Method of preparing aqueous suspensions of mineral materials or dried mineral materials, obtained products and use thereof

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical, paint and paper industry. Aqueous mineral materials are prepared by a) providing at least one mineral material in the form of an aqueous suspension or in dry form, b) providing at least one partially or completely lithium-neutralised water-soluble organic polymer selected from a group of homopolymers of acrylic or methacrylic acid and/or copolymers of acrylic and/or methacrylic acid with one or more acrylic, vinyl or allyl monomers, wherein the molar ratio of non-neutralised acid groups is in the range of 0-10%, c) combining the at least one partially or completely lithium-neutralised water-soluble organic polymer from step b) with at least one mineral material from step a). The obtained mineral materials or aqueous suspensions thereof are used in making paper, plastic and paint.

EFFECT: invention enables to obtain material having a stable pH, low Brookfield viscosity, which remains stable over time, and requires low content of dispersant and/or grinding enhancer.

34 cl, 13 tbl, 13 ex

 

The present invention concerns the technical sector of suspensions of mineral materials or dried mineral materials and their application in the field of paper, paints or plastics, and in particular, their use in the paper industry, for example, in the manufacture or coating of paper sheets.

In the method of manufacturing a sheet of paper, cardboard or similar product specialist in this field of technology has an increasing trend to replace the expensive part cellulose fibres more cheap mineral to reduce the cost of paper with improved properties, such as opacity and/or white.

This mineral material, with which the expert in the art is familiar, contains, for example, natural calcium carbonate, such as marble, calcite, limestone and/or chalk, and/or synthetic calcium carbonate, such as selenoamino and/or aragonite, and/or kaltsitnykh crystalline form, and a variety of similar fillers containing calcium carbonates, such as dolomite or fillers on the basis of the mixed carbonates of various metals, such as calcium associated with magnesium and analogues, various substances, such as talc or analogues, and mixtures of these fillers, such as, for example, a mixture of talc-calcium carbonate or calcium carbonate-Olin, or mixtures of natural calcium carbonate with aluminium hydroxide, mica or with synthetic or natural fibres or co-structures of minerals such as with the structure talc-calcium carbonate or talc-titanium dioxide.

For a long time usually used in wet grinding method as helping grinding agent of water-soluble polymers based on partially or fully neutralized polyacrylic acid or its derivatives (EP 0046573, EP 0100947, EP 0100948, EP 0129329, EP 0261039, EP 0516656, EP 0542643, EP 0542644, EP 0717051)to provide an aqueous suspension of minerals that meet the above criteria purification and viscosity, but these help grinding agents used in too large quantities, to allow the final product to have sufficient ability scattering of visible light required by the end user when using paper.

These documents indicate that there is a need to reduce polydispersity polymer used as a dispersing and/or help grinding agent, which has the disadvantage of high cost and difficulty of obtaining relevant polymers.

Accordingly, there is a need for water-soluble organic polymers, regardless of their polydispersity.

Another disadvantage of the local method of wet grinding, performed with conventional polymers, is the fact that they do not allow to obtain the desired stability of the pH of the aqueous suspensions of mineral in time.

The expert knows another type of solution is described in WO 02/49766, EP 0850685, WO 2008/010055, WO 2007/072168, obtain aqueous suspensions of purified mineral material with a high concentration of dry matter, at the same time having a low viscosity Brookfield, which remains stable over time. This known type of solution describes the application of a special dispersant as copolymers of acrylic acid with maleic acid or as a special value neutralize, or as the application of inorganic fluorine compounds used for input in aqueous suspension of mineral particles originating from stage mechanical and/or thermal concentration after stage wet grinding at low solids content without using a dispersing agent and contributing to the grinding agent.

In addition, the specialist in the art knows the U.S. patent 3006779, which describes a completely different solution based on inorganic dispersant consisting of a homogeneous mixture nutrifaster glass, zinc oxide, and salts or potassium hydroxide or lithium.

Finally, thesis entitled "Influence of polyelectrolyte adsorption on rheology of concentrated calcite dispersion" (Robert Ptzenhauser-1993), which describes the influence of different polyacrylates in relation to the suspension of calcite, proves that there were difficulties from the point of view of stability of the viscosity of the obtained suspensions with all studied polyacrylates, including lithium polyacrylate.

Accordingly, none of the known solutions provides professional solution to the problem of achieving water suspensions of purified mineral material, allowing the use of water-soluble organic polymers, regardless of their polydispersity, with a high concentration of dry substances with simultaneously low viscosity Brookfield, which remains stable over time, reduced the content of the dispersant and/or contributing to the grinding agent and/or thermally and/or mechanically increased solids content and pH stability over time.

Referring to the above problem of achieving an aqueous suspension of mineral material with the required properties while minimizing the requirements of the dispersant and/or contributing to the grinding agent without reducing the properties of the final products, such optical properties of paper, the present applicant has unexpectedly discovered that lithium-neutralized water-soluble organic polymers act as amplifiers of grinding and/or dispersing ability, allows in order to achieve water slurries or suspensions" mentioned purified mineral material with a high concentration of dry matter, having both a low viscosity Brookfield, which remains stable over time, reduced the amount of dispersant or contributing to the grinding agent, and the pH stability with time.

The applicant also unexpectedly found that the neutralization of the water-soluble organic acid polymer lithium ions makes it possible to use, as the amplifier grinding and/or dispersing ability, water-soluble organic polymer with a higher polydispersity than usually applied.

In some difficult conditions grinding or dispersing a lithium-neutralized water-soluble organic polymers, acting as amplifier grinding and/or dispersing ability, allow water slurries or suspensions" mentioned purified mineral material, whereas conventional polyacrylates do not allow to get any fluid and/or stable suspensions because of too high viscosity to Brookfield.

Thus, one aspect of the present invention is to provide a method of manufacturing aqueous suspensions of mineral particles under reduced content of the dispersant and/or thermally and/or mechanically increased solids content with low viscosity Brookfield, stable, modern, having a high content of dry solids, reduced the amount of dispersant or contributing to the grinding agent, which may have a higher polydispersity compared with conventional dispersant and pH stability over time.

Under a low viscosity by Brookfield remaining stable over time, it is understood that the initial viscosity Brookfield aqueous suspension of mineral material after 1 hour from receiving less than 4000 MPa·s, preferably below 2000 MPa·s, more preferably less than 500 MPa·s, measured after 1 minute of mixing when using a RVT model Brookfield viscometer at room temperature and rotation speed of 100 rpm with the appropriate spindle, and that the viscosity Brookfield aqueous suspension of mineral material after 8 days neprimerimogo storage is below 4000 MPa·s, preferably below 2000 MPa·s, more preferably less than 500 MPa·s, measured after 1 minute of mixing when using a RVT model Brookfield viscometer at room temperature and rotation speed of 100 rpm with the appropriate spindle.

Under a reduced content of the dispersant is assumed that the amount of dispersant or contributing to the grinding agent used to achieve the mineral material in the form of water susp is nsii at a certain viscosity to Brookfield, lower than the number used in the conventional dispersant or contributing to the grinding agent to achieve suspension of mineral material with the same viscosity at Brookfield and at the same value of content of solids.

Similarly, a higher polydispersity" means that according to this invention the dispersant or grinding agents used to achieve the mineral material in the form of an aqueous suspension at a certain viscosity to Brookfield, can have a higher polydispersity than the commonly used dispersing agents or conducive to grinding agents to achieve the mineral material at the same viscosity at Brookfield and at the same value of content of solids. In other words, dispersers or conducive to grinding agents of the present invention can provide a lower viscosity than conventional dispersers even at a higher polydispersity.

Conventional dispersing agents include the well-known polyacrylates described in various well-known documents or patents cited as prior art further below in this application.

The expression "pH stable in time" means that the mineral suspension will keep the same pH value in the low range, canprepare from 9.5 to 10.5 during at least 8 days of storage.

"High content of dry solids according to the present invention means a water slurry or suspension of mineral material having a solids content preferably from 10 wt.% up to 82 wt.%, more preferably, from 50 wt.% up to 81 wt.% and most preferably from 65 wt.% up to 80 wt.%, for example, from 70 wt.% up to 78 wt.% the total weight of the slurry or suspension.

The above aim is achieved by means of the method of manufacturing aqueous suspensions of mineral materials containing stages:

a) providing at least one mineral material in the form of an aqueous suspension or in dry form,

b) providing at least one partially or totally lithium-neutralized water-soluble organic polymer,

(C) combining at least one partially or totally lithium-neutralized water-soluble organic polymer from stage (b) with at least one mineral material from stage a).

In this method, lithium-neutralized water-soluble polymers act as amplifiers of the ability of a grinding and/or dispersion, and they act as amplifiers ability to disperse when not perform grinding stage, as specified above, while they also operate ka is the amplifier's ability grinding, when this stage is performed.

The resulting mineral material may be in dry form or in the form of suspension. They can be reclaimed or re-suspended after drying, as can be taken in any of the following preferred embodiments.

At least one mineral material for use in the present invention are preferably chosen from the group consisting of a natural calcium carbonate (GCC), such as marble, chalk, limestone or calcite, or precipitated calcium carbonate (PCC), as aragonite, vaterite and/or calcite; and minerals containing calcium carbonate such as dolomite or fillers on the basis of mixed carbonates, such as calcium associated with magnesium, such as talc or clay, and mixtures thereof, such as mixtures of talc-calcium carbonate or calcium carbonate-kaolin, or mixtures of natural calcium carbonate with aluminium hydroxide, mica or with synthetic or natural fibres or co-structures of minerals such as with the structure talc-calcium carbonate or talc-titanium dioxide.

Preferably, at least one mineral material is a natural calcium carbonate (GCC) or precipitated calcium carbonate (PCC), or a mixture of GCC and PCC, or a mixture of GCC and PCC and clay, or a mixture of GCC and PCC and talc, and most preferably is a GCC is selected among marble, chalk, calcite or limestone, or RCC, is selected among aragonite PCC or kaltsitnykh RCC, as rhombohedral PCC or Selenomethionine RCC.

The above method can be improved by using the optional number of stages:

Particularly preferred implementation comprises a stage of grinding (stage d), where stage C) can be performed before, during or after stage (d).

In addition, at least one partially or totally lithium-neutralized water-soluble organic polymer can be added before and/or during and/or after stage (a), if at least one mineral material is a RCC.

Thus, at least one partially or totally lithium-neutralized water-soluble organic polymer may also be added before, during or after the deposition of the synthetic calcium carbonate. For example, partially or totally lithium-neutralized water-soluble organic polymer can be added to the stage of carbonization.

If GCC is used in stage (d)may be preferably subjected to wet crushed natural calcium carbonate stage wet treatment up to stage d), which can remove impurities such as silica impurities, for example, by froth flotation.

Thus, for example, using the way the grinding and/or dispersion under reduced content of the dispersant and/or increased solids content, methods of making aqueous suspension of particulate mineral material that uses referred to, partially or totally lithium-neutralized water-soluble organic polymer selected as the amplifiers ability of grinding and/or dispersion, this method of manufacture can be optimized.

In addition, it may be advantageous to United and possibly crushed material obtained in stage d), were selected and/or concentrated (stage e).

"Screening" in the context of the present invention is performed using well-known devices for screening, such as sieves, sand centrifuges, etc. Under the "filter" should be understood enrichment by removing coarse particles having a particle size of greater than 45 μm. When the suspension is reduced, so that at least part of the solid material in the initial suspension is removed by filtration, this stage of screening is a dilution.

"Concentration" is, for example, by thermal concentration or mechanical concentration, for example, using a centrifuge, a filter press, a tubular press or combinations thereof.

If United and possibly crushed material is sieved and/or concentrate on stage (e), it may be preferable dispersing the material in the aqueous medium after filtration and/or concentration (stage f).

United and possibly crushed material obtained from any of the steps d) or e)or f), can be dried, if mineral material stage a) is provided in the form of a water suspension (stage g).

On the other hand, if the mineral material stage a) is provided in dry form, or when steps e), f) and g) are not met, merged, and possibly the ground material obtained in stage d)can dispergirujutsja in the aquatic environment (stage h).

In a preferred embodiment, the aqueous suspension obtained from stage (h), can be reduced (stage i), preferably in the presence of partially or totally lithium-neutralized water-soluble organic polymer.

In General, in adding at least one partially or totally lithium-neutralized water-soluble organic polymer, there are several preferred embodiments.

