WO2003074786A2 - Aqueous slurries of fine-particulate fillers, method for production and use thereof for the production of papers comprising fillers - Google Patents

Aqueous slurries of fine-particulate fillers, method for production and use thereof for the production of papers comprising fillers

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Publication number
WO2003074786A2
WO2003074786A2 PCT/EP2003/002043 EP0302043W WO03074786A2 WO 2003074786 A2 WO2003074786 A2 WO 2003074786A2 EP 0302043 W EP0302043 W EP 0302043W WO 03074786 A2 WO03074786 A2 WO 03074786A2
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WO
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Patent type
Prior art keywords
aqueous
paper
filler
fillers
slurries
Prior art date
Application number
PCT/EP2003/002043
Other languages
German (de)
French (fr)
Other versions
WO2003074786A3 (en )
Inventor
Anton Esser
Rudolf Lorz
Rainer Blum
Chafiq Belouadi
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

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Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES; PREPARATION OF CARBON BLACK; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02Compounds of alkaline earth metals or magnesium
    • C09C1/021Calcium carbonates
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63Inorganic compounds
    • D21H17/67Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/69Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or paper
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/14Pore volume

Abstract

The invention relates to aqueous slurries of fine-particulate fillers, at least partly coated with polymers and which may be obtained by treatment of aqueous slurries of fine-particulate fillers with at least one binder for paper coating inks, production of the aqueous slurries and use thereof for the production of paper comprising fillers, card comprising fillers and cardboards comprising fillers, by means of draining the pulp.

Description

Aqueous Anschlärπmungen of finely divided fillers, process for their preparation and their use for the production of filler containing papers

description

The invention relates to aqueous Anschlammungen of finely divided fillers which are at least partly coated with polymers, processes for their preparation and their use as an additive to paper stock in the production of filler-containing paper, filler-containing cardboard and filler-containing board.

From DE-B-25 16 097 discloses that, mixing aqueous suspensions of inorganic particles having a positive zeta potential with an anionic latex of a resin, the balance of the negative and positive charges of the particles of the inorganic material in the suspension is and the resin in the latex adjusted during mixing so that the essential loan be bound to the surface of the particles of the inorganic substance all the resin particles and the thus obtained coated particles have a zeta potential of substantially 0th However, the treatment of the inorganic particles with a latex requires that the inorganic particles be pretreated with a KAT-ionic agents, such as cationic starch, so that they have a positive zeta potential. The aqueous suspensions are added in the production of filler-containing paper to the paper stock.

In order to produce highly concentrated aqueous pigment slurries such as calcium carbonate slurries having a low viscosity is required, a dispersant such as low-molecular polyacrylic acids, see FIG. EP-A-0 002 771. The dispersed pigment particles have an anionic surface charge. The aqueous pigment slurries are used for example in the production of paper. For this purpose, in addition to use aqueous dispersions of precipitated calcium carbonate, which is usually processed in the absence of dispersants.

From EP-B 0 573 458 is a process for the preparation of aqueous slurries of finely divided fillers which are at least partly coated with polymers, known for the preparation of filled papers. In this method, first adding to an aqueous slurry of filler a cationic strength agent for paper and thereafter a non-ionic and / or anionic strength agent for paper or a nonionic or anionic size for paper. The cationic materials used are, however, always be used in an amount such that the finely divided fillers carry a cationic charge.

From DE-A-198 21 089 another method for the preparation of aqueous slurries of finely divided fillers is known to be at least partially coated with polymers. In this method, treating an aqueous slurry of filler in the absence of cationic strength agents for paper having min- least one Polymerlei ungsmittel in the form of an aqueous dispersion. However, such dispersions always contain polymeric emulsifiers, for example degraded starches or synthetic polymers.

The invention has for its object to provide more aqueous slurries of finely divided fillers, which result in papermaking compared with the known slurries papers with improved tenacity and printability.

The object of the invention is achieved with an aqueous

Anschlammungen of finely divided fillers which are at least partly coated with polymers, the slurries are obtainable by treating aqueous slurries of fine piece fillers with at least a binder for paper coating colors.

The aqueous suspensions include, for example, 1 to 50 wt .-%, preferably 10 to 40 wt .-% of at least one finely divided filler. The amount of binder is beispiels-, 0.1 to 5 wt .-%, preferably 0.5 to 3 wt .-%, based on fillers.

