WO2011019811A1 - Papier de haute résistance - Google Patents

Papier de haute résistance Download PDF

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Publication number
WO2011019811A1
WO2011019811A1 PCT/US2010/045162 US2010045162W WO2011019811A1 WO 2011019811 A1 WO2011019811 A1 WO 2011019811A1 US 2010045162 W US2010045162 W US 2010045162W WO 2011019811 A1 WO2011019811 A1 WO 2011019811A1
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WO
WIPO (PCT)
Prior art keywords
tether
starch
activator
polymer
cellulose fibers
Prior art date
Application number
PCT/US2010/045162
Other languages
English (en)
Inventor
Gangadhar Jogikalmath
Patrick D. Kincaid
Lynn Reis
David Soane
Original Assignee
Nanopaper, Llc
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 Nanopaper, Llc filed Critical Nanopaper, Llc
Priority to CA2768219A priority Critical patent/CA2768219C/fr
Priority to EP10808690.1A priority patent/EP2464786A4/fr
Publication of WO2011019811A1 publication Critical patent/WO2011019811A1/fr
Priority to US13/331,861 priority patent/US8980059B2/en
Priority to US14/614,999 priority patent/US9605383B2/en

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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
    • 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

Definitions

  • This application relates generally to making paper products.
  • High strength is desirable in many paper and paperboard applications.
  • One way to achieve this is by manufacturing dense, high-caliper sheets or boards. This requires the use of large amounts of expensive pulp, and produces a heavy product.
  • Another method of creating high strength in paper products is to add starch as sizing.
  • the sizing process uses cooked starch solutions to impart stiffness or strength to the paper.
  • the wet web is first dried to a pre-set moisture content and/or is re-wet to achieve uniform moisture content throughout; then the material is fed into a size press where a high loading of gelatinized starch is applied to the paper surface; then the material is dried again.
  • This process yields a strong paper, but involves a number of downstream processes that can be inefficient. Inefficiencies result from the number of steps involved in preparing the substrate, cooking the starch and applying it to form the finished product.
  • gelatinized starch can be added to the wet end of the papermaking process, but its retention on the pulp fibers is often poor. Moreover, the contamination of the Whitewater with gelatinized starch leads to increased biological oxygen demand of the effluent, so that the process is environmentally unfavorable.
  • Ungelatinized starch granules can also be added to the wet end of papermaking, but they are also poorly retained. Such starch granules can gelatinize during the drying process, imparting strength to the paper web once it is dry. Adding starch granules in this manner requires lower amounts of energy to dry the paper web, while also eliminating or reducing the use of a size press. As an alternative, ungelatinized starch granules can be incorporated as fillers. In their native state, ungelatinized starch granules do not absorb water like the gelatinized starches, so they can be applied to paper webs that have not been pre-dried.
  • these granules can be sprayed on the moving moist web, and gelatinization can be effected in the dryer. This yields an improvement in dry strength and stiffness of the paper.
  • the spraying process does not disperse starch uniformly throughout the thickness of the paper, leading to anisotropic properties.
  • FIG. 1 shows a graph comparing strength with starch loading.
  • FIG. 2 shows a graph comparing strength with starch retention.
  • FIG. 3 shows tensile strength of paper samples.
  • FIG. 4 shows results from hydrophobicity tests on paper samples.
  • the particulate additive can be an organic additive.
  • the organic additive can comprise starch, and the starch can be a cationic starch or a hydrophobic starch.
  • the particulate additive can be an inorganic additive.
  • a paper product comprising activating a population of cellulose fibers in a liquid medium with an activator, preparing a tether-bearing particulate additive, wherein the tether-bearing particulate additive comprises a tether capable of interacting with the activator; and adding the tether-bearing particulate additive to the activated population of cellulose fibers, thereby attaching the additive to the fibers by the interaction of the activator and the tether.
  • methods for increasing the strength of a paper product formed from a pulp slurry comprising cellulose fibers, comprising adding an activator polymer to the pulp slurry, forming complexes between the activator polymer and cellulose fibers in the pulp slurry, preparing tether-bearing starch granules, wherein the tether-bearing starch granules comprise a tether polymer capable of interacting with the activator polymer, and adding the tether-bearing starch granules to the pulp slurry, whereby the starch granules are attached to the cellulose fibers by the interaction of the activator polymer and the tether polymer, thereby increasing the strength of the paper product formed from the pulp slurry.
  • the invention is a paper product comprising starch granules, wherein said starch granules are attached to cellulose fibers of said paper product by an interaction between an activator polymer and a tether polymer, wherein the activator polymer is attached to the cellulose fibers and the tether polymer is attached to the starch granules.
