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
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline 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
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • D21H21/16—Sizing or water-repelling 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
  • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
  • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
  • Y10T428/277—Cellulosic substrate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31971—Of carbohydrate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31971—Of carbohydrate
  • Y10T428/31993—Of paper

Definitions

• the invention relates to oil and grease resistant/repellent paper and methods for making oil and grease resistant paper.
• Paper is a composite material containing small, interconnected discrete fibers, which provides a highly porous structure. Paper typically is made from cellulose fibers, which are usually formed into a sheet on a fine screen from a dilute water suspension or slurry, so that it incorporates randomly distributed fibers and air voids.
• the specific area of paper can be about 0.5-10 m 2 /g, in which the voids represent 25-70% of the paper volume, which leads to an apparent density of paper of less than about 0.8 g/cm 3 .
• a process for improving the grease- or oil-repellency of a cellulose material such as paper or paperboard, the process comprising treating or contacting a cellulose material with an aqueous dispersion comprising at least one modified nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose material.
• the process can comprise applying a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles to a cellulosic substrate to form a treated cellulosic substrate; and drying the treated cellulosic substrate to form an oil repellent cellulosic material.
• the fluorochemical can be selected from or can comprise at least one fluoroalkylsilane, cationic fluorochemical, or fluorinated polyacrylate.
• the disclosed provides for combining in an aqueous medium a nanoparticle component and a fluorochemical such as a fluoroalkylsilane to form a homogeneous aqueous dispersion comprising fluorochemical surface-modified nanoparticles, and then contacting the homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles with a cellulosic substrate to form an oil repellent cellulosic material.
• the process can further comprise drying or curing oil-repellent or -resistant cellulose material once prepared.
• the least one nanoparticle component and at least one fluorochemical of the type disclosed herein, and combined as disclosed herein work well because the inorganic nanoparticles and the fluorochemicals are obtained in separate processes and individually, have different affinities towards paper and paperboard. As a result of these different affinities, a separation can occur such that one component may penetrate the paper surface faster than the other component.
• this disclosure provides for the association of a fluorochemical with the rigid nanoparticle through chemical bonds, ionic bonds or polymerization on the inorganic/or organic seed particles, and forming such bonds can be achieved by selecting the fluorochemical from a fluoroalkylsilane, a cationic fluorochemical, or a fluorinated polymer such as a fluorinated polyacrylate, respectively.
• the resulting modified or functionalized particle appears to be a type of composite material that simultaneously delivers the fluorochemical and the nanoparticle and their respective influences, and thereby provides a “Lotus effect”.
• these fluorochemicals may be considered as “supported” in that they can interact with the rigid nanoparticles, depending on the nanoparticle composition, and this combined composition is added to the paper at the wet end, typically along with a retention aid, and/or at the size-press.
• the size-press solution contains starches or PVA, and the cellulosic support for the particles can be paper or board, made from hard wood and/or soft wood.
• the combination of at least one nanoparticle component and at least one fluorochemical acts to alter the paper or paperboard (cellulose material) surface geometry and surface energy, which enhances the grease- and oil-repellency properties.
• the specific fluorochemicals used in this process can modify the surface of the nanoparticles in a manner that allowed them to function in a manner that combines the useful attributes of the individual components in a synergistic fashion.
• Suitable nanoparticles include inorganic nanoparticles (such as silica, clay minerals, other inorganic nanoparticles), organic polymer nanoparticles (polystyrene, styrene acrylonitrile (SAN), and the like) having a glass transition temperature (Tg) greater than 100° C.; or combinations thereof.
• inorganic nanoparticles such as silica, clay minerals, other inorganic nanoparticles
• organic polymer nanoparticles polystyrene, styrene acrylonitrile (SAN), and the like having a glass transition temperature (Tg) greater than 100° C.; or combinations thereof.
• Tg glass transition temperature
• a process for improving the grease- and oil-resistance or grease- and oil-repellency of a cellulosic material comprising: a) combining in an aqueous medium a nanoparticle component and a fluorochemical to form a homogeneous aqueous dispersion comprising fluorochemical surface-modified nanoparticles; and b) contacting the homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles with a cellulosic substrate to form an oil repellent cellulosic material.
• a process for making an oil repellent cellulosic material comprising: a) applying a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles to a cellulosic substrate to form a treated cellulosic substrate; and b) drying the treated cellulosic substrate to form an oil repellent cellulosic material.
• the fluorochemical is selected from or comprises a fluoroalkylsilyl compound
• the process can comprise:
• a process comprising the following steps may be employed:
• the fluorochemicals used to surface-modify the nanoparticles can be cationic fluorochemicals, such that ionic interactions develop between the anionic inorganic nanoparticle and the cationic fluorochemical.
• anionic fluorochemicals can be used as well.
• the anionic nanoparticles can be treated first with a cationic polymer, such as polyamine, polyamidoamine, polyamidoamine epichlorohydrine (PAE), polyDADMAC (polydiallyldimethylammonium chloride), and/or a cationic copolymer of acrylamide.
• a cationic polymer such as polyamine, polyamidoamine, polyamidoamine epichlorohydrine (PAE), polyDADMAC (polydiallyldimethylammonium chloride), and/or a cationic copolymer of acrylamide.
