WO2002095128A9 - Polymere et son utilisation dans la production de papier et de carton - Google Patents

Polymere et son utilisation dans la production de papier et de carton

Info

Publication number
WO2002095128A9
WO2002095128A9 PCT/FI2002/000428 FI0200428W WO02095128A9 WO 2002095128 A9 WO2002095128 A9 WO 2002095128A9 FI 0200428 W FI0200428 W FI 0200428W WO 02095128 A9 WO02095128 A9 WO 02095128A9
Authority
WO
WIPO (PCT)
Prior art keywords
paper
strength
cationic
starch
web
Prior art date
Application number
PCT/FI2002/000428
Other languages
English (en)
Other versions
WO2002095128A1 (fr
Inventor
Anna-Liisa Tammi
Kari Nurmi
Original Assignee
Raisio Chem Ltd
Anna-Liisa Tammi
Kari Nurmi
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 Raisio Chem Ltd, Anna-Liisa Tammi, Kari Nurmi filed Critical Raisio Chem Ltd
Priority to EP02771660A priority Critical patent/EP1392919B1/fr
Priority to US10/478,138 priority patent/US20040149412A1/en
Priority to CA002448113A priority patent/CA2448113A1/fr
Priority to DE60235539T priority patent/DE60235539D1/de
Priority to AT02771660T priority patent/ATE459752T1/de
Publication of WO2002095128A1 publication Critical patent/WO2002095128A1/fr
Publication of WO2002095128A9 publication Critical patent/WO2002095128A9/fr

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
    • 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

Definitions

  • the invention relates to the chemistry of additives for paper making.
  • the in- vention relates to a polymer stabilized with a polysaccharide and being generally used as an additive in the production of paper.
  • Various paper making additives are used to improve the properties of paper.
  • Water soluble additives such as polyamides, polyamide-epichlorohydrin resins, melamin resins, urea-formaldehyde resins, polyacrylamides as well as preferably starch together with its derivatives are used to improve the strength properties.
  • Starch is an advantageous and preferred raw material of natural origin. The amount of starch required to improve the strength properties is relatively large.
  • starch As wood fiber is anionic in character, native starch has a quite low affinity thereto. Therefore, starch has been chemically modified into the cationic direction. Starch is cation- ized by attaching substituents having an ionic nitrogen group, such as primary, secondary, tertiary or quaternary ammonium groups, to the carbohydrate backbone. As a measure of the cationic character, the relative ratio of substituted to unsubstituted glucose units, i.e. a degree of substitution, is used. The cationic character can also be expressed as a percentage amount of ionic nitrogen based on the weight of the substituted starch.
  • substituents having an ionic nitrogen group such as primary, secondary, tertiary or quaternary ammonium groups
  • the dry strength properties of paper are usually improved by adding hydrogen bonds to OH groups of the fiber.
  • the paper strengthening additives of this kind include hydrophilic, water-soluble polymers such as starch, carboxymethylcellulose or synthetic polymers. These include polyacrylamides of which anionic, cationic and amphoteric are used. Their use is limited by a relative high price.
  • wet strength is usually meant the strength of a finished paper when it becomes wet, which strength is obtained by the formation of covalent bonds between the fibers. This property is of importance when making paper e.g. for filter paper or kitchen paper, and it can be be obtained through reactions between fibers and additives at a high temperature of the drying section of a paper machine.
  • Another wet strength the strength of a wet web during the production of paper is of great importance for the runnability of the machine, especially when proceeding to a drying section, because the web has been fully supported up to that point. It has been tried to improve this property mainly by increasing the dry solids content of the web in the press section.
  • starch In order to combine the properties of polyacrylamides and starches to improve the wet strength of paper, products have been prepared in which acrylamide or metacrylamide and an unsaturated organic acid are polymerized in the presence of starch. In this manner starch is formed to which polymerized side chains have been bound.
  • the starch is preferably cationic, having typically a degree of substitution of 0.01 - 0.70.
  • Japanese patent application JP 2-26944 discloses a polymer of an acrylamide or metacrylamide and methacrylamide acid, prepared in an aqueous solution containing a cationic polysaccharide. In addition to the tensile strength, attempts to improve the tear strength has been made. The cationic character of the polysaccharide is low, and the nitrogen content is 0.4%.
  • a product is prepared by polymerizing 50 - 95 mol-% of (meth)acrylamide and 5 - 50 mol-% of an ⁇ , ⁇ -unsaturated carboxylic acid in an aqueous solution containing 40 - 90 parts per weight of a cationic polysaccharide.
  • a vinylic component to be polymerized is entirely in the form of amide, and after the polymerization, part of the amide groups is hydrolyzed to carboxylic groups.
  • the number of the formed side chains of the starch is large in relation to the number of the cationic groups, because low cationic starch was used.
  • the runnability of paper in a machine can be improved by web wet strength im- proving agents.
  • the present invention relates particularly to the wet strength of a web, i.e. to the strength of a paper or paperboard web during the production with a dry solids content of about 20 - 60%).
  • the additive according to the invention improves in addition to the wet strength of a web also the surface resistance of the product.
  • the surface resistance is of particular signifi- cance for printing papers.
  • a polysaccharide having a strong cationic character is used, which in an aqueous solution is ready for use, and no time-consuming cooking is needed.
  • the degree of substitution of the cationic polysaccharide is about 0.02 - 0.50.
  • the polysaccharide used is preferably degraded starch.
  • the starch may be any known starch, e.g. potato, corn, waxy maize, barley, wheat or tapioca starch.
  • other useful polysaccharides are e.g. dextrine, amylopectin, amylose and mannose.
  • vinylic monomers are used in the product according to this invention.
  • the proportion of the monomers calculated on the dry solids content of the starting materials is not more than about 30%, preferably below 20%.
  • at least about 95% of the molar amount of the monomer component is amide.
  • polymerization initiators and pH adjusting agents are used as known in the art.
  • Suitable initiators are e.g. cerium salts, persulfates, hydroperoxides alone or together with a reducing metal salt, or azo compounds.
  • the cationic starch has a degree of substitution of 0.20; the cationization has been carried out by using a quaternary ammonium compound.
  • the cationic starch and water are mixed together in a reactor.
  • the pH of the solution is adjusted to 7 by using acetic acid, and 20% of both the tert-butyl hydroperoxide and the sodium metabisulfite aqueous solutions are added.
  • the temperature is raised to 60°C, and a nitrogen atmosphere is arranged in the reactor for the duration of the reaction.
  • reaction is continued for 120 minutes at 60°C under agitation.
  • the reaction can be initiated by various initiators, as in the above example by an oxidation- reduction-reagent pair, which includes i.a. a copper sulfate-hydrogen peroxide-pair, or e.g. by a cerium salt.
  • the catalyst may also be a persulfate or another catalyst commonly used in emulsion polymerization.
  • the wet tensile strength was determined freshly on wet sheets (about 35% dry solids).
  • a paper strip was drawn by a measuring device at constant speed (50 mm/min) and the tensile force required to cause fracturing of the paper was registered.
  • test product according to the invention improves the wet tensile strength of the sheets while the cationic starch alone does not.
  • Example 3 Laboratory sheets are prepared from a pulp consisting of 80% mechanical pulp and 20%> chemical pulp. The additions of the additives are given in kg/t. In the Example, the tested sheets were prepared using a fiber orientating sheeting mould in which the machine direction (MD) and the cross direction (CD) can be distinguished.
  • MD machine direction
  • CD cross direction
  • the product according to the invention significantly improves the wet web strength both in the machine direction and in the cross direction.
  • Example 4 Laboratory sheets are prepared from a pulp consisting of 15%> chemical pulp, 20% reject and 55%) mechanical pulp, and as filler kaolin, so that the ash level will be 20%. The additions of the additives are given in kg/t of the dry solids of the pulp. The sheets were prepared to a basis weight of 70 g/m 2 .
  • the IGT surface resistance was measured on these sheets, and a slight improvement could also be observed compared to the zero point as well as to the use of the pulp starch alone.
  • the IGT picking indicates how the surface of a paper, which has been printed with a printing ink, is able to resist abrasion before the surface becomes flocked and the fibers can be seen on the surface.
  • a product according to the invention may be used in paper and cardboard production, for example for stabilizing hydrophobic size dispersions.
  • sizes are e.g. AKD (alkyl ketene dimer) and ASA ( alkenyl succinic anhydride).
  • AKD alkyl ketene dimer
  • ASA alkenyl succinic anhydride

