US20120006499A1 - Debonders for Use in Papermaking - Google Patents

Debonders for Use in Papermaking Download PDF

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Publication number
US20120006499A1
US20120006499A1 US13/178,053 US201113178053A US2012006499A1 US 20120006499 A1 US20120006499 A1 US 20120006499A1 US 201113178053 A US201113178053 A US 201113178053A US 2012006499 A1 US2012006499 A1 US 2012006499A1
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United States
Prior art keywords
fiber
containing composition
polymer
transition temperature
temperature
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US13/178,053
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English (en)
Inventor
Gangadhar Jogikalmath
Lynn Reis
Scott I. Rabin
David S. Soane
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NanoPaper LLC
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NanoPaper LLC
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Priority to US13/178,053 priority Critical patent/US20120006499A1/en
Assigned to NANOPAPER, LLC reassignment NANOPAPER, LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JOGIKALMATH, GANGADHAR, RABIN, SCOTT I., SOANE, DAVID S., REIS, LYNN
Publication of US20120006499A1 publication Critical patent/US20120006499A1/en
Priority to US14/276,305 priority patent/US20140360690A1/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52—Epoxy resins
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic 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
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • 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
    • D21H21/24—Surfactants

Definitions

  • This application relates generally to hydrophilic debonders for defiberizing pulp boards.
  • Fast wicking of liquids is desirable in many commercial products such as diapers, personal hygiene, sanitary products, etc. Usually this is achieved by converting paperboard products into defiberized fluff pulp that has a high surface area to enable fast wicking. Such fluff pulp is utilized in a variety of different designs to enable wicking of bodily fluids from the point of insult.
  • Fluff pulp is formed from paperboards made by conventional papermaking technologies.
  • the absorbent core for hygienic products is typically manufactured on a continuous production line in which wood fluff pulp is provided as a sheet (manufactured, for example, by a wet-laid process) and is defiberized mechanically using means such as a hammermill.
  • the defiberized fluff pulp is then air-laid with particles of superabsorbent polymers or other super-absorbent materials capable of absorbing up to one hundred times their weight in water, thereby forming the absorbent core for the product.
  • Formation of fluff pulp from paperboard depends on mechanical mechanisms to break the strong intermolecular hydrogen bonds that form between neighboring cellulose fibers during the papermaking process. A significant amount of energy is required to overcome the strength of the intermolecular bonds and break a paperboard into individual fibers.
  • debonder compounds are used for this purpose.
  • Debonders bind to the fiber surface, preventing the formation of hydrogen bonds by acting as a spacer between neighboring cellulose molecules and fibers.
  • debonders contain a cationic group that attaches the molecule to the anionic fiber surface, and a hydrophobic chain that acts like a spacer between cellulose fibers/molecules. With fewer bonds between fibers, less energy is required to break the fibers apart. Although these debonders can reduce the energy required to produce fluff pulp, the hydrophobic moiety decreases the wicking property of the resulting fluff pulp. Hence there is a need for an approach that reduces the hydrogen bonding while unaffecting the hydrophilicity of the fluffed pulp. Desirably, an appropriate debonder would both decrease the energy of defiberization and maintain comparable or improved wicking speeds.
  • fiber-containing compositions are disclosed that are suitable for use in improving fluid distribution in materials such as paper-based materials and/or at least a portion of an absorbent fiber-based article.
  • the fiber-containing compositions can include a fibrous material comprising fibers.
  • a debonding agent can impart the fiber-containing composition with a transition temperature such that the debonding agent has a higher affinity for the fibers when the temperature is above a transition temperature relative to when the temperature is below the transition temperature, and/or the debonding agent enhances fluid distribution in the fiber-containing composition when the temperature of the debonding agent is below the transition temperature relative to when the temperature is above the transition temperature.
  • Such fiber-containing compositions can include, or be substantially free of, a conventional debonding agent such as a salt (e.g., ammonium salt) or other charged specie; for example, free of the salt and/or charged specie such that the presence of any such specie does not affect the wicking of the fiber-containing composition and/or the LCST behavior of a polymer composition in the debonding agent.
