EP1135555B1 - Verfahren zur herstellung von papier unter verwendung eines neuen retentionssystems aus einer gefällten kieselsäure und einem kationischen polymer - Google Patents

Verfahren zur herstellung von papier unter verwendung eines neuen retentionssystems aus einer gefällten kieselsäure und einem kationischen polymer Download PDF

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Publication number
EP1135555B1
EP1135555B1 EP98958307A EP98958307A EP1135555B1 EP 1135555 B1 EP1135555 B1 EP 1135555B1 EP 98958307 A EP98958307 A EP 98958307A EP 98958307 A EP98958307 A EP 98958307A EP 1135555 B1 EP1135555 B1 EP 1135555B1
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EP
European Patent Office
Prior art keywords
paper
silica
cationic polymer
retention
precipitated silica
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Expired - Lifetime
Application number
EP98958307A
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English (en)
French (fr)
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EP1135555A1 (de
Inventor
Marie-Odile Lafon
Herbert Hruschka
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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Anticipated expiration legal-status Critical
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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/31—Gums
    • D21H17/32—Guar or other polygalactomannan gum
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/10—Retention agents or drainage improvers

Definitions

  • the present invention relates to a novel process for the production of paper-based cellulose fiber paper in which a novel retention system comprising a suspension of precipitated silica and a cationic polymer is used to improve, in particular, the retention of the incorporated mineral fillers. .
  • the present invention also relates to a method of making paper using a retention system which substantially improves drainage (or dripping), i.e. the speed with which water flows from the suspension of fibers. More specifically, the invention relates to the use of an aqueous suspension of precipitated silica and a cationic polymer comprising a cationic galactomannan and / or a cationic starch.
  • the mechanical properties of the paper obtained according to the process of the invention are improved, for example stiffness and tear resistance as well as other properties such as whiteness.
  • the retention system according to the invention may have advantages as regards the quality and recyclability of the white water from the papermaking process as well as the papers broken during the manufacturing process.
  • Paper manufacturers have proposed various ways to reduce the cost of paper and try to improve its properties.
  • One of the approaches used is the addition of inexpensive mineral fillers in the papermaking process to replace the fiber.
  • certain mineral fillers are specifically used to improve certain properties of the paper.
  • titanium oxide is used in its anatase and / or rutile forms to improve the opacity of the papers, particularly in the case of laminated papers.
  • US-A-4961825 discloses a binder for use in a papermaking process, which binder comprises, on the one hand, a cationic or amphoteric carbohydrate, and, on the other hand, a colloidal silica sol.
  • the Applicant has developed a novel papermaking process using a novel retention system which significantly increases the retention of mineral fillers, fibers and other materials in the paper sheet.
  • Another object of the invention is to provide a retention system and a papermaking process in which the properties of the paper obtained, including, for example, the opacity yield of the mineral fillers, the tear strengths, the whiteness and other necessary properties are improved by optimizing the use of mineral fillers. Of course, optimization is done according to the type of load used.
  • Another object of the invention is to provide a paper having a high concentration of mineral fillers which has tear resistance and other acceptable characteristics.
  • the present invention is based on the development of a retention system and the papermaking process using it which significantly increases the retention of mineral fillers and other characteristics of the paper and which allows the optimization of the action. mineral fillers present in the pulp.
  • the amount of solids in the gelling system is 0.02 to 50% by weight, preferably 1 to 30% by weight, based on the weight of the paper stock or stock.
  • the ratio of the cationic polymer / precipitated silica should be between 1 and 10 by weight, and preferably, this ratio is between 2 and 6, the latter depending in particular on the degree of substitution of the precipitated silica and the cationic polymer.
  • the precipitation of the silica is carried out, the reaction medium is filtered and a filter cake is obtained which is washed if necessary. This cake is then disintegrated and thus forms a suspension of precipitated silica.
