EP0560813B1 - Une suspension aqueuse d'un pigment solide de carbonate de calcium - Google Patents

Une suspension aqueuse d'un pigment solide de carbonate de calcium Download PDF

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Publication number
EP0560813B1
EP0560813B1 EP91920520A EP91920520A EP0560813B1 EP 0560813 B1 EP0560813 B1 EP 0560813B1 EP 91920520 A EP91920520 A EP 91920520A EP 91920520 A EP91920520 A EP 91920520A EP 0560813 B1 EP0560813 B1 EP 0560813B1
Authority
EP
European Patent Office
Prior art keywords
paper
calcium carbonate
weight
cationic
aqueous suspension
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.)
Expired - Lifetime
Application number
EP91920520A
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German (de)
English (en)
Other versions
EP0560813A1 (fr
Inventor
John Claude Husband
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.)
Imerys Minerals Ltd
Original Assignee
ECC International Ltd
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Filing date
Publication date
Application filed by ECC International Ltd filed Critical ECC International Ltd
Publication of EP0560813A1 publication Critical patent/EP0560813A1/fr
Application granted granted Critical
Publication of EP0560813B1 publication Critical patent/EP0560813B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • This invention relates to suspensions of calcium carbonate pigments, to paper coating compositions formed from such suspensions and to coated paper made using said coating compositions, and to a paper-making process which includes the recycling of coated paper.
  • calcium carbonate pigments which have been treated to have specified particle size and surface area characteristics, can be anionically dispersed in water to form high solids paper coating compositions for gravure printing papers (GB-A-2139606A).
  • a high solids, aqueous suspension of a particulate calcium carbonate pigment characterised in that the particulate calcium carbonate pigment has a specific surface area, as measured by the BET N 2 method, of less than 7.5m 2 g -1 , and a particle size distribution such that not more than 1% by weight of the particles have an equivalent sperical diameter (esd) larger than 10 microns, at least 65% by weight of the particles have an equivalent sperical diameter smaller than 2 microns and not more than 10% by weight of the particles have an equivalent spherical diameter smaller than 0.25 microns; and in that the particulate calcium carbonate pigment is cationically dispersed with a dispersing agent which is a combination of a cationic polyelectrolyte and an anionic polyelectrolyte, with the cationic electroyte being used in an amount sufficient to render the pigment particles cationic.
  • a dispersing agent which is a combination of a cationic polyelectrolyt
  • a paper coating composition which has a solids content of at least 45% by weight, characterised in that it comprises a high solids, aqueous suspension according to the present invention, and a non-ionic or cationic adhesive.
  • a process for making paper which includes the step of recycling coated paper that has been reduced to a fibrous, recyclable state and then incorporated into a paper-making composition, characterised in that the coated paper is a paper which has been coated with a coating composition according to the invention.
  • a cationically dispersed, high solids, aqueous suspension of a calcium carbonate pigment in accordance with the present invention has very good rheological properties.
  • a cationic aqueous suspension, or slurry, having a given viscosity and prepared in accordance with the present invention can have a higher solids content than a slurry in which the calcium carbonate pigment has a broader particle size distribution.
  • a high solids, aqueous suspension according to the present invention should preferably have a solids content of at least 60% by weight solids.
  • the calcium carbonate pigment when ground to a particulate mass, exists in the form of regular, approximately spherical particles having a low mean particle aspect ratio.
  • the calcium carbonate may be in any form, natural or synthetic. Particularly preferred is ground marble, although precipitated calcium carbonate (PCC) and chalk are operable.
  • the calcium carbonate pigment employed in the present invention should have a specific surface area, as measured by the BET N 2 method, which is less than about 6.5m 2 g -1 , but preferably is at least 2m 2 g -1 .
  • a calcium carbonate material is ground, before dispersion, to the desired particle size distribution.
  • the grinding conditions can be adjusted in a manner known per se to produce pigments having varying particle size distributions.
  • Ground marble for use in the present invention is preferably formed by first crushing batches of marble in aqueous suspension in the absence of a chemical dispersing agent using a particulate grinding medium. Further size reduction can be achieved by dewatering the suspension of ground marble, for example by filtration in the absence of a flocculating agent, and then drying the pigment, and pulverising the dried product in a conventional mill.
