EP1042556B1 - Papierprodukte und verfahren zum auftragen von chemischen zusatzstoffen auf zellstofffasern - Google Patents

Papierprodukte und verfahren zum auftragen von chemischen zusatzstoffen auf zellstofffasern Download PDF

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Publication number
EP1042556B1
EP1042556B1 EP98964756A EP98964756A EP1042556B1 EP 1042556 B1 EP1042556 B1 EP 1042556B1 EP 98964756 A EP98964756 A EP 98964756A EP 98964756 A EP98964756 A EP 98964756A EP 1042556 B1 EP1042556 B1 EP 1042556B1
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EP
European Patent Office
Prior art keywords
chemical additive
fiber slurry
percent
fiber
slurry
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EP98964756A
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English (en)
French (fr)
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EP1042556A1 (de
Inventor
Mike Thomas Goulet
Jill A. Georger
Denise Alice Polderman
Maurice Alan Wyatt
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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Kimberly Clark Worldwide Inc
Kimberly Clark Corp
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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
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/04—Addition to the pulp; After-treatment of added substances in the pulp
    • 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
    • D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
    • 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
    • D21H21/14—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 function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D21H21/20—Wet strength agents
    • 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
    • D21H21/14—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 function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • 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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/30—Multi-ply
    • D21H27/38—Multi-ply at least one of the sheets having a fibrous composition differing from that of other sheets

Definitions

  • the present invention relates generally to paper products. More particularly, the invention concerns methods for applying chemical additives to cellulosic fibers and the paper products that can be obtained by the methods.
  • chemical additives are commonly added to fiber slurries in the wet end, before the fibers are formed into a web, dewatered and dried.
  • wet end additives are added to a fiber slurry that is between 0.5 and 5 percent consistency. The slurry may then be further diluted in the papermaking process before a final dilution oat the fan pump to the ultimate forming consistency.
  • wet end chemical addition has several advantages over topical spray, printing or size press chemical addition methods. For instance, wet end chemical addition provides a uniform distribution of chemical additives on the fiber surfaces. Additionally, wet end chemical addition allows a selected fiber fraction to be treated with a specific chemical additive in order to enhance the performance of the paper and/or the effectiveness of the chemical additive. Further, wet end chemical addition enables multiple chemistries to be added to a fiber slurry, either simultaneously or sequentially, prior to formation of the paper web.
  • EP 0226408 discloses a process in which a solve is applied to a formed web to increase the rate of water removal from the web.
  • US 4969976 discloses a method for making dry market pulp.
  • water soluble or water dispersible chemical additives are suspended in water and are not completely absorbed onto the cellulosic fibers.
  • chemical additives are often modified with functional groups to impart an electrical charge in water.
  • the electrokinetic attraction between charged additives and the anionically charged fiber surfaces aids the deposition and retention of chemical additives onto the fibers.
  • the amount of chemical additive that can be retained in the wet end generally follows an adsorption curve exhibiting diminishing effectiveness, similar to that described by Langmuir.
  • the adsorption of water soluble or water dispersible chemical additives may be significantly less than 100 percent, particularly when trying to achieve high chemical additive loading levels.
  • the present invention provides a method for applying chemical additives to cellulosic fibers in accordance with claim 1.
  • the invention provides a method for applying chemical additives to cellulosic fibers.
  • the method comprises the steps of: creating a fiber slurry comprising water, cellulosic fibers, and an adsorbable chemical additive; dewatering the fiber slurry to remove unadsorbed chemical additive; and redispersing the fibers with fresh water.
  • This method for processing cellulosic papermaking fibers enables chemical additives to be adsorbed by fibers while at the same time maintaining significantly lower levels of unadsorbed chemical additive in the water phase compared to traditional wet end chemical addition.
  • higher concentrations of the chemical additive on the fiber relative to the process water can be achieved as compared to what has been possible with prior methods.
  • the term “cellulosic” refers to papermaking fibers comprising an amorphous carbohydrate polymer, in contrast to synthetic fibers.
  • adsorbable is used herein to refer to a chemical additive that can be assimilated by the surface of a cellulosic fiber, in the absence of any chemical reaction involving the chemical additive and the cellulosic fiber.
  • unadsorbed refers to any portion of the chemical additive that is not adsorbed by the fiber and thus remains suspended in the process water.
  • fresh water is used herein to refer to water that is substantially free of the unadsorbed chemical additive. Most desirably, the fresh water is completely free of the chemical additive.
  • the fiber slurry is desirably dewatered to increase the consistency of the fiber slurry to about 20 percent or greater, and particularly to about 30 percent or greater, In order to remove the majority of the water containing the unadsorbed chemical additive.
  • the fibers are thereafter redispersed, desirably to decrease the consistency of the fiber slurry to a level suitable for papermaking, to about 20 percent or less, and more particularly to about 5 percent or less, such as about 3 to about 5 percent.
  • the present method allows for the production of fiber furnishes that are useful for making paper products, and particularly layered paper products.
  • the invention may provide a fiber furnish that has a higher chemical additive loading than could otherwise be achieved in combination with the relatively low level of unadsorbed chemical additive in the water. This is because chemical additive loading via traditional wet end addition is often limited by the level of unadsorbed chemical and its associated processing difficulties such as foam, deposits, chemical interactions, felt plugging, excessive dryer adhesion or release or a variety of paper physical property control issues caused by the presence of unadsorbed chemical in the water.
  • a fiber furnish of the present invention comprises water, cellulosic fibers, and an adsorbable chemical additive.
  • the amount of chemical additive adsorbed onto the fibers is about 2 kilograms per metric ton or greater, and the amount of unadsorbed chemical additive in the water is between 0 and about 20 percent of the amount of chemical additive adsorbed onto the fibers.
