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WO1999015596A1 - Compositions pigmentaires a base de kaolin a grande opacite et a rheologie amelioree - Google Patents

Compositions pigmentaires a base de kaolin a grande opacite et a rheologie amelioree Download PDF

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Publication number
WO1999015596A1
WO1999015596A1 PCT/US1998/016186 US9816186W WO9915596A1 WO 1999015596 A1 WO1999015596 A1 WO 1999015596A1 US 9816186 W US9816186 W US 9816186W WO 9915596 A1 WO9915596 A1 WO 9915596A1
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WIPO (PCT)
Prior art keywords
clay
suspension
polymer
weight
pigment composition
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1998/016186
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English (en)
Inventor
Mitchell J. Willis
Andrew J. Sharpe, Jr.
Huamin Gan
Raymond H. Young
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Catalysts LLC
Original Assignee
Engelhard Corp
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
Application filed by Engelhard Corp filed Critical Engelhard Corp
Priority to AU86871/98A priority Critical patent/AU8687198A/en
Publication of WO1999015596A1 publication Critical patent/WO1999015596A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/90—Other properties not specified above

Definitions

  • kaolin clay in paper coating serves to improve the brightness, gloss, printability and opacity of the coated paper. Opacity in such paper coatings is enhanced by the light scattering ability of the kaolin clay, and such ability can be estimated by the scattering coefficient as described in TAPPI, 1978, Vol. 61, No. 6, pages 78-80.
  • the selective flocculating treatment allegedly incorporates voids in the clay to form a low density, high bulking pigment which when used as a coating color pigment improves the opacity of paper coated therewith.
  • these patents do not disclose the use of polymers nor do they contain information regarding the ability to disperse the bulked clay to prepare clay-slurries having acceptable rheological characteristics for commercial use.
  • U.S. Patent 5,650,003 discloses the use of pigment compositions of cationized calcined clay and titanium dioxide. The clay is cationized with an amount of epichlorohydrin dimethylamine condensate sufficient to cationize the clay.
  • the pigment composition are said to result in solids slurries greater than about 55%, preferably between 59 and 61%.
  • this patent is silent with regard to hydrous clays that remain uncationized when treated with cationized epichlorohydrin dimethylamine condensates.
  • the manufacture of refined kaolin pigments usually necessitates sizing and purifying crude clay while the clay is in the form of a fluid deflocculated aqueous slurry, bleaching the clay while in a flocculated state, filtering the flocculated clay to remove liquid water and then dispersing the flocculated clay to form a high solids slurry that is sold as such or is dried, usually in a spray dryer, to provide a dry refined pigment capable of being mixed with water to form a dispersed fluid suspension.
  • the latter form of clay is frequently referred to as a "predispersed" grade of clay even though the clay is dry and is not present in dispersed state until it is mixed with water. It is economically desirable to maximize the solids content of the aqueous clay slurry for transportation purposes.
  • a high solids containing slurry requires less energy to dry or dewater compared to when the solids content is lower.
  • a further concern in the manufacture of bulking pigments from clay is to produce a bulked structure that is sufficiently durable to survive during various stages of production and end-use but is also capable of being dispersed to form high solids clay-water slurries having acceptable rheology.
  • the general wet processing scheme described above is employed to make bulked structures by adding a bulking agent before filtration, the bulked structure must still be present in the filter cake containing the bulked assemblages when the filter cake is "made down” into a fluid slurry.
  • the expressions "make down” and "made down” are conventional in the industry and refer to the preparation of dispersed pigment-water slurries.
  • the bulked structure must be sufficiently tenacious to survive the mechanical forces during such treatment. Bulking pigments must also be sufficiently stable under the influence of shear to maintain the bulked structure under the high shear rates encountered in pumping high solids clay water slurries. Moreover, a bulked structure must be capable of being retained when the deflocculated clay water slurry is formed into a coating color using standard make down equipment. Also, the bulked structure must survive during the coating application and subsequent calendering. Commercial bulking clays heretofore used by the paper industry are prepared by calcining fine particle size hydrous clays.
  • calcination "sets" the bulked structure such that it is sufficiently durable to survive during manufacturing handling and use.