  • an aqueous suspension of precipitated silica having a dry matter content of between 10 and 40% by weight, a viscosity of less than 4.10 -2 Pa.s for a shear of 50 s -1 and the amount of silica contained in the supernatant obtained after centrifugation of said suspension at 7,500 rpm for 30 minutes represents more than 50% of the weight of the silica contained in the suspension. More particularly, this aqueous suspension of precipitated silica has a solids content of between 15 and 35% by weight and, in addition, a viscosity which is less than 2.10 -2 Pa.s at a shear of 50 s -1 .
  • the precipitated silicas are generally precipitated at a pH around the neutral pH or at a basic pH, the gels being obtained at a pH that is usually acidic or very acidic.
  • the cationic polymer is a cationic galactomannan
  • it is preferably selected from galactomannans comprising at least two vicinal hydroxyl groups, in particular cationic guars.
  • guars As far as guars are concerned, it has been noticed that their reactive centers are particularly accessible, which makes it possible to use small amounts to reach a satisfactory effect.
  • the base guar in the cationic guar is of a natural type. Natural guar is extracted from the albumen of certain plant seeds, for example Cyamopsis Tetragonalobus.
  • the guar macromolecule is constituted by a linear main chain constructed from monomeric ⁇ -D-mannose sugars linked together by (1-4) bonds, and ⁇ -D-galactose side units linked to ⁇ -D-mannoses. by links (1-6).
  • cationic guars are formed by reaction between hydroxyl groups of the polygalactomannan and reactive quaternary ammonium compounds.
  • the degree of substitution of the cationic groups of the guar is generally at least 0.01 and preferably at least 0.05 and up to 1.0. within the scope of the invention, a suitable range is from 0.08 to 0.5. It is assumed that the molecular weight of guar gum ranges from 100,000 to 1,000,000 and generally is around 220,000.
  • the cationic polymer is a cationic starch
  • it is generally chosen from those having a degree of substitution of between approximately 0.1 and 0.05 and, preferably, between approximately 0.02 and 0.04 and more particularly, more than about 0.025 and less than about 0.04.
  • a starch is made cationic by substitution with an ammonium group by techniques known per se and may have varying degrees of substitution up to 0.1.
  • ammonium compounds can be used.
  • the cationic starch can be prepared by treating the basic starch with 3-chloro-2-hydroxypropyltrimethylammonium chloride or 2,3-ethoxypropyltrimethylammonium chloride. which makes it possible to obtain a cationic starch having a degree of substitution of 0.02 to 0.04.
  • the basic starch used to prepare the cationic starch may be selected from the group consisting of potato starch, wheat starch, corn starch, barley starch, oat starch, rice starch, starch. tapioca, and their mixture.
  • these will be formulated as aqueous solutions.
  • the mineral fillers used in the process are varied in nature and are chosen in particular according to the type of paper manufactured and its future use.
  • the mineral filler material that can be used includes any common inorganic filler whose surface is at least partially anionic in character.
  • mineral fillers mention may be made, without limitation, of kaolin, clay, chalk, calcium carbonate, titanium dioxide, silica, and mixtures thereof.
  • the mineral fillers are normally added in the form of an aqueous dispersion at the appropriate concentrations specific to the type of paper manufactured.
  • the possibility of adding mineral fillers to the paper pulp is limited by factors such as the retention of the charges on the fabric, the dewatering of the pulp on the fabric, the wet and dry resistance of the paper obtained.
  • the retention system of the invention it has become possible to produce paper which contains more fillers while retaining its mechanical properties.
  • the mechanical properties of the paper including the modulus of elasticity, tensile index, tensile energy absorption, etc.
  • the mechanical properties of the paper have values equal to or even greater than those previously achieved with papers. obtained from conventional paper stocks in which a retention agent of the prior art is optionally used.
  • the sheet after drying, has greatly improved strength characteristics when using the method according to the invention. It has also been found that when mineral fillers such as those mentioned above and the like are used in the paste, these mineral fillers are effectively retained in the sheet and, moreover, do not have a negative effect on the strength of the sheet. in contrast with the sheets obtained by a manufacturing method without gelling system according to the invention.
  • the retention system forms an association with the fibers and with the fibers. fillers to form a complex flocculating matrix.
  • the manufacture of the paper sheet necessarily passes through a dewatering step which can profoundly alter the structure of the colloids and their distribution.
