Cationic biowax emulsions for oil and water resistant molded fiber products

Abstract

The invention provides charge-modified cationic biowax emulsions that adsorb to cellulosic fibers to impart internal water and oil resistance to paper, board, and moldable fiber products. PAC is used as a charge modifier to impart cationic charge to the biowax particles. The PAC-modified cationic biowax compositions adsorb to cellulosic fibers and are retained internally in the products. The invention also provides methods for forming the charge-modified cationic biowax compositions and methods of manufacturing moldable fiber products for food and beverage packaging with oil and water resistance.

Description

CATIONIC BIOWAX EMULSIONS FOR OIL AND WATER RESISTANT MOLDED FIBER PRODUCTSRELATED APPLICATIONS

[0001]

[0001] The present invention relates to and claims benefit of priority to U.S. Provisional Application Number 63 / 665,932, filed on June 28, 2024, and Finnish Application Number Fl 20245994, filed on August 8, 2024, the contents of both are which are incorporated by reference in their entirety herein.FIELD OF THE INVENTION

[0002] The present invention relates to compositions and methods for forming charge-modified cationic biowax compositions for increasing oil and water resistance of moldable cellulosic fibers and molded pulp products. The invention also relates to methods of manufacturing of moldable fiber products for food and beverage packaging with oil and water resistant properties.BACKGROUND OF THE INVENTION

[0003] Molded pulp is an alternative to plastic packaging for its low cost, recyclability, and nonpolluting characteristics. In the food and beverage packaging industry, molded pulp products are manufactured as packaging materials to contain food or beverage for consumption or transport. These molded pulp products must be safe for contacting food and beverage and must be resistant to oil, grease, and water to prevent leaking or staining. However, the range of applications for molded pulp has been limited by its hydrophilicity and lipophilicity.

[0004] In order to effectively hold a variety of foods for both fast food dine-in service and takeout uses, molded fiber and pulp products must have the ability to resist both hot water and hot oil penetration. Traditionally, molded fiber manufacturers have used perfluoroalkyl substance (PFAS) to provide oil resistance and alkyl ketene dimers (AKDs) to provide water resistance. However, there has been growing regulatory pressure to stop using PFAS, prompting the industry to look for sustainable alternatives.

[0005] Paraffin wax emulsions are a potential alternative for replacing PFAS for imparting oil and grease resistance (OGR) to molded pulp. However, paraffin wax is neutral. Without cationic charge, paraffin wax particles have no affinity for fibers and can only be retained physically in the paper. Therefore, large amounts of paraffin wax emulsions must be added to achieve adequate OGR results, which is costly. Furthermore, paraffin wax is not biodegradable, taking up to 500 years to naturally degrade.

[0006] There remains an unmet need in the industry to identify non-PFAS based wet end chemistries that are renewably sourced, biodegradable, and impart water, oil, and grease resistance properties when applied internally to paper, board, and molded pulp products.

[0007] Biowaxes are hydrogenated bio-based oils including vegetable oil and animal oil. When applied to the surface of paper or board, biowaxes provide a marked increase in oil, grease, and water resistance. Furthermore, unlike paraffin wax, biowaxes derived from vegetable oils can becomposted and biodegrade relatively quickly in as few as 4-6 weeks. However, unmodified biowaxes are neutral to slightly negatively charged and, like paraffin waxes, have little affinity for cellulosic fibers, which hinders the full exploitation of biowaxes as PFAS alternatives at industrial scale.

[0008] Charge-modified cationic biowax emulsions are needed in the industry for adsorbing to cellulosic fibers to impart internal water, oil, and grease resistance to paper, board, and moldable fiber products. Making such charge-modified cationic biowax emulsions with high affinity for cellulosic fibers remains a challenge.

[0009] The present invention addresses this challenge by providing methods for forming novel charge-modified cationic biowax compositions for increasing oil and water resistance of paper, board, and moldable fiber products. The invention also provides methods of manufacturing moldable fiber products for food and beverage packaging with oil and water resistant properties.SUMMARY OF THE INVENTION

[0010] The present invention relates to compositions and methods for forming charge-modified cationic biowax compositions (BCC) for increasing oil and water resistance of moldable cellulosic fibers and molded fiber products. The invention also relates to methods of manufacturing of moldable fiber products for food and beverage packaging with oil and water resistant properties.

[0011] The inventive charge-modified cationic biowax compositions (BCC) are retained on the cellulosic fibers of moldable and non-moldable cellulosic products. Moldable cellulosic products comprising the inventive cationic biowax compositions (BCC) display increased water resistance, increased oil and grease resistance (OGR), increased 60-70 °C water resistance, and increased 60- 70 °C oil resistance, compared to equivalent cellulosic products without the inventive cationic biowax compositions.

[0012] In one aspect, the present invention provides a cationic biowax composition for increasing oil and / or water resistance of a cellulosic product, the cationic biowax composition comprising:

[0013] (a) a biowax emulsion comprising one or more biowaxes, optionally of plant and / or animal origin; and (b) a polyaluminum chloride (PAC).

[0014] In certain embodiments the cationic biowax composition in final form comprises:

[0015] (a) an inverse phase emulsion; (b) a cationic charge ranging from 0.2-0.8 mEq / g, 0.2-0.7 mEq / g, 0.2-0.6 mEq / g, 0.2-0.5 mEq / g, 0.2-0.45 mEq / g, 0.2-0.4 mEq / g, 0.2-0.3 mEq / g, or 0.2-0.25 mEq / g; (c) a total solids in said cationic biowax composition ranging from 15-25 wt%, 16-24 wt%, 18- 22 wt%, or 19-21 wt%; (d) a bulk viscosity of said cationic biowax composition ranging from 50-600 cPs, 50-500 cPs, 50-400 cPs, 50-300 cPs, 50-200 cPs, or 100-200 cPs; (e) a pH ranging from 5-8, 6-8, 6-7.5, 6-7, or 6.5-7; (f) a wt% of said biowax in said cationic biowax composition ranging from 40-90 wt%, 30-80 wt%, 20-70 wt%; (g) a wt% of said PAC in said cationic biowax composition ranging from 6-50 wt%, 10-40 wt%, 20-30 wt%; (h) a ratio of PAC (wt of PAC solution) to said biowax (dry wt) ranging from 1:1 to 3:1, 1.5:1 to 2.5:1, 1.6:1 to 2.4:1, 1.8:1 to 2.2:1 or about 2:1; (i) a renewable material content of 80-95 wt%, 80-90 wt%, 84-90 wt% or 86-88 wt%, wherein renewable material content refers to wt% of biowax and PAC in the total solids of the cationic biowax composition; or (j) any combination of (a)-(i).

[0016] In certain embodiments of the cationic biowax composition, the biowax emulsion comprises:

[0017] (a) an inverse phase biowax emulsion; (b) a neutral charge, a negative charge, or a charge ranging from 0 to -0.1 mEq / g, 0 to -0.08 mEq / g, 0 to -0.06 mEq / g, 0 to -0.04 mEq / g, or 0 to -0.02 mEq / g; (c) a total solids in said biowax emulsion ranging from 25-35 wt%, 26-34 wt%, 28-32 wt%, or 29-31 wt%; (d) a bulk viscosity of said biowax emulsion ranging from 600-800 cPs, 650-800 cPs, 700- 800 cPs, or 750-800 cPs; or (e) any combination of (a)-(d).

[0018] In certain embodiments of the cationic biowax composition, the biowax emulsion comprises:

[0019] (a) said one or more biowaxes, optionally of plant and / or animal origin; (b) one or more emulsifiers; (c) one or more surfactants; (d) one or more microcrystalline or paraffinic waxes; or (e) a mixture of (a) and any combination of (b)-(d).

[0020] In certain embodiments of the cationic biowax composition:

[0021] (a) said one or more biowaxes selected are from the group consisting of palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax, a plant oil wax, an animal oil wax, a blend of plant and animal oil waxes, or any combination thereof; (b) said one or more biowaxes comprise one or more hydrogenated bio-based oils selected from the group consisting of palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof, and wherein each of said hydrogenated bio-based oils has a higher melting point compared to the corresponding non-hydrogenated bio-based oil; (c) said one or more biowaxes comprise a melting point ranging from 55-98 °C, 60-95 °C, 65-90 °C, 70-85 °C, or 75-80 °C;(d) said one or more emulsifiers comprise (i) one or more lignosulfonates; (ii) one or more rosin sizing agents selected from the group consisting of fortified rosins, esterified rosins, rosin waxes, resin acid derivatives, gum rosins, wood rosins, tall oil rosins, rosin pastes, and rosin-based dispersants; or (iii) any combination of (i) and (ii); (e) said one or more surfactants comprise (i) one or more nonionic surfactants selected from the group consisting of ethoxylated alcohols, secondary alcohol ethoxylates, ethoxylated sorbitan esters, sorbitan esters, glycerol esters, and glycerol monostearate (GMS); (ii) one or more anionic surfactants selected from the group consisting of fatty alcohol ether sulfates, alkyl ether sulfates, and special soaps; or (iii) any combination of (i) and (ii); (f) said one or more microcrystalline or paraffinic waxes are selected from the group consisting of saturated hydrocarbon waxes, paraffinic hydrocarbon waxes, isoparaffinic hydrocarbon waxes, naphthenic hydrocarbon waxes, or a mixture thereof, wherein said one or more microcrystalline or paraffinic waxes comprise a congealing point of 50-110 °C, 65-100 °C, 70-90 °C, or 75-85 °C; or (g) any combination of (a)-(f).

[0022] In certain embodiments of the cationic biowax composition, the biowax emulsion comprises:

[0023] (a) said one or more biowaxes, optionally of plant and / or animal origin, in an amount ranging from 20-85 wt%, 20-80 wt%, 20-60 wt%, 25-55 wt%, 30-50 wt%, 35-45 wt% or 20-26 wt%; (b) said one or more lignosulfonates in an amount ranging from 0.1-8 wt%, 1-5 wt%, or 2-4 wt%; (c) said one or more rosin sizing agents in an amount ranging from 1-12 wt%, 2-10 wt%, 3-8 wt%, or 4-6 wt%; (d) said one or more surfactants in an amount ranging from 1-12 wt%, 2-12 wt%, 4-10 wt%, or 6-8 wt%;(e) said one or more microcrystalline or paraffinic waxes in an amount ranging from 1-12 wt%, 2-10 wt%, 3-9 wt%, 4-8 wt%, or 5-7 wt%; (f) a biocarbon content of 60-90 wt%, 70-80 wt%, or 75-80 wt%,wherein biocarbon content refers to wt% of total carbon content in the biowax emulsion that originates from said biowax; or (g) a mixture of (a) and any combination of (b)-(f).

[0024] In certain embodiments of the cationic biowax composition, said biowax emulsion comprises:

[0025] (a) castor oil wax; (b) said one or more lignosulfonates; (c) said one or more rosin sizing agents comprising fortified rosin; (d) said nonionic surfactants comprising secondary alcohol ethoxylates, glycerol monostearate (GMS), or a combination thereof; (e) said one or more microcrystalline or paraffinic waxes comprising a congealing point of 70-90 °C; or (f) a mixture of (a) and any combination of (b)-(e).

[0026] In certain embodiments of the cationic biowax composition, said biowax emulsion:

[0027] (a) comprises an oil-phase initially comprising (i) said one or more biowaxes and, (ii) said one or more emulsifiers, (iii) said one or more surfactants, (iv) said one or more microcrystalline or paraffinic waxes, or ( v) a mixture of (i) and any combination of (ii)-(iv); (b) comprises an aqueous phase initially comprising water; (c) optionally comprises a biocide; and (d) is optionally homogenized.

[0028] In certain embodiments of the cationic biowax composition, said PAC comprises:

[0029] (a) a high basicity PAC comprising a basicity ranging from 50-95%, 55-90%, 60-85%, 60-80%, 60-75%, 60-70%, or 60-65%, wherein said basicity is defined as the molar equivalent percent of hydroxide (OH) to aluminum (Al) in the PAC; (b) a PAC strength ranging from 15-30%, 20-30%, or 20- 23%, wherein said PAC strength is defined as %AI2O3 in the PAC.

[0030] In certain embodiments of the cationic biowax composition:

[0031] (a) said cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; and / or (b) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition.

[0032] In another aspect, the present invention provides a method for producing a cationic biowax composition for increasing oil and / or water resistance of a cellulosic product, the method comprising contacting:

[0033] (a) a biowax emulsion; and (b) a polyaluminum chloride (PAC) to form said cationic biowax composition, wherein said biowax emulsion comprises one or more biowaxes, optionally of plant and / or animal origin.