  • a criterion for durability of a bulked structure is the retention of improved opacification (light scattering).
  • the clay pigments formed are referred to as high opacity pigments.
  • the term high opacity pigment signifies a polymer-treated clay having light scattering properties of at least 0.10 m /g when measured at 577 nm by the black glass scatter technique described herein.
  • the improved pigment compositions of the present invention offer several advantages including the ability to form high solids containing slurries and a highly strength resilient pigments capable of maintaining its structural integrity under severe shearing conditions. Also the use of these improved pigment compositions provide an alternative to more expensive opacifying pigments such as titanium dioxide. Economic advantages of the pigments of this invention include lower transportation costs, pumping costs, and lower drying or dewatering costs. DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION
  • a clay having the following particle size distribution characteristics has been found to provide optimum rheology: a median particle size of 0.55 micrometers and a particle size distribution such that about 88 +/- 2% of the particles have an equivalent spherical diameter less than about 2 micrometers and not more than about 25% by weight, preferably not more than about 20% by weight, have an equivalent spherical diameter less than 0.3 micrometers. If the particle size is too coarse, gloss and opacity suffer although opacity will be greater than the clay before treatment with the poly quaternary polyamine. If the quantity of ultrafine particles,i.e., particles 0.3 micrometers and finer, is too great, the rheology of the pigment may be such that it has limited, if any, use.
  • the clay particles are therefore treated with a deflocculant (dispersing agent) which will give all the particles a negative electric charge, and cause them to repel each other when the particles are suspended in water.
  • the clay dispersant used at this stage is generally referred to as a "primary" dispersant.
  • Dispersants used to deflocculate suspensions of previously processed clay are termed “secondary" dispersants or deflocculants.
  • Suitable dispersing agents used for primary dispersion in practice of the present invention are conventional and include water soluble salts of a condensed phosphate, such as a pyrophosphate, e.g., tetrasodium pyrophosphate, (TSPP), a water soluble salt of a polysilicic acid, for example, sodium silicate, or a water soluble organic polymeric dispersing agent, for example a polyacrylate or a polymethylmethacrylate salt having a molecular weight in the range of about 500 to about 10,000.
  • the amount of dispersing agent used will generally be in the range of from about 0.025 to 0.2% by weight based on the weight of the dry clay.
  • particle size separations are performed using deflocculated aqueous suspensions having a solids content of about 20-40% by weight. Other solids levels may be used to carry out such separations.
  • the median particle size of the clay particles that are treated with the polyquaternary polyamine should range from 0.4 to 0.7 micrometers, equivalent spherical diameter (e.s.d.), preferably 0.5 to 0.6 micrometers, as determined by conventional sedimentation techniques using the SEDIGRAPH ® particle size analyzer, supplied by Micromeretics, Inc. From about 80% to 95% by weight of the particles should be finer than 2 micrometers, e.s.d. The content of fines below 0.3 micrometer e.s.d.
  • weight percent should be below 35 weight percent, preferably below 25 weight percent, and most preferably 20 weight percent or below. It should be understood that the measurements of the size of clay particles that are 0.3 micrometer or finer are of limited reproducibility. Thus, when a SEDIGRAPH ® analyzer is employed, the value for weight percent may be +/- 5% when tested by another operator or a different SEDIGRAPH ® analyzer is employed. Most preferably, median particle size is 0.6 +/- 0.05 micrometers, e.s.d., with 85 to 90% by weight of the particles finer than 2 micrometers, e.s.d., and less than about 20% by weight or less finer than 0.30 micrometers, e.s.d.
  • the Polyquaternary Polyamine polymer useful in this invention is a water soluble or dispersible cationic polyelectrolyte polymer or polymers derived from (i) reaction of secondary amines, such as dialkylamines, and difunctional epoxide compounds or precursors thereof or (ii) reaction of a lower dialkylamine (C r C 3 ), a difunctional epoxy type reactant (the same as (i)) and a third reactant selected from the group consisting of ammonia, primary amines, alkylenediamines of from 2-6 carbon atoms, and polyamines.