  • a conventional debonding agent such as a salt (e.g., ammonium salt) or other charged specie; for example, free of the salt and/or charged specie such that the presence of any such specie does not affect the wicking of the fiber-containing composition and/or the LCST behavior of a polymer composition in the debonding agent.
  • the debonding agent comprises a polymer composition exhibiting a lower critical solution temperature (LCST).
  • the polymer composition can include a copolymer and/or a blend of different polymer molecules.
  • the debonding agent can comprise a plurality of alkylene oxide units.
  • the debonding agent can comprise at least one of polyethylene oxide units and polypropylene oxide units.
  • the debonding agent can comprise a polymer with two distinct alkylene-oxide units, each alkylene-oxide unit can exhibit a different LCST at a given concentration and molecular weight distribution.
  • a debonding agent can be substantially free of a charged specie (e.g., an ammonium salt, a polyelectrolyte, or other specie carrying an ionic charge).
  • the fiber-containing composition exhibits a transition temperature in a range between about 5° C. and about 95° C.
  • the fiber-containing compositions disclosed herein can comprise a transition temperature-modifier capable of changing the LCST of the debonder agent in the fiber-containing composition.
  • a LCST modifier can comprise at least one of a chaotropic salt and a surfactant.
  • aspects of the invention are directed to methods of improving wicking of a fiber-based material as disclosed herein (e.g., an absorbent fiber-based article).
  • Such methods can include the steps of providing a fiber-containing composition comprising a polymeric debonding agent disposed with a plurality of fibers; and subjecting the fiber-containing composition to a temperature below a transition temperature such that the fiber-containing composition exhibits enhanced wicking relative to a fiber-composition without the debonding agent.
  • the polymeric debonding agent can be consistent with any of the debonding agents including a polymer composition as disclosed herein (e.g., a copolymer or a blend of different polymer molecules).
  • the polymer composition can exhibit LCST behavior.
  • the fiber-containing composition optionally includes an ammonium salt.
  • the fiber-containing composition can be free of ammonium salt, or substantially free of ammonium salt (e.g., in an amount capable of substantially affecting wicking of the fiber-containing composition).
  • the debonding agent can comprise a plurality of alkylene oxide units.
  • the fiber-containing composition can comprise a transition temperature modifier capable of changing the LCST of the debonding agent in the fiber-containing composition, the transition temperature modifier comprising at least one of a chaotropic salt and a surfactant.
  • the step of providing the fiber-containing composition comprises forming a mixture comprising at least a portion of the fiber-containing composition; and drying the mixture to provide the fiber-containing composition.
  • the step of forming the mixture which is optionally performed at a temperature below the transition temperature, can comprise forming the mixture with the debonding agent.
  • the debonding agent can be applied while the mixture is being dried.
  • the step of drying the mixture can comprise subjecting the mixture to a temperature above the transition temperature.
  • the step of drying can comprise using the debonding agent to inhibit hydrogen bonding between at least some fibers during the step of drying.
  • the method can comprise inserting a debonder composition in a paper-based mixture including fibers.
  • the debonder composition can include at least one polymeric component exhibiting a LCST) and at least one modifying component.
  • the modifying component can be selected to alter the LCST of the at least one polymeric component so that the altered LCST falls within a temperature range between about 5° C. and about 95° C.
  • the at least one polymeric component comprises a first block of a copolymer.
  • the at least one modifying component comprises a second block of the copolymer.
  • the copolymer can optionally comprise a plurality of alkylene-oxide unit types.
  • the plurality of alkylene-oxide unit types can comprise at least one of an ethylene-oxide and a propylene oxide.
  • the at least one polymeric component can comprise a first polymer comprising a repeat unit type, and the at least one modifying component can comprise a second polymer comprising a different repeat unit type.
  • the repeat unit type comprises an alkylene-oxide unit type
  • the different repeat unit type comprises a different alkylene-oxide unit type.
  • the at least one polymeric component comprises a first polymer characterized by a first repeat unit or a selected polymer type and the at least one modifying comprises a second polymer characterized by the first repeat unit or the selected polymer type, the first polymer and the second polymer differing in at least one of molecular weight, branching, and the first polymer having a second repeat unit not present in the second polymer.
  • the at least one modifying component can comprise a chaotropic salt and/or a surfactant.
