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-references to related applications

[0002] This application claims priority and all advantages of U.S. Provisional Patent Application No. 63 / 212,776, filed June 21, 2021, and U.S. Provisional Patent Application No. 63 / 121,500, filed December 4, 2020, the disclosure of which is incorporated herein by reference in its entirety. Invention Field

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

[0005] The performance of high-performance processed articles (such as paper products) often stems from their inclusion of fluoropolymers. The recent global trend of reducing the fluorine content in processed articles, particularly those used in the food industry, has resulted in products considered more environmentally friendly. However, these environmentally friendly articles typically lack certain performance properties compared to their fluorinated counterparts. Therefore, it remains possible to develop improved processed articles with high performance, or dispersions for manufacturing improved processed articles.

[0006] Summary and advantages of the invention

[0007] This disclosure provides a treated article. The treated article includes fibers, 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] This disclosure also provides a dispersion for manufacturing treated articles. The dispersion includes a solvent, a sizing agent, and a retention aid.

[0009] The treated products are typically fluorine-free and possess an excellent balance of performance properties. Specifically, the synergistic combination of sizing agents and retention aids produces treated products with excellent resistance to corn oil penetration and water repellency. Invention Details

[0011] This disclosure provides a dispersion for manufacturing processed articles. The dispersion comprises three main components: a solvent, a sizing agent, and a retention aid.

[0012] First, regarding the solvent, it can include various solvated liquids, or it can include a single liquid. Solvents generally include at least water. Other liquids optionally included in the solvent are water-miscible liquids. Specific examples of water-miscible solvents include at least one solvent selected from the group consisting 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 comprises water or a combination of water and at least one water-miscible solvent selected from the group consisting of propylene glycol, dipropylene glycol, and tripropylene glycol.

[0013] The dispersion generally comprises at least 40 parts by weight of solvent based on 100 parts by weight of the dispersion. Alternatively, the dispersion may comprise 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 of solvent based on 100 parts by weight of the dispersion. For example, the solvent may comprise water (e.g., tap water) and dipropylene glycol, wherein water is present in an amount of 50 to 75 parts by weight and dipropylene glycol is present in an amount of 15 to 40 parts by weight based on 100 parts by weight of the dispersion.

[0014] Now, when referring to sizing agents, sizing agents include waxes or components thereof. Those skilled in the art will understand that various waxes, particularly naturally occurring waxes, comprise combinations of individual components. For example, naturally occurring beeswax comprises palmitates, palmitoleates, and oleates of long-chain (e.g., 30-32 carbon) aliphatic alcohols, where each individual component is “its components” with respect to beeswax. For ease of reference, the term “wax or its components” will be collectively referred to as “wax” throughout the remainder of the description.

[0015] The wax in the sizing agent has an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401. Alternatively, the wax may 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 may 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 the purposes of this disclosure, any reference to the acid value of the wax refers to an acid value measured according to USP 401.

[0016] While the wax is not limited to any particular type, provided it has an acid value of 10 mg to 220 mg KOH / g, it is generally selected from the group consisting of stearates, beeswax (synthetic and natural), candelilla wax, palmitate, behenate, and combinations thereof. For example, the wax in a sizing agent may be beeswax or stearate, or both. Alternatively, the wax may be behenate or 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 may 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] Those skilled in the art will understand that sizing agents including waxes can be used in methods of manufacturing treated articles because, as described in further detail below, sizing agents can be fixed, retained, anchored, blended, or oriented within or by fibers within the treated article. Also described in further detail below, sizing agents may be referred to as internal sizing agents, external sizing agents, or both, depending on the specific method of blending the dispersion within the method of manufacturing the treated article.

[0019] Retention aids now refer to nitrogen-containing polymers selected from the group consisting of: (i) nitrogen-containing polymers of formula I, (ii) polyethyleneimine, (iii) polyaminoamide, (iv) copolymers formed from the reaction products of epichlorohydrin and dimethylamine, and (v) combinations thereof.