[0034] In certain embodiments of the method:

[0035] (a) the method further comprises emulsifying to form an inverse phase emulsion; (b) said cationic biowax composition in final form comprises a cationic charge ranging from 0.2-0.8 mEq / g, 0.2-0.7 mEq / g, 0.2-0.6 mEq / g, 0.2-0.5 mEq / g, 0.2-0.45 mEq / g, 0.2-0.4 mEq / g, 0.2-0.3 mEq / g, or 0.2- 0.25 mEq / g; (c) said cationic biowax composition in final form comprises a total solids in said cationicbiowax composition ranging from 15-25 wt%, 16-24 wt%, 18-22 wt%, or 19-21 wt%; (d) said cationic biowax composition in final form comprises a bulk viscosity of said cationic biowax composition ranging from 50-600 cPs, 50-500 cPs, 50-400 cPs, 50-300 cPs, 50-200 cPs, or 100-200 cPs; (e) said cationic biowax composition in final form comprises a pH ranging from 5-8, 6-8, 6-7.5, 6-7, or 6.5-7; (f) said cationic biowax composition in final form comprises a wt% of said biowax in said cationic biowax composition ranging from 40-90 wt%, 30-80 wt%, 20-70 wt%; (g) said cationic biowax composition in final form comprises a wt% of said PAC in said cationic biowax composition ranging from 6-50 wt%, 10-40 wt%, 20-30 wt%; (h) said cationic biowax composition in final form comprises a ratio of PAC (wt of PAC solution) to said biowax (dry wt) ranging from 1:1 to 3:1, 1.5:1 to 2.5:1, 1.6:1 to 2.4:1, 1.8:1 to 2.2:1 or about 2:1; (i) said cationic biowax composition in final form comprises a renewable material content of 80-95 wt%, 80-90 wt%, 84-90 wt% or 86-88 wt%, wherein renewable material content refers to wt% of biowax and PAC in the total solids of the cationic biowax composition; or (j) any combination of (a)-(i).

[0036] In certain embodiments of the method, said biowax emulsion comprises:

[0037] (a) an inverse phase biowax emulsion; (b) a neutral charge, a negative charge, or a charge ranging from 0 to -0.1 mEq / g, 0 to -0.08 mEq / g, 0 to -0.06 mEq / g, 0 to -0.04 m Eq / g, or 0 to -0.02 mEq / g; (c) a total solids in said biowax emulsion ranging from 25-35 wt%, 26-34 wt%, 28-32 wt%, or 29-31 wt%; (d) a bulk viscosity of said biowax emulsion ranging from 600-800 cPs, 650-800 cPs, 700- 800 cPs, or 750-800 cPs; or (e) any combination of (a)-(d).

[0038] In certain embodiments of the method said biowax emulsion is formed by an inverse phase emulsification method comprising:

[0039] (a) combining (i) said one or more biowaxes, optionally of plant and / or animal origin, (ii) one or more rosin sizing agents, (ill) one or more surfactants, and (iv) said one or more microcrystalline or paraffinic waxes, or (vi) a mixture of (i) and any combination of (ii)-(iv); (b) heating to 50-99 °C, 60- 99 °C, 70-99 °C, 75-98 °C, or 85-95 °C to form an oil-phase; (c) contacting an amount of hot water with said oil-phase, wherein said hot water is optionally 50-99 °C, 60-99 °C, 70-99 °C, 75-98 °C, or 85- 95 °C; and (d) emulsifying at 70-99 °C, 75-98 °C, or 85-95 °C to form said biowax emulsion.

[0040] In certain embodiments of the method said inverse phase emulsification method further comprises:

[0041] (i) emulsifying during step (d) for an amount of time ranging from 0.5-5 h, 0.5-4 h, or 1-3 h; (ii) after step (d), homogenizing the biowax emulsion; (iii) after step (d), cooling to a temperature ranging from 10-35 °C, 15-30 °C, or 20-25 °C, optionally using an ice-water bath, a cooling jacket, or a cooling core; (iv) after step (d), adding a biocide; or (v) any combination of (i)-(iv).

[0042] In certain embodiments of the method:

[0043] (a) said one or more biowaxes are selected from the group consisting of palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax, a plant oil wax, an animal oil wax, a blend of plant and animal oil waxes, or any combination thereof; (b) said one or more biowaxes comprise one or more hydrogenated bio-based oils selected from the group consisting of palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof, and wherein each of said hydrogenated bio-based oils has a higher meltingpoint compared to the corresponding non-hydrogenated bio-based oil; (c) said one or more biowaxes comprise a melting point ranging from 55-98 °C, 60-95 °C, 65-90 °C, 70-85 °C, or 75-80 °C; (d) said one or more emulsifiers comprise (i) one or more lignosulfonates; (ii) one or more rosin sizing agents selected from the group consisting of fortified rosins, esterified rosins, rosin waxes, resin acid derivatives, gum rosins, wood rosins, tall oil rosins, rosin pastes, and rosin-based dispersants; or (ill) any combination of (i) and (ii); (e) said one or more surfactants comprise (i) one or more nonionic surfactants selected from the group consisting of ethoxylated alcohols, secondary alcohol ethoxylates, ethoxylated sorbitan esters, sorbitan esters, glycerol esters, and glycerol monostearate (GMS); (ii) one or more anionic surfactants selected from the group consisting of fatty alcohol ether sulfates, alkyl ether sulfates, and special soaps; or (iii) any combination of (i) and (ii); (f) said one or more microcrystalline or paraffinic waxes are selected from the group consisting of saturated hydrocarbon waxes, paraffinic hydrocarbon waxes, isoparaffinic hydrocarbon waxes, naphthenic hydrocarbon waxes, or a mixture thereof, wherein said one or more microcrystalline or paraffinic waxes comprise a congealing point of 50-110 °C, 65-100 °C, 70-90 °C, or 75-85 °C; or (g) any combination of (a)-(f).

[0044] In certain embodiments of the method said biowax emulsion comprises:

[0045] (a) said one or more biowaxes in an amount ranging from 20-85 wt%, 20-80 wt%, 20-60 wt%, 25-55 wt%, 30-50 wt%, 35-45 wt% or 20-26 wt%; (b) said one or more lignosulfonates in an amount ranging from 0.1-8 wt%, 1-5 wt%, or 2-4 wt%; (c) said one or more rosin sizing agents in an amount ranging from 1-12 wt%, 2-10 wt%, 3-8 wt%, or 4-6 wt%; (d) said one or more surfactants in an amount ranging from 1-12 wt%, 2-12 wt%, 4-10 wt%, or 6-8 wt%; (e) said one or more microcrystalline or paraffinic waxes in an amount ranging from 1-12 wt%, 2-10 wt%, 3-9 wt%, 4-8 wt%, or 5-7 wt%; (f) a biocarbon content of 60-90 wt%, 70-80 wt%, or 75-80 wt%, wherein biocarbon content refers to wt% of total carbon content in the biowax emulsion that originates from said biowax; or (g) a mixture of (a) and any combination of (b)-(f).

[0046] In certain embodiments of the method said biowax emulsion comprises:

[0047] (a) castor oil wax; (b) said one or more lignosulfonates; (c) said one or more rosin sizing agents comprising fortified rosin; (d) said nonionic surfactants comprising secondary alcohol ethoxylates, glycerol monostearate (GMS), or a combination thereof; (e) said one or more microcrystalline or paraffinic waxes comprising a congealing point of 70-90 °C; or (f) a mixture of (a) and any combination of (b)-(e).

[0048] In certain embodiments of the method:

[0049] (a) said PAC comprises a high basicity PAC comprising a basicity ranging from 50-95%, 55- 90%, 60-85%, 60-80%, 60-75%, 60-70%, or 60-65%, wherein said basicity is defined as the molar equivalent percent of OH to Al in the PAC; (b) said PAC comprises a PAC strength ranging from 15- 30%, 20-30%, or 20-23%, wherein said PAC strength is defined as %AI2O3 in the PAC; (c) said moldable cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; (d) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii)an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or (e) any combination of (a)-(d).

[0050] In another aspect, the present invention provides a method of preparing a cellulosic product comprising oil and water resistance, the method comprising:

[0051] (a) contacting an aqueous suspension comprising cellulosic fibers and a cationic biowax composition according to any of the foregoing or obtainable by a method according to any of the foregoing, thereby forming a fiber stock composition; and (b) adding the fiber stock composition to the wet end of a paper machine.

[0052] In certain embodiments of the method the method further comprises:

[0053] (i) optionally contacting the fiber stock composition with one or more retention aids; and / or (ii) after step (b), removing sufficient water from the fiber stock composition to form a wet fibrous web and then pressing and drying the wet fibrous web to obtain said cellulosic product.

[0054] In certain embodiments of the method:

[0055] (a) said one or more retention aids comprise at least one polyacrylamide (PAM), at least one anionic polyacrylamide (APAM), at least one cationic polyacrylamide (CPAM), at least one amphoteric polyacrylamide (AmPAM), at least one polyvinylamine (PVAm) polymer, at least one glyoxalated polyacrylamide (GPAM), or any combination of the foregoing ; (b) said aqueous suspension comprising cellulosic fibers comprises (i) one or more cellulosic fibers selected from the group consisting of softwood fiber, hardwood fiber, recycled fiber, recycled old corrugated cardboard (OCC), recycled mixed office waste (MOW), recycled mixed office paper, refined fiber, mill broke fibers, coated broke, non-wood fibers, straw pulp, wheat pulp; (ii) a papermaking furnish comprising pulp, Kraft pulp, unbleached Kraft pulp, bleached pulp, unbleached pulp, process water from pulp, paper, and / or board production, neutral sulfite semi chemical (NSSC) pulp, mechanical pulp, non-wood pulp; (iii) a thick stock, a thick stock diluted with chemical water, synthetic water, white water, and / or process water, and a thin stock; or (iv) a mixture of any of (i)-(iii); (c) said cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; (d) any combination of (a)-(c).

[0056] In certain embodiments of the method:

[0057] (a) said cationic biowax composition is present in said fiber stock composition at a dosage of 10-100 dry Ib / t, 20-80 dry Ib / t, 20-60 dry Ib / t, or 20-40 dry Ib / t; (b) said one or more retention aids are present in said fiber stock composition at a dosage of 0.1-1 dry Ib / t, 0.2-0.8 dry Ib / t, 0.4-0.6 dry Ib / t, or 0.5-0.6 dry Ib / t; (c) said cationic biowax composition is retained internally on the cellulosic fibers of said cellulosic product; (d) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or (e) any combination of (a)-(d).

[0058] In another aspect, the present invention provides a fiber stock composition comprising:

[0059] (a) an aqueous suspension comprising cellulosic fibers; and (b) a cationic biowax composition according to any of the foregoing or obtainable by a method according to any of the foregoing.

[0060] In another aspect, the present invention provides a moldable cellulosic product comprising:

[0061] (a) an amount of cellulosic fibers; and

[0062] (b) a cationic biowax composition according to any of the foregoing or obtainable by a method according to any of the foregoing.

[0063] In certain embodiment said moldable cellulosic product comprising said cationic biowax composition:

[0064] (a) is used as a food package, a beverage package, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food, beverage, oil, water, and / or grease; (b) comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (ill) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition.BRIEF DESCRIPTION OF THE DRAWINGS

[0065] The invention will be described in more detail with reference to appended drawings, described in detail below.FIG 1 provides an exemplary schematic of charge modification of biowax particles with PAC to form the inventive PAC-modified cationic biowax composition (CBC) for increasing water, oil, and grease resistance of food and beverage packaging according to Example 2.FIG 2 shows an exemplary graph showing the effect of polyaluminum chloride ( PAC) concentration on hot oil absorption time (min) of handsheets prepared from recycled fibers and PAC-modified biowax emulsions according to Example 3.FIG 3 shows exemplary images of hot water and hot oil resistance testing of molded fiber bowls prepared from recycled and virgin fibers treated at with a combination of the inventive PAC- modified cationic biowax composition (CBC) and an emulsion anionic polyacrylamide (APAM) retention aid (E0645, MW 2-4 million Dalton, 30-45% anionic charge) according to Example 4. Oil penetration can be seen as dark staining.FIG 4 shows exemplary results of hot water and hot oil resistance testing of handsheets prepared from virgin fibers treated at with a combination of the inventive biowax + PAC composition and an emulsion anionic polyacrylamide (APAM) retention aid (E0645, MW 2-4 million Dalton, 30-45% anionic charge) according to Example 5.FIG 5 shows exemplary results of independent lab testing of hot water and hot oil resistance of molded fiber trays prepared from virgin fibers treated at with a combination of the inventive biowax + PAC composition and an emulsion anionic polyacrylamide (APAM) retention aid (E0645, MW 2-4 million Dalton, 30-45% anionic charge) according to Example 6.DETAILED DESCRIPTION OF THE INVENTION

[0066] Before describing the invention, the following definitions are provided. Unless stated otherwise all terms are to be construed as they would be by a person skilled in the art.Definitions

[0067] As used herein, all technical and scientific terms have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs unless clearly indicated otherwise.

[0068] As used herein, the singular forms "a," "an," and "the" may mean "one" but also include plural referents such as "one or more" and "at least one" unless the context clearly dictates otherwise. All technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this invention belongs unless clearly indicated otherwise.

[0069] As used herein, the term "or" in the claims is used to mean "and / or" unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and "and / or."

[0070] As used herein the term "or combinations thereof" as used herein refers to all permutations and combinations of the listed items preceding the term unless stated otherwise.Papermaking

[0071] As used herein, the term "aqueous suspension", "aqueous slurry", or "slurry" generally refer to a heterogeneous mixture of a fluid that contains insoluble or sparingly soluble solid particles sufficiently large for sedimentation. Suspensions and slurries of the present invention may also comprise some amount of solid particles, often termed colloidal particles, which do not completely settle or take a long time to settle completely.

