FABRIC RELEASE COMPOSITIONS AND METHODS THEREOF

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Application No. 63/726,200, filed on Nov. 27, 2024, the contents of which are hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

The invention relates to novel compositions used as release aids for papermaking applications. More particularly, it is directed to compositions comprising quaternized long-chain imidazolines and long chain fatty acids and methods of using the compositions as release aids in tissue making applications.

BACKGROUND

Tissue paper is typically produced by dry crepe (DC) and through-air-drying (TAD) processes. Different from DC, TAD is a process that involves transferring a tissue web from a forming fabric onto a structured fabric, known as TAD fabric which has a 3-dimensional character. The structured fabric is a woven structure of yarns that are mainly made of polymeric materials. Typical polymeric material for yarns is polyethylene terephthalate (PET). Shortly after the tissue web is transferred to the structured fabric, it goes through a molding box where the sheet is pulled by vacuum into close contact with the structured fabric. This serves to duplicate the structure and pattern of the fabric onto the wet tissue web so that once the sheet is partially dried through hot air passing through the sheet, the pattern remains in tissue paper. After that, the structured or patterned tissue paper is transferred to a Yankee cylinder for further drying and creping. The TAD process eliminates mechanical pressing of the sheet for water removal thus allowing for generation of higher quality tissue with increased bulk, softness, and water absorption.

Application of a TAD fabric release aid is commonly practiced and facilitates the transfer of the structured wet sheet onto the Yankee Dryer thus improving machine runnability and sheet quality. They are applied directly to the TAD fabric surface by spraying prior to transfer of the sheet from the forming fabric to the TAD fabric. In addition, by providing good sheet transfer, they help to prevent individual fibers from pulling out of sheet and remaining within the fabric. This helps keep the TAD fabric clean and allows optimum drying and molding of the sheet. Accordingly, it is desirable to provide methods for improving the release of a tissue web from a structured fabric in tissue making operations.

This background information is provided for the purpose of making information believed by the applicant to be of possible relevance to the present invention. No admission is necessarily intended, nor should it be construed, that any of the preceding information constitutes prior art against the present invention. In addition, the preceding information should not be construed to mean that a search has been made or that no other pertinent information as defined in 37 CFR § 1.56 (a) exists.

BRIEF DESCRIPTION OF THE FIGURES

The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.

The following drawings form part of the present specification and are included to further demonstrate certain aspects of the present invention. The invention may be better understood by reference to one or more of these drawings in combination with the detailed description of specific embodiments presented herein.

FIG. 1 displays data showing the percentage of tack reduction between a wet tissue web and a TAD fabric using 4 different anchor molecules. The rest of the components and quantities remains identical in the release aid formula.

FIG. 2 displays data showing the percentage of tack reduction between a wet tissue web and a TAD fabric without a wetting agent versus inclusion of two different wetting agents. The rest of components and quantities remains identical in the release aid formula.

FIG. 3 displays confocal laser scanning microscopy (CLSM) images of a TAD fabric treated with no fabric release (left) and with fabric release (right).

FIG. 4 displays CLSM images of TAD fabric samples treated with three different fabric release formulas at identical conditions.

SUMMARY

One aspect of the present disclosure pertains to a composition comprising one or more quaternized long-chain imidazolines of Formula (I-A) and/or (I-B) and one or more long chain fatty acids of Formula (II):

• • wherein
  • R¹ is linear or branched C₁₂-C₂₆ alkyl, or alkenyl groups or their mixture.
  • R² is linear or branched C₁₁-C₂₅ alkyl, or alkenyl groups or their mixture.
  • R³ is a C₁ to C₃ alkyl or benzyl group, and X is a halide or sulfate.
  • R⁴ is linear or branched C₁₁-C₂₅ alky, or alkenyl groups or their mixture.

In another aspect, the present disclosure provides a release aid composition, said composition comprising quaternized long-chain imidazolines (I) and long chain fatty acids (II), one or more emulsifier agents, and optionally one or more lubricant oils.

In another aspect, the present disclosure provides a method for reducing paper adhesion to a surface in a papermaking process, said method comprising contacting the composition disclosed herein with said surface. In some embodiments, the present disclosure provides a method for reducing paper adhesion to a surface in a papermaking process, said method comprising contacting a release composition disclosed herein with said surface.

