KR20150068975A - Paper with higher oil repellency - Google Patents

Paper with higher oil repellency Download PDF

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Publication number
KR20150068975A
KR20150068975A KR1020157012037A KR20157012037A KR20150068975A KR 20150068975 A KR20150068975 A KR 20150068975A KR 1020157012037 A KR1020157012037 A KR 1020157012037A KR 20157012037 A KR20157012037 A KR 20157012037A KR 20150068975 A KR20150068975 A KR 20150068975A
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KR
South Korea
Prior art keywords
ch
nanoparticles
method
cellulosic
paper
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KR1020157012037A
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Korean (ko)
Inventor
제임스 더블유. 존스톤
데이비드 에프. 타운샌드
코넬 하지오폴
레이키샤 디. 탈버트
찰스 쥐. 러프너
Original Assignee
조지아-퍼시픽 케미칼즈 엘엘씨
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Priority to US201261713354P priority Critical
Priority to US61/713,354 priority
Application filed by 조지아-퍼시픽 케미칼즈 엘엘씨 filed Critical 조지아-퍼시픽 케미칼즈 엘엘씨
Priority to PCT/US2013/064296 priority patent/WO2014059118A1/en
Publication of KR20150068975A publication Critical patent/KR20150068975A/en

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/12Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16Sizing or water-repelling agents
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/27Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277Cellulosic substrate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31971Of carbohydrate
    • Y10T428/31993Of paper

Abstract

The present invention provides a process for the preparation of oily and greasy cellulosic materials such as paper and paperboard comprising applying a homogeneous aqueous dispersion of fluoro compound surface modified nanoparticles to a cellulosic substrate to form a treated cellulosic Forming a gelling substrate, and then drying the treated cellulosic substrate to form a oil-based cellulosic material. Fluoro compounds that can be used to modify the nanoparticles include fluoroalkylsilanes, ionic fluoro compounds, or fluorinated polyacrylates obtained by seed emulsion polymerization of fluoroacrylates on the nanoparticles. Paper, paperboard or cellulosic fiber products modified by the method disclosed above have improved oil and grease resistance properties.

Description

Paper with higher oil repellency {Paper with higher oil repellency}

The present invention relates to oil and grease resistant / repellent paper and to a process for making oil and grease resistant paper.

Paper is a composite material containing small, interconnected discrete fibers, providing a highly porous structure. Paper is typically made of cellulosic fibers, which are usually formed into sheets on a fine screen from a dilute aqueous suspension or slurry, including randomly distributed fibers and air voids. For example, the specific area of the paper can be about 0.5-10 m < 2 > / g, where the pores account for 25-70% of the volume of the paper, so that the apparent density of the paper is less than about 0.8 g / cm3.

The porous structure of the paper also causes penetration of oils, greases, organic solvents, etc., as paper products made from untreated cellulose fibers become wet and rapidly lose their strength due to moisture penetration. Typically, materials such as waxes, silicones or fluorochemicals have been applied externally to cellulosic fiber products to provide certain oil resistance and oil and grease resistance means. However, due to environmental and health concerns for C8 telomeric water repellent and oil repellent products used in conventional fluorocompound processes, the C8 telomer fluoro compounds are substituted with C6 telomer and perfluoropolyether (PFPE) Fluoro compounds, which are considered to be at lower risk of decomposition into environmentally harmful products. These latter fluoro compounds are somewhat less efficient in oil resistance and grease resistance, and the conversion process itself is inefficient, costly, and time consuming.

Accordingly, there is a need in the art for improved methods and compositions for imparting oil and grease resistance to paper and paper products, particularly those involving the use of lower concentrations of fluoro compounds for environmental improvement and cost improvement There is a constant demand for. The invention also relates to a paper or cardboard having improved stiffness, print clarity, adhesion, peel and friction properties while still further extending the efficacy of the fluorocompounds and still maintaining oil and grease repellency and holdout properties. Or cellulosic fiber products. These demands increase with increased demand for grease / oil resistant or repellent paper for use in bakery products, pet food packaging, instant food, and the like. The preferred method is applicable to a wide range of paper products and will provide a more environmentally friendly manufacturing method while still maintaining efficiency performance against oil and grease resistance.

According to the present disclosure, there is provided a method of improving the grease repellency or oil repellency of a cellulosic material, such as paper or paperboard, comprising applying a cellulosic material to the cellulosic material comprising at least one modified nanoparticle component and at least one fluoro compound To form an oil-repellent cellulosic material. Typically, the method comprises the steps of: applying a homogeneous aqueous dispersion of a fluorocompound surface-modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And drying the treated cellulosic substrate to form a oil-repellent cellulosic material. The fluoro compound may be selected from or include at least one fluoroalkylsilane, a cationic fluoro compound, or a fluorinated polyacrylate.

In one aspect, the present disclosure relates to a process for forming a homogeneous aqueous dispersion comprising a fluorocompound surface modified nanoparticle in combination with a nanoparticle component and a fluoro compound, such as a fluoroalkylsilane, in an aqueous medium, Contacting a homogeneous aqueous dispersion of the fluorocompound surface-modified nanoparticles with a cellulosic substrate to form a oil-repellent cellulosic material. The method may further comprise drying or curing the oil-repellent or oil-resistant cellulosic material once prepared. By forming nanoparticles that are surface-modified with a fluorocompound by combining at least one kind of nanoparticle component and at least one kind of fluorocompounds, the fluorocompounds that impart oil repellency are used at a generally lower concentration, It has been found that the oily properties are unexpectedly improved. Thus, one aspect of the present disclosure is that while it may still provide the desired oil repellency characteristics, a more environmentally friendly and less costly process may be possible using lower concentrations of fluoro compounds.

Without being bound by theory, it is believed that the combination of at least one nanoparticle component and at least one fluoro compound disclosed herein, as disclosed herein, is advantageous because the inorganic nanoparticles and the fluoro compound are separated by a separate process And independently, have different affinities for paper and paperboard. As a result of this different affinity, separation may occur as one component penetrates the paper surface faster than the other component. In order to solve this problem, the present specification provides for bonding a fluoro compound to a rigid nanoparticle through chemical bonding, ionic bonding or polymerization on an inorganic or organic seed particle, and the formation of such a bond is carried out by using a fluoroalkylsilane , A cationic fluoro compound or a fluorinated polymer such as a fluorinated polyacrylate, respectively. The resulting modified or functionalized particles appear to be in the form of composites that simultaneously deliver the fluoro compound and nanoparticles and their individual effects, thus providing a 'Lotus effect'. In one aspect, these fluoro compounds may be considered "supported" in that they can interact with the rigid nanoparticles depending on the nanoparticle composition, and these combined compositions typically contain retention may be added to the paper at the wet end and / or size-press with the aid. When added in a size-press, the size-press solution may contain starch or PVA, and the cellulosic support for the particles may be paper or paperboard made from hardwood and / or softwood.

According to another aspect, and without being bound by theory, it is believed that the combination of one or more nanoparticle components and one or more fluoro compounds serves to modify the surface contour and surface energy of the paper or cardboard (cellulosic material) And improved oil-repellency properties. In particular, it is believed that the particular fluoro compounds used in the present process can modify the surface of the nanoparticles so that they can act in a manner that combines the useful properties of the individual components into a synergistic form. Suitable nanoparticles include inorganic nanoparticles (such as silica, clay minerals, and other inorganic nanoparticles), organic polymer nanoparticles (polystyrene, styrene acrylonitrile (SAN), Etc.) or combinations thereof.

In one exemplary aspect according to the present disclosure, a method of improving grease- and oil-resistance or grease- and oil-repellency of a cellulosic material such as paper, paperboard and other cellulosic materials, comprising the steps of: a) Combining the nanoparticle component and the fluoro compound to form a homogeneous aqueous dispersion comprising fluorocompound surface modified nanoparticles; And b) contacting the homogeneous aqueous dispersion of the fluorocompound surface-modified nanoparticles with a cellulosic substrate to form a oil-repellent cellulosic material. In another exemplary aspect, there is provided a method of making an oil-based cellulosic material, comprising the steps of: a) applying a homogeneous aqueous dispersion of a fluorocompound surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate ; And b) drying the treated cellulosic substrate to form a oil-based cellulosic material. Where the fluoro compound is selected from or comprises a fluoroalkylsilyl compound, the method may comprise the steps of:

a) combining nanoparticle components and a fluoroalkylsilane in an aqueous medium to form a homogeneous aqueous dispersion comprising fluoroalkylsilane surface-modified nanoparticles, wherein said fluoroalkylsilane has the formula: :

[F (CF 2) n CH 2 CH 2] m Si (OR) p, wherein

n is 2, 3, or 4,

m is 4-p,

p is 1, 2, or 3,

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl; And

b) contacting the homogeneous aqueous dispersion of the fluoroalkylsilyl surface-modified nanoparticles with a cellulosic substrate to form a oil-repellent cellulosic material.

According to another aspect of the present disclosure, in order to obtain a homogeneous aqueous dispersion of the fluorocompound surface modified nanoparticles, a method including the following steps can be used:

a) combining a nanoparticle component and a fluoro compound (e.g., a fluoroalkylsilane, a cationic fluoro compound, or both) in an aqueous medium to form a heterogeneous mixture; And

b) forming a homogeneous aqueous dispersion of nanoparticles wherein the nanoparticle component and the fluoro compound interact or react with each other in the heterogeneous mixture to form the heterogeneous mixture of the fluorocompound surface modified nanoparticles.

