WO1998024974A1 - Procede de fabrication de papier resistant a l'etat humide - Google Patents

Procede de fabrication de papier resistant a l'etat humide Download PDF

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Publication number
WO1998024974A1
WO1998024974A1 PCT/US1997/021414 US9721414W WO9824974A1 WO 1998024974 A1 WO1998024974 A1 WO 1998024974A1 US 9721414 W US9721414 W US 9721414W WO 9824974 A1 WO9824974 A1 WO 9824974A1
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WO
WIPO (PCT)
Prior art keywords
wet strength
agent
web
fiber
anionic compound
Prior art date
Application number
PCT/US1997/021414
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English (en)
Inventor
Tong Sun
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 CA002271384A priority Critical patent/CA2271384A1/fr
Priority to BR9713842-8A priority patent/BR9713842A/pt
Priority to AU53606/98A priority patent/AU729194B2/en
Priority to NZ336391A priority patent/NZ336391A/xx
Priority to EP97950660A priority patent/EP0943036A1/fr
Priority to JP52562898A priority patent/JP2001505627A/ja
Publication of WO1998024974A1 publication Critical patent/WO1998024974A1/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
    • D21H23/06—Controlling the addition
    • D21H23/08—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH
    • D21H23/10—Controlling the addition by measuring pulp properties, e.g. zeta potential, pH at least two kinds of compounds being added
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen

