US20140102651A1

US20140102651A1 - Greaseproof paper with lower content of fluorochemicals

Info

Publication number: US20140102651A1
Application number: US14/049,337
Authority: US
Inventors: James W. Johnston; David F. Townsend; Cornel Hagiopol; Lakeisha D. Talbert; Charles G. Ruffner
Original assignee: Georgia Pacific Chemicals LLC
Current assignee: Ecolab USA Inc
Priority date: 2012-10-12
Filing date: 2013-10-09
Publication date: 2014-04-17
Also published as: WO2014059121A1; BR112015008058A2; CL2015000914A1; CN104903515A; CN104903515B; EP2906752A1; EP2906752A4; MX2015004647A; CA2887362A1; KR20150068967A

Abstract

Methods for making and using aqueous dispersions for imparting grease/oil resistance to paper, paperboard and cellulose fiber products generally are provided. In particular, there are provided aqueous colloidal dispersions comprising nanoparticles of at least one colloidal clay and an aqueous fluorochemical, which can be applied to, on, or in paper, paperboard and cellulose fiber products. The paper and products that have been modified using these aqueous dispersions have good resistance to oil and grease penetration with lower overall amounts of aqueous fluorochemicals being required. Additional methods for imparting grease/oil resistance to paper, paperboard and cellulose fiber products generally are provided. In particular, there is provided a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising: a) applying a pretreatment composition comprising a cationic polymer to a cellulose fiber material in a size press to form a pretreated cellulose substrate; b) drying the pretreated cellulose substrate; and c) applying a fluorochemical composition to the dry pretreated cellulose substrate to form an oil-repellent cellulose fiber material.

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application No. 61/713,346, filed Oct. 12, 2012, the disclosure of which is incorporated by reference herein in its entirety.

TECHNICAL FIELD

The invention relates to grease/oil resistant paper and methods for making grease/oil resistant paper.

BACKGROUND OF THE INVENTION

Paper is a composite material containing small, interconnected discrete fibers, which typically 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. For example, the specific area of paper can be about 0.5-10 m²/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/cm³.
Just as paper products made from untreated cellulose fibers that become wet lose their strength rapidly due to water penetration, the porous structure of paper can also lead to its penetration by oil, grease, organic solvents, and the like. Conventionally, materials such as waxes, silicones, or fluorochemicals have been applied topically to cellulose fiber products to provide some measure of oil and grease resistance. However, environmental and health concerns about C8 telomer-based water and oil repellent products used in conventional fluorochemical treatments has required converting the C8 telomer fluorochemicals to C6 telomer and perfluoropolyether (PFPE) fluorochemicals, which are thought to have lower risk of degradation into products harmful to the environment. These latter fluorochemicals are somewhat less efficient at oil and grease resistance, and the conversion process itself is inefficient, costly, and time-consuming.
Therefore, there is a continuing need in the art for improved methods and compositions for imparting oil and grease resistance to paper and paper products, particularly those that involve the use of lower concentrations of fluorochemicals for environmental and cost improvements. This need is increasing with the increased demand for grease/oil resistant paper for use with bakery products, pet food packaging, instant and fast foods, and the like. Desirable methods would be applicable to a wide range of paper products and provide more environmentally benign manufacturing processes, while still maintaining efficient performance for oil and grease resistance.

SUMMARY OF THE INVENTION

According to this disclosure, there is provided a process for improving the grease- or oil-repellency of a cellulose fiber material such as paper or paperboard, the process comprising treating or contacting a cellulose fiber material with an aqueous dispersion comprising at least one nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose fiber material. The process can further comprise curing the oil-repellent cellulose fiber material once prepared. It has been discovered that the combination of both at least one nanoparticle component and at least one fluorochemical provides an unexpected improvement in the oil-repellent characteristics of the cellulose fiber material, while still allowing a lower overall concentration of fluorochemical to impart the oil-repellency. In another aspect, it has been found that the combination of both at least one nanoparticle component and at least one fluorochemical provides comparable oil-repellent characteristics of the cellulose fiber material using a lower concentration of fluorochemical to impart the oil-repellency. Therefore, it appears that the at least one nanoparticle component acts as an 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.
According to a further aspect, and while not intending to be bound by theory, it is thought that the combination of at least one nanoparticle component and at least one fluorochemical acts to alter the paper or paperboard (cellulose fiber material) surface geometry and surface energy, which enhances the grease- and oil-repellency properties. It is also believed that the fluorochemicals can function in a synergistic fashion in combination with the nanoparticles in a manner that combines the useful attributes of the individual components. Suitable nanoparticles include inorganic nanoparticles (such as silica, clay minerals, other inorganic nanoparticles, and combinations), organic polymer nanoparticles (polystyrene, styrene acrylonitrile (SAN), and the like) having a glass transition temperature (Tg) greater than 100° C.; or combinations thereof. Suitable fluorochemicals include conventional and unconventional fluorochemicals such as fluorinated small molecule, polymers, or copolymers that are useful in providing some oil-repellency and/or water-repellency.
It also has been discovered that sequential applications of inorganic nanoparticles followed by fluorochemicals works to provide an oil-repellent paper with smaller overall amounts of fluorochemicals that are typically required. In this aspect, it is thought that the initial nanoparticle application, typically carried out using an aqueous dispersion comprising at least one inorganic nanoparticle component and a film-forming polymer, imparts a nanoparticle physical barrier or surface treatment to the paper, which when followed by the subsequent fluorochemical treatment, operates to retain the fluorochemical substantially at the surface. This surface effect may explain why anionic fluorochemicals work very well in the disclosed processes, because the application of a cationic pre-coat to the paper, followed by the anionic fluorochemical is expected to effectively immobilize the fluorochemical at the surface.
Therefore, in one aspect, this disclosure provides a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising contacting a cellulose fiber material with an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose fiber material. The process can further comprise curing the oil-repellent cellulose fiber material.
In a further aspect, there is provided a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising: a) forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and b) contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material. If desired, the aqueous dispersion can further comprise a cationic polymer and/or the aqueous dispersion can further comprise a film-forming polymer.
According to yet another aspect, there is provided a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising: a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose fiber material In this aspect, the first aqueous dispersion, the second aqueous dispersion, or both can further comprise a cationic polymer and/or the aqueous dispersion can further comprise a film-forming polymer.
Still a further process is provided for improving the oil and grease resistance of a cellulose fiber material, the process comprising: a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising at least one fluorochemical to form an oil-repellent cellulose fiber material; wherein contacting step b) is carried out simultaneous or subsequent to contacting step a). Similarly in this aspect, the first aqueous dispersion, the second aqueous dispersion, or both can further comprise a cationic polymer and/or the aqueous dispersion can further comprise a film-forming polymer.
Yet a further aspect of the disclosure provides process for improving the oil and grease resistance of a cellulose fiber material, the process comprising: a) applying a pretreatment composition comprising a cationic polymer, a film-forming polymer, or a combination thereof to a cellulose fiber material to form a pretreated cellulose substrate; b) drying the pretreated cellulose substrate; and c) applying a fluorochemical composition to the dry pretreated cellulose substrate to form an oil-repellent cellulose fiber material.
A paper or paperboard made according to these disclosed processes are also provided. Therefore, another aspect of the disclosure provides a paper or paperboard treated with an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent paper or paperboard.
The following detailed description and appended claims set forth further embodiments and aspects of this disclosure.

DETAILED DESCRIPTION OF THE INVENTION

This disclosure encompasses new compositions, a process to make the compositions, and a process of treating paper and paperboard to impart oil and grease repellency using the disclosed compositions. According to one aspect, this disclosure provides a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising contacting a cellulose fiber material with an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose fiber material. Therefore, in an aspect, the process for improving the oil and grease resistance of a cellulose fiber material, can comprise:

- forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and
- contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material.