[0020] The nitrogen-containing polymers according to Formula I are shown below:

[0021]

[0022] In Formula I, (a), (b), (c), (d), and (e) individually represent the molar 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. 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)3N(R1)2, -COO(CH2)2N + (R1)3X-、-COO(CH2)3N + (R1)3X- and their combinations, provided that R x When R is -NH2 zY is -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, a straight-chain or branched alkyl or alkenyl group containing up to 22 carbons, and combinations thereof. R2 is independently selected from H, a monosaccharide, oligosaccharide, or polysaccharide structural moiety, a straight-chain or branched alkyl or alkenyl group containing up to 22 carbons, optionally containing a hydroxyl or aldehyde group, and combinations thereof. R3 is independently selected from a straight-chain or branched alkyl or alkenyl group containing up to 22 carbons, or combinations thereof. R4 is independently selected from a straight-chain or branched alkyl group containing up to 18 carbons, optionally substituted with a hydroxyl group, 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- is independently anion.

[0024] As described above, (a), (b), (c), (d), and (e) of Formula I individually represent the molar percentage of each repeating unit included in the nitrogen-containing polymer of Formula I. For ease of reference, a repeating unit having a molar percentage (a) will be referred to as repeating unit (a), a repeating unit having a molar percentage (b) will be referred to as repeating unit (b), a repeating unit having a molar percentage (c) will be referred to as repeating unit (c), a repeating unit having a molar percentage (d) will be referred to as repeating unit (d), and a repeating unit having a molar percentage (e) will be referred to as repeating unit (e). It should also be understood that the structural formula representing each individual repeating unit represents multiple discrete repeating units. The molar percentage for each repeating unit is the combined molar percentage of each discrete unit represented by the repeating unit. For example, when the nitrogen-containing polymer of Formula I includes 50 mol% of repeating unit (b)... (R0 is from (b) represents the repeating unit in an amount of 50 mol% (indicated by the symbol). (R0 is from When expressed as (b), the nitrogen-containing polymer comprises repeating units (b) in a total combined amount of 100 mol%. It should also be 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) can be 0 to 100 mol%, where the sum of (a), (b), (c), (d), and (e) is 100 mol%. This means that the nitrogen-containing polymer of Formula I does not include additional repeating units within its structure. When the mole percentage of (a) is zero, the nitrogen-containing polymer does not include repeating unit (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] Now, referring to the repeating unit (a), Typically, the molar percentage of repeating unit (a) within repeating unit (a) is less than 100 mol%. In other words, typically when repeating unit (a) is included in a 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 another repeating unit, the molar percentage (a) of repeating unit (a) is less than 30 mol%. However, when the molar percentage (a) of repeating unit (a) is 100 mol%, 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 their combinations. In other words, when the molar percentage of repeating unit (a) is 100 mol%, R is chosen. x This makes the repeating unit (a) include nitrogen.

[0027] Now, regarding the repeating unit (b), The repeating unit (b) may be included in the nitrogen-containing polymer of Formula I in a molar percentage of 0 to 100. When the nitrogen-containing polymer includes the repeating unit (b), the repeating unit (b) is typically included in an amount of at least 15 mol%. Alternatively, the repeating unit (b) may be included in an amount of at least 30, 40, 50, 60, 70, 80, or 90 mol%.

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

[0029] In some embodiments, the retention aid is a nitrogen-containing polymer of Formula I, and the combined molar percentage of repeating units (c) and (d) is less than 5 mol%. Alternatively, in these embodiments, the retention aid is a nitrogen-containing polymer of Formula I, and the repeating units (a), (b), and (e) collectively represent at least 95 mol% of the nitrogen-containing polymer. Alternatively, the retention aid 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 mol%.