  • secondary amines such as dialkylamines, and difunctional epoxide compounds or precursors thereof
  • C r C 3 lower dialkylamine
  • a difunctional epoxy type reactant the same as (i)
  • a third reactant selected from the group consisting of ammonia, primary amines, alkylenediamines of from 2-6 carbon atoms, and polyamines.
  • the group (i) polymers are disclosed in U.S. Pat.No. Re. 28,807 (Panzer, et. al.). The entire disclosure of this reissue patent is hereby incorporated by reference herein. As is stated in that reissue patent, the polyquaternary polymers of group (i) are derived from reaction of secondary amines, such as dialkylamines, and difunctional epoxide compounds or precursors thereof.
  • the water soluble or water dispersible polyquaternary polymers used as the second component in the present invention, consist essentially of the repeat units of
  • R and R are independently selected from the group consisting of lower alkyl (1-3 carbon atoms).
  • E is the residue obtained after bifunctional reaction of a compound selected from the group consisting of epihalohydrins, diepoxides, precursors for epihalohydrins and diepoxides, and mixtures thereof, m and n are integers of substantially equal value.
  • X ⁇ represents the anion forming a portion of the polyquaternary compound; m and n are integers both representing the molar quantities ofamine reactants and bifunctional reactant compound, respectively.
  • the polymers of group (i) involve only two reactants: a lower dialkylamine, and a difunctional epoxy type reactant.
  • these include dimethylamine, diethylamine, dipropylamine, and secondary amines containing mixtures of alkyl groups having 1 to 3 carbon atoms.
  • the preferred polymer of group (i) is formed from dimethylamine and epichlorohydrin reaction. Such reaction is detailed in Example 1 of the reissue patent.
  • the preferred polyquaternary polymers of group (i) are thought to have the structure:
  • Suitable commercially available polymers of the group(i) type are sold under the trade names SHARPFLOC ® 22, SHARPFLOC ® 23, and SHARPFLOC ® 24.
  • the molecular weight of these polymers are estimated to be in the range of approximately 2,000-10,000 atomic mass units (amu).
  • the particular molecular weights of these polymers are not critical as long as the polymers remains water soluble or water dispersible.
  • the group (ii) polymers which may be used in accordance with the invention may be generically characterized as branched polyquaternary ammonium polymers and are described in detail in U.S. Patent No. Re. 28,808 (Panzer, et al.). The entire disclosure of this reissue patent is hereby incorporated by reference.
  • the group (ii) water dispersible polyquaternary polymer consists essentially of repeating units of
  • R, R,, E, m, and n are the same as given above for the group (i) polymers.
  • A is the residue obtained after bifunctional reaction of a polyfunctional polyamine selected from the group consisting of ammonia, primary amines, alkylene diamines of 2 to 6 carbon atoms, polyalkylpolyamines of the structure
  • R 3 is an alkylene radical of about 2 to 6 carbon atoms, and R, is selected from the group consisting of hydrogen, alkyl of about 1 to 3 carbon atoms, and omega -aminoalkyls of about 2 to 6 carbon atoms, a polyglycolamine of a structure such as
  • a is an integer of about 1 to 5, piperazine heteroaromatic diamines, and polyamine-polybasic acid condensation products of molecular weight up to about
  • X ⁇ is an ion forming the anionic portion of said polyquaternary compound
  • m and p are integers which represent molar quantities ofamine reactants, the ratio of m to p being from about 99:1 to 85:15
  • the group (ii) polymers are formed from three reactants: a lower dialkylamine (C,-C 3 ), a difunctional epoxy type reactant (the same as in the group (i) polymers) and a third reactant selected from the group consisting of ammonia, primary amines, alkylenediamines of from 2-6 carbon atoms, and polyamines as defined hereinabove for A.
  • the preferred type of third reactant is ammonia or at least a trifunctional amine, i.e., an amine capable of reacting at no fewer than 3 sites on the amine or amines. Examples of such amines are all primary amines and/or polyfunctional amines such as ethylene diamine and diethylene triamine.