  • Disclosed herein are systems and methods for enhancing the attachment of a particulate additive to a fibrous matrix, so that the particles are efficiently and durably attached to the coarser fibrous matrix. Also disclosed herein are processes for manufacturing a paper product by forming a complex between a particulate additive (such as starch) and the fibers. The invention also encompasses paper made by the processes or method described herein.
  • a particulate additive such as starch
  • the systems and methods disclosed herein involve three components: activating the fibers as they are dispersed in a solution, attaching a tethering agent to the particulate additive, and adding the tether-bearing particulate additive to the dispersion containing the activated fibers, so that the additive is attached to the fibers by the interaction of the activating agent and the tethering agent.
  • these systems and methods can be used to treat fibers used in papermaking with a cationic polymer of a specific molecular weight and composition as an activator, to treat starch granules with an anionic polymer as a tethering agent, and to combine these separately-treated populations so that the starch granules are attached to the pulp fibers.
  • activation refers to the interaction of an activating material, such as a polymer, with suspended particles or fibers in a liquid medium, such as an aqueous solution.
  • An “Activator polymer” can carry out this activation.
  • high molecular weight polymers can be introduced into the particulate or fibrous dispersion as Activator polymers, so that these polymers interact, or complex, with the dispersed particles or fibers.
  • the polymer-fiber complexes interact with other similar complexes, or with other fibers, and form agglomerates.
  • This "activation" step can function as a pretreatment to prepare the surface of the suspended material (e.g., fibers) for further interactions in the subsequent phases of the disclosed system and methods.
  • the activation step can prepare the surface of the suspended materials to interact with other polymers that have been rationally designed to interact therewith in a subsequent "tethering" step, as described below.
  • an activating material such as a polymer
  • these coated materials can adopt some of the surface properties of the polymer or other coating. This altered surface character in itself can be advantageous for retention, attachment and/or dewatering.
  • activation can be accomplished by chemical modification of the suspended material.
  • oxidants or bases/alkalis can increase the negative surface energy of fibers or particles, and acids can decrease the negative surface energy or even induce a positive surface energy on suspended material.
  • electrochemical oxidation or reduction processes can be used to affect the surface charge on the suspended materials. These chemical modifications can produce activated particulates that have a higher affinity for tethered anchor particles as described below.
  • Suspended materials suitable for modification, or activation can include organic or inorganic particles, or mixtures thereof.
  • Inorganic particles can include one or more materials such as calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, other metal oxides and the like.
  • Organic particles can include one or more materials such as starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like. Particle sizes can range from a few nanometers to few hundred microns. In certain embodiments, macroscopic particles in the millimeter range may be suitable.
  • suspended materials may comprise materials such as lignocellulosic material, cellulosic material, minerals, vitreous material, cementitious material, carbonaceous material, plastics, elastomeric materials, and the like.
  • cellulosic and lignocellulosic materials may include wood materials such as wood flakes, wood fibers, wood waste material, wood powder, lignins, wood pulp, or fibers from woody plants.
  • the "activation" step may be performed using flocculants or other polymeric substances.
  • the polymers or flocculants can be charged, including anionic or cationic polymers.
  • anionic polymers can be used, including, for example, olefmic polymers, such as polymers made from polyacrylate, polymethacrylate, partially hydrolyzed polyacrylamide, and salts, esters and copolymers thereof (such as (sodium acrylate/acrylamide) copolymers), sulfonated polymers, such as sulfonated polystyrene, and salts, esters and copolymers thereof.
  • Suitable polycations include: polyvinylamines, polyallylamines, polydiallyldimethylammoniums (e.g., the chloride salt), branched or linear polyethyleneimine, crosslinked amines (including
  • Nonionic polymers suitable for hydrogen bonding interactions can include polyethylene oxide, polypropylene oxide, polyhydroxyethylacrylate, polyhydroxyethylmethacrylate, and the like.
  • an activator such as polyethylene oxide can be used as an activator with a cationic tethering material in accordance with the description of tethering materials below.
  • activator polymers with hydrophobic modifications can be used.
  • Flocculants such as those sold under the trademark MAGNAFLOC® by Ciba Specialty Chemicals can be used.
  • activators such as polymers or copolymers containing carboxylate, sulfonate, phosphonate, or hydroxamate groups can be used. These groups can be incorporated in the polymer as manufactured, alternatively they can be produced by neutralization of the corresponding acid groups, or generated by hydrolysis of a precursor such as an ester, amide, anhydride, or nitrile group. The neutralization or hydrolysis step could be done on site prior to the point of use, or it could occur in situ in the process stream.