[0030] When the retention aid is a nitrogen-containing polymer of Formula I and the repeating units (a), (b), and (e) are present in a total of 100 mol%, 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, And their combinations. In other embodiments of Formula II, R0 is independently selected from the group consisting of: H, And their combinations. In a further embodiment 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) nitrogen-containing polymers of formula II, wherein the combined molar percentage of (b) and (e) is 100 mol%, and R0 is independently selected from H, and combinations thereof; (ii) nitrogen-containing polymers of formula II, wherein the molar percentage of (a) is 100 mol%, wherein R x Represented by -R3NH2; and nitrogen-containing polymers of formula (iii) II, wherein the molar percentage of (b) is 100 mol%, and R0 is independently selected from H, The group consisting of (i) a nitrogen-containing polymer of formula II, wherein the molar percentage of the combination of (b) and (e) is 100 mol% and R0 is independently selected from H, When combined with other components, retention aids can be more narrowly defined as formula IIa:

[0034]

[0035] Similarly, in this embodiment, when the retention aid comprises a nitrogen-containing polymer of formula (ii), wherein the molar percentage of (a) is 100 mol%, wherein R x When represented by -R3NH2, retention aids can be more narrowly defined as formula IIb:

[0036]

[0037] Similarly, in this embodiment, when the retention aid comprises a nitrogen-containing polymer of formula (iii) II, wherein the molar percentage of (b) is 100 mol%, and R0 is independently selected from H, When combined with other substances to form a group, retention aids can be more narrowly defined as formula IIc:

[0038]

[0039] When a retention aid is represented by or includes formula IIa, (b1) and (b2) represent the mole percentages of associated repeating units, where the combined mole percentage of (b1) and (b2) equals the total mole percentage of (b) in formula II. In other words, repeating unit (b1) is the first repeating unit derived from repeating unit (b) of formula II, and repeating unit (b2) is the second repeating unit derived from repeating unit (b). Similarly, when a retention aid is represented by or includes formula IIc, (b1), (b2), and (b3) represent the mole percentages of associated repeating units, where the combined mole percentage of (b1), (b2), and (b3) equals the total mole percentage 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, based on the total amount of functional groups that can be hydrolyzed, partially hydrolyzed poly(N-vinylformamide) is hydrolyzed by 30 to 70%. Alternatively, based on the total amount of functional groups that can be hydrolyzed, partially hydrolyzed poly(N-vinylformamide) may be hydrolyzed by 30 to 60, 40 to 70, 40 to 60, or about 50%.

[0041] When the retention aid is or includes a nitrogen-containing polymer of formula IIb, the nitrogen-containing polymer may be referred to as polyallylamine. Although not required, polyallylamine typically has a weight-average molecular weight of 30,000 to 100,000 Daltons. Alternatively, 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, or chloride (CAS Registry No. 945630-11-5). While those skilled in the art will readily recognize that various reaction routes can be used to synthesize nitrogen-containing polymers of formula IIc, Example 5 of U.S. Patent No. 8,604,134 discloses a suitable method. Because it relates to nitrogen-containing polymers of formula IIc, the disclosure of U.S. Patent No. 8,604,134 is incorporated herein by reference.

[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-vinylformamide) with a degree of hydrolysis of 30 to 70%; (ii) a nitrogen-containing polymer of formula II, wherein (a) has a molar percentage of 100 mol%, wherein R x Represented by -R3NH2; and nitrogen-containing polymers of formula (iii) II, wherein the molar percentage of (b) is 100 mol%, and R0 is independently chosen from H, Groups formed by combining them.

[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) nitrogen-containing polymers of formula II, wherein the combined molar percentage of (b) and (e) is 100 mol%, and R0 is independently selected from H, The group consisting of (i) polyallylamines having a weight-average molecular weight of 30,000 to 100,000 Daltons; and (iii) nitrogen-containing polymers of formula II, wherein (b) has a molar percentage of 100 mol%, and R0 is independently selected from H, Groups formed by combining them.

