WO2006036092A1 - Additifs ameliorant la qualite des papiers - Google Patents
Additifs ameliorant la qualite des papiers Download PDFInfo
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- WO2006036092A1 WO2006036092A1 PCT/SE2004/001392 SE2004001392W WO2006036092A1 WO 2006036092 A1 WO2006036092 A1 WO 2006036092A1 SE 2004001392 W SE2004001392 W SE 2004001392W WO 2006036092 A1 WO2006036092 A1 WO 2006036092A1
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/04—Starch derivatives, e.g. crosslinked derivatives
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- 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
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
Definitions
- the present invention relates to the field of wet-end additives based on modified polysaccharides used to improve end-properties in paper and paper products.
- the invention relates to paper and paper products with new improved properties conferred by the use of additives made from water-soluble cationic polysaccharide graft copolymers, comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached.
- a favoured polysaccharide used in the invention is starch.
- the additives allow for improved adsorption to the fibres used in said paper and paper products, at the high conductivities present as a consequence of conditions of reduced or completely closed water circulation, resulting in significantly improved end-properties in said paper and paper products.
- Starch has long been used commercially in the paper industry both as retention and dry strength aid or additive, in paper production.
- additives are added to pulp as wet-end additives; i.e., the additives are added prior to sheet production, and are relatively effective in increasing the final dry strength of the resulting paper.
- Aldehyde-substituted acrylamidated starch polymers are other forms of modified cationic starches that have been described as wet strength additives [EP 0147 380].
- Cellulose fibres used for paper making possess, in their natural form, anionic charges, while most cationic starch additives contain polyvalent cationic charges.
- the performance of these additives, and subsequent end-properties in the products, such as increased dry tensile strength, z-strength and burst strength, are thought to be directly or indirectly dependent on the electrostatic interaction between the polyvalent cationic charges present on the additives and the anionic charges on the fibres.
- cluster cationization grafting cationic groups in a "cluster" onto starch backbone
- random cationization randomly grafting individual cationic groups onto starch backbone
- cluster cationization is beneficial for enhancing adsorption of any cationic polymeric additive added to cellulose fibres in conditions of, for example, high conductivity as a consequence of reduced or completely closed water circulation, leading to improved paper and paper products made from these fibres.
- the invention thus provides paper and paper products with improved properties at conditions where random cationized starch, as described above, is reduced in its efficiency to function, said improved properties being conferred by the use of additives made from water-soluble cationic starch graft copolymers, comprising a polymer backbone of starch, on which copolymers comprising one or more non-ionic monomer segments and one or more cationic monomer segments, are covalently attached.
- cluster cationic starch or alternatively, “cluster cationized starch”, has been adopted herein as a simplified term to describe the above named family of graft copolymer additives based on the specific use of a starch backbone.
- cluster cationic starch additives In conditions of, for example, high conductivity as a consequence of reduced or completely closed water circulation, cluster cationic starch additives have been shown to manifest improved adsorption to the fibres used in the manufacture of said paper and paper products, resulting in the latter possessing significantly improved end-properties. These properties have been found to be better than normally achieved with standard cationic starch additives.
- starch as the selected polysaccharide is a favoured mode in this invention
- alternative polysaccharides may be used in the synthesis of said graft copolymer additives, especially those containing a hydroxymethyl group, for example, at the 6th-position of the monosaccharide unit.
- Such polysaccharides include for example, starch-type polysaccharides such as alpha- 1,4 glucans, pullulan and other alpha- 1,3-glucans, cellulose-type polysaccharides including beta- 1,4-glucans, and other beta-glucans including chitin, fructans, galacto- and gluco- mannens including guar, and xylocans.
- the invention provides paper and paper products with improved properties conferred by the use of "cluster cationic polysaccharides” made from water-soluble cationic polysaccharide graft copolymers, comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more non-ionic monomer segments and one or more cationic monomer segments, are covalently attached.