In an aspect and some embodiments, this disclosure allows a reduction in the overall usage of fluorochemicals in providing oil-resistant paper, which addresses certain environmental and cost-reduction goals. Thus, it can be understood that oil and grease resistant compositions that reduce the amount of fluorochemicals used, but still retain good oil and grease resistance, are in demand. Therefore, it is desirable to further extend the effectiveness of fluorochemicals and to produce a paper or paperboard or cellulose fiber product with improved stiffness, print clarity, adhesion, release and friction characteristics while still retaining desirable oil and grease repellency and holdout attributes.
This disclosure provides oil and grease resistant aqueous dispersions comprising aqueous dispersions of inorganic nanoparticles that can be combined with traditional paper fluorochemicals. Paper and paperboard and cellulose fiber products treated according to the methods set out herein using the disclosed dispersions show superior oil and grease resistance properties over prior fluorochemical and silicone treated papers and paperboard and cellulose fiber products. Treated paper and paperboard and cellulose fiber products also can show improved stiffness, print clarity, adhesion, release and friction characteristics over prior fluorochemical or silicone treated papers and paperboard and cellulose fiber products. Thus, in an aspect, the nanoparticles appear to operate as a type of fluorochemical extender allowing oil and grease resistant properties on the papers and paperboard and cellulose fiber products at reduced fluorochemical levels on the weight of papers and paperboard and cellulose fiber products.
Inorganic nanoparticles can be particularly effective extenders for fluorochemicals in fluorochemical water and oil and grease resistance treatment compositions directed to papers and paperboard and cellulose fiber products. Specifically, the amount of fluorochemical required for a given oil and grease resistance effect is surprisingly reduced by inclusion of inorganic nanoparticles in the fluorochemical formulation or emulsion, resulting in effective oil and grease resistance at substantially reduced fluorine levels compared to the prior formulations. When papers and paperboard and cellulose fiber products are treated with the disclosed aqueous dispersions, the clay particles are essentially hydrophilic but are still effective as extenders of the hydrophobic properties that would otherwise be expected to depend on the fluorochemical concentration alone. Under certain conditions, aqueous dispersions of inorganic nanoparticles are shown to impart some of the same benefits expected from fluorochemicals alone.
In one aspect, an aqueous dispersion for oil and grease resistance is provided comprising at least one inorganic nanoparticle component and a fluorochemical is provided. In a further aspect, there is provided a process of imparting or improving oil and grease resistance to paper or paperboard by contacting or treating the paper or paperboard with an aqueous dispersion comprising at least one inorganic nanoparticle component and a fluorochemical. The inorganic nanoparticle component can be either natural or synthetic. The fluorochemical can comprise any chemical containing a carbon-fluorine moiety, particularly those fluorochemicals that have been used in conventional methods to impart oil and grease resistance to paper or paperboard.
In another aspect, a cellulose fiber substrate comprising a surface treatment comprising at least one inorganic nanoparticle component and a fluorochemical is provided. The cellulose fiber substrate can be any paper or paperboard type material.
Therefore, and as described in detail, there is provided a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:

- a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and
- b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose fiber material.
  In accordance with another aspect, the disclosure provides for a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
- a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material;
- b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising at least one fluorochemical to form an oil-repellent cellulose fiber material;
- wherein contacting step b) is carried out simultaneous or subsequent to contacting step a).
  In these aspects, the first aqueous dispersion, the second aqueous dispersion, or both can further comprise a cationic polymer and/or the aqueous dispersion can further comprise a film-forming polymer.

Inorganic Nanoparticle Component

An oil and grease resistance aqueous dispersion is disclosed comprising at least one inorganic nanoparticle component and a fluorochemical. The inorganic nanoparticle component can refer to particles substantially comprising or selected from minerals of the following geological classes: silica, smectites, kaolins, illites, chlorites, attapulgites, sepiolites, and combinations thereof. These classes include specific clays such as 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, phengite, and the like, including combinations thereof. The inorganic nanoparticles can be either synthetic or natural, including silica or synthetic hectorite, and Laponite® from Rockwood Additives Ltd. The Laponite® inorganic nanoparticles can be Laponite RD®, Laponite RDS®, Laponite JS®, and Laponite S482®.
In a further aspect, the inorganic nanoparticle (sometimes referred to as simply a nanoparticle or nanoclay when the particle is a clay) can be hydrated or anhydrous silicate minerals having a layered structure and may include, for example, alumino-silicate clays. Exemplary nanoclays include those marketed under the tradename Cloisite™ (marketed by Southern Clay Additives, Inc.). Nanoclays may be exfoliated to separate individual sheets, or may be non-exfoliated, and further, may be dehydrated or included as hydrated minerals. As mentioned, other nano-sized minerals of similar structure may also be included such as, for example, talc, micas including muscovite, phlogopite, phengite, and the like.
As further provided herein, the inorganic nanoparticle component can be present in the aqueous dispersion in an amount from about 0.01% to about 25% weight in solution, including about 1% to about 20%, about 0.05% to about 15%, about 0.01% to about 5%, about 0.05% to about 5%, about 0.5% to about 5%, and about 5% to about 15%.
One aspect provides that the aqueous dispersion comprising the inorganic nanoparticle component and/or inorganic nanoparticle component and the fluorochemical can further comprise a cationic polymer. By way of example, the cationic polymer can comprise or can be selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, and combinations thereof. For example, the cationic polymer can be selected from a polyamidoamine, wherein the polyamidoamine is a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA).
According to a further aspect, the aqueous dispersion comprising the inorganic nanoparticle component and/or inorganic nanoparticle component and the fluorochemical can further comprise a film-forming material, such as a film-forming polymer. The film-forming polymer material can be or can comprise a film-forming semi-crystalline polymer. The film-forming polymer also can be selected from or can comprise, hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, starch derivatives, and combinations thereof. Examples of starch derivatives include, but are not limited to, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and the like, including combinations thereof. Also as an example, suitable polyvinyl alcohols can have an average molecular weight of about 13,000 to about 124,000 Daltons. According to one embodiment, polyvinyl alcohols can have a degree of hydrolysis of from about 80% to about 99.9%. According to another embodiment, polyvinyl alcohols can have a degree of hydrolysis of from about 85% to about 95%. In yet another embodiment or aspect, suitable polyvinyl alcohols can have a degree of hydrolysis of from about 86% to about 90%. Also, according to other embodiments, polyvinyl alcohols can have a viscosity, measured at 20 degree centigrade using a 4% aqueous solution, of from about 2 to about 100 centipoise; alternatively, from about 10 to about 70 centipoise; or alternatively still, from about 20 to about 50 centipoise.
Aspects of this disclosure provide that the inorganic nanoparticle component comprises or is selected from silica. One aspect of this disclosure provides that when inorganic nanoparticle component comprises or is selected from silica, if desired, the silica can be modified with at least one silane coupling agent. Examples of silane coupling agents include, but are not limited to, substituted trialkoxysilanes, cationic polymers, and combinations thereof, and the silane coupling agent can comprises or can be selected from reagents of this type. For example, the silica can be modified with at least one silane coupling agent comprising or alternatively selected from a ureido substituted trialkoxysilane, an amino substituted trialkoxysilane, a sulfur substituted trialkoxysilane, an epoxy substituted trialkoxysilane, a methacryl substituted trialkoxysilane, a vinyl substituted trialkoxysilane, a hydrocarbyl substituted trialkoxysilane, an alkyl substituted trialkoxysilane, a haloalkyl substituted trialkoxysilane, or any combination thereof. As a further example, the silica can be modified with at least one silane coupling agent comprising or alternatively selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrichlorosilane, alkylmethyltrimethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, propyltri(2-methoxyethoxy)silane, and any combination thereof. Any combinations of two or more of these coupling agents are envisioned. Moreover, the silica can be modified with at least one silane coupling agent selected from, or alternatively, comprising, a ureido substituted trialkoxysilane, an amino substituted trialkoxysilane, a sulfur substituted trialkoxysilane, an epoxy substituted trialkoxysilane, a methacryl substituted trialkoxysilane, a vinyl substituted trialkoxysilane, a hydrocarbyl substituted trialkoxysilane, an alkyl substituted trialkoxysilane, a haloalkyl substituted trialkoxysilane, or any combination thereof.
In another aspect, the disclosure provides that when the inorganic nanoparticle component comprises or is selected from silica, the silica can be modified with at least one silane coupling agent, and the aqueous dispersion also can further comprises a cationic polymer. In this aspect, the cationic polymer can be selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine such as a polyamidoamine prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, and combinations thereof.