• the addition of the anionic fluorochemical to a cellulosic substrate such as paper can be performed in one step if desired, wherein the paper can be treated with anionic nanoparticles previously modified with a cationic polymer and then an anionic fluorochemical.
• the addition of the anionic fluorochemical to a cellulosic substrate such as paper can be performed in two steps if desired, wherein the anionic nanoparticles treated with a cationic polymer are used to treat the paper and then the dried paper is treated in a second step with anionic fluorochemicals.
• the process can further comprise curing the treated or contacted cellulose material. It has been discovered that the disclosed method provides an unexpected improvement in the oil-repellent characteristics of the cellulose material, while still allowing a lower overall concentration of fluorochemical to impart the oil-repellency. Therefore, it appears that the at least one nanoparticle component acts as a type of extender for the fluorochemical such that lower, more environmentally benign, and lower cost concentrations of fluorochemical can be used to provide the desired oil-repellent properties.
• novel nanoparticle compositions particularly inorganic nanoparticle compositions, which have been surface modified by a bi-phasic reaction with liquid fluoroalkylsilane (FAS) reagents in an aqueous medium or by intereaction with cationic fluorochemical reagents or by contacting or forming fluorinated polyacrylates or other polymers with or at the nanoparticle surface, which can be used to treat a cellulosic material and impart excellent oil-repellent properties.
• FAS liquid fluoroalkylsilane
• the aqueous dispersions of the disclosed composition typically are monophasic, optically transparent and stable without significant aggregation or precipitation and with little or no additional solvents or surfactants.
• the disclosed composition used in the treating process can comprises an aqueous dispersion of fluoroalkylsilyl surface modified nanoparticles, wherein the nanoparticles comprise or are selected from at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN), or combinations thereof, and wherein the fluoroalkylsilyl surface-functionalizing moiety can be described as [F(CF 2 ) n CH 2 CH 2 ] m Si(O—) p , wherein n is 2, 3, or 4; m is 4-p; and p is 1, 2, or 3.
• the composition can further comprise an additional non-fluorinated alkylsilyl surface-functionalizing moiety bonded to the surface of the nanoparticle having the formula[H(CH 2 ) x ] y Si(O—) z , wherein x is an integer from 1 to 12; y is 4-z; and z is 1, 2, or 3.
• the additional component can be methylsilyl.
• articles comprising the fluorochemical surface-modified nanoparticles are disclosed, for example, the article can include paper, paperboard or cellulose based articles, and the article can exhibit improved resistance to both grease and oil.
• Treated paper, paperboard, and cellulose based products also show improved stiffness, print clarity, adhesion, release and friction characteristics over conventional fluorochemical or silicone treated papers and paperboard and cellulose fiber products.
• the fluorochemical is a fluoroalkylsilane
• a process for improving the grease- or oil-resistance of a cellulosic material such as paper, paperboard, and other cellulose-based materials, the process comprising:
• fluorochemical used to modify the surface of the nanoparticles comprises at least one fluoroalkylsilane having the formula
• the process can comprise:
• a modified substrate comprises a fluorochemical surface-modified nanoparticle on at least one surface of the substrate, wherein the nanoparticle and the fluorochemical are as disclosed herein.
• the substrate can further comprise additional non-fluorinated moieties, such as non-fluorinated alkylsilyl moieties also as disclosed herein.
• the nanoparticles that work particularly well can be selected from silica, zirconia, titania, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof.
• the substrate itself a cellulose based substrate, typically a paper or paperboard.
• a process of making an oil and grease resistant cellulosic material comprises (i) applying an aqueous dispersion of fluorochemical surface modified nanoparticles to the substrate, wherein the aqueous dispersion comprises at least one of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures; and wherein the fluorochemical is as disclosed herein; and (ii) drying the substrate.
• the fluorochemical surface modified nanoparticles can be applied either on one or more surfaces or on the wet end so that it is in the interior of the substrate or a combination of these.
• the nanoparticle according to this disclosure can comprise silica, titania, zirconia, layered magnesium silicates, aluminosilicates, clays and mixtures thereof, for example the clay can be a synthetic clay such as hectorite clay.
• a useful combination of nanoparticles for surface modification can be, for example, a mixture of synthetic hectorite clay and silica.
• fluorochemical surface-modified nanoparticles including the fluoroalkylsilyl surface-modified nanoparticles, can be present at a concentration in the range of from about 0.01% to about 50% by weight of the total composition of the dispersion, for example in the range of from about 1% to about 40% by weight, including about 1% to about 8% by weight of the total composition.
• the fluorochemical surface-modified nanoparticles can be present at a concentration (by weight of the total composition of the dispersion) of about 0.01%, about 0.02%, about 0.05%, about 0.1%, about 0.2%, about 0.5%, about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12%, about 15%, about 18%, about 20%, about 25%, about 30%, about 30%, about 40%, about 50%, or about 50%, or any range between any of these concentrations.
• stable aqueous dispersions of fluorochemical surface modified nanoparticles wherein the nanoparticles are synthetic hectorite clay can be formed at a concentration in the range of from about 0.01% to about 12% by weight of the total composition, including about 1% to about 8% by weight of the total composition.
• the dispersion of the present invention can be diluted for more efficient application or to control the level of moisture imparted in the treatment process.