  • the methods disclosed herein can further comprise the step of maintaining the paper-based mixture at a temperature above a transition temperature to inhibit adhesion between at least a plurality of fibers of the paper-based mixture.
  • the methods disclosed herein can further comprise the step of maintaining the paper-based mixture at a temperature below the transition temperature such that the at least one polymeric component exhibits hydrophilic behavior.
  • FIG. 1 presents a bar graph depicting the measured tensile strength in lb f /in and measured wicking time in seconds for various samples of Example 8, the height of the bars indicating tensile strength on the left hand side of the graph, and the dots corresponding to each bar indicating the wicking time on the right hand side of the graph;
  • FIG. 2A presents a bar graph compares the measured tensile strength in lb f /in. and measured wicking time in seconds for a control sample, a sample utilizing an embodiment of the invention, and a conventional debonder sample tested in Example 8, the height of the bars indicating tensile strength on the left hand side of the graph, and the dots corresponding to each bar indicating the wicking time on the right hand side of the graph;
  • FIG. 2B presents a graph of measured wicking time in seconds against force for debonding in lb f /in. for the samples plotted in FIG. 2A , the types of samples are segregated in different locations of the graph as labeled;
  • FIG. 3A presents a graph of measured tensile strength in lb f /in. against weight percent concentration of L31 debonder in accord with the test results of Example 9, the bars corresponding with the range of tested results;
  • FIG. 3B presents a graph of measured wicking time in seconds against weight percent concentration of L31 debonder in accord with the test results of Example 9, the bars corresponding with the range of tested results;
  • FIG. 4 presents a bar graph depicting the measured maximum load/strip width in lb f /in. and measured wicking time in seconds for a control sample, a conventional debonder sample, and a sample utilizing an embodiment of the invention and the conventional debonder tested in Example 10, the height of the bars indicating tensile strength on the left hand side of the graph, and the dots corresponding to each bar indicating the wicking time on the right hand side of the graph.
  • debonding agents can be combined with fibers (e.g., cellulose-based fibers) to produce a material having substantial wicking properties while decreasing fiber-fiber interactions that can require substantial energy to overcome in materials processing.
  • the debonding agent can act to create a paper-based product exhibiting a transition temperature in which the agent has a higher affinity for the fibers at temperatures above the transition temperature, and a product exhibiting enhanced wicking properties at temperatures below the transition temperature.
  • a debonder agent can be substantially free of salt and/or charged species.
  • the presence of a charged specie can hinder performance of debonders such as are disclosed herein (e.g., by decreasing wicking and/or affecting debonder interactions with the fibers).
  • a debonding agent can include a polymer (either a portion of or the entirety of the molecule) or other material exhibiting a lower critical solution temperature (e.g., a copolymer containing ethylene oxide and propylene oxide units) that can be useful for enhancing wicking properties of fiber-containing compositions while hindering fiber-fiber attractions.
  • a lower critical solution temperature e.g., a copolymer containing ethylene oxide and propylene oxide units
  • LCST Lower Critical Solution Temperature
  • Such agents including certain polymers such as those containing ethylene oxide and propylene oxide monomers, are soluble in water or aqueous solutions at temperatures below the LCST, while heating the solutions leads to polymer precipitation from the solution above the LCST.
  • the LCST property of certain polymers can be used to support a class of debonder agents especially suitable for use in manufacturing liquid wicking materials such as fluff pulp because the papermaking exposes the pulp and additives to different temperatures during the manufacturing process.
  • the LCST of the debonder agent component acts to provide a transition temperature in the fiber-containing material utilizing the debonder agent. While this transition temperature is often close, if not the same, as the LCST, the presence of the other components of the material, or other environmental factors or components, can act to offset the transition temperature from the LCST.
  • a debonder can impart a sufficiently low transition temperature, thereby effectively reducing the solubility of the debonder at temperatures above the transition temperature.
  • the reduction in solubility tends to deposit the debonder on fiber surfaces, which can help inhibit fiber-fiber attractions due to hydrogen bonding.
  • the transition temperature which may include ambient use temperatures of a wicking material
  • the debonder can become soluble, thereby enhancing fluid distribution through the fiber network, e.g., relative to the use of conventional ammonium salt debonders which are hydrophobic and hinder wicking between the fibers.