  • the amount of adsorbed chemical additive is about 3 kg/metric ton or greater, particularly about 4 kg/metric ton or greater, and more particularly about 5 kg/metric ton or greater.
  • the amount of unadsorbed chemical additive in the water is between 0 and about 15 percent, particularly between 0 and about 10 percent, and more particularly between 0 and about 7 percent, of the amount of adsorbed chemical additive.
  • Another aspect of the invention resides in a method for making chemically treated paper products.
  • the method comprises the steps of: creating a first fiber slurry comprising water, cellulosic fibers, and an adsorbable chemical additive; creating a second fiber slurry that is substantially free of the adsorbable chemical additive; dewatering the first fiber slurry to remove unadsorbed chemical additive; redispersing the fibers in the first fiber slurry with fresh water; and forming a paper product using a layered headbox, the first fiber slurry supplied to a first headbox layer and the second fiber slurry supplied to a second headbox layer.
  • a method for making a paper product comprises the steps of: creating a fiber slurry comprising water, cellulosic fibers and a first adsorbable chemical additive; dewatering the fiber slurry to a consistency of about 20 percent or greater; passing the dewatered fiber slurry through a disperser to mechanically work the fibers; diluting the fiber slurry with fresh water that is substantially free of the first chemical additive to a consistency of about 5 percent or less; adding a second adsorbable chemical additive comprising a debonding agent or a softening agent to the fiber slurry; dewatering the fiber slurry to a consistency of about 20 percent or greater; diluting the fiber slurry with fresh water that is substantially free of the second chemical additive to a consistency of about 5 percent or less; and forming a paper product from the fiber slurry.
  • the first chemical additive may comprise, for example, a bonding agent to decrease the amount of lint from the product.
  • the present invention is particularly useful for adding chemical additives such as softening agents and debonding agents to the outer layer furnishes in a three layer paper product.
  • the center layer is adapted to provide strength development and control.
  • the present invention allows the softening agents and debonding agents to be applied to the outer layers while minimizing contamination of the center strength layer.
  • paper products formed from fibers that have been chemically treated to minimize the amount of residual, unadsorbed chemical additives in the process water.
  • These paper products exhibit high chemical "purity" on the fiber fraction that has been treated using the present method and offer the ability to achieve excellent chemical layer purity when using a stratified headbox and/or the ability to achieve fiber specific chemical treatment in papers made from blends of two or more fiber types.
  • the term "paper” is used herein to broadly include writing, printing, wrapping, sanitary, and industrial papers, newsprint, linerboard, tissue, napkins, wipers, towels, or the like.
  • the chemical additives that can be used in conjunction with the present invention include: dry strength aids, wet strength aids, softening agents, debonding agents, absorbency aids, sizing agents, dyes, optical brighteners, chemical tracers, opacifiers, dryer adhesive chemicals, and the like.
  • Additional forms of chemical additives may include: pigments, emollients, humectants, viricides, bactericides, buffers, waxes, fluoropolymers, odor control materials and deodorants, zeolites, perfumes, debonders, vegetable and mineral oils, humectants, sizing agents, superabsorbents, surfactants, moisturizers, UV blockers, antibiotic agents, lotions, fungicides, preservatives, aloe-vera extract, vitamin E, or the like.
  • Suitable chemical additives are adsorbable by the cellulosic Papermaking fibers and are water soluble or water dispersible.
  • softening agent refers to any chemical additive that can be incorporated into paper products such as tissue to provide improved tactile feel. These chemicals can also act as debonding agents or can act solely to improve the surface characteristics of tissue, such as by educing the coefficient of friction between the tissue surface and the hand.
  • debonding agent refers to any chemical that can be incorporated into paper products such as tissue to prevent or disrupt interfiber or intrafiber hydrogen bonding. Depending on the nature of the chemical, debonding agents may also act as softening agents. In contrast, the term “bonding agent” refers to any chemical that can be incorporated into tissue to increase or enhance the level of interfiber or intrafiber bonding in the sheet. The increased bonding can be either ionic, Hydrogen or covalent in nature.
  • water soluble refers to solids or liquids that will form a solution in water
  • water dispersible refers to solids or liquids of colloidal size or larger that can be dispersed into an aqueous medium.
  • the method for applying chemical additives to papermaking fibers may be used in a wide variety of papermaking operations, including wet pressing and creped or uncreped throughdrying operations.
  • various tissue making processes are disclosed in U.S. Patent 5,667,636 issued September 16, 1997 to S. A. Engel et al.; and U.S. Patent 5,607,551 issued March 4, 1997 to T. E. Farrington, Jr. et al.
  • the method may also be used in alternative processes, including: chemically pretreating pulp in a pulp mill before a dry lap machine or crumb baler; adding chemical additives in sequence to reduce interactions; removing chemical additives from a fiber slurry (neutralizing anionic components, sizing or softening formulations) after a chemical additive has been added to facilitate the removal process; or the like.
  • Fiber types may be used for the present invention including hardwood or softwoods, straw, flax, milkweed seed floss fibers, abaca, hemp, kenaf, bagasse, cotton, reed, and the like.
  • All known papermaking fibers may be used, including bleached and unbleached fibers, fibers of natural origin (including wood fiber and other cellulosic fibers, cellulose derivatives, and chemically stiffened or crosslinked fibers), some component portion of synthetic fibers (synthetic papermaking fibers include certain forms of fibers made from polypropylene, acrylic, aramids, acetates, and the like), virgin and recovered or recycled fibers, hardwood and softwood, and fibers that have been mechanically pulped (e.g., groundwood), chemically pulped (including but not limited to the kraft and sulfite pulping processes), thermomechanically pulped, chemithermomechanically pulped, and the like.