The invention also provides a process for preparing the aqueous Anschlammungen to give an aqueous slurry of at least one finely divided filler 0.1 to 5 wt .-% of at least one binder for paper coating colors, based on filler, added, or the aqueous slurry of fine particle of at least one entering the filler into an aqueous dispersion of a binder for paper coating colors and the loading stand parts respectively mixed. The molecular weight of the emulsifiers present in the binders for paper coatings is <2000th

Another object of the invention is the use of the aqueous slurries described above as an additive to paper stock in the production of filler-containing paper, cardboard or filler-containing board like füllstoffhalti- by draining the stock.

Suitable fillers are all commonly used in the paper industry 5 usable pigments, examples being calcium carbonate, which can be used in the form of lime, chalk, marble or precipitated calcium carbonate, talc, kaolin, bentonite, satin white, calcium sulfate, barium sulfate and titanium dioxide. The particle diameter of the finely divided fillers for example, between 10 40 and 90% less than 2 microns.

The fillers are processed, for example by placing it in water to form an aqueous slurry. Precipitated calcium carbonate is usually in the absence of dispersants

15 mittein slurried in water. In order to prepare aqueous slurries of the other fillers, as an anionic dispersing agent usually, for example, from 1000 to 40 000. If using an anionic dispersing agent such as polyacrylic acid having a molecular weight Mw, one set thereof beispiels-

20, 0.01 to 0.5 wt .-%, preferably 0.2 to 0.3 wt .-% for the preparation of aqueous filler slurries a. The finely divided in the presence of anionic dispersing in water dispersible th fillers are anionic. The aqueous slurries often contain from 15 to 25 wt .-% of at least

25 of a filler.

In order to prepare aqueous Anschlammungen the invention of finely divided fillers is treated using aqueous Conn mmungen of optionally anionically dispersed finely divided Füllstof- 0 fen with at least one binder for paper coating colors.

For example, it may be a 1 to 50 wt .-% of at least one finely divided filler-containing aqueous slurry of 0.1 to 5 wt .-%, based on fillers, of a binder for paper coating colors enforce or an aqueous slurry of a 5 particulate filler into an aqueous dispersion Add a binder for paper coating colors and blend the components, respectively. Treating the aqueous slurries of finely divided fillers with the binders for paper coating can be continuous or batchwise are 0th On combination of aqueous slurries of finely divided fillers and aqueous dispersions of binders for paper coating colors, the fillers are at least partly covered with binders or impregnated. The mixing of the components is carried out, for example, in a shear field. In most cases, it is 5 sufficient if the mixture is stirred or the components after combining them treated in a shear field of an Ultraturrax. The combination and mixing of the ingredients of the aqueous slurries can be effected, for example, in the temperature range of 0 ° C to 95 ° C., preferably 10 to 70 ° C. In most cases the components are mixed at the respective room temperature up to a temperature of 40 ° C. The pH value of the colors binders treated String aqueous slurries of fillers is for example 5 to 11, preferably 6 to 9, wherein the pH of calcium carbonate-containing slurries of preferably more than 6.5.

The binders preferably contain so-called main monomers in copolymerized form, selected from Ci to Cie alkyl (meth) acrylates, vinylaromatics having up to 20 carbon atoms, vinyl esters of carboxylic acids having 1 to 20 carbon atoms, vinyl halides, ethylenically unsaturated nitriles, nonaromatic hydrocarbons with a or two conjugated double bonds, or mixtures of these monomers. Mention may be made, for example, (meth) acrylates having a Cχ-Cιo-alkyl, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, isobutyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate. In particular, mixtures of the (meth) acrylic acid alkyl esters are suitable.

As vinyl esters of carboxylic acids having 1 to 20 carbon atoms, vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate are contemplated.

Suitable vinylaromatic compounds having up to 20 carbon atoms, vinyltoluene, α-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene, and preferably styrene are also suitable. Examples of ethylenically unsaturated nitriles are acrylonitrile and methacrylonitrile.

Vinyl halides are chlorine-, fluorine- or bromine-substituted ethylenically unsaturated compounds, preferably vinyl chloride and Viny1idenchlorid.

Examples of nonaromatic hydrocarbons having one or two conjugated olefinic double bonds of butadiene, isoprene and chloroprene and ethylene may be mentioned.