For example, at least one partially or totally lithium-neutralized water-soluble organic polymer is preferably added before and/or during and/or after the grinding stage d)if stage (e) and (f) are not executed.

At least one partially or totally lithium-neutralized water-soluble organic polymer can however also be added after the grinding stage d and before and/or during, and/or after stage e) filtration and/or concentration of the if stage e) perform alone.

In addition, you can add at least one partially or totally lithium-neutralized water-soluble organic polymer before and/or during and/or after the stage of dispersion (f).

If mineral material is provided in dry form in stage a) with the following sequentially stages d) and (h), preferably, when adding partially or totally lithium-neutralized water-soluble organic polymer is performed in one adding before, during or after stage h) or make for a lot of additions, each one of them before, during or after stage h).

If you are performing stage f) dispersion and if all or part of the number of partially or totally lithium-neutralized water-soluble organic polymer is added to the stage (f), partially or totally lithium-neutralized water-soluble organic polymer is preferably added before and/or during and/or after stage (d).

However, if no stage e), (f) or (g), all the number of partially or totally lithium-neutralized water-soluble organic polymer can be used to stage d), or part of the lithium-neutralized water-soluble organic polymer can be used to stage d), while the remaining is by the number added during stage (d).

If stage f) dispersion is followed by stage e), step (f) can be performed in the presence of lithium-neutralized water-soluble organic polymer, which may be different or the same as the polymer used in stage d).

Particularly preferably, when stage d) of the method of the present invention performed at pH above 7, preferably above 7.5, more preferably between 8.5 and 10.5, and most preferably between 9.5 and 10.5.

In this regard, the expert can easily determine that the pH will have the appropriate values in the properties view, which he wants to achieve, knowing that the pH depends on the addition of base, preferably a base with one - or divalent cation, most preferably sodium or calcium, for example, from the addition of alkaline preparation of biocide or release hydroxide such as CA(Oh)2during the grinding material, for example, during the co-grinding of precipitated calcium carbonate, natural calcium carbonate.

Throughout this application, the pH is measured at room temperature (21°C±1) within ±0.3.

At least one partially or totally lithium-neutralized water-soluble organic polymer is preferably selected from the group consisting of homopolymers of acrylic or methacrylic acid and/or copolymer of the acrylic and/or methacrylic acid, and/or copolymer of acrylic and/or methacrylic acid with one or more acrylic compounds, such as acrylamide, and/or vinyl or allyl monomers, fully or partially neutralized by a base containing a lithium ion, and/or its salt, or a combination of grounds containing lithium ion, and/or salts thereof with one or more neutralizing agents having a monovalent neutralizing function or a polyvalent neutralizing function such as, for univalent functions, agents, selected from the group consisting of alkaline cations, in particular sodium, potassium, ammonium or primary, secondary or tertiary aliphatic and/or cyclic amines, such as stearylamine, the ethanolamines (mono-, di-, triethanolamine), mono - and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, morpholine, or, for the polyvalent function, agents, selected from the group consisting of divalent alkaline earth metal cations, in particular magnesium and calcium, or zinc or strontium, trivalent cations such as, in particular, aluminum, or certain cations of higher valency, and mixtures thereof.

In the context of the present invention, the question is whether the polymer is water soluble or not, is determined by mixing this polymer in an amount corresponding to the most in the highest concentration, used in the proposed method, in aqueous medium at 25°C before visually ascertained opacity or lack of it, and then filter 0.2 µm membrane filter. If less than 0.1% of insoluble material regarding just added polymer remains on the filter, this polymer is water-soluble.

It should be noted that partially or totally lithium-neutralized water-soluble organic polymer can also be used in combination with a dispersant prior art described above.

"Partially neutralized with lithium" in this context means that only part of the acid groups neutralized polymer lithium ions, while the remaining counterions dissociated acid groups represent H3About+or neutralized by other ions, such as, inter alia, ions of alkali or alkaline earth metals, such as Na, K, or Mg, Ca, Sr or Al, and/or ammonium hydroxide or amines and/or alkanolamines, such as, for example, triethanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol or mixtures thereof.

Base containing lithium ion, preferably chosen among the main components such as lithium hydroxide, or oxide and/or its salts in dry form or in solution, and neutralization is carried out with the monomer, with whom containing a series of N 3About+before polymerization and/or polymer containing H3About+during and/or after polymerization of the monomer.

The mole fraction is not neutralized acid groups is preferably in the range from 0% to 75%, more preferably from 0% to 50%, and the mole fraction of neutralized not lithium acid groups is in the range from 0% to 75%, more preferably from 0% to 50%, most preferably from 0% to 10%.

If not neutralized by lithium acid groups are neutralized by magnesium ions, preferably, when the share of neutralisation of the active acid sites, including terminal groups, magnesium ranges from 0% to <40%, preferably from 0% to 30%, more preferably from 10 to 20%. It can also be, however, from >60 to 75%, for example, 70%, and in some cases preferably, when neutralized with magnesium acid groups are missing.

The degree of neutralization using divalent cation Mg very much depends on the Mw of the polymer. It is particularly interesting to have a high degree of Mg neutralization of the polymer with low Mw and low Mg neutralization of the polymer with high Mw.

At least one partially or totally lithium-neutralized water-soluble organic polymer, which can be added before, during and/or after stage (d), preferably is present in a number is the number from 0.001 wt.% up to 5 wt.%, preferably from 0.01 wt.% up to 2 wt.% and most preferably, from 0.05 wt.% up to 1 wt.% per all the dry mineral.

Also used a combination of a conventional polymer, such as a conventional polyacrylate, lithium-neutralized water-soluble organic polymer, or a combination of different lithium-neutralized water-soluble organic polymers.

A homopolymer of acrylic or methacrylic acid, and a copolymer of acrylic acid or methacrylic acid in combination with one or more other acrylic, vinyl or allyl monomers are prepared according to well known methods of radical polymerization or methods of copolymerization in solution, in a direct or reverse emulsion, in suspension or precipitation in appropriate solvents, in the presence of known catalytic systems and transfer agents, or by using the methods of controlled radical polymerization, such as the method known as reversible chain transfer mechanism accession-fragmentation (RAFT), the method known as radical polymerization atom transfer (ATRP), the method known as polymerization intermediate nitroxides (NMR) or the method known as free radical polymerization intermediate cobaloximes.

It can also be prepared using other vari the NTA, where a homopolymer or copolymer obtained by the copolymerization reaction, before or after complete or partial neutralization process and divided into several phases according to the statistical or dynamic methods known to the person skilled in the art using one or more polar solvents belonging to the group consisting of water, methanol, ethanol, propanol, isopropanol, butanols, acetone, tetrahydrofuran or mixtures thereof.

It should be noted that the nature of the monomers and the molecular weight of the polymers used in combination with the base containing lithium ion, it will be easy to choose the specialist according to the properties that he wants to achieve.

Such partially or totally lithium-neutralized water-soluble organic polymers are added to obtain an aqueous suspension of a material with low viscosity Brookfield, stable over time, which means that the initial viscosity Brookfield after 1 hour from receiving less than 4000 MPa·s, more preferably less than 2000 MPa·s, most preferably less than 500 MPa·s, in the range from 50 to 500 MPa·s, measured after 1 minute of mixing when using a RVT model Brookfield viscometer at room temperature (21°C±1) and the speed of rotation of 100 rpm with the appropriate spindle, and the viscosity is rachilde aqueous suspension of mineral material after 8 days of storage without stirring below 4000 MPa·s, preferably below 2000 MPa·s, more preferably less than 500 MPa·s at 100 rpm, measured after 1 minute of mixing when using a RVT model Brookfield viscometer at room temperature (21°C±1) and the rotation speed of 100 rpm with the appropriate spindle.

In this regard, it should be noted that in contrast to the commonly used polymers such viscosity can be achieved partially or totally lithium-neutralized water-soluble organic polymers, even if they have a high polydispersity, such as more than 2, preferably from 2.5 to 4, more preferably from 2.7 to 3.5, even more preferably from 2.8 to 3.3, for example, 3 and even up to 6.25 and above.

In a preferred embodiment, the mineral material contains GCC and PCC, where RCC is present in an amount of from 10 to 90 wt.%, preferably from 20 to 80 wt.%, and most preferably, from 30 to 70 wt.% the total weight of PCC and GCC.

Stage d) grinding method according to the present invention is preferably performed at a temperature above 20°C, more preferably from 50°C. to 120°C., especially above 60°C, for example, from 80°C to 105°C.

In addition, preferably, when the concentration of solids material in the form of an aqueous slurry, grinding on stage d) crushing varies from 10 to 82% (dry wt is the mineral material), preferably from 40 to 81%, most preferably from 60 to 80% and particularly preferably from 65% to 72%.

Mentioned aqueous suspension may occur from dispersions of mineral material in the form of a wet brick.

Particularly preferably, stage (d) are performed with a solids content of from 10 wt.% up to 35 wt.% in the calculation of the total mass of the suspension in the absence of any dispersing agents or auxiliary agents, grinding, and perform when the solids content of 60 wt.% up to 82 wt.% in the calculation of the total mass of the suspension in the presence of dispersing agents and/or auxiliary agents grinding.

The final solids content in the suspension containing mineral material ranges from 45 wt.% up to 82 wt.%.

Preferably, the mineral materials have a high end solid content ranging from 60 wt.% up to 75 wt.%, more preferably, from about 68 wt.% up to 73 wt.%, if stage d) grinding is done without any dispersant or auxiliary agent, grinding, and ranges from 65 wt.% up to 82 wt.%, preferably from 72 wt.% up to 78 wt.%, if stage d) grinding is performed in the presence of dispersing agents or auxiliary agents grinding.

Another purpose of this invention is the provision of mineral material obtained with the help of the person in accordance with this invention.

This mineral material preferably is in the form of an aqueous slurry having a solids content of from 80 to 82% by dry weight of mineral material, for example, 80,5% by dry weight of mineral material.

Particularly preferably, when the material contains at least one partially or totally lithium-neutralized water-soluble organic polymer in amounts of from 0.001 wt.% up to 5 wt.%, preferably from 0.01 wt.% up to 2 wt.% and most preferably, from 0.05 wt.% up to 1 wt.%, for example, 0.5 wt.% relative to the total dry mineral.

You may also crushed mineral material may contain a fraction of particles finer than 2 microns, greater than 50 wt.%, preferably more than 80 wt.%, more preferably more than 85 wt.%, even more preferably more than 98 wt.% the total mass of possible ground mineral material, using the Sedigraph™ 5100.

In this regard, particularly preferred if the mineral material contains a fraction of particles finer than 2 microns, from 57 to 63 wt.% the total mass of material, using the Sedigraph™ 5100.

It may also contain a fraction of particles finer than 1 μm, greater than 20 wt.%, preferably 75 wt.%, more preferably more than 85 wt.%, more than 95 wt.% in the calculation of the total mass of edinennogo and possibly crushed material, using the Sedigraph™ 5100.

In a preferred embodiment, the final mineral material has a d50approximately from 0.2 to 2 μm, preferably from 0.2 to 0.8 μm, and more preferably from 0.25 to 0.45 μm. The value of d50determine, using a Sedigraph 5100™.

Preferably, the joint and possibly crushed mineral material has a content of from 0.02 to 0.2 mg/m2lithium-neutralized water-soluble organic polymer, for example, to being 0.036 0.038 mg/m2for GCC, 0,063 mg/m2for rhombohedral PCC and 0.12 mg/m2for scalenohedral RCC per unit specific surface area, measured by way of the BET according to ISO 4652.

In a particularly preferred embodiment, the aqueous suspension of the joint and possibly crushed mineral material obtained using the method according to this invention has a viscosity at Brookfield, which are stable in time, where the initial viscosity Brookfield after 1 hour from receiving less than 4000 MPa·s, preferably below 2000 MPa·s, more preferably less than 500 MPa·s, for example, from 50 to 500 MPa·s, measured after 1 minute of mixing when using a RVT model Brookfield viscometer at room temperature and rotation speed of 100 rpm with the appropriate spindle, and vaskos the ü on Brookfield after 8 days of storage without mixing is less than 4000 MPa·s, preferably below 2000 MPa·s, more preferably below 1000 MPa·s, particularly 500 MPa·s, for example, from 50 to 500 MPa·s, measured after 1 minute of mixing when using a RVT model Brookfield viscometer at room temperature and rotation speed of 100 rpm with the appropriate spindle.