In another aspect, the present disclosure provides a method for reducing paper adhesion between a wet tissue web with a surface of a TAD fabric in a papermaking process, said method comprising contacting the composition disclosed herein with said surface. In some embodiments, the present disclosure provides a method for reducing paper adhesion between a wet tissue web and a surface of a dryer in a papermaking process, said method comprising contacting a release composition disclosed herein with said surface.

In a further aspect, the present disclosure provides a method for reducing paper adhesion between a wet tissue web and a surface of a dryer in a papermaking process, said method comprising contacting the composition disclosed herein with said surface. In some embodiments, the present disclosure provides a method for reducing paper adhesion between a wet tissue web and a surface of a dryer in a papermaking process, said method comprising contacting a release composition disclosed herein with said surface.

DETAILED DESCRIPTION

Definitions

The following definitions are provided to determine how terms used in this application, and in particular, how the claims are to be construed. The organization of the definitions is for convenience only and is not intended to limit any of the definitions to any particular category. The use of the terms “a” and “an” and “the” and “at least one” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The use of the term “at least one” followed by a list of one or more items (for example, “at least one of A and B”) is to be construed to mean one item selected from the listed items (A or B) or any combination of two or more of the listed items (A and B), unless otherwise indicated herein or clearly contradicted by context.

Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein.

All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context.

The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the invention.

The use of “or” means “and/or” unless stated otherwise.

The use of “comprise,” “comprises,” “comprising,” “include,” “includes,” and “including” are interchangeable and not intended to be limiting. Furthermore, where the description of one or more embodiments uses the term “comprising,” those skilled in the art would understand that, in some specific instances, the embodiment or embodiments can be alternatively described using the language “consisting essentially of” and/or “consisting of.”

As used herein, the term “about” refers to a ±10% variation from the nominal value. It is to be understood that such a variation is always included in any given value provided herein, whether or not it is specifically referred to.

Any ranges given either in absolute terms or in approximate terms are intended to encompass both, and any definitions used herein are intended to be clarifying and not limiting. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Moreover, all ranges disclosed herein are to be understood to encompass any and all subranges (including all fractional and whole values) subsumed therein.

“Alkenyl” refers to a straight or branched hydrocarbon, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 23, 25, or 26 carbons, and having one or more carbon-carbon double bonds. Alkenyl groups include, but are not limited to, ethenyl, 1-propenyl, 2-propenyl(allyl), iso-propenyl, 2-methyl-1-propenyl, 1-butenyl, and 2-butenyl. Alkenyl groups may be unsubstituted or substituted by one or more suitable substituents.

“Alkyl” refers to a straight-chain or branched alkyl substituent. Examples of such substituents include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isoamyl, hexyl, and the like.

The term of “Papermaking process” means any portion of a method of making paper products from pulp comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known to those skilled in the art. The papermaking process may also include a pulping stage, i.e. making pulp from a lignocellulosic raw material and bleaching stage, i.e. chemical treatment of the pulp for brightness improvement, papermaking is further described in the reference Handbook for Pulp and Paper Technologists, 3rd Edition, by Gary A. Smook, Angus Wilde Publications Inc., (2002) and The Nalco Water Handbook (3rd Edition), by Daniel Flynn, McGraw Hill (2009) in general and in particular pp. 32.1-32.44. “Papermaking process” includes methods of making paper products from pulp comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet and drying the sheet. The steps of forming the papermaking furnish, draining and drying may be carried out in any conventional manner generally known to those skilled in the art.

The terms “tissue paper web, paper web, web, paper sheet, sheet and paper product” all refer to sheets of paper made by a process comprising the steps of forming an aqueous papermaking furnish; depositing this furnish onto a foraminous surface, such as a Fourdrinier wire or TAD fabric, and removing the water from the furnish either by gravity or by vacuum assisted drainage. In the final step of the process, the desirable textural characteristics are imparted to the paper by means of the TAD fabric or creping, or a combination thereof, as the sheet is dried. An example of a paper machine and a papermaking process that may be used in conjunction with the teachings of the invention is disclosed in U.S. Pat. No. 5,944,954, the general principles of which are incorporated herein by reference. However, it is to be understood that the release aid of the invention can be used in other known papermaking processes and in other known paper machines for manufacturing tissue and/or towel paper products.