  • the particles of the pigment may be readily dispersed using a dispersing agent, in accordance with the invention, comprising a combination of an anionic polyelectrolyte and a cationic polyelectrolyte, the cationic polyelectrolyte being used in an amount sufficient to render the particles cationic.
  • chalk particles when in a raw state, do not carry a positive charge, because of natural anionic species absorbed to the particle surface, and the chalk particles should be subjected to vigorous agitation in order to strip off such anionic species and render the particles capable of being effectively dispersed at high solids using the combination of an anionic polyelectrolyte and cationic polyelectrolyte.
  • the raw pigment is received as a filter cake having a relatively high solids content.
  • the dispersing agent in order to provide a dispersed high solids slurry (45-80% by weight solids) which may then be subjected to vigorous mixing.
  • the particulate calcium carbonate pigment is dispersed with a combination of an anionic polyelectrolyte and a cationic polyelectrolyte, with the cationic electroyte being used in an amount sufficient to render the pigment particles cationic.
  • the amount of cationic polyelectrolyte used is in the range of from about 0.01% to about 1.5% by weight, based on the dry weight of calcium carbonate, and the amount of anionic polyelectroyte used is such that the weight ratio of the cationic polyelectrolyte to anionic polyelectroyte is in the range of from about 2:1 to about 20:1.
  • the anionic polyelectrolyte is a water-soluble vinyl polymer, an alkali metal or ammonium salt thereof or an alkali metal or ammonium salt of polysilicic acid.
  • the anionic polyelectrolyte is a poly(acrylic acid), a poly(methacrylic acid), a substituted poly(acrylic acid) or a substituted poly(methacrylic acid), or an alkali metal or ammonium salt of any of these acids.
  • the substituted poly(acrylic acid) may be a partially sulphonated polymer.
  • An especially effective anionic polyelectrolyte is an alkali metal or ammonium salt of a copolymer of acrylic acid and a sulphonic acid derivative of acrylic acid, in which the proportion of the sulphonic acid derivative monomer is preferably from 5% to 20% of the total number of monomer units.
  • the number average molecular weight of the anionic polyelectrolyte is preferably at least 500, but preferably no greater than 100,000.
  • the amount used is generally in the range of from about 0.01% to about 0.5% by weight based on the weight of dry pigment, and preferably is in the range of from about 0.1 to 0.2% by weight.
  • the cationic polyelectrolyte may be a water-soluble substituted polyolefin containing quaternary ammonium groups.
  • the quaternary ammonium groups may be in the linear polymer chain or may be in branches of the polymer chain.
  • the number average molecular weight of the substituted polyolefin is preferably at least 1500 but preferably no greater than 1,000,000, and is more preferably in the range of from 50,000 to 500,000.
  • the quantity required is generally in the range of from about 0.01% to about 1.5% by weight based on the weight of dry pigment.
  • Advantageous results have been obtained when the substituted polyolefin is a poly(diallyl di(hydrogen or lower alkyl)ammonium salt).
  • the lower alkyl groups which may be the same or different, may have, for example, up to four carbon atoms and each is preferably methyl.
  • the ammonium salt may be, for example, a chloride, a bromide, an iodide, HSO 4 - , CH 3 SO 4 - or nitrite.
  • the salt is a chloride.
  • the cationic polyelectrolyte is poly(diallyl dimethyl ammonium chloride).
  • the water-soluble substituted polyolefin may be the product of copolymerising epichlorohydrin and an aliphatic secondary amine, said product having the formula in which R and R', which may be the same of different, are each hydrogen or a lower alkyl group having from one to four carbon atoms, preferably methyl or ethyl and X is Cl - , Br - , I - , HSO 4 - , CH 3 SO 4 - or nitrite.
  • the preferred number average molecular weight of this epichlorohydrin product is in the range of from 50,000 to 300,000.
  • the cationic polyelectrolyte may be a water-soluble organic compound having a plurality of basic groups and preferably having a number average molecular weight of at least 10,000 but preferably no greater than 1,000,000. Most preferably, the number average molecular weight is at least 50,000.
  • These water-soluble organic compounds may be described as polyacidic organic bases, and are preferably compounds of carbon, hydrogen and nitrogen only and are free of other functional groups, such as hydroxy or carboxylic acid groups, which would increase their solubility in water and thus increase the likelihood of their being desorbed from the mineral in an aqueous suspension.
  • the organic compound is polyethyleneimine (PEI) having a number average molecular weight in the range 50,000 to 1,000,000.
  • PEI polyethyleneimine
  • a further example of a water-soluble organic compound which may be employed is a polyethylene diamine which may be a copolymer of ethylene diamine with an ethylene dihalide or with formaldehyde.
