Treated articles, methods of making treated articles, and dispersions for making treated articles

Abstract

A treatment article comprising a fiber, a sizing agent, and a retention aid. The sizing agent comprises a wax or component thereof having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401. The retention aid comprises a nitrogen-containing polymer independently selected from the group consisting of (i) a nitrogen-containing polymer of Formula I, (ii) a polyethyleneimine, (iii) a polyaminoamide, (iv) a copolymer formed from the reaction product of epichlorohydrin and dimethylamine, and (v) combinations thereof.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and all advantages of U.S. Provisional Patent Application No. 63 / 212,776, filed on June 21, 2021, and U.S. Provisional Patent Application No. 63 / 121,500, filed on December 4, 2020, the disclosures of which are incorporated by reference in their entireties. Field of the Invention

[0003] The following disclosure relates to a treatment article, a method of making a treatment article, and a dispersion for making a treatment article. Background of the Invention

[0005] The performance of high-performance treated articles (e.g., paper products) often results from the inclusion of fluoropolymers. The recent global trend to reduce the fluorine content in treated articles, particularly those used in the food industry, has resulted in articles that are considered more environmentally friendly. However, these environmentally friendly articles often lack some performance properties compared to their fluorinated counterparts. Therefore, it remains possible to develop improved treated articles with high performance, or dispersions for the manufacture of improved treated articles.

[0006] Summary of the invention and advantages

[0007] The present disclosure provides a treated article. The treated article includes a fiber, a sizing agent, and a retention aid. The sizing agent includes a wax or a component thereof having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401. The retention aid includes a nitrogen-containing polymer independently selected from the group consisting of: (i) a nitrogen-containing polymer of Formula I, (ii) polyethyleneimine, (iii) a polyaminoamide, (iv) a copolymer formed from the reaction product of epichlorohydrin and dimethylamine, and (v) combinations thereof.

[0008] The present disclosure also provides a dispersion for making a treated article. The dispersion includes a solvent, a sizing agent, and a retention aid.

[0009] The treated articles are generally fluorine-free and have an excellent balance of performance properties. Specifically, the synergistic combination of sizing agent and retention aid produces a treated article with excellent corn oil penetration prevention / resistance and hot water repellency. Detailed Description of the Invention

[0011] The present disclosure provides a dispersion for making a treated article. The dispersion includes three main components: a solvent, a sizing agent, and a retention aid.

[0012] Referring first to the solvent, the solvent can include various solvating liquids, or can include a single liquid. The solvent generally includes at least water. Other liquids that can optionally be included in the solvent are water-miscible liquids. Particular examples of water-miscible solvents include at least one solvent selected from the group of propylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diacetone alcohol, and combinations thereof. Most typically, the solvent includes water or a combination of water and at least one water-miscible solvent selected from the group of propylene glycol, dipropylene glycol, and tripropylene glycol.

[0013] The dispersion generally includes the solvent in an amount of at least 40 parts by weight based on 100 parts by weight of the dispersion. Alternatively, the dispersion can include the solvent in an amount of 40 to 90, 50 to 90, 60 to 90, 70 to 90, 80 to 90, 50 to 80, 60 to 80, or about 70 parts by weight based on 100 parts by weight of the dispersion. For example, the solvent can include water (e.g., tap water) and dipropylene glycol, where the water is present in an amount of 50 to 75 parts by weight and the dipropylene glycol is present in an amount of 15 to 40 parts by weight based on 100 parts by weight of the dispersion.

[0014] Referring now to the sizing agent, the sizing agent includes a wax or components thereof. Those of ordinary skill in the art understand that various waxes, and particularly naturally occurring waxes, include combinations of individual components. For example, naturally occurring beeswax includes palmitates, palmitoleates, and oleates of long chain (e.g., 30-32 carbon) aliphatic alcohols, where each individual component is a "component thereof" with respect to beeswax. For ease of reference, the term "wax or components thereof" will be referred to generically as "wax" throughout the remainder of the description.

[0015] The wax of the sizing agent has an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401. Alternatively, the wax can have an acid value of 10 to 200, 10 to 180, 10 to 160, 10 to 140, 10 to 120, 10 to 100, 10 to 80, 10 to 60, or 10 to 50 mg KOH / g. Still alternatively, the wax can have an acid value of 20 to 100, 20 to 80, 20 to 60, 25 to 45, or 150 to 220 mg KOH / g. For purposes of the present disclosure, any reference to the acid value of the wax is to the acid value as measured according to USP 401.

[0016] While the wax is not limited to any particular wax, provided that the wax has an acid value of 10 mg to 220 mg KOH / g, typically the wax is selected from the group consisting of stearates, beeswax (synthetic and natural), candelilla wax, palmitates, behenates, and combinations thereof. For example, the wax of the sizing agent can be beeswax or a stearate, or both. Alternatively, the wax can be a behenate or a palmitate, or both.

[0017] The wax is generally present in the dispersion in an amount of 10 to 50 parts by weight, based on 100 parts by weight of the dispersion. Alternatively, the wax can be present in an amount of 10 to 45, 10 to 40, 10 to 35, 15 to 50, 20 to 50, or 25 to 50 parts by weight, based on 100 parts by weight of the dispersion.

[0018] It is understood by those skilled in the art that sizing agents including waxes can be used in methods of making treated articles because, as described in further detail below, the sizing agents can be fixed, retained, anchored, incorporated, oriented, etc., within or by fibers within the treated article. Also as described in further detail below, the sizing agents can be referred to as internal sizing agents, external sizing agents, or both, depending on the specific method of incorporating the dispersion within the method of making the treated article.

[0019] Turning now to the retention aid, the retention aid comprises a nitrogen-containing polymer selected from the group consisting of: (i) a nitrogen-containing polymer of Formula I, (ii) polyethylene imine, (iii) a polyaminoamide, (iv) a copolymer formed from the reaction product of epichlorohydrin and dimethylamine, and (v) combinations thereof.

[0020] A nitrogen-containing polymer according to Formula I is shown below:

[0021]

[0022] In Formula I, (a), (b), (c), (d), and (e) individually represent the mole percentage of each repeating unit included in the nitrogen-containing polymer of Formula I. R0 is independently selected from the group consisting of:

[0023] hydrogen, and their combinations. z R is independently selected from H, -CH3 and combinations thereof. x independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R3OH, -OR1, -NR1R1, -R3NH2, -NH2, -COO(CH2)2N(R1)2, -COO(CH2)3N(R1)2, -COO(CH2)2N + (R1)3X - 、-COO(CH2)3N + (R1)3X - and their combination, provided that when R x When it is -NH2, R zis -CH3. Y is independently selected from H, -OH, -R1, -OR1, -NR1R1, -NH2 and combinations thereof. Z is independently selected from H, -OH, -C=O, -R1, -OR1, -NR1R1, -NH2 and combinations thereof. R1 is independently selected from H, straight or branched alkyl or alkenyl groups containing up to 22 carbons, and combinations thereof. R2 is independently selected from H, monosaccharide, oligosaccharide, polysaccharide structural parts, straight or branched alkyl or alkenyl groups containing up to 22 carbons, optionally containing hydroxyl or aldehyde groups, and combinations thereof. R3 is independently selected from straight or branched alkyl or alkenyl groups containing up to 22 carbons, or combinations thereof. R4 is independently selected from straight or branched alkyl groups containing up to 18 carbons, optionally substituted with hydroxyl groups, and combinations thereof. R5 is independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R1OH, -OR1, -CONH2, -CONHCHOHCHO, -NR1, -NR1R1, -R1NH2, -NH2, and combinations thereof. A is independently selected from C=O, -CH2, and combinations thereof. Finally, X - are independently anions.