  • the preferred group (ii) polymer is thought to have the structure:
  • Suitable commercially available polymers of the group (ii) type are sold under the trade names of SHARPFLOC ® 25, SHARPFLOC ® 26, SHARPFLOC ® 27, SHARPFLOC ® 28, SHARPFLOC ® 29, SHARPFLOC ® 30, SHARPFLOC ® 31, SHARPFLOC ® 32, and SHARPFLOC ® 33.
  • the molecular weight of these polymers are estimated to range from approximately 20,000 to 500,000 amu.
  • the particular molecular weights of these polymers are not critical as long as the polymers remain water soluble or water dispersible.
  • the amount of polymer needed to achieve the benefits of this invention range from 0.025 to 0.250 weight % , preferably from 0.05 to 0.20 weight %, most preferably from 0.100 to 0.150 weight % relative to the dry clay being treated. These treatment amounts are far less than the amount of polymer (cationic in nature) typically needed to cationize the clay particles (anionic in nature). As is understood by those skilled in the art, the precise optimum amount of polymer used to treat the clay may vary according the type of clay selected to be treated and according to the molecular weight and composition of the polymer used.
  • the manner by which the kaolin clay is treated with the polyquaternary polyamine polymer of the present inventions is by any suitable method that will cause bulking of the clay when contacted with the polymer. Such methods are described herein and also in U.S. Patent No. 4,738,726, the disclosure of which is incorporated by reference in its entirety.
  • Such methods include but are not limited to forming a fluid aqueous suspension of particles of kaolin clay, adding the water soluble or water dispersible polyquaternary amine polymer of this invention in an amount to substantially thicken and flocculate the fluid suspension.
  • the polymer or the aqueous suspension typically can be added at ambient temperatures or separately or together may be heated to about 150 to 180 ° F.
  • the resulting flocculated clay suspension may be acidified (preferably in the pH range of 2.5 to 4.0), bleached, filtered (to recover the bulked clay), washed with tap or heated tap water, and treated with a deflocculant (typically in an amount less than 0.2 to 0.3 wt % based on recovered clay) to provide fluid suspension of the claimed pigment composition.
  • the fluid suspension has a solids content in the range of 65 to 70% solids.
  • the fluid suspension may then be spray dried after or before permitting the suspension to age. Also, the clay suspension may be deflocculated before the polymer is added.
  • the light scattering (opacity) and gloss of the pigments were determined by coating the kaolin clay suspensions onto black glass plates at a coat weight of 7.0-14.0 g/m 2 (expressed as dry clay).
  • the reflectance of the coatings after drying in air at wavelengths of 577 nm is measured by means of an Elrepho reflectometer.
  • the reflectance values are converted by the use of Kubelka-Munk equations to light scattering values (m 2 /g).
  • the light scattering values are a measure of the opacity potential of the clay because the higher values indicate that light rather than passing through is reflected and scattered back. The higher the light scattering value, the higher the opacity potential of the clay.
  • Engelhard Corporation procedure PL-1 was used. Brookfield viscosity was measured using TJAPPI procedure T648 om-81 at 20 rpm using the #1 or #2 spindle. All slurries were formulated with optimum amount of dispersant, following the PL-3 procedure of Engelhard Corporation. Following are descriptions of PL-1 and PL-3 procedures.
  • PL-1 is the standard laboratory makedown method for hydrous clays at 70% solids under high shear conditions. Hydrous clays may also be madedown at other solids such as 68% solids for delaminated clays utilizing this procedure and adjusting the amount of water needed.
  • Waring Blendor ® mixer (Model 31 BL 46 belt driven by 3/4 HP motor, with pulley to provide 11 ,000 RPM).
  • Dispersant i.e., terra sodium pyrophosphate (TSPP) or organic such as Colloids C-211 (sodium polyacrylate based dispersant).
  • A. Follow the procedure outlined in steps C through G for the preparation of a 10% solids slurry, employing the previously determined optimum dispersant level (with some clays it may be necessary to start at slightly lower solids levels to produce a flowable mixture at optimum dispersant levels).
  • B. Add an additional quantity of clay until a non-flowable mixture is produced by the blender.
  • C. Add additional dry dispersant such as TSPP at the rate of 0.30% on the weight of the additional clay added in step B. Mix for 5 seconds.
  • This method determines the amount of dispersant to obtain minimum viscosity of clay.