Definitions

  • wet strength agents any material that when added to a paper web or sheet results in providing the sheet with a wet geometric tensile strength:dry geometric tensile strength ratio in excess of 0.1 will, for purposes herein, be termed a wet strength agent. Typically these materials are termed either as permanent wet strength agents or as “temporary" wet strength agents.
  • permanent will be defined as those resins which, when incorporated into paper or tissue products, will provide a product that retains 50% or more of its original wet strength after exposure to water for a period of at least five minutes.
  • Temporary wet strength agents are those which show less than 50% of their original wet strength after exposure to water for five minutes. Both classes of material find application in the present invention.
  • the substantivity or effectiveness of many cationic wet strength agents is limited by low retention of the wet strength agent on the cellulose fiber. Much of the applied chemical may not be retained on the fiber, but remains in solution or is washed off after application, for there are relatively few anionic sites on the cellulose surface to attract the charged wet strength agent, and in some cases there may be a large number of anionic sites on colloidal particles or other particles in the fiber suspension which may adsorb a large portion of the wet strength agent, limiting its effectiveness in increasing wet strength.
  • Cationic additives are sometimes used to help neutralize excess anionic sites on colloidal particles or "anionic trash" in the suspension, to allow more of a subsequently added cationic wet strength resin to attach to the fiber surface and not to be preferentially absorbed onto non-fiber components.
  • Cationic promoters typically include polyethyleneimine with a cationic charge of about 0.75 to 3.5 milliequivalents/gram, quaternized polyamines, such as polydiallyldimethylammonium chloride, or cationic starch.
  • Commonly used cationic resins include polyquatemary amines and are available from Cytec Industries under the trade names CYPRO 514, 515, 516.
  • Cationic promoters are added to the stock in advance of the wet strength resins to ensure adequate mixing and adequate contact with the fibers.
  • the cationic resins are generally used in an amount of about 1 to 10 pounds per ton or 0.05 to 0.5%.
  • the cationic promoter can be used at 0 to 0.5 wt %, typically the resins are used in an amount of about 0.02 to 0.3 wt % and preferably 0.1 to 0.2 wt %.
  • the manufacturer of the promoter will typically recommend a pH for its use.
  • the Cypro resins are effective over a pH of about 4 to 9.
  • anionic promoters does not increase the number of anionic sites on the fiber surface itself, and may decrease the number of such sites, such that the intrinsic potential of the cationic wet strength agent to increase wet strength is still limited by inadequate attachment sites on the cellulose surface.
  • the extent of anionic sites on the cellulose can be measured in terms of the carboxyl group content of cellulose, which is typically measured to be about 2 to 5 milliequivalent per 100 grams of cellulose, or higher.
  • an object of the present invention is to increase the number of anionic sites on the surface of papermaking fibers by pretreating the fibers, thus increasing the substantivity of subsequently added cationic wet strength agents that form covalent bonds with the cellulose.
  • a further object of the present invention is substantially increasing the wet strength of paper that can be achieved with a given dose of wet strength agent.
  • an object of the present invention is to increase the wet strength that can be achieved with a given quantity of wet strength resin by a factor greater than 20%, preferably greater than 40%, more preferably greater than 50%, and most preferably greater than 70%.
  • Another object of the invention is to provide a method for enhancing wet strength in paper capable of achieving wet tensile strength values in substantially unrefined paper of over 1500 g/in, preferably over 2000 g/in, and most preferably over 2300 g/in, based on a 60 gsm Tappi handsheet.
  • a further object of the invention is to provide wetdry strength ratios greater than about 0.2, preferably greater than about 0.3, more preferably above about 0.4, still more preferably between 0.2 and 0.5, and most preferably greater than 0.5.
  • the present invention resides in a method in which cellulosic fibers are pretreated with a fiber reactive anionic compound to increase the substantivity of cationic wet strength agents.
  • an aqueous slurry of papermaking fibers is treated with a substantially colorless fiber reactive anionic compound, wherein the fiber reactive anionic compound comprises a fiber reactive moiety suitable for forming a covalent bond (for example, an ether-type linkage) with hydroxyl or other groups on the cellulose surface.
  • the pH of the slurry must be adjusted to ensure that it is sufficiently high to drive the reaction of the reactive anionic compound with the cellulose.
  • the slurry can be at a high fiber consistency, preferably from about 5 to about 50%.
  • the slurry is diluted, if necessary, and mixed with a cationic wet strength agent.
  • the treated fibers are formed into a paper web using processes well known in the art and dried under conditions suitable for curing the wet strength agent.
  • the present invention also resides in a chemical treatment process that increases the number of anionic attachment sites for cationic polymers on cellulose by means of reaction between a triazine or other reactive group on a colorless reactive anionic compound further comprising at least one sulfonic or carboxylic group suitable for establishing an ionic bond with a cationic wet strength agent, followed by addition of a cationic polymer and alkalization to drive reaction of the reactive anionic compound with cellulose.
  • the invention also resides in a method of preparing paper with relatively high wet strength and low dry strength by first increasing anionic sites on the cellulose fibers with said fiber reactive anionic compound, followed by addition of a chemical debonder agent and a cationic wet strength agent.
  • the debonder agent may be applied to the fibers while the fibers are in solution, followed by addition of the cationic wet strength agent, whereafter the paper is formed, dewatered, and dried.
  • the debonder agent may be applied to dried or partially dried paper web that has been prepared with a fiber reactive anionic compound and a cationic wet strength agent. In either case, the debonder agent interferes with hydrogen bond formation, reducing the dry strength of the paper, while having relatively little effect on covalent bond formation.