[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) nitrogen-containing polymers of formula II, wherein the combined molar percentage of (b) and (e) is 100 mol%, and R0 is independently selected from H, and combinations thereof; (ii) nitrogen-containing polymers of formula II, wherein the molar percentage of (a) is 100 mol%, 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, the retention aid is a nitrogen-containing polymer of Formula I and the combined molar percentage of (b), (c), (d), and (e) is greater than 95 mol%. Alternatively or complementaryly, in some embodiments, when the retention aid is a nitrogen-containing polymer of Formula II, the molar concentration of repeating unit (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] Nitrogen-containing polymers of Formula IIIa are generally referred to as fully hydrolyzed poly(N-vinylformamide). In other words, unlike nitrogen-containing polymers of Formula IIa, virtually all functional groups in nitrogen-containing polymers of Formula IIIa are hydrolyzed.

[0051] In some embodiments, when the retention aid is a nitrogen-containing polymer of formula I, the molar percentage of (c) corresponding to repeating unit (c) is 100 mol%, such that the nitrogen-containing polymer is a polyacrylamide according to formula IV:

[0052]

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

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

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

[0056] Polydiallyl dimethyl ammonium chloride can be low molecular weight polydiallyl dimethyl ammonium chloride, high molecular weight polydiallyl dimethyl ammonium chloride, or a combination thereof. In particular, low molecular weight polydiallyl dimethyl ammonium chloride has a weight-average molecular weight of less than 200,000 Daltons. In contrast, high molecular weight polydiallyl dimethyl ammonium chloride has a weight-average molecular weight of 300,000 to 400,000 Daltons.

[0057] In each embodiment of the retention aid described above, when the dispersion has a pH of 7, the nitrogen-containing polymer may have a charge density of >+0.1 meq / g. Although not required, the nitrogen-containing polymer typically 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 comprises more than one repeating unit, the repeating units are typically randomly distributed within the nitrogen-containing polymer. Finally, in each embodiment of this disclosure, the dispersion typically does not contain (i.e., does not include) fluoropolymers and fluorinated performance additives.

[0058] The dispersion typically includes a 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 may be present in the dispersion in amounts 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 stearates, beeswax, candelilla wax, palmitic acid esters, behenicolates, and combinations thereof. The dispersion also includes a nitrogen-containing polymer of formula II:

[0060]

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

[0062] In other embodiments, the dispersion comprises a sizing agent selected from the group consisting of stearates, beeswax, candelilla wax, palmitic acid esters, behenicolates, and combinations thereof. The dispersion also comprises a nitrogen-containing polymer selected from the group consisting of formulas IIa, IIb, 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 of >+0.1 meq / g.

[0065] In some embodiments, the dispersion includes a sizing agent selected from the group consisting of stearates, beeswax, candelilla wax, palmitate, behenate, and combinations thereof. In different embodiments, the retention aid is a nitrogen-containing polymer selected from the group consisting of (i) polyethyleneimine, (ii) polyaminoamide, (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) polyaminoamide, (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, polyethyleneimine typically has a weight-average molecular weight of 40,000 to 100,000 Daltons, and based on the total number of amino groups in polyethyleneimine, 20 to 30% of the amino groups in polyethyleneimine are primary amines and 45 to 55% of the amino groups in polyethyleneimine are secondary amines. When the nitrogen-containing polymer is or includes polydiallyldimethylammonium chloride, polydiallyldimethylammonium chloride has a weight-average molecular weight of less than 200,000 Daltons or 300,000 to 400,000 Daltons.

[0067] In some embodiments, the dispersion comprises a sizing agent selected from the group consisting of stearates, beeswax, candelilla wax, palmitic acid esters, behenicol esters, and combinations thereof. In these embodiments, the retention aid may also comprise, or be, 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 its stability. The surfactant may be anionic, nonionic, cationic, amphoteric, or polymeric. Among these, anionic, nonionic, or cationic surfactants are commonly used. When included, the surfactant is typically 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 alkyl carbonate-based compounds, alkyl sulfate-based compounds, and alkyl phosphates. Specific examples of anionic surfactants include sodium dioctyl succinate sulfonate, sodium dodecyl 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 alkylene diamines. Suitable examples of cationic surfactants include primary to tertiary amines, pyridinium salts, alkylpyridinium salts, and quaternary ammonium salts such as alkyl halide quaternary ammonium salts.

