EP0560813A1 - Anorganischer materialschlamm. - Google Patents

Anorganischer materialschlamm.

Info

Publication number
EP0560813A1
EP0560813A1 EP91920520A EP91920520A EP0560813A1 EP 0560813 A1 EP0560813 A1 EP 0560813A1 EP 91920520 A EP91920520 A EP 91920520A EP 91920520 A EP91920520 A EP 91920520A EP 0560813 A1 EP0560813 A1 EP 0560813A1
Authority
EP
European Patent Office
Prior art keywords
inorganic material
paper
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.)
Granted
Application number
EP91920520A
Other languages
English (en)
French (fr)
Other versions
EP0560813B1 (de
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
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 ECC International Ltd filed Critical ECC International Ltd
Publication of EP0560813A1 publication Critical patent/EP0560813A1/de
Application granted granted Critical
Publication of EP0560813B1 publication Critical patent/EP0560813B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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 a cationically dispersed, high solids, aqueous suspension of an inorganic pigment or filler, such as calcium carbonate. It is known to disperse inorganic pigments and fillers such that the particles have an overall positive charge. Such cationically dispersed suspensions are useful in paper making (EP-0278602A) and paper coating. It has now been found that the rheology of a cationically dispersed suspension of a mineral pigment or filler can be improved by using a mineral having a particular particle size distribution.
  • a high solids, aqueous suspension of a cationically dispersed particulate inorganic material characterised in that the particulate inorganic material has a particle size distribution such that not more than 10% by weight of the particles have an equivalent spherical diameter (esd) smaller than 0.25 microns.
  • the high solids suspension should preferably be at least 60% by weight solids.
  • the inorganic material is a material which, when ground to a particulate mass, exists in the form of regular, approximate spherical particles having a low mean particle aspect ratio.
  • the material may be a calcium carbonate, in any form, natural or synthetic. Particularly preferred is ground marble, although precipitated calcium carbonate (PCC) and chalk are operable,
  • PCC precipitated calcium carbonate
  • Other possible inorganic materials are gypsum, talc and calcined kaolin clay.
  • other minerals having a plately structure e.g. layer lattice silicates such as kaolin clay, are within the scope of the present invention.
  • the inorganic material employed in the present invention should have a specific surface area, as measured by the BET N 2 method, of less than about 7.5m 2 g _1 , more preferably less than about 6.5m 2 g" 1 , and preferably at least 2m 2 g" 1 .
  • the particulate material should also preferably have a particle size distribution such that no greater than 1% of the particles have an esd larger than 10 microns and at least 65% have an esd smaller than 2 microns.
  • the inorganic material may be ground, before dispersion, to the desired particle size distribution.
  • the grinding conditions can be adjusted in a manner known per se to produce materials having varying distributions.
  • a cationic slurry prepared in accordance with the present invention can be formed into a slurry having a given viscosity at higher solids than a slurry in which the inorganic material has a broader particle size distribution.
  • the particles of the material may be dispersed using a dispersing agent 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.
  • 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.
  • the aqueous suspension of the present invention should preferably be subjected to vigorous mixing before or after dispersion.
  • the vigorous mixing should be sufficient to impart at least lOkJ energy per kg of the inorganic material, and 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 paper coating composition can be used in a method of coating a sheet member.
  • the thus formed coated paper is particularly suitable for recycling.
  • Ground marble for use in the present invention is preferably formed by crushing batches of marble in aqueous suspension in the absence of a chemical dispersing agent using a particulate grinding medium. Further size reduction is 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 particulate pigment is dispersed with the combination of an anionic polyelectrolyte and a cationic polyelectrolyte.
  • the anionic polyeletrolyte 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 polyeletrolyte 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, and 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, preferably in the range of from about 0.1 to 0.2% by weight.
  • the cationic polyelectrolyte may be a water- soluble substituted polyolefine 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 polyolefine is preferably at least 1500 and preferably no greater than 1,000,000, and is more preferably in the range of from 50,000 to 500,000.
  • the substituted polyolefine is a poly (diallyl di(hydrogen or lower alkyl)ammonium salt).
  • the lower alkyl groups which may be the same or different, may for example, have up to four carbon atoms and each is preferably methyl.
  • the ammonium salt may be, for example, a chloride, bromide, iodide, HS0 4 ⁇ , CH 3 S0 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 co-polymerising epichlorohydrin and an aliphatic secondary amine, said product having the formula
  • 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 -* HS0 4 _* CH 3 S0«- 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 and 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 clay 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 Kern Laser Z" meter.
  • the ratio of the weight of cationic polyelectrolyte to the weight of anionic polyelectrolyte used is preferably in the range of from 2:1 to 20:1, more preferably in the range of from 2:1 to 10:1.
  • 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 pigment is to be dispersed using a combination of an anionic and cationic polyelectrolyte
  • the pigment is 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.
  • the aqueous suspension 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 adhesive used in making the paper coating composition should be a non-ionic or a cationic adhesive. Such adhesives contrast with the anionic adhesives which are normally used in paper coating compositions in which the pigment is anionic. Thus, cationic caesin 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 lythography 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 coating composition may be coated on to a sheet member using normal paper coating machinery and under normal paper coating conditions. It has been found that the paper coated with a cationic composition in accordance with the present invention provides broadly similar results to that obtained with a conventional anionic system.
  • the coated paper which may be made using the present invention is of advantage when it is employed as "broke” or recycled paper in a paper making process.
  • a method for recycling paper includes the step of reducing the paper into a fibrous recyclable state and incorporating said fibre in a paper-making composition.
  • a paper-making composition may include conventional paper-making pulp, such as a bleached sulphite pulp and, typically, the broke fibre and the 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. Since the broke fibre will include a proportion of calcium carbonate 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.
  • aqueous slurry of the present invention is also particularly suited to paper filling and reference here is made to our EP-278602A.
  • the present invention will now be illustrated by the following Example: EXAMPLE Two calcium carbonate pigments were prepared by low solids sand grinding of marble flour. Adjustment of grinding conditions allowed products of varying widths of distribution to be compared. Sedigraph data was obtained as shown in Table 1 below (percentages given are weight %):
  • Polyacylate dose Polydadmac dose S wt% wt%
  • a ground marble having a broad 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)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Disintegrating Or Milling (AREA)
EP91920520A 1990-12-04 1991-11-28 Eine wässrige Suspension eines festen Kalziumkarbonatpigments Expired - Lifetime EP0560813B1 (de)