  • the result is a paper with an increased wet:dry tensile strength ratio. Such paper can have reduced stiffness and improved softness due to the reduced extent of hydrogen bonding, while still having high wet strength.
  • the first step in the method of this invention is providing an aqueous slurry of papermaking fibers. It is anticipated that wood pulp in all its varieties will normally comprise the papermaking fibers used in this invention. However, other cellulosic fibrous pulps, such as cotton liners, bagasse, rayon, kenaf, milkweed fibers, and the like can be used. Wood pulps useful herein include both sulphite and sulfate pulps as well as mechanical and thermomechanical pulps all well known to those skilled in the art, including chemithermomechanical pulp and bleached chemithermomechanical pulp.
  • High brightness pulps including chemically bleached pulps, are especially preferred for tissue making, but unbleached or semi-bleached pulps may also be used. Pulps derived from both deciduous and coniferous trees can be used. Recycled fibers are included within the scope of the present invention.
  • the second step of the present invention is chemical pretreatment of the fibers by adding an effective amount of a fiber reactive anionic compound to the fiber slurry.
  • the preferred amount of fiber reactive anionic compound added to the fiber slurry is from about 0.01 to about 4 wt % based on the dry fiber weight, preferably from about 0.05 to about 2 wt %, more preferably from about 0.08 to about 1.5%, and most preferably from about 0.1 to about 1 wt%.
  • the pretreatment of papermaking fibers to increase substantivity toward cationic compounds is achieved with colorless fiber reactive "dyes" modified to be without chromophore groups and further modified, if necessary, to ensure the presence of at least one anionic moiety such as a sulfonic or carboxylic group.
  • the anionic moiety serves as the site for ionic bonds with cationic groups of a cationic wet strength agent, helping to form a bridge between the fiber and the wet strength agent to hold the wet strength agent on the fiber, thus increasing the effectiveness of a given dose of wet strength agent in a papermaking furnish.
  • Suitable reactive anionic compounds are organic molecules comprising at least one anionic moiety such as a sulfonyl or carboxyl group and at least one fiber reactive group capable of forming a covalent bond such as an ether-type linkage to a hydroxyl group on cellulose, selected from the group consisting of monohalotriazine, dihalotriazine, trihalopyrimidine, dihalopyridazinone, dihaloquinoxaline, dihalophtalazine, halobenzothiazole, acrylamide, vinylsulfone, ⁇ -sulfatoethylsylfonamide, ⁇ - haloethylsulfone, and methylol, with dihalotriazine believed to be particularly advantageous because of an ability to allow reaction with the fiber to occur at lower temperatures than monohalotriazine and related compounds; and with chlorine as the preferred halogen.
  • dihalotriazine believed to be particularly advantageous because of an ability to allow reaction
  • the reactive anionic compound further comprises a bridging group between the fiber reactive moiety and the anionic group, said bridging group comprising an aliphatic, an aromatic, an inertly or essentially inertly substituted aromatic, a cyclic, a heterocyclic, or an inertly or essentially inertly substituted heterocyclic radical, characterized by low absorption of visible light.
  • the bridging group is bonded to the fiber reactive moiety by means of an -NH-group or by a peptide bond involving the group
  • the reactive anionic compound is substantially water soluble and has a molecular weight less than 5,000, preferably less than 3000, more preferably less than 1500, and preferably between 300 and 1000.
  • W is sulfonyl or carboxyl or salts thereof;
  • R is either an aliphatic, an aromatic, an inertly or essentially inertly substituted aromatic, a cyclic, a heterocyclic, or an inertly or essentially inertly substituted heterocyclic radical, characterized by low absorption of visible light, and preferably being resistant to attack or cleavage at 70°C over a pH range of 6 to 8, preferably 6 to 9, more preferably 5 to 9, and most preferably 4 to 10;
  • Y signifies NH or
  • X is a moiety suitable for forming a covalent bond such as an ether-type linkage to a hydroxyl group on cellulose, selected from the group consisting of monohalotriazine, dihalotriazine, trihalopyrimidine, dihalopyridazinone, dihaloquinoxaline, dihalophtalazine, halobenzothiazole, acrylamide, vinylsulfone, ⁇ -sulfatoethylsylfonamide, ⁇ -haloethylsulfone, and methylol, with dihalotriazine believed to be particularly advantageous because of an ability to allow reaction with the fiber to occur at lower temperatures than monohalotriazine and related compounds; and with chlorine as the preferred halogen; and
  • B is either hydrogen, a group of the formula Y-R, wherein Y and R are defined as above; or a group of the formula Y-R-W, wherein Y, R, and W are defined as above.
  • Related structures within the scope of this invention can have multiple sulfonyl or carbonyl groups attached to various locations of the molecule, including on segments of the bridging group or even directly attached to part of the fiber reactive group. Multiple fiber reactive groups may also be attached to one or more bridging groups, allowing the reactive anionic compound to attach to multiple adjoining sites on a cellulose surface.
  • the third step is adjusting the pH and temperature of the slurry to effectively drive the reaction between the fiber reactive anionic compound and the fiber.
  • the reactive anionic compound added in the second step may not react significantly with the cellulose until the pH and the temperature are both sufficiently high.
  • Alkalization is typically necessary to raise the pH above 6, preferably above 7, more preferably above 8, still more preferably between 8 and 11 , and most preferably between 8 and 10, in order to drive the reaction toward completion.
  • Alkaline agents such as sodium hydroxide, trisodium phosphate, sodium bicarbonate, and sodium carbonate, either singly or in combination, are preferred for their low cost, their chemical effectiveness, their general compatibility with tissue making operations, and their ease of handling and processing, but other alkaline compounds may be selected as well, including but not limited to calcium oxide, potassium hydroxide, potassium carbonate, and related compounds.
  • Alkalization of the fibrous slurry can be done either before, during, or after addition of the reactive anionic compound to the fibers in the second step. Based on experimental results, alkalization after addition of the reactive anionic compound is preferred because it results in higher yield and efficiency (higher substantivity of the wet strength agent, manifest by higher wet strength of paper at a given dosage of wet strength agent). Without limitation, it is believed that alkalization too early in the process can cause some hydrolysis of the reactive group of the reactive anionic compound, resulting in lower yield.