• other chemistries as may be known in the art can be combined with the aqueous dispersion of the instant invention at suitable concentration ranges.
• the composition can further comprise a fluorinated resin emulsion, an alkylated inorganic nanoparticle having no fluorine, and/or at least one member selected from a wetting agent, fluorochemical resin, surfactant, silicones, optical brighteners, antibacterial components, anti-oxidant stabilizers, coloring agents, light stabilizers, UV absorbers, wetting agents, starch, polyvinyl alcohol, retention aids and wet strength aids and mixtures thereof.
• the composition can be blended with additional wetting agents, anti-soil agents, fluorochemical resins, surfactants or mixtures thereof, as known in the art, in order to simplify the manufacturing process at hand. While the aqueous dispersion is generally compatible, it is naturally desirable to avoid the addition of materials that would coalesce or precipitate the nanoparticles or otherwise diminish efficacy or utility.
• the disclosed dispersions are found to be surprisingly stable and exist indefinitely at moderately high concentrations as transparent aqueous mixtures in spite of the intrinsically hydrophobic nature of fluorochemical modified surfaces, such as fluoroalkylated surfaces.
• the compositions can be useful to treat soft paper, paperboard and cellulose fiber articles, either applied to one or both sides on the dry end such as a size press or coater, or to the wet end such that the chemistry is throughout the article, or in both the dry and wet ends of the papermaking process, to impart several valuable attributes. Paper, paperboard and cellulose fiber articles treated with the various dispersions described have also been shown to have increased oil and grease repellency.
• fluoroalkylsilyl Surface-Modified Nanoparticles include but are not limited to fluoroalkylsilane having the formula:
• a process for making and using an aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles typically comprising: a) combining in an aqueous medium a nanoparticle component and a fluoroalkylsilane to form a heterogeneous mixture, and b) allowing the nanoparticle component and the fluoroalkylsilane in the heterogeneous mixture to react until the heterogeneous mixture forms a homogeneous aqueous dispersion of fluoroalkylsilane surface-modified nanoparticles.
• the fluoroalkylsilane surface-modified nanoparticles can comprise fluoroalkylsilyl moieties having the formula [F(CF 2 ) n CH 2 CH 2 ] m Si(O—) p .
• the step of combining in an aqueous medium a nanoparticle component and a fluoroalkylsilane can be carried out by preparing an aqueous dispersion of the nanoparticle component, followed by combining or adding the fluoroalkylsilane, as exemplified in the Examples provided herein.
• the step of combining in an aqueous medium a nanoparticle component and a fluoroalkylsilane can further comprises combining a non-fluorinated alkylsilane having the formula:
• X in each occurrence is independently halide or R 2 .
• the fluoroalkylsilane surface-modified nanoparticles can comprise non-fluorinated alkylsilyl moieties having the formula [H(CH 2 ) x ] y Si(O—) z or [H(CH 2 ) x ] y Si( ⁇ ) z or [H(CH 2 ) x ] y Si (O—) z (—) q , wherein “—” is a direct silicon-nanoparticle bond and y+z+q is 4, along with the fluoroalkylsilyl moieties having the formula [F(CF 2 ) n CH 2 CH 2 ] m Si(O—) p .
• this disclosure provides for a process for making oil repellent cellulosic material, the process comprising contacting or treating a cellulosic substrate with the an aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles prepared as diclosed herein.
• a process for making oil repellent cellulosic material comprising contacting a homogeneous aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles with a cellulosic substrate to form an oil repellent cellulosic material, in which the aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles is provided by combining in an aqueous medium a nanoparticle component and a fluoroalkylsilane to form a homogeneous aqueous dispersion comprising fluoroalkylsilane surface-modified nanoparticles, the fluoroalkylsilane having the formula [F(CF 2 ) n CH 2 CH 2 ] m Si(OR) p , as set forth herein.
• the step of combining in an aqueous medium a nanoparticle component and a fluoroalkylsilane can further comprises combining a non-fluorinated alkylsilane having the formula [H(CH 2 ) x ] y Si(OR 2 ) z , as disclosed herein.
• Suitable nanoparticle components used according to this disclosure include at least one member selected from silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures or combinations thereof.
• a further aspect provided is a process for making a fluoroaklysilyl surface modified nanoparticle selected from silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, the process comprising: (i) creating an aqueous dispersion of at least one member selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof; (ii) adding a water immiscible fluoroalkylsilane reagent to the aqueous dispersion to form a heterogeneous mixture where the fluoroalkylsilane reagent is: (F(CF 2 ) n
• the fluoroalkylsilane can be (F(CF 2 ) n CH 2 CH 2 ) m Si(O—R) p , where n can be 4, p can be 3 when m is 1 and R can be selected from methyl and ethyl.
• the nanoparticle can comprise silica, titania, zirconia, layered magnesium silicates, aluminosilicates, clays and mixtures thereof, for example the clay can be a synthetic hectorite clay, for example a mixture can be synthetic hectorite clay and silica.
• the fluoroalkylsilane moieties can be covalently bonded to the nanoparticle surface, creating a fluoroalkylsilyl moiety.