  • the activated suspended material e.g., fiber
  • the activated suspended material can also be an amine
  • modified material can include any material that has been modified by the attachment of one or more amine functional groups as described herein.
  • the functional group on the surface of the suspended material can be from modification using a multifunctional coupling agent or a polymer.
  • the multifunctional coupling agent can be an amino silane coupling agent as an example. These molecules can bond to a material's surface and then present their amine group for interaction with the particulate matter.
  • the polymer on the surface of a suspended fiber or particle can be covalently bound to the surface or interact with the surface of the particle and/or fiber using any number of other forces such as electrostatic, hydrophobic, or hydrogen bonding interactions.
  • a multifunctional coupling agent can be used such as a silane coupling agent.
  • Suitable coupling agents include isocyano silanes and epoxy silanes as examples.
  • a polyamine can then react with an isocyano silane or epoxy silane for example.
  • Polyamines include polyallyl amine, polyvinyl amine, chitosan, and polyethylenimine.
  • polyamines can also self-assemble onto the surface of the suspended particles or fibers to functionalize them without the need of a coupling agent.
  • polyamines can self-assemble onto the surface of the particles or fibers through electrostatic interactions. They can also be precipitated onto the surface in the case of chitosan for example. Since chitosan is soluble in acidic aqueous conditions, it can be precipitated onto the surface of suspended material by adding a chitosan solution to the suspended material at a low pH and then raising the solution pH.
  • the amines or a majority of amines are charged.
  • polyamines such as quarternary amines are fully charged regardless of the pH. Other amines can be charged or uncharged depending on the environment.
  • the polyamines can be charged after addition onto the suspended particles or fibers by treating them with an acid solution to protonate the amines.
  • the acid solution can be non-aqueous to prevent the polyamine from going back into solution in the case where it is not covalently attached to the particle or fiber.
  • the polymers or particles can complex via forming one or more ionic bonds, covalent bonds, hydrogen bonding and combinations thereof, for example. Ionic complexing is preferred.
  • the activator could be introduced into a liquid medium through several different means.
  • a large mixing tank could be used to mix an activating material with fine particulate materials.
  • Activated particles or fibers are produced that can be treated with one or more subsequent steps of attachment to tether-bearing anchor particles.
  • tethering refers to an interaction between an activated suspended particle or fiber and an anchor particle (as described below).
  • the anchor particle for example, a particulate additive, can be treated or coated with a tethering material.
  • the tethering material such as a polymer, forms a complex or coating on the surface of the anchor particles such that the tethered anchor particles have an affinity for the activated suspended material.
  • the selection of tether and activator materials is intended to make the two solids streams complementary so that the activated particles or fibers in the suspension become tethered, linked or otherwise attached to the anchor particle.
  • the tethering material acts as a complexing agent to affix the activated particles or fibers to an anchor material.
  • a tethering material can be any type of material that interacts strongly with the activating material and that is connectable to an anchor particle.
  • an anchor particle may comprise materials such as
  • cellulosic and lignocellulosic materials may include wood materials such as wood flakes, wood fibers, wood waste material, wood powder, lignins, or fibers from woody plants.
  • inorganic particles useful as anchor particles include clays such as attapulgite and bentonite.
  • the inorganic compounds can be vitreous materials, such as ceramic particles, glass, fly ash, PCC, GCC, chalk, TiO2, silica, bentonite, kaolin, talc, and the like.
  • the anchor particles may be solid or may be partially or completely hollow.
  • glass or ceramic microspheres may be used as particles.
  • Vitreous materials such as glass or ceramic may also be formed as fibers to be used as particles.
  • Cementitious materials may include gypsum, Portland cement, blast furnace cement, alumina cement, silica cement, and the like.
  • Carbonaceous materials may include carbon black, graphite, carbon fibers, carbon microparticles, and carbon nanoparticles, for example carbon nanotubes.
  • plastic materials may be used as anchor particles. Both thermoset and thermoplastic resins may be used to form plastic particles.
  • Plastic particles may be shaped as solid bodies, hollow bodies or fibers, or any other suitable shape.
  • Plastic particles can be formed from a variety of polymers.
  • a polymer useful as a plastic particle may be a homopolymer or a copolymer. Copolymers can include block copolymers, graft copolymers, and interpolymers.
  • suitable plastics may include, for example, addition polymers (e.g., polymers of ethylenically
  • Addition polymers can include, for example, polyolefins, polystyrene, and vinyl polymers.