  • mechanically pulped e.g., groundwood
  • the fibers can be prepared in a multiplicity of ways known to be advantageous in the art. Useful methods of preparing fibers include dispersion to impart curl and improved drying properties, such as disclosed in U.S. Patents 5,348,620 issued September 20, 1994 and 5,501,768 issued March 26, 1996, both to M. A. Hermans et al. and U.S. Patent 5,656,132 issued August 12, 1997 to Farrington, Jr. et al.
  • a single headbox or a plurality of headboxes may be used.
  • the headbox or headboxes may be stratified to permit production of a multilayered structure from a single headbox jet in the formation of a web.
  • the web is produced with a stratified or layered headbox to preferentially deposit shorter fibers on one side of the web for improved softness, with relatively longer fibers on the other side of the web or in an interior layer of a web having three or more layers.
  • the web is desirably formed on an endless loop of foraminous forming fabric which permits drainage of the liquid and partial dewatering of the web.
  • Multiple embryonic webs from multiple headboxes may be couched or mechanically or chemically joined in the moist state to create a single web having multiple layers.
  • FIG. 1 depicts stock preparation equipment used to apply chemical additives to papermaking fibers according to one embodiment of the present invention.
  • the stock preparation equipment comprises a first stock chest 10, a second stock chest 12, and a dewatering device 14 operably disposed between the stock chests. Papermaking fibers and water are added to the first stock chest 10 to form a fiber slurry 20.
  • the fiber slurry in the first stock chest desirably has a consistency of about 20 percent or lower, and particularly about 5 percent or lower, such as about 3 to about 5 percent.
  • the fiber slurry in the first stock chest is desirably under agitation using a mixing blade, rotor, recirculation pump, or other suitable device 18 for mixing the fiber slurry.
  • One or more chemical additives 24 are supplied from a reservoir 26 and added to the fiber slurry 20 in the first stock chest 10.
  • the amount of chemical additive 24 is suitably about 5 to about 20 kg./metric ton.
  • the chemical additive comprises an imidazoline-based debonding agent and is added in an amount from about 7.5 to about 15 kg./metric ton.
  • the fiber slurry and chemical additive are desirably allowed to remain together in the first stock chest under agitation for a residence time sufficient to allow the papermaking fibers to adsorb a substantial portion of the chemical additive 24.
  • a residence time of about 15 to about 30 minutes, for instance, may be sufficient.
  • the fiber slurry 20 is thereafter transferred through suitable conduits 27 and a pump 28 to the dewatering device 14.
  • the dewatering device comprises a belt press 14, although alternative dewatering devices such as a centrifuge, a nip thickening device or the like may be used.
  • the fiber slurry is injected between a pair of foraminous fabrics 30 such that press filtrate 32 is removed from the slurry.
  • the press filtrate 32 comprises a portion of the process water along with unadsorbed chemical additives 24 in the water.
  • the belt press 14 or other dewatering device suitably increases the fiber consistency of the slurry to about 20 percent or greater, and particularly about 30 percent or greater.
  • the unadsorbed chemical additive can be removed from the process or used as dilution water in prior stock preparation steps, but importantly it is not sent forward with the chemically treated furnish.
  • the thickened fiber slurry 20 is then transported through conduits 34 to the second stock chest 12.
  • the fiber slurry is then re-diluted with fresh water 35 from a suitable reservoir 36 and optionally agitated using a mixing device 18.
  • the fiber consistency of the slurry is suitably decreased to about 20 percent or less, and particularly about 5 percent or less, such as about 3 to about 5 percent.
  • the fiber slurry may then be removed from the second stock chest through suitable conduits 37 and a pump 38 for subsequent processing 39. Alternatively, the fiber slurry may be processed through the foregoing procedure again in an effort to further increase the chemical additive retention level.
  • Figure 2 depicts an alternative embodiment of the present invention in which stock preparation equipment is used to apply chemical additives to papermaking fibers and to mechanically treat the fibers.
  • the equipment comprises three stock chests 10, 12 and 40, two dewatering devices 14 and 42, two dilution water chests 44 and 46, and a disperser 48 for mechanically treating the papermaking fibers.
  • Papermaking fibers and water are added to the first stock chest 10 to form a fiber slurry 20.
  • the fiber slurry in the first stock chest desirably has a consistency of about 20 percent or lower, and particularly about 5 percent or lower.
  • One or more chemical additives 24 are supplied from a reservoir 26 and added to the fiber slurry 20 in the first stock chest 10 while under agitation 18.
  • the first chemical additive added to the fiber slurry is desirably a cationic bonding agent which is used to control lint in the finished product.
  • the first chemical additive is desirably not a softening agent or debonding agent that would reduce the efficiency of the disperser.
  • the fiber slurry is transferred through suitable conduits 27 and a pump 28 to a belt press 14 or other suitable dewatering device. Unadsorbed chemical additives in the water are removed with the press filtrate 32 during the pressing operation and stored in the first dilution water chest 44. The contents of the first dilution water chest may be used as either pulper make-up water or dilution water or may be discarded.
  • the dewatering device 14 suitably increases the fiber consistency of the slurry to about 20 percent or greater, and particularly about 30 percent or greater.
  • the thickened fiber slurry 20 is then transported through suitable conduits 34 to the disperser 48 for mechanical treatment of the fibers.
  • Dispersers suitable for use in the present method are disclosed in U.S. Patents 5,348,620 issued September 20, 1994 and 5,501,768 issued March 26, 1996, both to M. A. Hermans et al.
  • the fiber slurry is transported via conduits 50 to the second stock chest 12.