• the process of making an oil repellent cellulosic material also may comprise: a) applying or contacting a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles to a cellulosic substrate to form a treated cellulosic substrate; and b) drying the treated cellulosic substrate to form an oil repellent cellulosic material, and can further comprise adding a fluorinated resin emulsion to the aqueous dispersion prior applying the aqueous dispersion to the cellulosic substrate.
• the process can further comprise including an alkylated inorganic nanoparticle having no fluorine in the aqueous dispersion prior applying the aqueous dispersion to the cellulosic substrate.
• the process can further comprise adding at least one member selected from the group consisting of a wetting agent, anti-soil agent, fluorochemical resin, surfactant and mixtures thereof prior applying the aqueous dispersion.
• the fluoroalkyl moiety of the alkylsilane reactant can be a perfluoroalkane of two to four carbons in length, for example a four carbon nanofluoroalkane (n is 4), where m is 1 and p is 3, and where R is either methyl or ethyl.
• Extended perfluoroalkane chains can be used to achieve greater degrees of hydrophobicity in treated substrates.
• fluoroalkylsilyl reagents having perfluoroalkane chains longer than four carbon atoms are less suitable for making the disclosed aqueous dispersions as the addition of undesirable levels of solvents or surfactants would be required to stabilize both reactants and product dispersions in the disclosed process.
• 1,1,2,2-tetrahydro-nonafluorohexyl trimethoxysilane can be added slowly with stirring to a 25% (w/w) aqueous dispersion of colloidal silica (20 nm particles) with pH 9 to form a liquid-liquid emulsion of cloudy appearance.
• a recirculation pump and static mixer can be used with or without the mechanical stirrer to increase interfacial contact of the FAS with the colloidal silica if desired.
• the fluoroalkylsilyl minor liquid phase is consumed with stirring over a period of hours gradually reducing to a single liquid phase dispersion that remains stable in the absence of stirring.
• the resulting stable aqueous dispersion contains dispersed silica nanoparticles that have a covalently bonded hydrophobic layer on the particle surface, and this aqueous dispersion is used to treat or contact the cellulosic substrate.
• 1,1,2,2-tetrahydro-nonafluorohexyl trimethoxysilane (the “FAS” or fluoroalkylsilyl reagent) can be used (for example, added slowly to) a 5% (w/w) aqueous dispersion of synthetic hectorite clay nanoparticles sold by the trade name Laponite® RDS from Rockwood Additives Ltd.
• Laponite® RDS from Rockwood Additives Ltd.
• the dispersion of the present invention can be blended with fluorinated resin emulsions or with dispersions of alkylated inorganic nanoparticles having no fluorine.
• the dispersions of the fluoroalkyl modified clay nanoparticles described above can be blended with an aqueous dispersion of colloidal silica nanoparticles which have been surface modified with methyltrimethyoxysilane (MTMS) so that the resulting aqueous dispersion comprises two distinctly different nanoparticles.
• MTMS methyltrimethyoxysilane
• the substrate can comprise a fluoroalkylsilyl surface-modified nanoparticle on at least one surface, wherein the nanoparticle comprises at least one member selected from the group consisting of: titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof, and wherein the fluoroalkylsilyl is: (F(CF 2 ) n CH 2 CH 2 ) m Si(O—) p , where n is 2, 3 or 4, p is 1, 2 or 3, and m is (4-p).
• the nanoparticle of the present invention can comprise titania, zirconia, layered magnesium silicates, aluminosilicates, clays and mixtures thereof, for example the clay can be a synthetic hectorite clay, for example a mixture can be synthetic hectorite clay and zirconia.
• the fluoroalkylsilyl surface-modified nanoparticle can comprise (F(CF 2 ) n CH 2 CH 2 ) m Si(O—) p , where n can be 4, p can be 3 when m is 1, in which the fluoroalkylsilyl moiety can be covalently bonded to the nanoparticle surface.
• the substrate can have pores having an average diameter in the range of from about 100 to about 100,000 nanometers.
• the fluoroalkylsilane surface modified nanoparticle can form at least one layered structure on the substrate, wherein the layered structure has a thickness of about 10,000 nanometers or less, and a width and length of about 100,000 nanometers or more.
• the substrate can optionally comprise a component moiety bonded to the surface of the nanoparticle having the formula [H(CH 2 ) x ] y Si(O—) z , wherein x is an integer from 1 to 12, y is 4-z, and z is 1, 2, or 3.
• the nanoparticle can include silica, titania, zirconia, layered magnesium silicates, aluminosilicates, clays and mixtures thereof.
• a process for making an oil repellent cellulosic material comprising: a) applying a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles to a cellulosic substrate to form a treated cellulosic substrate; and b) drying the treated cellulosic substrate to form an oil repellent cellulosic material; wherein the fluorochemical can comprise or be selected from at least one cationic fluorochemical.
• the ionic bonds can be formed between the anionic nanoparticles and the cationic fluorochemicals.
• This disclosure also provides for a process for making an oil repellent cellulosic material, the process comprising the steps of: a) applying a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles (also termed nanoparticles that are surface-modified by a fluorochemical) to a cellulosic substrate to form a treated cellulosic substrate; and b) drying the treated cellulosic substrate to form an oil repellent cellulosic material, in which the fluorochemical can comprise or can be selected from at least one cationic fluorochemical.