  • Polyolefins can include, in embodiments, polymers prepared from C 2 -Ci 0 olefin monomers, e.g., ethylene, propylene, butylene, dicyclopentadiene, and the like.
  • poly( vinyl chloride) polymers, acrylonitrile polymers, and the like can be used.
  • useful polymers for the formation of particles may be formed by condensation reaction of a polyhydric compound (e.g., an alkylene glycol, a polyether alcohol, or the like) with one or more polycarboxylic acids.
  • a polyhydric compound e.g., an alkylene glycol, a polyether alcohol, or the like
  • Polyethylene terephthalate is an example of a suitable polyester resin.
  • Polyurethane resins can include, e.g., polyether polyurethanes and polyester polyurethanes.
  • Plastics may also be obtained for these uses from waste plastic, such as post-consumer waste including plastic bags, containers, bottles made of high density polyethylene, polyethylene grocery store bags, and the like.
  • plastic particles for anchor particles can be formed as expandable polymeric pellets.
  • Such pellets may have any geometry useful for the specific application, whether spherical, cylindrical, ovoid, or irregular.
  • Expandable pellets may be pre-expanded before using them. Pre-expansion can take place by heating the pellets to a temperature above their softening point until they deform and foam to produce a loose composition having a specific density and bulk. After pre- expansion, the particles may be molded into a particular shape and size. For example, they may be heated with steam to cause them to fuse together into a lightweight cellular material with a size and shape conforming to the mold cavity. Expanded pellets may be 2-4 times larger than unexpanded pellets.
  • expandable polymeric pellets may be formed from polystyrenes and polyolefms. Expandable pellets are available in a variety of unexpanded particle sizes. Pellet sizes, measured along the pellet's longest axis, on a weight average basis, can range from about 0.1 to 6 mm.
  • the expandable pellets may be formed by polymerizing the pellet material in an aqueous suspension in the presence of one or more expanding agents, or by adding the expanding agent to an aqueous suspension of finely subdivided particles of the material.
  • An expanding agent also called a "blowing agent” is a gas or liquid that does not dissolve the expandable polymer and which boils below the softening point of the polymer. Blowing agents can include lower alkanes and halogenated lower alkanes, e.g., propane, butane, pentane, cyclopentane, hexane, cyclohexane, dichlorodifluoromethane, and trifluorochloromethane, and the like.
  • elastomeric materials can be used as particles. Particles of natural or synthetic rubber can be used, for example.
  • various interactions such as electrostatic, hydrogen bonding or hydrophobic behavior can be used to affix an activated complex to a tethering material complexed with an anchor particle.
  • an anchor particle can be selected from any particulate matter that is desirably attached to cellulose fibers in the final paper product.
  • the tether-bearing anchor particle comprising the desirable additive can then interact with the activated cellulose fibers in the wet paper stream.
  • starch granules can be used as an anchor particle to be attached to the cellulose fibers, as is described in more detail below.
  • organic and inorganic particulate matter can be attached to celluose fibers to achieve desired properties.
  • inorganic materials like calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, various other metal oxides, and the like, can be used as anchor particles in accordance with these systems and methods.
  • organic particles such as starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like, can be used as anchor particles in accordance with these systems and methods.
  • polymers such as linear or branched polyethyleneimine can be used as tethering materials. It would be understood that other anionic or cationic polymers could be used as tethering agents, for example polydiallyldimethylammonium chloride (poly(D ADMAC). In other embodiments, cationic tethering agents such as epichlorohydrin dimethylamine (epi/DMA), styrene maleic anhydride imide (SMAI), polyethylene imide (PEI), polyvinylamine, polyallylamine, amine-aldehyde
  • epi/DMA epichlorohydrin dimethylamine
  • SMAI styrene maleic anhydride imide
  • PEI polyethylene imide
  • polyvinylamine polyallylamine
  • poly(dimethylaminoethyl acrylate methyl chloride quaternary) polymers and the like can be used.
  • cationic polymers useful as tethering agents can include quaternary ammonium or phosphonium groups.
  • polymers with quaternary ammonium groups such as poly(D ADMAC) or epi/DMA can be used as tethering agents.
  • polyvalent metal salts e.g., calcium, magnesium, aluminum, iron salts, and the like
  • cationic surfactants such as dimethyldialkyl(C8-C22)ammonium halides, alkyl(C8-C22)trimethylammonium halides, alkyl(C8-C22)dimethylbenzylammonium halides, cetyl pyridinium chloride, fatty amines, protonated or quaternized fatty amines, fatty amides and alkyl phosphonium compounds can be used as tethering agents.