  • slightly more of an alkaline compound is added to the slurry than would be needed to neutralize the acidic byproduct of reaction between the reactive anionic compound and a hydroxyl group of the cellulose.
  • the acidic byproduct is hydrogen chloride. Adding sufficient sodium hydroxide in the post- alkalization treatment to more than neutralize the hydrogen chloride, assuming complete reaction, has proven to be effective in achieving the desired reaction and the desired wet strength properties. Thorough mixing of the slurry during alkalization is desirable.
  • a temperature of 20°C to 150°C is typically needed for practically rapid reaction rates, with a preferred temperature range of 20 to 120°C, more preferably 20°C to 100°C, more preferably still 40 to 85°C, and most preferably 50 to 80°C.
  • a preferred temperature range of 20 to 120°C, more preferably 20°C to 100°C, more preferably still 40 to 85°C, and most preferably 50 to 80°C.
  • the optimum temperature will depend on which fiber reactive anionic compound is used. If the slurry is below a suitable temperature range, temperature elevation may be achieved by contact heating through the use of a heat exchanger, heated vessel walls, steam injection, or any of the many means known in the art. For uniformity of reaction, good mixing of the slurry during heating is desirable.
  • the adjustment of temperature need not be simultaneous with the addition of alkaline compounds or with the addition of fiber reactive anionic compound, but preferably will follow addition of the alkaline compound.
  • the proper temperature should be maintained for a sufficient period of time to drive the reaction to a useful degree of completion.
  • the fourth step is adding an effective amount of cationic wet strength agents and water to said aqueous slurry, creating a papermaking furnish.
  • Mixtures of compatible wet strength resins including those described previously, can be used in the practice of this invention. Additional compounds and fillers or solid components may be added. This step may be done simultaneously with the second step, or could even precede the second step, if desired, although better efficiency is obtained by performing the addition of cationic wet strength agents after chemical pretreatment of the fibers.
  • wet strength agent Any amount of wet strength agent may be added, but for efficient use and reasonable cost it is desirable that less than about 30 pounds per ton or 1.5 wt % on a dry fiber basis be added, preferably between about 0.02 to 1.5 wt %, more preferably between 0.02 to 1.0 wt %, and most preferably between about 0.05 to 0.8 wt %.
  • Any cationic wet strength agent suitable for papermaking may be used.
  • preferable agents should be capable of forming covalent bonds with cellulose.
  • the wet strength resins are water-soluble, cationic materials. That is to say, the resins are water-soluble at the time they are added to the papermaking furnish.
  • Particular permanent wet strength agents that are of utility in the present invention are typically water soluble, cationic oligomeric or polymeric resins that are capable of either crosslinking with themselves (homocrosslinking) or with the cellulose or other constituent of the wood fiber.
  • Such compounds have long been known in the art of papermaking. See, for example, U.S. Pat. Nos. 2,345,543 (1944), 2,926,116 (1965) and 2,926,154 (1960), all herein incorporated by reference.
  • One class of such agents include polyamine-epichlorohydrin, polyamide epichlorohydrin or polyamide-amine epichlorohydrin resins, collectively termed "PAE resins.” These materials have been described in patents issued to Keim (U.S. Pat. Nos.
  • polyethylenimine resins are also suitable for immobilizing fiber-fiber bonds.
  • Another class of permanent- type wet strength agents includes aminoplast resins (e.g., urea-formaldehyde and melamine-formaldehyde).
  • the permanent wet strength agent is typically added to the paper fiber in an amount up to about 20 pounds per ton or 1.0 wt %. The exact amount will depend on the nature of the fibers and the amount of wet strength required in the product. As in the case of the temporary wet strength agent, these resins are generally recommended for use within a specific pH range depending upon the nature of the resin. For example, the Amres resins are typically used at a pH of about 4.5 to 9.
  • Temporary wet strength agents are also useful in the method of this invention.
  • Suitable cationic temporary wet strength agents can be selected from agents known in the art such as dialdehyde starch, polyethylene imine, mannogalactan gum, glyoxal, and dialdehyde mannogalactan.
  • Also useful are cationic glyoxylated vinylamide wet strength resins as described in U.S. Pat. No. 3,556,932 issued to Coscia et al. on Jan. 19, 1971, and in U.S. Pat. No. 5,466,337, "Repulpable Wet Strength Paper,” issued to William B. Darlington and William G. Lanier on Nov. 14, 1995.
  • Useful water-soluble cation resins include polyacrylamide resins such as those sold under the Parez trademark, such as Parez 631 NC, by American Cyanamid Company of Stanford, Conn., generally described in the above-mentioned patent issued to Coscia et al. and in U.S. Pat. No. 3,556,933 issued to Williams et al. on Jan. 19, 1971.
  • the cationic temporary wet strength agent is provided by the manufacturer as an aqueous solution and is added to the pulp in an amount of about 0.05 to 0.4 wt % and more typically in an amount of about 0.1 to 0.2 wt %.
  • the pH of the pulp is adjusted prior to adding the resin.
  • the manufacturer of the resin will usually recommend a pH range for use with the resin.
  • the Parez 631 NC resin can be used at a pH of about 4 to 8.
  • the fifth step is depositing said papermaking furnish on a foraminous surface to form an embryonic web.
  • This step may further comprise dewatering and other operations known in the art prior to drying of the web.
  • the sixth and final step is drying the web. Any of the techniques known to those skilled in the papermaking art for drying wet fibrous webs can be used. Typically, the web is dried by heat supplied by air moving around, over, or through the web; by contact with a heated surface; by infrared radiation; by exposure to superheated steam, or by a combination of such methods. The exact point at which the wet strength agent begins to cure during the drying of the wet fibrous web is an indistinct one. What is required in the present invention is that the fibrous web be substantially dried and that the wet strength bonds of whatever nature as provided by the wet strength resin begin to form.