• a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles also termed nanoparticles that are surface-modified by a fluorochemical
• suitable cationic fluorochemicals can comprise or be selected from compounds such as those disclosed in GB 1,214,528, which is incorporated by reference herein in its entirety.
• the cationic fluorochemical can be a fluorinated cationic polyamidoamine such as a protonated, an alkylated, or an epoxidized amide-amine fluoro compound, resulting from a protonation reaction, an alkylation reaction, or the reaction of an epihalohydrin with an intermediate amide-amine fluoro compound of the formula:
• Z is a radical selected from perfluoro alkyl radicals of the formula C s F (2s+1) , where s is an integer having a value of from 3 to 20 inclusive, and cycloperfluoro alkyl radicals of the formula C t F (2t ⁇ 1) , where t is an integer having a value of from 4 to 6 inclusive;
• X is a radical selected from straight chain alkylene radicals of the formula (CH 2 ) p , where p is an integer having a value of from 2 to 14 inclusive, cycloaliphatic radicals, bridged cycloaliphatic radicals, —CH ⁇ CH—(CH 2 ) b —O—(CH 2 ) 2 —, —CH 2 —CH 2 —(CH 2 ) b —O—(CH 2 ) 2 —, —CH ⁇ CH—(CH 2 ) b —S—(CH 2 ) 2 —, —CH 2 —CH 2 —(CH 2 ) b —S—(CH 2 ) 2 — radicals, where b is zero or an integer of from 1 to 14 inclusive and —SO 2 —N(R)—(CH 2 ) q — radicals, where R is an alkyl radical containing from 1 to 6 carbon atoms and q is an integer of from 2 to 12 inclusive;
• y is 0 or 1
• n is an integer of from 2 to 6 inclusive
• n is an integer of from 2 to 100 inclusive.
• the cationic fluorochemical can be an epoxidized amide-amine fluoro compound, resulting from the reaction of an epihalohydrin with the intermediate amide-amine fluoro compound disclosed above, having the formula Z—(X) y —C(O)—NH[(CH 2 ) m —NH] n —C(O)—(X) y —Z. While not intending to be bound by theory, it is thought that the product initially resulting from the reaction between the epihalohydrin and the fluoro intermediate described immediately above may corresponds to the following formula:
• A is a halogen radical and Z, X, y, m and n are as previously defined.
• Z, X, y, m and n are as previously defined.
• the above described initial reaction product condenses through its epoxide group with additional quantities of the epihalohydrin, thereby likely assuming a more complex structure.
• the intermediate amide-amine fluoro compound of the formula Z—(X) y —C(O)—NH[(CH 2 ) m —NH] n —C(O)—(X) y —Z can be prepared by admixing and subsequently reacting a fluoro acid corresponding to the formula Z—(X) y —C(O)OH with at least one polyamine of the formula H 2 N—[(CH 2 ) m —NH] n H, wherein Z, X, y, m and n are as previously defined.
• suitable cationic fluorochemicals include those generated from perfluorooctanoic acid reacting with tetraethylenepentamine, and then with epichlorohydrin, to provide the cationic fluorochemical as illustrated in the following structure:
• the amide nitrogen is no longer available for protonation.
• more amide may be used after the fluorocarbon tail is attached.
• the alkylation with fluorinated epoxides is used to prepare the azetidinium moieties.
• suitable fluoro carboxylic acids (Z—(X) y —C(O)OH) used to prepare the cationic amido-amine fluoro compounds include, but are not limited to: perfluorobutanoic acid, (C 3 F 7 COOH); perfluorooctanoic acid (C 7 F 15 COOH); omega-perfluoroheptyl pentanoic acid (C 7 F 15 (CH 2 ) 4 COOH); omega-perfluoroheptyl undecanoic acid (C 7 F 15 (CH 2 ) 10 COOH); perfluoroheptyl methyl cyclobutane carboxylic acid; perfluoroheptyl substituted norbornene carboxylic acid; omega-perfluoroheptyl-beta-allyloxy-propionic acid (C 7 F 15 —CH ⁇ CHCH 2 —O—(CH 2 ) 2 COOH); omega-perfluoroheptyl-beta-propoxypropionic acid (C
• the polyamine compounds applicable for use in preparing the cationic amido-amine fluoro compounds include, but are not limited to H 2 N—[(CH 2 ) m —NH] 4 H wherein m is an integer of from 2 to 6 inclusive and n is an integer of from 2 to 100 inclusive, and can include combinations of compounds according to this formula.
• diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and bis-hexamethylenetriamine although these representative compounds are only exemplary. More than one of the polyamines corresponding to the above formula may be simultaneously utilized in the reaction system. If desired, crude residues containing mixtures of amines as the polyamine starting material can be employed.
• both linear and branched structures of the polyamine are envisioned.
• the polyamine compound contains two or more primary amine groups and the value of n exceeds about 8, it is likely that the resulting polyamine will exhibit a branched structure, such branched polyamines also being deemed readily applicable for use according to this disclosure.
• epihalohydrins including epichlorohydrin and epibromohydrin, may be utilized in accordance with this disclosure, with epichlorohydrin being preferred for reasons of economy and availability.