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 (en) 1990-12-04 1991-11-28 Inorganic material slurry

Publications (2)

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

Family

ID=10686470

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91920520A Expired - Lifetime EP0560813B1 (de) 1990-12-04 1991-11-28 Eine wässrige Suspension eines festen Kalziumkarbonatpigments

Country Status (13)

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

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
FI104502B (fi) 1997-09-16 2000-02-15 Metsae Serla Oyj Menetelmä paperirainan valmistamiseksi
FI105840B (fi) 1997-09-16 2000-10-13 Metsae Serla Oyj Menetelmä materiaalirainan päällystämiseksi
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 (en) * 2001-01-10 2002-08-29 Florida State University Research Foundation, Inc. Method of controlling the viscosity of a cementitious mixture using oppositely-charged polyelectrolytes
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
TR201802411T4 (tr) * 2015-02-27 2018-03-21 Omya Int Ag Katyonik katkı maddesine sahip yüksek katı maddeli PCC.

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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9210609A1 *

Also Published As

Publication number Publication date
ATE157415T1 (de) 1997-09-15
BR9107142A (pt) 1993-11-03
AU654514B2 (en) 1994-11-10
GB2251254B (en) 1994-06-29
ES2104735T3 (es) 1997-10-16
GB2251254A (en) 1992-07-01
GB9026362D0 (en) 1991-01-23
CA2088515A1 (en) 1992-06-05
DE69127458T2 (de) 1998-01-02
DE69127458D1 (de) 1997-10-02
NO931216D0 (no) 1993-03-31
WO1992010609A1 (en) 1992-06-25
NO300021B1 (no) 1997-03-17
DK0560813T3 (da) 1998-04-06
JPH06503127A (ja) 1994-04-07
AU8939991A (en) 1992-07-08
FI932475A0 (fi) 1993-05-31
FI932475A (fi) 1993-05-31
NO931216L (no) 1993-08-03
JP2919970B2 (ja) 1999-07-19
EP0560813B1 (de) 1997-08-27

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