In view of the foregoing, the aqueous suspension of mineral material, especially defined above, is an additional objective of the present invention. Particularly preferred is an aqueous suspension of mineral material, which

- has a solids content of from 80 to 82% by dry weight of mineral material, for example, 80,5% by dry weight of mineral material;

- has a viscosity Brookfield from 50 to 500 MPa·s, measured at 100 rpm; and

- contains preferably from 0.25 to 0.5 wt.%, more preferably, from 0.3 to 0.4 wt.%, relative to the dry weight of the mineral, at least one water-soluble organic polymer, preferably having an average molecular weight of from 3000 to 12000 g/mol, and in which at least 90% of the carboxyl groups neutralized by lithium ions.

Preferred mineral material in such suspensions contains calcium carbonate, selected from marble, chalk, limestone or mixtures thereof.

In General, the joint and possibly crushed mineral mater the al in dry form after stage g) preferably contains a mineral containing calcium carbonate and is selected from the group consisting of a natural calcium carbonate (GCC), such as marble, chalk, limestone or calcite, or precipitated calcium carbonate (PCC), such as aragonite, vaterite and/or calcite, and minerals containing calcium carbonate such as dolomite, or fillers on the basis of mixed carbonates, such as, in particular, calcium associated with magnesium and analogues or derivatives, various substances such as clay or talc, or analogs or derivatives, and mixtures of these fillers, such as for example, a mixture of talc-calcium carbonate or calcium carbonate-kaolin, or mixtures of natural calcium carbonate with aluminium hydroxide, mica or with synthetic or natural fibres or co-structures of minerals such as with the structure talc-calcium carbonate or talc-titanium dioxide.

Preferably, the mineral is a GCC or precipitated calcium carbonate (PCC), or a mixture of GCC and PCC, or a mixture of GCC and PCC and clay, or a mixture of GCC and PCC and talc.

Most preferably, it is a GCC selected from marble, chalk, calcite or limestone, or RCC, is selected from aragonite PCC or kaltsitnykh RCC, such as rhombohedral PCC or Selenomethionine RCC.

Finally, another objective of the present invention is the use of aqueous suspensions of mineral materials is a and/or dried mineral material according to this invention in any field, to apply mineral material and, in particular, in the field of paper, paint and plastics, and any other field that uses the aforementioned suspension and/or powders, in particular, used as suspensions in paper applications such as the manufacture of paper and/or paper coating and/or surface treatment of paper, or as filler during the manufacture of paper, cardboard or similar sheet. The dried powders are preferably used in plastics and/or paint, and re-suspended in water, again forming a suspension. Use as a filler may be direct as the composition of the filler during the manufacture of paper, cardboard or similar sheet, or indirect, as reuse of composite from waste paper, if the repeated use of composites from waste paper used in the manufacture of paper, cardboard or similar sheet.

Particularly preferably used in the paper, cover paper dyestuffs, paints and plastics.

Paper, paint, covering the paper dyes and plastics according to the invention are characterized in that they contain referred to the joint or perhaps crushed mineral materials or suspensions according to this invention.

Particularly preferred variants of the implementation in this regard is a covering dye, containing mineral materials according to this invention or their aqueous suspension having a solids content of from 75 to 78% by dry weight of mineral material, for example, 77% by dry weight of mineral material, and preferably having a viscosity Brookfield at 100 rpm <2000 MPa·s and more preferably <1000 MPa·s, for example, 500 MPa·S.

These cover the dyes may optionally contain synthetic binder having a particle diameter of from 0.08 to 0.12 μm.

The scope and benefits of this invention will be easier to understand due to the following examples, which are intended to illustrate certain embodiments of the present invention and are not limiting.

EXAMPLES

Example 1

This example concerns the preparation of material to be treated according to the present invention.

All sizes of particles and the average diameter was measured using the Sedigraph™ 5100, Micromeritics.

All weighted molecular weight (Mw), numerical molecular weight (Mn) and the polydispersity of the different polymers was measured as 100 mol.% sodium salt at pH 8 according to the method aqueous gel permeation chromatography (GPC), calibrated next of the five standards polyacrylate sodium secured from Polymer Standard Service, with rooms PSS-PAA 18, PSS-PAA 8K, PSS-PAA 5K, PSS-PAA 4K and PSS-PAA 3K.

Specific p is owed surface according to BET in m 2/g measured according to standard method ISO 4652.

Tests 1A and 1b:

These tests relate to the preparation of rhombohedral (R-)RCC d500.3 microns.

Because of this, 200 kg of calcium oxide (Tagger Kalk, Golling A) was added to 1700 litres 40°C tap water in the reactor with stirring; the contents of the reactor were mixed under continuous stirring for 30 minutes, and the resulting suspension of calcium hydroxide ("milk of lime") from 13.1% wt./mass. solids was then screened on a 100 μm sieve.

Precipitation of calcium carbonate was completed in 1800-liter cylindrical reactor made of stainless steel, equipped with a stirrer and samples for checking the pH and conductivity of the suspension.

1700 liters of a suspension of calcium hydroxide, obtained at the stage of clearing, as set out above, was added to the reactor carbonation, and the temperature of the reaction mixture brought up to the desired initial temperature of 16°C.

Gas with 20-30 vol.% CO2in the air then barbotirovany through the suspension at a speed of 200 m3/h under stirring suspension of 200 to 300 rpm gauge pressure in the feed gas was 150-200 mbar, corresponding to a hydrostatic pressure suspension of CA(Oh)2in the reactor.

During the carbonization temperature of the suspension is not regulated and allowed her to rise due to the heat released in ekzotermicheskimi deposition. After the conductivity has reached a minimum, aeration was continued for another 4 minutes and then stopped.

Aqueous suspension of precipitated calcium carbonate with 16.7% wt./mass. solids obtained by this stage of carbonization, then mark on 45 µm sieve and serve in a centrifuge for mechanical dewatering. The filtered mass is discharged from the centrifuge, re-dispersible in the water and turned in to 47.2% wt./mass. a suspension. During preparation of the suspension obtained rhombohedral (R-) RCA, 1.0% wt./mass. (calculated as dry matter on a dry calcium carbonate) anionic dispersant based on sodium polyacrylate having 12500 Mw and the polydispersity of 2.8, was added to this mixture.

The slurry is then forced to pass through vertical grinding mill (Dynomill™ 1.4 liters)containing ZrO beads of 0.6-1.2 mm as a medium to deagglomerate original sticky precipitated calcium carbonate discrete particles, to obtain the average particle size d50approximately 0.3 microns (Micromeritics Sedigraph™ 5100) after grinding.

The resulting suspension discrete ultrafine precipitated calcium carbonate is then further concentrated in a vacuum evaporator, getting the final suspension with 66.7% of the mass./mass. solid substances.

Physical properties konecne the th product are given in table 1A below.

Table 1A
The solids content in the suspension of PCC (%)The viscosity of the suspension RCA (MPa·s)
(Brookfield DV II, 100 rpm, spindle 3)
Polymorphic modification of RCCd50
(µm)
Navel BET
(m2/g)
66,7850rhombohedral calcite (R-RCA)0,2716,5

Mineral suspension, thus obtained, was then spray dried to a content of solids >99.5 wt.% and indicated Mineral 1A according to the prior art.

Using the same procedure as described above, the equivalent R-RCC, but in the presence of 2000 mass. ppm LiOH added to the stage of carbonization, was converted into slaked lime. During concentration of the suspension obtained R-RCA, 1.0% wt./mass. (calculated as dry matter on a dry calcium carbonate) anionic dispersant on the basis of lithium polyacrylate having 12500 Mw and the polydispersity of 2.8, was added to this mixture.

The slurry is then forced to pass through vertical grinding mill (Dynomill™ 1.4 liters)containing the second ZrO beads of 0.6-1.2 mm as the environment, to deagglomerate original sticky precipitated calcium carbonate discrete particles, to obtain the average particle size d50approximately 0.3 microns (Micromeritics Sedigraph™ 5100) after grinding.

The resulting suspension discrete ultrafine precipitated calcium carbonate is then further concentrated in a vacuum evaporator, getting the final suspension from 67.7% wt./mass. solid substances.

The physical properties of the final product are given in table 1b below.

Table 1b
The solids content in the suspension of PCC (%)The viscosity of the suspension RCA (MPa·s)
(Brookfield DV II, 100 rpm, spindle 3)
Polymorphic modification of RCCd50
(µm)
Navel BET
(m2/g)
67,7230rhombohedral calcite (R-RCA)0,2915,8

The suspension of precipitated in the presence of Li ions+had a lower viscosity at even higher solids contents in comparison with the suspension of the prior art using 0,063 mg/m2disperato the A.

The slurry is then spray dried to a content of solids >99.5 wt.% and indicated Mineral 1b according to this invention.

Test 2

This test relates to the preparation of natural crushed calcium carbonate Norwegian origin, with d5045 microns.

Pieces of Norwegian marble from the area Molde, having a diameter of 10-300 mm, was subjected to dry samoizmeneniyu to the grain size d50in the range of 42-48 μm. Mineral, thus obtained, was identified Mineral 2.

Test 3

This test relates to the preparation of natural crushed calcium carbonate Norwegian origin, with d500.8 μm.

Mineral 2 was subjected to wet grinding with 20 wt.% solids in tap water in a vertical grinding mill (Dynomill) in the recirculation mode without adding additives such as dispersing agents and/or assistants grinding to a grain size at which 60 wt.% particles have a diameter of <1 μm. After grinding the product had an average diameter of d500.8 μm and a specific surface area of 6.7 m2/year

After grinding, the suspension was concentrated using a tubular press forming crumbs from 80-83 wt.% solid substances.

Mineral, thus obtained, was defined as a Mineral 3.

Tests 4A and 4b

These tests relate to the preparation of two natural powdered carbon is s calcium Norwegian origin, with d500.6 microns.

Mineral 2 was subjected to wet grinding with 15-25 wt.% solids in tap water in a vertical grinding mill (Dynomill) in the recirculation mode without adding additives such as dispersing agents and/or assistants grinding to a grain size at which 75 wt.% particles have a diameter of <1 μm. After grinding the product had an average diameter of d500.6 μm and a specific surface area of 9.8 m2/, Mineral, thus obtained, was defined as a Mineral 4A.

After grinding, the suspension was concentrated using a tubular press getting a lot from 69.5 wt.% solid substances.

Mineral, thus obtained, was defined as a Mineral 4b.

Test 5

This test relates to the preparation of natural crushed calcium carbonate Norwegian origin, with d500.4 µm.

Mineral 2 was subjected to wet grinding with 20 wt.% solids in tap water in a vertical grinding mill (Dynomill) in the recirculation mode without adding additives such as dispersing agents and/or assistants grinding to a grain size at which 85 wt.% particles have a diameter of <1 μm. After grinding the product had an average diameter of d500.4 µm.

After grinding, the suspension was concentrated using a tubular press getting a lot from 78-80 wt.% solid substances.

The miner is, thus obtained, was defined as a Mineral 5.

Test 6

This test relates to the preparation of natural crushed calcium carbonate Norwegian origin, with d500.6 microns.

Mineral 2 was subjected to wet grinding with 78 wt.% solids in tap water in a vertical grinding mill (Dynomill) in the recirculation mode, using the additive according to this invention and according to prior art, to the granularity at which 65 wt.% particles have a diameter of <1 micron.

Mineral, thus obtained, was defined as a Mineral 6.

Tests 7a and 7b

This test relates to the preparation scalenohedral RCC with d50the 2.3 ám.

Because of this, 200 kg of calcium oxide (Tagger Kalk, Golling A) was added to 1700 litres 40°C tap water in the reactor with stirring; the contents of the reactor were mixed under continuous stirring for 30 minutes, and the resulting suspension of calcium hydroxide ("milk of lime") from 13.3% wt./mass. solids was then screened on a 100 μm sieve.

Precipitation of calcium carbonate was completed in 1800-liter cylindrical reactor made of stainless steel, equipped with a stirrer and samples for checking the pH and conductivity of the suspension.

1700 liters of a suspension of calcium hydroxide, obtained at the stage of clearing, as set out above, was added to the reactor carbonizes and, and the temperature of the reaction mixture brought up to the desired initial temperature 50°C.

Gas with 20-30 vol.% CO2in the air then barbotirovany through the suspension at a speed of 200 m3/h under stirring suspension of 200 to 300 rpm gauge pressure in the feed gas was 150-200 mbar, corresponding to a hydrostatic pressure suspension of CA(Oh)2in the reactor.

During the carbonization temperature of the suspension is not regulated and allowed her to rise due to the heat released in the exothermic precipitation.