[0024] As described above, (a), (b), (c), (d), and (e) of Formula I individually represent the mole percentage of each repeating unit included in the nitrogen-containing polymer of Formula I. For ease of reference, a repeating unit having a mole percentage of (a) will be referred to as repeating unit (a), a repeating unit having a mole percentage of (b) will be referred to as repeating unit (b), a repeating unit having a mole percentage of (c) will be referred to as repeating unit (c), a repeating unit having a mole percentage of (d) will be referred to as repeating unit (d), and a repeating unit having a mole percentage of (e) will be referred to as repeating unit (e). It should also be understood that the structural formula representing each individual repeating unit represents a plurality of discrete repeating units. The mole percentage for each repeating unit is the combined mole percentage of each discrete unit represented by the repeating unit. For example, when the nitrogen-containing polymer of Formula I includes repeating unit (b) in an amount of 50 mole %, (R0 is determined by ) and 50 mol% of the repeating unit (b) (R0 is determined by When (denoted by ), the nitrogen-containing polymer comprises 100 mole percent of the combined total amount of repeating units (b). It is also understood that the individual repeating units within the nitrogen-containing polymer of Formula I are randomly distributed.

[0025] Each individual mole percentage represented by (a), (b), (c), (d), and (e) may have a value from 0 to 100 mole %, wherein the sum of (a), (b), (c), (d), and (e) is 100 mole %. This means that the nitrogen-containing polymer of Formula I does not include additional units repeating within its structure. When the mole percentage of (a) is zero, the nitrogen-containing polymer does not include repeating units (a). Conversely, when the mole percentage of (a) is 100, the nitrogen-containing polymer does not include repeating units (b), (c), (d), and (e).

[0026] Referring now to the repeating unit (a), Typically, the mole percentage of (a) within repeating unit (a) is less than 100 mole %. In other words, typically when repeating unit (a) is included in the nitrogen-containing polymer of Formula I, the nitrogen-containing polymer includes at least one additional repeating unit. Typically, when repeating unit (a) is combined with additional repeating units, the mole percentage of (a) within repeating unit (a) is less than 30 mole %. However, when the mole percentage of (a) within repeating unit (a) is 100 mole %, R x Independently selected from -NR1R1, -R3NH2, -NH2, -COO(CH2)2N(R1)2, -COO(CH2)3N(R1)2, -COO(CH2)2N + (R1)3X - 、-COO(CH2)3N + (R1)3X - , and combinations thereof. In other words, when the mole percentage of repeating unit (a) is 100 mole %, R is selected x Such that repeating unit (a) comprises nitrogen.

[0027] Referring now to the repeating unit (b), Repeating units (b) can be included in the nitrogen-containing polymer of Formula I in an amount of 0 to 100 mole percent. When the nitrogen-containing polymer includes repeating units (b), repeating units (b) are typically included in an amount of at least 15 mole %. Alternatively, repeating units (b) can be included in an amount of at least 30, 40, 50, 60, 70, 80, or 90 mole %.

[0028] In some embodiments, R0 is independently selected from the group consisting of: H, and combinations thereof. In other words, in these embodiments, R0 does not include In other embodiments, R0 is independently selected from the group consisting of: H, In a further embodiment, R0 is independently selected from the group consisting of: H, and combinations thereof. Although not required, in each of the embodiments within this paragraph, the combined mole percentage of repeating units (c) and (d) is typically less than 5 mole%. In other words, in these embodiments, the combined mole percentage of repeating units (a), (b), and (e) is at least 95 mole%, and typically 100 mole%.

[0029] In some embodiments, the retention agent is a nitrogen-containing polymer of Formula I, and the combined mole percentage of repeating units (c) and (d) is less than 5 mole percent. Alternatively, in these embodiments, the retention agent is a nitrogen-containing polymer of Formula I, and the repeating units (a), (b), and (e) collectively represent at least 95 mole percent of the nitrogen-containing polymer. Alternatively, the retention agent is a nitrogen-containing polymer of Formula I, and the repeating units (a), (b), and (e) collectively represent at least 96, 97, 98, 99, or 100 mole percent.

[0030] When the retention aid is a nitrogen-containing polymer of Formula I and the repeating units (a), (b) and (e) are present in total at 100 mole %, the nitrogen-containing polymer is represented by Formula II:

[0031]

[0032] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, R0 is independently selected from the group consisting of: H, In other embodiments of Formula II, R0 is independently selected from the group consisting of: H, In further embodiments of Formula II, R0 is independently selected from the group consisting of: H, and their combinations.

[0033] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, the retention aid is independently selected from the group consisting of: (i) a nitrogen-containing polymer of Formula II, wherein the combined mole percentage of (b) and (e) is 100 mole %, and R0 is independently selected from the group consisting of H, and combinations thereof; (ii) a nitrogen-containing polymer of formula II, wherein the mole percentage of (a) is 100 mole%, wherein R x Represented by -R3NH2; and (iii) a nitrogen-containing polymer of formula II, wherein the mole percentage of (b) is 100 mol%, and R0 is independently selected from H, and combinations thereof. Within this embodiment, when the retention aid comprises (i) a nitrogen-containing polymer of formula II, wherein the combined mole percentage of (b) and (e) is 100 mole % and R0 is independently selected from H, When combined with the group consisting of, the retention aid can be more narrowly defined as Formula IIa:

[0034]

[0035] Likewise, within this embodiment, when the retention aid comprises (ii) a nitrogen-containing polymer of Formula II, wherein the mole percent of (a) is 100 mole percent, wherein R x When represented by -R3NH2, the retention aid can be more narrowly defined as Formula IIb:

[0036]

[0037] Likewise, within this embodiment, when the retention aid comprises (iii) a nitrogen-containing polymer of Formula II, wherein the mole percent of (b) is 100 mole percent, and R0 is independently selected from the group consisting of H, and combinations thereof, the retention aid can be more narrowly defined as Formula IIc:

[0038]

[0039] When the retention aid is represented by or includes Formula IIa, (b1) and (b2) represent the mole percentages of the associated repeating units, wherein the combined mole percentages of (b1) and (b2) equal the total mole percentages of (b) in Formula II. In other words, repeating unit (b1) is the first repeating unit derived from repeating unit (b) in Formula II, and repeating unit (b2) is the second repeating unit derived from repeating unit (b). Similarly, when the retention aid is represented by or includes Formula IIc, (b1), (b2), and (b3) represent the mole percentages of the associated repeating units, wherein the combined mole percentages of (b1), (b2), and (b3) equal the total mole percentages of (b) in Formula II.

[0040] When the retention aid is or includes a nitrogen-containing polymer of Formula IIa, the nitrogen-containing polymer may be referred to as partially hydrolyzed poly(N-vinylformamide). The degree of hydrolysis will determine the molar value of each repeating unit. Typically, the partially hydrolyzed poly(N-vinylformamide) is hydrolyzed by 30 to 70%, based on the total amount of functional groups capable of hydrolyzation. Alternatively, the partially hydrolyzed poly(N-vinylformamide) may be hydrolyzed by 30 to 60%, 40 to 70%, 40 to 60%, or about 50%, based on the total amount of functional groups capable of hydrolyzation.