  • the wetdry tensile strength ratio of the dried web should be at least 0.1 , preferably at least about 0.2, and more preferably at least about 0.3 when the process has been properly executed.
  • the "wetdry ratio" is the ratio of the geometric mean wet tensile strength divided by the geometric mean dry tensile strength.
  • GMT Geometric mean tensile strength
  • the final wet strength of the paper for a given dose of wet strength agent should be at least 10% higher than is achieved by the use of the wet strength agent without addition of the reactive anionic compound.
  • the present invention offers multiple advantages over prior art techniques for enhancing wet strength.
  • the present invention requires no coloration or dying of the fibers, and requires no bleaching or discharging of chromophores to maintain a white sheet.
  • the present invention requires no addition of NaCI or other chlorides to drive the reaction of the reactive anionic compound with the fiber.
  • the present invention does not require highly dilute fiber slurries in the fiber pretreatment step but has been demonstrated successfully at fiber consistencies as high as 30%.
  • the present invention does not rely on ionic bonds to enhance strength, but takes advantage of reactive wet strength agents that form covalent bonds with the cellulose surface, though ionic bonds do provide the initial attachment of the cationic polymer with the sulfonic groups of the reactive anionic compound.
  • fiber reactive anionic compounds in the present invention can also be coupled with chemical debonder agents to make paper with relatively high wet strength and low dry strength.
  • One or more fiber reactive anionic compounds are used with cationic wet strength resins to establish water-resistant covalent bonds, while chemical debonders are used to reduce the number of hydrogen bonds between fibers, thus reducing the dry strength of the paper. This is best done by first increasing anionic sites on the cellulose fibers with said fiber reactive anionic compound, according to steps one through three as previously described, followed by addition of a chemical debonder agent and a cationic wet strength agent.
  • the debonder agent may be applied to the fibers after step three while the fibers are in solution, followed by addition of the cationic wet strength agent as in step four, whereafter the paper is formed, dewatered, and dried according to steps five and six above.
  • the cationic wet strength resin be added after the debonder agent has been added to the slurry. Otherwise, the cationic wet strength agent may occupy most anionic sites on the fibers and interfere with retention of the chemical debonder agent.
  • Chemical debonder agents typically have a single cationic site, such as a quaternary ammonium salt, with fatty acid chains.
  • the debonder agent may be applied to the dried or partially dried paper web during step six through known means such as spraying, printing, coating, and the like.
  • the web has been dried enough to begin formation of covalent bonds in the web.
  • the web should then be at a solids level of preferably at least 40%, more preferably at least 60%, more preferably still at least 70%, most preferably at least 80%, and desirably between 60 and 90%.
  • the debonder maybe applied at other times, but for best results it should be either between steps 3 and 4 or during step 6 of the process described above.
  • the debonder agent interferes with hydrogen bond formation between the fibers, thus reducing the dry strength of the paper, while having relatively little effect on covalent bond formation.
  • the result is a paper with an increased wet:dry tensile strength ratio.
  • Such paper can have reduced stiffness and improved softness due to the reduced extent of hydrogen bonding, while still having high wet strength.
  • Desirable chemical debonder agents have less than five cationic sites per molecule and preferably no more than one cationic site which can bond with the anionic sites on the cellulose fiber surface. Large numbers of cationic sites could interfere with the anionic sites provided by the fiber reactive anionic compound if the debonder is applied to the fibers before covalent bonds have formed.
  • useful chemical debonder agents include fatty chain quaternary ammonium salts (QAS) such as Berocell 584, an ethoxylated QAS made by Eka Nobel, Inc.
  • debonder may be added at a level in the range of 0.1% to 2%, preferably 0.2% to 1.5%, and more preferably 0.5% to 1%.
  • Each batch of fiber slurry comprising 100 gm of fiber per batch, was then reloaded into the Hobart mixer and a Sandospace S solution, containing between 1 and 4 gm of Sandospace S was added during agitation of the pulp.
  • the mixture was thoroughly blended at 25°C for 25 minutes.
  • NaHCO 3 was added to each batch at a dose of 0.5 gm of NaHCO 3 per gm of Sandospace S (for a range of 0.5 to 2 gm of NaHCO 3 ), with the NaHCO 3 having been first dispersed in 5-10 ml of water prior to addition to the mixture of fiber, water, and Sandospace S.
  • Example 2 All steps were conducted as in Example 1 except that the NaHC0 3 solution was added prior to the addition of the Sandospace S solution, resulting in pre-alkalization rather than post alkalkization. Up to a 46% increase in wet strength with fiber reactive anionic compound was possible relative to paper made with the Kymene alone. Note that at 1% RAC (reactive anionic compound), a wet strength of 1606 g was achieved with pre- alkalization compared to 2374 g with post-alkalization.
  • RAC reactive anionic compound
  • the 60 gsm handsheets had a mean wet strength of 2160 g/inch and a mean dry strength of 4929 g/inch.
  • the wetdry tensile strength ratio for the handsheets of this example was 43.8%, in contrast to typical values of 30-35% for sheets with Kymene but without debonder, as in Example 1.
  • a handsheet made according to this Example but without any added debonder had a wetdry tensile strength ratio of 35.1%.
  • Handsheets were prepared as described in Example 3, except that no debonder was added to the fibrous slurry. A 1% by weight aqueous solution of Berocell liquid was prepared and sprayed onto the dried handsheets using a common household hand sprayer. Spray was applied evenly to both sides of the handsheets until the added liquid mass was approximately 100% of the dry handsheet mass, resulting in a total application of 1% pure Berocell to the fibers on a dry fiber basis (1 gram of added Berocell per 100 grams of fiber). Then the handsheets were dried at 105°C for 20 minutes and then cooled, conditioned, and tested for tensile strength. The mean wet strength was 2897 g/inch and the dry strength was 6551 g/inch, yielding a wetdry tensile ratio of 44.3%.