After the conductivity has reached a minimum, aeration was continued for another 4 minutes and then stopped.

The product obtained with this stage of carbonization, then mark on 45 µm sieve and re-dispersible in the form of an aqueous suspension of precipitated calcium carbonate from 17.4% wt./mass. solid substances.

The physical properties of the obtained precipitated calcium carbonate after carbonization are given in table 2A below.

Table 2A
The solids content in the suspension of PCC (%)The viscosity of the suspension RCA (MPa·s)
(Brookfield DV II, 100 rpm, spindle 2)
Polymorphic modification of RCCNavel BET
(m2/g)
17,415Selenomethionine calcite (S-RCA)2,36,3

Mineral suspension, thus obtained, was then spray dried to a content of solids >99.5 wt.% and indicated Mineral 7a according to the prior art.

Using the same procedure as described above, the equivalent S-RCC, but in the presence of 500 masses. ppm LiOH added to the stage of carbonization, was converted into slaked lime. The slurry is then spray dried to a content of solids >99.5 wt.% and indicated Mineral 7b according to this invention.

The physical properties of the obtained precipitated calcium carbonate after carbonization are given in table 2b below.

Table 2b
The solids content in the suspension of PCC (%)The viscosity of the suspension RCA (MPa·s)
(Brookfield DV II, 100 rpm, spindle 2)
Polymorphic modification of RCCd50
(µm)
Navel BET
(m2/g)
17,7 15Selenomethionine calcite (S-RCA)2,46,1

As can be seen in table 2A relative to table 2b, the presence of LiOH during deposition had no effect on the measured physical properties of S-RCC.

Test 8

This test relates to the preparation of a mixture of natural crushed chalk French origin and natural crushed dolomite Norwegian origin.

1 kg pieces Norwegian dolomite from the Bergen area was subjected to dry grinding in a ball mill to a grain size d50in the range of 10.9 μm. The resulting mineral watered approximately 188 g of water and then were selected on a 63 μm sieve. 323 g of material was left on the sieve, while the other 672,5 g of the material passed through a sieve with water, forming a suspension having a dry weight of 78.2%.

In parallel, 1 ton of natural crushed chalk French origin, with d502.5 μm and a relative humidity of 20%, was dried in a rotary dryer to a moisture content of approximately 0.2%, reaching d501,95 μm, due to the semi-autogenous grinding in the dryer at the exit from the dryer.

Then 134,5 g of dried so chalk was added to a suspension of dolomite, described above, was diluted with water, getting the suspension to 73,5% solids.

The mineral in this final suspen the AI was defined as a Mineral 8.

Example 2

This example relates to the introduction of a polyacrylate polymer in the dispersion dried by spraying RCC indicated Mineral 7a.

Test 9

This test illustrates the prior art.

To perform it, the Mineral 7a was dispersively when the solids content 60.1 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 1.50 wt.% on a dry mineral normal (50 mol.%/50 mol.%) sodium/magnesium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 10

This test illustrates the invention.

To perform it, the Mineral 7a was dispersively when the solids content 59.7 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.74 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by the use of RV type Brookfield viscometer, equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The results are collected in the following table 3.

Table 3
The test numberContent-the content of solids (wt.%)Dispersant in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3The viscosity Brookfield 8 days at 100 rpm, spindle 3
Pre-existing level of technology960,1%1,50%>4000 MPa·s>4000 MPa·s
Invention1059,7%0,74%117 MPa·s<200 MPa·s

The results clearly show the effectiveness of the method used in the Finance lithium-neutralized polyacrylate, to dispersing the RCC, and, in particular, demonstrate that it is impossible to obtain a suspension of PCC with a solids content of approximately 60,0 wt.% and viscosity Brookfield less than 150 MPa·s using a conventional polyacrylate.

Example 3

This example relates to the introduction of lithium-neutralized polyacrylate after wet grinding due to the dispersion of marble wet grinding with a mean diameter of d500.6 microns.

Test 11

This test illustrates the prior art.

To run it, 0.48 wt.% on a dry mineral normal (50 mol.%/50 mol.%) sodium/magnesium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in Mineral 4A at 20 wt.% solids to concentrate in the laboratory in open loop, the desire concentration in the laboratory when the solids content 68.5 wt.%. However, the trial was stopped because of too high viscosity due to the large increase in viscosity on Brookfield above 8000 MPa·S.

Test 12

This test illustrates the invention.

To run it, 0.32 wt.% on a dry mineral 100% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in a suspension of Mineral 4A at 20 wt.% solids to concentrate in the laboratory in the open loop case is Ergani solids 68.5 wt.%.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 13

This test illustrates the invention.

To run it, 0.32 wt.% on a dry mineral 100% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in a suspension of Mineral 4A at 20 wt.% solids to concentrate in the laboratory in open loop when the solids content 70.0 wt.%.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type viscometer Brukt the ice, equipped with spindle 3.

Test 14

This test illustrates the invention.

To run it, 0.32 wt.% on a dry mineral 100% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in a suspension of Mineral 4A at 20 wt.% solids to concentrate in the laboratory in open loop when the solids content of 70.7 wt.%.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 15

This test illustrates the invention.

To run it, 0.32 wt.% on a dry mineral 100% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in a suspension of Mineral 4A at 20 wt.% solids to concentrate in the laboratory in open loop when the solids content of 70.7 wt.%. Then an additional amount of 0.05% same 100 mol.% Li-neutralinoneutralino acid was added, to continue concentrating to the content of solids by 72.0 wt.%.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 16

This test illustrates the invention.

To run it, 0.32 wt.% on a dry mineral 100% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in a suspension of Mineral 4A at 20 wt.% solids to concentrate in the laboratory in open loop when the solids content of 70.7 wt.%. Then an additional amount of 0.05% same 100 mol.% lithium-neutralized polyacrylic acid was added to continue the concentration until a solids content of 72.6 wt.%.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type viscosite the RA of Brookfield, equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 17

This test illustrates the invention.

To run it, 0.32 wt.% on a dry mineral 100% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in a suspension of Mineral 4A at 20 wt.% solids to concentrate in the laboratory in open loop when the solids content of 70.7 wt.%. Then an additional amount of 0.05% same 100 mol.% lithium-neutralized polyacrylic acid was added to continue the concentration to the content of solids 73.6 wt.%.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with what pendelum 3.

The results are collected in the following table 4.

Table 4
The test numberThe content of solids (wt.%)Variance-Gator in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3The viscosity Brookfield 8 days at 100 rpm, spindle 3
Prior art1168,5%0,48%Too viscous for pumping
>4000 MPa·s
Too viscous for pumping
>4000 MPa·s
Invention1268,5%0,32%75 MPa·s<200 MPa·s
Invention1370,0%0,32%81 MPa·s<200 MPa·s
Invention14 70,7%0,32%98 MPa·s<200 MPa·s

Invention1572,0%0,37%101 MPa·s<200 MPa·s
Invention16to 72.6%0,37%104 MPa·s<200 MPa·s
Invention1773,6%0,37%108 MPa·s<200 MPa·s

The table clearly shows the effectiveness of the method of using a lithium-neutralized polyacrylate that is atomized marble wet grinding with a mean diameter of d500.6 microns.

Example 4

This example relates to the introduction of lithium-neutralized polymer after the stage of concentration due to dispersion of the residue on the filter is derived from concentrated marble wet grinding with a mean diameter of d500.6 microns.

Test 18

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solids content of 55.4 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 1.05 wt.% on a dry mineral normal (50 mol.%/50 mol.%) sodium/magnesium-neutralized polyacrylic acid of Mw=1000 and having a polydispersity of 3.3.

The viscosity Brookfield then measured at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 19

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solids content 67.8 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.88 wt.% on a dry mineral ordinary 100 mol.% potassium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type whisk is simetra of Brookfield, equipped with spindle 3.

Test 20

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solids content to 66.8 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.73 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 21

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solids content of 67.5 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.50 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=10000 and having a polydispersity of 3.4.

Initial Vascos the ü on Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer, equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 22

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solids content of 67.5 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.89 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=10000 and having a polydispersity of 3.4.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 23

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solid content in the society of 67.5 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 1.77 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=10000 and having a polydispersity of 3.4.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 24

This test illustrates the prior art.

To perform it, the Mineral 4b was dispersively when the solids content 67.2 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.49 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized copolymer of acrylic acid-maleic anhydride (50 wt.%/50 wt.%) with Mw=12000 and having a polydispersity of 3.0.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by the use of the RVT type Brookfield viscometer, equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 25

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content of 61.6 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.40 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=1000 and having a polydispersity of 3.3.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 26

This test illustrates the invention.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 27

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content 66,2 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.16 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one cha is and from receiving and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer, equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 28

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content 66,2 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.29 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour of odporucania and 8-day pH after 8 days of storage.

Test 29

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content of 69.5 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.17 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 30

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content 64,0 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.23 wt.% on a dry mineral partial (85 mol.%) lithium-neutralised polyacrylic acid of Mw=6000 and having the second polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 31

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content to 68.1 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.25 wt.% on a dry mineral (50 mol.%/50 mol.%) lithium/potassium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without stirring and the measure after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer, equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 32

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content of 63.2 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.21 wt.% on a dry mineral (85 mol.%/15 mol.%) lithium/sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 33

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content 64.6 wt.%, using a toothed disk Pendraulik stirrer(speed of 3500 to 5000 rpm for 5-10 minutes) and 0.16 wt.% on a dry mineral (93 mol.%/7 mol.%) lithium/sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 34

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content 64.6 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.26 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=50000 and having a polydispersity of 6.25.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer, about radovanovi spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

Test 35

This test illustrates the invention.

To perform it, the Mineral 4b was dispersively when the solids content 67.2 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.25 wt.% on a dry mineral (50 mol.%/50 mol.%) lithium/sodium-neutralized copolymer of acrylic acid-maleic anhydride (50 wt.%/50 wt.%) with Mw=12000 and having a polydispersity of 3.0.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two values of R is: initial pH after one hour from receiving and 8-day pH after 8 days of storage. The results are collected in the following table 5.

Table 5
The test numberContent-the content of solids (wt.%)Variance-Gator in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3The viscosity Brookfield 8 days at 100 rpm, spindle 3pH 1 hour/
8 days
Prior art1855,4%1,05%1130 MPa·s>2000 MPa·s-
Prior art1967,8%0,88%>4000 MPa·s>4000 MPa·s-
Prior art2066,8%0,73%>4000 MPa·s>4000 MPa·s -
Prior art2167,5%0,50%>4000 MPa·s>4000 MPa·s-

Prior art2267,5%0,89%>4000 MPa·s>4000 MPa·s-
Prior art2367,5%1,77%>4000 MPa·s>4000 MPa·s-
Prior art2467,2%0,49%121 MPa·s>500 MPa·s9,9/a 9.6
Invention2561,6%0,40%64 MPa·s<200 MPa·s 9,8/9,7
Invention2666,2%0,14%85 MPa·s<200 MPa·s10,1/a 10.1
Invention2766,2%0,16%56 MPa·s<200 MPa·s9,8/9,8
Invention2866,2%0,29%64 MPa·s<200 MPa·s9,8/9,8
Invention2969,5%0,17%69 MPa·s<200 MPa·s10,1/a 10.1
Invention3064,0%0,23%74 MPa·s<200 MPa·s10,0/10,0
Invention3168,1% 0,25%71 MPa·s<200 MPa·s9,7/a 9.6
Invention3263,2%0,21%52 MPa·s<200 MPa·s10,0/10,2
Invention3364,6%0,16%60 MPa·s<200 MPa·s9,6/9,4
Invention3464,6%0,26%84 MPa·s<200 MPa·s10,2/10,2
Invention3567,2%0,25%70 MPa·s<200 MPa·s10,1/a 10.1

The table clearly shows, by comparing lithium-neutralized polymer of the same, usually neutralized polymer and the corresponding solids content of the suspension, the effectiveness of the method when using Li-neutral is savannaha polyacrylate, to dispersing the filter residue originating from concentrated marble wet grinding with an average diameter d500.6 microns.

Example 5

This example relates to the introduction of lithium-neutralized polymer after the stage of concentration due to dispersion of solid crumbs on the filter >75 wt.% solids originating from concentrated marble wet grinding with a mean diameter of d500.8 μm.

Test 36

This test illustrates the prior art.

To perform it, the Mineral 3 was dispersively when the solids content 72.1 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 2.00 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer, equipped spinda who eat 3.