• Conditions under which the amide-amine fluoro compound can be epoxidized from the reaction of an epihalohydrin include those conditions as disclosed in GB 1,214,528, which is incorporated by reference herein in its entirety.
• suitable cationic fluorochemical for use according to this disclosure include those provided in U.S. Pat. No. 4,344,993, which is incorporated herein by reference in its entirety.
• ionic perfluorocarbons described in U.S. Pat. No. 4,344,993 can be used.
• These ionic perfluorocarbons that can be suitably employed include organic compounds generally represented by the formula:
• R f is a saturated fluoroaliphatic moiety containing a F 3 C-moiety and Z is a ionic moiety or a potentially ionic moiety.
• the fluoroaliphatic moiety can typically contain 3 to 20 carbons wherein substantially all are fully fluorinated, preferably from about 3 to about 10 of such carbons.
• This fluoroaliphatic moiety may be linear, branched or cyclic, preferably linear, and may contain an occasional carbon-bonded hydrogen or halogen other than fluorine, and further may contain a divalent sulfur or oxygen atom or a trivalent nitrogen atom bonded only to carbon atoms in the skeletal chain. More preferred are those linear perfluoroaliphatic moieties represented by the formula:
• n can be from about 3 to about 12, for example, from 5 to 10.
• Ionic or potentially ionic moieties advantageously further include those represented by the following formulas:
• the suitable cationic fluorochemical can be a cationic perfluorocarbon, including for example, 3-[((heptadecylfluorooctyl)sulfonyl)amino]-N,N,N-trimethyl-1-propanaminium iodide; 3-[((heptadecylfluorooctyl)carbonyl)amino]-N,N,N-trimethyl-1-propanaminium chloride, and/or a cationic perfluorocarbon sold by duPont under the tradename ZonylTM FSC.
• a cationic perfluorocarbon including for example, 3-[((heptadecylfluorooctyl)sulfonyl)amino]-N,N,N-trimethyl-1-propanaminium iodide; 3-[((heptadecylfluorooctyl)carbonyl)amino]-
• cationic fluorochemicals include but are not limited to those provided in U.S. Pat. No. 6,951,962, which is incorporated herein by reference in its entirety.
• suitable cationic fluorochemicals include those compounds having an oleophobic and hydrophobic fluorochemical group, which is substituted with an alkyl chain which has a hydrophilic group, where the fluorochemical portion of the fluorochemical group is further characterized as a monovalent, perfluorinated, alkyl or alkenyl, straight, branched or cyclic organic radical having three to twenty fluorinated carbon atoms, and which can be interrupted by divalent oxygen or sulfur atoms if desired.
• suitable cationic fluorochemical compounds include those that contains both a polyamine functionality and fluorinated groups.
• the polyamine can provide a type of molecular scaffolding upon which the fluorinated group and the cationic functionality are included or assembled.
• the polyamine functionality also can allow the nitrogens to be substituted with four groups such that they have a cationic character which aids in their function in accordance with the disclosure, for example, allows for interaction with the negatively charged nanoparticles.
• the fluorinated groups included in the cationic fluorochemical compounds may reduce the surface energy to the point that oil and grease will not wet the cellulosic substrate to which the homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles is applied.
• the low free surface energies are thought to make them particularly effective at repelling low surface energy materials such as oil and grease, thus repelling these substances from a treated substrate.
• the cationic fluorochemical compounds can include or be selected from those disclosed in U.S. Pat. No. 6,951,962, which is incorporated herein by reference in its entirety.
• suitable cationic fluorochemicals include those having the following structures:
• anionic fluorochemicals are possible because of ionic bonds between anionic nanoparticles and anionic fluorochemicals can be established through an intermediate cationic polymer.
• the anionic nanoparticles are modified first with a cationic non-fluorinated polymer, such as polyamines, polyamidoamines, polyamidoamine epichlorohydrine (PAE), polyDADMAC, cationic polyacrylamide, and combinations thereof.
• PAE polyamidoamine epichlorohydrine
• PAE polyDADMAC
• cationic polyacrylamide cationic polyacrylamide
• a process for making an oil repellent cellulosic material comprising: a) applying a homogeneous aqueous dispersion of fluorochemical surface-modified nanoparticles to a cellulosic substrate to form a treated cellulosic substrate; and b) drying the treated cellulosic substrate to form an oil repellent cellulosic material; wherein the fluorochemical comprises at least one fluorinated polyacrylate.
• association of a fluorochemical with the rigid nanoparticle occurs by polymerization on the nanosized seed particles, and the resulting association of the nanoparticle with the fluorinated polymer such as a fluorinated polyacrylate can occur. Therefore, this seeded emulsion polymerization can be used for the copolymerization of fluorinated acrylates and other fluorinated monomers and co-monomers on the nanoparticles, including along with co-monomers that are not fluorinated.
• the nanoparticles can be surface-modified with a fluorochemical that comprises or is selected from a polymeric fluoro compound, such as perfluorinated polyacrylates and perfluorinated polyurethanes (core-shell structure).
• a fluorochemical can be both an oleophobe and a hydrophobe.
• the substrate can be a paper, paperboard or cellulose fiber or cellulose based article wherein the composition imparts the same level of oil and grease repellency with lower levels of elemental fluorine used compared with coatings of traditional fluorochemical resin emulsions.