- cluster cationic polysaccharides made from water-soluble cationic polysaccharide graft copolymers, comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more non-ionic monomer segments and one or more cationic monomer segments, are covalently attached.
- Another objective of the present invention is a process or method for manufacturing new and improved paper and paper products comprising the use of said cluster cationic polysaccharide additives.
- the invention also provides in one specific case, a process or method for manufacturing new and improved paper and paper products comprising the use of said cluster cationic starch additives.
- the invention provides new dry and wet strength additives, namely, said cluster cationic polysaccharide additives, or in a more specific case, cluster cationic starch additives, which allow for improved adsorption to the fibres used in paper production, especially during production in conditions of, for example, high conductivity as a consequence of reduced or completely closed water circulation.
- the invention relates to cluster cationic polysaccharides, namely, said water-soluble polysaccharide graft copolymers comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached, wherein (a) said polysaccharide is present in amounts from about 80 mole %, (b) said nonionic monomer is present in amounts from about 1 to 90 mole % of the block copolymer, (c) said cationic monomer is present in amounts from about 10 to 99 mole %, of the grafted portion of the copolymer additive.
- said polysaccharide is present in amounts from about 80 mole %
- said nonionic monomer is present in amounts from about 1 to 90 mole % of the block copolymer
- said cationic monomer is present in amounts from about 10 to 99 mole %, of the grafted portion of the
- the invention also provides in one specific case, cluster cationic starch, namely, water-soluble starch graft copolymers comprising a polymer backbone of starch, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached, wherein (a) said starch is present in amounts from about 80 mole %, (b) said nonionic monomer is present in amounts from about 1 to 90 mole % of the block copolymer, (c) said cationic monomer is present in amounts from about 10 to 99 mole %, of the grafted portion of the copolymer additive.
- cluster cationic starch namely, water-soluble starch graft copolymers comprising a polymer backbone of starch, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached, wherein (a) said starch is present in amounts from about 80 mole %, (
- the invention may be used as starch additives, after further derivatization with cellulose reactive groups, such as aldehyde and epoxide groups, which react with cellulose after being adsorbed and are used to improve wet strength.
- cellulose reactive groups such as aldehyde and epoxide groups
- Figure 1 shows that a significantly greater amount of cluster cationic starch is adsorbed, compared to standard cationic starch, at high conductivities.
- Figure 2 shows a schematic diagram of the Formett dynamic Sheetformer used.
- Figure 3 shows that the increase or improvement in burst strength is more sustained with increasing conductivity, for the paper modified with "cluster cationic starch”.
- Figure 4 shows that the increase in Z-strength is more sustained with increasing conductivity, for the paper modified with "cluster cationic starch".
- Figure 5 shows that both the leachable metal ion (concentration) from the paper and conductivity in white water are significantly higher without effluent water.
- Figure 6 shows that conductivity increases with reduced effluent water.
- cluster cationic starch refers to additives made from water-soluble cationic starch graft copolymers, comprising a polymer backbone of starch, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached.
- cluster cationic polysaccharide(s) refers to additives made from water-soluble cationic polysaccharide graft copolymers, comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached.
- cluster cationization refers to the process of grafting copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, onto a polymer backbone comprising at least one selected polysaccharide.
- the polysaccharide used is starch.
- random cationization refers to the process of randomly grafting individual cationic groups onto a polymer backbone comprising at least one selected polysaccharide, or in one specific case, a starch backbone.
- grafting refers to the process of covalently attaching a non-ionic, cationic or anionic copolymer by either (a) covalently attaching the copolymer by in-situ polymerization of a vinyl monomer or (b) covalently attaching a preformed copolymer to the starch or other suitable polysaccharide backbone.
- luster is intended in this application to mean a copolymer of a specific molecular weight range, attached or grafted on to a starch polymer backbone, comprising segments of cationic monomer segments, covalently bonded in linear fashion to nonionic monomer segments; each segment type possessing a specific average molecular weight range.