  • polymers having hydrophobic modifications can be used as tethering agents.
  • tethering material can depend on the activating material.
  • a high affinity between the tethering material and the activating material can lead to a strong and/or rapid interaction there between.
  • a suitable choice for tether material is one that can remain bound to the anchor surface, but can impart surface properties that are beneficial to a strong complex formation with the activator polymer.
  • a polyanionic activator can be matched with a polycationic tether material or a polycationic activator can be matched with a polyanionic tether material.
  • a poly(sodium acrylate-co-acrylamide) activator is matched with a chitosan tether material.
  • a hydrogen bond donor should be used in conjunction with a hydrogen bond acceptor.
  • the tether material can be complementary to the chosen activator, and both materials can possess a strong affinity to their respective deposition surfaces while retaining this surface property.
  • cationic-anionic interactions can be arranged between activated suspended materials and tether-bearing anchor particles.
  • the activator may be a cationic or an anionic material, as long as it has an affinity for the suspended material to which it attaches.
  • the complementary tethering material can be selected to have affinity for the specific anchor particles being used in the system.
  • hydrophobic interactions can be employed in the activation-tethering system.
  • tether-bearing anchor particles could be designed to complex with a specific type of activated particulate matter.
  • the systems and methods disclosed herein could be used for complexing with organic waste particles, for example.
  • Other activation-tethering- anchoring systems may be envisioned for removal of suspended particulate matter in fluid streams, including gaseous streams.
  • the complexes formed from the anchor particles and the activated fibrous matter can form a homogeneous part of a fibrous product like paper and/or other paper products.
  • Paper products include, for example, products and materials made from cellulose pulp, including, but not limited to, papers,
  • the interactions between the activated suspended fibers and the tether-bearing anchor particles can enhance the mechanical properties of the complex that they form.
  • an activated suspended material can be durably bound to one or more tether-bearing anchor particles, so that the tether-bearing anchor particles do not segregate or move from their position on the fibers.
  • Increased compatibility of the activated fine materials with a denser (anchor) matrix modified with the appropriate tether polymer can lead to further mechanical stability of the resulting composite material.
  • cationic and anionic polymers for activators and tethering agents can be selected from a wide variety of available polymers, as described above.
  • Starch granules or other desirable particles can be selected as anchor particles, where their attachment to pulp fibers would be advantageous.
  • desirable particles include, but are not limited to inorganic and organic anchor particles such as have been described above (e.g., for inorganic materials, calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, various other metal oxides and the like, and for organic materials, starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like).
  • inorganic and organic anchor particles such as have been described above (e.g., for inorganic materials, calcium carbonate, dolomite, calcium sulfate, kaolin, talc, titanium dioxide, sand, diatomaceous earth, aluminum hydroxide, silica, various other metal oxides and the like, and for organic materials, starch, modified starch, polymeric spheres (both solid and hollow), carbon based nanoparticles such as carbon nanotubes and the like).
  • starch granules When starch granules are used as anchor particles for attachment to cellulose fibers, they can be used in their native state, or they can be modified with short amine side-groups, with amine polymers, or with hydrophobic side groups (each such starch encompassed by the term "modified starch"). The presence of amines on the surface of the starch granules can help in attaching an anionic tethering polymer.
  • cationic polymers can be used for activating the cellulose fibers.
  • the polycation can be linked to the fiber surface using a coupling agent, for example a bifunctional crosslinking agent such as a carbonyldiimidazole or a silane, or the polyamine can self-assemble onto the surface of the cellulose fiber through electrostatic, hydrogen bonding, or hydrophobic interactions.
  • the polyamine can spontaneously self-assemble onto the fiber surface or it can be precipitated onto the surface.
  • chitosan can be precipitated on the surface of the cellulose fibers to activate them.
  • chitosan is soluble only in an acidic solution, it can be added to a cellulose fiber dispersion at an acidic pH, and then can be precipitated onto the surface of the cellulose fibers by slowly adding base to the dispersion until chitosan is no longer soluble.
  • a difunctional crosslinking agent can be used to attach the polycation to the fiber, by reacting with both the polycation and the fiber.
  • a polycation such as a polyamine can be added directly to the fiber dispersion or slurry.
  • the addition level of the polycation can be between about 0.01% to 5.0% (based on the weight of the fiber), e.g., between 0.1% to 2%.
  • a polyamine like polyD ADMAC a separately treated population of tether-bearing starch granules can be mixed in thereafter, resulting in the attachment of the starch granules to the cellulose fibers by the interaction of the activator polymer and the tether polymer.