In the process for preparing an aqueous dispersion of the fluorocompound surface modified nanoparticles, the step of combining the nanoparticle component and the fluorocompound in an aqueous medium may be carried out, for example, by combining an aqueous dispersion of the nanoparticle component with a fluorocompound ≪ / RTI >

The fluoro compound used to modify the surface of the nanoparticles may be a cationic fluoro compound, which may result in ionic interactions between the anionic inorganic nanoparticles and the cationic fluoro compound. However, anionic fluoro compounds may also be used. For example, to use anionic fluoro compounds, the anionic nanoparticles may first be coated with a cationic polymer such as a polyamine, polyamidoamine, polyamidoamine epichlorohydrin (PAE), polyDADMAC (polydiallyl dimethyl Ammonium chloride), and / or a cationic polymer of acrylamide. If desired, the addition of the anionic fluoro compound to the cellulosic substrate, such as paper, can be carried out in a single step, wherein the paper can be treated with anionic particles previously modified with a cationic polymer and then with an anionic fluoro compound have. Alternatively, the addition of an anionic fluoro compound to a cellulosic substrate, such as paper, can be carried out in two stages if desired, wherein anionic nanoparticles treated with a cationic polymer are used to treat the paper and then dried The paper is treated with an anionic fluoro compound in the second step.

Once the cellulosic substrate has been treated or contacted with a homogeneous aqueous dispersion of the fluorocompound surface-modified nanoparticles to form the oleaginous cellulosic material, the method further comprises curing the treated or contacted cellulosic material . It has been found that the method disclosed above provides an unexpected improvement in the oil-repellent character of the cellulose material, while lowering the overall concentration of the fluoro compound imparting oil repellency. Thus, it is believed that one or more nanoparticle components act in the form of an extender for the fluoro compound, so that a lower concentration, more environmentally friendly, and more inexpensive fluoro compound can be used to provide the desired fluid properties see.

The following detailed description and the appended claims describe further embodiments and aspects of the disclosure.

According to one aspect of the composition herein, a two-phase reaction with a liquid fluoroalkylsilane (FAS) reagent in an aqueous medium, or by interaction with a cationic fluoro compound reagent, A novel nanoparticle composition, in particular an inorganic nanoparticle composition, which has been surface-modified by contacting polyacrylates or other polymers or by forming fluorinated acrylates or other polymers on the surfaces of the nanoparticles, is particularly useful for treating cellulosic materials and imparting superior oil repellency properties A method has been developed that can be used to < / RTI > The aqueous dispersions of the compositions herein are typically single phase, optically clear and stable, without significant aggregation or precipitation, with little or no additional solvent or surfactant. For example, in one aspect, the compositions herein used in the treatment process may comprise an aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles, wherein the nanoparticles comprise silica, titania, zirconia, layered magnesium silicate (S) selected from the group consisting of aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN), or combinations thereof, wherein the fluoroalkylsilyl surface functional moiety T is formula [F (CF 2) n CH 2 CH 2] m Si (O-) p, ( where n is 2, 3, or 4; m is 4-p a; p is 1, 2, or 3 ). ≪ / RTI > If desired, the composition is bonded to the surface of the nanoparticles and has the formula [H (CH 2 ) x ] y Si (O-) z wherein x is 1 to 12, y is 4-z, Or 3). ≪ / RTI > For example, the additional component may be methylsilyl.

According to another aspect, there is disclosed an article comprising said fluorocompound surface modified nanoparticles, said article comprising, for example, paper, cardboard or cellulose based articles, said article having improved grease resistance and oil resistance Lt; / RTI > Treated paper, cardboard and cellulose based products also exhibit improved stiffness, print clarity, cohesive strength, peel and friction characteristics as compared to conventional fluorocompounds or silicone treated paper and cardboard and cellulosic fiber products.

According to the present disclosure, there is provided a process for making an oil phase cellulosic material comprising the steps of:

a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And

b) drying the treated cellulosic substrate to form an oil-repellent cellulosic material.

The fluoro compound used in the present process may comprise at least one fluoroalkylsilane, a cationic fluoro compound or a fluorinated polyacrylate.

In another aspect, there is provided a method for improving the grease- and oil-resistance of a cellulosic material such as paper, cardboard and other cellulosic materials when the fluoro compound is a fluoroalkylsilane, the method comprising the steps of do:

a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And

b) drying the treated cellulosic substrate to form a oil-based cellulosic material;

Wherein the fluoro compound used to modify the surface of the nanoparticles comprises at least one fluoroalkylsilane having the formula:

[F (CF 2) n CH 2 CH 2] m Si (OR) p, wherein

n is 2, 3, or 4;

m is 4-p;

p is 1, 2, or 3;

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl.

If an initial step of preparing an aqueous dispersion of the fluoroalkylsilyl surface-modified nanoparticles is performed, the method may comprise the steps of:

a) combining a nanoparticle component and a fluoroalkylsilane in an aqueous medium to form a homogeneous aqueous dispersion comprising fluoroalkylsilane surface-modified nanoparticles, wherein said fluoroalkylsilane has the formula

[F (CF 2) n CH 2 CH 2] m Si (OR) p,

(Where n is 2, 3 or 4,

m is 4-p,

p is 1, 2, or 3,

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl; And

b) contacting the homogeneous aqueous dispersion of the fluoroalkylsilyl surface-modified nanoparticles with a cellulosic substrate to form a oil-repellent cellulosic material.

According to another aspect of the invention, if the step of preparing an aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles is carried out, the method may comprise the steps of:

a) combining the nanoparticle component and the fluoroalkylsilane in an aqueous medium to form a heterogeneous mixture, wherein the fluoroalkylsilane has the formula:

[F (CF 2) n CH 2 CH 2] m Si (OR) p,

Wherein n is 2, 3, or 4,

m is 4-p,

p is 1, 2, or 3,

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl; And

b) reacting the nanoparticle component with the fluoroalkylsilane in the heterogeneous mixture to form a homogeneous aqueous dispersion of the fluoroalkylsilane surface modified nanoparticles.

In the above process for preparing an aqueous dispersion of a fluoroalkylsilyl surface-modified nanoparticle, the combination step of the nanoparticle component and the fluoroalkylsilane in the aqueous medium may be carried out, for example, by mixing an aqueous dispersion of the nanoparticle component with a fluoroalkyl Lt; RTI ID = 0.0 > silane. ≪ / RTI >

In another aspect, a modified substrate is disclosed. The modified substrate comprises fluorocompound surface modified nanoparticles on at least one surface of the substrate, wherein the nanoparticles and the fluorocompounds are as disclosed herein. If desired, the substrate may further comprise an additional non-fluorinated moiety, such as a non-fluorinated alkylsilyl moiety as disclosed herein. When the substrate comprises an additional non-fluorinated alkylsilyl moiety such as trimethylsilyl, the nanoparticles that are particularly effective include silica, zirconia, titania, layered magnesium silicate, aluminosilicate, natural clay, ≪ / RTI > The substrate itself is a cellulosic substrate, typically paper or paperboard.

In yet another aspect, a method of making an oily and greasy cellulosic material is disclosed. The method comprises (i) applying an aqueous dispersion of a fluorocompound surface modified nanoparticle to a substrate, wherein the aqueous dispersion comprises one or more of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural Clay, synthetic clay and mixtures thereof; Said fluoro compound being as disclosed herein; And (ii) drying the substrate. The fluorocompound surface modified nanoparticles may be applied on one or more surfaces or applied to a wetted surface to be inside the substrate, or a combination thereof.

In one aspect, the nanoparticles according to the present disclosure may comprise silica, titania, zirconia, layered magnesium silicate, aluminosilicate, clay and mixtures thereof, for example the clay may be a synthetic clay such as a hectorite clay have. In another aspect, a useful combination of surface modifying nanoparticles can be, for example, a mixture of synthetic hectorite clay and silica.

When the fluoro compound provides a fluoroalkylsilyl moiety, such a fluoroalkylsilyl moiety may be covalently bonded to the surface of the nanoparticle. The fluorocompound surface modified nanoparticles, including fluoroalkylsilyl surface-modified nanoparticles, may be present in the range of about 0.01% to about 50% of the total weight of the composition, for example, about From 1% to about 40%, and includes from about 1% to about 8%. In another aspect, the fluorocompound surface modified nanoparticles comprise about 0.01%, about 0.02%, about 0.05%, about 0.1%, about 0.2%, about 0.5%, about 1% %, About 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 12% , About 20%, about 25%, about 30%, about 30%, about 40%, about 50%, or about 50%, or any number of these concentrations. For example, if the nanoparticles are synthetic hectorite clays, a stable aqueous dispersion of the fluorocompound surface modified nanoparticles may be formed at a concentration ranging from about 0.01% to about 12%, based on the total weight of the composition , From about 1% to about 8% by weight of the total composition.

Depending on the end use and the particular cellulosic substrate to be treated, the dispersions of the present invention may be diluted for more efficient application or to control the level of moisture imparted in the treatment process. Also, depending on the nature of the substrate to be treated, its intended use, and the manufacturing process, other chemical components that may be known in the art may be combined with the aqueous dispersions of the present invention in the appropriate concentration range.