Fluorochemical Component

Any fluorochemical, whether a traditional or conventional fluorochemical used in the paper industry of not, can be used in the compositions and methods of this disclosure. Generally, the fluorochemical component that can be used in the embodiments of this disclosure can comprise or can be selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, and hybrid fluorochemicals. Therefore, due to the [CF₂]_nmoieties in their structures, fluorochemicals generally show a strong hydrophobicity and low water solubility. To allow them to be used in aqueous solvent systems, the addition of ionic or hydrophilic groups or moieties (anionic, cationic, or nonionic) in the fluorochemical structure are used to impart water solubility or water dispersibility.
By way of example, the fluorochemical can comprise or can be selected from any liquid containing at least one dispersed or emulsified fluorine containing polymer or oligomer. The liquid can also contain other non-fluorine containing compounds. As provided herein, examples of fluorochemical compositions used in the disclosed process include or are selected from anionic, cationic, or non-ionic fluorochemicals such as the fluorochemical allophanates such as disclosed in U.S. Pat. No. 4,606,737; fluorochemical polyacrylates such as disclosed in U.S. Pat. Nos. 3,574,791 and 4,147,85; fluorochemical urethanes such as disclosed in U.S. Pat. No. 3,398,182; fluorochemical carbodiimides such as disclosed in U.S. Pat. No. 4,024,178; and fluorochemical guanidines such as disclosed in U.S. Pat. No. 4,540,497. These listed patents are hereby incorporated by reference in their entireties.
A short chain fluorochemical with less than or equal to six fluorinated carbons per fluorinated side-chain bound to the active ingredient polymer or surfactant also can be used. The short chain fluorochemicals can be made using fluorotelomer raw materials or by electrochemical fluorination. Another fluorochemical that can be used in the disclosed composition is a fluorochemical emulsion sold as Capstone® P-600 or P-620 or P-623 or P-640 (all referred to as “Capstone®”) from DuPont.
In some aspects, suitable fluorochemicals also can comprise or can be selected from fluorinated or perfluorinated polyacrylates, fluorinated or perfluorinated polyurethanes, perfluoropolyethers, compounds with one or two fluorinated or perfluorinated chains including those in the form of carboxylate and phosphate salts (including amphoteric and ammonium salt derivatives), a perfluoroalkyl chain or chains attached to a polar functional group, polytetrafluoroethylene, and perfluoroalkyl substituted carboxylic acids. Examples of perfluoroalkyl substituted carboxylic acid, include, for example, Ciba™ LODYNE™ 2000 sold by Ciba Specialty Chemicals of Tarrytown, N.Y. Fluorochemicals may exhibit oleophobic properties, hydrophobic properties, or both oleophobic and hydrophobic properties. In some embodiments, the fluorochemical is an oleophobe and in other embodiments, the fluorochemical is both an oleophobe and a hydrophobe. Still further embodiments include a fluorochemical that is a hydrophobe. Other suitable fluorochemicals that can be used in the various embodiments of this disclosure include, but are not limited to, perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), polytetrafluoroethylene (PTFE), perfluoro-n-decanoic acid (PFDA), or the like, is used in the processes and methods of this disclosure.
As further provided herein, the percent (%) elemental fluorine in the combined dispersion can be present, for example, in an amount from about 0.0001% to about 5% weight fluorine atoms present in dispersion, including about 0.001% to about 2%, about 0.001% to about 0.8%, about 0.005% to about 0.5%, about 0.005% to about 0.15%, about 0.01% to about 1%, about 0.025% to about 0.5%, and about 0.05% to about 0.5%.
The following is provided to further elaborate the suitable fluorochemicals for use in the disclosed processes.
Anionic Fluorochemicals.
Anionic fluorochemicals, such as fluorinated or perfluorinated carboxylic acids (perfluoroacids), including perfluorinated fatty acids, are suitable fluorochemicals for use according to this disclosure. These anionic fluorochemicals can include fluorocarboxylic acids having an ether bond (perfluoro-ether acids), an example of which is illustrated in the following structure, where the chain length and number of ether linkages and the like can vary:
Other examples of suitable perfluoro-ether acids can include the family of perfluoro-ether acids illustrated in the following structure, where n can be 1 to 6 or greater, for example:
Similarly, a family of anionic fluorochemical having the following C₆-C₁₀perfluorurate-ethyl group can be used to advantage in the methods disclosed herein:
Other useful anionic fluorochemicals in the methods according to this disclosure include, for example, the bis(perfluoroalkyl-alkylthio)alkanoic acids such as those disclosed in U.S. Pat. No. 4,485,251. (“U.S. Pat. No.” is abbreviated “US” throughout.) Phosphate esters, such as those provided in U.S. Pat. No. 3,112,241; U.S. Pat. No. 3,096,207; U.S. Pat. No. 2,597,702; and in S. Fukuda, et al., Nordic Pulp & Paper Research Journal, 20, 496-501 (2005), are useful as well. For example, compounds having the following structure can be used alone or in combination with alkyl ketene dimer (AKD) such as Hercon™ 76, as in U.S. Pat. No. 5,714,266:
Polyfluoroalkyl phosphates can be used in accordance with this disclosure. If desired, a chelating agent such as EDTA can be used to improve the performance of fluoroalkyl phosphates, including perfluorinated phosphates. For example, the di(fluoroalkyl) phosphate esters, such as those phosphate esters disclosed in U.S. Pat. No. 5,004,825, work well in the methods of this disclosure. Perfluorinated phosphates, including those provided in U.S. Pat. No. 6,315,822, also can be converted to poly-phosphates by using propylene glycol during esterification (see, for example, U.S. Pat. No. 6,447,588). Phosphates made from perfluoroisopentyl propylene epoxide (U.S. Pat. No. 3,919,361) having a reduced number of fluorine atoms in their molecule are suitable as well, such as the species illustrated here:
A larger number of CF₃groups are in bis[4-heptafluoroisopropoxy-3,3,4,4-tetrafluorobutyl]ammonium phosphate as in U.S. Pat. No. 3,692,885. Phosphoric esters of N-ethyl perfluorooctanesulfonamidoethyl alcohol (see U.S. Pat. Nos. 3,094,547 and 5,271,806) are suitable fluorochemicals for use in this disclosure, and soluble forms of these compounds may involve salts with sodium hydroxide or diethanol amine (see U.S. Pat. Nos. 6,447,588 and 3,812,217).
Examples of the use of perfluoropolyethers phosphates in making greaseproof paper are found at, for example, U.S. Pat. No. 3,492,374 and U.S. Pat. No. 6,790,890. Thus, perfluoropolyethers phosphates can be used by adding reactive groups able to react with cellulose (see for example, U.S. Pat. No. 6,221,434), applying the new compounds at the size press, followed by cured at about 100° C. for about 3 minutes, as an exemplary process.
In a further aspect, perfluoro phosphates can be reacted with the polycationic polymer ethylene-methacrylate having cationic pendant groups to yield a poly-salt soluble perchloroethylene, as illustrated in U.S. Pat. No. 3,817,958, and this solution can then be used according to the present disclosure.
Cationic Fluorochemicals.
Cationic fluorochemicals also constitute suitable fluorochemicals for use according to this disclosure. One advantage of using cationic fluorochemicals is that these compounds can interact with anionic paper and remain anchored on the surface. If cationic fluorochemicals are added to the wet end, the cationic charges will assist in their retention. The addition of a reactive functionality (such as azetidinium or epoxy groups) also can improve their efficiency by chemical bonds between cellulose fibers and the fluorochemical, in which a curing step may or may not be employed.
In the various aspects of this disclosure, the 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. For example, 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—(X)_y—C(O)—NH[(CH₂)_m—NH]_n—C(O)—(X)_y—Z, wherein
Z is a radical selected from perfluoro alkyl radicals of the formula C_sF_(2s+1), where s is an integer having a value of from 3 to 20 inclusive, and cycloperfluoro alkyl radicals of the formula C_tF_(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 (CH₂)_p, where p is an integer having a value of from 2 to 14 inclusive, cycloaliphatic radicals, bridged cycloaliphatic radicals, —CH═CH—(CH₂)_b—O—(CH₂)₂—, —CH₂—CH₂—(CH₂)_b—O—(CH₂)₂—, —CH═CH—(CH₂)_b—S—(CH₂)₂—, —CH₂—CH₂—(CH₂)_b—S—(CH₂)₂— radicals, where b is zero or an integer of from 1 to 14 inclusive and —SO₂—N(R)—(CH₂)_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;
m is an integer of from 2 to 6 inclusive;
and n is an integer of from 2 to 100 inclusive.
For example, 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)_yC—(O)—NH[(CH₂)_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:
wherein:
A is a halogen radical and Z, X, y, m and n are as previously defined. However, as the reaction proceeds, 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[(CH₂)_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 H₂N—[(CH₂)_m—NH]_nH, wherein Z, X, y, m and n are as previously defined.
For example, 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 (see Great Britain Patent No. 1,214,528):
The amide nitrogen is no longer available for protonation. In order to have the right hydrophilic-hydrophobic balance, more amide is needed after the fluorocarbon tail was attached. Alkylation with fluorinated epoxides is performed (polymer analogous reaction).
In this structure, the amide nitrogen is no longer available for protonation. In order to have the right hydrophilic-hydrophobic balance, more amide may be used after the fluorocarbon tail is attached. Also as disclosed, the alkylation with fluorinated epoxides is used to prepare the azetidinium moieties.
In one aspect, 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, (C₃F₇COOH); perfluorooctanoic acid (C₇F₁₅COOH); omega-perfluoroheptyl pentanoic acid (C₇F₁₅(CH₂)₄COOH); omega-perfluoroheptyl undecanoic acid (C₇F₁₅(CH₂)₁₀COOH); perfluoroheptyl methyl cyclobutane carboxylic acid; perfluoroheptyl substituted norbornene carboxylic acid; omega-perfluoroheptyl-beta-allyloxy-propionic acid (C₇F₁₅—CH═CHCH₂—O—(CH₂)₂COOH); omega-perfluoroheptyl-beta-propoxypropionic acid (C₇F₁₅—(CH₂)₃—O—(CH₂)₂COOH); omegaperfluoroheptyl-beta-allylthiopropionic acid (C₇F₁₅—CH═CHCH₂—S—(CH₂)₂COOH); omega-perfluorohepryl-beta-propylthiopropionic acid (C₇F₁₅—(CH₂)₃—S—(CH₂)₂COOH); and, omega-(N-methyl)-perfluoroheptanesulfonamide hendecanoic acid (C₇F₁₅—SO₂—N(CH₃)—(CH₂)₁₀—COOH).
According to a further aspect, the polyamine compounds applicable for use in preparing the cationic amido-amine fluoro compounds include, but are not limited to H₂N—[(CH₂)_m—NH]₄H 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. Thus, among the applicable polyamines are included: 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. Moreover, both linear and branched structures of the polyamine are envisioned. For example, when 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.
All available 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.
Also by way of example, 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. For example, the “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_fZ, wherein
R_fis a saturated fluoroaliphatic moiety containing a F₃C-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:
C_nF_2n+1, wherein
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:
wherein:

- R is hydrogen or hydrocarbyl such as lower alkyl having 1-3 carbons;
- R′ is hydrocarbylene or oxyhydrocarbylene such as alkylene having 1 to 6 carbons, arylene, oxyarylene, aralkylene or similar divalent hydrocarbon or oxyhydrocarbon moiety;
- each R″ is individually hydrogen, hydrocarbyl such as lower alkyl having 1 to 5 carbons or hydroxyhydrocarbyl; and
- X⁻ is an anion, especially an inorganic anion such as halide, sulfate or carboxylate such as acetate; and
- M⁺ is a cation such as an alkali metal cation or ammonium.