[0069] Without adhering to any particular theory, it is believed that the first portion of the amino group of the retention aid associates with oxygen atoms present in the ester and / or acid of the sizing agent via hydrogen or electrostatic bonding. It is further believed that the remaining portion of the amino group associates with hydroxyl groups present on fibers, such as cellulose-based pulp fibers, also included in the treated article. In other words, the retention aid is combined or associated with both the sizing agent and the fiber. As further described below, in the process of manufacturing the treated article, the retention aid is bound to both the sizing agent and the fiber, fixing, retaining, anchoring, blending, orienting the retention aid between adjacent fibers and on the surface of adjacent fibers to form a dense network / matrix. It is further believed that the specific sizing agent and retention aid of this disclosure have strong interactions, resulting in the effective dispersion of the retention aid and sizing agent throughout the treated article. Compared to conventionally treated articles prepared using dispersions not of this disclosure, treated articles prepared using dispersions of this disclosure have relatively fewer cavitation 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 cavities and / or channels. This reduction in the relative amount of cavities and channels is significant and provides treated articles with enhanced barrier properties. Specifically, treated articles prepared with the dispersions of this disclosure exhibit relatively higher resistance to both water and oil penetration compared to conventionally treated articles.

[0070] This disclosure also provides a treated article formed from the dispersion. The treated 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, fibers having the ability to bind with the amine groups of the retention aid may be advantageously selected.

[0071] The processed articles can be paper products, food packaging, non-food contact packaging, wood or building materials, nonwovens, molded fibers, such as cardboard, takeaway containers, bowls, etc., or any paper substrate, especially paper substrates with favorable water and / or oil resistance.

[0072] Fibers can be natural fibers, synthetic fibers, semi-synthetic fibers, inorganic fibers, and combinations thereof. Specific examples of natural fibers include those derived from plants or wood, also known as cellulose fibers, such as bamboo fiber, bentgrass 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 fibers are derived from wood, the wood can be softwood and / or hardwood. Other examples of natural fibers include cotton, hemp, wool, silk, etc. Specific examples of synthetic fibers include polyamide fibers, polyester fibers, polyvinyl alcohol fibers, polyacrylonitrile fibers, polyvinyl chloride fibers, polypropylene fibers, etc. In some embodiments, the fiber is pulp fiber derived from bleached and unbleached sulfate (kraft paper) hardwood or softwood pulp, groundwood pulp, recycled cellulose fibers, and bleached chemithermomechanical pulp (BCTMP), and combinations thereof.

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

[0074] Treated articles may also include components other than retention aids, sizing agents, and fibers. For example, treated articles may also include starch, resins, crosslinking agents, catalysts, inorganic or organic fillers, coagulants, carriers (e.g., dextrin), retaining agents, flocculants, buffers, bactericides, biocides, metal ion sealants, hydrophobic agents (e.g., alkenyl succinic anhydride and / or alkyl vinyl ketone dimers), and various combinations of such components.

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

[0076] Specific examples of resins suitable for processing articles include, but are not limited to, polyvinyl alcohol, polyvinyl chloride latex, etc.

[0077] Specific examples of crosslinking agents suitable for treating articles include, but are not limited to: condensates or pre-condensates of urea or melamine-formaldehyde, hydroxymethyl-dihydroxyethylidene-urea or derivatives thereof, urone, hydroxymethyl-ethylidene-urea, hydroxymethyl-propylene-urea, hydroxymethyl-triazine, 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 processing products include, but are not limited to, ammonium chloride, alkanolamine salts, zirconium acetate, and combinations thereof.

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

[0080] The specific components present in the treated product and their respective amounts can vary depending on the specific fibers used in the pulp and the intended end use of the treated product.