  • Embodiments of debonders can be designed to enable addition at different points along the paper making line.
  • the debonder molecule can be added at the wet end or after the slurry has been deposited onto the moving wire, e.g., at a temperature below the transition temperature such that the debonder component is water soluble when added to the slurry.
  • the temperature will be elevated above the transition temperature, causing the debonder component to precipitate out of solution onto the fiber surface. This precipitation may help in the drying process by inhibiting the hydrogen bonding between neighboring fibers.
  • the temperature of the paper falls below the transition temperature, so that the molecule reverts back to a hydrophilic state. This enhances the wicking properties of the dried paper sheet, because the now-hydrophilic debonder does not prevent flow of water through the fibrous web, as do many debonders in current use.
  • polymer refers to a molecule comprising repeat units, wherein the number of repeat units in the molecule is greater than about 10 or about 20. Repeat units can be adjacently connected, as in a homopolymer. The units, however, can be assembled in other manners as well. For example, a plurality of different repeat units can be assembled as a copolymer. If A represents one repeat unit and B represents another repeat unit, copolymers can be represented as blocks of joined units (e.g., A-A-A-A-A-A-A . . .
  • polymers include homopolymers, copolymers (e.g., block, inter-repeating, or random), cross-linked polymers, linear, branched, and/or gel networks, as well as polymer solutions and melts. Polymers can also be characterized as having a range of molecular weights from monodisperse to highly polydisperse.
  • a “type of polymer” refers to a polymer formed from a particular set of repeat units, e.g., A units and B units.
  • a designated polymer type can or cannot have all the polymer molecules be of the same molecular weight and/or have the repeat units oriented identically.
  • debonder agents can be utilized in a number of different dispositions, e.g., having a polymer where at least one section of the polymer exhibits LCST behavior. These include polymers where the segments are known to exhibit LCST behavior to those skilled in the art.
  • suitable debonders can include polymers having segments such as polyalkylene oxides (e.g., polyethylene oxide (PEO) or polypropylene oxide (PPO) or a mix of such oxides), ethyl(hydroxyethyl)cellulose, poly(N-vinylcaprolactam), poly(methylvinyl ether), poly(N-isopropylacrylamide), and derivatives of such including those understood by ones skilled in the art.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • the polymer composition can comprise only uncharged species.
  • the polymer composition can be at least substantially free of polyelectrolytes (e.g., being substantially or totally free of charges associated with the polymer structure).
  • the transition temperature of a fiber-containing composition and/or the behavior of a debonder agent can be substantially dictated by the LSCT of the polymer as opposed to the charges of a specie interacting with fibers.
  • Polymer composition can include a homopolymer, a copolymer, or a blend of polymers.
  • a blend of polymers can include polymers of different types, e.g., a blend of at least one homopolymer and one copolymer, a blend of copolymers, a blend of a type of polymer where the molecules differ in molecular weight and/or branching.
  • a blend of polymers of a debonder agent can be disposed as an emulsion (e.g., a blend of a polymer rich in polypropylene oxide segments and a polymer rich in polyethylene oxide segments). The emulsion can allow polymers having different solubilities to be blended to form an appropriate debonding agent.
  • the polymers can have a character that is different from that of conventional ammonium salts used as debonders (e.g., being anionic or neutral in nature).
  • an anchoring group such as a cationic group or a chemical group such as epoxy or anhydride
  • the presence of an anchoring group can enhance the stability of the attachment of the debonder to a cellulose fiber.
  • the polymer composition can be formulated to impart a selected transition temperature range for the fiber-containing composition utilizing the debonder agent.
  • the polymer composition can be advantageous to select the polymer composition such that the transition temperature is in the range of temperatures relevant to a papermaking process, e.g., selecting the polymer composition such that wet end processing of paper typically takes place at temperatures below the transition temperature and drying takes place at temperatures above the transition temperature.
  • the components of the polymer composition (e.g., the polymers of a blend or the blocks of a copolymer) of a debonder agent are selected such as to impart a transition temperature for the fiber-containing composition in a range from about 5° C. to about 95° C.