The composition may further comprise one or more additives selected from the group consisting of fluorinated resin emulsions, fluorinated alkylated inorganic nanoparticles and / or wetting agents, fluorocarbon resins, surfactants, silicones, fluorescent emitters, antimicrobial components, antioxidant stabilizers, colorants, photostabilizers, A UV absorber, a wetting agent, a starch, a polyvinyl alcohol, a retention aid, and wet strength aids and mixtures thereof. Alternatively, the composition may be admixed with an additional wetting agent, an anti-soil agent, a fluorocompound resin, a surfactant, or a mixture thereof, as is known in the art, to simplify the manufacturing process in question have. While the aqueous dispersion is generally miscible, it is of course desirable to avoid addition of materials that can condense or precipitate the nanoparticles, otherwise the effectiveness or availability is reduced.

In one aspect, despite the inherently hydrophobic nature of the fluoro compound modified surface, such as the fluoroalkylated surface, the dispersion herein is surprisingly stable and can be infinitely present in a transparent aqueous mixture at rather high concentrations It turned out. The composition may be useful for treating soft paper, paperboard and cellulosic fiber products, which may be applied on dry ends such as size presses or coaters during the papermaking process, on dry ends such that the chemical components are throughout the article, At both the end and wet end, it can be applied to one or both sides of soft paper, cardboard and cellulose fiber products to impart some valuable qualities. The paper, cardboard and cellulose fibers treated with the various dispersions described above also exhibited increased oil and grease repellency.

Fluoroalkylsilyl surface modified nanoparticles. The fluoroalkylsilanes used to provide the fluoroalkylsilyl surface modified nanoparticles by surface modification of the nanoparticles include, but are not limited to, fluoroalkylsilanes of the formula:

[F (CF 2) n CH 2 CH 2] m Si (OR) p, wherein

n is 2, 3, or 4,

m is 4-p,

p is 1, 2, or 3,

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl.

In one aspect, there is provided a method of making and using an aqueous dispersion of a fluoroalkylsilyl surface-modified nanoparticle, said method comprising: a) combining a nanoparticle component with a fluoroalkylsilane in an aqueous medium to form a heterogeneous Forming a mixture; and b) reacting the nanoparticle component with the fluoroalkylsilane in the heterogeneous mixture to form a homogeneous aqueous dispersion of the fluoroalkylsilane surface-modified nanoparticles, wherein the heterogeneous mixture comprises . In the disclosed process, with the fluoro-alkyl silane surface-modified nanoparticles may include alkylsilyl moiety fluoroalkyl having the formula [F (CF 2) n CH 2 CH 2] m Si (O-) p. The step of combining the nanoparticle component and the fluoroalkylsilane in the aqueous medium may be carried out by preparing an aqueous dispersion of the nanoparticle component and then combining or adding the fluoroalkylsilane, Lt; / RTI >

Also in this method, the step of combining the nanoparticle component and the fluoroalkylsilane in the aqueous medium may further comprise combining the non-fluorinated alkylsilanes having the formula:

[H (CH 2) x] y Si (OR 2) z , or [H (CH 2) x] Si (X) z, where

x is an integer from 1 to 12;

y is 4-z;

z is 1, 2 or 3;

R 2 is in each case C 1 -C 6 hydrocarbyl or -C (O) R 3 , wherein R 3 is independently C 1 -C 6 hydrocarbyl;

X is independently in each occurrence a halide or R < 2 & gt ;.

In the above aspect, as the fluoro-alkyl silane surface-modified nanoparticles formula [F (CF 2) n CH 2 CH 2] m Si (O-) p a fluoroalkyl silyl moiety with expression as having the formula H (CH 2) x] y Si (O- ) z , or [H (CH 2) x] y Si (-) z , or [H (CH 2) x] y Si- (O-) z (-) q, having Non-fluorinated alkylsilyl moieties wherein "-" is a silicon-nanoparticle direct bond and y + z + q is 4.

According to another aspect, the present disclosure provides a method of making an oil-based cellulosic material comprising contacting a cellulosic substrate with an aqueous dispersion of a fluoroalkylsilyl surface-modified nanoparticle prepared as described herein Or < / RTI > For example, a method of making an oleophobic cellulosic material is disclosed, comprising contacting a homogeneous aqueous dispersion of fluoroalkylsilyl surface-modified nanoparticles with a cellulosic substrate to form a oleophobic cellulosic material Wherein the aqueous dispersion of the fluoroalkylsilyl surface modified nanoparticles is formed by combining the nanoparticle component and the fluoroalkylsilane in an aqueous medium to form a homogeneous aqueous dispersion comprising the fluoroalkylsilane surface modified nanoparticles provided by being, and to the fluoro-alkyl silane comprises a formula [F (CF 2) n CH 2 CH 2] m Si (OR) p as described herein. The step of combining the nanoparticle component and the fluoroalkylsilane in an aqueous medium can be carried out by combining the non-fluorinated alkylsilanes having the formula H (CH 2 ) x ] y Si (OR 2 ) z , as described herein .

Suitable nanoparticle components for use in accordance with the present invention include at least one selected from silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, and mixtures and combinations thereof. For example, there is provided, in another aspect, a process for the production of fluoroalkylsilyl surface modified nanoparticles selected from silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, ) Producing at least one aqueous dispersion selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, and mixtures thereof; (ii) subul comprising horn to form a heterogeneous mixture by the addition of alkyl silane reagent to Mars fluoro in the aqueous dispersion, wherein the fluoro-alkyl silane reagent (F (CF 2) n CH 2 CH 2) m Si ( OR) p where n is 2, 3 or 4, p is 1, 2 or 3, m is (4-p) and R is methyl, ethyl, n- the step isobutyl and -C (O) selected from CH 3); And (iii) mixing or stirring or leaving the heterogeneous mixture to form a homogeneous aqueous dispersion of the fluoroalkylsilane surface-modified nanoparticles. In one example, as the fluoro-alkyl silane is a (F (CF 2) n CH 2 CH 2) and m Si (OR) p, wherein when m is 1 n can be 4 days, p may be 3, R can be selected from methyl and ethyl. In another example, the nanoparticles may comprise silica, titania, zirconia, layered magnesium silicate, aluminosilicate, clay and mixtures thereof, for example the clay may be a synthetic hectorite clay, Can be synthetic hectorite and silica. The fluoroalkylsilane moiety may covalently bond to the nanoparticle surface to produce a fluoroalkylsilyl moiety.

The process for preparing an oleophilic cellulose material also includes the steps of: a) contacting or otherwise applying a homogeneous aqueous dispersion of the fluorocompound surface modified nanoparticles to a cellulosic substrate to form a treated cellulosic substrate; And b) drying the treated cellulosic substrate to form a cellulosic cellulosic substrate, wherein a fluororesin emulsion is added to the aqueous dispersion before applying the aqueous dispersion to the cellulosic substrate The method comprising the steps of: Additionally, the method may further comprise the step of including fluorine-free alkylated inorganic nanoparticles in the aqueous dispersion before applying the aqueous dispersion to the cellulosic substrate. Further, the method may further include adding at least one selected from the group consisting of a wetting agent, an antifouling agent, a fluorocarbon resin, a surfactant, and a mixture thereof before applying the aqueous dispersion. Optionally, the nanoparticles may be used to contact the nanoparticles before, during, or after contacting the fluoroalkylsilane, with a compound having the formula:

[H (CH 2) x] y Si (OR 2) z or [H (CH 2) x] y Si (X) z, where

x is an integer from 1 to 12;

y is 4-z;

z is 1, 2 or 3;

R 2 is in each case C 1 -C 6 hydrocarbyl or -C (O) R 3 , wherein R 3 is independently C 1 -C 6 hydrocarbyl;

X is independently at each occurrence a halide or R < 2 & gt ;.

That is, the compound having the formula [H (CH 2 ) x ] y Si (OR 2 ) z or [H (CH 2 ) x ] y Si (X) z is added at substantially the same time as the addition of the fluoroalkylsilane, Before, or after < / RTI > For example, in the optional compounds X may be selected from methoxy, ethoxy, propoxy, butoxy, acetoxy and chloride leaving groups. Recycling pumps and static mixers may be used in the method to further increase interfacial contact between immiscible fluoroalkylsilanes and nanoparticles in the process.

Also illustratively according to an embodiment, the fluoroalkylsilane reactant used in step (ii) of the process for producing fluoroalkylsilyl surface modified nanoparticles is (F (CF 2 ) n CH 2 CH 2 ) m Si (OR) p wherein n is 2, 3 or 4, p is 1, 2 or r 3, (m + p) is 4 and R is methyl, ethyl, n- butyl, isobutyl and may be -C (O) CH 3 Im). In another embodiment, the fluoroalkyl moiety of the alkylsilane reactant is a perfluoroalkane of 2 to 4 carbon atoms in length, such as a 4 carbon heteroatom (n is 4), wherein m is 1 and p is 3 and R may be methyl or ethyl. An extended perfluoroalkane chain can be used to obtain a greater degree of hydrophobicity in the treated substrate. However, fluoroalkylsilyl reagents having longer perfluoroalkanes (n greater than 4) chains longer than 4 carbon atoms are less suitable for the preparation of the aqueous dispersions described, which stabilizes both reactants and product dispersions in the process Because addition of an undesirable amount of solvent or surfactant is required.