[0081] This disclosure also provides a method for manufacturing a treated article. The method includes providing a pulp comprising fibers. The pulp can be provided in any suitable manner. For example, the pulp can be prepared, obtained, purchased, etc. When the step of providing the pulp includes preparing the pulp, the pulp can be prepared according to methods known in the art. For example, in embodiments where the fibers are cellulose fibers, the pulp can be prepared by: mechanical pulping; thermomechanical pulping; chemothermomechanical pulping; chemical pulping, such as kraft paper pulping, sulfite pulping, and soda pulping; recycling pulping; organic solvent pulping, etc. Alternatively, the pulp can be prepared by purchasing or otherwise obtaining dried cellulose fibers, which are generally referred to in the art as "commercial pulp." In these embodiments, the commercial pulp is generally reconstituted with water, a process known 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, fibers are present in the slurry in amounts ranging from greater than 0 to 5, alternatively 0.2 to 3.75, or alternatively 0.3 to 3 parts by weight per 100 parts by weight of slurry. It should be understood, of course, that fibers may be present in the slurry in amounts different from those described above, depending on the presence or absence of various optional components described in more detail below. The remainder of the slurry typically contains water or a combination of water and a water-miscible solvent.

[0083] In some embodiments where the fibers are cellulose fibers, the pulp fibers are typically refined. Generally, pulp fibers are refined by subjecting the pulp to shear forces, which separates cellulose clumps or fiber clusters into individual fibers. Typically, the pulp fibers are not refined until the pulp is prepared or supplied; that is, "commercial pulp" is generally unrefined until it has been reformulated with water to form pulp.

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

[0085] The method also includes forming a treated article from a slurry comprising a dispersion. Typically, the slurry is formed into at least one sheet. For clarity, at least one sheet is referred to herein only as "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 metallic substrate, such as stainless steel or a substance referred to in the art as monofilament. The relative dimensions of the sheet (e.g., thickness, length, width) can vary depending on various factors, such as the desired end use of the treated article formed via the method.

[0086] Once formed, the sheet is typically dried to remove excess solvent (e.g., water and / or water-miscible solvents). The sheet can be dried via vacuum and / or foil dehydration. Alternatively, the sheet can be dried via pressure dehydration, where pressure is applied to the sheet. When the sheet is dried via pressure dehydration, the pressure used is typically from 0.5 to 200 psig. Furthermore, the sheet can be dried via shrink dehydration, where the sheet is dried by exposure to paper machine clothing, which absorbs excess water and / or water-miscible solvents from the sheet. Additionally, the sheet can be dried by shrink drying, where the sheet comes into contact with metal rollers having a smooth surface. The metal rollers used in shrink drying are typically heated, for example, to 150 to 280°F. Any combination of these methods, or other methods known in the art for drying sheets to remove excess water and / or water-miscible solvents, can be employed. In some embodiments, all the methods for drying sheets described above are employed, typically in the order they are presented above.

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

[0088] The step of applying a dispersion to at least one surface of a sheet is not particularly limited, as long as it enables close 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, metering size press coating, film coating, gravure coating, flexographic coating, roll coating, rotor dampening, bubbling, gate roll coating, beaver knife coating, doctor blade coating, gravure coating, reverse roll coating, slide roll coating, transfer (offset) roll coating, doctor blade coating, roller-knife coating, J coating, air knife coating, curtain coating, and combinations thereof.

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

[0090] This disclosure further provides another method for manufacturing treated articles. Unlike the methods described above, this method does not form a dispersion and subsequently add the dispersion to a slurry. Instead, the retention aid and sizing agent are added to the slurry separately, rather than being combined into a single composition beforehand. In other words, instead of adding a dispersion comprising a retention aid and a sizing agent to the slurry, the retention aid is added to the slurry, rather than being pre-combined with the sizing agent. Similarly, the sizing agent is added to the slurry, rather than being pre-combined with the retention aid. The order in which the sizing agent and retention aid are added is not limited in this embodiment. For example, the sizing agent can be added to the slurry, followed by the retention aid, or vice versa. Of course, the sizing agent and retention aid can also be added simultaneously, rather than being pre-combined with each other.

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

[0092] In one embodiment, the reaction product is formed when the retention aid is polyethyleneimine and the sizing agent, for example, comprises an alkyl acid (e.g., stearic acid). In this embodiment, the retention aid is typically 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 by the reaction between a sizing agent and a primary amine group of formula IIa.