- copolymer additive(s) or "graft copolymer additive(s)” or “graft copolymer(s)” as used herein, all refer to the final graft-and-backbone structure of the copolymer as a whole, which is essentially the additive macromolecule.
- monomer segments may be interpreted to mean a polymer (if >1 monomer), or alternatively, the polymerized result of the relevant monomer molecule, possessing a specific molecular weight range.
- dry strength additive refers to an additive added during paper production, to increase or improve the final properties (for example, strength) of the paper.
- burst strength* refers to the resistance to an impact perpendicular to the plane as described by standard methods, DIN 53141, SCAN P24:99 and Tappi T807. (*The goals and details of these and other test methods for measuring strength properties of paper and paper products (with or without additives) are further discussed under the section "Detailed Description”.
- z-strength* refers to the strength measured in the thickness direction of the paper as described by standard methods, SCAN P80:98 and Tappi T541. (*The goals and details of these and other test methods for measuring strength properties of paper and paper products (with or without additives) are further discussed under the section “Detailed Description”.)
- fibres used in this application and to which the "cluster cationic starch” additive is intended to be used on, includes all fibres employed in the production of tissue and containerboard paper, including pulp fibres from chemical pulp, chemo-mechanical pulp and/or chemo-thermo mechanical pulp (CTMP) and recycled fibres.
- CMP chemo-thermo mechanical pulp
- tissue paper is intended to include all types of tissue paper, including the types described in the following paragraphs:
- Tissue paper emerging from the tissue machine as a single-ply paper sheet which may then be converted to the final tissue product in many different ways, for example, by being embossed, laminated to a multi-ply product, rolled or folded.
- Tissue paper comprising one or more layers. In the case of more than one layer, this layering is accomplished either in a multi-layered headbox, by forming a new layer on top of an already formed layer or by couching together already formed layers. These layers cannot, or only with considerable difficulty, be separated from each other and are joined mainly by hydrogen bonds.
- the different layers may be identical or may have different properties with respect to, for example, fibre composition and chemical composition. Physical properties which are important for tissue and towel paper includes softness, both bulk and surface softness and thickness (bulk).
- Laminated multi-ply tissue products comprise at least two tissue plies, which are often joined by either adhesive or mechanically.
- the adhesive may be applied all over the paper or just in regions, for example dots or lines, or only along the edges of the product.
- the mechanical methods of joining mainly include embossing; either over the entire area of the plies or only along the edges, termed "edge embossing". In the final product the plies are mostly easily detectable and can often be separated from each other as single plies.
- containerboard products refers to liner and fluting (corrugated medium) products with basis weights ranging from 70 to 440 g/m 2 produced from recycled fibre material, from chemo-thermo mechanical pulp (CTMP) or from chemical pulp (also combinations thereof).
- Containerboard is the raw material when producing corrugated board, the fluting (corrugated medium) being the wavy layer placed in between and separating two flat layers of papers, the liners. Some type of glue is also used to adhere the different layers.
- Multiple layer corrugated board is produced when additional corrugated medium and liner layer is added to the initial structure.
- Containerboard paper may as such comprise one or more layers.
- this layering is accomplished by forming a new layer on top of an already formed layer or by couching together already formed layers. These layers cannot, or only with considerable difficulty, be separated from each other and are joined mainly by hydrogen bonds.
- the different layers may be identical or may have different properties regarding, for example, fibre composition and chemical composition.
- White-top testliner is an example of a two layer structure with one brown/gray and one high brightness layer.
- Containerboard being the raw materials for producing corrugated board, can be pressed intensively to high sheet density to give high in-plane strength. Extended nip pressing is therefore widely spread within this sector.
- the paper is, when based on recovered paper, usually treated with native starch in a sizepress and then dried again to further improve strength properties.
- the size press has very important drawbacks since it is the production bottleneck on many containerboard machines and for the increase in energy consumption due to the fact that the paper has to be dried twice, before and after the size press, instead of just once. This is the reason why most mills struggle to use wet-end starch, which is particularly difficult in this type of machines, as the containerboard mills together with cardboard and some tissue mills have reached the highest degrees of water closure in the paper industry.