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Abstract

Procédé permettant d'améliorer l'efficacité d'additifs cationiques aqueux renforçant la résistance à l'état humide grâce au prétraitement de surfaces cellulosiques par des composés anioniques réactifs qui permet de créer, sur la surface cellulosique, des sites anioniques supplémentaires capables de retenir sur la cellulose une proportion élevée de tels additifs cationiques renforçant la résistance à l'état humide. Les additifs renforçant la résistance à l'àtat humide sont durcis ou mis en réaction avec la surface cellulosique. La matière fibreuse résultante se caractérise par une résistance à l'état humide inhabituellement élevée pour des doses inhabituellement faibles d'additifs cationiques. Les composés anioniques réactifs préférés comprennent des composés possédant un groupe réactif adapté à une liaison covalente avec des groupes hydroxyl sur la cellulose, et possédant également des groupes terminaux sulfoniques, ou d'autres groupes terminaux anioniques, capables d'attirer des composés cationiques renforçant la résistance à l'état humide dans une solution aqueuse.
PCT/US1997/021414 1996-12-04 1997-11-25 Procede de fabrication de papier resistant a l'etat humide WO1998024974A1 (fr)

Priority Applications (6)

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CA002271384A CA2271384A1 (fr) 1996-12-04 1997-11-25 Procede de fabrication de papier resistant a l'etat humide
BR9713842-8A BR9713842A (pt) 1996-12-04 1997-11-25 Método para fabricar papel com resistência úmida
AU53606/98A AU729194B2 (en) 1996-12-04 1997-11-25 Method for making wet strength paper
NZ336391A NZ336391A (en) 1996-12-04 1997-11-25 method for making wet strength paper by adding a colourless reactive eanionic compound to the slurry
EP97950660A EP0943036A1 (fr) 1996-12-04 1997-11-25 Procede de fabrication de papier resistant a l'etat humide
JP52562898A JP2001505627A (ja) 1996-12-04 1997-11-25 湿潤強度紙製造方法

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US76033196A 1996-12-04 1996-12-04
US08/760,331 1996-12-04

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WO1998024974A1 true WO1998024974A1 (fr) 1998-06-11

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EP (1) EP0943036A1 (fr)
JP (1) JP2001505627A (fr)
KR (1) KR20000069273A (fr)
CN (1) CN1240010A (fr)
AU (1) AU729194B2 (fr)
BR (1) BR9713842A (fr)
CA (1) CA2271384A1 (fr)
ID (1) ID22290A (fr)
NZ (1) NZ336391A (fr)
WO (1) WO1998024974A1 (fr)