[0096]

[0097] The reaction products are represented by formula IIa':

[0098]

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

[0100] In another embodiment, the reaction product is formed by the reaction between a sizing agent and a primary amine group of formula IIb.

[0101]

[0102] The reaction products are represented by formula IIb':

[0103]

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

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

[0106]

[0107] The reaction products are represented by formula IIc':

[0108]

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

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

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

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

[0113] To assess repulsion, 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 it. The result is qualitatively recorded as acceptable (P) or unacceptable (F).

[0114] To assess Cobb absorbency, the sheet was first weighed and clamped into a Cobb ring apparatus. 100 grams of precisely weighed room temperature tap water was placed on the sheet within the Cobb ring apparatus and allowed to stand for one minute and 45 seconds. The water was then drained and the sheet was released. The sheet was then clamped between two sheet-formed blotting papers, and a 10 kg Cobb roller was rolled across the sheet, once forward and once in the opposite direction (a total of two passes, each in opposite directions). The sheet was then immediately weighed, and the absorbency was subsequently calculated using the initial weight and the exposed weight.

[0115] To evaluate the Cobb oil leakage test, the sheet was first weighed. A clean, circular Whatman No. 4 quantifier circle was placed under the sheet as absorbent paper for leakage. A 20mm diameter template was then placed on the sheet to define the initial exposure area. A 0.5g oil sample was then collected using a pipette, and corn oil was subsequently added to the sheet within the 20mm diameter template, allowing the oil to spread evenly across the template. After the oil was delivered to the sheet, the pipette was weighed to determine the precise mass of oil added to the sheet. Once the oil was evenly distributed, the template was removed, and a 300g weight was placed centered on top of the oil, allowing it to stand for 120 seconds. The sheet-shaped absorbent paper was then placed on top of the sheet, and a 10kg Cobb roller was rolled across the sheet, once forward and once in the opposite direction (a total of two passes, each in opposite directions) to absorb excess oil on the sheet surface. The exposed sheet and the Whatman 4 grading circle were then weighed, and the absorption rate was calculated.

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123] Table I

[0124]

[0125] The results shown in Table I above demonstrate that, when articles are treated with dispersions, dispersions of this disclosure, including retention aids and sizing agents containing waxes or components thereof, and having an acid value of 10 mg to 220 mg KOH / g, produce excellent articles.

[0126] All combinations of the above-described embodiments throughout this disclosure are hereby expressly covered 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 expressly covered embodiments may include any one or more elements described above selected and combined from any part of the invention.

[0127] One or more of the values ​​described above may vary by ±5%, ±10%, ±15%, ±20%, ±25%, etc., as long as the variance remains within the scope of the invention. Unexpected results can be obtained independently of all other members, by each member of the Markush group. Each member may be relied upon individually and or in combination, and provides appropriate support for a particular embodiment within the scope of the appended claims. The subject matter of all combinations of single and multiple dependencies in the independent and dependent claims is explicitly covered herein. This disclosure includes descriptive terms illustratively and not restrictively. Many modifications and variations of this disclosure are possible in accordance with the teachings above, and this disclosure may be practiced in ways different from those explicitly described herein.

[0128] It should also be understood that any scopes and subscopes relied upon in the various embodiments describing this disclosure fall independently and collectively within the scope of the appended claims, and are to be understood as describing and covering all scopes, including whole and / or partial values, even if such values ​​are not explicitly stated herein. Those skilled in the art will readily recognize that the enumerated scopes and subscopes are sufficient to describe and implement the various embodiments of this disclosure, and that such scopes and subscopes may be further described as related halves, thirds, quarters, fifths, etc. By way of example only, the scope of “0.1 to 0.9” may be further described as 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 collectively within the scope of the appended claims, and may be individually and / or collectively relied upon to provide appropriate support for a particular embodiment within the scope of the appended claims. Furthermore, regarding language defining or modifying scope, such as “at least,” “greater than,” “less than,” “no more than,” and the like, it should be understood that such language includes subscopes and / or upper or lower limits. As another example, the range "at least 10" includes subranges from at least 10 to 35, from at least 10 to 25, from 25 to 35, and so on, and each subrange can be relied upon individually and / or collectively to provide appropriate support for a particular embodiment within the scope of the appended claims. Finally, individual numerical values ​​within the disclosed range can be relied upon and provide appropriate support for a particular embodiment within the scope of the appended claims. For example, the range "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 a particular embodiment within the scope of the appended claims.