Besides the principal monomers the binder may optionally comprise further monomers in copolymerized form, for example, hydroxyl group-containing monomers such as hydroxyalkyl acrylates or monomers having alkoxy groups, such as are obtainable by alkoxylation of hydroxy monomers with alkoxides, in particular ethylene oxide or propylene monomers having acid or anhydride groups, or salts thereof, such as (meth) acrylic acid, maleic acid, vinylsulfonic acid. The binders are preferably made of a polymer, the wt .-% of the main monomer, more preferably at least 35 contains at least 20 wt .-% and most preferably at least 50 wt .-% of at least one copolymerized principal monomers.

The binder may also least 1 wt .-%, more preferably contain in copolymerized form at least 3 wt .-%, particularly preferably (mere short Säuremono-) at least 15 wt .-% of monomers having at least one acid group. The acid groups of the polymerisation sats may be neutralized before the subsequent application, at least partially, if necessary. Preferably, at least 30 mol%, particularly preferably neutralized 50 to 100% of the acid groups. Suitable bases are volatile bases such as ammonia or non-volatile bases such as alkali metal hydroxides, in particular sodium hydroxide.

Binders preferably used are, for example, aqueous dispersions of copolymers of

(A) styrene and / or acrylonitrile or methacrylonitrile,

(B) acrylic acid esters and / or methacrylic acid esters of Cι ~ to Ciβ-alcohols, and optionally

(C) acrylic acid, methacrylic acid, maleic acid and / or itaconic acid.

More preferably eligible binders are polymers of (a) styrene, (b) butadiene, and (c) optionally, acrylic acid or methacrylic acid. And copolymers based on (meth) acrylic esters or vinyl acetate, and other monoethylenically unsaturated monomers are used as binders for color Papierstreich- for the treatment of aqueous suspensions of fillers of interest. The glass transition temperature of the polymer is, for example, -40 to + 50 ° C and is preferably below 6 ° C.

The binders for paper coating are preferably prepared by free radical polymerization of the above monomers in an aqueous medium in the presence of protective colloids or emulsifiers. Suitable protective colloids are, for example, polyvinyl alcohols or partly hydrolysed polyvinyl acetates. Is preferably used for the inventive treatment of finely divided fillers such a binder stabilized by means of protective colloids or emulsifiers having a molecular weight Mw <2000th Particularly preferred aqueous dispersions of the binder, which comprise, as emulsifier for the polymer anionic emulsifiers such as sodium lauryl sulfate, disulfo-Cι -alkyldiphenyloxid or mixtures thereof. However, it is also possible to use such aqueous dispersions of polymers as binders, which are stabilized with the aid of nonionic, cationic or amphoteric emulsifiers. Customary emulsifiers are ethoxylated fatty alcohols (degree of ethoxylation: 3 to 50, alkyl radical: Cβ- C36) / ethoxylated mono-, di- and trialkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: Cβ- to Cι 2), alkali metal salts of dialkyl esters of Sulfobersteinsäure and alkali metal and ammonium salts of alkylsulfates (alkyl radical: CQ to Cι 2), of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: Cι 2 - to Ciβ), (ethoxylated alkyl phenols of ethoxylation: 3 to 50, alkyl radical : C- to Cg), of alkylsulfonic acids (alkyl radical: Cι - to Cia) and (of alkylarylsulfonic alkyl radical: C 9 - to Ciβ) • the maximum particle size of the polymer contained in the aqueous dispersions, for example, 50 to 300 nm, preferably 80 to 150nm. The binders contain, for example 0.1 to 5, preferably 0.5 to 3 wt .-% of at least one emulsifier.

Particularly preferred are aqueous slurries of precipitated calcium carbonate, which is free from dispersants, and manufactured by ground calcium carbonate, which is available with molecular weights from 1,000 to 15,000 by milling of lumpy calcium carbonate or marble in the presence of anionic polymeric dispersants such as polyacrylic acids. preferably anionic adjusted aqueous dispersions of copolymers are used for this based on styrene and butadiene or styrene and acrylic esters as binders, which are stabilized by means of emulsifiers, which have a molecular weight Mw <2000th