In one aspect of the method of the present disclosure, the 1, 1, 2, 2-tetrahydro-nonafluorohexyltrimethoxysilane is present in an amount of 25% (w / w) of a colloidal silica (20 nm particles) May be slowly added to the dispersion with stirring to form a liquid-liquid emulsion with a cloudy appearance. Optionally, if desired, recirculation pumps and static mixers may be used with or without a mechanical stirrer to increase the interfacial contact of the FAS with the colloidal silica. The fluoroalkylsilylminer liquid phase is consumed as it agitates for several hours and is gradually reduced to a stable single liquid phase dispersion without stirring. The resulting stable aqueous dispersion contains dispersed silica nanoparticles having a hydrophobic layer covalently bonded on the particle surface and the aqueous dispersion is used to treat or contact the cellulosic substrate.

According to another aspect of the method herein, 5% (w / w) of clay nanoparticles of synthetic hectorite sold under the trade name Laponite® RDS by Rockwood Additives Ltd. is used to prepare fluoroalkylsilyl surface modified nanoparticles, 1,1,2,2-tetrahydrononafluorohexyltrimethoxysilane ("FAS" or fluoroalkylsilyl reagent) can be used (for example, slowly added) . Alternatively, the dispersions of the present invention may be blended with dispersions of alkylated inorganic nanoparticles blended with fluorinated resin emulsions or containing no fluorine. For example, the fluoroalkyl modified clay nanoparticles dispersions described above can be blended with aqueous dispersions of colloidal silica nanoparticles surface-modified with methyltrimethoxysilane (MTMS), and the resulting aqueous dispersion Water contains two distinctly different nanoparticles.

Also disclosed are descriptions and methods for making and using fluoroalkylsilyl surface-modified nanoparticles. The substrate comprises fluoroalkylsilyl surface modified nanoparticles on at least one surface, wherein the nanoparticles are selected from the group consisting of titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, and mixtures thereof comprises at least one member, and the alkylsilyl group to the fluoro (F (CF 2) n CH 2 CH 2) m Si (O-) p ( wherein n is 2, 3 or 4, p is 1,2, or 3, and m is (4-p)). The nanoparticles of the present invention may comprise titania, zirconia, layered magnesium silicate, aluminosilicate, clay and mixtures thereof, for example the clay may be a synthetic hectorite clay, for example the mixture may be a synthetic hectorite Clay and zirconia.

In embodiments, alkylsilyl the surface-modified nanoparticles are to the fluoro (F (CF 2) n CH 2 CH 2) m Si (O-) p ( where, m is 1 when n may be four days, p May be 3, wherein the fluoroalkylsilyl moiety may covalently bond to the surface of the nanoparticle. The substrate may comprise pores having an average diameter in the range of about 100 to 100,000 nanometers. The fluoroalkylsilane surface modified nanoparticles may form one or more layered structures on a substrate wherein the layered structure is about 10,000 nanometers or less in thickness and about 100,000 nanometers or more in length and length. Wherein the substrate is an oxide of the formula [H (CH 2 ) x ] y Si (O-) z wherein x is an integer from 1 to 12, y is s 4 -z, z is 1, 2 Or 3.). ≪ / RTI > When the nanoparticles comprise the optional component moieties, the nanoparticles may comprise silica, titania, zirconia, layered magnesium silicate, aluminosilicate, clay or mixtures thereof.

According to another aspect, there is provided a method of making an oleophobic cellulosic material, comprising the steps of: a) applying a homogeneous aqueous dispersion of a fluoro compound surface-modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate ; And b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material, wherein the fluoro compound comprises or may be selected from one or more cationic fluoro compounds. In this aspect, an ionic bond may be formed between the anionic nanoparticle and the cationic fluoro compound.

Cationic Fluoro compounds . The present disclosure also provides a method of making an oil-based cellulosic material, comprising the steps of: a) providing a homogeneous aqueous dispersion of a fluorocompound surface-modified nanoparticle (also referred to as a fluorocompound surface-modified nanoparticle) Applying to the cellulosic substrate to form a treated cellulosic substrate; And b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material, wherein the fluoro compound comprises or may be selected from one or more cationic fluoro compounds. In this regard, suitable cationic fluoro compounds may include or be selected from compounds such as those disclosed in GB 1,214,538, which are incorporated herein by reference in their entirety. For example, the cationic fluoro compound may be a fluorinated cationic polyamidoamine such as a hydrogenated, alkylated, or epoxidated amide-amine fluoro compound, which may be subjected to a hydrogenation reaction, an alkylation reaction or an epi- Can be produced by the reaction of a hydrin with an intermediate amide-amine fluoro compound of the formula:

Z- (X) y -C (O ) -NH [(CH 2) m -NH] n -C (O) - (X) y -Z, wherein

Z is a radical selected from a perfluoroalkyl radical of the formula C s F (2s + 1) , wherein s is an integer having a value from 3 to 20, and cycloporfluoroalkyl of the formula C t F (2t-1) Radical, wherein t is an integer having a value of from 4 to 6;

X has the formula (CH 2) p of the straight-chain alkylene radical, in which p is an integer having a value of from 2 to 14, a cyclic aliphatic radical, a bridged cyclic aliphatic radical, a -CH = CH- (CH 2) b -O - (CH 2) 2 -, -CH 2 -CH 2 - (CH 2) b -O- (CH 2) 2 -, -CH = CH- (CH 2) b -S- (CH 2) 2 -, -CH 2 -CH 2 - (CH 2 ) b -S- (CH 2) 2 - radical, where b is an integer, and -SO 2 -N (R) 0 or 1 to 14 - (CH 2) q - radical Wherein R is an alkyl radical containing from 1 to 6 carbon atoms and q is an integer from 2 to 12;

y is 0 or 1;

m is an integer from 2 to 6;

And n is an integer from 2 to 100.

For example, the cationic fluoro compound may be an epoxidized amide-amine fluoro compound, which can be prepared by reacting an epihalohydrin with a compound of the formula Z- (X) y -C (O) -NH [(CH 2 ) m- NH 2] n -C (O) - (X) y -Z. Without wishing to be bound by theory, it is believed that the product initially formed from the reaction between the epihalohydrin and the immediately preceding fluoro intermediate may correspond to the following formula:

Figure pct00001
, here:

A is a halogen radical and Z, X, y, m and n are as previously defined. However, as the reaction proceeds, the abovementioned initial reaction product will condense with an additional amount of epihalohydrin through its epoxide group, thereby taking on a more complex structure.

Formula Z- (X) y -C (O ) -NH [(CH 2) m -NH] n -C (O) - (X) intermediates amides of y -Z - amine fluoro compound of the formula Z- (X ) y- C (O) OH with one or more polyamines of the formula H 2 N - [(CH 2 ) m -NH] n H, wherein Z, X , y, m and n are as previously defined.

For example, suitable cationic fluoro compounds include those produced by reacting perfluorooctanoic acid with tetraethylenepentamine and then reacting with epichlorohydrin, which is cationic as exemplified in the following structure Fluoro compounds;

Figure pct00002
.

In this structure, the amide nitrogen is no longer hydrogenated. To have a proper hydrophilic-hydrophobic balance, more amide can be used after the fluorocarbon tail is attached. As also disclosed, alkylation with fluorinated epoxides is used to produce azetidinium moieties.

In one aspect, suitable fluorocarboxylic acids (Z- (X) y -C (O) OH) used in the preparation of cationic amido-amine fluoro compounds include, but are not limited to, (C 3 F 7 COOH); Perfluoro octanoic acid (C 7 F 15 COOH); Omega-perfluoro heptane tilpe acid (C 7 F 15 (CH 2 ) 4 COOH); Omega-perfluoroheptylundecanoic acid (C 7 F 15 (CH 2 ) 10 COOH); Perfluoroheptylmethylcyclobutanecarboxylic acid; Perfluoroheptyl substituted norbornenecarboxylic acid; Omega-perfluoroheptyl-beta-allyloxy-propionic acid (C 7 F 15 -CH = CHCH 2 -O- (CH 2) 2 COOH); Omega-perfluoroheptyl-beta-propoxypropionic acid (C 7 F 15 - (CH 2 ) 3 -O- (CH 2 ) 2 COOH); Omega perfluoroheptyl-beta-allylthiopropionic acid (C 7 F 15 -CH = CHCH 2 -S- (CH 2 ) 2 COOH); Omega-perfluoroheptyl-beta-propylthiopropionic acid (C 7 F 15 - (CH 2 ) 3 -S- (CH 2 ) 2 COOH); And omega- (N-methyl) -perfluoroheptanesulfonamidehexanoic acid (C 7 F 15 -SO 2 -N (CH 3 ) - (CH 2 ) 10 -COOH).

According to another aspect, the polyamine compound that can be used to prepare the cationic amido-amine fluoro compound includes, but is not limited to, H 2 N - [(CH 2 ) m -NH] 4 H (where m is an integer from 2 to 6 And n is an integer from 2 to 100, and may include combinations of compounds according to the above formulas. Thus, among the applicable polyamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and bis-hexamethylenetriamine, nonetheless, representative compounds of these are exemplary only. At least one polyamine corresponding to the above formula may be used simultaneously in the reaction system. If desired, a crude residue may be introduced, including an amine mixture, as the polyamine starting material. Moreover, both linear and branched structures of polyamines are expected. For example, if the polyamine compound comprises two or more primary amine groups and the value of n is greater than about 8, the resulting polyamine is expected to show a branched structure, and such branched polyamines are also of course applicable for use in accordance with the present disclosure It is considered possible.