For example, in one aspect, 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 Zonyl™ FSC. Examples of other preferred cationic perfluorocarbons, as well as methods of preparation, are those listed in U.S. Pat. No. 3,775,126.
Examples of cationic fluorochemicals and the preparation of cationic fluorochemicals includes the general scheme set out in U.S. Pat. No. 6,951,962, in which: 1) polyamine such as polyethyleneimine (PEI) is reacted with a reactive fluorochemical such as fluorinated epoxides to modify the polyamine; and 2) the modified polyamine is then reacted with epichlorohydrin, to provide a reactive cationic fluorochemical. Subsequent treatment of cellulosic materials can include, for example, spraying the cellulosic materials with cationic fluorochemical and heating to about 150° C. for curing. Some cationic fluorochemicals are also cationic surfactants (see GB 1,214,528), in which nitrogen atoms in the main chain provide cationic charges and water dispersibility.
Additional further examples of 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. For example, 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.
In an aspect, suitable cationic fluorochemical compounds include those that contains both a polyamine functionality and fluorinated groups. For example, 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. While not theory bound, 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. Thus, 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.
In accordance with an aspect, 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. For example, suitable cationic fluorochemicals include those having the following structures:
wherein:

- R⁸, R⁹, R¹⁰, R¹¹, R¹²are selected from J, H, —(CH₂)_1-6H, —(CH₂CH₂O)_1-10H, —(CH₂CHOH)_1-10CH₃, —CH(CH₃)CH₂OH, —CH₂CH(OH)CH₂Cl,

—CH₂CH(OH)CH₂OH, —CH₂CO₂ ⁻M⁺ (M is a group 1 or 2 metal), —(CH₂)_1-6NH_2,1,0(R⁸)_0,1,2,

- wherein any two of R⁸, R¹⁰, R¹¹, or R¹²can be the same carbon chain,
- R⁷is selected from H, —CH₂CH(OH)CH₂, which can be cross-linked to nitrogen on K or L or M on a different fluoro(hydroxyl)alkyl, polyalkyl amino halohydrin or organo sulfonate, where at least one of R⁸, R⁹, R¹⁰, R¹¹, R¹²is a fluorochemical as denoted by “J”, and J is selected from the following moieties:

wherein, according to the conventional rules of chemical valence:

- A is selected from —(CH₂)_1-9—, —CH₂CHI(CH₂)_1-9BCH₂—, —CH═CH(CH₂)_1-9BCH₂—, —(CH₂)_1-11BCH₂—, —(CH₂)_1-2B(CH₂)_1-10BCH₂—, where B is selected from O, CO₂, CO₂[(CH₂)_1-2O]_1-10, OCH₂CO₂, OCH₂CO₂CO₂[(CH₂)_1-2O]_1-10, S, SO₂, SCH₂CO₂, C(O)S, SCH₂C₂O[(CH₂)_1-2O]_1-10, S[(CH₂)_1-2O]_1-10, S(O)NR′, C(S)NR′, S(O)NR′CH₂CH₂O, C(O)NR′, OCH₂C(O)NR′, OPO₃, NR′, SCH₂C(O)NR′, —N(R)CH₂CO₂, where R′ is selected from H, —(CH₂)_1-6;
- R is selected from H, —(CH₂)_1-6H;
- R_Fis selected from F(CF₂)_4-18, CF₃CF(CF₃)(CF₂)_3-5, CF₃CF₂CF(CF₃)(CF₂)_3-5, H(CF₂)_4-18, HCF₂CF(CF₃)(CF₂)_3-5, HCF₂CF₂CF(CF₃)(CF₂)_3-5, cycloperfluoroalky radicals of the formula C₂F_(2z−1)wherein z is an integer from 4-6 inclusive;
- n, p, q, s, t, v, and w are integers;
- p is 0 or 1;
- n is 1-6;
- v+q+w+s=an integer from 3 to about 1000;
- q, w, s each may be zero if desired;
- t is w+s;
- Q is selected from Cl⁻, Br⁻, I⁻, CH₃C₆H₄SO₂ ⁻, CH₃SO₂ ⁻, and the like; and
- K, L and M are randomly distributed along the polyamine and T is an amine on the end of the polyamine chain.

Amphoteric Fluorochemicals.
Further, fluorochemicals that can exhibit acid and basic (amphoteric) properties and function as an anionic or cationic fluorochemical can be used in accordance with this disclosure. For example, polyethyleneimine (PEI) modified with allyl glycidyl ether (AGE) can be reacted with chloroacetic acid sodium salt in which a fraction, for example about 20%, of secondary amines are consumed, and the allyloxy group can be reacted with CF₃(CF₂)₇CF₂I in the presence of sodium meta-bisulfate and AIBN to provide the fluoro functionalization, such as disclosed in U.S. Pat. No. 6,436,306, as illustrated in the following structure:
Thus, for example, the fluorochemical can comprise or can be selected from a perfluoroalkyl- or alkenyl-substituted polyamino acid which comprises an oligomer or copolymer of an aliphatic diamino carboxylic acid, which perfluoroalkyl- or alkenyl-substituted polyamino acid contains at least one perfluoroalkyl or alkenyl group attached to nitrogen atoms through a linking group, such as disclosed in U.S. Pat. No. 6,436,306, U.S. Pat. No. 6,156,222, and U.S. Pat. No. 6,365,676.
Further, poly-perfluoroalkyl-substituted alcohols and acids, and derivatives thereof, including those in which two allylic double bonds can be attached by a reaction with allyl chloride or allyl glycidyl ether to amino-acids (such as ethylenediamine di-acetic acid) are useful in the present disclosure. Such compounds are disclosed in, for example, U.S. Pat. No. 5,491,261.
Non-Ionic Fluorochemicals.
According to a further aspect of this disclosure, suitable fluorochemicals include the non-ionic fluorochemical, such as those disclosed in U.S. Pat. No. 3,409,647, having the following structure:
Similar compounds with ether and/or ester linkages, including those having a higher fluorine content (U.S. Pat. No. 3,514,487) also can be used, such as those illustrated here:
In addition, fluorinated alkyl ketene dimer (AKD) can be emulsified and used in the present disclosure, such as the emulsification with cationic starch and sodium lignin sulfonate as disclosed in U.S. Pat. No. 5,252,754.
Polymeric Fluorochemicals.
Many conventional fluorochemicals are polymeric, and these materials also are useful in accordance with this disclosure. The polymer can be prepared by simple homopolymerization of fluorochemical monomers, or by copolymerizing fluorochemical and non-fluorinated comonomers, in which the non-fluorinated comonomer such as alkyl, alkoxyalkyl, glycidyl and cationic (meth)acrylates serve as “internal” diluents, as in U.S. Pat. No. 4,579,924 and U.S. Pat. No. 5,558,940. Possible co-monomers also include, for example, vinyl esters, vinylidene chloride, acrylic esters, vinyl halides, and the like. In addition, a non-fluorinated “external” diluent can be used to blend with a polymeric fluorochemical, such as a non-fluorinated copolymer such as (poly n-octyl methacrylate) blended with fluorochemical copolymer.
Perfluorinated copolymers can show both water repellency and oil and grease resistance and repellency, especially at elevated temperatures (for example, 90-240° C.). Generally, perfluorinated copolymers are used as dispersions in water and are more likely to remain on the paper surface. The copolymers of fluorinated methacrylates or acrylates can be are copolymerized with cationic methacrylates, such as illustrated in the following structures, and/or reactive comonomers (such as glycidyl methacrylate or methylol acrylamide), either in an emulsion or in solution (organic solvents), and subsequently used as aqueous dispersions (see for example, U.S. Pat. No. 5,247,008).
While the ratio of fluorinated to non-fluorinated monomer in copolymer can vary over a wide range, good oil repellency can be obtained from about 60% to about 90% fluorinated monomer in copolymer. Good oil repellency performance also can be obtained from about 75% to about 85% fluorinated monomer in copolymer.
Hybrid Fluorochemicals.
Silicon compounds are known for their hydrophobic properties, and various combinations of a fluorochemical and a silicon compound may show a synergetic effect and provide an added benefit to the methods of this disclosure. One example is illustrated in the following reaction to generate a “hybrid” fluorochemical that can be used according to this disclosure.
In the resulting “hybrid” fluorochemical structure, the siloxane group can be added by a chain transfer reaction to a mercapto siloxane during the free radical polymerization of a perfluoro acrylate, as illustrated in U.S. Patent Application Publication No. 2010/0018659. Again, this method and the hybrid fluorochemicals illustrated are merely examples of the fluorochemicals that can be used in the fluorochemical component of this disclosure.