  • a second chemical additive or second group of chemical additives 52 are supplied from a reservoir 53 and added to the fiber slurry 20 in the second stock chest 12 while under agitation 18.
  • the fiber slurry may optionally be diluted with filtrate 56 from a source described hereinafter.
  • the fiber consistency of the slurry is suitably decreased to about 20 percent or lower, and particularly about 5 percent or lower, such as about 3 to about 5 percent.
  • the second chemical additive 52 comprises a softening agent and/or a debonding agent, and the fiber slurry is not subjected to high shear refining forces such as those generated in a disperser once the softening and/or debonding agent is added to the fiber slurry.
  • the fiber slurry 20 is transferred from the second stock chest 12 through suitable conduits 58 and a pump 59 to the second dewatering device 42. Unadsorbed portions of the second chemical additive 52 in the water are removed with the press filtrate 56 during the pressing operation and stored in the second dilution water chest 46. The contents of the second dilution water chest may be added to the second stock chest 12 as described above or may be discarded.
  • the second dewatering device 42 suitably increases the fiber consistency of the slurry to about 20 percent or greater, and particularly about 30 percent or greater.
  • the thickened fiber slurry 20 is then transported through conduits 58 to the third stock chest 40.
  • the fiber slurry is then re-diluted with fresh water 35 from a suitable reservoir 36 and optionally agitated using a mixing device 18.
  • the fiber consistency of the slurry is suitably decreased to about 20 percent or lower, and particularly about 5 percent or lower, such as about 3 to about 5 percent.
  • the fiber slurry may then be removed from the third stock chest through suitable conduits 37 and a pump 38 for subsequent processing 39. Alternatively, the fiber slurry may be returned to the second stock chest 12 for repeated application of the second chemical additive 52.
  • One suitable process 39 for making paper products from the fiber slurries 20 of Figures 1 or 2 is the uncreped throughdrying method depicted in Figure 3 .
  • the uncreped throughdrying method is also disclosed in U.S. Patent 5,656,132 issued August 12, 1997 to Farrington, Jr. et al.
  • a twin wire former having a layered papermaking headbox 60 injects or deposits a stream from the fiber slurry 20 onto the forming fabric 62 to form a cellulosic web 64.
  • the web is then transferred to fabric 66, which serves to support and carry the newly-formed wet web downstream in the process as the web is partially dewatered to a consistency of about 10 dry weight percent. Additional dewatering of the wet web can be carried out, such as by vacuum suction, while the wet web is supported by the forming fabric.
  • the wet web is then transferred from the forming fabric 66 to a transfer fabric 70 traveling at a slower speed than the forming fabric in order to impart increased MD stretch into the web.
  • a kiss transfer is carried out to avoid compression of the wet web, preferably with the assistance of a vacuum shoe 72.
  • the transfer fabric can be a fabric having impression knuckles or it can be a smoother fabric such as Asten 934, 937, 939, 959 or Albany 94M. If the transfer fabric is of the impression knuckle type described herein, it can be utilized to impart some of the same properties as the throughdrying fabric and can enhance the effect when coupled with a throughdrying fabric also having the impression knuckles. When a transfer fabric having impression knuckles is used to achieve the desired CD stretch properties, it provides the flexibility to optionally use a different throughdrying fabric, such as one that has a decorative weave pattern, to provide additional desirable properties not otherwise attainable.
  • the web is then transferred from the transfer fabric to a throughdrying fabric 74 with the aid of a vacuum transfer roll 76 or a vacuum transfer shoe.
  • the throughdrying fabric can be traveling at about the same speed or a different speed relative to the transfer fabric. If desired, the throughdrying fabric can be run at a slower speed to further enhance MD stretch. Transfer is preferably carried out with vacuum assistance to ensure deformation of the sheet to conform to the throughdrying fabric, thus yielding desired bulk, flexibility, CD stretch and appearance.
  • the throughdrying fabric is preferably of the impression knuckle type.
  • the level of vacuum used for the web transfers can be from about 3 to about 15 inches (about 75 to about 380 millimeters) of mercury, preferably about 10 to about 15 inches (about 254 to about 380 millimeters) of mercury.
  • the vacuum shoe (negative pressure) can be supplemented or replaced by the use of positive pressure from the opposite side of the web to blow the web onto the next fabric in addition to or as a replacement for sucking it onto the next fabric with vacuum.
  • a vacuum roll or rolls can be used to replace the vacuum shoe(s).
  • the web While supported by the throughdrying fabric, the web is final dried to a consistency of about 94 percent or greater by the throughdryer 80 and thereafter transferred to a carrier fabric 82.
  • the dried basesheet is transported to the reel 84 using carrier fabric 82 and an optional carrier fabric 86.
  • An optional pressurized turning roll 88 can be used to facilitate transfer of the web from carrier fabric 82 to fabric 86.
  • Suitable carrier fabrics for this purpose are Albany International 84M or 94M and Asten 959 or 937, all of which are relatively smooth fabrics having a fine pattern.
  • the roll of tissue may then be calendered, slit, surface treated with emollient or softening agents, embossed, or the like in subsequent operations to produce the final product form.
  • a softening/debonding agent was added during production of a multi-fiber, three-layer tissue using a conventional, stuffbox chemical addition method.
  • the furnish used for the outer two layers comprised 70% Eucalyptus fibers, 29% tissue broke and 1% recycled fiber corestock.
  • the outer layer furnish components were blended at the pulper. After repulping, the furnish was transferred to a chest and treated with a bonding agent, Parez 631 NC which is commercially available from Cytec Industries, Inc., at a dosage of 1 kg./metric ton. After allowing the slurry to mix for 20 minutes, the furnish was thickened to greater than 30% consistency using a dewatering press and treated in a disperser to impart curl to the fibers.