  • the cationic polyelectrolyte is employed in an amount sufficient to render the mineral particles cationic.
  • the zeta potential of the particles will normally be at least +20mV after treatment, typically in the range of from +30 to +40 mV and usually no greater than +50 to +60mV. These potentials have been measured using a dilute (0.02 weight %) solids suspension using a supporting electrolyte of potassium chloride (10 -4 M) with a "Pen Kem Laser Z" meter.
  • the ratio, by weight, of cationic polyelectrolyte to anionic polyelectrolyte used is generally in the range of from about 2:1 to about 20:1, and preferably is in the range of from 2:1 to 10:1.
  • the calcium carbonate pigment is preferably mixed with the anionic polyeletrolyte before mixing with the cationic polyelectrolyte. This appears to enable a more fluid suspension to be obtained at a higher solids concentration.
  • Aqueous suspensions of the present invention should preferably be subjected to vigorous mixing before or after dispersion of the pigment.
  • the vigorous mixing should be sufficient to impart at least 10kJ energy per kg of the inorganic material, but preferably no more than about 50kJ per kg.
  • the amount of energy input will be in the range of from 18-36kJ per kg of the inorganic material.
  • the high solids aqueous suspension of the present invention can be "made down" into a paper coating composition by dilution (if necessary) to a solids concentration of at least 45% by weight and by addition of an adhesive, which should be non-ionic or cationic in nature.
  • an adhesive which should be non-ionic or cationic in nature.
  • Such adhesives contrast with the anionic adhesives which are normally used in paper coating compositions in which the pigment is anionic.
  • cationic casein and cationic starch adhesives can be used as well as cationic or non-ionic latices.
  • Such cationic and non-ionic adhesives are readily commercially available.
  • the particular cationic or non-ionic adhesive used will depend, for example, on the printing process to be used, e.g. offset lithography requires the adhesive to be water-insoluble.
  • the amount of adhesive should preferably be of the order of from 7 to 25% by weight, based on the weight of pigment whilst, for gravure printing paper, the adhesive should be used in an amount of 4-15% by weight, based on the weight of pigment.
  • the precise quantity of adhesive required will depend upon the nature of the adhesive and the material being coated, but this can readily be determined by the person skilled in the art.
  • the paper coating composition may also include other conventional paper coating composition adjuvants such as an insolubilising agent (e.g. a melamine formaldehyde resin), a lubricant such as calcium stearate and a catalyst to catalyze cross-linking of the cationic latex if present: a suitable such catalyst is sodium bicarbonate.
  • an insolubilising agent e.g. a melamine formaldehyde resin
  • a lubricant such as calcium stearate
  • the quantities of these adjuvants required are known to those skilled in the art.
  • a full discussion of the constituents of paper coating compositions and of the methods of applying such compositions to paper is given in Chapter XIX, Volume III of the second edition of the book by James P. Casey entitled “Pulp and Paper: Chemistry and Technology”.
  • a further discussion is given in
  • the paper coating compositions of the invention can be used in a method of coating a sheet member using normal paper coating machinery and under normal paper coating conditions.
  • coated paper which is obtained using coating compositions of the present invention is particularly suitable for use in a recycling process which includes the step of reducing the paper into a fibrous recyclable state and incorporating said fibre in a paper-making composition.
  • a coated paper which is made using a coating composition of the present invention is of advantage when it is employed as "broke", or recycled paper, as part of a paper-making composition.
  • Such a paper-making composition may include conventional paper-making pulp, such as a bleached sulphite pulp.
  • the broke fibre and the conventional pulp will be employed in a ratio of from 10:90 to 60:40.
  • a filler for instance a calcium carbonate filler and also a retention aid.
  • broke fibre will include a proportion of calcium carbonate pigment from the coating, it is possible to reduce the amount of calcium carbonate filler employed to give a total quantity of filler in the range of from 5 to 20 percent by weight of the total paper-making composition.
  • the weight of dried broke added (fibre and filler) should preferably be in the range of from about 5 to 30 percent by weight of fibre.
  • the broke fibre employed is derived from a coated paper in accordance with the present invention
  • the amount of retention aid employed in the paper making composition can be reduced.
  • a ground marble having a broad particle size distribution gives approximately 4 units lower solids for a given rheology when cationically dispersed.