[0041] When the retention aid is or includes a nitrogen-containing polymer of Formula IIb, the nitrogen-containing polymer may be referred to as a polyallylamine. Although not required, the polyallylamine typically has a weight average molecular weight of 30,000 to 100,000 daltons. Alternatively, the polyallylamine may have a weight average molecular weight of 30,000 to 90,000, 30,000 to 80,000, 30,000 to 70,000, 40,000 to 90,000, 50,000 to 80,000, 60,000 to 70,000, or about 65,000 daltons.

[0042] When the retention aid is or includes a nitrogen-containing polymer of Formula IIc, the nitrogen-containing polymer may be referred to as formamide, N-vinyl-homopolymer, hydrolyzed N-(3-carboxy-1-oxopropyl)N-[2-hydroxy-3-(trimethylammonium)propyl] derivative, chloride (CAS Reg. No. 945630-11-5). While those skilled in the art will readily recognize that a variety of reaction pathways can be used to synthesize the nitrogen-containing polymer of Formula IIc, Example 5 of U.S. Pat. No. 8,604,134 discloses a suitable method. The disclosure of U.S. Pat. No. 8,604,134 is incorporated herein by reference as it relates to nitrogen-containing polymers of Formula IIc.

[0043] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, the retention aid is independently selected from the group consisting of: (i) partially hydrolyzed poly(N-vinyl formamide), wherein the degree of hydrolysis is from 30 to 70%; (ii) a nitrogen-containing polymer of Formula II, wherein the mole percent of (a) is 100 mole percent, wherein R x Represented by -R3NH2; and (iii) a nitrogen-containing polymer of formula II, wherein the mole percentage of (b) is 100 mol%, and R0 is independently selected from H, and their combinations.

[0044] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, the retention aid is independently selected from the group consisting of: (i) a nitrogen-containing polymer of Formula II, wherein the combined mole percentage of (b) and (e) is 100 mole %, and R0 is independently selected from the group consisting of H, and combinations thereof; (ii) a polyallylamine having a weight average molecular weight of 30,000 to 100,000 Daltons; and (iii) a nitrogen-containing polymer of formula II, wherein the mole percentage of (b) is 100 mole %, and R0 is independently selected from H, and their combinations.

[0045] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, the retention aid is independently selected from the group consisting of: (i) a nitrogen-containing polymer of Formula II, wherein the combined mole percentage of (b) and (e) is 100 mole %, and R0 is independently selected from the group consisting of H, and combinations thereof; (ii) a nitrogen-containing polymer of formula II, wherein the mole percentage of (a) is 100 mole%, wherein R x represented by -R3NH2; and (iii) formamide, N-vinyl-homopolymer, hydrolyzed N-(3-carboxy-1-oxopropyl)N-[2-hydroxy-3-(trimethylammonium)propyl] derivative, chloride (CAS Registry No. 945630-11-5); and combinations thereof.

[0046] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, the molar concentration of repeating units (a) is zero, such that Formula II is further defined by Formula III:

[0047]

[0048] When the retention aid is a nitrogen-containing polymer of formula III, the retention aid can be further defined as formula IIIa:

[0049]

[0050] The nitrogen-containing polymer of formula IIIa can generally be referred to as fully hydrolyzed poly(N-vinylformamide). In other words, unlike the nitrogen-containing polymer of formula IIa, substantially all functional groups capable of being hydrolyzed in the nitrogen-containing polymer of formula IIIa are hydrolyzed.

[0051] In some embodiments, when the retention aid is a nitrogen-containing polymer of Formula I, the mole percent of (c) corresponding to repeating units (c) is 100 mole percent, such that the nitrogen-containing polymer is a polyacrylamide according to Formula IV:

[0052]

[0053] When the retention aid is a polyacrylamide, the polyacrylamide typically has a weight average molecular weight of 5,000,000 to 6,000,000 Daltons.

[0054] In various embodiments, the retention aid is a nitrogen-containing polymer selected from the group consisting of: (i) polyethylene imine, (ii) polyaminoamide, (iii) polydiallyldimethylammonium chloride, and (iv) combinations thereof.

[0055] When the retention aid is a polyethyleneimine, the polyethyleneimine typically has a weight average molecular weight of 40,000 to 100,000 Daltons. Additionally, typically 15 to 35% of the amine groups within the polyethyleneimine are primary amines and 35 to 65% of the amine groups within the polyethyleneimine are secondary amines, based on the total number of amine groups within the polyethyleneimine. Alternatively, 20 to 30% or about 25% of the amine groups within the polyethyleneimine are primary amines and 45 to 55% or about 50% of the amine groups within the polyethyleneimine are secondary amines, based on the total number of amine groups within the polyethyleneimine.

[0056] The polydiallyldimethylammonium chloride can be a low molecular weight polydiallyldimethylammonium chloride, a high molecular weight polydiallyldimethylammonium chloride, or a combination thereof. In particular, the low molecular weight polydiallyldimethylammonium chloride has a weight average molecular weight of less than 200,000 Daltons. In contrast, the high molecular weight polydiallyldimethylammonium chloride has a weight average molecular weight of 300,000 to 400,000 Daltons.

[0057] In each embodiment of the retention aid described above, the nitrogen-containing polymer can have a charge density of > +0.1 meq / g when the dispersion has a pH of 7. While not required, typically the nitrogen-containing polymer has a charge density of +5 to +13 meq / g. Additionally, in each embodiment of the retention aid described above, when the nitrogen-containing polymer includes more than one repeating unit, the repeating units are typically randomly distributed within the nitrogen-containing polymer. Finally, in each embodiment of the present disclosure, the dispersion typically does not contain (i.e., does not include) a fluorine-containing polymer and a fluorine-containing performance additive.

[0058] The dispersion typically includes the retention aid in an amount of 0.1 to 12 parts by weight based on 100 parts by weight of the dispersion. Alternatively, the retention aid can be present in the dispersion in an amount of 0.1 to 12, 0.3 to 12, 0.5 to 12, 0.7 to 12, 0.9 to 12, 2.0 to 12, 3.0 to 12, 4.0 to 12, 5.0 to 12, 0.1 to 10, 0.1 to 8, 0.1 to 6, or 0.1 to 4 parts by weight based on 100 parts by weight of the dispersion.

[0059] In some embodiments, the dispersion includes a sizing agent selected from the group consisting of a stearate, beeswax, candelilla wax, a palmitate, a behenate, and combinations thereof. The dispersion also includes a nitrogen-containing polymer of Formula II:

[0060]

[0061] In these embodiments, the nitrogen-containing polymer has a charge density of > +0.1 meq / g when the dispersion has a pH of 7.

[0062] In other embodiments, the dispersion includes a sizing agent selected from the group consisting of stearates, beeswax, candelilla wax, palmitates, behenates, and combinations thereof. The dispersion also includes a nitrogen-containing polymer selected from the group consisting of Formula IIa, Formula IIb, Formula IIc, and combinations thereof:

[0063]

[0064] In these embodiments, when the dispersion has a pH of 7, the nitrogen-containing polymer has a charge density > +0.1 meq / g.