  • the disperser was operated with a power input of 80 kilowatts and an exit stock temperature of about 82.2°C (180°F). After dispersing, the fibers were stored in a high density chest until needed during tissue manufacturing.
  • the outer layer furnish consisting of the dispersed Eucalyptus/broke/corestock blend, was diluted to 3.5% consistency in a chest using the filtrate from the earlier thickness process.
  • the center layer furnish comprised 100% northern bleached softwood kraft fibers. This furnish was refined at an energy input of 2 horsepower days a /metric ton for dry strength development. Parez 631 NC was also added to this furnish at a dosage of 5.8 kg./metric ton to achieve wet tensile strength control. Dry strength control was achieved by varying the ratio of center layer to outer layer furnish. a 1 horsepower day - 64 MJ
  • a one-ply, uncreped through air dried tissue was produced using a pilot tissue machine. This same tissue machine was used for Examples 1-4.
  • the machine contains a 3 layer headbox, of which the outer layers contain the same furnish (70% Eucalyptus, 29% broke, 1% corestock) and the center layer was 100% softwood fiber.
  • the resulting three-layered sheet structure was formed on a twin-wire, suction form roll, former.
  • the speed of the forming fabrics was 1143 cm per sec. (2250 feet per minute) (fpm).
  • the newly-formed web was then dewatered to a consistency of about 20-27 percent using vacuum suction from below the forming fabric before being transferred to the transfer fabric, which was travelling (914 cm/sec (1800 feet per minute) (25% rush transfer).
  • a vacuum shoe pulling about 25.4 cm (10 inches) of mercury vacuum was used to transfer the web to the transfer fabric.
  • the web was then transferred to a throughdrying fabric travelling at a speed of about 914 cm/sec (1800 fpm).
  • the web was carried over a pair of Honeycomb throughdryers operating a temperatures of about 163°C (325°F) and dried to final dryness of about 94-98 percent consistency.
  • the air dry basis weight of the sheet was 27.5 gsm.
  • the final fiber ratio in the sheet was 32% softwood fiber (in center layer) and 68% Eucalyptus/broke/corestock blend (outer layers).
  • the final strength of the tissue was 800 grams per 7.62 cm (3 inch) width (geometric mean tensile strength).
  • the improved chemical addition method shown in Figure 1 was used to treat a furnish with a softening/debonding agent.
  • the treated furnish was then used as the outer layer furnish in a multi-fiber, three-layered tissue structure. Because the improved chemical addition method removes most non-retained softening/debonding agent from the water phase during tissue forming, the resultant product can be produced at equivalent tensile strength, higher softener/debonder content and a lower softwood fiber content than a tissue made with the identical softening agent using the conventional chemical addition method described in Example 1.
  • Example 2 the furnish used for the outer two layers comprised 70% Eucalyptus fibers, 29% tissue broke and 1% recycled fiber corestock.
  • the outer layer furnish was blended during repulping and placed in a stock chest at 3.5% consistency.
  • the furnish was then treated with a bonding agent, Parez 631 NC from Cytec Industries, Inc., at a dosage of 1 kg./metric ton.
  • a softening/debonding agent, C-6092 from Witco Corp. was added at a dosage of 7.5 kg. of active chemical/metric ton of fiber.
  • the slurry was dewatered using a belt press to approximately 32% consistency.
  • the filtrate from the dewatering process was used as pulper make-up water for subsequent batches but not sent forward in the stock preparation or tissuemaking process.
  • the thickened pulp was then passed through a disperser with a power input of 80 kilowatts and a stock temperature of about 82.2°C (180°F) to impart curl to the fibers. After the dispersing operation, the stock was placed in a high density storage chest until needed during tissue manufacturing.
  • a one-ply, uncreped, through air dried tissue was made using a three layered headbox, as described in Example 1.
  • the furnish for the outer two layers comprised the chemically treated 32% consistency Eucalyptus/broke/corestock furnish blend, which had been re-diluted to 3% consistency with fresh water in a chest under agitation.
  • the center layer consisted of 100% softwood fibers refined at an energy input of 2 horsepower days/metric ton, to whcih 5.8 kg./metric ton of Parez 631 NC was added for wet strength control. Finished product dry strength control was achieved by adjusting the ratio of center layer and outer layer furnish in the sheet.
  • the air dry basis weight of the sheet was 27.5 gsm.
  • the final fiber ratio in the sheet was 17% softwood fiber (in center layer) and 83% Eucalyptus/broke/corestock blend (outer layers).
  • the final strength of the tissue was 802 grams per 7.62 cm (3 inch) width (geometric mean tensile strength).
  • the improved chemical addition method shown in Figure 2 was used to first treat a furnish with a bonding agent, mechanically modify the fibers using a disperser, and then treat the furnish with a softening/debonding agent.
  • the chemically treated furnish was used as one furnish in a multi-fiber, three-layered tissue structure. Because the improved chemical addition method removes most non-retained softening/debonding agent from the water phase during tissue forming, the resultant product was much stronger (at equal fiber composition) than a tissue made with similar softening agent using the conventional chemical addition method described in Example 1.
  • the softener/debonder is not present on the furnish during the dispersing operation, there is a more efficient transfer of energy to the fibers. This results in a higher level of debonding than demonstrated in Example 2 due to the fiber curl properties imparted during dispersing.
  • Example 3 the furnish used for the outer two layers comprised 70% Eucalyptus fibers, 29% tissue broke and 1% recycled fiber corestock.
  • the outer layer furnish was blended during repulping and placed in a stock chest at 3.5% consistency.
  • the furnish was then treated with a bonding agent, Parez 631 NC from Cytec Industries, Inc., at a dosage of 1 kg./metric ton.