The tissue web can be comprised of various types of natural and synthetic fibers including wood pulps of chemical and mechanical types, non-wood fibers, vegetable fibers, fibers from agricultural residues, recycled fibers and synthetic fibers such as polypropylene. The tissue web can also be comprised of particulate fillers, such as kaolin clay, titanium dioxide, and/or calcium carbonate.

All percentages, ratios and proportions herein are by weight unless otherwise specified.

The term “Through-Air-Dry (TAD)” refers to a specialized type of tissue machine that uses a unique drying process to create tissue products. This process includes uncreped TAD (UCTAD) and creped TAD (CTAD) machines.

The term “Dry Crepe (DC)” refers to conventional wet press tissue machines. This is the most common type of tissue machines, and the creping process occurs on the Yankee Dryer when paper sheets are dried.

The term “release aid composition” used interchangeably herein with “release aid”, refers to a composition that aids in the separation of paper such as tissue paper web (or tissue web) from a papermaking surface e.g., by lowering the adhesion of the web from the surface.

The quaternized long-chain imidazoline of this invention are commonly manufactured through two-step reactions. The first step is to react long-chain fatty acids or their derivative with a diamine, commonly ethylenediamine. This reaction leads to the formation of an imidazoline ring by dehydration. The second step is to quaternize imidazoline with an alkylating agent such as methyl chloride or dimethyl sulfate to introduce a permanent positive charge on the nitrogen atom in the imidazoline ring, turning it into a quaternary ammonium compound. Quaternized long-chain imidazolines are commercially available from a variety of sources including The Lubrizol Corp. Burlington Chemical Co. PCC-Chemax, Colonial Chemical, Solvay, and Evonik Corporation etc. under the tradename AddCo, Burco, Colateric, Miranol, and Arosurf, etc.

The long-chain fatty acids of this invention are independent from the long-chain fatty acids used to make long-chain imidazolines. The weight ratio of the composition of quaternized long-chain imidazoline to long chain fatty acid may be in any ratio from 10:1 of quaternized long-chain imidazoline to long chain fatty acid to 1:10 of quaternized long-chain imidazoline to long chain fatty acid. In some embodiments, the ratio of quaternized long-chain imidazoline to long chain fatty acid is about 10:1, or about 9:1, or about 8:1, or about 7:1, or about 6:1, or about 5:1, or about 4:1, or about 3:1, or about 2:1, or about 1:1, or about 1:2, or about 1:3, or about 1:4, or about 1:5, or about 1:6, or about 1:7, or about 1:8, or about 1:9, or about 1:10. In other embodiments, the weight ratio of quaternized long-chain imidazoline to long chain fatty acid is about 1:1.

The term “emulsifier agent” is used interchangeably with “emulsifying agent” and “emulsifier” to refer to a compound or substance that acts as a stabilizer for emulsions, preventing liquids that ordinarily don't mix from separating.

The term “polar hydrophobe” refers to a molecule that is primarily hydrophobic, i.e., water repelling, but contains a polar function group.

The term “nonpolar hydrophobe” refers to a molecule that lacks polar functional groups and is primarily composed of carbon and hydrogen atoms arranged in a way that does not create a significant molecular dipole moment.

In the UCTAD process as described in the U.S. Pat. No. 5,607,551, the release aid is applied to the TAD fabric. In the CTAD process as descripted in U.S. Pat. No. 5,944,954, the release aid is applied to the TAD fabric and optionally to the creping cylinder. In conventional DC machines as descripted in U.S. Pat. No. 8,071,667, the release aid is applied to the creping cylinder.

For application to the TAD fabric and/or the creping cylinder, the composition is emulsified with water to form an emulsion comprising about 0.01 to about 5 percent by weight of the release composition.

Typically, about 0.5 mg/m2 to about 100 mg/m2 of the release aid described herein is applied to the TAD fabric or creping cylinder. As used herein, mg/m² refers to the amount of release composition measured in milligrams relating to the surface area of the fabric or cylinder surface in square meters to which it is applied.