[0065] In some embodiments, the dispersion includes a sizing agent selected from the group consisting of stearates, beeswax, candelilla wax, palmitates, behenates, and combinations thereof. In various embodiments, the retention agent is a nitrogen-containing polymer selected from the group consisting of: (i) polyethyleneimine, (ii) polyaminoamides, (iii) polydiallyldimethylammonium chloride, and (iv) combinations thereof. In one embodiment, the sizing agent is behenate, and the retention aid is a nitrogen-containing polymer selected from the group consisting of: (i) polyethyleneimine, (ii) polyaminoamides, (iii) polydiallyldimethylammonium chloride, and (iv) combinations thereof. Additionally, when the dispersion has a pH of 7, the nitrogen-containing polymer has a charge density of >+0.1 meq / g.

[0066] When the nitrogen-containing polymer is or includes polyethyleneimine, the polyethyleneimine typically has a weight average molecular weight of 40,000 to 100,000 Daltons, and 20 to 30% of the amine groups in the polyethyleneimine are primary amines and 45 to 55% of the amine groups in the polyethyleneimine are secondary amines, based on the total number of amine groups in the polyethyleneimine. When the nitrogen-containing polymer is or includes polydiallyldimethylammonium chloride, the polydiallyldimethylammonium chloride has a weight average molecular weight of less than 200,000 Daltons or from 300,000 to 400,000 Daltons.

[0067] In some embodiments, the dispersion includes a sizing agent selected from the group consisting of stearates, beeswax, candelilla wax, palmitates, behenates, and combinations thereof. In these embodiments, the retention aid may also include or be a polyacrylamide having a weight average molecular weight of 5,000,000 to 6,000,000 Daltons.

[0068] Although not required, the dispersion may also include a surfactant to improve the stability of the dispersion. The surfactant may be an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, or a polymeric surfactant. Among these, anionic surfactants, nonionic surfactants, or cationic surfactants are generally used. When included, the surfactant is generally present in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the dispersion. Suitable examples of anionic surfactants include compounds based on alkyl carbonates, compounds based on alkyl sulfates, and alkyl phosphates. Specific examples of anionic surfactants include dioctyl succinic acid sodium salt, sodium lauryl sulfate, and sodium lauryl sulfate. Suitable examples of nonionic surfactants include ethylene oxide and / or propylene oxide adducts of alcohols having 1 to 18 carbon atoms, ethylene oxide and / or propylene oxide adducts of alkylphenols, and ethylene oxide and / or propylene oxide adducts of alkylene glycols and / or alkylenediamines. Suitable examples of cationic surfactants include primary amines to tertiary amines, pyridinium salts, alkylpyridinium salts, and quaternary ammonium salts such as alkyl halide quaternary ammonium salts.

[0069] Without being held to any particular theory, it is believed that the first portion of the amine group of the retention aid associates via hydrogen or electrostatic bonding with the oxygen atoms present in the ester and / or acid of the sizing agent. It is further believed that the remainder of the amine group associates or binds to hydroxyl groups present on fibers, such as cellulose-based pulp fibers, that are also included in the treated article. In other words, the retention aid associates or binds to both the sizing agent and the fibers. As further described below, during the method of making the treated article, the retention aid binds to both the sizing agent and the fibers to fix, retain, anchor, blend, orient, etc. the retention aid between adjacent fibers and on the surfaces of adjacent fibers to form a dense network / matrix. It is further believed that the specific sizing agents and retention agents of the present disclosure have a strong interaction, which results in the retention aid and sizing agent being effectively dispersed throughout the treated article. Compared to conventional treated articles not prepared with the dispersion of the present disclosure, the treated articles prepared with the dispersion of the present disclosure have relatively fewer air pockets and channels within the treated article. This result is believed to be achieved because the sizing agent and retention aid effectively fill or seal these air pockets and / or channels. This reduction in the relative amount of air pockets and channels is significant and provides treated articles with enhanced barrier properties. Specifically, treated articles prepared with the dispersions of the present disclosure have relatively higher resistance to both water and oil penetration than conventional treated articles.

[0070] The present disclosure also provides a treatment article formed from the dispersion. The treatment article includes a retention aid, a sizing agent, and fibers. The type of fiber is not limited to any particular type, but in some embodiments, it may be advantageous to select fibers that have the ability to bind to the amine groups of the retention aid.

[0071] The treated article can be a paper product, food packaging, non-food contact packaging, wood or building material, nonwovens, molded fibers such as cardboard, takeout containers, bowls, etc., or any paper substrate, especially paper substrates with advantageous water and / or oil repellency.

[0072] Fiber can be natural fiber, synthetic fiber, semi-synthetic fiber, inorganic fiber, and their combination.The specific example of natural fiber includes those derived from plant or wood, also can be referred to as cellulose fiber, such as bamboo fiber, bentgrass (bent grass) fiber, sawgrass fiber, bagasse fiber, straw fiber, hay fiber, spruce fiber, pine fiber, fir fiber, larch fiber, eucalyptus fiber, poplar fiber, birch fiber etc.When natural fiber is derived from wood, wood can be softwood and / or hardwood.Other examples of natural fiber include cotton, hemp, wool, silk etc.The specific example of synthetic fiber includes polyamide fiber, polyester fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, polyvinyl chloride fiber, polypropylene fiber etc.In some embodiments, fiber is pulp fiber, from bleached and unbleached sulfate (kraft) hardwood or softwood pulp, groundwood pulp, recycled cellulose fiber, and bleached chemical thermomechanical pulp (BCTMP), and their combination.

[0073] In one embodiment, the treated article (i.e., the dried and finished treated article ready for the consumer) may include fibers in an amount of 16 to 99.8 parts by weight, a sizing agent in an amount of 0.1 to 80 parts by weight, and a retention aid in an amount of 0.1 to 4 parts by weight, each based on 100 parts by weight of the treated article. Alternatively, the treated article may include fibers in an amount of 47 to 99.8 parts by weight, a sizing agent in an amount of 1 to 50 parts by weight, and a retention aid in an amount of 0.2 to 3 parts by weight, each based on 100 parts by weight of the treated article. Still alternatively, the treated article may include fibers in an amount of 78 to 97.2 parts by weight, a sizing agent in an amount of 2.5 to 20 parts by weight, and a retention aid in an amount of 0.3 to 2 parts by weight, each based on 100 parts by weight of the treated article.

[0074] The treatment preparation may also include components other than retention aids, sizing agents, and fibers. For example, the treatment preparation may also include starch, resins, crosslinking agents, catalysts, inorganic or organic fillers, coagulants, carriers (e.g., dextrins), retaining agents, flocculants, buffers, bactericides, biocides, metal ion sealants, hydrophobic agents (e.g., alkenyl succinic anhydrides and / or alkyl ketene dimers), and the like, as well as various combinations of such components.

[0075] Specific examples of starches suitable for treating the article include, but are not limited to, hydroxyethylated starch, cationic starch, amphoteric starch, oxidized starch, phosphorylated starch, enzyme-modified starch, and combinations thereof.

[0076] Specific examples of resins suitable for treating the article include, but are not limited to, polyvinyl alcohol, polyvinyl chloride latex, polyvinyl alcohol, and the like.

[0077] Specific examples of crosslinking agents suitable for treating the article include, but are not limited to, urea or melamine-formaldehyde condensates or precondensates, hydroxymethyl-dihydroxyethylene-urea or derivatives thereof, urone, hydroxymethyl-ethylene-urea, hydroxymethyl-propylene-urea, hydroxymethyl-triazone, dicyandiamide-formaldehyde condensates, hydroxymethyl carbamates, hydroxymethyl (meth) acrylamide, polymers thereof, divinyl sulfone, polyamides or cationic derivatives thereof, pyridinium salts of ethylene glycol chloromethyl ether, glyoxal, and combinations thereof.