Test 37

This test illustrates the invention.

To perform it, the Mineral 3 was dispersively when the solids content 72.1 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.24 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

The results are collected in the following table 6.

Table 6
The test numberContent-the content of solids (wt.%)Variance-Gator in calc. on a dry mineral (wt.%)/td> The initial viscosity Brookfield at 100 rpm, spindle 3The viscosity Brookfield 8 days at 100 rpm, spindle 3pH
1 hour/
8 days
Pre-existing level of technology3672,1%2,00%>4000 MPa·s>4000 MPa·s-
Invention3772,1%0,24%81 MPa·s<200 MPa·s10,1/9,9

The table clearly shows the effectiveness of the method when using lithium-neutralized polyacrylate that is atomized marble wet grinding with an average diameter d500.8 μm.

Example 6

This example relates to the introduction of lithium-neutralized polyacrylate after wet grinding due to the dispersion of the residue on the filter is derived from concentrated marble wet grinding with a mean diameter of d500.4 µm.

Test 38

This test illustrates the prior art.

To perform it, the Mineral 5 was dispersively when shadergenerator substances 65.0 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 2.00 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

Then, it was not possible to measure the viscosity Brookfield as suspension of calcium carbonate was close to a solid state.

Test 39

This test illustrates the prior art.

To perform it, the Mineral 5 was dispersively when the solids content 72.1 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.78 wt.% on a dry mineral ordinary 100 mol.% sodium-neutralized copolymer of acrylic acid-maleic anhydride (50 wt.%/50 wt.%) with Mw=12000 and having a polydispersity of 3.0.

The viscosity Brookfield then measured at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 40

This test illustrates the invention.

To perform it, the Mineral 5 was dispersively when the solids content 72.1 wt.%, using a toothed disk Pendraulik stirrer (speed of 3500 to 5000 rpm for 5-10 minutes), and 0.24 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

Nacha is inuu the viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer, equipped with spindle 3.

The viscosity Brookfield after 8 days storage at room temperature without mixing was measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Measured two pH initial pH after one hour from receiving and 8-day pH after 8 days of storage.

The results are collected in the following table 7.

39
Table 7
The test numberThe solids content (wt.%)Disperse-tor in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3The viscosity Brookfield 8 days at 100 rpm, spindle 3pH
1 hour/ 8 days
Pre-existing level of technology3865,0%2,00%no pumps-Xia, almost solidno pumps-SJ
Pre-existing level of technology72,1%0,78%175 MPa·s280 MPa·s9,8/9,5
The image-a buy4072,1%0,24%81 MPa·s<200 MPa·s10.2 and/or 10.3

The table clearly shows the effectiveness of the method when using lithium-neutralized polyacrylate that is atomized marble wet grinding with an average diameter d500.4 µm.

Example 7

This example refers to the addition of lithium-neutralized polyacrylate in two different stages of the method. First Addendum perform during the wet grinding of the RCC, and the second addition made after grinding stage and during the stage of thermal concentration RCC wet grinding with a mean diameter of d500.3 microns.

Test 41

This test illustrates the invention.

To perform it, the Mineral 1b was subjected to wet grinding with a solids content of 62.5 wt.% in tap water in the presence of 0.67 wt.% on a dry mineral 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000, a polydispersity of 2.5 and pH=8,73 vertical grinding mill (Dynoill) in recirculated air mode to grain, at which 50 wt.% particles have a diameter of <0.3 microns.

The viscosity Brookfield, then measured at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with a spindle 3, was 78 MPa·S.

Then, the suspension is additionally thermally concentrated, adjusting the viscosity during concentration by further adding the same lithium-neutralized polyacrylic acid, as used during grinding.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The viscosity Brookfield after 30 days of storage at 60°C without mixing was measured after two minutes of mixing at room temperature and 1,500 rpm using a conventional laboratory stirrer, and the viscosity Brookfield was measured under the same conditions and equipment as in the previous tests.

Measured two pH initial pH after one hour from the receipt and 30-day pH after 30 days of storage.

The results obtained are presented in table 8:

Table 8
wt.% litievogo the polyacrylate, added in the second stageThe solids content (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3The viscosity Brookfield at 100 rpm, spindle 3, after 30 dayspH
1 hour/
30 days
0,80%66,0%128 MPa·s<200 MPa·s-
0,80%67,5%128 MPa·s<200 MPa·s-
0,80%68,6%160 MPa·s<200 MPa·s9,6/9,7
0,89%70,6%317 MPa·s410 MPa·s-
0,89%72,1%607 MPa·s820 MPa·s9,8/9,8

Test 42

This test illustrates the prior art.

For comparison, the same procedure as in test 41 used to get WM is ansii the same Mineral 1A with 100 mol.% sodium-neutralized polyacrylic acid prior art, having a polydispersity of 2.5, as above.

The results obtained are presented in table 9:

Table 9
wt.% sodium polyacrylate added at the second stageThe solids content (wt.%)The viscosity Brookfield at 100 rpm, spindle 3
0,80%55,0%2000-3000 MPa·s
0,80%62,5%Pasta: >4000 MPa·s

It was impossible to obtain a solids content of 67 wt.%, using 0.80 wt.% sodium polyacrylate as the viscosity increased above 5000 MPa·S.

Example 8

This example illustrates the use of lithium-neutralized polymer in the grinding method with a high solids content.

Test 43

This test illustrates the prior art.

To perform it, the Mineral 2 was subjected to wet grinding at 77-80 wt.% solids in water in the presence of 100 mol.% sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 in the vertical grinding mill (Dynomill) mode Retz is kuleli to grain, at which 50 wt.% particles have a diameter of <0.7 mcm.

Test 44

This test illustrates the invention.

For comparison, used the same procedure to obtain a suspension with 100 mol.% lithium-neutralized polyacrylic acid of the same party polyacrylic acid having a polydispersity of 2.5, as above.

The results obtained are presented in table 10:

Table 10
TestSolid suspension (wt.%)Dispersant in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3
MPa·s
The viscosity Brookfield 8 days at 100 rpm, spindle 3
MPa·s
The distribution size
Sedigraph 5100 wt.%
pH 1 hour/ 8 days
Prior art4378,00,7very viscous, cannot be pumped to the mill--9,3/9,5
Image is eenie 4478,10,58149<200 MPa·s<2 μm 92
<1 μm 64
<0.2 μm 16
9,6/9,4

The table clearly shows the effectiveness of the method according to this invention.

Example 9

This example shows that neutralization of lithium allows the use of a polymer with a high polydispersity by comparing the results obtained, on the one hand, by neutralizing polyacrylic acid sodium according to the prior art and, on the other hand, by neutralizing polyacrylic acid lithium according to this invention.

Test 45

This test illustrates the prior art.

To run it, 100 mol.% sodium-neutralized polyacrylic acid was prepared by mixing three different 100 mol.% sodium-neutralized polyacrylic acid in a mass ratio of 1:1:1. For the expert it is clear that this mixture should have a much higher polydispersity compared with each single polymer in the mixture.

The first 100 mol.% sodium-neutralized polyacrylic acid had Mw=1000 and a polydispersity of 3.3, the second 100 mol.% sodium-neutralized polyacrylic acid had Mw=3500 and polydisper is of 2.9 and a third had Mw=6000 and a polydispersity of 2.5. The corresponding mixture had 3300 Mw and the polydispersity >3.

After cooking this 100 mol.% sodium-neutralized polyacrylic acid, the Mineral 4b was dispersively when the solids content of 66.9 wt.%, using a toothed disk Pendraulik stirrer (speed of 3000 rpm for 5-10 minutes), and 2,60 wt.% on a dry mineral cooked 100 mol.% sodium-neutralized polyacrylic acid.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer™, equipped with a spindle 6.

The viscosity of Brookfield™ was 6690 MPa·s, and the pH was 9,3.

Test 46

This test illustrates the invention.

To run it, 100 mol.% lithium-neutralized polyacrylic acid was prepared by mixing three different 100 mol.% lithium-neutralized polyacrylic acid in a mass ratio of 1:1:1. For the expert it is clear that this mixture should have a much higher polydispersity compared with each single polymer in the mixture.

The first 100 mol.% lithium-neutralized polyacrylic acid had Mw=1000 and a polydispersity of 3.3, the second 100 mol.% lithium-neutralized polyacrylic acid had Mw=3500 and a polydispersity of 2.9, and the third had Mw=6000 and polidispersity of 2.5. The corresponding mixture had 3300 Mw and the polydispersity >3.

After cooking this 100 mol.% lithium-neutralized polyacrylic acid, the Mineral 4b was dispersively when the solids content of 68.8 wt.%, using a toothed disk Pendraulik stirrer (speed of 3000 rpm for 5-10 minutes), and 0.23 wt.% on a dry mineral cooked 100 mol.% lithium-neutralized polyacrylic acid.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer™, equipped with a spindle 6.

The viscosity of Brookfield™ was 70 MPa·s, and the pH was 10,0.

The comparison of these two results clearly shows that the use of lithium-neutralized polyacrylic acid allows more to reduce the amount of polymer used to obtain a much more fluid suspension of calcium carbonate at higher solids content.

Example 10

This example illustrates the use of mineral suspensions according to the invention for coating paper and plastic.

Test 47

This test illustrates the invention in the application of the coating.

To perform it, the Mineral 4A concentrated by laboratory evaporation from the receiving solids 20 wt.% up to 75 wt.%, using continuous addition of 100 mol.% lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5.

Then selected the different samples during the concentration of the Mineral 4A corresponding to the contents solids from 55.4 wt.% to 75.5 wt.%, as well as varying amounts used polymer from 0,203 wt.% to 0,273 wt.% calculated on a dry mineral samples were collected for preparation of the respective dyes paper coatings prepared using 12 parts (calculated on dry basis) Acronal S 360 D, BASF, binders, coating paper and 88 parts (calculated on a dry basis), and was applied on a plastic substrate (Synteape, Argo Wiggins) at different mass application.

The dissipation factor S is greater than 100 m2/kg for the mass of coating 20 g/m2reflecting the ability of the coating to disperse visible light, measured according to the method described in WO 02/49766 (pages 8-10). Accordingly, the ability to disperse light is expressed by the coefficient of light scattering, Kubelka-Munch defined using a method well known to the experts, described in the publications Kubelka and Munch (Zeitschrift für Technische Physik 12,539, (1931)), de Kubelka (J.Optical Soc.Am. 38(5),448,(1948) et J.Optical Soc.Am. 44(4),330,(1954)).

The results are collected in the following table 11

/tr>
Table 11
The test numberWt.% Li-Poliak-relateThe solids content (wt.%) suspension of pigmentThe solids content (wt.%) covering dyeDissipation factor (S) at 20 g/m2mass coverage (m2/kg)
Invention47a0,20355,453,0199,5
Invention47b0,23465,260,0194,5
Invention47c0,25669,160,0177,4
Invention47d0,26471,060,0to 151.8
Invention47e0,26472,3 60,0147,3
Invention47f0,26473,860,0to 140.5
Invention47g0,27375,560,0for 125.8

The table clearly shows the effectiveness of the method of using a lithium-neutralized polyacrylate that is atomized marble wet grinding with a mean diameter of d500.6 μm, the coating process.

Test 48

This test illustrates the invention.

To perform it, the Mineral 2 (which has a specific surface area according to BET of 1.4 m2/g) was subjected to wet grinding with 77 wt.% solids in water in the presence of 0.33 wt.%, relative to the dry weight of the mineral, 93 mol.% Li/7 mol.% sodium-neutralized polyacrylic acid of Mw=6000, Mn=2400 g/mol and having a polydispersity of 2.5 1500 litre vertical Kobasa mill containing 0.6-1 mm grinding balls made of zirconium silicate, operating in the continuous mode, achieving such grit that 58 wt.% the particles had a diameter of <2 μm.

At the entrance of the mill slurry of Mineral 2 the chalk pH of 9.7. The maximum temperature at the exit of the mill achieved during grinding was 97°C. the resulting mineral was in the form of suspension from 80.5 wt.% solids, and it is known as the Mineral 9. This suspension had a viscosity Brookfield 175 MPa·s at 25°C., measured at 100 rpm

Then, from the suspension of the Mineral 9 preparing the dye coating paper, comprising, in parts per hundred parts of dry Mineral 9, of the following:

- 8 pieces carboxylating styrene-butadiene synthetic binder having a particle diameter of from 0.08 to 0.12 μm;

- 0.1 parts of carboxymethyl cellulose;

0.5 parts of acrylate rheology modifier.