  • the furnish was dewatered using a belt thickening press to greater than 30% consistency.
  • the thickened pulp was then passed through a disperser with a power input of 80 kilowatts and a stock temperature of about 82.2°C (180°F) to impart curl to the fibers.
  • the high consistency pulp was then diluted to 3.5% consistency with a combination of fresh water and thickener filtrate (containing unadsorbed softening/debonding agent, as shown in Figure 2 ).
  • the furnish was next treated with 7.5 kg./metric ton of a softening/debonding agent, C-6092 from Witco Corp., and allowed to mix for 20 minutes.
  • the furnish was then dewatered using a belt press to approximately 32% consistency.
  • the filtrate from the dewatering process was used as partial dilution water for the high consistency stock dilution step, as previously mentioned.
  • the stock was placed in a high density storage chest until needed during tissue manufacturing.
  • a one-ply, uncreped, through air dried tissue was made using a three layered headbox, as described in Example 1.
  • the furnish for the outer two layers comprised the chemically treated 32% consistency Eucalyptus/broke/corestock furnish blend, which had been re-diluted to 3% consistency with fresh water in a chest under agitation.
  • the center layer comprised 100% softwood fibers refined at an energy input of 2 horsepower b days/metric ton, to which 5.8 kg./metric ton of Parez 631 NC was added for wet strength control. Finished product dry strength control was achieved by adjusting the ratio of center layer and outer layer furnish in the sheet.
  • the air dry basis weight of the sheet was 27.5 gsm.
  • the final fiber ratio in the sheet was 24% softwood fiber (in center layer) and 76% Eucalytpus/broke/corestock blend (outer layers).
  • the final strength of the tissue was 806 grams per 7.62 cm (3 inch) width (geometric mean tensile strength).
  • Example 3 This example is similar to Example 3, except that 15 kg./metric ton of C-6092 softener/debonder was added to the outer layer furnish (instead of 7.5 kg./metric tone in Example 3). Because the improved chemical addition method has removed most non-retained softening/debonding agent from the water phase during tissue formation, the resultant product contains 55% more softening/debonding agent than the product described in Example 1, at equivalent tensile strength and fiber composition.
  • the stock preparation and tissue manufacturing procedures were identical to Example 3.
  • the air dry basis weight of the sheet was 27.5 gsm.
  • the final fiber ratio in the sheet was 31% softwood fiber (in center layer) and 60% Eucalyptus/broke/corestock blend (outer layers).
  • the final strength of the tissue was 795 grams per 7.62 cm (3 inch) width (geometric mean tensile strength).
  • a layered tissue sheet can be made with a geometric mean tensile strength of about 800 grams per 7.62 cm (3 inch) width (795 grams per 3 inch width), under the processing conditions described in Exmaple 5, that contains 31% softwood fiber and 5.9 kg./metric ton of retained C-6092 softener/debonder by using the improved chemical addition method.
  • a layered tissue sheet with a geometric mean tensile strength of 800 g./7.62 cm/(3") width contains 32% softwood fiber but only 3.8 kg./metric ton of retained C-6092 softener/debonder.
  • tissue fiber/chemistry combinations can be produced at target strength levels that could not otherwise be made using conventional chemical addition methods.
  • the tissues were manufactured with generally constant basis weight and strength by adjusting the relative amounts of softwood and hardwood. Of course, various alternatives are possible such as maintaining generally constant strength and softwood/hardwood proportion and adjusting the basis weight.
  • TABLE 1 Examples 1 - 4 Example Strength g./7.62 cm (3") % Center Layer % Outer Layer Debonder Add-on Debonder Retained 1 800 32 68 4.4 3.8 2 802 17 83 6.2 4.6 3 806 24 76 5.7 3.8 4 795 31 69 10.4 5.9
  • the % Center Layer and % Outer Layer refer to the weight percent of fibers in the appropriate layers.
  • the Debonder Add-on reflects the chemical additive that is added to the furnish in kg./metric ton of the entire sheet. This is calculated based on the add-on level to the outer layer furnish and the amount of the outer layer furnish in the final sheet.
  • the Debonder Retained reflects the amount of chemical additive adsorbed onto the tissue.
  • the Debonder Retained can be determined using the following procedure suitable for imidazoline-based chemical additives such as Witco C-6092 that are added to the tissue.
  • the procedure references the percent add-on, which has been converted to kg./metric ton (multiplied by 10) in Table 1.
  • a sample of the tissue is weighed and extracted in a sealed container for a given amount time on a flatbed shaker at ambient conditions. After the extraction, the tissue is removed and the extract allowed to settle. The extract is then analyzed by ultraviolet spectrometer. After the percent extracted is calculated, the add-on percent can be determined by reference to an add-on correlation curve that is generated as described below.
  • the following equipment and chemicals are used: pipets, 1, 3, 5, 10 and 100 mL; volumetric flasks, 100 and 1000 mL; sealed containers, e.g. specimen cups; a flatbed shaker, such as an orbital flatbed shaker (Lab Line Orbital Shaker Model No. 3590, Lab Line Instruments, Inc.); an ultraviolet spectrometer (Hewlett Packard Model 8451A Diode Array Spectrophotometer, Hewlett Packard); methanol, reagent grade; imidazoline, standard such as Witco C-6092; beakers, 30 mL; and control tissues that differ from the tissue being tested only by the absence of the chemical additive being tested.
  • a flatbed shaker such as an orbital flatbed shaker (Lab Line Orbital Shaker Model No. 3590, Lab Line Instruments, Inc.); an ultraviolet spectrometer (Hewlett Packard Model 8451A Diode Array Spectrophotometer, Hewlett Packard); m
  • a stock standard imidazoline solution (1000 ppm active) is prepared: Weigh 0.1250 grams of C-6092 (80% active) into a 30mL beaker; transfer quantitatively to a 100mL flask with methanol; and dilute to mark with methanol and invert several times.