[0078] Specific examples of catalysts suitable for the purpose of treating the article include, but are not limited to, ammonium chloride, alkanolamine salts, zirconium acetate salts, and combinations thereof.

[0079] Specific examples of the inorganic filler include, but are not limited to, silica, alumina, sericin, resin powder, talc, kaolin, precipitated calcium carbonate, ground calcium carbonate, bentonite, clay, titanium dioxide and the like.

[0080] The specific components present in the treatment article, and their respective amounts, can vary depending upon the specific fibers employed in the slurry and the desired end use of the treatment article.

[0081] The present disclosure also provides a method for making a treated article. The method includes providing a slurry including fibers. The slurry can be provided in any suitable manner. For example, the slurry can be prepared, obtained, purchased, etc. When the step of providing the slurry includes preparing the slurry, the slurry can be prepared according to methods well known in the art. For example, in an embodiment where the fibers are cellulose fibers, the slurry can be prepared by mechanical pulping; thermomechanical pulping; chemical thermomechanical pulping; chemical pulping methods such as the kraft process, sulfite process, and soda process; recycling pulping; organic solvent pulping, etc. Alternatively, the slurry can be prepared by purchasing or otherwise obtaining dried cellulose fibers, which are generally referred to in the art as "market pulp." In these embodiments, the market pulp is generally reconstituted with water, which is referred to as water pulping. Depending on the desired appearance of the treated article, the fibers can be bleached. When bleaching, the fibers can be bleached with, for example, chlorine, chlorine dioxide, oxygen, ozone, hydrogen peroxide, etc.

[0082] Typically, the fibers are present in the slurry in an amount of from greater than 0 to 5, alternatively 0.2 to 3.75, alternatively 0.3 to 3 parts by weight based on 100 parts by weight of the slurry. Of course, it is understood that the fibers may be present in the slurry in amounts other than those described above, depending on the presence or absence of various optional components as described in more detail below. The remainder of the slurry typically comprises water or a combination of water and a water-miscible solvent.

[0083] In some embodiments where the fibers are cellulose fibers, the fibers of the pulp are typically refined. Typically, the fibers of the pulp are refined by subjecting the pulp to shear forces, which separate cellulose clumps or fiber clusters into individual fibers. Generally speaking, the fibers of the pulp are not refined until the pulp is prepared or provided, i.e., "market pulp" is typically not refined until it has been reconstituted in water to form a pulp.

[0084] The method also includes combining the dispersion with the slurry. In this embodiment of the method, those of ordinary skill in the art recognize that the sizing agent may be more commonly referred to as an internal sizing agent. Once combined, the slurry and the dispersion are typically mixed so that the dispersion is dispersed throughout the slurry.

[0085] The method also includes forming a treated article from a slurry comprising the dispersion. Typically, the slurry is formed into at least one sheet. For clarity, at least one sheet is referred to herein as simply a "sheet," which should be understood to encompass even multiple sheets. Methods for forming treated articles into sheets are well known in the art. For example, sheets are typically formed on a metal substrate, such as stainless steel or a substance known in the art as monofilament thread. The relative dimensions of the sheet (e.g., thickness, length, width) may vary depending on various factors, such as the desired end use of the treated article formed by the method.

[0086] Once formed, the sheet is typically dried to remove excess solvent (e.g., water and / or a water-miscible solvent). The sheet can be dried via vacuum and / or foil dehydration. Alternatively, the sheet can be dried via pressurized dehydration, wherein pressure is applied to the sheet. When the sheet is dried via pressurized dehydration, the pressure utilized is typically 0.5 to 200 psig. In addition, the sheet can be dried via shrinkage dehydration, wherein the sheet is dried by exposure to a paper machine felt (clothing), which absorbs excess water and / or a water-miscible solvent from the sheet. In addition, the sheet can be dried by shrinkage drying, wherein the sheet is contacted with a metal roller having a smooth surface. The metal roller utilized in shrinkage drying is typically heated, for example, 150 to 280°F. Any combination of these methods, or other methods of drying the sheet to remove excess water and / or a water-miscible solvent known in the art, can be employed. In some embodiments, all of the methods described above for drying the sheet are employed, typically in the order in which they are introduced above.

[0087] The present disclosure also provides a method for providing a surface-treated article. The method includes forming a sheet from a fiber slurry (e.g., a paper pulp) as described above, except that a dispersion is not combined with the fiber slurry before forming the sheet. Instead, the dispersion is applied to at least one surface of the sheet after the sheet is formed. In this embodiment of the method, those of ordinary skill in the art recognize that the sizing agent may be more commonly referred to as an external sizing agent. The dispersion may be applied to the sheet before removing excess water from the sheet or when the sheet is considered to be dry.

[0088] The step of applying the dispersion to at least one surface of the sheet is not particularly limited as long as it is capable of forming intimate contact between the dispersion and the sheet. For example, the dispersion can be applied to at least one surface of the sheet by spraying, brushing, padding, size press coating, metered size press coating, film press coating, gravure coating, flexographic coating, roll coating, rotor dampening, foaming, gate roll coating, bill knife coating, bar coating, gravure coating, reverse roll coating, slide roll coating, transfer (offset) roll coating, doctor blade coating, knife-over-roll coating, J coating, air knife coating, curtain coating, and combinations thereof.

[0089] In some embodiments, the method for forming the treated article combines the two methods described above. Specifically, in this embodiment, the dispersion is added to the slurry before forming the sheet, and then the dispersion is applied to at least one surface of the sheet after the sheet is formed. One of ordinary skill in the art will recognize that this method includes both internal and external sizing steps.

[0090] The present disclosure further provides another method for manufacturing treated articles. Unlike the aforementioned method, this method does not form a dispersion and then add the dispersion to the slurry. On the contrary, the retention agent and the sizing agent are added to the slurry separately, without first being combined into a single composition. In other words, instead of adding a dispersion comprising a retention agent and a sizing agent to the slurry, the retention agent is added to the slurry, rather than the retention agent being combined with the sizing agent in advance. Similarly, the sizing agent is added to the slurry, rather than the sizing agent being combined with the retention agent in advance. The order in which the sizing agent and the retention agent are added is not limited in this embodiment. For example, the sizing agent can be added to the slurry, followed by the retention agent, or vice versa. Of course, the sizing agent and the retention agent can also be added simultaneously, rather than being combined with each other in advance.

[0091] The present invention also provides another embodiment of the dispersion that is different from the above embodiment. In this embodiment, the dispersion includes the reaction product of a sizing agent and a retention agent. Although not required, a reaction product can be formed when the amine group present on the retention agent reacts with the alkyl acid of the sizing agent. In some embodiments, the dispersion may include the reaction product, rather than separately including the sizing agent and the retention agent. Alternatively, the dispersion may include a solvent, a retention agent, a sizing agent, and also include the reaction product between the retention agent and the sizing agent. For example, the reaction product may be an amidation reaction between the amine group of the retention agent, typically a primary amine group, and the alkyl acid of the sizing agent.

[0092] In one embodiment, a reaction product is formed when the retention agent is polyethyleneimine and the sizing agent, for example, the sizing agent includes an alkyl acid (e.g., steric acid). In this embodiment, the retention agent is generally represented by the chemical structure shown below:

[0093]

[0094] Where n represents the number of repeating units.