- Several mills in Europe are completely closed; for example, they are only introducing water to the process to make up for the steam loss during drying. Detailed description of the invention
- the invention relates to paper and paper products with new improved properties conferred by the use of additives made from water-soluble cationic polysaccharide graft copolymers, comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached.
- additives are referred to as "cluster cationic polysaccharides" in this application.
- the various paper and paper products to which this invention relates to include all types of tissue paper, as defined earlier.
- the various paper and paper products to which this invention also relates to include all types of containerboard products, both liner and corrugated medium (fluting) as defined earlier.
- a favoured polysaccharide used in the invention is starch. It was observed that by grafting cationic groups in a "cluster" onto the backbone of starch additives ("cluster cationization”) instead of randomly grafting individual cationic groups onto starch backbone (“random cationization”), the adsorption of said starch additives onto cellulose fibres is less affected by increases in conductivity or electrolyte concentration. The observed improved adsorption occurs at conditions of high conductivity, from about 3000 ⁇ S/cm, such as from about 4000 ⁇ S/cm, such as from about 5000 ⁇ S/cm.
- Cluster cationic starch additives were found to manifest improved adsorption to the fibres used in the manufacture of said paper and paper products, resulting in the latter possessing significantly improved end- properties. These end-properties have been found to be better than normally achieved with traditional cationic starch additives.
- in-plane and out-of-plane strength properties are important parameters for assessing the quality of containerboard.
- Paper is essentially a 2-dimensional material and in-plane strength refers to strength measurements in this plane while out-of-plane strength measurement refers to measurements perpendicular to this plane.
- Both in- and out-of-plane properties are measured in tensile and compression modes. The complexity of this assessment has led to the use and development of various related methods measure these properties. For example, in-plane compressive strength is measured using the Short span compression test, SCT (ISO 9895) or the Ring crush test, RCT (SCAN P-34).
- in-plane tensile strength involves measurement of various tensile properties (strength, stretch-at-break, energy absorption and stiffness, using standard methods such as ISO 1924 and SCAN P-67).
- the assessment of out-of- plane strength on paper involves measurement of burst strength (using, for example, standard methods such as ISO 2759 and SCAN P-24).
- burst strength using, for example, standard methods such as ISO 2759 and SCAN P-24.
- CMT corrugated medium test
- CCT corrugated crush test
- Out-of-plane tensile strength properties are measured on the paper using methods including Ply bond (TUM 403), Scott Bond (Tappi T-569), Z- strength (SCAN P-80), Z-directional toughness (SCAN P-90) and Pick resistance (Tappi T-459).
- cluster cationization is beneficial for enhancing adsorption of any cationic polymeric additive added to cellulose fibres at the high conductivities present as a consequence of reduced or completely closed water circulation systems, leading to improved paper and paper products made from these fibres.
- an increase/improvement in burst strength from about 0.1 to about 0.4 MN/kg, such as from about 0.2 to about 0.3 MN/kg was observed.
- An increase/improvement in the Z-strength from about 20 kN/m 2 , such as from about 40 kN/m 2 , and such as from about 60 kN/m 2 , was also observed.
- cluster cationic starch is used herein to describe a specific case of cluster cationic polysaccharides, namely, water-soluble cationic starch graft copolymers, comprising a polymer backbone of starch, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached.
- the starch used may be derivatized with other functional groups, for example aldehyde and epoxide groups, to improve the wet strength.
- the starch used may be selected from the group consisting of potato, corn, wheat and tapioca starch.
- starch polymer used as the backbone polymer is a granular alpha-(l-4) linked glucan, consisting of two components; amylose, which is linear with a Mw from 200,000 to 700,000 g/mole (See A.H. Young,
- amylopectin which is highly branched, possessing a Mw from 10 to 500 million (same reference above), depending on the starch source.
- the total amount of monomer units of the starch included in the copolymer additives range from about 80 to about 99 mole %, such as from about 95 to about 99 mole %, of the copolymer additive.