  • Standard imidazoline solutions (10, 30, 50, 100 ppm) are prepared: Into four 100 mL volumetric flasks, add 1, 3, 5, and 10 mL of the 1000 ppm stock standard imidazoline solution; and dilute to marks with methanol. The standards are 10, 30, 50 and 100 ppm, respectively.
  • Spiking solutions 1000 and 5000ppm are prepared: Weigh out 1.250 and 6.250 grams of C-6092 into 50 ml beakers; transfer quantitatively to a 1000 ml flask with distilled water; shake well and allow to dissolve before diluting to mark. If excessive foaming occurs, fill to the stem of the flask and add a small amount of methanol to eliminate the foam and dilute to mark then invert several times. This makes a 1000 ppm and 5000 ppm spiking solutions.
  • a minimum of three replicates should be performed for each level of add-on and for blanks. There should be at least four levels of add-on to generate a curve. Spiking solutions should be made with distilled water, so that the spiked sample can be dried in a 60 degree Celsius oven.
  • Sample Analysis Weigh out 5.00 grams sample in a specimen container and add 100 mL of methanol. Place on the flatbed shaker and extract for 1 ⁇ 2 hour. Remove the tissue and allow to settle. Read the extracts at 238nm wavelength and subtract the mean blank absorptance reading. Calculate the ppm from the standard curve and then calculate the percent extracted value. Using the Add-on correlation curve, calculate the percent add-on with the percent extracted value.
  • Imidazoline has a peak absorptance at 238nm wavelength. While blank tissue extracts do not have this peak absorptance at 238nm, it does have some absorptance that interferes with the quantitation. Blanks are quite reproducible and can be subtracted for the determination. It is important that the weight of the sample, volume of methanol, and the extraction time be kept constant. An add-on correlation curve should be generated for different tissue samples, because various chemicals used in the tissue process can affect the binding of the imidazoline thus affecting the recovery. Percent add-on also affects the percent recovery; using various levels of add-on in constructing the correlation curve helps to determine the add-on value.
  • a laboratory scale experiment was conducted. The objective of this experiment was to demonstrate how much unadsorbed chemical is present in systems that do not use the improved addition method and compare this to systems in which the same amount of chemical is added using the improved method.
  • the furnish used in this experiment was 100% Eucalyptus fibers.
  • the chemical additive used was C-6092, a softener/debonder commercially available from Witco Corp. The addition levels were 0.5% and 1.0% active debonder on dry fiber.
  • adsorbable chemical additive is added to a slurry of water and cellulosic fibers in an amount of 5 kilograms per metric ton or greater.
  • the remaining 1200 grams of slurry were filtered using a Whatman 4 filter paper and Buchner funnel apparatus. This filtration step simulates the dewatering step of the improved chemical addition method shown in Figure 1 .
  • the filter pad (at approximately 25% consistency) was split into two sections of approximately equal mass. One section was placed in the hood to dry at room temperature. This sample will be referred to as 2A.
  • the other half of the filter pad (approximately 600 g.) was redispersed to 2.5% consistency using distilled water.
  • the slurry was mechanically agitated for 15 minutes and then filtered using a Whatman 4 filter paper and Buchner funnel apparatus. This filtration step simulates the dewatering that occurs in the forming and vacuum dewatering zones of a tissue machine.
  • the filter pad was placed in a hood to dry at room temperature. This sample will be referred to as 3A.
  • Steps 1 - 3 were repeated using a 1.0% addition level of C-6092.
  • the corresponding samples were coded 1B, 2B and 3B.

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Claims (22)

  1. Ein Verfahren, welches umfasst:
    Erzeugen eines Faserbreis (20), welcher Wasser, zellulosische Fasern und ein adsorbierbares chemisches Additiv umfasst;
    dadurch gekennzeichnet, dass das adsorbierbare chemische Additiv zu dem Brei aus Wasser und zellulosischen Fasern in einer Menge von ungefähr 5 Kilogramm pro metrischer Tonne oder mehr zugegeben wird, und dass das Verfahren des Weiteren die Schritte umfasst:
    Entwässern des Faserbreis, um nicht-adsorbiertes chemisches Additiv (24) zu entfernen und einen verdickten faserigen Brei bereitzustellen; und
    Verdünnen des verdickten faserigen Breis mit Frischwasser (35).
  2. Das Verfahren gemäß Anspruch 1, wobei das Erzeugen des Faserbreis das Hinzugeben des adsorbierbaren chemischen Additivs zu einer wässrigen Lösung umfasst, welche das Wasser und zellulosische Fasern umfasst.
  3. Das Verfahren gemäß Anspruch 1 oder 2, wobei der Faserbrei eine Konsistenz von 20 Prozent oder weniger aufweist, und vorzugsweise 5 Prozent oder weniger.
  4. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei der Schritt des Entwässerns die Konsistenz des Faserbreis bis ungefähr 30 Prozent oder mehr erhöht.
  5. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei der Schritt des Verdünnens des verdickten faserigen Breis die Konsistenz des verdickten Faserbreis bis ungefähr 5 Prozent oder geringer erniedrigt.
  6. Das Verfahren gemäß einem der vorherigen Ansprüche, welches des Weiteren das Aufbewahren des entfernten unadsorbierten chemischen Additivs getrennt von dem Faserbrei umfasst.
  7. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei das Frischwasser gänzlich frei von unadsorbiertem chemischem Additiv ist.