  • the changes in the structure of the aggregates of filler loads affect the retention rate of these and the opacity of the paper obtained.
  • a flocculate is formed within the cellulosic network which traps the charges in order to preserve during this critical stage the properties that the particles possess in suspension.
  • the components of the retention system are added within the paper making device as a mixture or separately. However, according to a preferred embodiment of the invention, the optimum results are obtained when the retention system based on precipitated silica and cationic polymer is formed in situ in the pulp.
  • this can be done by firstly adding the cationic polymer (guar and / or starch) in the form of an aqueous solution and adding separately to the pulp of the precipitated aqueous silica solution in a mixing tank or in a point of the device where there is appropriate agitation, so that the two components are dispersed with the paper-forming components and thus act simultaneously with each other and with the paper-forming components.
  • the cationic polymer guar and / or starch
  • the pH of the mother paste is not excessively critical and is generally less than 11, and preferably 5 to 9 .
  • the write-printing paper is one of the very positive-yielding ways, i.e., increased charge retention phenomenon and improved paper mechanical qualities.
  • the majority of the fillers used is calcium carbonate.
  • the amount of retention system to be used varies depending on the desired effect and the characteristics of the particular components that are selected in the preparation of said system. For example, for a given precipitation silica in a retention system, if it contains cationic guar gum with a DS of 0.3 instead of a DS of 0.7, more retention system will be required. .
  • This method consists of measuring the chemical retention of the charges while avoiding the formation of the fibrous mattress responsible for mechanical retention by filtration effect.
  • a 500 ml sample of the dispersion of fibers + fillers + retention system + optionally additives to be tested, kept under agitation only the first 100 ml are withdrawn through a sieve.
  • the global retention values (fibers + charges) and the retention retention are calculated.
  • a filter bowl equipped with a 600 ⁇ m opening grid was used.
  • This example shows the chemical retention obtained with the BRITT Jar test.
  • the suspensions are prepared by defibrating the cellulose in 500 ml of demineralized water in a Dispermat-type bowl for 10 minutes at 2,000 rpm.
  • the mixture obtained is then transferred to a 10-liter mixer with a stirring blade, then diluted to the concentration of 0.5% fiber, and finally kept under stirring all the time manipulations to ensure, during sampling , a perfect homogeneity.
  • the stirring rate is set according to the desired shear and is stirred for 30 seconds.
  • the starch is added followed by stirring for 30 seconds.
  • the silica is then introduced (in the tests comprising this product). Then stirred for 30 seconds.
  • the 100 ml collected are then filtered on BÜCHNER with WHATMANN No. 42 filters (ash-free filters, previously dried for 1 hour at 105 ° C. and then weighed at ⁇ 0.0001 g).
  • the filter residue is then carefully removed, dried for 1 hour at 105 ° C., then cooled in a desiccator and weighed ( ⁇ 0.0001). This allows the calculation of the overall retention rate.
  • Formulation A ' Formulation B ' Formulation C ' Paper fibers: 60% eucalyptus - 40% long sulphate fiber (Shopper-Riegler index 24 ° SR) 100 shares 100 shares 100 shares Charge: Calcium carbonate OMYALITE 90 50 shares 50 shares 50 shares Hi CAT 142 cationic starch 0.5% dry / fiber 0.5% dry / fiber 0.5% dry / fiber Jaguar C-17 cationic guar 0.05% dry / fiber 0.05% dry / fiber 0.05% dry / fiber Precipitated silica A 0.2% dry / fiber Colloidal silica B 0.2% dry / fiber
  • the suspension is prepared as in Example 1, with stirring for 15 minutes after addition of the starch, and then addition of cationic guar. A stirring time of 15 seconds is observed before the optional addition of silica A or B.
  • the suspension is prepared in a manner identical to that of Example 1.
  • the product Aqualenc 18 is added.
  • the type A silica is added and, finally, the guar is added under a stirring of 1000 rpm. .
  • This example gives the charge retention obtained on a shredder.
  • Formulation A Formulation B
  • the dough thus defibrated is introduced into a stirred tank of 10 liters. Then diluted with filtered water to a total volume of 4 liters. Then the diluted dough is stirred for 1 minute and about 500 ml of suspension is taken and placed in a test tube.
  • test tube The contents of the test tube are poured into the bowl of the tablet machine. It is mixed by bubbling and then the form is made by drawing under vacuum.
  • the form is then recovered on a cardboard support and placed in a vacuum dryer. We then weigh the form and readjust the sample volume to obtain a grammage of 60 g / m 2 .