The aqueous suspensions of fillers according to the invention are used as an additive to paper stock in the production of filler-containing paper, filler-containing cardboard or filler-containing board by draining of the paper. They can be stored for a long time or not prepared immediately prior to papermaking in the paper mill and processed directly. They are added to the paper stock in an amount such that filler-containing papers are formed, for example, containing 5 to 50 wt .-%, preferably 15 to 35 wt .-% of filler. The aqueous slurries are suitable in particular for producing paper with filler contents of 30 to 50 wt .-%. The aqueous Anschlammungen of fillers may be added during the papermaking both the thick stock and the thin stock. They can be used in the presence of commonly used in the paper industry, additives such as sizing agents, fixatives, dehydrating agents, strength agents or retention agents. According to the invention with a binder for paper coatings treated aqueous pigment slurries can be used for the production of all filler grades of paper, such as newsprint, SC-paper (supercalandriertes paper), wood-free or wood-containing printing and writing papers. For the production of such papers, for example used pulp components as Hauptrohstoff-, thermomechanical pulp (TMP), che o- thermomechanisehern pulp (CTMP), pressure groundwood (PGW) and sulfite and sulfate pulp. In order to achieve a high filler retention, the addition of retention agents to the stock is recommended. The retention agents may be added, for example, to the thick stock or the thin stock. Suitable retention agents are used, for example, high molecular weight polyacrylamides (the molecular weights of the polymers are in excess of 2 million) or by using so-called micro-particle systems, said first adding a polymeric cationic retention agent to the stock, then subjecting the stock to shear and then bentonite or finely divided silica in amounts up to 2 wt .-%, based on dry fiber, is added.

In the manufacture of wood-free papers can additionally add optical brightener to the paper stock. The amounts of optical brighteners are, for example, 0.3 to 3.0, preferably 0.6 to 1.5 wt .-%, based on dry paper stock.

Due to the treatment of aqueous slurries of finely divided fillers with the aqueous dispersions of binders for paper coating colors aqueous filler slurries that can be processed into paper in which the dusts in the printing and copying process is reduced compared to filler-containing papers, the filler not treated with a binder to obtain were.

The percentages in the examples are by weight, unless the context is clear otherwise.

The aqueous Anschlammungen of fillers prepared in Examples 1 to 5 and Comparative Example 1 were then each tested for their suitability for the production of filled papers. The particle size of the dispersed fillers was in the Examples and Comparative Example 1 each for 90% of the particles is <2 microns. example 1

1.8 g of a 50% commercial aqueous dispersion of a stabilized with anionic emulsifiers copolymers of styrene and n-butyl acrylate with a glass transition temperature of 5 ° C (Acronal® S 504) were placed in a beaker and then with water to a solids content of 10 % diluted. Were then added in water 150g of a 20% slurry of precipitated calcium carbonate (PCC). During the addition of the slurry and thereafter the mixture was stirred using a Heiltof stirrer at 1000 revolutions per minute (rpm). The pH of the mixture was then adjusted to 8.5.

example 2

0.6 g of a 50% commercial aqueous dispersion of a stabilized with anionic emulsifiers copolymers based on styrene and n-butyl acrylate with a glass transition temperature of 5 ° C (Acronal® S 504) were placed in a beaker and subsequently with drinking water diluted has a solids content of 10%. Thereafter, this solution was added 150g of a 20% slurry of PCC is added into water. During the addition of the PCC slurry and thereafter, the mixture was stirred using a stirrer at 1000 rpm Heiltof-. The pH of the mixture was subsequently adjusted to 8.5.

example 3

1.8 g of a 50% commercial aqueous, an anionic emulsifier containing styrene-butadiene dispersion

(Styronal® 8736) with a glass transition temperature of 5 ° C were placed in a beaker and then diluted with water to a solids content of 10%. Thereafter, this solution was added 150 g of a 20% aqueous PCC slurry added. During the addition and then the mixture was stirred using a stirrer at 1000 rpm Heiltof-. The pH of the mixture was then adjusted to 8.5.

example 4

0.6 g of a 50% commercially available aqueous solution containing an anionic emulsifier styrene-butadiene dispersion (Styronal® 8736) with a glass transition temperature of 5 ° C were placed in a beaker and then diluted with water to a solids content of 10%. Then this solution was added 150 g of a 20% aqueous PCC slurry added. During the addition of the slurry and thereafter the mixture was stirred using a stirrer at 1000 rpm Heiltof-. The pH of the mixture was then adjusted to 8.5.

example 5

1.8 g of a 50% commercial aqueous styrene-acrylate dis- persion (Acronal® S 504) with a glass transition temperature of 5 ° C were placed in a beaker and then diluted with water to a solids content of 10%. Thereafter, this solution was added 150 g of a 20% aqueous slurry of finely divided calcium carbonate was added, the acrylic acid by grinding calcium carbonate in an aqueous medium in the presence of a low molecular weight poly was prepared as a dispersant (anionic dis- pergiertes ground calcium carbonate GCC - -). During the supply of the GCC slurry would, and then the mixture was stirred using a Heiltof stirrer at 1000 rpm. The pH of the mixture was then adjusted to 8.5.