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WO1999045201A1 (fr) * 1998-03-06 1999-09-10 Kimberly-Clark Worldwide, Inc. Procede de fabrication de papier presentant une resistance accrue a l'humidite
WO2000029670A1 (fr) * 1998-11-12 2000-05-25 Paper Technology Foundation Inc. Compositions pour le renfort et le traitement de materiaux lignocellulosiques
WO2000056978A1 (fr) * 1999-03-19 2000-09-28 Weyerhaeuser Company Procede d'accroissement de la retention de la charge de feuilles de fibres cellulosiques
US6194057B1 (en) 1998-11-12 2001-02-27 Paper Technology Foundation Inc. Partially impregnated lignocellulosic materials
US6211357B1 (en) 1999-12-09 2001-04-03 Paper Technology Foundation, Inc. Strengthening compositions and treatments for lignocellulosic materials
WO2001031122A1 (fr) * 1999-10-25 2001-05-03 Kimberly-Clark Worldwide, Inc. Papier a hautes performances a l'etat humide, utilisant des composes anioniques polymeres, et son procede de production
WO2001038638A1 (fr) * 1999-11-23 2001-05-31 Kimberly-Clark Worldwide, Inc. Produits de papier hygienique a aptitude au rinçage amelioree
US6281350B1 (en) 1999-12-17 2001-08-28 Paper Technology Foundation Inc. Methods for the reduction of bleeding of lignosulfonates from lignosulfonate-treated substrates
US6537615B2 (en) 1998-11-12 2003-03-25 Paper Technology Foundation Inc. Steam-assisted paper impregnation
US6537616B2 (en) 1998-11-12 2003-03-25 Paper Technology Foundation Inc. Stam-assisted paper impregnation
US6610174B2 (en) 1999-10-25 2003-08-26 Kimberly-Clark Worldwide, Inc. Patterned application of polymeric reactive compounds to fibrous webs
WO2004001127A2 (fr) * 2002-06-19 2003-12-31 Lanxess Corporation Produits de papier resistants et dispersables
US6787545B1 (en) 1999-08-23 2004-09-07 Shiongi & Co., Ltd. Pyrrolotriazine derivatives having spla2-inhibitory activities
WO2014105689A1 (fr) * 2012-12-26 2014-07-03 Kimberly-Clark Worldwide, Inc. Fibres cellulosiques modifiées ayant une liaison à l'hydrogène réduite
US9410292B2 (en) 2012-12-26 2016-08-09 Kimberly-Clark Worldwide, Inc. Multilayered tissue having reduced hydrogen bonding
US9416494B2 (en) 2012-12-26 2016-08-16 Kimberly-Clark Worldwide, Inc. Modified cellulosic fibers having reduced hydrogen bonding
CN106457860A (zh) * 2014-04-28 2017-02-22 惠普发展公司，有限责任合伙企业 轻质数字印刷介质
US10391094B2 (en) 2010-11-07 2019-08-27 Impact Biomedicines, Inc. Compositions and methods for treating myelofibrosis
US20220412634A1 (en) * 2017-01-16 2022-12-29 Domtar Paper Company,Llc Disposable ice pack

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JP4013188B2 (ja) * 2002-02-22 2007-11-28 星光Ｐｍｃ株式会社 （メタ）アクリルアミド系ポリマー、その製造方法、製紙用薬品、及びそれを含有する紙
JP4522692B2 (ja) * 2003-11-28 2010-08-11 ダイヤニトリックス株式会社 抄紙用粘剤
FR2916768B1 (fr) * 2007-05-31 2009-07-24 Arjowiggins Licensing Soc Par Feuille de securite resistante au froissement, son procede de fabrication et un document de securite la comprenant
CN104074098A (zh) * 2014-06-25 2014-10-01 金东纸业（江苏）股份有限公司 一种造纸浆料的配制方法以及造纸浆料