[0072] As used herein, the terms "fiber suspension" and "aqueous suspension of cellulosic fibers" generally refer to a suspension of cellulosic fibers and pulp from which paper or board is made. The cellulosic fibers and pulp may contain virgin fibers and / or recycled fibers. The suspension may also contain , optional fillers, dyes, process water, and / or white water. The suspension may contain a mixture of water, dissolved paper pulp, and optionally other soluble or insoluble components produced or added during the stock preparation phase of papermaking. For example, the fiber suspension may comprise at least 5 %, preferably 10-30 %, more preferably 11-19 % of mineral filler. Mineral filler may be any filler conventionally used in paper and board manufacturing, such as ground calcium carbonate, precipitated calcium carbonate, clay, talc, gypsum, titanium dioxide, synthetic silicate, aluminum trihydrate, barium sulphate, magnesium oxide or their any of mixtures.

[0073] As used herein, the terms "broke" or "mill broke" refer to paper, which during the paper making process becomes suitable only for repulping. Broke may contain trimmings or paper that is out of specification. Broke is re-used material which never left the mill is not regarded as recycled or recovered. Broke is a valuable source of fiber and is recycled internally at the mill. As used herein, the term "coated broke" refers to broke that contains coatings that are applied to the base sheet of paper as it is being manufactured. When the broke contains these coatings, it presents special problems in recycling to recover fiber values because the coatings introduce materials which would not normally be present in the original stock of fiber used to manufacture the base paper sheet. The coated broke may also contain dyes and / or other additives.

[0074] The term "cellulosic" refers to a substance made from cellulose or a derivative of cellulose. The term "lignocellulosic" refers to a substance derived from plant dry matter or biomass, which comprises at least cellulose and hemicellulose, which are carbohydrate polymers, and lignin, an aromatic-rich polymer. All pulp and fiber products, including molded pulp and molded fiber products described herein may be cellulosic and / or lignocellulosic. In general, as used herein, the terms cellulosic and lignocellulosic are used interchangeably with identical meaning.

[0075] As used herein, the term "fiber" refers to the basic structural unit of paper or board.

[0076] The terms "cellulosic product" and "lignocellulosic product" refers to refers a paper and / or paperboard product formed from plant dry matter from any source, virgin or recycled, which may be coated, printed, and / or formed into a packaging product. For example, such products include paper products made from pulp, such as by methods comprising forming an aqueous cellulosic papermaking furnish, adding the furnish to the wet end of a paper machine, draining the furnish on a wire to form a sheet, and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known in the art.

[0077] The terms "fiber stock" and "furnish" generally refer to an aqueous suspension of cellulosic fibers, optional fillers, optional dyes, optional chemical and / or polymeric additives, and optionallyother soluble or insoluble components used to manufacture paper or board. A papermaking furnish or fiber stock is added to the wet end of a paper machine and then drained and dried to form a cellulosic product comprising paper, board, or a moldable fiber product.

[0078] A fiber stock may be a "thick stock" or a "thin stock". As used herein, the term "thick stock" generally refers to an aqueous suspension of papermaking pulp and other materials with a consistency of about 1 to 5%. As used herein, the term "thin stock" generally refers to an aqueous suspension of papermaking pulp and other materials, after having been diluted to a consistency below 1% with whitewater or other process water at a fan pump.

[0079] The terms "moldable fiber product" or "moldable pulp product" refer to products containing moldable cellulosic fibers, which may be molded or shaped into containers or utensils for use as a food package, a beverage package, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food, beverage, oil, water, and / or grease. Formation of moldable fiber product may be achieved by any conventional means known in the art, such as by thermoforming.

[0080] The terms "molded fiber product" or "molded pulp product" refer to products containing moldable cellulosic fibers, which have been formed into containers or utensils for use as a food package, a beverage package, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food, beverage, oil, water, and / or grease.

[0081] The term "oil resistance", "oil and grease resistance", or "OGR" refers to the ability to prevent wicking or flow of hydrophobic liquids into and across the surface of a paper, board, molded fiber product, or molded pulp product. Higher internal OGR is achieved by rendering the internal fibers of a cellulosic substrate more lipophobic by adding the inventive PAC-modified biowax composition, which adsorbs to and is retained internally on the fibers.

[0082] As used herein, the terms "recycled fiber" and "recovered fiber", refer to paper, paperboard, and fibrous wastes from retail stores, office buildings, homes, manufacturing plants, and so forth, after they have passed through their end-usage as a consumer item. Manufacturing wastes include: dry paper and paperboard waste generated after completion of the papermaking process including by way of example: envelope cuttings, bindery trimmings, and other paper and paperboard waste resulting from printing, cutting, forming, and other converting operations; bag, box, and carton manufacturing wastes; mill wrappers, and rejected unused stock; and repulped finished paper and paperboard from obsolete inventories of paper and paperboard manufacturers, merchants, wholesalers, dealers, printers, converters, or others. In particular the term "recycled fibers" includes recycled fibers derived by processing of paper and other consumer cellulosic materials, e.g., paper, old corrugated containerboard (OCC), mixed office waste (MOW), old magazine (OMG), unbleached kraft pulp, neutral sulphite semi chemical (NCCS) pulp and / or mechanical pulp. Source materials for recycled fibers may be selected from old corrugated containerboard, mixed office waste, old newsprint, old magazines, double liner kraft, and any mixtures thereof. Mixed waste (MXW) denotes recycled mixture of recycled board, such as OCC, white lined chipboard and / or folding boxboard, and recycled paper, such as old newsprint, old magazines and / or office waste papers. Mixed office waste denotes recycled fiber material mainly containing copying papers, printer papers and offset papers. Double lined kraft denotes recycled fiber material comprising clean sorted unprinted corrugatedcardboard cartons, boxes, sheet or trimmings, e.g., of kraft or jute liner. White lined chipboard (WLC) denotes multiply board comprising deinked fiber material and / or un-deinked recycled fiber material originating e.g., from OCC, mixed office waste or old newspapers (ONP) in or more of the layers.

[0083] The term "retained internally" refers to the result of a chemical additive being "fixed" or adsorbed to cellulosic fibers of a paper product. Internally retained additives tend to be present throughout the bulk of the paper product as opposed to being applied only to a surface.

[0084] The terms "wet end of a paper machine" or "wet end" generally refer to the parts of a papermaking process between pulping (or bleaching) and wet-pressing of the paper.

[0085] The term "water resistance" refers to the ability to prevent wicking or flow of aqueous liquids into and across the surface of a paper, board, molded fiber product or molded pulp product. Higher internal water resistance is achieved by rendering the internal fibers of a cellulosic substrate more hydrophobic by adding the inventive PAC-modified biowax composition, which adsorbs to and is retained internally on the fibers.

[0086] The term "white water" generally refers to process water within a paper machine system, especially referring to water that is drained from paper as the sheet is being formed.Biowax Emulsions, Charge Modifiers, and Chemical Additives

[0087] The term "bio-based" refers to any material that is (i) directly extracted from the biomass (natural materials) such as polysaccharides, proteins, and lipids, (ii) that is synthesized from the bioderived materials, (ill) that is a biodegradable material, or (iv) that originates from sustainable and / or renewable resources. Such materials include monomers, polymers, lipids, or oils that are directly produced and extracted from microorganisms, vegetable, or animals and then subjected to further processing techniques, such as hydrogenation, hydrolysis, esterification, fermentation, or enzymatic reactions.

[0088] The term "bio-based oil" refers to any oil derived or sourced, wholly or in part, from a plant or animal, including but not limited to, palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof.

[0089] The term "biowax" refers to any wax or waxy substance derived or sourced from a bio-based oils. For example, biowaxes may be formed by partial or complete hydrogenation of bio-based oils or mixtures of bio-based oils to form biowax materials that have a higher melting point compared to the corresponding non-hydrogenated bio-based oil.

[0090] The term "biowax emulsion" refers to an emulsion or mixture of immiscible liquids containing one or more biowaxes and water that have been emulsified into an inverse phase emulsion. Biowax emulsions may also contain one or more emulsifiers, one or more rosin sizing agents, one or more lignosulfonates, one or more surfactants, or one or more microcrystalline or paraffinic waxes, or any other material appropriate for formulation as a biowax-based barrier composition for paper or board. The components of a biowax emulsion may be added together or separately and emulsification may be achieved by any convenient means of mixing, with or without heating.

[0091] The term "emulsifier" refers to a substance that stabilizes an emulsion by reducing the surface tension or interfacial tension between two liquids or by adsorbing at the oil / water interface and preventing oil-droplets and / or water-droplets from coalescing. As used herein, "co-emulsifiers" include lignosulfonates, rosin size, surfactants, or any emulsifier known in the art.

[0092] The term "lignosulfonate" refers to a sulfonated lignin, which is a byproduct from the sulfite pulping process. Lignosulfonates are water-soluble, sulfonated derivatives of lignin that are produced during the sulfite pulping process of wood. During the process, lignin is extracted from wood chips and is then sulfonated using hydrogen sulfite. The sulfonation process introduces sulfonic acid groups onto the lignin structure, resulting in a water-soluble polymer that can be used for various industrial applications.

[0093] The term "rosin size" or "rosin sizing agent" refers to one or more alkali-treated rosins used as a dry powder or emulsion to surface-size paper products. Rosin size is often added to paper or board in the presence of aluminum species, and is used to increase barrier properties to water, moisture, and water vapor. The term "fortified rosin" refers to a major component of most rosin size products, produced by reacting the levopimaric acid component of rosin with maleic anhydride. Fortified rosin sizing agent is produced by the reaction with gum rosin and fumaric acid or maleic anhydride under suitable conditions. This is Diels-alder adduct which acts as a very effective sizing agent. The Diels-Alder adduct contains extra carboxyl groups and produces more proficient sizing response than the unreacted resin acids. It is common that the rosin which is extract from tall oil is fortified with fumaric acid. In this case some of the abietic acid and related compounds are converted into tricarboxylic species.

[0094] As used herein, "inverse phase emulsion" refers to an invert emulsion (water-in-oil) consisting of two liquid phases: dispersed phase (water) and continuous phase (oil). Exemplary inverse phase emulsions are formed by heating at least one biowax and other hydrophobic components to form an oil-phase. Water or an aqueous solution is then added to the oil-phase and the mixture is emulsified and optionally homogenized to form the inverse phase emulsion. Coemulsifiers, rheology modifiers, surfactants, microcrystalline or paraffinic waxes, or biocides may also be added.

[0095] The term "microcrystalline wax" refers to a type of hydrocarbon wax produced by de-oiling petrolatum, as part of the petroleum refining process, contains a relatively higher percentage of isoparaffinic (branched) hydrocarbons and naphthenic hydrocarbons compared to paraffin wax, and is characterized by the fineness of its crystals. Microcrystalline waxes generally consist of hydrocarbon waxes that predominantly comprise saturated acyclic and cyclic hydrocarbons or contains such structures as a major portion of the molecules therein. Naphthenic hydrocarbons are a type of organic compound of carbon and hydrogen that contains one or more saturated cyclic (ring) structures, or contains such structures as a major portion of the molecule. Other Naphthenic compounds are sometimes called naphthenes, cycloparaffins, or hydrogenated benzenes.

[0096] As used herein, the terms "polyaluminum chloride" and "PAC" refer to a group of water- soluble aluminum salts having the general formula Aln(0H)mCI(3n-m), where 0 < m < 3n. "PAC basicity" or "B" is formally defined as the equivalent mole percent of OH and Al in the PAC molecule, B=[OH] / [AI] * 100%=m / 3n * 100%. Commercially available PAC products are characterised by theirPAC basicity ( i.e., molar ratio of hydroxide to aluminum x 100%) and PAC strength ( i.e., percent equivalent of aluminum oxide in the PAC formulation). As a general rule, the higher the basicity, the higher the polymeric content and thus cationic charge density and efficiency. The PAC basicity of a given product is an averaged parameter with the actual aluminum speciation being a complex mixture that can vary from monomeric aluminum (AI+3) to a range of partially neutralized PACI molecules. PAC is generally used in the papermaking industry to increase drainage rates in neutral and alkaline processes, as a retention aid, to increase sizing efficiency and to reduce cationic demand. In certain embodiments of the present invention, PAC is used as a charge modifier to impart cationic charge to biowax particles. It was surprisingly found that PAC was the only chargemodifier of all tested candidates to successfully impart cationic charge to biowax particles, thereby forming the inventive PAC-modified cationic biowax compositions and facilitating adsorption of biowax to cellulosic fibers.

[0097] The term "retention aid" generally refers to a chemical or polymeric additive that is added to a papermaking furnish to increase the percentage of desired material, e.g., typically fibers, fillers, fines, and chemical or polymeric additives, that is retained in a paper or board. Exemplary retention aids may comprise at least one polyacrylamide (PAM), at least one anionic polyacrylamide (APAM), at least one cationic polyacrylamide (CPAM), at least one amphoteric polyacrylamide (AmPAM), at least one polyvinylamine (PVAm) polymer, at least one glyoxalated polyacrylamide (GPAM), or any combination of the foregoing.