Process for Improving the Oil and Grease Resistance of a Cellulose Fiber Material

In a further aspect, a process of making an oil and grease resistant cellulose fiber substrate using the oil and grease resistant aqueous dispersions discussed above is provided. Such process comprises applying said aqueous dispersions onto said cellulose fibers on the dry end (size press or coater) or wet end of a papermaking process in an amount resulting in said at least one inorganic nanoparticle component present in an amount from about 100 ppm (parts per million—particle weight per weight of the dry paper fiber) to about 4000 ppm OWPF (on weight of paper fiber; the amount of solids that were applied after drying off the solvent), including from about 500 ppm to about 1500 ppm OWPF, from about 500 ppm to about 1000 ppm OWPF, from about 1000 ppm to about 1500 ppm, from about 1000 ppm to about 2000 ppm OWPF, and from about 1500 ppm to about 2000 ppm OWPF, on the surface of the cellulose fiber substrate; and said fluorochemical present in an amount that results in an elemental fluorine content of from about 25 ppm to about 1000 ppm OWPF, including from about 25 to about 500 ppm OWPF, from about 75 ppm to about 150 ppm OWPF, from about 75 ppm to about 200 ppm OWPF, from about 100 ppm to about 200 ppm OWPF, and from about 140 ppm to about 150 ppm OWPF, on the surface of said cellulose substrate. The fluorochemical and inorganic nanoparticle can be added to the wet end or dry end of a paper process. The treated cellulose fiber substrate can then be cured. (Curing refers to the process of drying the solvent used to carry the solution onto the substrate and/or melt spreading the fluorochemical. This can optionally be done using a heating step.).
The disclosed oil and grease resistance aqueous dispersion can be made using various techniques. One technique comprises contacting at least one inorganic nanoparticle component with water to form an aqueous inorganic nanoparticle solution. Aqueous solvent mixtures containing low molecular weight alcohols (such as methanol, ethanol, isopropanol, and the like) can also be used to disperse the clay. The inorganic nanoparticle component can be present in an amount from about 0.01% to about 25% weight in solution, including about 1% to about 20%, about 0.05% to about 15%, about 0.01% to about 5%, about 0.05% to about 5%, about 0.5% to about 5%, and about 5% to about 15%. When Laponite® is used as the inorganic nanoparticle, the concentration can be from about 0.05% to about 25% weight in solution, including from about 0.05% to 1% w/w and from about 5% to about 15% w/w. The aqueous inorganic nanoparticle solution can then be contacted with a fluorochemical to form the oil and grease resistant aqueous dispersion. The percent (%) elemental fluorine in the combined dispersion can be present in an amount from about 0.0001% to about 5% weight fluorine atoms present in dispersion, including about 0.001% to about 2%, about 0.001% to about 0.8%, about 0.005% to about 0.5%, about 0.005% to about 0.15%, about 0.01% to about 1%, about 0.025% to about 0.5%, and about 0.05% to about 0.5%. When Capstone® RCP (partially fluorinated condensation polymer) is used as the fluorochemical, the concentration can be from about 0.005% to about 0.5%, including from about 0.005% to about 0.15% depending on the wet pick-up percentage of the application to the fibers.
When formulating the aqueous dispersions, the weight percent of inorganic nanoparticle component generally should remain higher than the weight percent fluorine. Therefore, it is expected that in embodiments where a inorganic nanoparticle treatment step occurs prior to a combined inorganic nanoparticle and fluorochemical treatment step, nanoparticle absorption occurs in both steps and therefore a benefit is obtained by using an excess of the inorganic nanoparticle component to the fluorochemical component. For example, typical weight percent ratios of inorganic nanoparticles to fluorine range from about 5000:1 to about 2:1, including about 3000:1, about 1500:1, about 1000:1, about 500:1, about 100:1, about 50:1, about 25:1, and about 10:1.
The disclosed oil and grease resistant aqueous dispersion can be applied to various types of paper and paperboard and cellulose products as a surface treatment. The disclosed oil and grease resistant aqueous dispersions can be applied to a paper or paperboard or cellulose fiber structure using various techniques known in the art. Such techniques include spraying, dipping, coating, foaming, painting, brushing, and rolling the aqueous dispersion on to the cellulose substrate. After application, the paper or paperboard or cellulose can then be heat cured at a temperature of from about 25° C. to about 200° C., including from about 30° C. to about 125° C.; and a time of from about 1 second to about 40 minutes, including 5 minutes.
Once applied, the inorganic nanoparticle component can be present in an amount from about 200 ppm to about 4000 ppm OWPF, including from about 500 ppm to about 1500 ppm OWPF, from about 500 ppm to about 1000 ppm OWPF, from about 1000 ppm to about 1500 ppm OWPF, from about 1000 ppm to about 2000 ppm OWPF and from about 1500 ppm to about 2000 ppm OWPF, on the surface of the fiber, yarn or textile. The fluorochemical can also be present in an amount that results in an elemental fluorine content of from about 25 ppm to about 1000 ppm OWPF, including from about 25 ppm to about 500 ppm OWPF, from about 75 ppm to about 150 ppm OWPF, from about 75 ppm to about 200 ppm OWPF, from about 100 ppm to about 200 ppm OWPF, and from about 140 ppm to about 150 ppm OWPF, on the surface of the paper and paperboard and cellulose. When applying the aqueous dispersions, the OWPF of the inorganic nanoparticle component should remain higher than the OWPF of fluorine. Typical OWPF ratios of nanoparticles to fluorine can range from about 80:1 to about 1.5:1, including about 27:1, about 20:1, about 13:1, about 10:1, about 7.5:1, and about 5:1. Additional components can be added to the oil and grease resistant compositions disclosed above. Such components can include 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.
The nanoparticles are shown to act as a fluorochemical extender allowing oil and grease resistant properties on the paper and paperboard and cellulose at reduced fluorine levels on the weight of paper fiber.

DEFINITIONS

To define more clearly the terms used herein, the following definitions are provided, which are applicable to this disclosure unless otherwise indicated, as long as the definition does not render indefinite or non-enabled any claim to which that definition is applied, for example, by failing to adhere to the conventional rules of chemical valence. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2^ndEd (1997) can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls.
While 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.
While mostly familiar to those versed in the art, the following definitions are provided in the interest of clarity.
The term “clay” as used herein 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.
As used herein, the term “nanoparticle” is used to describe a multidimensional particle in which one of its dimensions is less than 100 nm in length.
As used herein, the term “on weight of paper fiber” or OWPF is used to describe the amount of solids that were applied after drying off the solvent.
The term “wet pick-up” or WPU is used herein to describe the amount of solution weight that was applied to the paper fiber before drying off the solvent.
The term “fluorochemical” or FC is used here to refer to a chemical having a carbon-fluorine bond, and can include such compounds and compositions as anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, and fluorochemical compounds that comprise regions that can be described according to two or more different types or categories of fluorochemical compounds, which are referred to herein as “hybrid” fluorochemicals.
The term “cellulose fiber material” is typically used to refer to paper, paperboard, and cellulose fibers at any stage of their use, for example, being used in the preparation and paperboard.
The term “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). Non-limiting examples of hydrocarbyl groups include linear, branched, and cyclic hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclopentyl, vinyl, and the like.
The term “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_nH_2n+1. Unless otherwise specified, 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.
Unless otherwise specified, 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. For example, unless otherwise specified, 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. Moreover, 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.
In any application before the United States Patent and Trademark Office, the Abstract of this application is provided for the purpose of satisfying the requirements of 37 C.F.R. §1.72 and the purpose stated in 37 C.F.R. §1.72(b) “to enable the United States Patent and Trademark Office and the public generally to determine quickly from a cursory inspection the nature and gist of the technical disclosure.” Therefore, the Abstract of this application is not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein. Moreover, any headings that may be employed herein are also not intended to be used to construe the scope of the claims or to limit the scope of the subject matter that is disclosed herein. Any use of the past tense to describe an example that may otherwise be indicated as constructive or prophetic is not intended to reflect that the constructive or prophetic example has actually been carried out.
Applicants reserve the right to proviso out any selection, group, element, or aspect, for example, to limit the scope of any claim to account for a prior disclosure of which Applicants may be unaware.

EXAMPLES

The following examples are provided to illustrate various embodiments of the disclosure and the claims. Unless otherwise specified, reagents were obtained from commercial sources. Standard analytical methods were used to characterize the resins. Selections of alternative fluorochemicals, inorganic nanoparticles, and cellulosic fibers having different surface chemistries will necessitate minor adjustments to the variables herein described.
Performance Tests.
For the following performance tests, all examples were performed using the following protocol. Paper having a basis weight of 34 g/m²was 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.

Comparative Example 1

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 change reflects the strong oil absorption into the paper.

Comparative Example 2

Paper treated in a size-press with a solution of 1% fluorochemicals (Daikin 8112) shows an initial contact angle for Castor oil of 60 degrees. The contact angle remains unchanged after 30 minutes.

Example 3

The same paper used in Comparative Examples 1 and 2 was pretreated in size-press with a solution of 5% starch (Penford 280) and 2.75% sodium salt of a 1:1 styrene-fumaric acid copolymer. After drying, the pre-coated paper was treated with a size-press solution with a lower concentration (0.5%) of the same fluorochemical (Daikin 8112). The initial contact angle for Castor oil was 65 degree that remains constant over 30 minutes.