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paper (AREA)
  • Silicon Compounds (AREA)

Claims (14)

  1. Verfahren zur Papierherstellung durch Bildung und Trocknung einer wässrigen Papiermasse, die die Cellulose-haltige Masse und mineralische Füllstoffe enthält, wobei man zu dem Ganzstoff vor der Blattbildung ein Retentionssystem hinzufügt, das umfasst:
    (i) ein kationisches Polymer, ausgewählt aus einem kationischen Amidon, einem kationischen Galaktomannan und/oder deren Gemisch,
    (ii) und Siliziumoxid,
    dadurch gekennzeichnet, dass das Siliziumoxid eine Suspension aus ausgefälltem Siliziumoxid ist, die aus dem Filterkuchen besteht der bei der Fällungsreaktion entstanden ist.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass die wässrige Suspension des ausgefällten Siliziumoxids einen Gehalt an Trockenmasse aufweist, der zwischen 10 und 40 Gew.-% liegt, eine Viskosität von weniger als 4·10-2 Pa.s für ein Schergefälle von 50 s-1 aufweist und eine Menge an Siliziumoxid, das sich im Überstand befindet, der nach der Zentrifugation dieser Suspension bei 7500 Umdrehungen pro Minute für 30 Minuten erhalten wird, die mehr als 50 Gew.-% des in der Suspension enthaltenen Siliziumoxids ausmacht.
  3. Verfahren zur Papierherstellung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das kationische Polymer ein Galaktomannan ist, das mindestens zwei vicinale Hydroxylgruppen enthält.
  4. Verfahren zur Papierherstellung gemäß dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass das Galaktomannan einen Substitutionsgrad von mindestens 0,01 und vorzugsweise von mindestens 0,05 aufweist und bis zu 1,0 gehen kann.
  5. Verfahren zur Papierherstellung gemäß einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass das kationische Polymer ein kationisches Amidon ist, das einen Substitutionsgrad aufweist, der zwischen etwa 0,1 und 0,05 liegt und vorzugsweise zwischen etwa 0,02 und 0,04.
  6. Verfahren zur Papierherstellung gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die mineralischen Füllstoffe ausgewählt sind aus der Gruppe bestehend aus Kaolin, Ton, Kreide, Calciumcarbonat, Titanoxid, Siliziumoxid und deren Gemischen.
  7. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass der pH-Wert des Ganzstoffs zwischen 5 und 9 gehalten wird.
  8. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Menge an Feststoffen in dem Retentionssystem bei 0,02 bis 50 Gew.% liegt, bezogen auf das Gewicht des Ganzstoffs.
  9. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Gewichtsverhältnis von kationisches Polymer/ausgefälltes Silizumoxid zwischen 1 und 10 liegen muss und vorzugsweise dieses Verhältnis zwischen 2 und 6 liegt, wobei dieses vom Substitutionsgrad des ausgefällten Siliziumoxids und des kationischen Polymers abhängt.
  10. Verfahren gemäß einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Retentionssystem auf Grundlage des ausgefällten Siliziumoxids und des kationischen Polymers in situ in der Papiermasse gebildet wird.
  11. Verfahren zur Papierherstellung gemäß dem vorhergehenden Anspruch, dadurch gekennzeichnet, dass die in situ-Bildung des Retentionssystems durch die Zugabe des kationischen Polymers in Form einer wässrigen Lösung zu einem ersten Zeitpunkt und die Zugabe der wässrigen Lösung des ausgefällten Siliziumoxids zur Papiermasse zu einem zweiten Zeitpunkt in einem Mischgefäß oder an einem Ort in der Vorrichtung, an dem eine angemessene Bewegung vorliegt, erfolgt.
  12. Papier das aus einem Verfahren gemäß einem der vorhergehenden Ansprüche erhalten werden kann.
  13. Verwendung des Papiers gemäß Anspruch 12 als laminiertes Papier, Durchschreibpapier oder Packpapier.
  14. Verwendung des Papiers gemäß Anspruch 13 als Durchschreibpapier.
EP98958307A 1997-08-01 1998-12-02 Verfahren zur herstellung von papier unter verwendung eines neuen retentionssystems aus einer gefällten kieselsäure und einem kationischen polymer Expired - Lifetime EP1135555B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9709891A FR2766849B1 (fr) 1997-08-01 1997-08-01 Procede de fabrication de papier utilisant un nouveau systeme de retention comprenant une silice precipitee et un polymere cationique
PCT/FR1998/002598 WO2000032873A1 (fr) 1997-08-01 1998-12-02 Procede de fabrication de papier utilisant un nouveau systeme de retention comprenant une silice precipitee et un polymere cationique