[0098] As used herein, "surfactant" refers to a chemical which tends to act as emulsifiers by reducing the surface tension or interfacial tension between two liquids. Surfactants tend to be amphiphilic and comprise a hydrophilic water-soluble head and a hydrophobic organic-soluble tail. In oil water mixtures, surfactants migrate to the interface between oil and water wherein organic- soluble tail tails project into the organic oil phase, while the water-soluble ends remain in contact with the water phase, thereby stabilizing emulsions. When there are a sufficient amount of surfactant molecules present in a solution they combine together to form structures called micelles. "Nonionic surfactants" have a neutral hydrophilic end. "Anionic surfactants" bear a negative charge at the hydrophilic end.Polymers

[0099] As used herein "acrylamide" refers to a neutral monomer of molecular formula: C3H5NO and a molecular weight of 71.08 g / mol.

[0100] As used herein, the term "amphoteric polymer" refers to polymers containing anionic and cationic monomers and optionally neutral monomers such as acrylamide. Amphoteric polymers contain both anionic and cationic groups on their macromolecular chains. These polymers exhibit both attraction and repulsion in their electrostatic intermolecular interactions (resulting in anti- polyelectrolyte association called "Amphoteric Effect") and they exhibit excellent salt tolerance, especially in high Ca+2 aqueous compositions.

[0101] As used herein, "anionic monomer" refers to a monomer which possesses a negative charge in aqueous solution at a pH above a certain threshold depending on the pKa values of acidic protons contained therein. The "anionic monomers" may be neutral at low pH (e.g., from a pH of about 0-1, 0-2, or 0-3) and become anionic as the pH of solution is increased. Non-limiting representativeanionic monomers include acrylic acid, sodium acrylate, ammonium acrylate, methacrylic acid, 2- acrylamido-2-methylpropanesulfonic acid (AMPS), vinyl sulfonic acid, styrene sulfonic acid, maleic acid, sulfopropyl acrylate or methacrylate or other water-soluble forms of these or other polymerizable carboxylic or sulphonic acids, sulfomethylated acrylamide, ally sulfonate, itaconic acid, acrylamidomethylbutanoic acid, fumaric acid, vinylphosphonic acid, allylphosphonic acid, phosphonomethylated acrylamide, methacrylate, itaconate, 2-acrylamido 2-methyl propane sulphonate, sulfoalkyl(meth)acrylic acids, sulfonated styrenes, unsaturated dicarboxylic acids, sulfoalkyl(meth)acrylamides, vinyl acetate, n-vinylformamide, n-vinylacetamide, n-vinylcaprolactam, n-vinylimidazole, n-vinylpyridine, n-vinylpyrolidone, acrylamidopropyltrimonium chloride, salts of said acids and the like, or another anionic ethylenica lly unsaturated compound.

[0102] As used herein, the term "cationic monomer" generally refers to a monomer that possesses a positive charge. Examples thereof include acryloyloxy ethyl trimethylammonium chloride (0.9) monomers. Cationic monomers may also be selected from 2-(acryloyloxy)ethyl trimethylammonium chloride ("AETAC" or "Q9"), methacryloyloxyethyltrimethylammonium chloride ("MAETAC"), methacrylamidopropyltrimethylammonium chloride ("MAPTAC"), acrylamidopropyltrimethylammonium chloride ("APTAC"), methacryloyloxyethyldimethylammonium sulfate, diallyldimethylammonium chloride ("DADMAC"); dialkylaminoalkyl acrylates and dialkylaminoalkyl methacrylates and their quaternary or acid salts, including but not limited to, dimethylaminoethyl acrylate ("DMAEA"), dimethylaminoethyl methacrylate ("DMAEA"), dimethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl acrylate methyl sulfate quaternary salt, dimethylaminoethyl acrylate benzyl chloride quaternary salt, dimethylaminoethyl acrylate sulfuric acid salt, dimethylaminoethyl acrylate hydrochloric acid salt, diethylaminoethyl acrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl chloride quaternary salt, dimethylaminoethyl methacrylate methyl sulfate quaternary salt, dimethylaminoethyl methacrylate benzyl chloride quaternary salt, dimethylaminoethyl methacrylate sulfuric acid salt, dimethylaminoethyl methacrylate hydrochloric acid salt, dimethylaminoethyl methacryloyl hydrochloric acid salt; dialkylaminoalkylacrylamides and methacrylamides and their quaternary or acid salts, including but not limited to, acryloylamidopropyltrimethylammonium chloride, dimethylaminopropyl acrylamide, dimethylaminopropyl acrylamide methyl sulfate quaternary salt, dimethylaminopropyl acrylamide sulfuric acid salt, dimethylaminopropyl acrylamide hydrochloric acid salt, methacrylamidopropyltrimethylammonium chloride, dimethylaminopropyl methacrylamide, dimethylaminopropyl methacrylamide methyl sulfate quaternary salt, dimethylaminopropyl methacrylamide sulfuric acid salt, dimethylaminopropyl methacrylamide hydrochloric acid salt, diethylaminoethylacrylate, diethylaminoethylmethacrylate; and diallyldialkylammonium halides, including but not limited to, diallyldiethylammonium chloride and diallyldimethylammonium chloride ("DADMAC"), and any combination thereof.

[0103] As used herein, "cationic glyoxalated polyacrylamides (GPAMs)" or "GPAM" generally refers to a polymer obtained by reacting glyoxal and a "base polymer" to form a glyoxalated polymer backbone. In general, GPAM comprises a reactive polymer that can covalently bond with cellulose upon dehydration. Exemplary GPAMS are reactive cationic polymers containing reactive aldehydes, which react with carboxylate and -OH moieties on cellulosic and lignocellulosic fibers to formcovalent bonds. Exemplary GPAMS are used as wet and / or dry strength additives and as retention aids and drainage aids in papermaking.

[0104] As used herein, "nonionic monomer" refers to a monomer which possesses a net charge of zero in aqueous solution. Non-limiting examples of nonionic monomers include, acrylamide, N- alkylacrylamides, N,N-dialkylacrylamides, methacrylamide, N-vinylmethylacetamide or formamide, vinyl acetate, vinyl pyrrolidone, alkyl methacrylates, acrylonitrile, N-vinylpyrrolidone other acrylic (or other ethylenically unsaturated) ester or other water insoluble vinyl monomers such as styrene or acrylonitrile.

[0105] As used herein, "polyacrylamide" or "PAM" generally refer to polymers and co-polymers comprising acrylamide moieties, and the terms encompass any polymers or copolymers, including terpolymers, comprising acrylamide moieties, e.g., one or more acrylamide (co)polymers of acrylamide and additional monomers capable of copolymerizing with acrylamide. PAMs described herein may be produced in one of various forms, including, for example, dry (powder ) form (e.g., DPAM), emulsion polyacrylamide (EPAM), or liquid polyacrylamide (aqueous solution). Amphoteric polyacrylamides (AmPAM) may be formulated in dry (powder ) form (e.g., AmDPAM), or emulsion form (AmEPAM).

[0106] As used herein, the term "anionic polyacrylamide (APAM)" refers to a copolymer of acrylamide and anionic monomers, such as acrylic acid or ATBS, and also encompasses acrylamide polymers which are partially or completely hydrolyzed following polymerization to form acrylate or acrylic acid side chains.

[0107] As used herein, "cationic polyacrylamide (CPAM)" refers to a copolymer of acrylamide and cationic monomers, such as DADMAC or Q.9.

[0108] As used herein, "amphoteric polyacrylamide (AMPAM)" refers to a terpolymer (or higher order polymer) of acrylamide, cationic monomers, and anionic monomers, which may also encompass acrylamide groups which are partially or completely hydrolyzed following polymerization to form acrylate or acrylic acid side chains.

[0109] As used herein, "PVAm", "polyvinylamine", and "vinyl amine polymer" refer to any polymer having vinyl amine units (i.e., 1-aminoethylene units or N-ethenylamine units). PVAms are highly cation ically charged at typical operating pH for papermaking applications. PVAm adsorbs spontaneously and irreversibly to cellulosic fiber surfaces in water, thereby generating cationic surface properties on the fiber and may be used as retention aids. Exemplary PVAms are used as wet and / or dry strength additives and as retention aids and drainage aids in papermaking.

[0110] As used herein, "polymer", "polymeric additive", and similar terms are used in their ordinary sense as understood by one skilled in the art, and thus may be used herein to refer to or describe a large molecule (or group of such molecules) that may comprise recurring units. Polymers may be formed in various ways, including by polymerizing monomers and / or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer may comprise a "homopolymer" that may comprise substantially identical recurring units that may be formed by, for example, polymerizing a particular monomer. Unless otherwise specified, a polymer may also comprise a "copolymer" that may comprise two or more different recurring units that may beformed by, for example, copolymerizing, two or more different monomers, and / or by chemically modifying one or more recurring units of a precursor polymer. Unless otherwise specified, a polymer or copolymer may also comprise a "terpolymer" or a "tetrapolymer" which generally refer to polymers that comprise three, four, or more different recurring monomer units. The term "polymer" as used herein is intended to include both the acid form of the polymer as well as its various salts. Polymers may be amphoteric in nature, that is, containing both anionic and cationic substituents, although not necessarily in the same proportions. Polymer molecular weights may be measured by various methods known to persons of skill in the art. For example, weight average molecular weight may be measured using gel permeation chromatography (G PC) . Polymer molecular weights may be measured by various methods known to persons of skill in the art. For example, weight average molecular weight may be measured using gel permeation chromatography (GPC). Additionally, polymer molecular weights may be measured by GPC / Light Scattering / Viscometry also known as Triple Detection GPC which employs Refractive Index Detector (with or without UV Detector), Dilute Solution Viscometry and Light Scattering all in series to determine molecular weights, distribution and related solution parameters.Terms and Units

[0111] As used herein, the term "ppm" refers to parts per million on the basis of milligrams of solute per liter of aqueous solution or slurry (e.g., mg / L).

[0112] As used herein, the terms "Ib / t" and "Ibs / ton" denote pounds of dry mass of added material (e.g., additive, solute, and / or particle) per ton of suspended solids.

[0113] As used herein, the term "% by wt" or "wt%" denotes the dry mass of additive per total dry mass of solids in a formulation, solution, suspension, slurry, or solid, multiplied by 100%.

[0114] As used herein, the term "total solids" or "consistency" generally refers to percent oven dry mass of all solids in a formulation, emulsion, solution, stock, slurry, suspension, furnish, or solid, such as a paper or board (100% * oven dry mass / total mass).Description of the Invention

[0115] Biowax emulsions are an alternative to PFAS for imparting water, oil, and grease resistance to molded fiber products. However, unmodified biowaxes are neutral to slightly negatively charged. Without cationic charge, the biowax particles have little to no affinity for negatively charged cellulosic fibers. This lack of affinity limits the internal fixation of biowaxes and hinders the full exploitation of biowaxes as PFAS alternatives at industrial scale.

[0116] The present invention solves this problem by providing stable, charge-modified cationic biowax compositions that adsorb to cellulosic fibers to impart internal water, oil, and grease resistance to paper, board, and moldable fiber products. In preferred embodiments PAC is used as a charge modifier to impart cationic charge to biowax particles. It was surprisingly found that PAC was the only charge-modifier of all tested candidates to successfully impart cationic charge to biowax particles, thereby forming the inventive PAC-modified cationic biowax compositions and facilitating adsorption of biowax to cellulosic fibers.

[0117] The inventive PAC-modified cationic biowax compositions adsorb to cellulosic fibers and are retained internally in paper, board, and moldable fiber products. The inventive PAC-modifiedY1cationic biowax compositions are also renewably sourced, biodegradable, and impart water, oil, and grease resistance to paper, board, and molded pulp products.

[0118] The invention also provides methods for forming the stable, charge-modified cationic biowax compositions and methods of manufacturing moldable fiber products containing for food and beverage packaging with oil and water resistant properties.

[0119] Raw materials used to make biowax emulsions can be any bio-based oil waxes, such as palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax and blend of plant and animal oil wax. The PAC modified cationic biowax emulsions are retained on fibers when internally added to the wet end fiber slurry. Without addition of internal size agent, the inventive PAC-modified biowax composition was found to increase resistance hot (70 °C) water penetration at a dosage range of 40- 80 Ib / ton. Kiefel LabFormer trials indicate that the inventive PAC-modified biowax composition is commercially viable in the North American for molded fiber product end use performance.PAC-Modified Cationic Biowax Compositions

[0120] In one aspect, the present invention provides a cationic biowax composition for increasing oil and / or water resistance of a cellulosic product, the cationic biowax composition comprising:

[0121] (a) a biowax emulsion comprising one or more biowaxes, optionally of plant and / or animal origin; and (b) a polyaluminum chloride (PAC).