  • Starch granules can be treated with a variety of anionic polymers, such as anionic
  • polyacrylamide which then act as tethers.
  • individual retention aids such as polyacrylamide are known in the art to help with the retention of starch granules within a cellulose matrix, the drainage of the paper web is severely affected by the use of these agents individually.
  • a complimentary polycation e.g., polyD ADMAC
  • polyanion as a tether attached to the starch granules in accordance with these systems and methods avoids this problem, reducing the water retention in the paper web and leading to efficient drainage.
  • the use of these systems and methods eliminates the requirement for cooking the starch before using it, thereby eliminating the gelatinizing ("cooking") step, and decreasing energy utilization.
  • the systems and methods described herein result in a percent starch retention within the cellulose matrix of a paper product of at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90% or at least about 90%. In certain aspects, the systems and methods result in a starch retention of at least about 85%. Percent starch retention is the amount of starch retained within the cellulose matrix as a percentage of the total amount of starch added to the pulp slurry. An exemplary method of determining starch retention is described in more detail in the Examples.
  • Starch that is to be treated in accordance with these systems and methods can be further derivatized or coated with moieties that impart desirable properties, e.g., hydrophobicity, oleophobicity or both. Starches thus modified may be also termed
  • Preferred oil resistant coating formulations are aqueous solutions of cellulose derivatives such as methylcellulose, ethyl cellulose, propyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethylhydroxypropyl cellulose, and ethylhydroxyethyl cellulose, cellulose acetate butyrate, which may further comprise polyvinyl alcohol and/or its derivatives.
  • cellulose derivatives such as methylcellulose, ethyl cellulose, propyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, ethylhydroxypropyl cellulose, and ethylhydroxyethyl cellulose, cellulose acetate butyrate, which may further comprise polyvinyl alcohol and/or its derivatives.
  • Another group of preferred oil resistant coating compositions are latex emulsions such as the emulsions of polystyrene, styrene-acrylonitrile copolymer, carboxylated styrene-butadiene copolymer, ethylene - vinyl chloride copolymer, styrene-acrylic copolymer, polyvinyl acetate, ethylene -vinyl acetate copolymer, and vinyl acetate-acrylic copolymer.
  • the starch granule thus coated with grease resistant formulations could be attached to the activated pulp fibers via tethering, such that the surface segregation of the starch granule will modify the surface of the paper product.
  • the presence of hydrophobic starch also improves the hydrophobicity of the resulting paper without needing an internal sizing such as alkyl succinic anhydride (ASA), alkyl ketene dimer (AKD) or Rosin.
  • ASA alkyl succinic anhydride
  • ALD alkyl ketene dimer
  • Rosin Rosin.
  • the gelatinized hydrophobic starch sizes the entire thickness of the paper. This property is useful in reducing the coating requirements in making coated sheets. The coating applied using a roller or a metering bar or any such methods, would remain on the surface of the paper and not impregnate the bulk of the paper thus needing less coating to achieve the same amount of gloss and surface finish.
  • the addition of a coating agent to the starch can improve its mechanical properties such as bending stiffness or tensile strength, or could improve its optical properties (e.g., TiO2 nanoparticles bound to starch).
  • the slurry can be subjected to additional steps in order to make a paper product.
  • the slurry can be mixed, drained of water, added to a handsheet maker, dried and/or pressed, or any combination thereof.
  • An exemplary method of making a handsheet is described in the Examples below.
  • a 0.5% slurry was prepared by blending 3.5% by weight softwood and hardwood pulp mixture (in the ratio of 20:80) in water.
  • Example 2 Control recycled pulp
  • a 0.5% slurry was prepared by blending 3.1% recycled deinked pulp in water.
  • Handsheets were prepared using a Mark V Dynamic Paper Chemistry Jar and Hand-Sheet Mold from Paper Chemistry Laboratory, Inc. (Larchmont, NY).
  • Handsheets were prepared without addition of polymers as controls, using the control pulps as described in Example 1 and 2. Handsheets were prepared with the addition of polymers as experimental samples, as described below. For preparing each
  • Instron 3343 Samples of handsheets for tensile testing were initially cut into 1 in wide strips with a paper cutter, then attached within the Instron 3343. The gauge length region was set at 4 in and the crosshead speed was 1 in/minute. Thickness was measured to provide stress data as was the weight to be able to normalize the data by weight of samples. The strips were tested to failure with an appropriate load cell. At least three strips from each control or experimental handsheet sample were tested and the values were averaged together.
  • Sta Lok 356 or Filmkote starches were dispersed in water such that the solids content was about 20 to 25% to get a slurry of cationic and hydrophobic starches respectively.