  8. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei genügend Einwirkzeit zur Adsorption gewährt wird nachdem das chemische Additiv hinzugegeben wurde.
  9. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei das entfernte unadsorbierte chemische Additiv in einem Verfahrensschritt vor dem Entwässern des Faserbreis wiederverwendet wird.
  10. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei das adsorbierbare chemische Additiv ein Debonding-Mittel umfasst.
  11. Das Verfahren gemäß einem der Ansprüche 1 bis 9, wobei das adsorbierbare chemische Additiv einen Weichmacher umfasst.
  12. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei das chemische Additiv ein Debonding-Mittel oder einen Weichmacher umfasst und wobei der Faserbrei nicht hohen Refiner-Scherkräften ausgesetzt ist sobald das chemische Additiv zum Faserbrei hinzugegeben wurde.
  13. Das Verfahren gemäß einem der vorherigen Ansprüche, wobei der verdünnte Faserbrei mit einem zweiten adsorbierbaren chemischen Additiv behandelt wird, ein zweites Mal entwässert wird, um unadsorbierte chemische Additive zu entfernen, und ein zweites Mal verdünnt wird.
  14. Das Verfahren gemäß Anspruch 13, wobei das zweite chemische Additiv einen Weichmacher umfasst.
  15. Das Verfahren gemäß Anspruch 13, wobei das zweite chemische Additiv ein Debonding-Mittel umfasst.
  16. Das Verfahren gemäß einem der vorherigen Ansprüche, welches des Weiteren das Bilden eines Papierprodukts umfasst, welches eine Vielzahl an Schichten umfasst, wobei eine aber nicht alle der Schichten aus dem Faserbrei gebildet sind, der das adsorbierbare chemische Additiv enthält.
  17. Das Verfahren gemäß Anspruch 1, welches des Weiteren umfasst:
    Entwässern des Faserbreis, der Wasser, zellulosische Fasern und das adsorbierbare chemische Additiv umfasst, zu einer Konsistenz von ungefähr 20 Prozent oder mehr;
    Führen des entwässerten Faserbreis durch einen Dispenser, um die Fasern mechanisch zu bearbeiten;
    Verdünnen des Faserbreis mit Frischwasser, das im Wesentlichen frei ist von dem ersten chemischen Additiv bis zu einer Konsistenz von ungefähr 5 Prozent oder weniger;
    Hinzugeben eines zweiten adsorbierbaren chemischen Additivs, welches ein Debonding-Mittel oder einen Weichmacher umfasst, zum Faserbrei;
    Entwässern des Faserbreis bis zu einer Konsistenz von ungefähr 20 Prozent oder mehr;
    Verdünnen des Faserbreis mit Frischwasser, das im Wesentlichen frei ist von dem zweiten chemischen Additiv bis zu einer Konsistenz von ungefähr 5 Prozent oder weniger; und
    Bilden eines Papierprodukts aus dem Faserbrei.
  18. Das Verfahren gemäß Anspruch 17, wobei das erste chemische Additiv ein Bindemittel umfasst.
  19. Das Verfahren gemäß einem der vorherigen Ansprüche, welches des Weiteren die Schritte umfasst des Erzeugens eines zweiten Faserbreis (26), der im Wesentlichen frei ist von dem adsorbierbaren chemischen Additiv; und
    Bilden eines Papierprodukts unter Verwendung eines in Lagen aufgebauten Auflaufkastens, wobei der erste Faserbrei, der das adsorbierbare chemische Additiv umfasst, einer ersten Auflaufkastenlage zugeführt wird, und wobei der zweite Faserbrei einer zweiten Auflaufkastenlage zugeführt wird.
  20. Das Verfahren gemäß einem der vorherigen Ansprüche, welches des Weiteren den Schritt des Bildens eines Papierprodukts umfasst, welches ein Rückhaltevermögen für chemisches Additiv von ungefähr 4 Kilogramm pro metrischer Tonne oder mehr aufweist.
  21. Das Verfahren gemäß einem der Ansprüche 1 bis 19, welches des Weiteren den Schritt des Bildens eines Papierprodukts umfasst, welches ein Rückhaltevermögen für chemisches Additiv von ungefähr 5 Kilogramm pro metrischer Tonne oder mehr aufweist.
  22. Das Verfahren gemäß Anspruch 21, wobei das Produkt eine zentrale Schicht, welche im Wesentlichen aus Weichholzfasern besteht, und zwei äußere Schichten umfasst, welche ungefähr 70 Prozent oder mehr Hartholzfasern umfassen.
EP98964756A 1997-12-24 1998-12-17 Papierprodukte und verfahren zum auftragen von chemischen zusatzstoffen auf zellstofffasern Expired - Lifetime EP1042556B1 (de)

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AU739322B2 (en) 2001-10-11
PL340766A1 (en) 2001-02-26
CA2310692A1 (en) 1999-07-08
AR017855A1 (es) 2001-10-24
WO1999034057A1 (en) 1999-07-08
BR9814354B1 (pt) 2010-06-01
ID24904A (id) 2000-08-31
CA2310692C (en) 2008-08-05
IL135910A0 (en) 2001-05-20
AU2001099A (en) 1999-07-19
TW440641B (en) 2001-06-16
KR20010033530A (ko) 2001-04-25
DE69841662D1 (de) 2010-06-24
CN1224757C (zh) 2005-10-26
TR200001834T2 (tr) 2001-01-22
BR9814354A (pt) 2001-10-16
CO5040185A1 (es) 2001-05-29
JP2002500286A (ja) 2002-01-08
KR100543841B1 (ko) 2006-01-23
CN1283244A (zh) 2001-02-07
EP1042556A1 (de) 2000-10-11

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