Landscapes

  • Paper (AREA)
  • Extrusion Of Metal (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un copolymère stabilisé avec un polysaccharide cationique, qui est utilisé comme additif destiné à la production de papier ou de carton et pouvant améliorer la résistance d'une bande humide. Dans ledit copolymère, un acrylamide ou métacrylamide, un acide carboxylique vinylique et éventuellement d'autres monomères vinyliques sont utilisés comme monomères. La résistance à l'état humide d'une bande correspond à la résistance d'une bande de papier ou de carton pendant la production pour une teneur en matière sèche de 20 à 60 %. L'additif de l'invention améliore non seulement la résistance de la bande humide, mais également la résistance superficielle du produit. Par comparaison avec les additifs de la technique antérieure, un rapport relatif faible entre le nombre de chaînes latérales et les groupes cationiques est utilisé, puisqu'un polysaccharide ayant un caractère cationique supérieur offre une meilleure stabilité.
PCT/FI2002/000428 2001-05-23 2002-05-20 Polymere et son utilisation dans la production de papier et de carton WO2002095128A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP02771660A EP1392919B1 (fr) 2001-05-23 2002-05-20 Polymere et son utilisation dans la production de papier et de carton
US10/478,138 US20040149412A1 (en) 2001-05-23 2002-05-20 Polymer and use thereof in the production of paper and board
CA002448113A CA2448113A1 (fr) 2001-05-23 2002-05-20 Polymere et son utilisation dans la production de papier et de carton
DE60235539T DE60235539D1 (de) 2001-05-23 2002-05-20 Polymer und seine verwendung bei der herstellung von papier und pappe
AT02771660T ATE459752T1 (de) 2001-05-23 2002-05-20 Polymer und seine verwendung bei der herstellung von papier und pappe