- the starch is present in amounts from about 0.2 to about 10 wt%, such as between from about 1 to about 5 wt%, such as from about 2 to about 4 wt% of the finished paper product.
- the starch used in the additives may also be replaced with other polysaccharides especially those containing a hydroxymethyl group, covalently attached at one or more of the positions of the monosaccharide unit; for example, at the 6th-position of the monosaccharide unit.
- polysaccharides include for example, starch-type polysaccharides such as alpha- 1,4 glucans, pullulan and other alpha-l,3-glucans, cellulose-type polysaccharides including beta-l,4-glucans, and other beta-glucans including chitin, fructans, galacto- and gluco-mannens including guar, and xylocans.
- the copolymer additive comprises a selected polysaccharide backbone on which copolymers comprising one or more cationic monomer segments and one or more non-ionic monomer segments are grafted.
- the grafted segments together form the "cluster", as referred to in “cluster cationic polysaccharides", or in one specific case, “cluster cationic starch".
- One section of this grafted copolymer (the segment comprising cationic polymer, originating from the cationic monomer) is positively charged, whereas the other section of the same grafted copolymer (i.e, the segment comprising nonionic polymer, originating from the nonionic or anionic monomer) is uncharged and /or negatively charged.
- cluster cationized starch highly charged regions interspersed between uncharged regions are now present on the starch molecules.
- the net charge on the additive is, however, positive (cationic).
- cluster cationization results in the grafting of cationic and non-ionic monomer segments in an ordered block or "cluster".
- the block copolymer is the grafted entity.
- the grafted portion of the copolymer additive possesses a weight average molecular weight range of from about 500 to about 20000 g/mol, such as from about 800 to 15000 g/mol, 1000 to 10000 g/mol.
- the amount of grafted portion in the additive range from about 1 to about 20 mole %, such as from about 3 to about 18 mole %, such as from about 5 to 15 mole %, of the total graft polymer additive.
- the grafted portion of the copolymer additive possesses a cationic charge density of from about 0.5 to about 10 milliequivalents/g; such as from about 1.5 to about 9 milliequivalents/g; such as from about 2.5 to about 7.5 milliequivalents/g.
- the copolymer additive itself possesses a lower cationic charge density of from about 0.05 to about 1 milliequivalents/g; such as from about 0.1 to about 0.8 milliequivalents/g; such as from about 0.15 to about 0.6 milliequivalents/g.
- the grafted portion of the copolymer additive comprises from about 5 to about 50 cationic monomer segments, each of average weight from about 160 to about 240 g/mole, and from about 1 to about 50 nonionic monomer segments, each of average molecular weight from about 50 to about 100 g/mole.
- the cationic monomer is selected from the group comprising methyl chloride tertiary or quartenary salts of dimethylaminoethyl methacrylate, and methyl chloride tertiary or quartenary salts of methyl diallyl amine and dimethyl sulfate tertiary or quartenary salts of dimethylaminoethyl methacrylate.
- reactants may include trimethyleaminoethyleacrylate, trimemyleaminomethyleacrylate, trimethyleaminopropylemethacrylamide, or 3- acrylamide-3-methylebutyletrimethyleammoniumchloride, plus mannich modified polyacrylamide (PAM).
- PAM mannich modified polyacrylamide
- the cationic monomer segment(s) within the grafted portion of the graft copolymer additive is present in amounts from about 10 to about 99 mole %, such as from about 20 to about 80 mole %, of the grafted portion.
- the nonionic monomer is a vinyl monomer, such as acrylamide.
- the total amount of nonionic monomer, such as acrylamide, included in the copolymer additive should generally be in the ranges typically from about 1 to about 90 mole %, such as from about 1 to about 18 mole %, such as from about 1 to about 17 mole %, such as from about 1 to about 15 mole %, of the grafted portion of the copolymer additive.
- an anionic monomer can also be incorporated, selected from the group comprising acrylic acids.