  • Optimum dispersion is determined by the PL-3 procedure which involves making small additions of dispersant to a slurry, mixing and then determining the Brookfield viscosity. The dispersant level before the viscosity increases (becomes poorer) is the optimum dispersant level.
  • Pigment 500 oven dried grams or 250 grams for calcined clay
  • C. Determine the Brookfield viscosity of the sample.
  • D. While mixing the sample using the Talboy mixer, add 0.05% dispersant based on pigment weight and continue mixing for five minutes.
  • Optimum viscosity is the amount of dispersant added before the viscosity increases or there is no viscosity change. The solids, dispersant level and Brookfield and Hercules viscosity are reported at optimum viscosity.
  • TAPPI Procedure T648 om-81 gives further description of the procedures used to measure high shear viscosity. It is common to report high shear viscosity of clay- water as either dyne-cm x 10 5 torque at 1100 rpm bob speed or as bob speed in rpm at which the maximum torque of 16 x 10 5 dyne-cm was obtained. Similarly, the coating color viscosity is reported as either dyne-cm x 10 5 torque at 4400 rpm bob speed or as bob speed in rpm at which the maximum torque of 64 x 10 5 dyne-cm was obtained.
  • the precision is based on a dyne-cm x 10 5 reading at 1100 rpm and rpm reading at 16 dyne-cm x 10 5 because these are the values reported for products.
  • the 95% confidence level for the precision for three operations at two different viscosities follows:
  • SF-22 SHARPFLOC 22 ® polymer of approx. 5000 atomic mass units (amu)
  • SF-26 SHARPFLOC 26 ® polymer of approx. 50,000 to 100,000 amu
  • DADMAC Polydiallyldimethyl ammonium chloride of approximately 150,000 to
  • the results of Table 2 show a clear advantage in rheological properties of SAMPLES 1-5 prepared with the SHARPFLOC ® epichlorohydrin polyamines according to the present invention as compared with SAMPLES C-6 and C-7 which used the DADMAC-based polymers.
  • the pigment compositions of the present invention not only are capable producing high solids containing slurries having solids content approximately the same or exceeding the DADMAC-based SAMPLES C-6 and C-7, but more importantly show that the pigment compositions of this invention achieve the high-solids content at Brookfield viscosities an order of magnitude lower than the DADMAC-based samples. This is a clear benefit for the pigment compositions of the present invention in terms of having high-solids containing slurries that can be more easily handled, i.e., by virtue of a lower viscosity.
  • SAMPLE 4 of EXAMPLE 3 was measured after adding into the slurry additional SF-26 treated clay to raise the Brookfield from 197 cp to 303 cp. Also, the CONTROL of EXAMPLE 3 was measured after adding dry untreated clay to raise the CONTROL Brookfield viscosity closer to 300 cp. The results are summarized in Table 4.
  • the results of the CONTROL represent the maximum amount of solids achievable for the untreated clay, i.e., the theoretic target for the polymer-treated clays to meet.
  • the pigment compositions of this invention provide an advance over other known hydrous kaolin clays treated with cationic polymers in achieving % solids closer to theoretical maximum based on comparable viscosities.
  • the results of Table 5 indicate the ability of pigment compositions representative of this invention to attain lower Brookfield viscosity under similar treatment amounts and conditions with a narrowing of the particle size distribution. While the Hercules end point for SAMPLE 6 at 67.0% solids is lower than comparative SAMPLE C-6, achieving a HEP value of 585 rpm at 16 dyne is still an acceptable high shear result for most applications. Therefore, the pigment compositions of this invention demonstrate acceptable high shear properties while providing improved low shear rheology, i.e., improved Brookfield viscosity.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne des compositions pigmentaires à base de kaolin aqueuses, à grande opacité et à rhéologie améliorée, ces compositions présentant une grande résistance au cisaillement à un niveau acceptable. Les compositions pigmentaires s'utilisent comme charges ou revêtements pour le papier et la peinture et permettent de réduire le besoin en pigments opacifiants tels que le dioxyde de titane. La rhéologie améliorée et la capacité de la composition pigmentaire de former des coulis contenant des solides plus grands, en comparaison avec des kaolins hydratés connus qui sont traités avec des polymères cationiques, constituent des avantages économiques en ce qui concerne le transport, la capacité de pompage et la déshydratation.