All available epihalohydrins, including epichlorohydrin and epibromohydrin, may be utilized in accordance with the present disclosure, with epichlorohydrin being preferred for economic reasons and ease of use. The conditions under which an amide-amine fluoro compound can be epoxidized from the reaction of epihalohydrins include the conditions disclosed in GB 1,214,528, which is incorporated herein by reference in its entirety.

Also as examples, suitable cationic fluoro compounds for use in accordance with the present disclosure include those provided in U. S. Patent No. 4,344, 993, which is incorporated herein by reference in its entirety. For example, "ionic perfluorocarbon" as disclosed in U.S. Patent No. 4,344,993 may be used. These ionic perfluorocarbons, which may be suitably introduced, generally include organic compounds represented by the formula:

R f Z, where

R f is a saturated fluorinated aliphatic moiety containing an F 3 C-moiety and Z is an ionic moiety or a potential ionic moiety. The fluorinated aliphatic moieties may typically comprise from 3 to 20 carbons wherein substantially all are fully fluorinated, preferably from about 3 to about 10 such carbons are fluorinated. The fluorinated aliphatic moiety may be linear, branched or cyclic, and may be linear, and may sometimes include hydrogen or halogen attached to the carbon in addition to fluorine, and additionally may contain a divalent sulfur or oxygen atom or trivalent nitrogen Atoms, which are bound only to the carbon atoms of the backbone chain. More preferred are linear perfluoroaliphatic moieties represented by the formula:

C n F 2n +1 , where

n can be from about 3 to about 12, and can be, for example, from 5 to 10. The ionic or potential ionic moieties advantageously further include those represented by the formula:

Figure pct00003
, here:

R is hydrogen or hydrocarbyl such as lower alkyl having 1-3 carbons;

R 'is an alkylene, arylene, oxyarylene, aralkylene or similar divalent hydrocarbon having 1 to 6 carbons or a hydrocarbylene or oxyhydrocarbylene such as an oxyhydrocarbyl moiety;

Each R "is independently hydrogen, hydrocarbyl or hydroxyhydrocarbyl, such as lower alkyl having 1 to 5 carbons; and

X - is an anion, especially an inorganic anion such as a carboxylate such as a halide, sulfate or acetate; And

M + is a cation such as an alkali metal cation or ammonium.

For example, in one aspect, a suitable cationic fluoro compound may be a cationic perfluorocarbon, which may be, for example, 3 - [((heptadecylfluorooctyl) sulfonyl) amino] -N, N , N-trimethyl-1-propanaminium iodide; And the cationic perfluoro (perfluoroalkyl) sulfonic acid sold by DuPont under the trade name Zonyl TM FSC, and / or the sulfonated perfluoro And the like. Examples of other preferred cationic perfluorocarbons as well as methods of preparation are those listed in U.S. Patent 3,775,126.

Additional examples of cationic fluoro compounds include, but are not limited to those provided in U.S. Patent No. 6,951,962, which is hereby incorporated by reference in its entirety. For example, suitable cationic fluoro compounds include compounds having a lipophilic and hydrophobic fluoro compound group substituted with an alkyl chain having a hydrophilic group, wherein the fluoro compound portion of the fluoro compound group also has from 2 to 20 Is characterized by a monovalent, perfluorinated, alkyl or alkenyl, linear, branched or cyclic organic radical having 1 to 5 carbon atoms, which may be in the middle of the divalent oxygen or sulfur atom, if desired.

In one aspect, suitable cationic fluoro compounds include those comprising both polyamine functional groups and fluorinated groups. For example, the polyamine may provide a form of molecular scaffolding, which may include or contain fluorinated groups and cationic functional groups. The polyamine functionalities can also cause the nitrogen to be substituted into four groups, which have cationic characteristics, which aid their action in accordance with the present disclosure, for example, allowing them to interact with negatively charged nanoparticles. While not wishing to be bound by theory, the fluoride groups contained in the cationic fluoro compounds will reduce the surface energy to such an extent that the oil and grease do not wet the cellulosic substrate, including homogeneous aqueous solutions of the fluoro compound surface modified nanoparticles The dispersion is applied. Thus, low free surface energy is believed to be particularly effective in repelling low surface energy materials such as oil and grease, thus repelling these materials from the treated substrate.

According to one aspect, the cationic fluoro compounds may include or be selected from those disclosed in U.S. Patent No. 6,951,962, which is incorporated herein by reference in its entirety. For example, suitable cationic fluoro compounds include those having the structure:

Figure pct00004
, here:

R 8, R 9, R 10 , R 11, R 12 is J, H, - (CH 2 ) 1-6 H, - (CH 2 CH 2 O) 1-10 H, - (CH 2 CHOH) 1- 10 CH 3, -CH (CH 3 ) CH 2 OH, -CH 2 CH (OH) CH 2 Cl,

Figure pct00005
, -CH 2 CH (OH) CH 2 OH, -CH 2 CO 2 - M + (M is a group 1 or group 2 metal), - (CH 2) 1-6 NH 2, 1,0 (R 8) 0, 1, 2 ,

Wherein R 8 , R 10 , R 11 , or R 12 Any two of which may be the same carbon chain,

R 7 is selected from H, -CH 2 CH (OH) CH 2 , which can be bridged to a nitrogen of K or L or M on another fluoro (hydroxyl) alkyl, polyalkylaminohalohydrin, or organosulfonate Wherein R 8 , R 9 , R 10 , R 11 , R 12 Is at least one of the fluorine compounds represented by "J ", and J is selected from the following moieties:

Figure pct00006

Figure pct00007

Here, according to the usual rules of chemical valence:

A is - (CH 2) 1-9 -, -CH 2 CHI (2 CH) 1-9 BCH 2 -, -CH CH = (CH 2) 1-9 BCH 2 -, - (CH 2) 1-11 BCH 2 -, - (CH 2 ) 1-2 B (CH 2 ) 1-10 BCH 2 - wherein B is O, CO 2 , CO 2 [(CH 2 ) 1-2 O] 1-10 , OCH 2 CO 2 , OCH 2 CO 2 CO 2 [(CH 2 ) 1-2 O] 1-10 , S, SO 2 , SCH 2 CO 2 , C (O) S, SCH 2 C 2 O [ 2 ) 1-2 O] 1-10 , S [(CH 2 ) 1-2 O] 1-10 , S (O) NR ', C (S) NR', S (O) NR'CH 2 CH 2 O, C (O) NR ' , OCH 2 C (O) NR', OPO 3, NR ', SCH 2 C (O) NR', is selected from -N (R) CH 2 CO 2 , where R 'is H, - (CH 2) is selected from 1-6;

R is H, - (CH 2) 1-6 is selected from H;

R F is F (CF 2) 4-18, CF 3 CF (CF 3) (CF 2) 3-5, CF 3 CF 2 CF (CF 3) (CF 2) 3-5, H (CF 2) 4 -18, HCF 2 CF (CF 3 ) (CF 2) 3-5, HCF 2 CF 2 CF (CF 3) (CF 2) 3-5, cycloalkyl hydroperoxide fluoroalkyl of the formula C 2 F (2z-1) Radical where z is an integer from 4 to 6;

n, p, q, s, t, v, and w are integers;

p is 0 or 1;

n is 1-6;

v + q + w + s = 3 to about 1000;

q, w, s each may be 0 when desired;

t is w + s;

It is selected from, and Q is a C1 -, Br -, I - , CH 3 C 6 H 4 SO 2 - -, CH 3 SO 2; And

K, L, and M are randomly distributed along the polyamine and T is the amine at the end of the polyamine chain.

In accordance with another aspect, the use of an anionic fluoro compound is possible because an ionic bond between the anionic nanoparticle and the anionic fluoro compound can be established through the intermediate cationic polymer. For example, the cationic nanoparticles are first modified with cationic non-fluorinated polymers such as polyamines, polyamidoamines, polyamidoamine epichlorohydrin (PAE), poly DADMCD, cationic polyacrylamide, and combinations thereof . Subsequently, the cationic fluoro compound may be used to form a fluorocompound surface-modified nanoparticle.

Fluorinated emulsion Polymer . According to a further aspect of the present invention there is provided a process for preparing an oleophobic cellulosic material comprising the steps of: a) applying a homogeneous aqueous dispersion of fluorosurfactant surface modified nanoparticles to a cellulosic substrate to form a treated cellulosic Forming a substrate; And b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material, wherein the fluoro compound comprises one or more fluorinated polyacrylates. In this respect, the bonding of the fluoro compound to the rigid nanoparticles occurs by polymerization on the nanosized seed particles, and the bond between the fluoropolymer and the nanoparticles, such as the fluorinated polyacrylate, may occur. Thus, such seed emulsion polymerization can be used for copolymerization with fluorinated acrylates and other fluorinated monomers and comonomers on the nanoparticles, including non-fluorinated comonomers. In this respect, surface modified with a fluoro compound comprising or selected from polymeric fluoro compounds such as perfluoropolyacrylate and perfluorinated polyurethane (core shell structure). In a typical embodiment, the fluoro compound may be oleophobic and hydrophobic.

Various embodiments and aspects herein provide that the substrate can be a paper, cardboard or cellulose fiber or cellulose based article, wherein the composition has a lower content of fluorine elements compared to traditional fluoro compound resin emulsion coatings To give the same level of oil and grease repellency. It has been found that the coated substrates of the present invention, or internally contained substrates, or combinations thereof, exhibit excellent oil and grease repellency while using less fluorine elements than found in conventional fluorocompound resin coatings. The method of making a substrate having an aqueous dispersion of nanoparticles comprises applying an aqueous dispersion of the fluoroalkylsilyl surface-modified nanoparticles to a substrate and drying the substrate.