Obtained covering the dye had a solids content of 77% by dry weight and the viscosity Brookfield 510 MPa·s at 25°C., measured at 100 rpm Good viscosity, among other properties, has led to good behavior during the subsequent coating of paper.

Example 11

This example relates to the introduction of various amounts of lithium-neutralized polyacrylate after wet grinding due to the dispersion of marble wet grinding with a mean diameter of d500.6 microns.

Test 49

This test illustrates the prior art.

To run it, different amounts of normal (100 mol.%) 2-amino-2-methyl-1-propanol (amp) neutralized policr the gross acid of Mw=6000 and having a polydispersity of 2.5 was placed in the Mineral 4b when 66.1 wt.% solid substances.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 50

This test illustrates the invention.

To run it, different amounts (50 mol.%/50 mol.%) USAID/hydroxide lithium-neutralised polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in the Mineral 4b when 68.6 wt.% solid substances.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The results are collected in the following table 12.

Table 12
The test numberThe solids content (wt.%)Dispersant in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3
Prior art49A66,1% 0,50%>4000 MPa·s
Prior art49b66,1%1,05%3000 MPa·s
Prior artS66,1%1,28%3000 MPa·s
Prior art49d66,1%1,48%3000 MPa·s
Prior art49E66,1%1,98%3250 MPa·s
Invention50A68,6%0,28%1450 MPa·s
Invention50b68,6%0,40%476 MPa·s
Invention5068,6%0,43%252 MPa, the
Invention50d68,6%0,48%132 MPa·s
Invention50 ppm68,6%0,49%123 MPa·s
Invention50f68,6%0,52%119 MPa·s

The table clearly shows the effectiveness of the method when using lithium-neutralized polyacrylate that is atomized marble wet grinding with an average diameter d500.6 microns.

Test 51

This test illustrates the prior art.

To run it, 0.73 wt.% dry calcium carbonate ordinary 100 mol.% sodium-neutralized polyacrylic acid of Mw=6000 and having a polydispersity of 2.5 was placed in the Mineral 4b when 65.5 wt.% solid substances.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

Test 52

This test illustrates the invention.

So done shall be his, carboxyl group, a polyethylene-acrylic acid neutralized using lithium hydroxide. The molar ratio of the monomers, polyethylene-acrylic acid was 80/20. Such neutralized EAA was placed in the Mineral 4b when 65.5 wt.% solid substances.

The initial viscosity Brookfield then measured after one hour from the receipt, and after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The results are collected in the following table 13.

Table 13
The test numberThe solids content (wt.%)Dispersant in calc. on a dry mineral (wt.%)The initial viscosity Brookfield at 100 rpm, spindle 3
Pre-existing level of technology5165,5%0,73%>3000 MPa·s
Invention52a65,5%0,08%1490 MPa·s
And the acquisition 52b65,5%0,104%228 MPa·s
InventionS65,5%0,116%200 MPa·s
Invention52d65,5%0,171%165 MPa·s
InventionE65,5%0,284%170 MPa·s

One part of the sample from the test e then kept at rest for 1 day, 3 days, 6 days, and the viscosity Brookfield then measured after one minute of stirring at room temperature and 100 rpm by using RVT type Brookfield viscometer equipped with spindle 3.

The results were 216 MPa·s, 247 MPa·s and 308 MPa·s, respectively.

The other part of the sample stored at room temperature under stirring for 7 days, gave a viscosity Brookfield 274 MPa·S.

These results and the results presented in table 13 also show the efficiency of lithium-neutralized polymer according to this invention.

Note the R 12

This example relates to the dispersion of the mixture filtered natural dolomite dry grinding and natural chalk dry grinding with the introduction of lithium-neutralized polyacrylate.

Test 53

This test illustrates the invention.

1082 g of the suspension of the Mineral 8 obtained in test 8 was dispersively by adding, under stirring in a glass using a toothed disc stirrer (diameter 4 cm), or 0.035%, based on dry weight of suspension, polyacrylate in the form of a 35 wt.% solution, where 100% of the carboxyl groups neutralized with lithium, and the polyacrylate has a polydispersity of 2.5. The resulting suspension had a viscosity Brookfield 160 MPa·s (measured at 100 rpm, using disk 3).

It should be noted that under these conditions, mixing in the presence of Cretaceous dolomite fraction of Mineral 8 was additionally divided.

The resulting dispersion was then selected on a 63 µm sieve, getting 12.2 g on the sieve, while the remaining 783 g of solids passed through a sieve with water to form a diluted slurry having a dry weight of 72.3%.

Example 13

This example illustrates the use of lithium-neutralized polymer in the two-stage method for continual shredding with a high content of solids in industrial scale (i.e. to obtain products in tons).

Test 54

E is from the test illustrates the invention.

To perform it, the Mineral 2 (which has a specific surface area according to BET of 1.4 m2/g) was subjected to wet grinding with 76.5 wt.% solids in water in the presence of 0.3 wt.%, relative to the dry weight of the mineral, 93 mol.% Li/7 mol.% sodium-neutralized polyacrylic acid of Mw=6000, Mn=2400 g/mol and having a polydispersity of 2.5, 160 litre vertical Kobasa mill containing 300 kg of 0.6-1 mm grinding balls made of zirconium silicate, when the feeding speed of the Mineral 2 245 liters/hour, operating in the continuous mode, achieving such grit that 60 wt.% the particles had a diameter of <2 μm. At the entrance of the mill slurry of Mineral 2 had a pH of 9.7. The maximum temperature at the exit of the mill achieved during grinding, was 73°C. the resulting mineral was in the form of a suspension with 80 wt.% solids, and it is known as the Mineral 10. This suspension had a viscosity Brookfield 185 MPa·s at 25°C., measured at 100 rpm Mineral 10 had a specific surface area by BET 8.4 m2/year

Mineral 10 then diluted, reaching a solids content of 78 wt.%, and additionally crushed in the same mill as described above, when the feed speed of 10 Mineral 235 liters/hour, dosing of 0.3 wt.%, relative to the dry weight of the mineral, 93 mol.% Li/7 mol.% sodium-neutralized polyacrylic key is lots with Mw=6000, Mn=2400 g/mol and a polydispersity of 2.5 at the entrance of the mill and dosing of 0.1 wt.%, relative to the dry weight of the mineral, the same polymer at the exit of the mill. Grinding is performed so that the particles emerging from the mill, had the following particle size distributions:

91 wt.% <2 μm

62.4 wt.% <1 μm

At the entrance of the mill slurry of Mineral 10 had a pH of 10.1. The maximum temperature at the exit of the mill achieved during grinding, was 90°C. the Obtained mineral was in the form of a suspension of 80.3 wt.% solids, and it is known as the Mineral 10. This suspension had a viscosity Brookfield 335 MPa·s at 25°C., measured at 100 rpm, and the pH of 9.8. Mineral 10 had a specific surface area according to BET of 13.1 m2/year

1. Method of making mineral water materials containing stage, where
a) provide at least one mineral material in the form of an aqueous suspension or in dry form,
b) provide at least one partially or totally lithium-neutralized water-soluble organic polymer selected from the group of homopolymers of acrylic or methacrylic acid and/or copolymers of acrylic and/or methacrylic acid with one or more acrylic, vinyl or allyl monomers, and the mole fraction is not neutralized acid groups is in the range from 0% to 10%,
c) comprise at least one partially or totally lithium-neutralized water-soluble organic polymer from stage (b) with at least one mineral material from stage a).

2. The method according to claim 1, characterized in that at least one mineral material is crushed (stage d), and stage C) can be performed before, during or after stage (d).

3. The method according to claim 1, characterized in that at least one mineral material chosen from the group consisting of a natural calcium carbonate (GCC), such as marble, chalk, limestone or calcite, or precipitated calcium carbonate (PCC), as aragonite, vaterite and/or calcite, preferably rhombohedral PCC or Selenomethionine RCC; and the minerals containing calcium carbonate such as dolomite or fillers on the basis of mixed carbonates, such as calcium associated with magnesium, such as talc or clay, and mixtures thereof, such as a mixture of GCC and PCC, or a mixture of GCC and PCC and clay, or a mixture of GCC and PCC and talc, or a mixture of calcium carbonate-kaolin, or mixtures of natural calcium carbonate with aluminium hydroxide, mica or with synthetic or natural fibres, or costructure minerals, such as astructure talc-calcium carbonate or talc-titanium dioxide.

4. The method according to claim 3, characterized in that the GCC is subjected stage wet treatment up to stage d).

5. The method according to claim 2, characterized in that the joint and optional crushed material is sieved and/or concentrate (stage e)), and this material is preferably dispersed in the aqueous medium after stage e) filtration and/or concentration (stage f)).

6. The method according to claim 5, characterized in that the joint and optional chopped dried material (stage g)).

7. The method according to claim 6, characterized in that the joint and optional crushed mineral material from stage d) is dispersed in the aquatic environment, if he is supplied in dry form on stage) (stage h)), and the aqueous suspension obtained from stage (h), ground (stage i), preferably in the presence of partially or totally lithium-neutralized water-soluble organic polymer.

8. The method according to claim 7, characterized in that at least one partially or totally lithium-neutralized water-soluble organic polymer is added before and/or during and/or after stage (a), if at least one mineral material is a RCA and/or add to and/or during and/or after stage (d), if at least one mineral material is a GCC, or if stages e) and f) do not perform; and/or add after grinding stage d) and before and/or during and/or after stage e) disqualification add to and/iLive time and/or after the stage of dispersion (f)if stage (f) hold.

9. The method according to claim 7, characterized in that stage a) is performed in the dry form with the following sequentially stages d) and (h), where the addition of partially or totally lithium-neutralized water-soluble organic polymer is performed in one adding before, during or after stage h) or make for a lot of additions, each one of them before, during or after stage h).

10. The method according to claim 7, characterized in that if the stage f) is conducted, and if all or part of the quantity of at least one partially or totally lithium-neutralized water-soluble organic polymer is added to the dispersion (f)at least one partially or totally lithium-neutralized water-soluble organic polymer is added before and/or during and/or after the grinding stage d).

11. The method according to claim 2, characterized in that, if no stage e), f) or g), the entire quantity of lithium-neutralized water-soluble organic polymer is used to stage d), or part of the lithium-neutralized water-soluble organic polymer is used to stage d), whereas the remaining amount added during stage (d).

12. The method according to claim 5, characterized in that, if the stage f) dispersion is followed by stage e), stage (f) is performed in the presence of l is the tie-neutralized water-soluble organic polymer, which may be different or the same as the polymer used in stage d).

13. The method according to claim 2, characterized in that the stage of grinding d) is performed at pH above 7, preferably above 7.5, more preferably between 8.5 and 10.5, and most preferably between 9 and 10, for example, a 9.5.

14. The method according to claim 1, characterized in that at least one partially or totally lithium-neutralized water-soluble organic polymer is completely or partially neutralized by a base containing lithium ion, which is preferably selected from alkaline components such as lithium hydroxide or oxide in dry form or in solution, and perform neutralization with a monomer containing N3About+before polymerization and/or polymer containing H3About+after polymerization of the monomer, and the mole fraction is not neutralized acid groups is in the range from 0% to 75%, more preferably from 0% to 50%, or a combination containing ion lithium base with one or more neutralizing agents containing monovalent or polyvalent neutralizing function, for example, for the monovalent function selected from the group consisting of cations of alkali metals, in particular sodium, potassium, ammonium or the primary, secondary or tertiary aliphatic and/or cyclic amines, t is such as stearylamine, the ethanolamines (mono-, di-, triethanolamine), mono - and diethylamine, cyclohexylamine, methylcyclohexylamine, aminomethylpropanol, morpholine, or, for the polyvalent function, agents, selected from the group consisting of divalent alkaline earth metal cations, in particular magnesium and calcium, or zinc or strontium, trivalent cations such as, in particular, aluminum, or certain cations of higher valency, and mixtures thereof.

15. The method according to claim 1, characterized in that at least one partially or totally lithium-neutralized water-soluble organic polymer is present in amount of from 0.001 wt.% up to 5 wt.%, preferably, from 0.01 wt.% up to 2 wt.% and most preferably, from 0.05 wt.% up to 1 wt.% relative to the total dry mineral material.

16. The method according to claim 3, characterized in that at least one mineral material contains GCC and PCC, where RCC is present in an amount of from 10 to 90 wt.%, preferably from 20 to 80 wt.%, and most preferably from 30 to 70 wt.% the total weight of PCC and GCC.