  • a polymer composition can be designed to achieve a certain LCST, and thus impart a corresponding transition temperature when the composition acts as a portion of a debonder agent in a fiber-containing composition, by utilizing a first component having a designated LCST and another component to modify the first LCST.
  • polymer having different alkylene oxide segment types can be utilized to tailor a transition temperature in a range from about 5° C. to about 95° C.
  • polymers made of propylene oxide monomers exhibit a LCST of around 5-10° C. while those made with ethylene oxide exhibit a LCST of ⁇ 90° C.
  • These transition temperatures are concentration and molecular weight dependent, and can also be affected by the presence of other components in a fiber-containing composition.
  • the ratio of EO and PO blocks in the molecule can determine the LCST of the resulting copolymer.
  • a copolymer formed using these components can have an LCST that falls between these two temperatures, depending on the relative content of EO and PO blocks in the polymer.
  • a blend of polypropylene oxide polymers and polyethylene oxide polymers can also be used with the transition temperature dictated at least in part by the sizes of the individual polymers and their relative amounts.
  • features of a polymer composition utilizing PPO segments and PEO segments are disclosed. It is understood, however, that such features can also be imparted generally to other polymer composition consistent with other embodiments of the present invention. Accordingly, such features are not confined to PEO/PPO segment compositions, and can be extended generally to other polymer compositions that can physically achieve such features, consistent with embodiments of the present invention.
  • the debonder molecule binds to the pulp because the temperature of the aqueous environment reduces the solubility of either or both the EO or the PO units.
  • the debonder molecule can be chosen such that the transition temperature of the composition would be in the range of temperatures seen on a papermaking line. For example, a composition with a transition temperature of 35° C. can be deposited into the wet slurry in the headbox where it would precipitate onto the fibers due to the fact that the temperature in the headbox is higher ( ⁇ 45° C.) than the transition temperature of the debonder.
  • commercially available polymers can display certain advantageous properties of a hydrophilic debonder imparting a transition temperature that allows its precipitation during the drying phase of papermaking, as described above, along with its reversion to a hydrophilic state at room temperature.
  • a hydrophilic debonder imparting a transition temperature that allows its precipitation during the drying phase of papermaking, as described above, along with its reversion to a hydrophilic state at room temperature.
  • PLURONIC® line of polyethylene oxide (PEO)-polypropylene oxide (PPO) block copolymers BASF
  • a debonder molecule can be prepared that self-assembles around cellulose fibers, thereby preventing hydrogen bonding between neighboring fibers.
  • the debonder molecule can be a polymer.
  • EO ethyleneoxide
  • PO propyleneoxide
  • the temperature-sensitive solubility behavior of the PPO and PEO blocks in the polymer backbone can produce an affinity towards the cellulose fibers when the temperature of the solution is above the transition temperature of either of the EO or PO based blocks, so that the polymer attaches itself to the cellulose fiber.
  • the LCST of a polymer composition can be changed by the use of chaotropic salts such as those based on potassium, sodium, and calcium.
  • chaotropic salts such as those based on potassium, sodium, and calcium.
  • potassium salts function well as chaotropic agents for EO based polymers, with the EO blocks self-assembling around potassium ions forming a crown ether like structure.
  • the presence of chaotropic salts can alter the solution behavior of the debonders by precipitating them out of solution at temperatures lower than the actual LCST.
  • adding salt to the polymer can change the structure of water around the molecules, leading to an association of the polymer with the salt and subsequent precipitation, effectively lowering the LCST of the polymer.
  • a PEO-containing polymer has an LCST of 90° C.
  • a chaotropic salt in the solution preferably sodium based
  • Other polymer/salt systems can exhibit similar behaviors, for example, systems using NaCl and the like, whereby a polymer/salt arrangement can self-assemble around the cellulosic fibers.
  • the LCST of the polymer in solution can also be changed by adding suitable surfactants, for example sodium dodecylsulfate or sodium laureth sulfate.
  • suitable surfactants for example sodium dodecylsulfate or sodium laureth sulfate.
  • Pluronic L31 [PEO-PPO-PEO] increased the LCST by about 5° C.
  • PROSOFT ® ammonium salt-containing debonders (Hercules, Inc., Wilmington DE)
  • a 0.6% slurry was prepared by mixing 84.45 g refurnished softwood pulp (22.5% solids) in 3 L of water for 6-10 minutes.