Landscapes

  • Paper (AREA)
  • Glass Compositions (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Colloid Chemistry (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Disintegrating Or Milling (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (7)

  1. Une suspension aqueuse à haute teneur en matières solides, d'un pigment particulaire de carbonate de calcium, pour des compositions de revêtement pour papier, dans laquelle le pigment particulaire de carbonate de calcium possède une surface spécifique, telle que mesurée par la méthode BET avec N2, de moins de 7,5 m2g-1, et une distribution de la taille particulaire telle que pas plus de 1% en poids des particules ont un diamètre sphérique équivalent (d.s.e.) supérieur à 10 microns, au moins 65% en poids des particules ont un diamètre sphérique équivalent inférieur à 2 microns, et pas plus de 10% en poids des particules ont un diamètre sphérique équivalent inférieur à 0,25 microns; dans laquelle le pigment particulaire de carbonate de calcium est cationiquement dispersé avec un agent dispersant qui est la combinaison d'un polyélectrolyte cationique et d'un polyélectrolyte anionique, l'électrolyte cationique étant utilisé dans une quantité suffisante pour rendre les particules de pigment cationiques.
  2. Une suspension aqueuse, à haute teneur en matières solides, telle que revendiquée dans la revendication 1, caractérisée en ce que le pigment de carbonate de calcium possède une surface spécifique, telle que mesurée par la méthode BET avec N2, dans le domaine allant de 2,0 à 6,5 m2g-1.
  3. Une suspension aqueuse, à haute teneur en matières solides, telle que revendiquée dans la revendication 1, caractérisée en ce que la quantité d'électrolyte cationique utilisée est dans le domaine allant d'environ 0,01% à environ 1,5% en poids, par rapport au poids sec du carbonate de calcium, et la quantité de polyélectrolyte anionique utilisée est telle que le rapport massique du polyélectrolyte cationique sur le polyélectrolyte anionique est comprise dans le domaine allant d'environ 2:1 à environ 20:1.
  4. Une suspension aqueuse à haute teneur en matières solides, telle que revendiquée dans la revendication 1, 2 ou 3, caractérisée en ce que la suspension aqueuse a été mélangée vigoureusement, avant et après dispersion du pigment de carbonate de calcium, de sorte qu'on a conféré à la suspension 10 à 50 kJ d'énergie par kg de carbonate de calcium.
  5. Une composition de revêtement pour papier ayant une teneur en matières solides d'au moins 45% en poids, caractérisée en ce qu'elle comprend une suspension aqueuse à haute teneur en matières solides, telle que revendiquée dans la revendication 1, 2, 3, ou 4, et un adhésif non ionique ou cationique.
  6. Un papier revêtu qui comprend un revêtement formé à partir d'une composition de revêtement pour papier telle que revendiquée dans la revendication 5.
  7. Un procédé pour fabriquer du papier, qui comprend l'étape consistant à recycler du papier revêtu qui a été réduit sous une forme fibreuse, recyclable, et qui a ensuite été incorporé à une composition de fabrication de papier, caractérisé en ce que le papier enduit est un papier tel que revendiqué dans la revendication 6.
EP91920520A 1990-12-04 1991-11-28 Une suspension aqueuse d'un pigment solide de carbonate de calcium Expired - Lifetime EP0560813B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9026362A GB2251254B (en) 1990-12-04 1990-12-04 Calcium carbonate slurry
GB9026362 1990-12-04
PCT/GB1991/002110 WO1992010609A1 (fr) 1990-12-04 1991-11-28 Bouillie d'un materiau inorganique

Publications (2)

Publication Number Publication Date
EP0560813A1 EP0560813A1 (fr) 1993-09-22
EP0560813B1 true EP0560813B1 (fr) 1997-08-27

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP91920520A Expired - Lifetime EP0560813B1 (fr) 1990-12-04 1991-11-28 Une suspension aqueuse d'un pigment solide de carbonate de calcium

Country Status (13)

Country Link
EP (1) EP0560813B1 (fr)
JP (1) JP2919970B2 (fr)
AT (1) ATE157415T1 (fr)
AU (1) AU654514B2 (fr)
BR (1) BR9107142A (fr)
CA (1) CA2088515A1 (fr)
DE (1) DE69127458T2 (fr)
DK (1) DK0560813T3 (fr)
ES (1) ES2104735T3 (fr)
FI (1) FI932475A (fr)
GB (1) GB2251254B (fr)
NO (1) NO300021B1 (fr)
WO (1) WO1992010609A1 (fr)