17. The method according to claim 2, characterized in that stage (d) grinding is performed at a temperature above 20°C, more preferably from 50°C. to 120°C., especially above 60°C, for example from 80°C to 105°C.

18. The method according to claim 2, characterized in that the concentration of solid substances of mineral material in the form of water suspe the Ziya, grinding on stage d) crushing varies from 10 to 82% (by dry weight of mineral material), preferably from 40 to 81%, most preferably from 60 to 80% and particularly preferably from 65% to 72%, and stage of grinding d) are performed with a solids content of from 10 wt.% up to 35 wt.% in the calculation of the total mass of the suspension in the absence of any dispersing agents or auxiliary agents, grinding, and perform when the solids content of 60 wt.% up to 82 wt.% in the calculation of the total mass of the suspension in the presence of dispersing agents and/or auxiliary agents grinding.

19. The method according to p, characterized in that the solids content of the final suspension of mineral material ranges from 45 wt.% up to 82 wt.%, and is preferably from 60 wt.% up to 75 wt.%, more preferably from 68 wt.% up to 73 wt.%, if stage d) grinding is done without any dispersant or auxiliary agent, grinding, and ranges from 65 wt.% up to 82 wt.%, preferably from 72 wt.% up to 78 wt.%, if stage d) grinding is performed in the presence of dispersing agents or auxiliary agents grinding.

20. The method according to claim 1, characterized in that use a combination of a conventional polymer with this lithium-neutralized water-soluble organic polymer, or that use a combination of different lithium neutrons is set for a water-soluble organic polymers.

21. Mineral material obtained by the method according to any one of claims 1 to 20.

22. Mineral material according to item 21, characterized in that it is in the form of an aqueous slurry having a solids content of from 80 to 82% by dry weight of mineral material, for example 80,5% by dry weight of mineral material.

23. Mineral material according to item 21, characterized in that it contains at least one partially or totally lithium-neutralized water-soluble organic polymer in amounts of from 0.001 wt.% up to 5 wt.%, preferably from 0.01 wt.% up to 2 wt.% and most preferably, from 0.05 wt.% up to 1 wt.% relative to the total dry mineral.

24. Mineral material according to item 21, characterized in that it has the d50approximately from 0.2 to 2 μm, preferably from 0.2 to 0.8 μm, most preferably from 0.25 to 0.45 μm, and preferably contains a fraction of particles finer than 2 microns, from 57 to 63 wt.% the total mass of material, and more preferably contains a fraction of particles finer than 2 microns, greater than 50 wt.%, preferably more than 80 wt.%, more preferably more than 85 wt.%, even more preferably more than 98 wt.%, and/or the fraction of particles finer than 1 μm, greater than 20 wt.%, preferably 75 wt.%, more preferably more than 85 wt.%, more than 95 wt.% per full m the SSA material, where the value of d50determine, using a Sedigraph 5100™.

25. Mineral material according to item 23, characterized in that it has a content of from 0.02 to 0.2 mg/m2lithium-neutralized water-soluble organic polymer, for example from to being 0.036 0.038 mg/m2for GCC, 0,063 mg/m2for rhombohedral PCC and 0.12 mg/m2for scalenohedral RCC per unit specific surface area, measured by way of the BET according to ISO 4652.

26. Mineral material according to item 22, wherein the viscosity Brookfield final suspension of mineral material is stable over time, where the initial viscosity Brookfield this aqueous suspension of mineral material after 1 h from receiving less than 4000 MPa·s, preferably below 2000 MPa·s, more preferably below 500 MPa·s, for example from 50 to 500 MPa·s, measured at 100 rpm, the viscosity Brookfield aqueous suspension of mineral material after 8 days of storage without mixing is less than 4000 MPa·s, preferably below 2000 MPa·s, more preferably lower than 1000 MPa·s, particularly 500 MPa·s, for example from 50 to 500 MPa·s, measured at 100 rpm

27. Aqueous suspension of mineral material according to any one of p-26, characterized in that
- she has a solids content of from 80 to 82% by dry weight of mineral material, for example, 80.5 per cent on the ground is a mass of mineral material;
- she has a viscosity Brookfield from 50 to 500 MPa·s, measured at 100 rpm; and
- it contains preferably from 0.25 to 0.5 wt.%, more preferably from 0.3 to 0.4 wt.%, relative to the dry weight of the mineral, at least one water-soluble organic polymer, preferably having an average molecular weight of from 3000 to 12000 g/mol, and in which at least 90% of the carboxyl groups neutralized by lithium ions.

28. The use of mineral materials on any of PP-26 or their aqueous suspensions according to item 27 in the paper, cover paper dyestuffs, paints and plastics.

29. Cover the paper with a dye containing mineral material according to any one of p-26 or its aqueous suspension according to item 27.

30. Covering paper dye clause 29, characterized in that it has a solids content of from 75 to 78% by dry weight of mineral material, for example, 77% by dry weight of mineral material, and preferably has a viscosity Brookfield at 100 rpm less than 2000 MPa·s and more preferably less than 1000 MPa·s, for example 500 MPa·S.

31. Cover the paper with a dye according to any one of p or 30, characterized in that it contains a synthetic binder having a particle diameter of from 0.08 to 0.12 μm.

32. Paper containing mineral materials on any of PP-26 or aqueous suspension according to item 27.

33. PLA is Tiki, containing mineral materials on any of PP-26 or aqueous suspension according to item 27.

34. Paints containing mineral materials on any of PP-26 or aqueous suspension according to item 27.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: dense layer of silicon dioxide is deposited on the surface of titanium dioxide particles from a gas phase, said silicon dioxide layer being doped with at least one doping element selected from a group which includes Sn, Sb, In, Y, Zn, F, Mn, Cu, Mo, Cd, Ce, W and Bi or mixtures thereof. A dense layer of silicon dioxide can be deposited on the surface of titanium dioxide from a liquid phase, said silicon dioxide layer being doped with at least one doping element selected from a group which includes Sb, In, Ge, Y, Nb, F, Mo, Ce, W and Bi or mixtures thereof.

EFFECT: invention increases photostability of titanium dioxide pigment particles.

27 cl, 18 dwg

FIELD: chemistry.

SUBSTANCE: invention can be used to produce a pigment suitable in making paper for ink-jet printing. Precipitated calcium carbonate is obtained by mixing quicklime with water in a reactor or a tank with a mixer, followed by filtration of the calcium hydroxide suspension to remove all residual contaminants and/or non-reactive quicklime. The filtered suspension is then fed into a stainless steel reactor fitted with a mixer. Temperature is kept in the range of 10-70°C, after which the suspension is fed into a carbonisation reactor, where a carbon dioxide-containing gas is bubbled through the suspension. The carbonisation step is carried out at carbonisation gas flow rate of less than 30 litres per minute per kilogram of calcium hydroxide during precipitation under normal conditions. The suspension is removed from the tank when conductivity reaches the minimum level and pH drops below 8, wherein large particles are removed through a filter. The obtained calcium carbonate can be used as a pigment.

EFFECT: invention improves the quality of ink-jet printing while reducing the cost of production of paper for ink-jet printing.

15 cl, 5 dwg, 17 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: titanium dioxide based pigment contains titanium dioxide particles in rutile form, having a coating. The coating contains aluminium phosphate, aluminium oxide, titanium oxide and silicon oxide. The particles are characterised by specific surface area, calculated according to a Brunauer-Emmet-Teller (BET) equation, of at least 15 m2/g. To obtain coated pigments, an aqueous suspension of uncoated titanium dioxide particles is prepared first, followed by addition of aluminium-containing and phosphorus-containing components. Further, while maintaining pH 4-9, an alkaline silicon-containing component and at least one pH regulating component, one of which is an acidic titanium-containing component, are then added. The formed suspension is then filtered, washed and dried and the precipitate is ground to obtain coated particles.

EFFECT: invention increases opacity of decorative paper.

22 cl, 5 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention can be used in production of tissue paper. Surface-treated natural calcium carbonate is used as filler in tissue paper products, where said calcium carbonate is a product of reaction of natural calcium carbonate with an acid and carbon dioxide. The carbon dioxide is formed in situ by treatment with the acid and/or is fed from an external source. The surface-treated natural calcium carbonate is obtained as an aqueous suspension having pH higher than 6.0, measured at 20°C.

EFFECT: invention improves softness of tissue paper products such as facial tissue, toilet paper, ornamental paper, towels, napkins or tissue paper cloths.

47 cl, 1 dwg, 5 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: titanium dioxide based pigment, containing titanium dioxide particles, has a coating layer containing aluminium phosphate and aluminium oxide, and said layer additionally contains hollow particles. To obtain said pigment, aqueous suspension of titanium dioxide is prepared first, and aluminium- and phosphorus-containing components are then added, after which hollow particles are added and pH of the suspension is brought to 4-9. Also, aqueous suspension of titanium dioxide can be obtained at pH not lower than 10, and aluminium- and phosphorus-containing components can then be added while maintaining pH of at least 10, after which hollow particles are added. Further, pH of the suspension is brought to 4-9 and an aluminium oxide coating is then applied at pH from 4 to 9.

EFFECT: invention increases opaqueness and retention of pigment when making decorative paper.

22 cl, 1 dwg, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical industry. The method of producing jointly ground calcium carbonate material, which contains ground calcium carbonate (GCC) and precipitated calcium carbonate (PCC) with coefficient of curvature at least equal to approximately 30, preferably at least approximately 40 and even more preferably at least approximately 45, comprises the following steps: a) obtaining at least one calcium carbonate material, optionally, in form of an aqueous suspension; b) combined grinding of GCC and PCC, optionally, with at least another mineral material which is selected from talc, clay, Al2O3, TiO2 or mixtures thereof; c) optional sieving and/or concentration of the jointly ground calcium carbonate obtained after step (b); d) optional drying of the jointly ground calcium carbonate material obtained after step (b) or (c). The coefficient of curvature is defined as d30/d70×100, where d30 and d70 denote equivalent spherical diameters, relative which 30 wt % and 70 wt % particles have a smaller size.

EFFECT: invention enables to improve optical properties of enamel paper and exclude the PCC deagglomeration step.

40 cl, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in chemical industry. The method of producing jointly ground calcium carbonate material, which contains ground calcium carbonate (GCC) material and precipitated calcium carbonate (PCC) comprises the following steps: a) obtaining at least one calcium carbonate material, optionally, in form of an aqueous suspension; b) combined grinding of GCC and PCC, optionally, with at least another mineral material which is selected from talc, clay, Al2O3, TiO2 or mixtures thereof; c) optional sieving and/or concentration of the jointly ground calcium carbonate obtained at step (b); d) optional drying of the jointly ground calcium carbonate material obtained at step (b) or (c). The fraction of particles of the obtained material with size smaller than 1 mcm is greater than 80%, preferably greater than 85%, more preferably greater than 90% and even more preferably greater than 95%. BET specific surface area is less than 25 m2/g.

EFFECT: invention enables to increase lustre of enamel paper.

44 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: suspension containing calcium carbonate is obtained by adding one or more zirconium compounds and possibly one or more other additives which do not contain phosphate, acting as a dispersant and/or an additive which assists in grinding. Calcium carbonate in dry form and/or in form of an aqueous dispersion or filtered residue is added an aqueous suspension and/or aqueous emulsion and/or aqueous solution containing one or more zirconium compounds. The zirconium compounds used is ammonium zirconium carbonate or calcium zirconium carbonate or mixture thereof.

EFFECT: invention enables to avoid the use of phosphate dispersants when preparing stable aqueous suspensions of calcium carbonate and increases content of solid substance in the suspension.

17 cl, 22 ex

FIELD: printing industry.

SUBSTANCE: to produce a precipitated calcium carbonate, a suspension of calcium hydroxide is made by mixing of quicklime with water in a reactor with a mixer or in a tank, then the produced suspension is filtered via a 100-mcm filter. The filtered suspension is sent into a reactor of stainless steel equipped with a mixer. Temperature from 10 to 70°C is set, afterwards the suspension is sent into a reactor or a tank for carbonisation, where a carbon-containing gas is bubbled through the suspension. The suspension is drained from the tank, when electric conductivity achieves the minimum level, and pH falls below 8. Coarse particles are removed at a 45-mcm filter. At the same time the carbonisation stage is carried out at speed of carbonising gas flow of below 30 litres per minute under normal conditions per kg of calcium hydroxide in process of deposition. Concentration of precipitated calcium carbonate is increased using a cationic, anionic or combined disperser under quite moderate or mild conditions, which do not cause considerable damage of aggregates/agglomerates, until concentration from 25 to 60% is achieved, preferably in the range from 35 to 50%, most preferably - from 39 to 40 wt % of hard substances.