[0122] In certain embodiments the cationic biowax composition in final form comprises:

[0123] (a) an inverse phase emulsion; (b) a cationic charge ranging from 0.2-0.8 m Eq / g, 0.2-0.7 mEq / g, 0.2-0.6 mEq / g, 0.2-0.5 mEq / g, 0.2-0.45 mEq / g, 0.2-0.4 mEq / g, 0.2-0.3 mEq / g, or 0.2-0.25 mEq / g; (c) a total solids in said cationic biowax composition ranging from 15-25 wt%, 16-24 wt%, 18- 22 wt%, or 19-21 wt%; (d) a bulk viscosity of said cationic biowax composition ranging from 50-600 cPs, 50-500 cPs, 50-400 cPs, 50-300 cPs, 50-200 cPs, or 100-200 cPs; (e) a pH ranging from 5-8, 6-8, 6-7.5, 6-7, or 6.5-7; (f) a wt% of said biowax in said cationic biowax composition ranging from 6-40 wt%, 6-35 wt%, 6-30 wt%, 6-20 wt% 6-15 wt%, or 40-90 wt%, 30-80 wt%, 20-70 wt%; (g) a wt% of said PAC in said cationic biowax composition ranging from 6-80 wt%, 10-70 wt%, 12-60 wt%, 15-50 wt%, 20-40 wt%, or 25-35 wt% or 6-50 wt%, 10-40 wt%, 20-30 wt%; (h) a ratio of PAC (wt of PAC solution) to said biowax (dry wt) ranging from 1:1 to 3:1, 1.5:1 to 2.5:1, 1.6:1 to 2.4:1, 1.8:1 to 2.2:1 or about 2:1; (i) a renewable material content of 80-95 wt%, 80-90 wt%, 84-90 wt% or 86-88 wt%, wherein renewable material content refers to wt% of biowax and PAC in the total solids of the cationic biowax composition; or (j) any combination of (a)-(i).

[0124] In certain embodiments of the cationic biowax composition, the biowax emulsion comprises:

[0125] (a) an inverse phase biowax emulsion; (b) a neutral charge, a negative charge, or a charge ranging from 0 to -0.1 mEq / g, 0 to -0.08 mEq / g, 0 to -0.06 mEq / g, 0 to -0.04 mEq / g, or 0 to -0.02 mEq / g; (c) a total solids in said biowax emulsion ranging from 25-35 wt%, 26-34 wt%, 28-32 wt%, or 29-31 wt%; (d) a bulk viscosity of said biowax emulsion ranging from 600-800 cPs, 650-800 cPs, 700- 800 cPs, or 750-800 cPs; or (e) any combination of (a)-(d).

[0126] In certain embodiments of the cationic biowax composition, the biowax emulsion comprises:

[0127] (a) said one or more biowaxes, optionally of plant and / or animal origin; (b) one or more emulsifiers; (c) one or more surfactants; (d) one or more microcrystalline or paraffinic waxes; or (e) a mixture of (a) and any combination of (b)-(d).

[0128] In certain embodiments of the cationic biowax composition:

[0129] (a) said one or more biowaxes selected are from the group consisting of palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax, a plant oil wax, an animal oil wax, a blend of plant and animal oil waxes, or any combination thereof; (b) said one or more biowaxes comprise one or more hydrogenated bio-based oils selected from the group consisting of palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof, and wherein each of said hydrogenated bio-based oils has a higher melting point compared to the corresponding non-hydrogenated bio-based oil; (c) said one or more biowaxes comprise a melting point ranging from 55-98 °C, 60-95 °C, 65-90 °C, 70-85 °C, or 75-80 °C;(d) said one or more emulsifiers comprise (i) one or more lignosulfonates; (ii) one or more rosin sizing agents selected from the group consisting of fortified rosins, esterified rosins, rosin waxes, resin acid derivatives, gum rosins, wood rosins, tall oil rosins, rosin pastes, and rosin-based dispersants; or (ill) any combination of (i) and (ii); (e) said one or more surfactants comprise (i) one or more nonionic surfactants selected from the group consisting of ethoxylated alcohols, secondary alcohol ethoxylates, ethoxylated sorbitan esters, sorbitan esters, glycerol esters, and glycerol monostearate (GMS); (ii) one or more anionic surfactants selected from the group consisting of fatty alcohol ether sulfates, alkyl ether sulfates, and special soaps; or (ill) any combination of (i) and (ii); (f) said one or more microcrystalline or paraffinic waxes are selected from the group consisting of saturated hydrocarbon waxes, paraffinic hydrocarbon waxes, isoparaffinic hydrocarbon waxes, naphthenic hydrocarbon waxes, or a mixture thereof, wherein said one or more microcrystalline or paraffinic waxes comprise a congealing point of 50-110 °C, 65-100 °C, 70-90 °C, or 75-85 °C; or (g) any combination of (a)-(f).

[0130] In certain embodiments of the cationic biowax composition, the biowax emulsion comprises:

[0131] (a) said one or more biowaxes, optionally of plant and / or animal origin, in an amount ranging from 20-85 wt%, 20-80 wt%, 20-60 wt%, 25-55 wt%, 30-50 wt%, 35-45 wt% or 20-26 wt%; (b) said one or more lignosulfonates in an amount ranging from 0.1-8 wt%, 1-5 wt%, or 2-4 wt%; (c) said one or more rosin sizing agents in an amount ranging from 1-12 wt%, 2-10 wt%, 3-8 wt%, or 4-6 wt%; (d) said one or more surfactants in an amount ranging from 1-12 wt%, 2-12 wt%, 4-10 wt%, or 6-8 wt%;(e) said one or more microcrystalline or paraffinic waxes in an amount ranging from 1-12 wt%, 2-10 wt%, 3-9 wt%, 4-8 wt%, or 5-7 wt%; (f) a biocarbon content of 60-90 wt%, 70-80 wt%, or 75-80 wt%, wherein biocarbon content refers to wt% of total carbon content in the biowax emulsion that originates from said biowax; or (g) a mixture of (a) and any combination of (b)-(f).

[0132] In certain embodiments of the cationic biowax composition, said biowax emulsion comprises:

[0133] (a) castor oil wax; (b) said one or more lignosulfonates; (c) said one or more rosin sizing agents comprising fortified rosin; (d) said nonionic surfactants comprising secondary alcohol ethoxylates, glycerol monostearate (GMS), or a combination thereof; (e) said one or more microcrystalline or paraffinic waxes comprising a congealing point of 70-90 °C; or (f) a mixture of (a) and any combination of (b)-(e).

[0134] In certain embodiments of the cationic biowax composition, said biowax emulsion:

[0135] (a) comprises an oil-phase initially comprising (i) said one or more biowaxes and, (ii) said one or more emulsifiers, (iii) said one or more surfactants, (iv) said one or more microcrystalline or paraffinic waxes, or ( v) a mixture of (i) and any combination of (ii)-(iv); (b) comprises an aqueous phase initially comprising water; (c) optionally comprises a biocide; and (d) is optionally homogenized.

[0136] In certain embodiments of the cationic biowax composition, said PAC comprises:

[0137] (a) a high basicity PAC comprising a basicity ranging from 50-95%, 55-90%, 60-85%, 60-80%, 60-75%, 60-70%, or 60-65%, wherein said basicity is defined as the molar equivalent percent of hydroxide (OH) to aluminum (Al) in the PAC; (b) a PAC strength ranging from 15-30%, 20-30%, or 20- 23%, wherein said PAC strength is defined as %AI2O3 in the PAC.

[0138] In certain embodiments of the cationic biowax composition:

[0139] (a) said cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; and / or (b) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition.Methods for Producing PAC-Modified Cationic Biowax Compositions

[0140] In another aspect, the present invention provides a method for producing a cationic biowax composition for increasing oil and / or water resistance of a cellulosic product, the method comprising contacting:

[0141] (a) a biowax emulsion; and (b) a polyaluminum chloride (PAC) to form said cationic biowax composition, wherein said biowax emulsion comprises one or more biowaxes, optionally of plant and / or animal origin.

[0142] In certain embodiments of the method:

[0143] (a) the method further comprises emulsifying to form an inverse phase emulsion; (b) said cationic biowax composition in final form comprises a cationic charge ranging from 0.2-0.8 mEq / g, 0.2-0.7 mEq / g, 0.2-0.6 mEq / g, 0.2-0.5 mEq / g, 0.2-0.45 mEq / g, 0.2-0.4 mEq / g, 0.2-0.3 mEq / g, or 0.2- 0.25 mEq / g; (c) said cationic biowax composition in final form comprises a total solids in said cationic biowax composition ranging from 15-25 wt%, 16-24 wt%, 18-22 wt%, or 19-21 wt%; (d) said cationic biowax composition in final form comprises a bulk viscosity of said cationic biowax composition ranging from 50-600 cPs, 50-500 cPs, 50-400 cPs, 50-300 cPs, 50-200 cPs, or 100-200 cPs; (e) said cationic biowax composition in final form comprises a pH ranging from 5-8, 6-8, 6-7.5, 6-7, or 6.5-7; (f) said cationic biowax composition in final form comprises a wt% of said biowax in said cationic biowax composition ranging from 6-40 wt%, 6-35 wt%, 6-30 wt%, 6-20 wt% 6-15 wt%, or 40-90 wt%, 30-80 wt%, 20-70 wt%; (g) said cationic biowax composition in final form comprises a wt% of saidPAC in said cationic biowax composition ranging from 6-80 wt%, 10-70 wt%, 12-60 wt%, 15-50 wt%, 20-40 wt%, or 25-35 wt% or 6-50 wt%, 10-40 wt%, 20-30 wt%; (h) said cationic biowax composition in final form comprises a ratio of PAC (wt of PAC solution) to said biowax (dry wt) ranging from 1:1 to 3:1, 1.5:1 to 2.5:1, 1.6:1 to 2.4:1, 1.8:1 to 2.2:1 or about 2:1; (i) said cationic biowax composition in final form comprises a renewable material content of 80-95 wt%, 80-90 wt%, 84-90 wt% or 86-88 wt%, wherein renewable material content refers to wt% of biowax and PAC in the total solids of the cationic biowax composition; or (j) any combination of (a)-(i).

[0144] In certain embodiments of the method, said biowax emulsion comprises:

[0145] (a) an inverse phase biowax emulsion; (b) a neutral charge, a negative charge, or a charge ranging from 0 to -0.1 mEq / g, 0 to -0.08 mEq / g, 0 to -0.06 mEq / g, 0 to -0.04 mEq / g, or 0 to -0.02 mEq / g; (c) a total solids in said biowax emulsion ranging from 25-35 wt%, 26-34 wt%, 28-32 wt%, or 29-31 wt%; (d) a bulk viscosity of said biowax emulsion ranging from 600-800 cPs, 650-800 cPs, 700- 800 cPs, or 750-800 cPs; or (e) any combination of (a)-(d).

[0146] In certain embodiments of the method said biowax emulsion is formed by an inverse phase emulsification method comprising:

[0147] (a) combining (i) said one or more biowaxes, optionally of plant and / or animal origin, (ii) one or more rosin sizing agents, (iii) one or more surfactants, and (iv) said one or more microcrystalline or paraffinic waxes, or (v) a mixture of (i) and any combination of (ii)-(iv); (b) heating to 50-99 °C, 60- 99 °C, 70-99 °C, 75-98 °C, or 85-95 °C to form an oil-phase; (c) contacting an amount of hot water with said oil-phase, wherein said hot water is optionally 50-99 °C, 60-99 °C, 70-99 °C, 75-98 °C, or 85- 95 °C; and (d) emulsifying at 70-99 °C, 75-98 °C, or 85-95 °C to form said biowax emulsion.

[0148] In certain embodiments of the method said inverse phase emulsification method further comprises:

[0149] (i) emulsifying during step (d) for an amount of time ranging from 0.5-5 h, 0.5-4 h, or 1-3 h; (ii) after step (d), homogenizing the biowax emulsion; (iii) after step (d), cooling to a temperature ranging from 10-35 °C, 15-30 °C, or 20-25 °C, optionally using an ice-water bath, a cooling jacket, or a cooling core; (iv) after step (d), adding a biocide; or (v) any combination of (i)-(iv).

[0150] In certain embodiments of the method:

[0151] (a) said one or more biowaxes are selected from the group consisting of palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax, a plant oil wax, an animal oil wax, a blend of plant and animal oil waxes, or any combination thereof; (b) said one or more biowaxes comprise one or more hydrogenated bio-based oils selected from the group consisting of palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof, and wherein each of said hydrogenated bio-based oils has a higher melting point compared to the corresponding non-hydrogenated bio-based oil; (c) said one or more biowaxes comprise a melting point ranging from 55-98 °C, 60-95 °C, 65-90 °C, 70-85 °C, or 75-80 °C; (d) said one or more emulsifiers comprise (i) one or more lignosulfonates; (ii) one or more rosin sizing agents selected from the group consisting of fortified rosins, esterified rosins, rosin waxes, resin acid derivatives, gum rosins, wood rosins, tall oil rosins, rosin pastes, and rosin-based dispersants; or (iii) any combination of (i) and (ii); (e) said one or more surfactants comprise (i) oneor more nonionic surfactants selected from the group consisting of ethoxylated alcohols, secondary alcohol ethoxylates, ethoxylated sorbitan esters, sorbitan esters, glycerol esters, and glycerol monostearate (GMS); (ii) one or more anionic surfactants selected from the group consisting of fatty alcohol ether sulfates, alkyl ether sulfates, and special soaps; or (ill) any combination of (i) and (ii); (f) said one or more microcrystalline or paraffinic waxes are selected from the group consisting of saturated hydrocarbon waxes, paraffinic hydrocarbon waxes, isoparaffinic hydrocarbon waxes, naphthenic hydrocarbon waxes, or a mixture thereof, wherein said one or more microcrystalline or paraffinic waxes comprise a congealing point of 50-110 °C, 65-100 °C, 70-90 °C, or 75-85 °C; or (g) any combination of (a)-(f).