[0095] In another embodiment, the reaction product is formed from the reaction between a sizing agent and a primary amine group of Formula IIa,

[0096]

[0097] So that the reaction product is represented by Formula IIa':

[0098]

[0099] In Formula IIa', R6 represents C(=O)R1. Although not required, R1 is typically a straight or branched alkyl or alkenyl group containing 17 to 21 carbon atoms.

[0100] In another embodiment, the reaction product is formed from the reaction between a sizing agent and a primary amine group of Formula lib,

[0101]

[0102] So that the reaction product is represented by Formula IIb':

[0103]

[0104] In Formula IIb', R6 represents C(=O)R1. Although not required, R1 is typically a straight or branched chain alkyl or alkenyl group containing 17 to 21 carbon atoms.

[0105] In another embodiment, the reaction product is formed from the reaction between a sizing agent and a primary amine group of formula IIc,

[0106]

[0107] So that the reaction product is represented by formula IIc':

[0108]

[0109] In Formula IIb', R6 represents C(=O)R1. Although not required, R1 is typically a straight or branched chain alkyl or alkenyl group containing 17 to 21 carbon atoms.

[0110] In other embodiments, the reaction product can be more generally described as the reaction product of at least one of (a), (b) or (c) comprising a primary amine in formula I and an alkyl acid of a sizing agent. Typically, the alkyl acid comprises 17 to 21 carbon atoms. In each case, the primary amine reacts with the alkyl acid such that the primary amine (NH2) group is replaced by NC(=O)R1. Typically, R1 is an alkyl chain comprising 17 to 21 carbon atoms. Example

[0111] The treated articles were prepared and evaluated by first making a dispersion and combining the dispersion with a paper stock. The composition of each dispersion is provided below. To prepare the paper stock, wood pulp was mixed in water to dilute the wood pulp to approximately 0.3% solid pulp by weight based on the total weight of the paper stock. The dispersion was then combined with the paper stock and further mixed. Sheets were then formed using a Noram TAPPI handsheet former and dried using an Adirondack drum dryer at 260°F. The resulting dried sheets were conditioned in a controlled humidity chamber at 23°C and 50% relative humidity for at least 4 hours.

[0112] The dried sheets were then evaluated for water repellency at room temperature and 85°C. Corn oil repellency was also evaluated for the dried sheets at room temperature. The dried sheets were also evaluated for Cobb water absorption and Cobb oil leakage. The results are shown in Table I below.

[0113] To evaluate repellency, a drop of water or corn oil is placed on the sheet at a specified temperature. After 15 seconds, the sheet is evaluated to determine whether the specific liquid has penetrated the sheet. The results are qualitatively recorded as pass (P) or fail (F).

[0114] To evaluate Cobb water absorbency, the sheet is first weighed and clamped into a Cobb ring apparatus. 100 grams of accurately weighed room temperature tap water is placed on the sheet in the Cobb ring apparatus and allowed to stand for one minute and 45 seconds. The water is then poured out and the sheet is released. The sheet is then sandwiched between two sheet-forming blotters and a 10 kg Cobb roller is rolled across the sheet, once forward and once in the reverse direction (a total of two passes, each in the opposite direction). The sheet is then immediately weighed and the absorbency is calculated using the initial weight and exposure weight.

[0115] In order to evaluate the Cobb oil leakage test, first the sheet is weighed. A clean circle of Whatman No. 4 qualitative circles is placed under the sheet as absorbent blotting paper for leakage. Then a 20mm diameter sample plate is placed on the sheet to define the initial exposure area. Then use a pipette to collect an oil sample of 0.5 gram, and subsequently corn oil is added to the sheet in the 20mm diameter sample plate, and the oil is spread over the sheet until it evenly spreads over the sample plate. After the oil is delivered to the sheet, the pipette is weighed to determine the exact mass of the oil added to the sheet. Once the oil is evenly distributed, the sample plate is removed, and 300 grams of weights are centered on the top of the oil, and it is allowed to stand for 120 seconds. Then the sheet forming blotting paper is placed on the top of the sheet, and a 10kg Cobb roller rolls across the sheet, once forward and once reverse (a total of twice, each time through in the opposite direction), to absorb the excessive oil on the sheet surface. The exposed sheet and Whatman No. 4 qualitative circle were then weighed and the % absorbance calculated.

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148] Table I

[0149]

[0150]

[0151] Additional treatment articles were prepared and evaluated using the following method. Paper stock was made from wood pulp by mixing the wood pulp in water to dilute the wood pulp to about 0.3 wt% solid paper stock based on the total weight of the paper stock. A dilute solution of a retention aid was then combined with the stock and stirred for 60 seconds. A wax dispersion was then added to the stock and mixed for an additional minute. A sheet was then formed using a Noram TAPPI sheet former and dried at 260 °F using an Adirondack drum dryer. The resulting dried sheet was conditioned in a controlled humidity cabinet at 23 °C and 50% relative humidity for at least 4 hours. The composition of the wax dispersion and retention aid are described below. The tests performed on the resulting sheet are reported in Table II below.

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175]

[0176]

[0177]

[0178]

[0179]

[0180]

[0181]

[0182]

[0183]

[0184]

[0185]

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193]

[0194] Table II

[0195]

[0196]

[0197] The results shown above in Tables I and II indicate that the dispersions of the present disclosure including a retention aid and a sizing agent comprising a wax or a component thereof having an acid value of 10 to 220 mg KOH / g produce excellent articles when the dispersions are used to prepare and / or treat articles.

[0198] All combinations of the above embodiments throughout the disclosure are hereby expressly encompassed in one or more non-limiting embodiments, even if such disclosure is not described verbatim in a single paragraph or section above. In other words, the embodiments expressly encompassed may include any one or more elements described above selected and combined from any part of the invention.

[0199] One or more of the values ​​recited above may vary by ±5%, ±10%, ±15%, ±20%, ±25%, etc., so long as the variance remains within the scope of the invention. Unexpected results may be obtained with each member of the Markush group, independent of all other members. Each member may be relied upon individually and or in combination and provide appropriate support for a particular embodiment within the scope of the appended claims. The subject matter of all combinations of single and multiply dependent independent and dependent claims is expressly contemplated herein. The present disclosure includes the words described by way of example, not limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings, and the present disclosure may be practiced in ways other than as expressly described herein.

[0200] It is also understood that any ranges and subranges relied upon in describing the various embodiments of the present disclosure are independently and generally within the scope of the appended claims and are understood to describe and encompass all ranges, including the entirety and / or partial values ​​therein, even if such values ​​are not explicitly stated herein. One skilled in the art will readily recognize that the enumerated ranges and subranges are sufficient to describe and enable the various embodiments of the present disclosure, and that such ranges and subranges may be further delineated as being related to half, third, quarter, fifth, and so forth. As just one example, a range of "0.1 to 0.9" may be further delineated as being the lower third, i.e., 0.1 to 0.3, the middle third, i.e., 0.4 to 0.6, and the upper third, i.e., 0.7 to 0.9, which are individually and generally within the scope of the appended claims and may be relied upon individually and / or generally to provide appropriate support for a particular embodiment within the scope of the appended claims. Additionally, with respect to language defining or modifying ranges, such as "at least," "greater than," "less than," "no more than," and the like, it is understood that such language includes subranges and / or upper or lower limits. As another example, a range of "at least 10" includes subranges from at least 10 to 35, subranges from at least 10 to 25, subranges from 25 to 35, and so on, and each subrange can be relied upon individually and / or collectively to provide appropriate support for specific embodiments within the scope of the appended claims. Finally, individual numerical values ​​within the disclosed ranges can be relied upon and provide appropriate support for specific embodiments within the scope of the appended claims. For example, a range of "from 1 to 9" includes individual integers (e.g., 3) as well as individual numerical values ​​including decimal points (or fractions) (e.g., 4.1), which can be relied upon and provide appropriate support for specific embodiments within the scope of the appended claims.