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5731034A (en) * 1990-12-04 1998-03-24 Ecc International Limited Method of coating paper
US5169443A (en) * 1991-11-13 1992-12-08 Engelhard Corporation Paper coating kaolin pigments there preparation and use
GB2275876B (en) * 1993-03-12 1996-07-17 Ecc Int Ltd Grinding alkaline earth metal pigments
US5755930A (en) * 1994-02-04 1998-05-26 Allied Colloids Limited Production of filled paper and compositions for use in this
DE19529661C1 (de) * 1995-08-11 1997-04-03 Ctp Papierhilfsmittel Gmbh Streichmasse für Papier
US5827398A (en) * 1996-02-13 1998-10-27 Allied Colloids Limited Production of filled paper
FI105840B (fi) 1997-09-16 2000-10-13 Metsae Serla Oyj Menetelmä materiaalirainan päällystämiseksi
FI104502B (fi) 1997-09-16 2000-02-15 Metsae Serla Oyj Menetelmä paperirainan valmistamiseksi
FI108950B (fi) 1998-03-13 2002-04-30 M Real Oyj Menetelmä päällystetyn puuvapaan paperin valmistamiseksi
FI111649B (fi) 1998-05-11 2003-08-29 M Real Oyj Kalsiumoksalaatista valmistetun kalsiumkarbonaatin käyttö pigmenttinä
WO2002066393A1 (fr) * 2001-01-10 2002-08-29 Florida State University Research Foundation, Inc. Procede de reglage de la viscosite d'un melange a base de ciment a l'aide de polyelectrolytes a charges opposees
US7261771B2 (en) 2002-01-09 2007-08-28 Nanostrata Inc. Method of controlling the viscosity of a cementitious mixture using oppositely-charged polyelectrolytes
US8017014B2 (en) 2005-06-01 2011-09-13 Nalco Company Method for improving flux in a membrane bioreactor
FR2910480B1 (fr) * 2006-12-21 2012-10-19 Kabongo Isaac Mulumba Procede d'impression avec les produits naturels; poudre des pierres, sables et autres produits naturels ayant les proprietes proche des produits cites, avec des machines d'imprimerie existantes comme les encres traditionnelles.
CN107429153B (zh) * 2015-01-15 2021-04-09 益瑞石滑石欧洲公司 包含颗粒状无机材料的泡沫形成用组合物
EP3061729B1 (fr) * 2015-02-27 2017-12-27 Omya International AG PCC à haute teneur en solides avec additif cationique

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1308143A (en) * 1969-04-21 1973-02-21 Ici Ltd Manufacture of paper
GB1505641A (en) * 1974-04-19 1978-03-30 Grace W R & Co Process of preparing a filler composition for paper
FR2468688A1 (fr) * 1979-10-29 1981-05-08 Omya Sa Composition pour le couchage de papier a haute teneur en matiere solide
DE3316949C3 (de) * 1983-05-09 1995-03-23 Pluss Stauffer Ag Calciumcarbonat
US4738726A (en) * 1985-05-06 1988-04-19 Engelhard Corporation Treatment of clays with cationic polymers to prepare high bulking pigments
US4816074A (en) * 1985-07-12 1989-03-28 E.C.C. America Inc. Kaolinite aggregation using sodium silicate
US4799964A (en) * 1985-07-29 1989-01-24 Grain Processing Corporation Preparation of filler compositions for paper
JPS62223396A (ja) * 1986-03-24 1987-10-01 三菱製紙株式会社 填料内添紙の製造方法
GB8701491D0 (en) * 1987-01-23 1987-02-25 Ecc Int Ltd Aqueous suspensions of calcium

Also Published As

Publication number Publication date
GB2251254B (en) 1994-06-29
AU8939991A (en) 1992-07-08
JPH06503127A (ja) 1994-04-07
AU654514B2 (en) 1994-11-10
WO1992010609A1 (fr) 1992-06-25
NO300021B1 (no) 1997-03-17
EP0560813A1 (fr) 1993-09-22
FI932475A0 (fi) 1993-05-31
DK0560813T3 (da) 1998-04-06
NO931216L (no) 1993-08-03
GB2251254A (en) 1992-07-01
GB9026362D0 (en) 1991-01-23
JP2919970B2 (ja) 1999-07-19
ATE157415T1 (de) 1997-09-15
ES2104735T3 (es) 1997-10-16
CA2088515A1 (fr) 1992-06-05
BR9107142A (pt) 1993-11-03
DE69127458T2 (de) 1998-01-02
DE69127458D1 (de) 1997-10-02
NO931216D0 (no) 1993-03-31
FI932475A (fi) 1993-05-31

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