[0152] In certain embodiments of the method said biowax emulsion comprises:

[0153] (a) said one or more biowaxes, optionally of plant and / or animal origin, in an amount ranging from 20-85 wt%, 20-80 wt%, 20-60 wt%, 25-55 wt%, 30-50 wt%, 35-45 wt% or 20-26 wt%; (b) said one or more lignosulfonates in an amount ranging from 0.1-8 wt%, 1-5 wt%, or 2-4 wt%; (c) said one or more rosin sizing agents in an amount ranging from 1-12 wt%, 2-10 wt%, 3-8 wt%, or 4-6 wt%; (d) said one or more surfactants in an amount ranging from 1-12 wt%, 2-12 wt%, 4-10 wt%, or 6-8 wt%; (e) said one or more microcrystalline or paraffinic waxes in an amount ranging from 1-12 wt%, 2-10 wt%, 3-9 wt%, 4-8 wt%, or 5-7 wt%; (f) a biocarbon content of 60-90 wt%, 70-80 wt%, or 75-80 wt%, wherein biocarbon content refers to wt% of total carbon content in the biowax emulsion that originates from said biowax; or (g) a mixture of (a) and any combination of (b)-(f).

[0154] In certain embodiments of the method said biowax emulsion comprises:

[0155] (a) castor oil wax; (b) said one or more lignosulfonates; (c) said one or more rosin sizing agents comprising fortified rosin; (d) said nonionic surfactants comprising secondary alcohol ethoxylates, glycerol monostearate (GMS), or a combination thereof; (e) said one or more microcrystalline or paraffinic waxes comprising a congealing point of 70-90 °C; or (f) a mixture of (a) and any combination of (b)-(e).

[0156] In certain embodiments of the method:

[0157] (a) said PAC comprises a high basicity PAC comprising a basicity ranging from 50-95%, 55- 90%, 60-85%, 60-80%, 60-75%, 60-70%, or 60-65%, wherein said basicity is defined as the molar equivalent percent of OH to Al in the PAC; (b) said PAC comprises a PAC strength ranging from 15- 30%, 20-30%, or 20-23%, wherein said PAC strength is defined as %AI2O3 in the PAC; (c) said moldable cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; (d) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (ill) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or (e) any combination of (a)-(d).Methods for Preparing Water and Oil Resistant Moldable Fiber Products

[0158] In another aspect, the present invention provides a method of preparing a cellulosic product comprising oil and water resistance, the method comprising:

[0159] (a) contacting an aqueous suspension comprising cellulosic fibers and a cationic biowax composition according to any of the foregoing or obtainable by a method according to any of the foregoing, thereby forming a fiber stock composition; and (b) adding the fiber stock composition to the wet end of a paper machine.

[0160] In certain embodiments of the method the cationic biowax composition is formed separately and then added to the aqueous suspension comprising cellulosic fibers. In other embodiments, the cationic biowax composition is formed in situ, by adding a biowax emulsion and PAC, simultaneously or separately in any order, to the aqueous suspension comprising cellulosic fibers.

[0161] In certain embodiments of the method the method further comprises:

[0162] (i) optionally contacting the fiber stock composition with one or more retention aids; and / or (ii) after step (b), removing sufficient water from the fiber stock composition to form a wet fibrous web and then pressing and drying the wet fibrous web to obtain said cellulosic product.

[0163] In certain embodiments of the method:

[0164] (a) said one or more retention aids comprise at least one polyacrylamide (PAM), at least one anionic polyacrylamide (APAM), at least one cationic polyacrylamide (CPAM), at least one amphoteric polyacrylamide (AmPAM), at least one polyvinylamine (PVAm) polymer, at least one glyoxalated polyacrylamide (GPAM), or any combination of the foregoing ; (b) said aqueous suspension comprising cellulosic fibers comprises (i) one or more cellulosic fibers selected from the group consisting of softwood fiber, hardwood fiber, recycled fiber, recycled old corrugated cardboard (OCC), recycled mixed office waste (MOW), recycled mixed office paper, refined fiber, mill broke fibers, coated broke, non-wood fibers, straw pulp, wheat pulp; (ii) a papermaking furnish comprising pulp, Kraft pulp, unbleached Kraft pulp, bleached pulp, unbleached pulp, process water from pulp, paper, and / or board production, neutral sulfite semi chemical (NSSC) pulp, mechanical pulp, non-wood pulp; (iii) a thick stock, a thick stock diluted with chemical water, synthetic water, white water, and / or process water, and a thin stock; or (iv) a mixture of any of (i)-(iii); (c) said cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; (d) any combination of (a)-(c).

[0165] In certain embodiments of the method:

[0166] (a) said cationic biowax composition is present in said fiber stock composition at a dosage of 10-100 dry Ib / t, 20-80 dry Ib / t, 20-60 dry Ib / t, or 20-40 dry Ib / t; (b) said one or more retention aids are present in said fiber stock composition at a dosage of 0.1-1 dry Ib / t, 0.2-0.8 dry Ib / t, 0.4-0.6 dry Ib / t, or 0.5-0.6 dry Ib / t; (c) said cationic biowax composition is retained internally on the cellulosic fibers of said cellulosic product; (d) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oilresistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or (e) any combination of (a)-(d).

[0167] In another aspect, the present invention provides a fiber stock composition comprising:

[0168] (a) an aqueous suspension comprising cellulosic fibers; and (b) a cationic biowax composition according to any of the foregoing or obtainable by a method according to any of the foregoing.

[0169] In another aspect, the present invention provides a moldable cellulosic product comprising:

[0170] (a) an amount of cellulosic fibers; and (b) a cationic biowax composition according to any of the foregoing or obtainable by a method according to any of the foregoing.

[0171] In certain embodiment said moldable cellulosic product comprising said cationic biowax composition:

[0172] (a) is used as a food package, a beverage package, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food, beverage, oil, water, and / or grease; (b) comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (ill) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition.

[0173] The methods and compositions illustratively disclosed herein suitably may be practiced in the absence of any element which is not specifically disclosed herein and / or any element specifically disclosed herein. Exemplary embodiments of the invention and its advantages are further disclosed in the following examples.EXAMPLES

[0174] The examples provided herein are for illustrative purposes so that the invention may be more fully understood. These examples should not be construed as limiting the invention in any way.Example 1: Preparation of charge-modified cationic biowax compositions (CBC)

[0175] Cationic biowax compositions (CBC) were prepared and evaluated as internal water, oil, and grease resistance aids in handsheets and molded fiber products.BIOWAX EMULSIONS

[0176] Biowax emulsions were prepared from castor wax, rosin size, nonionic and anionic surfactants, microcrystalline wax, and other additives according to Table 1. The components were blended to form an inverse phase emulsion and then cooled using a quick cooling process.

[0177] Inverse phase emulsions were formed by combining components according to Table 1 in a reactor and heating to a temperature ranging from 90-95 °C to form an oil-phase, to which was added an amount of hot water. The mixture was emulsified at 75-98 °C for 0.5-4 h, homogenized, and then cooled to a temperature ranging from 15-25 °C. A biocide was then added.

[0178] Quick cooling was achieved by cooling the resulting inverse phase emulsion by means of an ice-water bath, a cooling jacket, or a cooling core to a temperature ranging from 15-25 °C.

[0179] The final biowax emulsion (BE1) using castor wax (24%) yielded a bulk viscosity of 98 cPs and total solids of 30%. The charge of the biowax emulsion is slightly negative at -0.08 mEq / g.Table 1: Biowax Emulsions.*nonionic surfactants: ethoxylated alcohols and estersCHARGE MODIFIERS

[0180] Charge modifier candidates and their characteristics are shown in Table 2. The charge modifier candidates were combined with the slightly negative biowax emulsions to potentially impart a cationic charge to the biowax emulsion, with the goal of forming charge-modified cationic biowax compositions (CBC) for increasing oil and water resistance of cellulosic products.Table 2: Charge modifier candidates.CATIONIC BIOWAX COMPOSITIONS (CBC)

[0181] Cationic biowax compositions (CBC1-4) were prepared by combining biowax emulsion (BE1) and charge modifier candidates (PAC, polyamine, CPAM, or AhtSO a) according to Table 3 and emulsifying to form stable charge-modified cationic biowax compositions as inverse phase emulsions. A control composition was also prepared without biowax. Properties of CBC1-4 and the control are shown in Table 3.Table 3: Charge-modified cationic biowax compositions (CBC) and OGR results.*OGR- Oil and Grease Resistance**Pass - 1 h 60 °C hot oil holdout; Fail - 1 h 60 °C hot oil penetration to opposite face***Fail - aluminum salt deposits formed at pH 6-7

[0182] The compositions of Table 3 provide initial proof of concept that charge modifiers, such as PAC, can be co-emulsified with biowax emulsions to form charge-modified cationic biowax compositions (CBC) with a high percentage of solids from renewable content (i.e., biowax + PAC) for potentially increasing oil and water resistance of cellulosic products, such as moldable fiber products.Example 2: Evaluation of charge modifiers.

[0183] Charge-modified cationic biowax compositions (CBC1-4) were evaluated against the control to determine which charge modifier candidates were effective additives for improving oil and grease resistance (OGR) of molded fibers. Results showing Pass / Fail indications for 1 h 60 °C hot oil holdout testing are shown in Table 3.

[0184] It was found that, in order to function as a charge modifier, aluminum sulfate requires acidic conditions (e.g., pH 3-4), which are detrimental to overall stability of the furnish and not optimal for papermaking. At pH ranges that are suitable for papermaking (e.g., pH 5-8, 6-8, 6-7.5, 6-7, or 6.5-7), aluminum sulfate hydrolyzed and produced unwanted deposits of insoluble aluminum solids, thereby failing to function as an effective charge modifier. Other charge modifier candidates (e.g., polyamine, CPAM) failed to facilitate adsorption of the biowax to fibers.

[0185] It was surprisingly found that PAC was the only charge modifier candidate to facilitate adsorption of the biowax to fibers and improve water and oil resistance of the molded fiber products. These results indicate that PAC is effective a charge modifier for biowax emulsions a neutral pH or at pH 6-7.

[0186] Without being bound to theory, it can be rationalized that PAC was the only effective charge modifier capable of rendering the surface of the biowax particles cationic, thereby facilitating adsorption of the PAC-modified cationic biowax particles to anionic cellulosic fibers. This allows for internal retention of the PAC-modified cationic biowax particles in moldable cellulosic products, thereby enhancing their water and oil resistance. Moldable cellulosic products include food packaging, beverage packaging, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food, beverage, oil, water, and / or grease.

[0187] Further, without being bound to theory, it can be rationalized that PAC has small particle size; whereas, cationic polymers (polyamine, CPAM) have relatively large particle sizes. Therefore, the small PAC particles may better penetrate, contact, and interact with the relatively small biowax particles. A schematic of charge modification of biowax particles with PAC is shown in FIG 1. This likely results in more efficient charge modification of the biowax particles and may cause increased local cationic character of the charge-modified cationic biowax particles. This, in turn, results in more efficient adsorption of the charge-modified cationic biowax particles onto cellulosic fibers, thereby producing moldable fibers with relatively high water, oil, and grease resistance.

[0188] These results provide proof of concept that PAC is and effective charge modifier for imparting cationic charge to biowax particles. The PAC-modified cationic biowax particles adsorb to cellulosic fibers and are retained internally and impart water, oil, and grease resistance to paper, board, and molded pulp products.Example 3: Hot oil resistance of handsheets containing PAC-modified cationic biowax compositions (CBC).

[0189] PAC-modified cationic biowax compositions were evaluated to determine effective dosages and ratios of PAC:biowax (wt:wt) for facilitating adsorption of biowax to cellulosic fibers and improving hot oil resistance of cellulosic fiber products.

[0190] Hand sheets were prepared from an aqueous suspension of recycled cellulosic fibers containing 100% mixed office waste (MOW) and 9% filler. Prior to handsheet formation, the aqueous fiber suspensions were treated with PAC-modified cationic biowax composition (CBC1) at various dosages. The final dosages of biowax in the fiber slurries was 40 or 80 Ib / t and the final dosages of PAC ranged from 20-160 Ib / t.HOT OIL RESISTANCE TESTING

[0191] Hot oil resistance of handsheets containing PAC-modified cationic biowax composition (CBC1) was measured by dropping hot oil (60 °C, 0.5 g) onto the top surface of the handsheet sample and determining the amount of time (min) for the hot oil drop to be absorbed into the sheet and stain the opposite surface of the sheet, which indicated the hot oil absorption time. Longer hot oil absorption time indicated higher oil resistance. Results for hot oil resistance testing are shown in FIG 2.

