WO1999034057A1 - Produits de papier et procedes pour l'application d'additifs chimiques sur des fibres cellulosiques - Google Patents

Produits de papier et procedes pour l'application d'additifs chimiques sur des fibres cellulosiques Download PDF

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Publication number
WO1999034057A1
WO1999034057A1 PCT/US1998/026834 US9826834W WO9934057A1 WO 1999034057 A1 WO1999034057 A1 WO 1999034057A1 US 9826834 W US9826834 W US 9826834W WO 9934057 A1 WO9934057 A1 WO 9934057A1
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WO
WIPO (PCT)
Prior art keywords
chemical additive
fibers
fiber slurry
fiber
percent
Prior art date
Application number
PCT/US1998/026834
Other languages
English (en)
Inventor
Mike Thomas Goulet
Jill A. Georger
Denise Alice Polderman
Maurice Alan Wyatt
Original Assignee
Kimberly-Clark Worldwide, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kimberly-Clark Worldwide, Inc. filed Critical Kimberly-Clark Worldwide, Inc.
Priority to KR1020007007032A priority Critical patent/KR100543841B1/ko
Priority to IL13591098A priority patent/IL135910A0/xx
Priority to DE69841662T priority patent/DE69841662D1/de
Priority to CA002310692A priority patent/CA2310692C/fr
Priority to BRPI9814354-9A priority patent/BR9814354B1/pt
Priority to PL98340766A priority patent/PL340766A1/xx
Priority to AU20010/99A priority patent/AU739322B2/en
Priority to JP2000526701A priority patent/JP2002500286A/ja
Priority to EP98964756A priority patent/EP1042556B1/fr
Publication of WO1999034057A1 publication Critical patent/WO1999034057A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • 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 at 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.
  • water soluble or water dispersible chemical additives are suspended in water and are not completely adsorbed onto the cellulosic fibers.
  • chemical additives are often modified with functional groups to impart an electrical charge when in water.
  • the electrokinetic attraction between charged additives and the anionically charged fiber surfaces aids in 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 invention resides in 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.
  • another aspect of the invention resides in 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 inco ⁇ orated 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 reducing 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
  • the method may also be used in alternative processes, including: chemically pre- treating 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.
  • Figure 1 depicts a schematic process flow diagram of a method according to the present invention for treating papermaking fibers with chemical additives.
  • Figure 2 depicts a schematic process flow diagram of a method according to the present invention for both treating papermaking fibers with chemical additives and mechanically treating the fibers using a disperser.
  • Figure 3 depicts a schematic process flow diagram for a method of making an uncreped tissue sheet.
  • 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 particulariy 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 particulariy 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 particulariy 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 particulariy 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 particulariy 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., which are incorporated herein by reference.
  • 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 particulariy 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 particulariy 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.
  • 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., which is incorporated herein by reference.
  • 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.
  • 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.
  • 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.
  • Example 1 (Comparative)
  • 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.
  • 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.
  • 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 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 thickening process.
  • the center layer furnish comprised 100% northern bleached softwood kraft fibers. This furnish was refined at an energy input of 2 horsepower days/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 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 contained 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 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 traveling 1800 feet per minute (25% rush transfer).
  • a vacuum shoe pulling about 10 inches of mercury vacuum was used to transfer the web to the transfer fabric.
  • the web was then transferred to a throughdrying fabric traveling at a speed of about 1800 fpm.
  • the web was carried over a pair of Honeycomb throughdryers operating at temperatures of about 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 3 inch width (geometric mean tensile strength).
  • Example 2 For this example, 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.
  • 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.
  • 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.
  • C-6092 from Witco Corp.
  • 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 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 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.
  • Example 3 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 3 inch width (geometric mean tensile strength).
  • Example 3 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.
  • 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 180° F to impart curl to the fibers.
  • the high consistency, dispersed pulp was then stored in a chest until sufficient quantities could be produced.
  • 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 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% Eucalyptus/broke/corestock blend (outer layers).
  • the final strength of the tissue was 806 grams per 3 inch width (geometric mean tensile strength).
  • Example 4 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 ton 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.
  • 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 69% Eucalyptus/broke/corestock blend (outer layers).
  • the final strength of the tissue was 795 grams per 3 inch width
  • a layered tissue sheet can be made with a geometric mean tensile strength of about 800 grams per 3 inch width (795 grams per 3 inch width), under the processing conditions described in Example 4, 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./3" width contains 32% softwood fiber but only 3.8 kg./metric ton of retained C-6092 softener/ debonder. The reason for this difference in retained C-6092 at equivalent tissue strength, it is hypothesized, is because the debonding characteristic of the unadsorbed
  • C-6092 in the conventional chemical addition method compromises the strength development of the softwood fibers in the center layer. As a result, more softwood fiber is needed to achieve the same finished product tensile strength.
  • 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.
  • “Strength” refers to the geometric mean tensile strength which is calculated for purposes of the present invention according to the formula: ⁇ j[(MDtensile)(CDtensile)] .
  • the "MD tensile" strength of a tissue sample is the conventional measure, known to those skilled in the art, of load per sample width at the point of failure when a tissue web is stressed in the machine direction.
  • “CD tensile” strength is the analogous measure taken in the cross-machine direction. MD and CD tensile strength are measured using an Instron tensile tester using a 3-inch jaw width, a jaw span of 4 inches, and a crosshead speed of 10 inches per minute. Prior to testing the sample is maintained under TAPPI conditions (73°F, 50% relative humidity) for 4 hours before testing. Tensile strength is reported in units of grams per 3 inch width (at the failure point).
  • 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. In general, 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 8451 A 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 8451 A 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. Generate a Standard Solution Curve: With the UV spectrophotometer set at 238 nm wavelength, reference the instrument using a methanol sample. Read the absorptance of the standard solutions (10, 30, 50 and 100 ppm), then plot a curve of the concentration versus absorptance. Generate a first-order equation fit of the data.
  • 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. Generate an Add-On Correlation Curve: 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.
  • % Extracted (1/10 dilution) ppm reading X 0.1 X 10 X 100/5000. Construct an Add-on Correlation curve with the percent extracted values (y-axis) versus the corresponding add-on level (x-axis). Select the best fitting curve (first or second order). 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 ⁇ A 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.
  • Example 5 To better illustrate the ability for the improved chemical addition method to remove unadsorbed chemicals from the furnish of a papermaking process, 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.
  • 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 1 B, 2B and 3B.