Example 4

The same paper as in Comparative Examples 1 and 2 was pretreated in size-press with a solution 1% of cationic polymer (PAE: polyamidoamine epichlorohydrin). After drying, the pre-coated paper was treated with a lower concentration (0.5%) of the same fluorochemical (Daikin 8112). The initial contact angle was 102 degree that remains constant over 30 minutes.
Other samples according to this disclosure can be prepared in a similar manner, with the differences adjusted according to the weight percent and, for example, type of stock Laponite™ solution made and the addition of Capstone™ RCP to the samples. For illustrative purposes only, the following constructive example describes the method of preparing one sample: A 5% by weight stock solution of Laponite™ RDS was made by incrementally adding the selected nanoclay to stirring water that is heated to about 38° C. After this addition is completed, the vessel is moved to a cool stir plate and continued to stir until the solution is dispersion clear and at room temperature. In a bottle were combined 6 wt % Capstone™ RCP, 60 wt % of the Laponite™ dispersion, and the remainder dionized water.
The mixture prepared in this fashion is then applied to the a paper substrate, sufficient to achieve full coverage, by any method such as spraying, dipping, coating, foaming, painting, brushing, and/or rolling the aqueous dispersion onto the substrate. After application, the treated paper is then cured in a convection oven at about 150° C. for 5-15 minutes, as an example.
Processes such as these can be used to prepare samples having about 5% WPU, resulted in about 1500 ppm OWF of clay nanoparticles and 150 ppm OWF of elemental flourine on the paper surface. Processes such as these also can be used to prepare samples having about 10% WPU, resulted in from about 1000-2000 ppm OWF of clay nanoparticles and from about 75 ppm-200 ppm OWF elemental fluorine, on the paper surface. Similar processes also can be used with a 13.3 wt % Capstone™ RCP solution and following a spray pattern similar to the method described above at a 10% wet-pick up, which resulted in 640 ppm OWF of elemental fluorine on the paper surface.
According to further examples, there has been developed a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:

- forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and
- contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material.
  wherein
- a) the at least one inorganic nanoparticle component comprises synthetic hectorite and is present in an amount from about 0.05% to about 15% weight in the dispersion; and
- b) the at least one fluorochemical is present in the dispersion in an amount to provide from about 0.005% to about 0.5% weight fluorine atoms in the dispersion; and
- c) the weight ratio of the at least one inorganic nanoparticle component to the fluorine atoms is from about 5000:1 to about 2:1.
  In this example, if desired, the at least one inorganic nanoparticle component can be present in an amount from about 200 ppm to about 4000 ppm OWPF on the oil-repellent cellulose fiber material, the at least one fluorochemical is present in an amount to provide a fluorine content from about 25 ppm to about 1000 ppm OWPF on the oil-repellent cellulose fiber material, or both conditions can be met.

Also by way of example, there has been developed a process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:

- forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and
- contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material.
  wherein
- a) the at least one inorganic nanoparticle component comprises synthetic hectorite and is present in an amount from about 500 ppm to about 1500 ppm OWPF on the oil-repellent cellulose fiber material; and
- b) the at least one fluorochemical has perfluorinated side-chains with less than or equal to six fluorinated carbons per fluorinated side-chain and is present in an amount from about 75 ppm to about 200 ppm OWPF on the oil-repellent cellulose fiber material.

In further accordance with the examples, the cellulose fiber material can be selected from paper and paperboard, and typically, the step of contacting the paper and paperboard or any suitable cellulose fiber material with the aqueous dispersion can be carried out by spraying, dipping, coating, foaming, painting, brushing, rolling, and any combination thereof.
Further attributes, features, and embodiments of the present invention can be understood by reference to the following numbered aspects of the disclosed invention. Reference to disclosure in any of the preceding aspects is applicable to any preceding numbered aspect and to any combination of any number of preceding aspects, as recognized by appropriate antecedent disclosure in any combination of preceding aspects that can be made. The following numbered aspects are provided:
1. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and
contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material.
2. The process according to the preceding aspect, wherein the aqueous dispersion further comprises a cationic polymer.
3. The process according to any of the preceding aspects, wherein the cationic polymer is selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, and combinations thereof.
4. The process according to any of the preceding aspects, wherein the polyamidoamine is a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA).
5. The process according to any of the preceding aspects, wherein the aqueous dispersion further comprises a film-forming polymer.
6. The process according to any of the preceding aspects, wherein the film-forming polymer is selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof
7. The process according to any of the preceding aspects, further comprising curing the oil-repellent cellulose fiber material.
8. The process according to any of the preceding aspects, wherein the inorganic nanoparticle component comprises silica, clay, or combinations thereof
9. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent.
10. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from a substituted trialkoxysilane, a cationic polymer, or combinations thereof.
11. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from a ureido substituted trialkoxysilane, an amino substituted trialkoxysilane, a sulfur substituted trialkoxysilane, an epoxy substituted trialkoxysilane, a methacryl substituted trialkoxysilane, a vinyl substituted trialkoxysilane, a hydrocarbyl substituted trialkoxysilane, an alkyl substituted trialkoxysilane, a haloalkyl substituted trialkoxysilane, or any combination thereof
12. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrichlorosilane, alkylmethyltrimethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, propyltri(2-methoxyethoxy)silane, and any combination thereof
13. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component comprises smectites, kaolins, illites, chlorites, attapulgites, sepiolites, or combinations thereof.
14. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is selected from 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, phengite, and any combination thereof.
15. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is synthetic.
16. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is synthetic hectorite.
17. The process according to any of the preceding aspects, wherein the at least one fluorochemical is selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, and hybrid fluorochemicals.
18. The process according to any of the preceding aspects, wherein the at least one fluorochemical is selected from fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.
19. The process according to any of the preceding aspects, wherein the at least one fluorochemical comprises a fluorochemical urethane.
20. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is present in an amount from about 0.01% to about 25% by weight in the aqueous dispersion.
21. The process according to any of the preceding aspects, wherein the at least one fluorochemical is present in the aqueous dispersion in an amount from about 0.0001% to about 5% weight fluorine atoms.
22. The process according to any of the preceding aspects, wherein
a) the at least one inorganic nanoparticle component comprises synthetic hectorite and is present in an amount from about 0.05% to about 15% weight in the dispersion;
b) the at least one fluorochemical is present in the dispersion in an amount to provide from about 0.005% to about 0.5% weight fluorine atoms in the dispersion; and
c) the weight ratio of the at least one inorganic nanoparticle component to the fluorine atoms is from about 5000:1 to about 2:1.
23. The process according to any of the preceding aspects, wherein:
a) the at least one inorganic nanoparticle component is present in an amount from about 200 ppm to about 4000 ppm OWPF on the oil-repellent cellulose fiber material;
b) the at least one fluorochemical is present in an amount to provide a fluorine content from about 25 ppm to about 1000 ppm OWPF on the oil-repellent cellulose fiber material; or
c) the process is characterized by both conditions a) and b).
24. The process according to any of the preceding aspects, wherein the cellulose fiber material is selected from paper and paperboard.
25. The process according to any of the preceding aspects, wherein the contacting a cellulose fiber material with the aqueous dispersion comprises spraying, dipping, coating, foaming, painting, brushing, rolling, and any combination thereof
26. The process according to any of the preceding aspects, wherein:
a) the at least one inorganic nanoparticle component comprises synthetic hectorite and is present in an amount from about 500 ppm to about 1500 ppm OWPF on the oil-repellent cellulose fiber material; and
b) the at least one fluorochemical has perfluorinated side-chains with less than or equal to six fluorinated carbons per fluorinated side-chain and is present in an amount from about 75 ppm to about 200 ppm OWPF on the oil-repellent cellulose fiber material.
27. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and
b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent cellulose fiber material.
28. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and
b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising at least one fluorochemical to form an oil-repellent cellulose fiber material;
wherein contacting step b) is carried out simultaneous or subsequent to contacting step a).
29. The process according to any of the preceding aspects, wherein the first aqueous dispersion, the second aqueous dispersion, or both further comprise a cationic polymer.
30. The process according to any of the preceding aspects, wherein the cationic polymer is selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, and combinations thereof
31. The process according to any of the preceding aspects, wherein the polyamidoamine is a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA).
32. The process according to any of the preceding aspects, wherein the first aqueous dispersion, the second aqueous dispersion, or both further comprise a film-forming polymer.
33. The process according to any of the preceding aspects, wherein the film-forming polymer is selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof
34. The process according to any of the preceding aspects, further comprising curing the oil-repellent cellulose fiber material.
35. The process according to any of the preceding aspects, wherein the cellulose fiber material is selected from paper and paperboard.
36. The process according to any of the preceding aspects, wherein the inorganic nanoparticle component comprises silica, clay, or combinations thereof
37. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent.
38. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from a substituted trialkoxysilane, a cationic polymer, or combinations thereof.
39. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from a ureido substituted trialkoxysilane, an amino substituted trialkoxysilane, a sulfur substituted trialkoxysilane, an epoxy substituted trialkoxysilane, a methacryl substituted trialkoxysilane, a vinyl substituted trialkoxysilane, a hydrocarbyl substituted trialkoxysilane, an alkyl substituted trialkoxysilane, a haloalkyl substituted trialkoxysilane, or any combination thereof.
40. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrichlorosilane, alkylmethyltrimethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, propyltri(2-methoxyethoxy)silane, and any combination thereof
41. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component comprises smectites, kaolins, illites, chlorites, attapulgites, sepiolites, or combinations thereof.
42. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is selected from 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, phengite, and any combination thereof.
43. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is synthetic hectorite.
44. The process according to any of the preceding aspects, wherein the at least one fluorochemical is selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, and hybrid fluoro chemicals.
45. The process according to any of the preceding aspects, wherein the at least one fluorochemical is selected from fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.
46. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is present in an amount from about 0.01% to about 25% by weight in the aqueous dispersion.
47. The process according to any of the preceding aspects, wherein the at least one fluorochemical is present in the aqueous dispersion in an amount from about 0.0001% to about 5% weight fluorine atoms.
48. A paper or paperboard made according to any of the preceding aspects.
49. A paper or paperboard treated with an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical to form an oil-repellent paper or paperboard.
50. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
a) applying a pretreatment composition comprising a cationic polymer, a film-forming polymer, or a combination thereof to a cellulose fiber material to form a pretreated cellulose substrate;
b) drying the pretreated cellulose substrate; and
c) applying a fluorochemical composition to the dry pretreated cellulose substrate to form an oil-repellent cellulose fiber material.
51. The process according to any of the preceding aspects, wherein the cationic polymer is selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, and combinations thereof.
52. The process according to any of the preceding aspects, wherein the polyamidoamine is a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA).
53. The process according to any of the preceding aspects, wherein the cationic polymer is prepared by reacting an epihalohydrin with a compound having the formula:
Z—(X)_y—C(O)—NH[(CH₂)_m—NH]_nC(O)—(X)_y—Z, wherein