Also provided are various articles made from a substrate comprising the fluoroalkylsilyl surface modified nanoparticles provided herein. More particularly, the article comprises a composition comprising the fluoroalkylsilyl surface-modified nanoparticles described herein. The nanoparticles may include at least one selected from the group consisting of titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, and mixtures thereof, wherein the fluoroalkylsilyl moiety is It can be as described. Optionally, the nanoparticles may further comprise a non-fluorinated alkylsilyl moiety as disclosed herein. Articles may include, but are not limited to, paper, cardboard, cellulosic fiber products, and other cellulose based articles. When the article is paper, cardboard, cellulose fibers or cellulose based articles or contains an optional non-fluorinated alkylsilyl moiety, the nanoparticles may also comprise silica.

Typically and in one aspect, the article can comprise a total concentration of fluorine ranging from about 10 ppm to 500 ppm (w / w) of the exposed substrate, and from about 50 ppm to about 300 ppm w / w. For paper, paperboard, cellulosic fibers or cellulosic articles, the substrate holds fluoroalkylsilyl surface modifying nanoparticles in the range of about 0.01% to about 2.0% by weight of the exposed substrate, From about 0.1% to about 1.0% by weight of the composition; Or the substrate comprises fluorine elements in the range of about 0.0001 wt.% To about 0.10 wt.% Of the exposed substrate, including about 0.0001 wt.% To 0.010 wt.% Of the exposed substrate. In embodiments, the substrate holds fluoroalkylsilyl surface modified nanoparticles in the range of from about 0.01 to about 3 grams per square meter of surface area, including from about 0.1 to about 2 grams per square meter of surface area.

Definition .

In order to more clearly define the terms used herein, the following definitions are provided, unless otherwise indicated, for example, by not adhering to the usual rules of chemical valence, Unless the claim is made unclear or not possible. It is to be understood that, unless the terminology used herein is specifically defined, it does not conflict with any other disclosure or definition that is applied herein, or that any claim that the definition is applied to is unclear or unavailable, The definition from the IUPAC Compendium, 2nd Edition (1997) of Chemical Terminology may be applied. The definitions or usage provided herein govern to the extent that any definition or idiom provided by any document incorporated herein by reference conflicts with the definition or idiom provided herein.

Although compositions and methods are described in terms of "comprising" various components or steps, the compositions and methods may also be "consisting essentially of" or "consisting essentially of" the various components or steps.

For the sake of clarity, the following definitions are provided, even if most familiar to those skilled in the art.

As used herein, the term "nanoparticles" is used to describe multidimensional particles in which one dimension is less than 100 nm in length.

The abbreviation "FAS" refers to a fluoroalkylsilane reagent used to impart a fluorinated organic functionality, including, but not limited to, the inorganic particles of the present invention. FAS reagents specifically, the formula (F (CF 2) n CH 2 CH 2) m Si (OR) p ( where n is 2, 3 or 4; p is 1 or more and; m is 1 or more and; m + p is 4; for example, R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or -C (O) CH 3 and the like. It is to be understood that other structures having perfluorinated alkyl end functionality are contemplated by the present disclosure, although less preferred for the methods of manufacture disclosed herein. And FAS reagents are also formula (F (CF 2) n CH 2 CH 2) m Si (X) may include the structure of p, where n is 2, 3, or 4, p is at least 1, m is 1 or more, m + p is 4, and X is a halogen such as chlorine, bromine or iodine. FAS reagents, and may comprise the structure of the p (X), where n> 2, and, m + p is 3, R 'also equation (F (CF 2) n CH 2 CH 2) m SiR silicon atom Methyl or ethyl, and X is a halogen such as chlorine, fluorine or iodine bonded to a silicon atom.

The term "clay " as used herein refers to clay minerals such as hydrated aluminum phyllosilicate minerals. Clay minerals that may be used herein include 1: 1 and 2: 1 clays and may be selected from the group consisting of smectite (e.g., montmorillonite, nontronice, sapolite, etc.) Kaolinite (e.g. kaolinite, dickite, halloysite, nacrite, etc.), ilite (e.g. illite, clay-mica ), Etc.), chlorite (e.g., clinochlore, chamosite, nimite, pennantite, etc.) and attapulgites, sepiolites ), ≪ / RTI > and the like, or may be made essentially, or selected therefrom. They are selected from the group consisting of montmorillonite, bentonite, pyrophllite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite, kaolinite, dickite, antigorite, anauxite, indellite, chrysotile, bravisite, ), Suscovite, paragonite, biotite, correnite, penninite, donbassite, sudoite, pennine, ), Sepiolite, and polygorskyte. ≪ / RTI > The clay minerals of the present invention can be synthetic or natural and are stripped to form aqueous microdispersions. An example of one embodiment of the invention uses synthetic hectorite clay nanoparticles sold under the trade name Laponite® from Rockwood Additives Ltd. Preferred embodiments of the present invention use RDS®, Laponite JS® and Laponite RD®. Thus, also as used herein, the term "clay" refers to clay minerals such as hydrated aluminum phyllosilicate minerals, including 1: 1 and 2: 1 clays, and smectite (e.g. montmorillonite, Kaolinite (e.g., kaolinite, dickite, haloisite, and nacrite), ilite (e.g., ilite, clay-mica, etc.) , Chitosite, nemite, pennantite, and the like), and other minerals and classes such as ataplulite, sepiolite, and the like, or may be made essentially or selected therefrom.

Aqueous "dispersion" is a colloidal dispersion, meaning a system of finely divided small sized particles, such as nanoparticles, that are uniformly dispersed in a manner that is not easily filtered or gravitationally separated.

Aqueous "microdispersion" means a dispersion of particles predominantly having a size of less than about 100 nm in one or more dimensions.

An "insoluble" aqueous microdispersion is an aqueous microdispersion that is stable for a prolonged period (2 months or 3 months) without a water-miscible surfactant.

"Layered structure" is one in which an overlap of nanoparticles is observed, in which a flat layer or sheet is observed rather than a circular, ball-like or lumpy aggregation structure.

Similar terms such as the term " cellulosic material "or" cellulosic fiber material "or" cellulosic material "are typically used in the manufacture of, for example, It is used to mean cellulosic fibers.

The term "hydrocarbyl" is used herein in accordance with the definition embodied by IUPAC: a monovalent group formed by the removal of a hydrogen atom from a hydrocarbon (i.e., a group comprising only carbon and hydrogen). Non-limiting examples of hydrocarbyl groups include straight chain, branched, and cyclic hydrocarbyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, cyclopentyl, vinyl,

The term "alkyl" group is used in accordance with the definition embodied herein by IUPAC: a monovalent group derived from an alkane by removing a hydrogen atom from any carbon atom having the formula -C n H 2n +1 . Unless specifically indicated otherwise, alkyl includes groups derived from an alkane by removal of a hydrogen atom from a primary, secondary, or tertiary carbon. Thus, unless otherwise specifically indicated, non-limiting examples of alkyl groups include straight chain, branched, and cyclic groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, cyclopentyl, Type alkyl group.

Unless specifically stated otherwise, any carbon containing group in which the number of carbon atoms is not specified may be 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 combinations thereof. For example, unless otherwise specifically indicated, any carbon containing group may contain 1 to 30 carbon atoms, 1 to 25 carbon atoms, 1 to 20 carbon atoms, 1 to 15 carbon atoms, 1 to 10 carbon atoms, or 1 To 5 carbon atoms, and the like. Also, other determinants or qualifying terms may be utilized to indicate the presence or absence of certain substituents, specific regiochemistry and / or stereochemistry, or the presence or absence of a base structure or skeleton of a branch.

In any application by the USPTO, the summary of the present application is incorporated herein by reference. 1.72 and 37 C.F.R. The purpose described in 1.72 (b) is provided for the United States Patent and Trademark Office and the general public to determine from a cursory inspection of the nature and gist of the technical disclosure. Accordingly, the summary of the present application is not intended to be used to conjecture the scope of the claims or to limit the scope of the subject matter disclosed herein. Furthermore, any headings that may be introduced herein are also not intended to be used to conjecture the scope of the claims or to limit the scope of the subject matter disclosed herein. Any use of past tenses to illustrate embodiments which may otherwise be prescriptive or prophetic may not be presumed or intended to reflect that the prophetic embodiment has been practically carried out.

Applicants will appreciate, for example, that, to limit the scope of any claim to limit the scope of the present disclosure to those of ordinary skill in the art, Rights.

Example

The following embodiments are provided to illustrate various implementations of the present specification and claims. Unless specifically indicated otherwise, reagents were obtained from commercial sources. Standard analytical methods were used to describe composition properties.

Various TAPPI test methods such as T454 om-89 turpentine oil test for grease resistance of paper, T507 cm-85 impervious, (non-absorbent) size paper of flexible packaging material and T441 om-90 water A TAPPI sizing test method including, but not limited to, Cobb test, UM 557 kit test for grease, oil and wax of paper and paperboard can be used.

Performance testing. For the following performance tests, all embodiments were performed using the following protocol. Paper having a basis weight of 34 g / m 2 was passed through a size-press solution for 15 seconds and dried in a drum dryer at 105 ° C for 20 seconds. The dry paper was kept at 25 [deg.] C and 50% humidity for at least 24 hours before testing. The paper was tested by measuring the contact angle against Castor oil as a function of time using a Rame-Hart gauges Model 250.