- the total amount of anionic monomer included in the copolymer additives range from about 0 to about 6 mole %, such as from about 0 to 4 mole %, such as from about 0 to about 2 mole %, of the grafted portion of the copolymer additive.
- modified cationic starches traditionally used in paper manufacturing have most often the cationic charges more or less randomly distributed on the polymer backbone.
- cluster cationic starch additives has the effect of increasing the local cationic charge density, i.e., present on the cationic parts of the grafted copolymer, without changing the average cationic charge in the starch.
- the invention also relates to a process or method for manufacturing new and improved paper and paper products possessing better end-product properties than normally achieved with standard cationic starches, comprising the use of said cluster cationic polysaccharide additives.
- the invention also provides a process or method for manufacturing new and improved paper and paper products at the high conductivities present as a consequence of reduced or completely closed water circulation conditions comprising the use of said cluster cationized starch additives.
- the invention relates to cluster cationic polysaccharides, namely, water-soluble polysaccharide graft copolymers comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, are covalently attached, wherein (a) said polysaccharide is present in amounts from about 80 mole % of the copolymer additive, (b) said nonionic monomer is present in amounts from about 1 to 90 mole % of the grafted portion of the copolymer additive, (c) said cationic monomer is present in amounts from about 10 to 99 mole % of the grafted portion of the copolymer additive.
- cluster cationic polysaccharides namely, water-soluble polysaccharide graft copolymers comprising a polymer backbone of at least one selected polysaccharide, on which copolymers comprising one or more nonionic monomer segments and
- the invention also provides cluster cationic starch, namely, water-soluble starch graft copolymers comprising a polymer backbone of starch, onto which block copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, have been grafted, wherein (a) said starch is present in amounts from about 80 mole % of the copolymer additive, (b) said nonionic monomer is present in amounts from about 1 to 90 mole % of the grafted portion of the copolymer additive, (c) said cationic monomer is present in amounts from about 10 to 99 mole % of the grafted portion of the copolymer additive.
- cluster cationic starch namely, water-soluble starch graft copolymers comprising a polymer backbone of starch, onto which block copolymers comprising one or more nonionic monomer segments and one or more cationic monomer segments, have been grafted
- said starch is present in amounts from about 80 mo
- the invention may be used as starch additives, after further derivatization with any cellulose reactive groups, including aldehyde and epoxide groups, which react with cellulose after being adsorbed and are used to improve wet strength.
- any cellulose reactive groups including aldehyde and epoxide groups, which react with cellulose after being adsorbed and are used to improve wet strength.
- TMAEMA metalacryloyloxy-ethyl
- TMAEMA trimethylammoniumchloride
- the standard cationic starch used for comparison was Pearlbond 903, obtained from Lyckeby Starkelsen, Sweden.
- the measured charge density was 0.15 ⁇ -equivalents/g for both the cluster cationic starches and for the reference starch.
- Figure 1 shows the adsorbed concentrations (mg/g) of cluster cationic starch and standard cationic starch vs. the measured starch charge (meq./g). It is clear from figure 1 that a significantly greater amount of cluster cationized starch is adsorbed to fibres, compared to standard cationic starch, at high conductivities.
- the electrolyte concentration, obtained with sodium chloride and measured as conductivity, used in this experiment was 5,6 mS/cm. (This conductivity value corresponds to a typical situation in a recycled fibre mill.
- the aim of this experiment was to show that paper produced using fibres modified with cluster cationic starch show greater burst strength than when using fibres modified with standard cationic starch, at conditions of high conductivity.
- Paper with a basis weight of 150 g/m 2 was produced with a Formette Dynamic sheetformer.
- the equipment which is schematically illustrated in Figure 2, comprises at least one furnish container (1) with a mixer, a pump (2), connected to the furnish container (1), a pressure compensation vessel (3), connected to the pump (2) and a rotating vertically standing drum (4).
- the drum (4) is a tubular wire (5) placed co-axially with the drum so that water can flow from the inner side of the wire (5) to the outer side.