• Substrates coated or containing internally, or a combination of both with the present invention have been found to exhibit superior oil and grease repellency with less elemental fluorine than found in coatings of traditional fluorochemical resins.
• the process of making the substrate with the aqueous dispersion of nanoparticles comprises applying the aqueous dispersion of fluororalkylsilyl surface modified nanoparticles to a substrate; and drying the substrate.
• an article comprises a composition, the composition comprising the fluoroalkylsilyl surface-modified nanoparticle described herein.
• the nanoparticle can comprises at least one member selected from the group consisting of titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay and mixtures thereof, and the fluoroalkylsilyl moiety can be as disclosed herein.
• the nanoparticle can further comprise a non-fluorinated alkylsilyl moiety also as disclosed herein.
• Articles can include but are not limited to paper, paperboard, cellulose fiber articles, and other cellulose based articles.
• the article is paper, paperboard, cellulose fiber, or cellulose based articles, or includes the optional non-fluorinated alkylsilyl moieties
• the nanoparticles can also include silica.
• the articles can comprise a total concentration of fluorine in a range of from about 10 ppm to about 500 ppm by weight (w/w) of exposed substrate, including about 50 ppm to about 300 ppm w/w of exposed substrate.
• the substrate retains the fluoroalkylsilyl surface modified nanoparticle at a weight in the range of from about 0.01% to about 2.0% by weight of the exposed substrate, including from about 0.1% to about 1.0% by weight of the exposed substrate; or wherein the substrate retains elemental fluorine in the range of from about 0.0001% to about 0.10% by weight of the exposed substrate, including from about 0.0001% to about 0.010% by weight of the exposed substrate.
• the substrate can retain fluoroalkylsilyl surface modified nanoparticles in the range of from about 0.01 to about 3 grams per square meter of surface area, including from about 0.1 to about 2 grams per square meter of surface area.
• compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components or steps.
• nanoparticle is used to describe a multidimensional particle in which one of its dimensions is less than 100 nm in length.
• FAS fluoroalkylsilane reagents used to impart fluorinated organic functionality including, but not limited to, the inorganic particles of this invention.
• clay refers to a clay mineral, such as hydrous aluminum phyllosilicate minerals.
• Clay minerals that can be used in this disclosure include 1:1 and 2:1 clays, and can comprise, consist essentially of, or be selected from smectites (such as montmorillonite, nontronice, sapolite, and the like), kaolins (such as kaolinite, dickite, halloysite, nacrite, and the like), illites (such as illite, clay-micas and the like), chlorites (such as clinochlore, chamosite, nimite, pennantite, and the like), and other minerals and classes such as attapulgites, sepiolites, and the like.
• smectites such as montmorillonite, nontronice, sapolite, and the like
• kaolins such as kaolinite, dickite, halloysite, nacrite, and the like
• illites such as illite,
• clays of the invention may be either synthetic or natural and are exfoliated to be capable of forming aqueous micro dispersions.
• An example of one embodiment of the present invention uses synthetic hectorite clay nanoparticles sold by the trade name Laponite® from Rockwood Additives Ltd.
• Preferred embodiments of the present invention use Laponite RDS®, Laponite JS®, and Laponite RD®.
• the term “clay” can refer to a clay mineral, such as hydrous aluminum phyllosilicate minerals, and can include 1:1 and 2:1 clays, and can comprise, consist essentially of, or be selected from smectites (such as montmorillonite, nontronice, sapolite, and the like), kaolins (such as kaolinite, dickite, halloysite, nacrite, and the like), illites (such as illite, clay-micas and the like), chlorites (such as clinochlore, chamosite, nimite, pennantite, and the like), and other minerals and classes such as attapulgites, sepiolites, and the like.
• smectites such as montmorillonite, nontronice, sapolite, and the like
• kaolins such as kaolinite, dickite, halloysite, nacrite, and the like
• illites such as illite, clay-mica
• An aqueous “dispersion” means a colloidal dispersion, which is a system of finely divided particles of small size, such as nanoparticles, which are uniformly dispersed in a manner such that they are not easily filtered or gravitationally separated.
• aqueous “micro dispersion” is used to describe a dispersion of particles predominately having at least one dimension that is less than about 100 nm in extent.
• a “non-solubilized” aqueous micro dispersion is an aqueous micro dispersion that is stable for extended periods of time (two or more months) without water compatible surfactants.
• a “layered structure” is one in which the overlap of nanoparticles is observed, and where flat layers or sheets are observed rather than round, globular or clumped aggregate structures.
• cellulosic material or similar terms such as “cellulose fiber material” or “cellulose material” are typically used to refer to paper, paperboard, and cellulose fibers at any stage of their use, for example, being used in the preparation of paper and paperboard.
• hydrocarbyl is used herein in accordance with the definition specified by IUPAC: a univalent group formed by removing a hydrogen atom from a hydrocarbon (that is, a group containing only carbon and hydrogen).
• hydrocarbyl groups include linear, branched, and cyclic hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclopentyl, vinyl, and the like.
• alkyl group is used herein in accordance with the definition specified by IUPAC: a univalent group derived from an alkane by removal of a hydrogen atom from any carbon atom, having the formula —C n H 2n+1 .