  • Handsheets were prepared using a Mark V Dynamic Paper Chemistry Jar and Hand-Sheet Mold from Paper Chemistry Laboratory, Inc. (Larchmont, N.Y.). The appropriate volume of 0.6% pulp slurry was functionalized with the appropriate polymer(s) (based on dry weight), as listed above. Polymer additions were done at 10 minute intervals. This combined slurry was added to the handsheet maker. The slurry was mixed at a rate of 1100 RPM for 5 seconds, 700 RPM for 5 seconds, and 400 RPM for 5 seconds. The water was then drained off. The subsequent sheet was then transferred off of the wire, pressed and dried.
  • wicking speed was determined by the time taken by the water level to reach the different heights.
  • Handsheets were produced with the method in Example 2 using of the solution prepared in Example 1.
  • the final paper weight was approximately 19 g for the control sheets.
  • the final basis weight was about 670 gms.
  • Handsheets were produced with the method in Example 2 using of the solution prepared in Example 1.
  • a debonder selected from the list in Table A and/or Table B was added at a concentration of up to 10% of the final paper weight and mixed for 10 minutes into the solution prepared in Example 1.
  • the concentration of salt in the solution By changing the concentration of salt in the solution, the temperature at which cloudiness was observed in the polymer solution could be lowered or increased (cloudiness indicating polymer precipitation).
  • Different concentration solutions of hydrophilic debonders selected from the list in Table A and/or Table B were made in water. To these solutions, salt solutions were added to make 0.1M, 0.2M and 0.3M final salt concentration. The salts were at least one of sodium chloride, potassium chloride, and potassium sulfate.
  • the polymer-salt solutions were heated to different temperatures to observe the onset of precipitation of the polymer by monitoring cloudy streaks of polymer precipitation from solutions.
  • Tensile load at failure was measured for paper strips treated with hydrophilic debonders and conventional debonders (post-headbox treatment) by dipping 1 ′′ by 6′′ strips of 670 GSM basis weight paper strips in 50 mL centrifuge tubes containing solutions containing BASF Pluronic polymers in deionized water at concentration of 1%/wt, until the strips were saturated for approximately 2 minutes. The samples were then pressed and dried at 110° C. for 45 minutes. The protocol of Example 3 was used to determine the Energy and Max Load values. Corresponding wicking speeds were measured using the protocol described in Example 4; the wicking time corresponded with the time required for the water level to reach 6 cm. For this experiment, samples were prepared using polymers listed in Table 1 below, with an untreated sample as the control. Table 1 and FIG. 1 show the maximum tensile load at failure along with wicking time.
  • FIG. 2A shows the comparison of pulp treated with conventional debonder such as Prosoft TQ2028, with Pluronic L31 polymer, and untreated control pulp.
  • the samples with debonder utilized about 1 weight percent of the debonder.
  • the graph of FIG. 2A shows that L31 reduces tensile strength without affecting the wicking speed while the conventional debonder affects wicking speed negatively.
  • FIG. 2B graphs the results of FIG. 2A in terms of wicking time against the tensile strength.
  • samples corresponding to virgin fibers have a high tensile strength, which indicate substantial fiber-fiber interactions.
  • the use of conventional debonders results in a desired lowering of tensile strength at the expense of a higher wicking time.
  • the tested new debonders in accord with some embodiments of the invention, lower the tensile strength without resulting in a substantial increase in wicking time.
  • Samples were prepared by dipping 1 ′′ by 6′′ strips of 670 GSM basis weight paper strips in 50 mL centrifuge tubes containing solutions containing BASF Pluronic polymer L31 in deionized water at concentrations ranging from 0 to 10%/wt, until the strips were saturated for approximately 2 minutes. The samples were then pressed and dried at 110° C. for 45 minutes. The tensile load at failure was then measured using the apparatus described in Example 3, and the wicking time was measured using the protocol of Example 4; the wicking time corresponded with the time required for the water level to reach 6 cm. Table 2, FIGS. 3A and 3B below show the results of these tests.
  • Samples were made by dipping untreated and conventional-debonder-treated 1′′ by 6′′ strips of 670 GSM basis weight paper in 50 mL centrifuge tubes containing solutions containing a hydrophilic debonder.
  • the hydrophilic debonder the BASF Pluronic polymer L35 in deionized water was used at concentration of 1%/wt. Sample strips remained in contact with this solution for approximately 2 minutes, until the strips were saturated. The samples were then pressed and dried at 110° C. for 45 minutes.
  • the tensile load at failure was then measured, using the apparatus described in Example 3 and the wicking time was measured using the protocol of Example 4; the wicking time corresponded with the time required for the water level to reach 6 cm. The results of these tests are shown in FIG. 4 .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paper (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
US13/178,053 2009-01-08 2011-07-07 Debonders for Use in Papermaking Abandoned US20120006499A1 (en)