- Within the drum there is also a nozzle (6) that moves up and down.
- the nozzle (6) is connected to pressure compensation vessel (3).
- the nozzle pressure is adjusted with pressurised air (7) that is added to the pressure compensation vessel (3).
- the circulation of the drum was started (1200 r/minute) and water was sprayed onto the brass wire so that a water film was evolved on the wire.
- the furnish pump was started and nozzle moves up and down and sprays the furnish onto the wire until the furnish container was empty.
- the sheet was dewatered on the rotating drum for about a minute until no more water was removed.
- the wire with the wet paper web was then taken out of the drum and placed on a blotting paper.
- the wire was removed and another blotting paper was placed on the other side of the wet paper web.
- the paper web and the blotting paper was then pressed in a cylinder press one time at 3 bars pressure.
- the paper was loosened from the blotting papers and clamped in a frame and dried in 15O 0 C for 10 minutes.
- the paper was subjected to 24 hours of conditioning at 23 0 C, 50 % relative humidity (RH) before testing; the paper properties were also tested in at the same conditions.
- Basis weight masses of a unit area of paper, expressed as grams per square meter (g/m 2 )
- thickness and density were measured and evaluated according to standard method SCAN-C 28:76. Burst strength was measured according to SCAN-P 24:77 (DIN 53141).
- the conductivity was measured by submerging a HANNA Instrument HI 8733 conductivity meter into the furnish container.
- Paper with a basis weight of 150 g/m 2 was produced with a Formette Dynamic sheetformer (see Figure 2).
- the equipment comprises at least one furnish container (1) with a mixer, a pump (2), connected to the furnish container (1), a pressure compensation vessel (3), connected to the pump (2) and a rotating vertically standing drum (4).
- the drum (4) is a tubular wire (5) placed co-axially with the drum so that water can flow from the inner side of the wire (5) to the outer side.
- Within the drum there is also a nozzle (6) that moves up and down.
- the nozzle (6) is connected to pressure compensation vessel (3).
- the nozzle pressure is adjusted with pressurised air (7) that is added to the pressure compensation vessel
- the fibres to be used were disintegrated at 80 °C for 4 minutes with a pilot desintegrator. A sufficient amount of fibres for the sheet to be produced was mixed with water in the furnish container until a fibre concentration of 5.0 g/1. The conductivity was adjusted to the desired value by adding a 50/50 weight % NaCl/CaCl 2 (powder). The pH was found to be with this treatment about 7.0 ⁇ 0.2 without adjustment. If there were any preferred paper additives they were thereafter added to the furnish.
- the paper was subjected to 24 hours of conditioning at 23 0 C 5 50 % relative humidity (RH) before testing; the paper properties were also tested at the same conditions.
- Grammage, thickness and density was measured and evaluated according to standard method SCAN-C 28:76.
- Z-strength (strength in the thickness direction of the paper) was evaluated according to SCAN-P 80:98.
- Conductivity was measured by submerging a HANNA Instrument HI 8733 Conductivity meter into the furnish container.
- the aim of this experiment was to display that the values of metal ion concentration measured in the water extract from paper produced at various paper mill locations reflect the ion concentration in the white water system.
- White water refers to paper-mill water clouded by suspended fibres and paper additives, typically draining from forming wires, thickeners, save- alls, or grinders.
- the various paper mills have different degrees of closure of the white water system.
- the mills in Argovia and Djursland have completely closed white water systems, resulting in no waste water being released to the effluent. Some water is, however, lost through evaporation and is subsequently replaced.
- the paper mills at De Hoop and Lucca have partly closed white water systems and emit about 5 kg water / kg of produced paper (note that 1 ton(ne) equals 1000 kg).
- Samples were taken from the paper mills and were prepared according to the method SS-EN 647. After filtration through a 0.45 ⁇ m Millipore filter, the metal content (including Al, B, Ba, Ca, Cu, Fe, K, Mg, Mn, Md, Na and Zn) was measured with an inductive plasma instrument according to ISO 11885. As can be observed in figure 4, paper mills with closed white water systems show a higher metal ion concentration in the extract from paper, compared to the paper mills with partly closed white water systems.