[0192] These results demonstrate that PAC-modified cationic biowax composition (CBC1) facilitate adsorption of the biowax to fibers and improve hot oil resistance of handsheets in a dose dependent manner. Longer (>60 min) hot oil absorption times were observed for PAC:biowax dosage (wt / wt) ratios ranging from 1.25:1 to 2:1. No staining was observed for PAC dosages above 80 Ib / t.

[0193] These results provide initial proof of concept that the inventive PAC-modified cationic biowax composition (CBC1) can be used to improve hot oil resistance of cellulosic products for use in food packaging, beverage packaging, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food oil and / or grease.Example 4: Hot water and hot oil resistance of moldable fiber bowls containing PAC-modified cationic biowax compositions (CBC) and an anionic polymer retention aid.

[0194] A PAC-modified cationic biowax composition (CBC1) was evaluated in combination with an anionic polymer retention aid for facilitating adsorption of biowax to moldable cellulosic fibers and improving hot water and hot oil resistance of molded fiber bowls.

[0195] Molded fiber bowls were prepared from an aqueous suspension of cellulosic fibers (recycled and virgin). Prior to bowl formation, the aqueous fiber suspensions were treated with PAC-modified cationic biowax composition (CBC1) with a ratio of PAC:biowax of 2:1. The final dosage of PAC- modified biowax composition in the fiber slurries was 20 or 40 Ib / t. An emulsion anionic polyacrylamide (APAM) retention aid (E0645; MW 2-4 million Dalton, 30-45% anionic charge) was also added to the fiber slurries at 0.5 Ib / t. Blank samples were treated with no biowax and no charge modifier.HOT OIL AND HOT WATER RESISTANCE TESTING

[0196] Hot oil (60 °C) resistance testing was performed according to Example 3. Resistance to hot oil absorption over 30 min (30-min hot oil holdout) was evaluated. No oil staining on the opposite face of the bowl after 30 min was considered a 30-min holdout pass.

[0197] Hot water (60 °C) resistance testing was performed in the same manner as hot oil resistance testing by substituting hot water (60 °C) in place of hot oil. Resistance to hot water absorption over 30 min (30-min hot water holdout) was evaluated. No water staining on the opposite face of the bowl after 30 min was considered a 30-min holdout pass.

[0198] Results are shown in FIG 3. These results indicate a 30-min holdout pass for both hot oil and hot water at 40 Ib / t dosage of PAC-modified cationic biowax composition (CBC1) and 0.5 Ib / t of anionic polymer retention aid. For the remaining samples, oil or water penetration can be seen as dark staining on the molded fiber bowl samples, which indicates a 30-min holdout failure.

[0199] These results provide initial proof of concept that a combination of the inventive PAC- modified cationic biowax composition (CBC1) and an anionic retention aid can be used to improve hot oil and hot water resistance of cellulosic products for use in food packaging, beverage packaging, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food oil and / or grease. These results further suggest that the anionic retention aid improved the retention of the PAC-modified biowax composition on fibers.Example 5: Commercial viability testing of handsheets containing PAC-modified cationic biowax compositions (CBC) and an anionic polymer retention aid.

[0200] A PAC-modified cationic biowax composition (CBC1) was evaluated in combination with an anionic polymer retention aid for facilitating adsorption of biowax to cellulosic fibers and imparting commercially viable hot water and hot oil resistance to handsheets.

[0201] Handsheets were prepared from an aqueous suspension of 100% virgin cellulosic fibers . Prior to handsheet formation, the aqueous fiber suspensions were treated with PAC-modified cationic biowax composition (CBC1) with a ratio of PAC:biowax of 2:1. The final dosage of PAC-modified biowax composition in the fiber slurries was 20 or 40 Ib / t. The emulsion anionic polyacrylamide (APAM) retention aid (E0645; MW 2-4 million Dalton, 30-45% anionic charge) was also added to the fiber slurry at 0.5 Ib / t.

[0202] Hot oil (60 °C) and hot water (70 °C) resistance testing was performed according to Example 4. Hot oil holdout was evaluated over 1 h and 3 h. Hot water holdout was evaluated over 15 min and 30 min.

[0203] Results are shown in FIG 4. Pass / Fail indications for 1 h and 3 h hot oil holdout testing and 15 min and 30 min hot water holdout testing are shown. Pass indicates no hot liquid penetration over the indicated time.

[0204] These results indicate a 1 h and 3 h hot oil holdout pass and a 15 min and 30 min hot water holdout pass at both 20 Ib / t and 40 Ib / t of PAC-modified cationic biowax composition (CBC1) and 0.5 Ib / t of anionic polymer retention aid.

[0205] These results provide proof of concept that a combination of the inventive PAC-modified cationic biowax composition (CBC1) and an anionic retention aid can be used to provide commercially viable hot oil and hot water resistance to cellulosic products for use in food packaging, beverage packaging, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food oil and / or grease. These results provide further proof of concept that the anionic retention aid improved the retention of the PAC-modified biowax composition on fibers.Example 6: Commercial viability testing of molder fiber trays containing PAC-modified cationic biowax compositions (CBC) and an anionic polymer retention aid.

[0206] A PAC-modified cationic biowax composition (CBC1) was evaluated in combination with an anionic polymer retention aid for facilitating adsorption of biowax to moldable cellulosic fibers and imparting commercially viable hot water and hot oil resistance to molded fiber trays.

[0207] Molded fiber trays were prepared from an aqueous suspension of cellulosic fibers (virgin) using a pilot scale Kiefel thermoforming machine. Prior to handsheet formation, the aqueous fiber suspensions were treated with a PAC-modified cationic biowax composition (CBC1) with a ratio of PAC:biowax of 2:1. The final dosage of PAC-modified biowax composition in the fiber slurries was 20 or 40 Ib / t. The emulsion anionic polyacrylamide (APAM) retention aid (E0645; MW 2-4 million Dalton, 30-45% anionic charge) was also added to the fiber slurry at 0.5 Ib / t.

[0208] Hot oil (60 °C) and hot water (70 °C) resistance testing was performed according to Example 4. Hot oil holdout was evaluated over 1 h and 3 h. Hot water holdout was evaluated over 30 min and 60 min.

[0209] Results are shown in FIG 5. Pass / Fail indications for 1 h and 3 h hot oil holdout testing and 30 min and 60 min hot water holdout testing are shown. Pass indicates no hot liquid penetration over the indicated time.

[0210] These results indicate a 1 h and 3 h hot oil holdout pass and a 30 min and 60 min hot water holdout pass at both 20 Ib / t and 40 Ib / t of PAC-modified cationic biowax composition (CBC1) and 0.5 Ib / t of anionic polymer retention aid.

[0211] These results provide proof of concept that a combination of the inventive PAC-modified cationic biowax composition (CBC1) and an anionic retention aid can be used to provide commercially viable hot oil and hot water resistance to cellulosic products for use in food packaging, beverage packaging, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food oil and / or grease. These results provide further proof of concept that the anionic retention aid improved the retention of the PAC-modified biowax composition on fibers.

[0212] In the preceding disclosure which includes the examples, different procedures and various steps have been described. It will, however, be evident that various modifications and changes may be made thereto, and additional procedures may be implemented, without departing from the broader scope of the procedures as set forth in the claims that follow.

Claims

CLAIMSWhat is claimed is:

1. A cationic biowax composition for increasing oil and / or water resistance of a cellulosic product, the cationic biowax composition comprising:(a) a biowax emulsion comprising one or more biowaxes, optionally of plant and / or animal origin; and(b) a polyaluminum chloride (PAC).

2. The cationic biowax composition of claim 1, which in final form comprises:(a) an inverse phase emulsion;(b) a cationic charge ranging from 0.2-0.8 mEq / g, 0.2-0.7 mEq / g, 0.2-0.6 mEq / g, 0.2-0.5 mEq / g, 0.2-0.45 mEq / g, 0.2-0.4 mEq / g, 0.2-0.3 mEq / g, or 0.2-0.25 mEq / g;(c) a total solids in said cationic biowax composition ranging from 15-25 wt%, 16-24 wt%, 18-22 wt%, or 19-21 wt%;(d) a bulk viscosity of said cationic biowax composition ranging from 50-600 cPs, 50-500 cPs, 50-400 cPs, 50-300 cPs, 50-200 cPs, or 100-200 cPs;(e) a pH ranging from 5-8, 6-8, 6-7.5, 6-7, or 6.5-7;(f) a wt% of said biowax in said cationic biowax composition ranging from 40-90 wt%, 30-80 wt%, 20-70 wt%,(g) a wt% of said PAC in said cationic biowax composition ranging from 6-50 wt%, 10-40 wt%, 20-30 wt%;(h) a ratio of PAC (wt of PAC solution) to said biowax (dry wt) ranging from 1:1 to 3:1, 1.5:1 to 2.5:1, 1.6:1 to 2.4:1, 1.8:1 to 2.2:1 or about 2:1;(i) a renewable material content of 80-95 wt%, 80-90 wt%, 84-90 wt% or 86-88 wt%, wherein renewable material content refers to wt% of biowax and PAC in the total solids of the cationic biowax composition; or(j) any combination of (a)-(i).

3. The cationic biowax composition of claim 1 or 2, wherein said biowax emulsion comprises:(a) an inverse phase biowax emulsion;(b) a neutral charge, a negative charge, or a charge ranging from 0 to -0.1 mEq / g, 0 to -0.08 mEq / g, 0 to -0.06 mEq / g, 0 to -0.04 mEq / g, or 0 to -0.02 mEq / g;(c) a total solids in said biowax emulsion ranging from 25-35 wt%, 26-34 wt%, 28-32 wt%, or 29-31 wt%;(d) a bulk viscosity of said biowax emulsion ranging from 600-800 cPs, 650-800 cPs, 700-800 cPs, or 750-800 cPs;(e) one or more biowaxes, optionally of plant and / or animal origin;(f) one or more emulsifiers;(g) one or more surfactants;(h) one or more microcrystalline or paraffinic waxes; or(i) a mixture of (e) and any combination of (f)-(h);(j) said one or more biowaxes selected are from the group consisting of palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax, a plant oil wax, an animal oil wax, a blend of plant and animal oil waxes, or any combination thereof;(k) said one or more biowaxes comprise one or more hydrogenated bio-based oils selected from the group consisting of palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof, and wherein each of said hydrogenated bio-based oils has a higher melting point compared to the corresponding non-hydrogenated bio-based oil;(l) said one or more biowaxes comprise a melting point ranging from 55-98 °C, 60-95 °C, 65- 90 °C, 70-85 °C, or 75-80 °C;(m) said one or more emulsifiers comprise (i) one or more lignosulfonates; (ii) one or more rosin sizing agents selected from the group consisting of fortified rosins, esterified rosins, rosin waxes, resin acid derivatives, gum rosins, wood rosins, tall oil rosins, rosin pastes, and rosin-based dispersants; or (iii) any combination of (i) and (ii);(n) said one or more surfactants comprise (i) one or more nonionic surfactants selected from the group consisting of ethoxylated alcohols, secondary alcohol ethoxylates, ethoxylated sorbitan esters, sorbitan esters, glycerol esters, and glycerol monostearate (GMS); (ii) one or more anionic surfactants selected from the group consisting of fatty alcohol ether sulfates, alkyl ether sulfates, and special soaps; or (iii) any combination of (i) and (ii);(o) said one or more microcrystalline or paraffinic waxes are selected from the group consisting of saturated hydrocarbon waxes, paraffinic hydrocarbon waxes, isoparaffinic hydrocarbon waxes, naphthenic hydrocarbon waxes, or a mixture thereof, wherein said one or more microcrystalline or paraffinic waxes comprise a congealing point of 50-110 °C, 65-100 °C, 70-90 °C, or 75-85 °C;(p) any combination of (a)-(o).

4. The cationic biowax composition of any one of the foregoing claims, wherein said biowax emulsion comprises:(a) said one or more biowaxes, optionally of plant and / or animal origin, in an amount ranging from 20-85 wt%, 20-80 wt%, 20-60 wt%, 25-55 wt%, 30-50 wt%, 35-45 wt% or 20-26 wt%;(b) said one or more lignosulfonates in an amount ranging from 0.1-8 wt%, 1-5 wt%, or 2-4 wt%;(c) said one or more rosin sizing agents in an amount ranging from 1-12 wt%, 2-10 wt%, 3-8 wt%, or 4-6 wt%;(d) said one or more surfactants in an amount ranging from 1-12 wt%, 2-12 wt%, 4-10 wt%, or 6-8 wt%;(e) said one or more microcrystalline or paraffinic waxes in an amount ranging from 1-12 wt%, 2-10 wt%, 3-9 wt%, 4-8 wt%, or 5-7 wt%;(f) a biocarbon content of 60-90 wt%, 70-80 wt%, or 75-80 wt%, wherein biocarbon content refers to wt% of total carbon content in the biowax emulsion that originates from said biowax; and / or(g) a mixture of (a) and any combination of (b)-(f);(h) castor oil wax;(i) said one or more lignosulfonates;(j) said one or more rosin sizing agents comprise a fortified rosin;(k) said nonionic surfactants comprise secondary alcohol ethoxylates, glycerol monostearate (GMS), or a combination thereof;(l) said one or more microcrystalline or paraffinic waxes comprise a congealing point of 70- 90 °C; or(m) a mixture of comprising any combination of (h)-(l);(n) an oil-phase initially comprising (i) said one or more biowaxes and, (ii) said one or more emulsifiers, (iii) said one or more surfactants, (iv) said one or more microcrystalline or paraffinic waxes, or (v) a mixture of (i) and any combination of (ii)-(iv);(o) an aqueous phase initially comprising water;(p) a biocide;(q) is homogenized; and / or(r) any combination of (a) to (q).