Claims

1. A dispersion for use in a method for making a treatment article, the dispersion comprising: a solvent; a sizing agent comprising a wax or component thereof having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401; and a retention aid comprising a nitrogen-containing polymer as shown in Formula IIIa: where (b) and (e) individually represent the mole percent (mol%) of each repeating unit included in the nitrogen-containing polymer of Formula IIIa, and the combined mole% of (b) and (e) is 100 mole%.

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

3. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent is independently selected from the group consisting of a stearate, beeswax, candelilla wax, a palmitate, a behenate, and combinations thereof.

4. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent has an acid value of 150 to 220 mg KOH / g.

5. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent is a stearate.

6. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent is beeswax.

7. The dispersion as defined in any one of claims 1 to 2, 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.

8. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent is candelilla wax.

9. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent is a palmitate.

10. The dispersion as defined in any one of claims 1 to 2, wherein the sizing agent is a behenate.

11. A fiber pulp comprising: the dispersion as defined in any one of claims 1 to 2; a fiber; and a second solvent that is the same as or different from the solvent of the dispersion.

12. A method of making a treatment article, the method comprising: combining the dispersion as defined in any one of claims 1 to 2 with a fiber pulp; and forming a treatment article from the fiber pulp comprising the dispersion.

13. A method of making a treatment article, the method comprising: forming an article from a fiber pulp, wherein the article has a top surface and a bottom surface; and applying the dispersion as defined in any one of claims 1 to 2 to at least one surface of the article to form the treatment article.

14. A method of making a treatment article, the method comprising: providing a fiber pulp comprising a fiber and water; combining a sizing agent with the fiber pulp, the sizing agent comprising a wax or 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 pulp, the retention aid comprising a nitrogen-containing polymer as shown in Formula IIIa: wherein (b) and (e), individually, represent the mole percent (mol%) of each repeating unit included in the nitrogen-containing polymer of Formula Ilia, and the combined mol% of (b) and (e) is 100 mol%; and forming the fiber slurry comprising the sizing agent and the retention aid into a treatment article.

15. A treatment article comprising: a fibrous substrate; a sizing agent comprising a wax or component thereof having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401; and a retention aid comprising a nitrogen-containing polymer as shown in Formula Ilia: wherein (b) and (e), individually, represent the mole percent (mol%) of each repeating unit included in the nitrogen-containing polymer of Formula Ilia, and the combined mol% of (b) and (e) is 100 mol%.

16. A method of making the dispersion of any one of claims 1 to 2, the method comprising: combining the solvent, the sizing agent, and the retention aid.

17. A dispersion for use in a method for making a treatment article, the dispersion comprising: a solvent; and a reaction product between: I. a sizing agent comprising a wax or component thereof having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401; and II. a retention aid comprising a nitrogen-containing polymer as shown in Formula Ilia: wherein (b) and (e), individually, represent the mole percent (mol%) of each repeating unit included in the nitrogen-containing polymer of Formula Ilia, and the combined mol% of (b) and (e) is 100 mol%.

18. A method for making a treatment article, the method comprising: providing a fibrous substrate; applying a sizing agent comprising a wax or component thereof having an acid value of 10 mg to 220 mg KOH / g as measured according to USP 401; and applying a retention aid comprising a nitrogen-containing polymer as shown in Formula Ilia: wherein (b) and (e), individually, represent the mole percent (mol%) of each repeating unit included in the nitrogen-containing polymer of Formula Ilia, and the combined mol% of (b) and (e) is 100 mol%.

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