- Z is a radical selected from an alkyl radical of the formula C_sH_(2s+1), where s is an integer having a value of from 3 to 20 inclusive, and cycloalkyl radicals of the formula C_tH_(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 (CH₂)_p, where p is an integer having a value of from 2 to 14 inclusive, cycloaliphatic radicals, bridged cycloaliphatic radicals, —CH═CH—(CH₂)_b—O—(CH₂)₂—, —CH₂—CH₂—(CH₂)_b—O—(CH₂)₂—, —CH═CH—(CH₂)_b—S—(CH₂)₂—, —CH₂—CH₂—(CH₂)_b—S—(CH₂)₂— radicals, where b is zero or an integer of from 1 to 14 inclusive and —SO₂—N(R)—(CH₂)_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;
- m is an integer of from 2 to 6 inclusive;
- and n is an integer of from 2 to 100 inclusive.

54. The process according to any of the preceding aspects, wherein the film-forming polymer is selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof.
55. The process according to any of the preceding aspects, wherein the pretreatment composition further comprises an anionic polymer.
56. The process according to any of the preceding aspects, wherein the anionic polymer is selected from a copolymer of styrene with fumaric acid, maleic acid, glutaconic acid, traumatic acid, muconic acid, and combinations thereof.
57. The process according to any of the preceding aspects, further comprising curing the oil-repellent cellulose fiber material.
58. The process according to any of the preceding aspects, wherein the fluorochemical composition comprises anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, or hybrid fluorochemicals.
59. The process according to any of the preceding aspects, wherein the fluorochemical composition is selected from fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.
60. The process according to any of the preceding aspects, wherein the fluorochemical composition comprises a fluorochemical urethane.
61. The process according to any of the preceding aspects, wherein the cationic polymer, the film-forming polymer, or the combination thereof is present in the pretreatment composition in an amount from about 0.01% to about 25% by weight in the aqueous dispersion.
62. The process according to any of the preceding aspects, wherein the cationic polymer, the film-forming polymer, or the combination thereof is present in the pretreatment composition in an amount from about 0.1% to about 10% by weight in the aqueous dispersion.
63. The process according to any of the preceding aspects, wherein the fluorochemical composition comprises at least one fluorochemical present in an aqueous medium in an amount from about 0.0001% to about 5% by weight.
64. The process according to any of the preceding aspects, wherein the fluorochemical composition comprises at least one fluorochemical present in an aqueous medium in an amount from about 0.01% to about 3% by weight.
65. The process according to any of the preceding aspects, wherein applying the pretreatment composition occurs in a size-press.
66. The process according to any of the preceding aspects, wherein the cellulose fiber material is selected from paper and paperboard.
67. The process according to any of the preceding aspects, wherein applying the pretreatment composition to the cellulose fiber material comprises spraying, dipping, coating, foaming, painting, brushing, rolling, and any combination thereof
68. The process according to any of the preceding aspects, wherein pretreatment composition or the fluorochemical composition further comprises an inorganic nanoparticle component.
69. The process according to any of the preceding aspects, wherein inorganic nanoparticle component comprises silica, clay, or combinations thereof
70. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent.
71. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from a substituted trialkoxysilane, a cationic polymer, or combinations thereof.
72. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from a ureido substituted trialkoxysilane, an amino substituted trialkoxysilane, a sulfur substituted trialkoxysilane, an epoxy substituted trialkoxysilane, a methacryl substituted trialkoxysilane, a vinyl substituted trialkoxysilane, a hydrocarbyl substituted trialkoxysilane, an alkyl substituted trialkoxysilane, a haloalkyl substituted trialkoxysilane, or any combination thereof.
73. The process according to any of the preceding aspects, wherein the silica is modified with at least one silane coupling agent selected from methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, decyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrichlorosilane, alkylmethyltrimethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, propyltri(2-methoxyethoxy)silane, and any combination thereof.
74. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component comprises smectites, kaolins, illites, chlorites, attapulgites, sepiolites, or combinations thereof.
75. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is selected from 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, phengite, and any combination thereof.
76. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is synthetic.
77. The process according to any of the preceding aspects, wherein the at least one inorganic nanoparticle component is synthetic hectorite.
78. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
a) applying a pretreatment composition comprising a cationic polymer, a film-forming polymer, or a combination thereof to a cellulose fiber material to form a pretreated cellulose substrate;
b) drying the pretreated cellulose substrate; and
c) applying a fluorochemical composition comprising at least one inorganic nanoparticle component and at least one fluorochemical to the dry pretreated cellulose substrate to form an oil-repellent cellulose fiber material.
79. The process according to any of the preceding aspects, wherein the fluorochemical composition further comprises a cationic polymer.
80. The process according to any of the preceding aspects, wherein the cationic polymer is selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, and combinations thereof.
81. The process according to any of the preceding aspects, further comprising curing the oil-repellent cellulose fiber material.
82. The process according to any of the preceding aspects, wherein the cellulose fiber material is selected from paper and paperboard.
83. A paper or paperboard made according to the process of according to any of the preceding aspects.
Any suitable combinations of the above described attributes, features, and embodiments set out in the above-numbered aspects of the present invention are also encompssed by this disclosure. Examples of additional aspects and combinations of the above numbered aspects of the invention that are provided herein include, but are not limted to, following numbered aspects:
1. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and
contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material.
2. The process according to the according to the preceding aspect, wherein the aqueous dispersion further comprises a cationic polymer selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA); and combinations thereof.
3. The process according to any of the preceding aspects, wherein the aqueous dispersion further comprises a film-forming polymer selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof.
4. The process according to any of the preceding aspects, wherein the inorganic nanoparticle component comprises silica, silica modified with at least one silane coupling agent, clay, or combinations thereof, and wherein:
a) the at least one inorganic nanoparticle component comprises smectites, kaolins, illites, chlorites, attapulgites, sepiolites, 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, phengite, synthetic hectorite, or any combination thereof; and
b) the silane coupling agent comprises a substituted trialkoxysilane, a cationic polymer, or combinations thereof.
5. The process according to any of the preceding aspects, wherein the at least one fluorochemical is selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, hybrid fluorochemicals, fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.
6. The process according to any of the preceding aspects, wherein
a) the at least one inorganic nanoparticle component comprises synthetic hectorite and is present in an amount from about 0.01% to about 25% weight in the dispersion or from about 200 ppm to about 4000 ppm OWPF on the oil-repellent cellulose fiber material;
b) the at least one fluorochemical is present in the dispersion in an amount to provide from about 0.0001% to about 5% weight fluorine atoms in the dispersion or from about 25 ppm to about 1000 ppm OWPF on the oil-repellent cellulose fiber material; or
c) both conditions a) and b) exist.
7. A paper or paperboard made according to the process of any of the preceding aspects.
8. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and
b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising i) at least one fluorochemical or ii) at least one inorganic nanoparticle component and at least one fluorochemical, to form an oil-repellent cellulose fiber material.
9. The process according to any of the preceding aspects, wherein the first aqueous dispersion, the second aqueous dispersion, or both further comprise:
a) a cationic polymer selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), and combinations thereof; or
b) a film-forming polymer selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof.
10. The process according to any of the preceding aspects, wherein the inorganic nanoparticle component comprises silica, silica modified with at least one silane coupling agent, clay, or combinations thereof, and wherein:
a) the at least one inorganic nanoparticle component comprises smectites, kaolins, illites, chlorites, attapulgites, sepiolites, 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, phengite, synthetic hectorite, or any combination thereof; and
b) the silane coupling agent comprises a substituted trialkoxysilane, a cationic polymer, or combinations thereof.
11. The process according to any of the preceding aspects, wherein the at least one fluorochemical is selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, hybrid fluorochemicals, fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.
12. A paper or paperboard made according to the process of any of the preceding aspects.
13. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:
a) applying a pretreatment composition comprising a first cationic polymer, a film-forming polymer, or a combination thereof to a cellulose fiber material to form a pretreated cellulose substrate;
b) drying the pretreated cellulose substrate; and
c) applying a fluorochemical composition comprising: i) at least one fluorochemical; or ii) at least one inorganic nanoparticle component and at least one fluorochemical to the dry pretreated cellulose substrate to form an oil-repellent cellulose fiber material.
14. The process according to any of the preceding aspects, wherein:
a) the first cationic polymer is selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), and combinations thereof;
b) the fluorochemical composition further comprises a second cationic polymer selected independently from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), and combinations thereof; or
c) both conditions a) and b) are present.
15. The process according to any of the preceding aspects, wherein the cationic polymer is prepared by reacting an epihalohydrin with a compound having the formula:
Z—(X)_y—C(O)—NH[(CH₂)_m—NH]_n—C(O)—(X)_y—Z, wherein