Claims

1. A dispersion for use in a method for producing a treated article, the dispersion comprising: solvents; a sizing agent comprising a naturally occurring wax or a component thereof having an acid value of 10 to 220 mg KOH / g as measured according to USP 401; and A retention aid comprising a nitrogen-containing polymer of formula I: wherein (a), (b), (c), (d) and (e) individually represent the mole percentage of each repeating unit included in the nitrogen-containing polymer of Formula I, each individual mole percentage represented by (a), (b), (c), (d) and (e) is from 0 to 100 mole %, and the sum of (a), (b), (c), (d) and (e) is 100 mole %, wherein R0 is independently selected from the group consisting of: H, and their combinations, and in: R z independently selected from H, -CH3 and combinations thereof, R x independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R3OH, -OR1, -NR1R1, -R3NH2, -NH2, -COO(CH2)2N(R1)2, -COO(CH2)2N + (R1)3X - 、-COO(CH2)3N + (R1)3X - and their combination, provided that when R x When it is -NH2, R z is -CH3, Y is independently selected from H, -OH, -R1, -OR1, -NR1R1, -NH2 and combinations thereof, R1 is independently selected from H, linear or branched alkyl or alkenyl groups containing up to 22 carbons, and combinations thereof, R2 is independently selected from H, monosaccharide, oligosaccharide, polysaccharide moiety, linear or branched alkyl or alkenyl groups of up to 22 carbons, optionally containing hydroxyl or aldehyde groups, and combinations thereof, R3 is independently selected from a linear or branched alkyl or alkenyl group or a combination thereof containing up to 22 carbons, R4 is independently selected from linear or branched alkyl groups containing up to 18 carbons, optionally substituted with hydroxyl groups, and combinations thereof, R5 is independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R1OH, -OR1, -CONH2, -CONHCHOHCHO, -NR1, -NR1R1, -R1NH2, -NH2, and combinations thereof, A is independently selected from C=O, -CH2, and combinations thereof, and X - are independently anions.

2. The dispersion of claim 1 wherein the combined mole percentage of (c) and (d) is less than 5 mole percent.

3. The dispersion of claim 2, wherein R0 is independently selected from the group consisting of: H, and their combinations.

4. The dispersion of claim 3, wherein R0 is independently selected from the group consisting of: H, and their combinations.

5. The dispersion of claim 1 , wherein the combined mole percentages of (a), (b), and (e) are 100 mole percent, such that the nitrogen-containing polymer is represented by Formula II:

6. The dispersion of claim 5, wherein the retention aid is independently selected from the group consisting of: i. The nitrogen-containing polymer of formula II, wherein the combined mole percentage of (b) and (e) is 100 mole %, and R0 is independently selected from H, and groups consisting of combinations thereof; ii. The nitrogen-containing polymer of formula II, wherein the mole percentage of (a) is 100 mole %, and R x is -R3NH2; and iii. The nitrogen-containing polymer of formula II, wherein the mole percentage of (b) is 100 mole %, and R0 is independently selected from H, and their combinations.

7. The dispersion of claim 6, wherein the retention aid is independently selected from the group consisting of: i. The nitrogen-containing polymer of formula II as further defined according to formula IIa: ii. The nitrogen-containing polymer of formula II as further defined according to formula IIb: and iii. The nitrogen-containing polymer of formula II as further defined according to formula IIc:

8. The dispersion as claimed in claim 7, wherein the retention aid is the nitrogen-containing polymer of formula IIa.

9. The dispersion as claimed in claim 1, wherein the nitrogen-containing polymer has a charge density of > +0.1 meq / g at a pH of 7.

10. The dispersion according to any one of claims 1 to 9, wherein the sizing agent is at least two independently selected from the group consisting of stearate, beeswax, candelilla wax, palmitate and behenate.

11. The dispersion according to any one of claims 1 to 9, wherein the sizing agent has an acid value of 150 to 220 mg KOH / g.

12. The dispersion of any one of claims 1 to 9, wherein the sizing agent is a stearate.

13. The dispersion of any one of claims 1 to 9, wherein the sizing agent is beeswax.

14. The dispersion of any one of claims 1 to 9, wherein the sizing agent is candelilla wax.

15. The dispersion of any one of claims 1 to 9, wherein the sizing agent is palmitate.

16. The dispersion of any one of claims 1 to 9, wherein the sizing agent is a behenate.

17. The dispersion according to any one of claims 1 to 9, wherein the sizing agent is present in an amount of 10 to 50 parts by weight, and the retention aid is present in an amount of 0.1 to 12 parts by weight, each based on 100 parts by weight of the dispersion.

18. A dispersion for use in a method of making a treated article, the dispersion comprising: solvents; a sizing agent present in an amount of 10 to 50 parts by weight based on 100 parts by weight of the dispersion, wherein the sizing agent comprises a wax or component thereof independently selected from the group consisting of stearates, beeswax, candelilla wax, palmitates, behenates, and combinations thereof, wherein the wax or component thereof has an acid value of 10 to 220 mg KOH / g as measured according to USP 401; and A retention aid present in an amount of 0.1 to 12 parts by weight based on 100 parts by weight of the dispersion, wherein the retention aid is selected from the group consisting of: i. Nitrogen-containing polymers according to formula IIa: ii. Nitrogen-containing polymers according to formula IIb: iii. Nitrogen-containing polymers according to formula IIc: and iv. their combination, wherein (a), (b1), (b2), (b3), and (e) represent the mole percentages of individual repeating units; wherein each of (b1), (b2) and (e) is present in Formula IIa and the sum of (b1), (b2) and (e) is 100 mol %; wherein in formula IIb (a) is 100 mol %; and wherein each of (b1), (b2) and (b3) is present in Formula IIc and the sum of (b1), (b2) and (b3) is 100 mol %.

19. A fiber slurry comprising: The dispersion according to any one of claims 1 to 9; fiber; and A second solvent that is the same as or different from the solvent of the dispersion.

20. A method of making a treated article, the method comprising: combining the dispersion according to any one of claims 1 to 9 with a fiber slurry; and A treated article is formed from the fiber slurry including the dispersion.

21. A method of making a treated article, the method comprising: forming an article from the fiber slurry, wherein the article has a top surface and a bottom surface; and The dispersion of any one of claims 1 to 9 is applied to at least one surface of the article to form the treated article.