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US14/276,305 US20140360690A1 (en) 2009-01-08 2014-05-13 Debonders for use in papermaking

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US13/178,053 US20120006499A1 (en) 2009-01-08 2011-07-07 Debonders for Use in Papermaking

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Cited By (3)

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US20140360690A1 (en) * 2009-01-08 2014-12-11 Nanopaper, Llc Debonders for use in papermaking
US8926796B2 (en) 2011-11-09 2015-01-06 Nanopaper, Llc Bulk and stiffness enhancement in papermaking

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ES2127518T3 (es) * 1994-03-18 1999-04-16 Procter & Gamble Preparacion de fibras celulosicas individualizadas, reticuladas con acido policarboxilico.
US6969443B1 (en) * 1998-12-21 2005-11-29 Fort James Corporation Method of making absorbent sheet from recycle furnish
EP1825043B1 (fr) * 2004-12-10 2016-10-12 Solvay USA Inc. Procede d'hydrophilisation durable de surface hydrophobe
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WO2010080958A1 (fr) * 2009-01-08 2010-07-15 Nanopaper, Llc Agents non liants à utiliser dans la fabrication de papier

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US7854822B2 (en) * 2004-12-02 2010-12-21 Rayonier Trs Holdings Inc. Plasticizing formulation for fluff pulp and plasticized fluff pulp products made therefrom
US20130068407A1 (en) * 2011-03-25 2013-03-21 Nanopaper, Llc Volatile debonder formulations for papermaking

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Publication number Priority date Publication date Assignee Title
US20140360690A1 (en) * 2009-01-08 2014-12-11 Nanopaper, Llc Debonders for use in papermaking
US20130068407A1 (en) * 2011-03-25 2013-03-21 Nanopaper, Llc Volatile debonder formulations for papermaking
US8747615B2 (en) 2011-03-25 2014-06-10 Nanopaper, Llc Volatile debonder formulations for papermaking
US9273432B2 (en) * 2011-03-25 2016-03-01 Nanopaper, Llc Volatile debonder formulations for papermaking
US8926796B2 (en) 2011-11-09 2015-01-06 Nanopaper, Llc Bulk and stiffness enhancement in papermaking

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US20140360690A1 (en) 2014-12-11

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