16. The process according to any of the preceding aspects, wherein the film-forming polymer is selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof
17. The process according to any of the preceding aspects, wherein the pretreatment composition further comprises an anionic polymer.
18. The process according to any of the preceding aspects, wherein the anionic polymer is selected from a copolymer of styrene with fumaric acid, maleic acid, glutaconic acid, traumatic acid, muconic acid, and combinations thereof.
19. The process according to any of the preceding aspects, wherein the fluorochemical composition comprises anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, or hybrid fluoro chemicals.
20. The process according to any of the preceding aspects, wherein:
a) the cationic polymer, the film-forming polymer, or the combination thereof is present in the pretreatment composition in an amount from about 0.01% to about 25% by weight in the aqueous dispersion;
b) the fluorochemical composition comprises at least one fluorochemical present in an aqueous medium in an amount from about 0.0001% to about 5% by weight; or
c) both conditions a) and b) are present.
21. The process according to any of the preceding aspects, wherein pretreatment composition or the fluorochemical composition further comprises an inorganic nanoparticle component comprising: silica; silica modified with at least one silane coupling agent selected from a substituted trialkoxysilane, a cationic polymer, or combinations thereof; clay; or combinations thereof.
22. A paper or paperboard made according to the process of any of the preceding aspects.
This invention has been described above with reference to the various aspects of the disclosed oil and grease resistance and methods of making paper and paperboard having improved oil and grease resistance. Obvious modifications and alterations will occur to others upon reading and understanding the proceeding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the claims.

Claims

We claim:

1. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:

forming an aqueous dispersion comprising at least one inorganic nanoparticle component and at least one fluorochemical; and

contacting a cellulose fiber material with the aqueous dispersion to form an oil-repellent cellulose fiber material.

2. The process of claim 1, wherein the aqueous dispersion further comprises a cationic polymer selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA); and combinations thereof.

3. The process of claim 1, wherein the aqueous dispersion further comprises a film-forming polymer selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof.

4. The process of claim 1, wherein the inorganic nanoparticle component comprises silica, silica modified with at least one silane coupling agent, clay, or combinations thereof, and wherein:

a) the at least one inorganic nanoparticle component comprises smectites, kaolins, illites, chlorites, attapulgites, sepiolites, 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, phengite, synthetic hectorite, or any combination thereof; and

b) the silane coupling agent comprises a substituted trialkoxysilane, a cationic polymer, or combinations thereof.

5. The process of claim 1, wherein the at least one fluorochemical is selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, hybrid fluorochemicals, fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.

6. The process of claim 1, wherein

a) the at least one inorganic nanoparticle component comprises synthetic hectorite and is present in an amount from about 0.01% to about 25% weight in the dispersion or from about 200 ppm to about 4000 ppm OWPF on the oil-repellent cellulose fiber material;

b) the at least one fluorochemical is present in the dispersion in an amount to provide from about 0.0001% to about 5% weight fluorine atoms in the dispersion or from about 25 ppm to about 1000 ppm OWPF on the oil-repellent cellulose fiber material; or

c) both conditions a) and b) exist.

7. A paper or paperboard made according to the process of claim 1.

8. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:

a) contacting a cellulose fiber material with a first aqueous dispersion comprising at least one inorganic nanoparticle component to form a nanoparticle-treated cellulose fiber material; and

b) contacting the nanoparticle-treated cellulose fiber material with a second aqueous dispersion comprising i) at least one fluorochemical or ii) at least one inorganic nanoparticle component and at least one fluorochemical, to form an oil-repellent cellulose fiber material.

9. The process of claim 8, wherein the first aqueous dispersion, the second aqueous dispersion, or both further comprise:

a) a cationic polymer selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), and combinations thereof; or

b) a film-forming polymer selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof.

10. The process of claim 8, wherein the inorganic nanoparticle component comprises silica, silica modified with at least one silane coupling agent, clay, or combinations thereof, and wherein:

11. The process of claim 8, wherein the at least one fluorochemical is selected from anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, hybrid fluorochemicals, fluorochemical allophanates, fluorochemical polyacrylates, fluorochemical urethanes, fluorochemical carbodiimides, fluorochemical quanidines, and combinations thereof.

12. A paper or paperboard made according to the process of claim 8.

13. A process for improving the oil and grease resistance of a cellulose fiber material, the process comprising:

a) applying a pretreatment composition comprising a first cationic polymer, a film-forming polymer, or a combination thereof to a cellulose fiber material to form a pretreated cellulose substrate;

b) drying the pretreated cellulose substrate; and

c) applying a fluorochemical composition comprising: i) at least one fluorochemical; or ii) at least one inorganic nanoparticle component and at least one fluorochemical to the dry pretreated cellulose substrate to form an oil-repellent cellulose fiber material.

14. The process of claim 13, wherein:

a) the first cationic polymer is selected from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), and combinations thereof;

b) the fluorochemical composition further comprises a second cationic polymer selected independently from a polyamine, a poly-vinyl amine, a polyethylene imine (PEI), a polyamidoamine, a polyamidoamine epichlorohydrin (PAE), a polyacrylamide, a starch, a prepolymer derived from condensation of adipic acid and diethylenetriamine (DETA), and combinations thereof; or

c) both conditions a) and b) are present.

15. The process of claim 13, wherein the cationic polymer is prepared by reacting an epihalohydrin with a compound having the formula:

Z—(X)_y—C(O)—NH[(CH₂)_m—NH]_n—C(O)—(X)_y—Z, wherein

Z is a radical selected from an alkyl radical of the formula C_sH_(2s+1), where s is an integer having a value of from 3 to 20 inclusive, and cycloalkyl radicals of the formula C_tH_(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 (CH₂)_p, where p is an integer having a value of from 2 to 14 inclusive, cycloaliphatic radicals, bridged cycloaliphatic radicals, —CH═CH—(CH₂)_b—O—(CH₂)₂—, —CH₂—CH₂—(CH₂)_b—O—(CH₂)₂—, —CH═CH—(CH₂)_b—S—(CH₂)₂—, —CH₂—CH₂—(CH₂)_b—S—(CH₂)₂— radicals, where b is zero or an integer of from 1 to 14 inclusive and —SO₂—N(R)—(CH₂)_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;

m is an integer of from 2 to 6 inclusive;

and n is an integer of from 2 to 100 inclusive.

16. The process of claim 13, wherein the film-forming polymer is selected from hemicellulose, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol (PVOH), styrene-maleic anhydride (SMA), styrene acrylic acid (SAA), alginates, guar gum, pectin, starch, ethylated starches, cationic starches, oxidized starches, acetylated starches, cyanoethylated starches, and combinations thereof.

17. The process of claim 13, wherein the pretreatment composition further comprises an anionic polymer.

18. The process of claim 13, wherein the anionic polymer is selected from a copolymer of styrene with fumaric acid, maleic acid, glutaconic acid, traumatic acid, muconic acid, and combinations thereof.

19. The process of claim 13, wherein the fluorochemical composition comprises anionic fluorochemicals, cationic fluorochemicals, amphoteric fluorochemicals, non-ionic fluorochemicals, polymeric fluorochemicals, or hybrid fluorochemicals.

20. The process of claim 13, wherein:

a) the cationic polymer, the film-forming polymer, or the combination thereof is present in the pretreatment composition in an amount from about 0.01% to about 25% by weight in the aqueous dispersion;

b) the fluorochemical composition comprises at least one fluorochemical present in an aqueous medium in an amount from about 0.0001% to about 5% by weight; or

c) both conditions a) and b) are present.

21. The process of claim 13, wherein pretreatment composition or the fluorochemical composition further comprises an inorganic nanoparticle component comprising: silica; silica modified with at least one silane coupling agent selected from a substituted trialkoxysilane, a cationic polymer, or combinations thereof; clay; or combinations thereof.

22. A paper or paperboard made according to the process of claim 13.