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Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999045201A1 (fr) * 1998-03-06 1999-09-10 Kimberly-Clark Worldwide, Inc. Procede de fabrication de papier presentant une resistance accrue a l'humidite
AU738654B2 (en) * 1998-03-06 2001-09-20 Research Foundation Of The State University Of New York, The Method for improved wet strength paper
WO2000029670A1 (fr) * 1998-11-12 2000-05-25 Paper Technology Foundation Inc. Compositions pour le renfort et le traitement de materiaux lignocellulosiques
US6114471A (en) * 1998-11-12 2000-09-05 The Proctor & Gamble Company Strengthening compositions and treatments for lignocellulosic materials
US6537615B2 (en) 1998-11-12 2003-03-25 Paper Technology Foundation Inc. Steam-assisted paper impregnation
US6194057B1 (en) 1998-11-12 2001-02-27 Paper Technology Foundation Inc. Partially impregnated lignocellulosic materials
US6537616B2 (en) 1998-11-12 2003-03-25 Paper Technology Foundation Inc. Stam-assisted paper impregnation
WO2000056978A1 (fr) * 1999-03-19 2000-09-28 Weyerhaeuser Company Procede d'accroissement de la retention de la charge de feuilles de fibres cellulosiques
US6824649B2 (en) 1999-03-19 2004-11-30 Weyerhaeuser Company Method for increasing filler retention of cellulosic fiber sheets
US6514384B1 (en) 1999-03-19 2003-02-04 Weyerhaeuser Company Method for increasing filler retention of cellulosic fiber sheets
US6787545B1 (en) 1999-08-23 2004-09-07 Shiongi & Co., Ltd. Pyrrolotriazine derivatives having spla2-inhibitory activities
WO2001031122A1 (fr) * 1999-10-25 2001-05-03 Kimberly-Clark Worldwide, Inc. Papier a hautes performances a l'etat humide, utilisant des composes anioniques polymeres, et son procede de production
US6610174B2 (en) 1999-10-25 2003-08-26 Kimberly-Clark Worldwide, Inc. Patterned application of polymeric reactive compounds to fibrous webs
WO2001038638A1 (fr) * 1999-11-23 2001-05-31 Kimberly-Clark Worldwide, Inc. Produits de papier hygienique a aptitude au rinçage amelioree
US6548427B1 (en) 1999-11-23 2003-04-15 Kimberly-Clark Worldwide, Inc. Sanitary tissue products with improved flushability
EP1250196A4 (fr) * 1999-12-09 2003-07-02 Paper Technology Foundation In Compositions pour le renfort et le traitement de materiaux lignocellulosiques
US6306464B2 (en) 1999-12-09 2001-10-23 Paper Technology Foundation Inc Strengthening compositions and treatments for lignocellulosic materials
US6211357B1 (en) 1999-12-09 2001-04-03 Paper Technology Foundation, Inc. Strengthening compositions and treatments for lignocellulosic materials
EP1250196A1 (fr) * 1999-12-09 2002-10-23 Paper Technology Foundation Inc. Compositions pour le renfort et le traitement de materiaux lignocellulosiques
US6281350B1 (en) 1999-12-17 2001-08-28 Paper Technology Foundation Inc. Methods for the reduction of bleeding of lignosulfonates from lignosulfonate-treated substrates
US6458419B2 (en) 1999-12-17 2002-10-01 Paper Technology Foundation Inc. Methods for the reduction of bleeding of lignosulfonates from lignosulfonate-treated substrates
US6620461B2 (en) 1999-12-17 2003-09-16 Paper Technology Foundation Inc. Methods for the reduction of bleeding of lignosulfonates from lignosulfonate-treated substrates
US6623806B2 (en) 1999-12-17 2003-09-23 Paper Technology Foundation Inc. Methods for the reduction of bleeding of lignosulfonates from lignosulfonate-treated substrates
WO2004001127A3 (fr) * 2002-06-19 2004-04-22 Bayer Chemicals Corp Produits de papier resistants et dispersables
WO2004001127A2 (fr) * 2002-06-19 2003-12-31 Lanxess Corporation Produits de papier resistants et dispersables
US10391094B2 (en) 2010-11-07 2019-08-27 Impact Biomedicines, Inc. Compositions and methods for treating myelofibrosis
WO2014105689A1 (fr) * 2012-12-26 2014-07-03 Kimberly-Clark Worldwide, Inc. Fibres cellulosiques modifiées ayant une liaison à l'hydrogène réduite
US9410292B2 (en) 2012-12-26 2016-08-09 Kimberly-Clark Worldwide, Inc. Multilayered tissue having reduced hydrogen bonding
US9416494B2 (en) 2012-12-26 2016-08-16 Kimberly-Clark Worldwide, Inc. Modified cellulosic fibers having reduced hydrogen bonding
CN106457860A (zh) * 2014-04-28 2017-02-22 惠普发展公司，有限责任合伙企业 轻质数字印刷介质
US20220412634A1 (en) * 2017-01-16 2022-12-29 Domtar Paper Company,Llc Disposable ice pack

Also Published As

Publication number Publication date
BR9713842A (pt) 2000-10-31
EP0943036A1 (fr) 1999-09-22
AU729194B2 (en) 2001-01-25
KR20000069273A (ko) 2000-11-25
CA2271384A1 (fr) 1998-06-11
AU5360698A (en) 1998-06-29
NZ336391A (en) 2000-09-29
ID22290A (id) 1999-09-30
CN1240010A (zh) 1999-12-29
JP2001505627A (ja) 2001-04-24

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