Abstract

Des additifs chimiques peuvent être adsorbés en grande quantité sur les fibres cellulosiques entrant dans la fabrication du papier, avec une dose minimale d'additifs chimiques non adsorbés subsistant dans l'eau utilisée pour la fabrication du papier. Cette invention concerne un procédé consistant à traiter un boue de fibres au moyen d'une quantité excédentaire d'additifs chimiques, en prévoyant un temps de séjour suffisant pour que l'adsorption ait lieu et; à procéder à une redispersion à l'eau douce de la pulpe filtrée. Le filtrat résultant du processus d'épaississement, qui renferme l'additif chimique non adsorbé, n'est pas réintroduit avec les fibres traitées chimiquement dans le processus de traitement. Ce procédé convient pour la fabrication de produits de papier améliorés.
PCT/US1998/026834 1997-12-24 1998-12-17 Produits de papier et procedes pour l'application d'additifs chimiques sur des fibres cellulosiques WO1999034057A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
KR1020007007032A KR100543841B1 (ko) 1997-12-24 1998-12-17 종이 제품, 및 화학 첨가제를 셀룰로오스계 섬유에 가하는방법
IL13591098A IL135910A0 (en) 1997-12-24 1998-12-17 Paper products and methods for applying chemical additives to cellulosic fibers
DE69841662T DE69841662D1 (de) 1997-12-24 1998-12-17 Papierprodukte und verfahren zum auftragen von chemischen zusatzstoffen auf zellstofffasern
CA002310692A CA2310692C (fr) 1997-12-24 1998-12-17 Produits de papier et procedes pour l'application d'additifs chimiques sur des fibres cellulosiques
BRPI9814354-9A BR9814354B1 (pt) 1997-12-24 1998-12-17 método para criar, desidratar e diluir uma pasta de fibra que compreende água, fibras ceculósicas e um aditivo quìmico adsorvìvel e método para formar um produto de papel da pasta de fibra.
PL98340766A PL340766A1 (en) 1997-12-24 1998-12-17 Paper articles and method of using chemical additives to cellulose fibre
AU20010/99A AU739322B2 (en) 1997-12-24 1998-12-17 Paper products and methods for applying chemical additives to cellulosic fibers
JP2000526701A JP2002500286A (ja) 1997-12-24 1998-12-17 紙製品およびセルロース繊維に化学添加剤を付与する方法
EP98964756A EP1042556B1 (fr) 1997-12-24 1998-12-17 Produits de papier et procedes pour l'application d'additifs chimiques sur des fibres cellulosiques

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US7146897P 1997-12-24 1997-12-24
US60/071,468 1997-12-24
US1067598A 1998-01-22 1998-01-22
US09/010,675 1998-01-22

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PL340766A1 (en) 2001-02-26
CO5040185A1 (es) 2001-05-29
EP1042556B1 (fr) 2010-05-12
CN1283244A (zh) 2001-02-07
KR100543841B1 (ko) 2006-01-23
CN1224757C (zh) 2005-10-26
JP2002500286A (ja) 2002-01-08
BR9814354A (pt) 2001-10-16
CA2310692A1 (fr) 1999-07-08
BR9814354B1 (pt) 2010-06-01
TW440641B (en) 2001-06-16
AU2001099A (en) 1999-07-19
DE69841662D1 (de) 2010-06-24
EP1042556A1 (fr) 2000-10-11
IL135910A0 (en) 2001-05-20
CA2310692C (fr) 2008-08-05
KR20010033530A (ko) 2001-04-25
ID24904A (id) 2000-08-31
TR200001834T2 (tr) 2001-01-22
AU739322B2 (en) 2001-10-11
AR017855A1 (es) 2001-10-24

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