EFFECT: invention makes it possible to produce porous stable agglomerates of precipitated calcium carbonate with size of 1-5 mcm.

22 cl, 5 dwg, 17 tbl, 9 ex

FIELD: printing industry.

SUBSTANCE: to produce a precipitated calcium carbonate, a suspension of calcium hydroxide is made by mixing of quicklime with water in a reactor with a mixer or in a tank, then the produced suspension is filtered via a 100-mcm filter. The filtered suspension is sent into a reactor of stainless steel equipped with a mixer. Temperature from 10 to 70°C is set, afterwards the suspension is sent into a reactor or a tank for carbonisation, where a carbon-containing gas is bubbled through the suspension. The suspension is drained from the tank, when electric conductivity achieves the minimum level, and pH falls below 8. Coarse particles are removed at a 45-mcm filter. At the same time the carbonisation stage is carried out at speed of carbonising gas flow of below 30 litres per minute under normal conditions per kg of calcium hydroxide in process of deposition. Concentration of precipitated calcium carbonate is increased without using an agent that promotes dispersion or with application of a cationic disperser under quite moderate or mild conditions, which do not cause considerable damage of aggregates/agglomerates, until concentration from 15 to 50% is achieved, preferably in the range from 20 to 30%, most preferably - from 23 to 26 wt % of hard substances.

EFFECT: invention makes it possible to produce porous stable agglomerates of precipitated calcium carbonate.

22 cl, 5 dwg, 9 tbl, 12 ex

FIELD: textiles, paper.

SUBSTANCE: cardboard comprises solid cardboard substrate of bleached sulphate pulp (BSP) and a coating applied to the cardboard substrate to form a coated structure. The said coated structure has a surface density, thickness of the sheet and the Parker surface smoothness. The Parker surface smoothness is at most about 3 microns, and the surface density is at most about Y2 or Y3 or Y4 pound/3000 foot2, where Y2, Y3 and Y4 are functions of the said thickness (X) of the sheet in points which are calculated using the equation: Y2=3.71+13.14X-0.1602X2 or Y3=3.63+12.85X-0.1566X2, or Y4=3.50+12.41X-0.1513X2.

EFFECT: invention provides a coated cardboard with increased smoothness with the required parameters of thickness and the surface density to ensure high-quality printing.

13 cl, 10 dwg, 1 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: invention can be used to produce a pigment suitable in making paper for ink-jet printing. Precipitated calcium carbonate is obtained by mixing quicklime with water in a reactor or a tank with a mixer, followed by filtration of the calcium hydroxide suspension to remove all residual contaminants and/or non-reactive quicklime. The filtered suspension is then fed into a stainless steel reactor fitted with a mixer. Temperature is kept in the range of 10-70°C, after which the suspension is fed into a carbonisation reactor, where a carbon dioxide-containing gas is bubbled through the suspension. The carbonisation step is carried out at carbonisation gas flow rate of less than 30 litres per minute per kilogram of calcium hydroxide during precipitation under normal conditions. The suspension is removed from the tank when conductivity reaches the minimum level and pH drops below 8, wherein large particles are removed through a filter. The obtained calcium carbonate can be used as a pigment.

EFFECT: invention improves the quality of ink-jet printing while reducing the cost of production of paper for ink-jet printing.

15 cl, 5 dwg, 17 tbl, 9 ex

FIELD: chemistry.

SUBSTANCE: invention relates to organic fibres having a mineralised surface, which includes organic fibres having a length in the millimetre range, the surface of which is at least partially coated with finely dispersed nanoparticles alkali-earth metal carbonates using binding materials based on copolymers which contain, as monomers, one or more dicarboxylic acids or one or more monomers from a group of diamines, triamines, dialkanolamines or trialkanolamines, and epichlorohydrin, a method of producing such organic fibres having a mineralised surface, aqueous suspensions thereof, use thereof in paper production, in finishing paper surfaces, plastic surfaces, cement and clay, in paint and lacquer, and use of binding substances according to the present invention to coat organic fibres with nanoparticles of alkali metal carbonates.

EFFECT: providing fibre-pigment or filler composites, as well as aqueous suspensions thereof, which not only have good optical properties and good printing properties, but also have an insignificant or no tendency to segregate in treatment conditions thereof, and also enable to obtain paper or cardboard having high content of filler of nanoparticles which are otherwise hard to hold due to their fineness.

37 cl, 8 tbl, 13 dwg

FIELD: textiles, paper.

SUBSTANCE: paper base is intended for internal and external sizing, which has high dimensional stability, and can be used in pulp and paper industry. Paper base contains cellulose fibers, at least one filler, and sizing agent. At that the paper base has a coefficient of hygroextension from 0.6 to 1.5%. The Scott internal constraint in the transverse direction is not greater than 300 J/m2, and/or Scott internal constraint in the longitudinal direction is not greater than 300 J/m2. Also a method of manufacturing the paper base and versions of paper base are proposed.

EFFECT: increased dimensional stability and durability of the surface of the paper base.

26 cl, 24 dwg, 15 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention can be used in making paper products. The gypsum product essentially consists of undamaged crystals, having weight-average diameter D50 0.1 - 2.0 mcm and particle size distribution width less than 2.0. The shape factor of the crystals is equal to at least 2.0 and the aspect ratio is equal to 1.0-10. The gypsum product is obtained by reacting calcium sulphate hemihydrate and/or calcium sulphate anhydrite and water in the presence of a crystal habit modifier. The reaction mixture has dry substance content of 50-84 wt %. The crystal habit modifier is used in amount of 0.01-5.0% of the weight of the calcium sulphate hemihydrate and/or calcium sulpohate anhydrite and is selected from a group consisting of ethylenediamine succinic acid, iminodisuccinic acid, ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, nitrilotriacetic acid, N-bis-(2-(1,2-dicarboxyethoxy)ethylasparticacid, di-, tetra- and hexaaminostilbene sulphonic acid and salts thereof, such as sodium aminotriethoxy succinate (Na6-TCA), as well as alkylbenzene sulphonates. The crystallised or extracted gypsum is dispersed, treated with biocides, sieved and bleached.

EFFECT: high lustre and opacity due to that the gypsum particles are flat and have equal size.

18 cl, 11 dwg, 5 ex

FIELD: chemistry.

SUBSTANCE: mixture is prepared from calcium sulphate semihydrate and/or calcium sulphate anhydrite and water with dry substance content of said mixture ranging from 34 to 84 wt %. The mixture is stirred until formation of a crystalline gypsum product. The reaction mixture can further be mixed with a calcium sulphate dihydrate or a crystal habit modifier selected from ethylene diamine amber acid, amino diamber acid, ethylene diamine tetraacetic acid, diethylene triamine pentaacetic acid, nitrilotriacetic acid, N-bis-(2-(1,2-dicarboxyethoxy)ethylaspartic acid, di-tetra- and hexaaminostilbene sulphonic acid and salts thereof, such as sodium aminotriethoxy succinate (Na6-TCA), as well as akylbenzene sulphonates. Water is used at temperature 0-100°C. Crystallised gypsum is dispersed using a dispersant in amount of 0.01-5.0 wt %, treated with a biocide, sieved and bleached. The obtained gypsum product essentially consists of intact gypsum crystals with size 0.1-2.0 mcm, shape factor 2.0-5.0 and aspect ratio 1.0-10.

EFFECT: simple method.

23 cl, 33 dwg, 28 ex

FIELD: textiles, paper.

SUBSTANCE: composition comprises: a) a filler, b) a cationic inorganic compound - polyaluminumchloride, c) a cationic organic compound, and d) anionic polysaccharide. The filler is present in an amount of at least about 1% by weight, based on the total weight of the composition. Anionic polysaccharide is present in an amount from about 1 to about 100 kg/ton based on the weight of the filler. The composition is substantially free of fibers. Filler composition of the version contains the components a), b), c) and d), as defined above. The only difference is that the component c) is a cationic polyamine condensation polymer, and the component d) has a degree of substitution of stoichiometrically excess anionic groups of up to about 0.65. At that each of b) and c) components present in an amount from about 0 to about 30 kg/ton based on the weight of the filler. At that the composition comprises at least one of b) and c) components. Methods of obtaining compositions of filler comprise mixing a), b), c) and d), as defined above. The invention also relates to a filler composition, which is obtained by this method, an application of the filler composition as an additive to an aqueous suspension of cellulose in the production process of paper and to manufacturing paper comprising adding a filler composition to an aqueous suspension of cellulose. The invention also relates to a paper obtained with this method, and paper comprising the filler composition.

EFFECT: improvement of composition.

35 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: suspension containing calcium carbonate is obtained by adding one or more zirconium compounds and possibly one or more other additives which do not contain phosphate, acting as a dispersant and/or an additive which assists in grinding. Calcium carbonate in dry form and/or in form of an aqueous dispersion or filtered residue is added an aqueous suspension and/or aqueous emulsion and/or aqueous solution containing one or more zirconium compounds. The zirconium compounds used is ammonium zirconium carbonate or calcium zirconium carbonate or mixture thereof.

EFFECT: invention enables to avoid the use of phosphate dispersants when preparing stable aqueous suspensions of calcium carbonate and increases content of solid substance in the suspension.

17 cl, 22 ex

FIELD: printing industry.

SUBSTANCE: to produce a precipitated calcium carbonate, a suspension of calcium hydroxide is made by mixing of quicklime with water in a reactor with a mixer or in a tank, then the produced suspension is filtered via a 100-mcm filter. The filtered suspension is sent into a reactor of stainless steel equipped with a mixer. Temperature from 10 to 70°C is set, afterwards the suspension is sent into a reactor or a tank for carbonisation, where a carbon-containing gas is bubbled through the suspension. The suspension is drained from the tank, when electric conductivity achieves the minimum level, and pH falls below 8. Coarse particles are removed at a 45-mcm filter. At the same time the carbonisation stage is carried out at speed of carbonising gas flow of below 30 litres per minute under normal conditions per kg of calcium hydroxide in process of deposition. Concentration of precipitated calcium carbonate is increased using a cationic, anionic or combined disperser under quite moderate or mild conditions, which do not cause considerable damage of aggregates/agglomerates, until concentration from 25 to 60% is achieved, preferably in the range from 35 to 50%, most preferably - from 39 to 40 wt % of hard substances.

EFFECT: invention makes it possible to produce porous stable agglomerates of precipitated calcium carbonate with size of 1-5 mcm.

22 cl, 5 dwg, 17 tbl, 9 ex

FIELD: printing industry.

SUBSTANCE: to produce a precipitated calcium carbonate, a suspension of calcium hydroxide is made by mixing of quicklime with water in a reactor with a mixer or in a tank, then the produced suspension is filtered via a 100-mcm filter. The filtered suspension is sent into a reactor of stainless steel equipped with a mixer. Temperature from 10 to 70°C is set, afterwards the suspension is sent into a reactor or a tank for carbonisation, where a carbon-containing gas is bubbled through the suspension. The suspension is drained from the tank, when electric conductivity achieves the minimum level, and pH falls below 8. Coarse particles are removed at a 45-mcm filter. At the same time the carbonisation stage is carried out at speed of carbonising gas flow of below 30 litres per minute under normal conditions per kg of calcium hydroxide in process of deposition. Concentration of precipitated calcium carbonate is increased without using an agent that promotes dispersion or with application of a cationic disperser under quite moderate or mild conditions, which do not cause considerable damage of aggregates/agglomerates, until concentration from 15 to 50% is achieved, preferably in the range from 20 to 30%, most preferably - from 23 to 26 wt % of hard substances.

EFFECT: invention makes it possible to produce porous stable agglomerates of precipitated calcium carbonate.

22 cl, 5 dwg, 9 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to use in paint of calcium carbonate which is obtained by dry-grinding in the presence of a grinding aid agent. Said agent is a copolymer containing a) 0.5-50% of at least one anionic monomer selected from acrylic acid, methacrylic acid and mixtures thereof, and b) 50-99.5% of at least one nonionic monomer taken in amount of 0.05-5% of the dry mass of calcium carbonate.

EFFECT: paints containing calcium carbonate obtained using the described method have high viscosity stability with preservation of optical properties of the paints.

7 cl, 3 tbl, 4 ex

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