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI20011085A FI113968B (fi) 2001-05-23 2001-05-23 Kationisella polysakkaridilla stabiloitu liuospolymeeri
FI20011085 2001-05-23

Publications (2)

Publication Number Publication Date
WO2002095128A1 WO2002095128A1 (fr) 2002-11-28
WO2002095128A9 true WO2002095128A9 (fr) 2003-01-23

Family

ID=8561260

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2002/000428 WO2002095128A1 (fr) 2001-05-23 2002-05-20 Polymere et son utilisation dans la production de papier et de carton

Country Status (9)

Country Link
US (1) US20040149412A1 (fr)
EP (1) EP1392919B1 (fr)
AT (1) ATE459752T1 (fr)
CA (1) CA2448113A1 (fr)
DE (1) DE60235539D1 (fr)
ES (1) ES2340840T3 (fr)
FI (1) FI113968B (fr)
PT (1) PT1392919E (fr)
WO (1) WO2002095128A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20080083153A (ko) 2005-12-15 2008-09-16 다우 글로벌 테크놀로지스 인크. 첨가제 조성물을 함유하는 개선된 셀룰로오스 물품
US8916640B2 (en) 2006-07-06 2014-12-23 Dow Global Technologies Llc Blended polyolefin dispersions
US8476326B2 (en) * 2006-09-22 2013-07-02 Dow Global Technologies Llc Fibrillated polyolefin foam
CN101878250B (zh) 2007-09-28 2014-07-02 陶氏环球技术有限责任公司 较高结晶度烯烃分散体
WO2012148405A1 (fr) 2011-04-28 2012-11-01 Hewlett-Packard Development Company, L.P. Support utilisé lors de l'impression par presse à bobines à jet d'encre à vitesse élevée numérique
US11447618B2 (en) 2016-03-01 2022-09-20 Kemira Oyj Polymer composition, its use and a surface size
JP7047310B2 (ja) * 2017-09-28 2022-04-05 荒川化学工業株式会社 紙力増強剤及び紙
CN109749012A (zh) * 2019-01-24 2019-05-14 湖北中之天科技股份有限公司 一种环保型无氯聚丙烯酰胺湿强剂的生产方法及在造纸中的应用

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US3006806A (en) * 1957-02-15 1961-10-31 Olin Mathieson Sized paper and process therefor
JPS5691075A (en) * 1979-12-26 1981-07-23 Kao Corp Size composition
DE3162325D1 (en) * 1980-12-12 1984-03-22 Bayer Ag Paper-sizing agents and a process for their preparation
US4372814A (en) * 1981-05-13 1983-02-08 United States Gypsum Company Paper having mineral filler for use in the production of gypsum wallboard
US4684708A (en) * 1985-03-11 1987-08-04 Akzo N.V. Cationic grafted starch copolymers
DE3702712A1 (de) * 1987-01-30 1988-08-11 Basf Ag Leimungsmittel fuer papier auf basis feinteiliger waessriger dispersionen
JP2622965B2 (ja) * 1987-03-02 1997-06-25 星光化学工業株式会社 製紙用添加剤
US4866151A (en) * 1987-03-25 1989-09-12 National Starch And Chemical Corporation Polysaccharide graft polymers containing acetal groups and their conversion to aldehyde groups
IT1224421B (it) * 1987-12-29 1990-10-04 Lamberti Flli Spa Galattomannani modificati e realtivo procedimento di preparazione
JP2620806B2 (ja) * 1988-07-11 1997-06-18 星光化学工業株式会社 製紙用添加剤と製紙方法
US4954220A (en) * 1988-09-16 1990-09-04 E. I. Du Pont De Nemours And Company Polysilicate microgels as retention/drainage aids in papermaking
US5338406A (en) * 1988-10-03 1994-08-16 Hercules Incorporated Dry strength additive for paper
US5049634A (en) * 1989-09-22 1991-09-17 National Starch And Chemical Investment Holding Corporation Derivatized and/or crosslinked products from acetal- and aldehyde-containing polysaccharide graft polymers
US5122231A (en) * 1990-06-08 1992-06-16 Cargill, Incorporated Cationic cross-linked starch for wet-end use in papermaking
DE4127733A1 (de) * 1991-08-22 1993-02-25 Basf Ag Pfropfpolymerisate aus saccharidstrukturen enthaltenden naturstoffen oder deren derivaten und ethylenisch ungesaettigten verbindungen und ihre verwendung
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Also Published As

Publication number Publication date
FI113968B (fi) 2004-07-15
ES2340840T3 (es) 2010-06-10
FI20011085A0 (fi) 2001-05-23
DE60235539D1 (de) 2010-04-15
EP1392919B1 (fr) 2010-03-03
ATE459752T1 (de) 2010-03-15
EP1392919A1 (fr) 2004-03-03
US20040149412A1 (en) 2004-08-05
WO2002095128A1 (fr) 2002-11-28
CA2448113A1 (fr) 2002-11-28
PT1392919E (pt) 2010-03-26
FI20011085A (fi) 2002-11-24

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