  • 1% by weight of anionic polyacrylamide magnafloc LT30 was used as the tethering agent.
  • Example 6 Process for preparing handsheets from activated pulp and tethered starch
  • Starch retention was determined by first analyzing the effluent created after making the handsheets in Example 6. A piece of VWR Grade 413 filter paper with 5 ⁇ m particle retention was initially dried in an oven at 110°C to remove any moisture and then weighed. The effluent from the handsheet preparation carried out in Example 5 was then filtered through the paper using vacuum filtration. The filter paper was dried again at HO 0 C to remove any moisture, and was weighed to determine the lost solids from the handsheet. These solids included the fines from the papermaking process and starch granules. To normalize for only the starch contribution to the effluent, a control experiment was run using the effluent from the preparation of a control pulp using the activator polymer but no starch addition. The filtered solid content in the control effluent was subtracted from the filtered solid content in the starch-bearing effluent, to yield the amount of starch therein. This amount was used to determine the starch retention of the pulp in Example 6.
  • Example 8 Effect on starch retention of polymeric retention aids added to cellulose pulp -(no starch tethering) [0069] Experiments were carried out to evaluate the starch retention effects of various polymers that can be used to functionalize cellulose fibers. A pulp slurry prepared in accordance with Example 1 was treated with the various polymers listed in Table 1 , at the loading levels listed in the Table. The Table lists the effects of the various cellulose fiber polymeric treatments on starch retention, where starch retention was measured in accordance with Example 7. The anionic polyacrylamide (LT 30) resulted in good starch retention, but was observed during the experiment to adversely affect the drainage of water.
  • LT 30 anionic polyacrylamide
  • Example 9 The Effect of Starch Loading on Strength
  • Samples were prepared as in Example 6, where the amount of tether-bearing starch (Sta Lok 356) ranged from 0.18g to 2.Og, i.e., initial loadings of 4% to 33% of the solids weight.
  • the tether-bearing starch was prepared in accordance with Example 5. Samples were made both with activator and tether and without either activator or tether. For samples made with activator, tether and the anchor (ATA), the tether used on the starch was 1% MagnaFloc LT30 by solids and the activator on the pulp was 1% polyD ADMAC by solids. Starch retention was measured as set forth in Example 7, and the max load for each sample was measured using an Instron as in Example 4.
  • Example 10 The Effect of Starch Loading on Strength and Hydrophobicity
  • Samples were prepared as in Example 6 with tether-bearing Sta Lok 356 starch. Starch retention was measured as set forth in Example 7, and the tensile strength for each sample was measured using an Instron as in Example 4. As set forth in Table 3, certain of the samples were treated with polyD ADMAC as activator in concentrations of 1% by solids, and with MagnaFloc LT30 as the tethering agent attached to the starch in concentrations of 1% by solids all in accordance with Example 6. These samples are designated as ATA Process samples in the table below (Table 3).
  • Graph 2 (FIG. 2) illustrates the effect of starch retention on the strength of the paper.
  • Graph 2 compares the difference between strength of the handsheets made with the ATA Process compared to handsheets that have not been treated with any polymer addition.
  • Example 11 Effect of hydrophobic starch loading on strength of paper made with recycled fibers
  • Recycled fibers are relatively weak due to fiber length reduction during fiber recovery and processing.
  • the ATA process is applied to improve the strength of handsheets made from recycled fibers by incorporating starch within the fibrous web.
  • a recycled pulp slurry prepared in accordance with Example 3 was treated in accordance with Example 6, using Filmkote hydrophobic starches as tether-bearing starches.
  • Filmkote starches of varying degrees of hydrophobicity were used, as set forth in Graph 3 (FIG. 3).
  • the starch Filmkote 550 is more hydrophobic than Filmkote 54.
  • the tensile strength of the paper samples was measured as set forth in Example 4.
  • the ATA process as applied to recycled paper improved the strength of the paper samples by amounts from about 25-40%.
  • Example 12 Effect of hydrophobic starch loading on hydrophobicity of paper made with recycled fibers

Abstract

L'invention porte sur des systèmes et sur des procédés pour fixer des additifs en particules à une population de fibres de cellulose dispersées dans une solution aqueuse. Les fibres de cellulose sont traitées avec un agent d'activation qui forme des complexes avec celles-ci. L'additif en particules est fixé à une amarre qui est apte à interagir avec l'agent d'activation, de façon à former ainsi un aditif en particules portant une amarre. L'additif en particules portant une amarre peut être ajouté à la suspension activée de fibres de cellulose. L'interaction résultante entre l'amarre et l'agent d'activation forme des complexes durables qui fixent l'additif en particules aux fibres de cellulose. A l'aide de ces systèmes et de ces procédés, des additifs utiles tels que des amidons peuvent être fixés à des fibres de cellulose, communiquant des propriétés avantageuses telles qu'une résistance accrue à des produits de papier formés à l'aide de celles-ci. Ces systèmes et ces procédés sont particulièrement utiles pour la fabrication de papier à l'aide de fibres de pâte vierge, de fibres recyclées, ou d'une quelconque combinaison de celles-ci.