Comparative Example 1 according to the teaching of DE-A-198 21 089

3g of a 33% commercial aqueous Polymerleimungsdis- persion on the basis of a graft polymer of acrylonitrile and n-butyl acrylate on degraded starch Basoplast® 250 D having a glass transition temperature of 45 ° C were placed in a beaker and subsequently with water to a solids content diluted by 10%. Then this solution was added 150 g of a 20% aqueous PCC slurry added. During the addition of the slurry and thereafter the mixture was stirred using a Heiltof stirrer at 1000 rpm. The pH of the mixture was then adjusted to 8.5 switched.

Preparation of filler-containing paper

A mixture of TMP (thermomechanical pulp) and wood pulp was beaten speck-free in the ratio of 70/30 at a solids concentration of 4% in a laboratory pulper until a freeness of 60 - was achieved 65th The pH of the stock was in the range between 7 and 8. The beaten stock was thinned then comparable with drinking water to a solids concentration of 0.35%.

To determine the behavior of the aqueous filler slurries described above in the manufacture of filler-containing paper, was placed in each 500 ml of the paper stock suspension and in each case the pulp treated according to the examples and the comparative example slurries and a cationic retention aid (Polymin KE 2020). The metered amount of Retenti- onsmittels were 0.01% polymer, based on dry content of the paper stock suspension. The amount of the slurry was adjusted with the aid of several preliminary experiments so that the ash content of the finished paper sheets with the fabric was 32%.

In addition, sheets were prepared using the indicated in Table 1 20% aqueous slurries of precipitated calcium carbonate (PCC slurry) and ground calcium carbonate produced (GCC slurry).

The paper sheets were each fabricated on a Rapid-Köthen sheet formers according to ISO 5269/2 with a sheet weight of 80 g / m2 and then dried for 7 minutes at 90 ° C and then calendered with a line pressure of 200 N / cm.

Testing of the Paper Sheets

After a storage time in the climatic chamber at a constant 23 ° C and 50% humidity for 12 hours, the dry breaking length of the sheets according to DIN 54540, and the porosity of the sheets according to Bendtsen (ISO 5636-3) were tested. The dry pick resistance of the paper was determined using the IGT printability (ISO 3783).

The Tropfenwegschlagtest that is grow a measure of the Wasseraufnahmever-, was carried out on paper samples having a size of 50 x 50 mm. The samples were separated from each other, kept at least 8 hours in a conditioned room (standard climate for pretreatment and testing according to ISO 187). The sample to be tested is placed on the edge of a glass beaker. advertising the abandoned dropwise using a syringe 5 ul of demineralized water, the drops should not fall on the paper surface on the paper surface. At the same time a stopwatch is started and the time required until the water level of the drop on the paper surface is no longer visible.

Table 1

As is apparent from Table 1, filler-containing paper can be improved significantly with both anionically dispersed GCC slurries as well as with PCC slurries that have been treated with a coating binders in their respective strength properties without porosity and water absorption behavior of the papers clearly influenced become.