- Figure 5 shows the leachable metal ion concentration (mg/kg) and conductivity ( ⁇ S/cm) with and without effluent water. The figure indicates that both the leachable metal ion concentration and conductivity are significantly higher without effluent water.
- Figure 6 which shows the conductivity ( ⁇ S/cm) vs. effluent water (m 3 /T) in containerboard mills, substantiates this trend, since conductivity is shown to decrease with increasing volume of effluent water.
- the metal content extractable from a paper sample may be used as a measure of the metal content in the water containment area, i.e., where the paper originates from. These values may be used to characterize the paper product(s).
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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FR3012146A1 (fr) * | 2013-10-23 | 2015-04-24 | Ct Tech De L Ind Des Papiers Cartons Et Celluloses | Particules organiques, procede de preparation et utilisation dans la fabrication du papier |
US20170362345A1 (en) * | 2014-12-22 | 2017-12-21 | E I Du Pont De Nemours And Company | Polymeric blend containing poly alpha-1,3-glucan |
US10731297B2 (en) | 2015-10-26 | 2020-08-04 | Dupont Industrial Biosciences Usa, Llc | Water insoluble alpha-(1,3-glucan) composition |
US10738266B2 (en) | 2015-06-01 | 2020-08-11 | Dupont Industrial Biosciences Usa, Llc | Structured liquid compositions comprising colloidal dispersions of poly alpha-1,3-glucan |
US10895028B2 (en) | 2015-12-14 | 2021-01-19 | Dupont Industrial Biosciences Usa, Llc | Nonwoven glucan webs |
US11230812B2 (en) | 2015-10-26 | 2022-01-25 | Nutrition & Biosciences Usa 4, Inc | Polysaccharide coatings for paper |
US11351104B2 (en) | 2015-02-06 | 2022-06-07 | Nutrition & Biosciences USA 4, Inc. | Colloidal dispersions of poly alpha-1,3-glucan based polymers |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3012146A1 (fr) * | 2013-10-23 | 2015-04-24 | Ct Tech De L Ind Des Papiers Cartons Et Celluloses | Particules organiques, procede de preparation et utilisation dans la fabrication du papier |
US20170362345A1 (en) * | 2014-12-22 | 2017-12-21 | E I Du Pont De Nemours And Company | Polymeric blend containing poly alpha-1,3-glucan |
JP2018501396A (ja) * | 2014-12-22 | 2018-01-18 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | ポリアルファ−1,3−グルカンを含有するポリマーブレンド |
US10800859B2 (en) * | 2014-12-22 | 2020-10-13 | Dupont Industrial Biosciences Usa, Llc | Polymeric blend containing poly alpha-1,3-glucan |
US11351104B2 (en) | 2015-02-06 | 2022-06-07 | Nutrition & Biosciences USA 4, Inc. | Colloidal dispersions of poly alpha-1,3-glucan based polymers |
US11918676B2 (en) | 2015-02-06 | 2024-03-05 | Nutrition & Biosciences USA 4, Inc. | Colloidal dispersions of poly alpha-1,3-glucan based polymers |
US10738266B2 (en) | 2015-06-01 | 2020-08-11 | Dupont Industrial Biosciences Usa, Llc | Structured liquid compositions comprising colloidal dispersions of poly alpha-1,3-glucan |
US10731297B2 (en) | 2015-10-26 | 2020-08-04 | Dupont Industrial Biosciences Usa, Llc | Water insoluble alpha-(1,3-glucan) composition |
US11230812B2 (en) | 2015-10-26 | 2022-01-25 | Nutrition & Biosciences Usa 4, Inc | Polysaccharide coatings for paper |
US10895028B2 (en) | 2015-12-14 | 2021-01-19 | Dupont Industrial Biosciences Usa, Llc | Nonwoven glucan webs |
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