PCT/US1998/016186 1997-09-24 1998-08-05 Compositions pigmentaires a base de kaolin a grande opacite et a rheologie amelioree Ceased WO1999015596A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU86871/98A AU8687198A (en) 1997-09-24 1998-08-05 High opacity kaolin pigment compositions of improved rheology

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US93670297A 1997-09-24 1997-09-24
US08/936,702 1997-09-24

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046323A1 (fr) * 1999-12-22 2001-06-28 Clariant Finance (Bvi) Limited Pigments blancs modifies de maniere cationique, fabrication et utilisation
US6811600B2 (en) 2003-01-23 2004-11-02 Engelhard Corporation Chemically bulked kaolin clay pigment compatible with calcium carbonate and manufacture thereof
US7019134B2 (en) 1999-12-22 2006-03-28 Clariant Finance (Bvi) Limited Amphoteric optical brighteners, their aqueous solutions, their production and their use
WO2007125312A3 (fr) * 2006-04-24 2007-12-27 Imerys Minerals Ltd Compositions de barrières

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3738945A (en) * 1972-02-04 1973-06-12 H Panzer Polyquaternary flocculants
EP0245553A2 (fr) * 1986-05-12 1987-11-19 Engelhard Corporation Traitement d'argiles par des polymères cationiques pour préparer des pigments à haut pouvoir opacifiant
EP0430582A1 (fr) * 1989-11-22 1991-06-05 Engelhard Corporation Kaolins structurés pour le remplissage du papier
WO1996013554A2 (fr) * 1994-10-19 1996-05-09 Engelhard Corporation Suspensions de kaolin calcine stabilisees par voie cationique
US5650003A (en) * 1995-12-18 1997-07-22 Nord Naolin Company Cationized pigments and their use in papermaking

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3738945A (en) * 1972-02-04 1973-06-12 H Panzer Polyquaternary flocculants
EP0245553A2 (fr) * 1986-05-12 1987-11-19 Engelhard Corporation Traitement d'argiles par des polymères cationiques pour préparer des pigments à haut pouvoir opacifiant
EP0430582A1 (fr) * 1989-11-22 1991-06-05 Engelhard Corporation Kaolins structurés pour le remplissage du papier
WO1996013554A2 (fr) * 1994-10-19 1996-05-09 Engelhard Corporation Suspensions de kaolin calcine stabilisees par voie cationique
US5650003A (en) * 1995-12-18 1997-07-22 Nord Naolin Company Cationized pigments and their use in papermaking

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001046323A1 (fr) * 1999-12-22 2001-06-28 Clariant Finance (Bvi) Limited Pigments blancs modifies de maniere cationique, fabrication et utilisation
AU777651B2 (en) * 1999-12-22 2004-10-28 Clariant Finance (Bvi) Limited Cationically modified white pigments, their production and use
US6911116B2 (en) 1999-12-22 2005-06-28 Clariant Finance (Bvi) Limited Cationically modified white pigments, their production and use
US7019134B2 (en) 1999-12-22 2006-03-28 Clariant Finance (Bvi) Limited Amphoteric optical brighteners, their aqueous solutions, their production and their use
CN1293150C (zh) * 1999-12-22 2007-01-03 克莱里安特财务(Bvi)有限公司 阳离子改性的白颜料，其制备方法和用途
US6811600B2 (en) 2003-01-23 2004-11-02 Engelhard Corporation Chemically bulked kaolin clay pigment compatible with calcium carbonate and manufacture thereof
WO2004067840A3 (fr) * 2003-01-23 2005-03-17 Engelhard Corp Pigment d'argile kaolinique chimiquement charge compatible avec du carbonate de calcium et fabrication dudit pigment
WO2007125312A3 (fr) * 2006-04-24 2007-12-27 Imerys Minerals Ltd Compositions de barrières
EP2410025A1 (fr) * 2006-04-24 2012-01-25 Imerys Minerals Limited Compositions de barrieres

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Publication number Publication date
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