Claims

claims
1. An aqueous slurries of finely divided fillers which are to-least partly coated with polymers, characterized in that they are obtainable by treating aqueous slurries of finely divided fillers with at least a binder for paper coating colors.
2. An aqueous slurry according to claim 1, characterized in that it contains .-% contain 1 to 50 of at least one finely divided filler and that the amount of binder is 0.1 to 5 wt .-%, based on fillers is.
3. An aqueous slurry according to claim 1 or 2, characterized in that they contain 10 to 40 wt .-% of at least one filler.
4. An aqueous slurry according to any of claims 1 to 3, by DA in that the binders for paper coating colors containing only emulsifiers having a molecular weight M w <2000th
5. An aqueous slurry according to any of claims 1 to 4, data carried in that the binders for paper coating colors at least one anionic, cationic, nonionic and / or amphoteric emulsifier.
6. A process for the preparation of the aqueous slurries according to claims 1 to 5, characterized in that, added to an aqueous slurry of at least one finely divided filler 0.1 to 5 wt .-% of at least one binder for paper coating colors, based on the filler or aqueous slurry of at least one finely divided filler enters into an aqueous dispersion of a binder for paper coating and the ingredients mixed in each case.
7. The method according to claim 6, characterized in that the molecular weight of the emulsifiers is con- tained in the binders for paper coating colors <2000th
8. Use of the aqueous slurries according to claims 1 to 5 as an additive to paper stock in the production of filler-containing paper, filler-containing cardboard or filler stoffhaltiger board by draining of the paper stock.
PCT/EP2003/002043 2002-03-05 2003-02-28 Aqueous slurries of fine-particulate fillers, method for production and use thereof for the production of papers comprising fillers WO2003074786A3 (en)

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FR2873127A1 (en) * 2004-07-13 2006-01-20 Omya Development Ag Process for the manufacture of self-binding pigmentary particles, dry or in aqueous suspension or dispersion containing inorganic materials and binders
WO2009004077A1 (en) 2007-07-05 2009-01-08 Basf Se Aqueous suspensions of fine particulate fillers, method for producing the same and use thereof for producing papers having a high filler content and a high dry strength
WO2010000728A1 (en) 2008-07-03 2010-01-07 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
WO2010000726A1 (en) * 2008-07-03 2010-01-07 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
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FR2873127A1 (en) * 2004-07-13 2006-01-20 Omya Development Ag Process for the manufacture of self-binding pigmentary particles, dry or in aqueous suspension or dispersion containing inorganic materials and binders
WO2006008657A2 (en) 2004-07-13 2006-01-26 Omya Development Ag Method for producing pigmentary particles that are self-binding, dry, or in an aqueous suspension or dispersion, and contain inorganic materials and binding agents
WO2006008657A3 (en) * 2004-07-13 2006-05-04 Omya Development Ag Method for producing pigmentary particles that are self-binding, dry, or in an aqueous suspension or dispersion, and contain inorganic materials and binding agents
US9011593B2 (en) 2004-07-13 2015-04-21 Omya International Ag Process for the manufacture of self-binding pigmentary particles, dry or in aqueous suspension or dispersion, containing inorganic matter and binders
CN1984968B (en) 2004-07-13 2014-10-29 Omya国际股份公司 The method of producing self-binding pigmentary particles comprising an inorganic material and a binder in dry form or in the form of an aqueous suspension or dispersion of
US9644100B2 (en) 2004-07-13 2017-05-09 Omya International Ag Process for the manufacture of self-binding pigmentary particles, dry or in aqueous suspension or dispersion, containing inorganic matter and binders
US8080595B2 (en) 2007-05-11 2011-12-20 Omya Development Ag Process for grinding in an aqueous medium of mineral matter and binders using a reverse emulsion of a polymer acrylamide with an acrylic monomer
WO2009004077A1 (en) 2007-07-05 2009-01-08 Basf Se Aqueous suspensions of fine particulate fillers, method for producing the same and use thereof for producing papers having a high filler content and a high dry strength
US8227529B2 (en) 2007-07-05 2012-07-24 Basf Se Aqueous slurries of finely divided fillers, a process for their preparation and their use for the production of papers having a high filler content and high dry strength
KR20110027836A (en) * 2008-07-03 2011-03-16 바스프 에스이 Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
JP2011526657A (en) * 2008-07-03 2011-10-13 ビーエーエスエフ ソシエタス・ヨーロピアBasf Se Aqueous suspensions of finely divided fillers, use of the aqueous suspension for producing the preparation and the filler-containing paper
US8613833B2 (en) 2008-07-03 2013-12-24 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of filler-containing papers
WO2010000728A1 (en) 2008-07-03 2010-01-07 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
WO2010000726A1 (en) * 2008-07-03 2010-01-07 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
KR101639086B1 (en) 2008-07-03 2016-07-12 바스프 에스이 Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
US8449721B2 (en) 2008-07-03 2013-05-28 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of fluid-containing papers
US8465584B2 (en) 2008-12-03 2013-06-18 Basf Se Aqueous suspensions of fine-particulate fillers, method for the manufacture thereof and use thereof for the manufacture of papers containing fillers

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