Comparative Example 1. Uncoated paper was tested with the contact angle measurement described above and found to exhibit an initial oil contact angle of 30 degrees. After a 30 second contact time, the contact angle decreased to 19 degrees. The change reflects strong oil absorption into the paper.

Comparative Example 2. Paper treated in a size-press with a solution of 1% fluoro compound (Daikin 8112) shows an initial contact angle of 60 degrees with Castor oil. The contact angle is maintained unchanged after 30 minutes.

Example 3. The same paper used in Comparative Examples 6 and 7 was pre-treated in a size-press with a 0.5% solution of modified silica, i.e., silica nanoparticles modified with silane. After drying, the initial contact angle was measured at 75 degrees, which remained constant after 30 minutes.

Example 4. The same paper used in Comparative Examples 7 and 8 was pre-treated in a size-press with a 0.4% solution of silica particles modified with 0.8% cationic polymer (PAE: polyamidoamine epichlorohydrin). After drying, the paper pretreated with a 1% solution of the same fluoro compound (Daikin 8112) was treated. The initial contact angle was 102 degrees and remained constant after 30 minutes.

Additional features, features, and embodiments of the invention may be understood by reference to the following numbered aspects of the disclosed invention. It will be appreciated that any reference to the disclosure of any of the foregoing aspects may be applied to any of the aforementioned numbered aspects and any of the aforementioned aspects in any combination of the above- . ≪ / RTI > The following numbered aspects are provided:

1. A method for producing an oil-based cellulosic material, comprising the steps of:

a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And

b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material.

2. The method according to the above aspect, wherein the fluorine compound comprises at least one fluoroalkylsilane, an ionic fluoro compound or a fluorinated polyacrylate.

3. The method of any one of the preceding aspects, wherein said at least one fluoroalkylsilane has the formula:

[F (CF 2 ) n CH 2 CH 2 ] m Si (OR) p ,

n is 2, 3 or 4;

m is 4-p;

p is 1, 2 or 3;

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl. .

4. A method according to any one of the preceding aspects, wherein said at least one cationic fluoro compound is selected from amines, polyamines, quaternary ammonium salts or combinations thereof.

5. The method according to any one of the preceding aspects, wherein the at least one cationic fluoro compound comprises an azetidinium group.

6. The method of any one of the preceding aspects, wherein the at least one cationic fluoro compound is prepared from the reaction of an epihalohydrin with a compound of the formula:

Z- (X) y -C (O ) -NH [(CH 2) m -NH] n -C (O) - (X) y -Z, wherein

Z is selected in each case from an acyclic group C s F (2s + 1) (where s is an integer from 3 to 20) and a cyclic group C t F (2t-1) wherein t is an integer from 4 to 6 ;

When each X is (CH 2) p (with the proviso that p is a numeral from 2 to 14), a cyclic aliphatic radical, a bridged cyclic aliphatic radical, a -CH = CH- (CH 2) b -O- (CH 2) 2 -, -CH 2 -CH 2 - ( CH 2) b -O- (CH 2) 2 -, -CH = CH- (CH 2) b -S- (CH 2) 2 -, -CH 2 -CH 2 - (CH 2) b -S- ( CH 2) 2 - radical (wherein b is an integer of 0 or 1 to 14) -SO 2 -N (R) - (CH 2) q - radical (where R is from 1 to An alkyl radical containing 6 carbon atoms and q is an integer from 2 to 12;

y is 0 or 1 in each case;

m is an integer from 2 to 6;

n is an integer from 2 to 100;

7. The method of any one of the preceding aspects, wherein the ionic fluoro compound is an anionic compound retained on the nanoparticle and having an intermediate cationic polymer.

8. The method according to any one of the preceding aspects, wherein the fluorinated polyacrylate is obtained by seed emulsion polymerization of fluoro acrylate on the nanoparticles.

9. The method according to any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles comprise a non-fluorinated alkylsilyl moiety having the formula:

[H (CH 2 ) x ] y Si (O-) z , where

x is an integer from 1 to 12;

y is 4-z;

z is 1, 2 or 3;

10. The method according to any one of the preceding aspects, wherein the cellulosic substrate comprises a component selected from paper, cardboard and cellulose fibers.

11. The method of any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles form a layered structure having a thickness on the cellulosic substrate of less than about 10,000 nanometers.

12. The method of any one of the preceding aspects, wherein the nanoparticles are selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN) ≪ / RTI >

13. The method according to any one of the preceding aspects, wherein the nanoparticles comprise silica, natural clay or synthetic clay.

14. The method according to any one of the preceding aspects, wherein the nanoparticles comprise at least one clay selected from smectite, kaolin, ilite, chlorite, attapulgite, sepiolite, or a combination thereof.

15. The method of any one of the preceding aspects, wherein the nanoparticles are selected from the group consisting of montmorillonite, bentonite, pyrophyllite, hectorite, saponite, saponite, nontronite, talc, But are not limited to, vermiculite, kaolinite, dickite, haloisite, nacrite, antigorite, ilite anoxite, indelite, creosote, brabesite, sucukbite, paragonite, biotite, A site, a diatomite, a penneine, a sepiolite, a polyglycateate, a clinochle, a chomosite, a nemite, a phenanthite muskbite, a flocite or a pengeite.

16. The method according to any one of the preceding aspects, wherein the nanoparticles comprise synthetic hectorite.

17. The method of any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles are present in the aqueous dispersion at a concentration of from about 0.01% to about 50% by weight of the total composition.

18. The method according to any one of the preceding aspects, wherein the homogeneous aqueous dispersion further comprises an emulsion polymer.

19. The method according to any one of the preceding aspects, wherein the emulsion polymer is a fluorinated resin emulsion.

20. The method according to any one of the preceding aspects, wherein the aqueous dispersion of the fluorocompound surface modified nanoparticles further comprises an alkylated inorganic nanoparticle free of fluorine content.

21. The method of any one of the preceding aspects, wherein the aqueous dispersion of the fluoroalkylsilane surface-modified nanoparticles comprises a wetting agent, an antifouling agent, an anti-stain agent, a fluorocompound resin, a surfactant , Silicon, a fluorescent agent, an antimicrobial component, an antioxidative stabilizer, a colorant, a photostabilizer, a UV absorber, a starch, a polyvinyl alcohol, a retention enhancer, a wet strength enhancer or any combination thereof.

22. An article comprising an oil-repellent cellulosic material made according to the process according to any of the preceding aspects.

23. The article of any of the preceding aspects, wherein the fluorine concentration on the oleaginous cellulosic material is from about 10 weight ppm (w / w) to about 500 weight ppm (w / w).

24. The article of any of the preceding aspects, wherein the fluorine concentration on the oleaginous cellulosic material is from about 0.0001 wt% to about 0.10 wt%.

25. The article of any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles are present on the oleaginous cellulosic material at a concentration of about 0.01% to about 2.0% by weight.

26. The method of any one of the preceding aspects, wherein the fluorocompound surface-modified nanoparticles are present in the oil-repellent cellulosic material at about 0.01 to about 3 g / m 2 of the surface area of the oil-repellent cellulosic material article.

27. A paper or paperboard made according to the method according to any of the preceding aspects.

28. Paper or paperboard treated with a homogeneous aqueous dispersion comprising fluorocompound surface-modified nanoparticles to form oil-based paper or paperboard.

Any suitable combination of features, features, and implementations described above in the numbered aspects of the invention is also included herein. Examples of additional aspects and combinations of the numbered aspects of the present invention provided herein include, but are not limited to, the following numbered aspects:

1. A method for producing an oil-based cellulosic material, comprising the steps of:

a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And

b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material.

2. The method according to the above aspect, wherein the fluorine compound comprises at least one fluoroalkylsilane, an ionic fluoro compound or a fluorinated polyacrylate.

3. The method of any one of the preceding aspects, wherein said at least one fluoroalkylsilane has the formula:

[F (CF 2 ) n CH 2 CH 2 ] m Si (OR) p ,

n is 2, 3 or 4;

m is 4-p;

p is 1, 2 or 3;

R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl. .

4. A method according to any one of the preceding aspects, wherein said at least one ionic fluoro compound is selected from amines, polyamines, quaternary ammonium salts, cationic fluoro compounds comprising an azetidinium group, or combinations thereof.

5. A method according to any of the preceding aspects, wherein said at least one ionic fluoro compound is prepared from the reaction of an epihalohydrin with a compound of the formula:

Z- (X) y -C (O ) -NH [(CH 2) m -NH] n -C (O) - (X) y -Z, wherein

Z is selected from the non-cyclic group C s F (2s + 1) (where s is an integer from 3 to 20) and the cyclic group C t F (2t-1) (where t is an integer from 4 to 6) Being;

X is in each case (CH 2 ) p where p is an integer from 2 to 14, a cyclic aliphatic radical, a bridged cyclic aliphatic radical, -CH = CH- (CH 2 ) b -O- (CH 2 ) 2 -, -CH 2 -CH 2 - (CH 2) b -O- (CH 2) 2 -, -CH = CH- (CH 2) b -S- (CH 2) 2 -, -CH 2 -CH 2 - (CH 2) b -S- (CH 2) 2 - radical (wherein b is an integer of 0 or 1 to 14) -SO 2 -N (R) - (CH 2) q - radical (wherein R 1 is Lt; / RTI > is an alkyl radical containing from 1 to 6 carbon atoms and q is an integer from 2 to 12;

y is 0 or 1 in each case;

m is an integer from 2 to 6;

n is an integer from 2 to 100;

6. The method of any one of the preceding aspects, wherein the ionic fluoro compound is an anionic compound retained on the nanoparticle and having an intermediate cationic polymer.