PCT/US2010/045162 2009-08-12 2010-08-11 Papier de haute résistance WO2011019811A1 (fr)

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CA2768219A CA2768219C (fr) 2009-08-12 2010-08-11 Papier de haute resistance
EP10808690.1A EP2464786A4 (fr) 2009-08-12 2010-08-11 Papier de haute résistance
US13/331,861 US8980059B2 (en) 2009-08-12 2011-12-20 High strength paper
US14/614,999 US9605383B2 (en) 2009-08-12 2015-02-05 High strength paper

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US23344809P 2009-08-12 2009-08-12
US61/233,448 2009-08-12

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US20120152476A1 (en) * 2009-08-12 2012-06-21 Nanopaper, Llc High strength paper
WO2012122257A3 (fr) * 2011-03-08 2012-11-08 Nanopaper, Llc Produits fibreux à haute performance
WO2013033368A1 (fr) * 2011-09-01 2013-03-07 Nanopaper, Llc Additifs pour fabrication de papier
RU2483151C1 (ru) * 2011-11-10 2013-05-27 Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации Способ изготовления бумаги для печати
WO2013082007A1 (fr) * 2011-11-29 2013-06-06 Soane Labs, Llc Composites contenant de la pâte fonctionnelle pour applications de cloison sèche
WO2013188630A2 (fr) * 2012-06-15 2013-12-19 Nanopaper, Llc Additifs pour fabrication de papier
EP3018175B1 (fr) 2014-11-07 2019-02-06 Omya International AG Procédé de préparation de particules de charge floculées
US11155965B2 (en) 2014-11-07 2021-10-26 Omya International Ag Process for the preparation of flocculated filler particles

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US6849156B2 (en) * 2001-07-11 2005-02-01 Arie Cornelis Besemer Cationic fibers
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US6303000B1 (en) * 1998-08-31 2001-10-16 Omnova Solutions Inc. Paper making process utilizing a reactive cationic starch composition
US6849156B2 (en) * 2001-07-11 2005-02-01 Arie Cornelis Besemer Cationic fibers
US20060257678A1 (en) * 2005-05-10 2006-11-16 Benson Olester Jr Fiber reinforced optical films

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8980059B2 (en) * 2009-08-12 2015-03-17 Nanopaper, Llc High strength paper
US20120152476A1 (en) * 2009-08-12 2012-06-21 Nanopaper, Llc High strength paper
WO2012122257A3 (fr) * 2011-03-08 2012-11-08 Nanopaper, Llc Produits fibreux à haute performance
US20140224443A1 (en) * 2011-09-01 2014-08-14 Nanopaper, Llc Additives for papermaking
WO2013033368A1 (fr) * 2011-09-01 2013-03-07 Nanopaper, Llc Additifs pour fabrication de papier
RU2483151C1 (ru) * 2011-11-10 2013-05-27 Российская Федерация, От Имени Которой Выступает Министерство Промышленности И Торговли Российской Федерации Способ изготовления бумаги для печати
WO2013082007A1 (fr) * 2011-11-29 2013-06-06 Soane Labs, Llc Composites contenant de la pâte fonctionnelle pour applications de cloison sèche
WO2013188630A3 (fr) * 2012-06-15 2014-02-20 Nanopaper, Llc Additifs pour fabrication de papier
WO2013188630A2 (fr) * 2012-06-15 2013-12-19 Nanopaper, Llc Additifs pour fabrication de papier
US9587353B2 (en) 2012-06-15 2017-03-07 Nanopaper, Llc Additives for papermaking
EP3018175B1 (fr) 2014-11-07 2019-02-06 Omya International AG Procédé de préparation de particules de charge floculées
US11155965B2 (en) 2014-11-07 2021-10-26 Omya International Ag Process for the preparation of flocculated filler particles
US11326307B2 (en) 2014-11-07 2022-05-10 Omya International Ag Process for the preparation of flocculated filler particles

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CA2768219C (fr) 2016-01-26
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EP2464786A1 (fr) 2012-06-20

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