Publications (2)

Publication Number Publication Date
EP1135555A1 EP1135555A1 (de) 2001-09-26
EP1135555B1 true EP1135555B1 (de) 2007-01-24

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP98958307A Expired - Lifetime EP1135555B1 (de) 1997-08-01 1998-12-02 Verfahren zur herstellung von papier unter verwendung eines neuen retentionssystems aus einer gefällten kieselsäure und einem kationischen polymer

Country Status (10)

Country Link
EP (1) EP1135555B1 (de)
AT (1) ATE352670T1 (de)
AU (1) AU1439699A (de)
CA (1) CA2354647C (de)
DE (1) DE69836985T2 (de)
DK (1) DK1135555T3 (de)
ES (1) ES2277396T3 (de)
FR (1) FR2766849B1 (de)
NO (1) NO331149B1 (de)
WO (1) WO2000032873A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2799663B1 (fr) * 1999-10-15 2001-12-07 Rhodia Chimie Sa Utilisation de galactomannanes comme agent emulsifiant
FR2879631B1 (fr) * 2004-12-16 2007-02-23 Snf Sas Soc Par Actions Simpli Procede pour la fabrication de papier

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0017353B2 (de) * 1979-03-28 1992-04-29 Ciba Specialty Chemicals Water Treatments Limited Herstellung von Papier und Pappe
JPS60209098A (ja) * 1984-03-28 1985-10-21 三井東圧化学株式会社 軽量紙およびその製法
SE8403062L (sv) * 1984-06-07 1985-12-08 Eka Ab Forfarande vid papperstillverkning
US5176891A (en) * 1988-01-13 1993-01-05 Eka Chemicals, Inc. Polyaluminosilicate process
FR2627176B1 (fr) * 1988-02-11 1990-06-15 Rhone Poulenc Chimie Suspension aqueuse stable de silice de precipitation
SE9003954L (sv) * 1990-12-11 1992-06-12 Eka Nobel Ab Saett foer framstaellning av ark- eller banformiga cellulosafiberinnehaallande produkter
US5194120A (en) * 1991-05-17 1993-03-16 Delta Chemicals Production of paper and paper products
FR2722185B1 (fr) * 1994-07-07 1996-09-27 Rhone Poulenc Chimie Suspension concentree de silice de precipitation, procedes pour sa preparation et utilisations de cette suspension

Also Published As

Publication number Publication date
CA2354647A1 (fr) 2000-06-08
ES2277396T3 (es) 2007-07-01
FR2766849A1 (fr) 1999-02-05
FR2766849B1 (fr) 1999-12-24
DE69836985D1 (de) 2007-03-15
NO20012666D0 (no) 2001-05-30
EP1135555A1 (de) 2001-09-26
DK1135555T3 (da) 2007-05-21
DE69836985T2 (de) 2007-06-28
NO20012666L (no) 2001-08-02
AU1439699A (en) 2000-06-19
WO2000032873A1 (fr) 2000-06-08
ATE352670T1 (de) 2007-02-15
NO331149B1 (no) 2011-10-24
CA2354647C (fr) 2006-09-19

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