7. The method according to any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles comprise a non-fluorinated alkylsilyl moiety having the formula:

[H (CH 2 ) x ] y Si (O-) z , where

x is an integer from 1 to 12;

y is 4-z;

z is 1, 2 or 3;

8. The method according to any one of the preceding aspects, wherein the cellulosic substrate comprises a component selected from paper, cardboard and cellulose fibers.

9. The method of any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles form a layered structure having a thickness on the cellulosic substrate of less than about 10,000 nanometers.

10. The method of any one of the preceding aspects, wherein the nanoparticles are selected from the group consisting of silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN) ≪ / RTI >

11. The method according to any one of the preceding aspects, wherein the nanoparticles comprise at least one clay selected from smectite, kaolin, ilite, chlorite, attapulgite, sepiolite, or a combination thereof.

12. The method of any one of the preceding aspects, wherein the nanoparticles are selected from the group consisting of montmorillonite, bentonite, pyrophyllite, hectorite, saponite, saponite, naltronite, talc, But are not limited to, vermiculite, kaolinite, dickite, haloisite, nacrite, antigorite, ilite anoxite, indelite, creosote, brabesite, sucukbite, paragonite, biotite, A site, a water phase, a pen nine, a sepiolite, a polyglycateate, a clino chloe, a chomosite, a nemite, a phenantite musocobite, a flocophite, a synthetic hectorite or a phengite.

13. The method of any one of the preceding aspects, wherein the fluorocompound surface modified nanoparticles are present in the aqueous dispersion at a concentration of from about 0.01% to about 50% by weight of the total composition.

14. The method according to any one of the preceding aspects, wherein the homogeneous aqueous dispersion further comprises an emulsion polymer or a fluorinated resin emulsion.

15. The method of any one of the preceding aspects, wherein the aqueous dispersion of the fluorocompound surface modified nanoparticles is a wetting agent, an antifouling agent, an anti-stain agent, a fluorocompound resin, a surfactant, The present invention relates to a process for the preparation of a composition comprising a silicone, a fluorescent agent, an antimicrobial component, an antioxidative stabilizer, a colorant, a photostabilizer, a UV absorber, a starch, a polyvinyl alcohol, Further comprising:

16. Paper or paperboard made according to any of the preceding aspects.

17. An article comprising an oil-repellent cellulosic material produced by a process comprising the steps of:

a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And

b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material.

18. The method of any one of the preceding aspects, wherein the fluorine concentration on the oleaginous cellulosic material is from about 10 wt ppm (w / w) to about 500 wt ppm (w / w), or from about 0.0001 wt% % By weight.

19. The method of any one of the preceding aspects, wherein the fluorocompound surface-modified nanoparticles are present on the oleaginous cellulosic material at a concentration of about 0.01 wt.% To about 2.0 wt.%, Or the oleaginous cellulosic Lt; RTI ID = 0.0 > g / m2 < / RTI > of the surface area of the material.

20. Paper or paperboard treated with a homogeneous aqueous dispersion comprising fluorocompound surface-modified nanoparticles to form oil-based paper or paperboard.

The present invention has been described with reference to various aspects of paper and paperboard manufacturing methods having disclosed oil repellency and improved oil repellency. Obvious modifications and alterations will occur to others upon reading and understanding the above detailed description. It is intended that the invention be construed as including all such modifications and alterations as fall within the scope of the claims.

Claims (20)

  1. A method for producing an oil-based cellulosic material, the method comprising the steps of:
    a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And
    b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material.
  2. The method of claim 1 wherein said fluoro compound comprises at least one fluoroalkylsilane, an ionic fluoro compound, or a fluorinated polyacrylate.
  3. 3. The method of claim 2 wherein said at least one fluoroalkylsilane has the formula:
    [F (CF 2 ) n CH 2 CH 2 ] m Si (OR) p ,
    n is 2, 3 or 4;
    m is 4-p;
    p is 1, 2 or 3;
    R is C 1 -C 6 hydrocarbyl or -C (O) R 1 , wherein R 1 is independently C 1 -C 6 hydrocarbyl.
  4. The method of claim 2, wherein said at least one ionic fluoro compound is selected from amines, polyamines, quaternary ammonium salts, cationic fluoro compounds comprising an azetidinium group, or combinations thereof.
  5. 3. The method of claim 2 wherein said at least one ionic fluoro compound is prepared from the reaction of an epihalohydrin with a compound of formula:
    Z- (X) y -C (O ) -NH [(CH 2) m -NH] n -C (O) - (X) y -Z, wherein
    Z is independently selected from the group consisting of a non-cyclic group C s F (2s + 1) , where s is an integer from 3 to 20 and a cyclic group C t F (2t-1) , wherein t is an integer from 4 to 6 Selected;
    X is in each case (CH 2 ) p where p is an integer from 2 to 14, a cyclic aliphatic radical, a bridged cyclic aliphatic radical, -CH = CH- (CH 2 ) b -O- (CH 2 ) 2 -, -CH 2 -CH 2 - (CH 2) b -O- (CH 2) 2 -, -CH = CH- (CH 2) b -S- (CH 2) 2 -, -CH 2 -CH 2 - (CH 2) b -S- (CH 2) 2 - radical (wherein, b is an integer of 0 or 1 to 14), and -SO 2 -N (R) - ( CH 2) q - radical (where , R is an alkyl radical containing from 1 to 6 carbon atoms and q is an integer from 2 to 12;
    y is 0 or 1 in each case;
    m is an integer from 2 to 6;
    n is an integer from 2 to 100;
  6. 3. The method of claim 2, wherein the ionic fluoro compound is an anionic compound retained on the nanoparticle and having an intermediate cationic polymer.
  7. The method according to claim 1, wherein the fluorine compound surface-modified nanoparticles comprise a non-fluorinated alkylsilyl moiety having the formula:
    [H (CH 2 ) x ] y Si (O-) z , where
    x is an integer from 1 to 12;
    y is 4-z;
    z is 1, 2 or 3;
  8. The method of claim 1, wherein the cellulosic substrate comprises a component selected from paper, cardboard, and cellulose fibers.
  9. The method of claim 1, wherein the fluorocompound surface modified nanoparticles form a layered structure having a thickness of less than about 10,000 nanometers on a cellulosic substrate.
  10. The method of claim 1, wherein the nanoparticles comprise silica, titania, zirconia, layered magnesium silicate, aluminosilicate, natural clay, synthetic clay, polystyrene, styrene acrylonitrile (SAN), or combinations thereof.
  11. The method of claim 1, wherein the nanoparticles comprise at least one clay selected from smectite, kaolin, ylite, chlorite, attapulgite, sepiolite or combinations thereof.
  12. The method of claim 1, wherein the nanoparticles are selected from the group consisting of montmorillonite, bentonite, pyrophyllite, hectorite, saponite, saponite, nontronite, talc, bidalite, Such as halite, nacrite, antigorite, ilite anoxite, indelite, creosote, brassite, succobite, paragonite, biotite, corenite, pennite, Wherein the composition comprises nine, sepiolite, polyglycateate, clino chloe, chamoisite, nemite, phenanthite muskbite, flocophite, synthetic hectorite or pengeite.
  13. The method of claim 1, wherein the fluorocompound surface modified nanoparticles are present in the aqueous dispersion at a concentration of from about 0.01% to about 50% by weight of the total composition.
  14. The method of claim 1, wherein the homogeneous aqueous dispersion further comprises an emulsion polymer or a fluorinated resin emulsion.
  15. The method according to claim 1, wherein the aqueous dispersion of the fluorine compound surface-modified nanoparticles is a wetting agent, an antifouling agent, an anti-stain agent, a fluorocarbon resin, a surfactant, silicone, Wherein the composition further comprises an antioxidant stabilizer, a colorant, a photostabilizer, a UV absorber, a starch, a polyvinyl alcohol, a retention enhancer, a wet strength enhancer, an alkylated inorganic nanoparticle without fluorine content, or any combination thereof.
  16. Paper or paperboard produced according to the method of claim 1.
  17. An article comprising an oil-repellent cellulosic material produced by a process comprising the steps of:
    a) applying a homogeneous aqueous dispersion of a fluorocompounds surface modified nanoparticle to a cellulosic substrate to form a treated cellulosic substrate; And
    b) drying the treated cellulosic substrate to form a oil-repellent cellulosic material.
  18. The article of claim 17, wherein the fluorine concentration on the oleaginous cellulosic material is from about 10 wt ppm (w / w) to about 500 wt ppm (w / w), or from about 0.0001 wt% to about 0.10 wt%.
  19. 18. The method of claim 17, wherein the fluorocompound surface-modified nanoparticles are present on the oleaginous cellulosic material at a concentration of about 0.01% to about 2.0% by weight, or the surface area of the oleaginous cellulosic material is about 0.01 To about 3 g / m < 2 >.
  20. A paper or paperboard treated with a homogeneous aqueous dispersion comprising fluorocompound surface-modified nanoparticles to form oil-based paper or paperboard.
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