the aqueous suspension is in the range between 9.2 ml / g and 48.5 ml / g or between 16.2 ml / g and 31.2 ml / g. 20. Aqueous suspension according to one or more of the preceding claims, characterized in that the dispersant mixture, in each case more preferably, from 70-98% by weight of cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte and
2-30% by weight anionic partially neutralized polyelectrolyte and / or amphoteric partially neutralized anionic polyelectrolyte or 75-95% by weight of cationic polyelectrolyte and / or amphoteric cationic polyol electrolyte and
5-25% by weight anionic partially neutralized polyelectrolyte and / or amphoteric partially neutralized anionic polyelectrolyte or from 80-90% by weight of cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte and
10-20 wt .-% anionic partially neutralized polyelectrolyte and / or amphoteric partially neutralized anionic polyelectrolyte or from 80 wt .-% cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte and
20% by weight anionic partially neutralized polyelectrolyte and / or amphoteric partially neutralized anionic polyelectrolyte or 90 wt .-% cationic polyelectrolyte and / or amphoteric cationic polyelectrolyte and
10 wt .-% anionic partially neutralized polyelectrolyte and / or amphoteric partially neutralized anionic polyelectrolyte, wherein the mixing ratio of cationic polyelectrolyte to amphoteric cationic polyelectrolyte blended with the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte 0-100 wt% or 0-30 wt% or 0-20 wt% cationic polyelectrolyte and 100-0 wt is 0% or 70-100% by weight or 80-100% by weight of amphoteric cationic polyelectrolyte, or 0% by weight of cationic polyelectrolyte and 100% by weight of amphoteric cationic polyelectrolyte. 21. Aqueous suspension according to one or more of the preceding claims, characterized in that the molar composition of the individual component in the partially neutralized anionic polyelectrolyte in the mixture with the cationic and / or amphoteric cationic polyelectrolyte between OMol% to 100mol% acrylic acid and 100mol % to 0 mol% of other monomers, the other monomers containing carboxyl groups and / or containing sulfonic acid groups and / or acidic phosphoric ester groups, and the molar composition of the individual components in the partially neutralized anionic amphoteric polyelectrolyte in the mixture with the cationic and / or amphoteric cationic polyelectrolyte between 0 mol% to 99 mol% of acrylic acid and 100% to 1 mol% of other monomers, wherein the other monomers containing carboxyl groups and / or containing sulfonic acid or acid phosphoric ester groups and / or one or more compounds from the group ppe of the compounds according to the general formula of claim 14. 22. An aqueous suspension according to one or more of the preceding claims, characterized in that the more preferably 2-80 mol% or 3-70 mol% or 3-39 mol% or 3-35 mol% or 3-30 Mol% or 3-10 mol% of the acid groups of the anionic polyelectrolyte are neutralized, wherein the anionic polyelectrolyte is in particular a partially neutralized acrylic acid. 23. Aqueous suspension according to one or more of the preceding claims, characterized in that the minerals or fillers or pigments contain elements from the second and / or third main group and / or from the fourth subgroup of the Periodic Table of the Elements, wherein calcium and / or silicon-containing and / or aluminum-containing and / or titanium halides minerals and / or fillers and / or pigments are used, wherein calcium carbonate minerals and / or fillers and / or pigments, in particular natural calcium carbonate and / or precipitated calcium carbonate and / or marble and / or Chalk and / or dolomite and / or dolomite-containing calcium carbonate are preferred. 24. Aqueous suspension according to one or more of the preceding claims, characterized in that they are more preferred, consists of 97.0% by weight to 99.89% by weight or 98.5% by weight - 99.8% by weight. -% or 99.2% by weight to 99.65% by weight of minerals and / or fillers and / or pigments and water and 0.11% by weight - 3.0% by weight or 0.2% by weight to 1 , 5% by weight or 0.35% by weight to 0.8% by weight of a mixture of cationic and / or amphoteric cationic and partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte, with a solids content of 60-80% by weight or 60-75 wt .-% or 60-70 wt .-%, based on the dry mineral or the dry filler or the dry pigment, or that it consists of 99.6Gew .-% or 99.05Gew. -% or. 99.1% by weight minerals and / or fillers and / or pigments and water and 0.4% by weight or 0.95% by weight or 0.9% by weight of a mixture of cationic and / or amphoteric cationic and partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte, at a solids content of 67% by weight or 67% by weight or 60% by weight, based on dry mineral or the dry filler or the dry pigment in a Grain distribution, so that 60 wt .-% or 70 wt .-% and 90 wt .-% of the particles have an equivalent spherical diameter <2 pm. 25. A process for preparing an aqueous suspension (slurry), in particular according to one or more of the preceding claims, characterized by the following process steps: a) an aqueous suspension of minerals and / or fillers and / or pigments is wet-ground together with a dispersing and Mahlhilfsmittelmischung in particular according to one or more of claims 1-24, wherein b) a part of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte before grinding and c) "in part of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte during milling and / or d) a part of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte after milling, e) and the cationic and / or amphoteric cationic polyelectrolyte completely before grinding or only f) a part of the cationic and / or amphoteric cationic polyelectrolyte before grinding and g) a portion of the cationic and / or amphoteric cationic polyelectrolyte during milling and / or h) a portion of the cationic and / or amphoteric cationic polyelectrolyte are added after grinding. 26. A process for the preparation of an aqueous suspension of fillers according to claim 25, characterized in that a) 10-90 wt .-% or 20-40Gew .-% or 25-35Gew .-% or 30Gew .-% of the partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte before grinding and b) 10-90% by weight or 60-80% by weight or 65-75% by weight or 70% by weight of the partially neutralized anionic and / or partially acidified amphoteric anionic polyelectrolyte during the grinding and / or c) 0-80% by weight ^: % orw. 0-20 oaw .-% and 0-10Gew .-% of partially neutralized anionic and / or partially neutralized amphoteric anionic polyelectrolyte after milling, and d) 50-100Gew .-% or 50-100Gew .-% or 70-100Gew .-% or 100Gew .-% of the cationic and / or cationic amphoteric polyelectrolyte before grinding and e) 0-50 wt .-% or 0-50Gew .-% or 0-30Gew .-% of the cationic and / or cationic amphoteric polyelectrolyte during the milling and / or f) 0-50Gew .-% or 0-50Gew .-% or 0-30Gew .-% of the cationic and / or amphoteric cationic polyelectrolyte are added after grinding. 27. Use of the aqueous suspension of minerals and / or fillers and / or pigments according to one or more of the preceding claims in papermaking or in paper production, furthermore for surface treatment (pigmentation) of the paper surface in the size press of the paper machine and in the paper coating, preferably in the pre-coat or in the top coat in the Papierstreicherei, in groundwood for contaminant control, in Stre¬ ine committee for Störstoffbekämpfung (pitch control), in the circulation water of the paper machine for COD reduction (chemical oxygen demand reduction), in the wastewater treatment plant, for pre-flocculation anionically stabilized pigment and / or mineral and / or filler suspensions in papermaking or for pre-flocculation (immobilization) of coating colors in the coating.