5. The cationic biowax composition of any one of the foregoing claims, wherein:(a) said PAC comprises a high basicity PAC comprising a basicity ranging from 50-95%, 55- 90%, 60-85%, 60-80%, 60-75%, 60-70%, or 60-65%, wherein said basicity is defined as the molar equivalent percent of hydroxide (OH) to aluminum (Al) in the PAC; and / or(b) said PAC comprises a PAC strength ranging from 15-30%, 20-30%, or 20-23%, wherein said PAC strength is defined as %AI2O3 in the PAC;(c) said cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers; and / or(d) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or(e) any combination of (a) to (d).

6. A method for producing a cationic biowax composition for increasing oil and / or water resistance of a cellulosic product, the method comprising contacting:(a) a biowax emulsion; and(b) a polyaluminum chloride (PAC) to form said cationic biowax composition, wherein said biowax emulsion comprises one or more biowaxes, optionally of plant and / or animal origin.

7. The method of claim 6, wherein:(a) the method further comprises emulsifying to form an inverse phase emulsion;(b) said cationic biowax composition in final form comprises a cationic charge ranging from 0.2-0.8 mEq / g, 0.2-0.7 mEq / g, 0.2-0.6 mEq / g, 0.2-0.5 mEq / g, 0.2-0.45 mEq / g, 0.2-0.4 mEq / g, 0.2-0.3 mEq / g, or 0.2-0.25 mEq / g;(c) said cationic biowax composition in final form comprises a total solids in said cationic biowax composition ranging from 15-25 wt%, 16-24 wt%, 18-22 wt%, or 19-21 wt%;(d) said cationic biowax composition in final form comprises a bulk viscosity of said cationic biowax composition ranging from 50-600 cPs, 50-500 cPs, 50-400 cPs, 50-300 cPs, 50-200 cPs, or 100-200 cPs;(e) said cationic biowax composition in final form comprises a pH ranging from 5-8, 6-8, 6- 7.5, 6-7, or 6.5-7;(f) said cationic biowax composition in final form comprises a wt% of said biowax in said cationic biowax composition ranging from 40-90 wt%, 30-80 wt%, 20-70 wt%;(g) said cationic biowax composition in final form comprises a wt% of said PAC in said cationic biowax composition ranging from 6-50 wt%, 10-40 wt%, 20-30 wt%;(h) said cationic biowax composition in final form comprises a ratio of PAC (wt of PAC solution) to said biowax (dry wt) ranging from 1:1 to 3:1, 1.5:1 to 2.5:1, 1.6:1 to 2.4:1, 1.8:1 to 2.2:1 or about 2:1;(i) said cationic biowax composition in final form comprises a renewable material content of 80-95 wt%, 80-90 wt%, 84-90 wt% or 86-88 wt%, wherein renewable material content refers to wt% of biowax and PAC in the total solids of the cationic biowax composition; or(j) any combination of (a)-(i); and / or(k) said biowax emulsion comprises an inverse phase biowax emulsion;(l) said biowax emulsion comprises a neutral charge, a negative charge, or a charge ranging from 0 to -0.1 mEq / g, 0 to -0.08 mEq / g, 0 to -0.06 mEq / g, 0 to -0.04 mEq / g, or 0 to -0.02 mEq / g;(m) said biowax emulsion comprises a total solids in said biowax emulsion ranging from 25- 35 wt%, 26-34 wt%, 28-32 wt%, or 29-31 wt%;(n) said biowax emulsion comprises a bulk viscosity of said biowax emulsion ranging from 600-800 cPs, 650-800 cPs, 700-800 cPs, or 750-800 cPs; or(o) any combination of (a)-(n); and / or said biowax emulsion is formed by an inverse phase emulsification method comprising:(p) combining (i) said one or more biowaxes, optionally of plant and / or animal origin, (ii) one or more rosin sizing agents, (ill) one or more surfactants, and (iv) said one or more microcrystalline or paraffinic waxes, or (vi) a mixture of (i) and any combination of (ii)-(iv);(q) heating to 50-99 °C, 60-99 °C, 70-99 °C, 75-98 °C, or 85-95 °C to form an oil-phase;(r) contacting an amount of hot water with said oil-phase, wherein said hot water is optionally 50-99 °C, 60-99 °C, 70-99 °C, 75-98 °C, or 85-95 °C; and(s) emulsifying at 70-99 °C, 75-98 °C, or 85-95 °C to form said biowax emulsion.

8. The method of claim 7, wherein(a) said inverse phase emulsification method further comprises:(i) emulsifying during step (d) for an amount of time ranging from 0.5-5 h, 0.5-4 h, or 1- 3 h;(ii) after step (d), homogenizing the biowax emulsion;(iii) after step (d), cooling to a temperature ranging from 10-35 °C, 15-30 °C, or 20-25 °C, optionally using an ice-water bath, a cooling jacket, or a cooling core;(iv) after step (d), adding a biocide; or(v) any combination of (i)-(iv);(b) said one or more biowaxes are selected from the group consisting of palm oil wax, castor oil wax, soybean oil wax, fish oil wax, tallow oil wax, a plant oil wax, an animal oil wax, a blend of plant and animal oil waxes, or any combination thereof;(c) said one or more biowaxes comprise one or more hydrogenated bio-based oils selected from the group consisting of palm oil, castor oil, soybean oil, fish oil, tallow oil, a plant oil, an animal oil, a blend of plant and animal oils, or any combination thereof, and wherein each of said hydrogenated bio-based oils has a higher melting point compared to the corresponding non-hydrogenated bio-based oil;(d) said one or more biowaxes comprise a melting point ranging from 55-98 °C, 60-95 °C, 65- 90 °C, 70-85 °C, or 75-80 °C;(e) said one or more emulsifiers comprise (i) one or more lignosulfonates; (ii) one or more rosin sizing agents selected from the group consisting of fortified rosins, esterified rosins, rosin waxes, resin acid derivatives, gum rosins, wood rosins, tall oil rosins, rosin pastes, and rosin-based dispersants; or (iii) any combination of (i) and (ii);(f) said one or more surfactants comprise (i) one or more nonionic surfactants selected from the group consisting of ethoxylated alcohols, secondary alcohol ethoxylates, ethoxylated sorbitan esters, sorbitan esters, glycerol esters, and glycerol monostearate (GMS); (ii) one or more anionic surfactants selected from the group consisting of fatty alcohol ether sulfates, alkyl ether sulfates, and special soaps; or (iii) any combination of (i) and (ii);(g) said one or more microcrystalline or paraffinic waxes are selected from the group consisting of saturated hydrocarbon waxes, paraffinic hydrocarbon waxes, isoparaffinic hydrocarbon waxes, naphthenic hydrocarbon waxes, or a mixture thereof, wherein said one or more microcrystalline or paraffinic waxes comprise a congealing point of 50-110 °C, 65-100 °C, 70-90 °C, or 75-85 °C; or(h) any combination of (a)-(g).method of any one of claims 6-8, wherein said biowax emulsion comprises:(a) said one or more biowaxes in an amount ranging from 20-85 wt%, 20-80 wt%, 20-60 wt%, 25-55 wt%, 30-50 wt%, 35-45 wt% or 20-26 wt%;(b) said one or more lignosulfonates in an amount ranging from 0.1-8 wt%, 1-5 wt%, or 2-4 wt%;(c) said one or more rosin sizing agents in an amount ranging from 1-12 wt%, 2-10 wt%, 3-8 wt%, or 4-6 wt%;(d) said one or more surfactants in an amount ranging from 1-12 wt%, 2-12 wt%, 4-10 wt%, or 6-8 wt%;(e) said one or more microcrystalline or paraffinic waxes in an amount ranging from 1-12 wt%, 2-10 wt%, 3-9 wt%, 4-8 wt%, or 5-7 wt%;(f) a biocarbon content of 60-90 wt%, 70-80 wt%, or 75-80 wt%, wherein biocarbon content refers to wt% of total carbon content in the biowax emulsion that originates from said biowax; or(g) a mixture of (a) and / or any combination of (b)-(f);(h) castor oil wax;(i) one or more lignosulfonates;(j) said one or more rosin sizing agents comprise a fortified rosin;(k) said nonionic surfactants comprising secondary alcohol ethoxylates, glycerol monostearate (GMS), or a combination thereof;(l) said one or more microcrystalline or paraffinic waxes comprise a congealing point of 70- 90 °C; or(m) a mixture of (h) and / or any combination of (i)-(l);(n) said PAC comprises a high basicity PAC comprising a basicity ranging from 50-95%, 55- 90%, 60-85%, 60-80%, 60-75%, 60-70%, or 60-65%, wherein said basicity is defined as the molar equivalent percent of OH to Al in the PAC;(o) said PAC comprises a PAC strength ranging from 15-30%, 20-30%, or 20-23%, wherein said PAC strength is defined as %AI2O3 in the PAC;(p) said moldable cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers;(q) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (iii) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or(r) any combination of (n)-(q); and / or(s) any combination of (a) to (r).

10. A method of preparing a cellulosic product comprising oil and water resistance, the method comprising:(a) contacting an aqueous suspension comprising cellulosic fibers and a cationic biowax composition according to any one of claims 1-5 or obtainable by a method according to any one of claims 6-9, thereby forming a fiber stock composition; and(b) adding the fiber stock composition to the wet end of a paper machine.

11. The method of claim 10, wherein the method further comprises:(i) optionally contacting the fiber stock composition with one or more retention aids; and / or(ii) after step (b), removing sufficient water from the fiber stock composition to form a wet fibrous web and then pressing and drying the wet fibrous web to obtain said cellulosic product.

12. The method of claim 10 or 11, wherein:(a) in claim 11, said one or more retention aids comprise at least one polyacrylamide (PAM), at least one anionic polyacrylamide (APAM), at least one cationic polyacrylamide (CPAM), at least one amphoteric polyacrylamide (AmPAM), at least one polyvinylamine (PVAm) polymer, at least one glyoxalated polyacrylamide (GPAM), or any combination of the foregoing ;(b) said aqueous suspension comprising cellulosic fibers comprises (i) one or more cellulosic fibers selected from the group consisting of softwood fiber, hardwood fiber, recycled fiber, recycled old corrugated cardboard (OCC), recycled mixed office waste (MOW), recycled mixed office paper, refined fiber, mill broke fibers, coated broke, non-wood fibers, straw pulp, wheat pulp; (ii) a papermaking furnish comprising pulp, Kraft pulp, unbleached Kraft pulp, bleached pulp, unbleached pulp, process water from pulp, paper, and / or board production, neutral sulfite semi chemical (NSSC) pulp, mechanical pulp, non-wood pulp; (iii) a thick stock, a thick stock diluted with chemical water, synthetic water, white water, and / or process water, and a thin stock; or (iv) a mixture of any of (i)-(iii);(c) said cellulosic product comprises a cellulosic or lignocellulosic fiber product, a paper or board, a moldable fiber product, a moldable paper product, a moldable board product, any product comprising moldable cellulosic fibers, a molded fiber product, a molded paper product, a molded board product, any product comprising molded cellulosic fibers;(d) any combination of (a)-(c).

13. The method of claim 10, 11, or 12, wherein:(a) said cationic biowax composition is present in said fiber stock composition at a dosage of 10-100 dry Ib / t, 20-80 dry Ib / t, 20-60 dry Ib / t, or 20-40 dry Ib / t;(b) said one or more retention aids are present in said fiber stock composition at a dosage of 0.1-1 dry Ib / t, 0.2-0.8 dry Ib / t, 0.4-0.6 dry Ib / t, or 0.5-0.6 dry Ib / t;(c) said cationic biowax composition is retained internally on the cellulosic fibers of saidcellulosic product;(d) said cellulosic product comprising said cationic biowax composition further comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (ill) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition; or(e) any combination of (a)-(d).

14. A fiber stock composition comprising:(a) an aqueous suspension comprising cellulosic fibers; and(b) a cationic biowax composition according to any one of claims 1-5 or obtainable by a method according to any one of claims 6-13.

15. A moldable cellulosic product comprising:(a) an amount of cellulosic fibers; and(b) a cationic biowax composition according to any one of claims 1-5 or obtainable by a method according to any one of claims 6-13; optionally wherein(c) said moldable cellulosic product comprises said cationic biowax composition:(d) said moldable cellulosic product is used as a food package, a beverage package, or any cellulosic product suitable for contacting, transporting, and / or storing materials comprising food, beverage, oil, water, and / or grease;(e) said moldable cellulosic product comprises (i) an increased water resistance, (ii) an increased oil and grease resistance (OGR), (ill) an increased 60-70 °C water resistance, (iv) an increased 60-70 °C oil resistance, or any combination of (i) to (iv), compared to an equivalent cellulosic product without said cationic biowax composition.

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