22. A method of making a treated article, the method comprising: providing a fiber slurry comprising fibers and water; combining a sizing agent with the fiber sizing agent, the sizing agent comprising a naturally occurring wax or a component thereof, having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401; A retention aid is combined with the fiber slurry, the retention aid comprising a nitrogen-containing polymer of Formula I, wherein (a), (b), (c), (d) and (e) individually represent the mole percentage of each repeating unit included in the nitrogen-containing polymer of Formula I, each individual mole percentage represented by (a), (b), (c), (d) and (e) is from 0 to 100 mole %, and the sum of (a), (b), (c), (d) and (e) is 100 mole %, wherein R0 is independently selected from the group consisting of: H, and their combinations, and in: R z independently selected from H, -CH3 and combinations thereof, R x independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R3OH, -OR1, -NR1R1, -R3NH2, -NH2, -COO(CH2)2N(R1)2, -COO(CH2)2N + (R1)3X - 、-COO(CH2)3N + (R1)3X - , and their combinations, Y is independently selected from H, -OH, -R1, -OR1, -NR1R1, -NH2 and combinations thereof, R1 is independently selected from H, linear or branched alkyl or alkenyl groups containing up to 22 carbons, and combinations thereof, R2 is independently selected from H, monosaccharide, oligosaccharide, polysaccharide moiety, linear or branched alkyl or alkenyl groups of up to 22 carbons, optionally containing hydroxyl or aldehyde groups, and combinations thereof, R3 is independently selected from a linear or branched alkyl or alkenyl group or a combination thereof containing up to 22 carbons, R4 is independently selected from linear or branched alkyl groups containing up to 18 carbons, optionally substituted with hydroxyl groups, and combinations thereof, R5 is independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R1OH, -OR1, -CONH2, -CONHCHOHCHO, -NR1, -NR1R1, -R1NH2, -NH2, and combinations thereof, A is independently selected from C=O, -CH2, and combinations thereof, and X - are independently anionic; and The fiber slurry including the sizing agent and the retention aid is formed into a treated article.

23. A method of making a treated article, the method comprising: providing a fiber slurry comprising fibers and water; combining a sizing agent with the fiber sizing agent, the sizing agent comprising a naturally occurring wax or a component thereof, having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401; combining a retention aid with the fiber slurry, wherein the retention aid is selected from the group consisting of: i. Nitrogen-containing polymers according to formula IIa: ii. Nitrogen-containing polymers according to formula IIb: iii. Nitrogen-containing polymers according to formula IIc: and iv. their combination, wherein (a), (b1), (b2), (b3), and (e) represent the mole percentages of individual repeating units; wherein each of (b1), (b2) and (e) is present in Formula IIa and the sum of (b1), (b2) and (e) is 100 mol %; wherein in formula IIb (a) is 100 mol %; and wherein each of (b1), (b2) and (b3) is present in Formula IIc and the sum of (b1), (b2) and (b3) is 100 mol %; and The fiber slurry including the sizing agent and the retention aid is formed into a treated article.

24. A treatment article comprising: fibrous matrix; a sizing agent comprising a naturally occurring wax or a component thereof having an acid value of 10 to 220 mg KOH / g as measured according to USP 401; and A retention aid comprising a nitrogen-containing polymer of formula I, wherein (a), (b), (c), (d) and (e) individually represent the mole percentage of each repeating unit included in the nitrogen-containing polymer of Formula I, each individual mole percentage represented by (a), (b), (c), (d) and (e) is from 0 to 100 mole %, and the sum of (a), (b), (c), (d) and (e) is 100 mole %, wherein R0 is independently selected from the group consisting of: H, and their combinations, and in: R z independently selected from H, -CH3 and combinations thereof, R x independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R3OH, -OR1, -NR1R1, -R3NH2, -NH2, -COO(CH2)2N(R1)2, -COO(CH2)2N + (R1)3X - 、-COO(CH2)3N + (R1)3X - , and their combinations, Y is independently selected from H, -OH, -R1, -OR1, -NR1R1, -NH2 and combinations thereof, R1 is independently selected from H, linear or branched alkyl or alkenyl groups containing up to 22 carbons, and combinations thereof, R2 is independently selected from H, monosaccharide, oligosaccharide, polysaccharide moiety, linear or branched alkyl or alkenyl groups of up to 22 carbons, optionally containing hydroxyl or aldehyde groups, and combinations thereof, R3 is independently selected from a linear or branched alkyl or alkenyl group or a combination thereof containing up to 22 carbons, R4 is independently selected from linear or branched alkyl groups containing up to 18 carbons, optionally substituted with hydroxyl groups, and combinations thereof, R5 is independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R1OH, -OR1, -CONH2, -CONHCHOHCHO, -NR1, -NR1R1, -R1NH2, -NH2, and combinations thereof, A is independently selected from C=O, -CH2, and combinations thereof, and X - are independently anions.

25. The treated article of claim 24, wherein the combined mole percentages of (a), (b), and (e) are 100 mole percent, such that the nitrogen-containing polymer is represented by Formula II:

26. The treatment article of claim 25, wherein the retention aid is independently selected from the group consisting of: i. The nitrogen-containing polymer of formula II, wherein the combined mole percentage of (b) and (e) is 100 mole %, and R0 is independently selected from H, and groups consisting of combinations thereof; ii. The nitrogen-containing polymer of formula II, wherein the mole percentage of (a) is 100 mole %, and R x is -R3NH2; and iii. The nitrogen-containing polymer of formula II, wherein the mole percentage of (b) is 100 mole %, and R0 is independently selected from H, and their combinations.

27. The treatment article of claim 26, wherein the retention aid is independently selected from the group consisting of: i. The nitrogen-containing polymer of formula II as further defined according to formula IIa: ii. The nitrogen-containing polymer of formula II as further defined according to formula IIb: and iii. The nitrogen-containing polymer of formula II as further defined according to formula IIc:

28. A method for preparing a dispersion according to any one of claims 1 to 9, the method comprising: The solvent, the sizing agent, and the retention aid are combined.

29. A dispersion for use in a method for making a treated article, the dispersion comprising: solvent; and The reaction product between:

1. A sizing agent comprising a wax or a component thereof having an acid value of 10 to 220 mg KOH / g as measured according to USP 401; and II. A retention aid comprising a nitrogen-containing polymer of formula I, wherein (a), (b), (c), (d) and (e) individually represent the mole percentage of each repeating unit included in the nitrogen-containing polymer of Formula I, each individual mole percentage represented by (a), (b), (c), (d) and (e) is from 0 to 100 mole %, and the sum of (a), (b), (c), (d) and (e) is 100 mole %, wherein R0 is independently selected from the group consisting of: H, and their combinations, and in: R z independently selected from H, -CH3 and combinations thereof, R x independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R3OH, -OR1, -NR1R1, -R3NH2, -NH2, -COO(CH2)2N(R1)2, -COO(CH2)2N + (R1)3X - 、-COO(CH2)3N + (R1)3X - and their combination, provided that when R x When it is -NH2, R z is -CH3, Y is independently selected from H, -OH, -R1, -OR1, -NR1R1, -NH2 and combinations thereof, R1 is independently selected from H, linear or branched alkyl or alkenyl groups containing up to 22 carbons, and combinations thereof, R2 is independently selected from H, monosaccharide, oligosaccharide, polysaccharide moiety, linear or branched alkyl or alkenyl groups of up to 22 carbons, optionally containing hydroxyl or aldehyde groups, and combinations thereof, R3 is independently selected from a linear or branched alkyl or alkenyl group or a combination thereof containing up to 22 carbons, R4 is independently selected from linear or branched alkyl groups containing up to 18 carbons, optionally substituted with hydroxyl groups, and combinations thereof, R5 is independently selected from H, -OH, -COOH, -COOR1, -OCOR1, -R1, -R1OH, -OR1, -CONH2, -CONHCHOHCHO, -NR1, -NR1R1, -R1NH2, -NH2, and combinations thereof, A is independently selected from C=O, -CH2, and combinations thereof, and X - are independently anions.

Images