• the alkyl can include groups derived from an alkane by removal of a hydrogen atom from a primary, secondary, or tertiary carbon. Therefore, unless otherwise specified, non-limiting examples of alkyl groups include linear, branched, and cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, cyclopentyl, and the like.
• any carbon-containing group for which the number of carbon atoms is not specified can have, according to proper chemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms, or any range or combination of ranges between these values.
• any carbon-containing group can have from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20 carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, or from 1 to 5 carbon atoms, and the like.
• other identifiers or qualifying terms may be utilized to indicate the presence or absence of a particular substituent, a particular regiochemistry and/or stereochemistry, or the presence of absence of a branched underlying structure or backbone.
• TAPPI testing methods including but not limited to T454 om-89 Turpentine Test for Grease Resistance of Paper, T507 cm-85 Grease resistance of Flexible Packaging Materials, T441 om-90 Water Absorptiveness of Sized (Non-Bibulous) Paper and Paperboard (Cobb test), UM 557 Repellency of Paper and Board to Grease, Oil and Waxes (Kit test), can be used.
• Paper having a basis weight of 34 g/m 2 was passed through a size-press solution for 15 seconds and dried at 105° C. for 20 seconds on a drum dryer. The dried paper was conditioned for at least 24 hours at 25° C. and 50% humidity before testing. The paper was tested by measuring the contact angle for Castor oil as a function of time using a Rame-Hart goniometer Model 250.
• Uncoated paper was tested by measuring the contact angle as described and was found to exhibit an initial oil contact angle of 30 degrees. After 30 seconds contact time, the contact angle decays down to 19 degrees. This changed reflects the strong oil absorption into the paper.
• Paper treated in a size-press with a solution of 1% fluorochemicals shows an initial contact angle for Castor oil of 60 degrees. The contact angle remains unchanged after 30 minutes.
• a process for making an oil repellent cellulosic material comprising:
• the fluorochemical comprises at least one fluoroalkylsilane, ionic fluorochemical, or fluorinated polyacrylate.
• the at least one cationic fluorochemical is selected from an amine, a polyamine, a quaternary ammonium salt, or a combination thereof
• the cellulosic substrate comprises a component selected from paper, paperboard, and cellulose fiber.
• the nanoparticle comprises silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN), or combinations thereof
• nanoparticle comprises silica, natural clay, or synthetic clay.
• the nanoparticle comprises at least one clay selected from smectites, kaolins, illites, chlorites, attapulgites, sepiolites, or combinations thereof.
• the nanoparticle comprises montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, halloysite, nacrite, antigorite, illite anauxite, indellite, chrysotile, bravaisite, suscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, polygorskyte, clinochlore, chamosite, nimite, pennantite muscovite, phlogopite, or phengite.
• nanoparticle comprises synthetic hectorite.
• homogeneous aqueous dispersion further comprises an emulsion polymer.
• aqueous dispersion of fluorochemical surface-modified nanoparticles further comprises an alkylated inorganic nanoparticle having no fluorine content.
• aqueous dispersion of fluoroalkylsilane surface-modified nanoparticles further comprises a wetting agent, an anti-soil agent, an anti-stain agent, a fluorochemical resin, a surfactant, a silicone, an optical brightener, an antibacterial component, an anti-oxidant stabilizer, a coloring agent, a light stabilizer, a UV absorber, starch, polyvinyl alcohol, a retention aid, a wet strength aid, or any combination thereof
• a process for making an oil repellent cellulosic material comprising:
• the fluorochemical comprises at least one fluoroalkylsilane, ionic fluorochemical, or fluorinated polyacrylate.
• the at least one ionic fluorochemical is selected from an amine, a polyamine, a quaternary ammonium salt, a cationic fluorochemical comprising azetidinium groups, or a combination thereof
• the cellulosic substrate comprises a component selected from paper, paperboard, and cellulose fiber.
• the nanoparticle comprises silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN), or combinations thereof
• the nanoparticle comprises at least one clay selected from smectites, kaolins, illites, chlorites, attapulgites, sepiolites, or combinations thereof.
• the nanoparticle comprises montmorillonite, bentonite, pyrophyllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, halloysite, nacrite, antigorite, illite anauxite, indellite, chrysotile, bravaisite, suscovite, paragonite, biotite, corrensite, penninite, donbassite, sudoite, pennine, sepiolite, polygorskyte, clinochlore, chamosite, nimite, pennantite muscovite, phlogopite, synthetic hectorite, or phengite.
• homogeneous aqueous dispersion further comprises an emulsion polymer or a fluorinated resin emulsion.
• the aqueous dispersion of fluorochemical surface-modified nanoparticles further comprises a wetting agent, an anti-soil agent, an anti-stain agent, a fluorochemical resin, a surfactant, a silicone, an optical brightener, an antibacterial component, an anti-oxidant stabilizer, a coloring agent, a light stabilizer, a UV absorber, starch, polyvinyl alcohol, a retention aid, a wet strength aid, an alkylated inorganic nanoparticle having no fluorine content. or any combination thereof.
• An article comprising an oil repellent cellulosic material made by a process comprising:

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• 2013
  • 2013-10-09 US US14/049,346 patent/US20140106165A1/en not_active Abandoned
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