The release aid composition may be applied to the TAD fabric and creping cylinder by any means suitable for achieving uniform application of the formulation onto the fabric or cylinder, for example by spraying or flooded nip application of the emulsion.

In an embodiment, the aqueous release aid composition is applied to the TAD fabric by means of a spray boom located after the fabric cleaning station but before the pick-up shoe transfer point. At the pick-up shoe transfer point, the wet tissue sheet is transferred to the TAD fabric for transport through the TAD(s).

For application to the Yankee dryer in the CTAD process or in conventional DC processes, the release aid is sprayed onto the Yankee dryer in emulsion form prior to the point where the wet paper web contacts the dryer.

The spraying applications described above may be further improved by a variety of means, for example by using spray booms designed for double or triple coverage, by oscillating the spray boom and by recirculation of the diluted release aid emulsion from the outlet of the spray boom to improve mixing and reduce the possibility of separation.

In an embodiment, an adhesive that is also in aqueous form is applied to the Yankee dryer along with the release aid. The release aid provides lubrication between the Yankee dryer surface and the doctor blade used to crepe the tissue paper from the Yankee dryer. The release aid also allows the tissue paper to release from the adhesive during the creping process.

The term “Yankee adhesive” refers to an adhesive suitable for use on a Yankee dryer in the papermaking process. In particular, said adhesive can remain stable at high temperatures in the range of 90 to 150° C. Examples of Yankee adhesives include adhesives comprising poly(aminoamide)-epihalohydrin (PAE) resins, polyvinyl alcohol (PVOH) resins, polyethyleneimine (PEI) resins, polyvinyl acetate (PVAM) resins, polyamine (PA) resins, polyvinylamine (PVAm), and polyvinylpyrrolidone (PVP) resins.

The term “CLSM” refers to confocal laser scanning microscopy.

In the event that the above definitions or a description stated elsewhere in this application is inconsistent with a meaning (explicit or implicit) which is commonly used, in a dictionary, or stated in a source incorporated by reference into this application, the application and the claim terms in particular are understood to be construed according to the definition or description in this application, and not according to the common definition, dictionary definition, or the definition that was incorporated by reference. In light of the above, in the event that a term can only be understood if it is construed by a dictionary, if the term is defined by the Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition, (2005), (Published by Wiley, John & Sons, Inc.) this definition shall control how the term is to be defined in the claims.

One aspect of the invention generally relates to novel compositions comprising quaternized long-chain imidazolines and long chain fatty acids and release aid compositions comprising said compositions disclosed herein. The compositions disclosed herein used in release aid compositions effectively reduce adhesion between a tissue web and surfaces found in a tissue making process. By acting as more efficient anchor molecules, this composition promotes better spreading and retention of lubricant oil, a non-polar hydrophobe, across the fabric surface, particularly on sanded areas. Given the limited affinity of PET, a common fabric/felt material, to lubricant oil due to a mismatch in polar and non-polar hydrophobic properties, an effective anchor molecule that has high affinity to both fabric and lubricant oil is essential for a release aid formulation for improved release performance. While quaternized long-chain imidazolines and long-chain fatty acids have been used individually as anchor molecules in existing release formulations, their combined use has not been previously explored. The disclosed composition, among other polar hydrophobes studied, demonstrates superior anchoring properties for PET fabrics. Furthermore, when used in conjunction with a wetting agent, the release performance of this composition is further enhanced due to accelerated spreading on the fabric surface.

To apply the composition to the TAD fabric surface, it is emulsified as an aqueous based emulsion with a emulsion particle size up to 5 micrometers. The emulsion is then applied to the surface of the TAD fabric, and the surface of TAD fabric is placed in contact with the tissue web. The tissue web continues through the tissue making process to produce a finished tissue product.

As used herein, the term “Formula I” consists of Formula (I-A), Formula (I-B), or a combination in ratio of Formula and any (I-A) Formula (I-B):

One aspect of the invention pertains to a composition comprising one or more quaternized long-chain imidazolines of Formula I and one or more long chain fatty acids of Formula (II):

Without wishing to be limited by a particular theory, imidazoline of Formulas I-A and/or I-B in the presence of fatty acid of Formula II compositions disclosed herein may be presented as an alternative chemical form based on intermolecular interactions as shown below as III and IV, respectively:

In some embodiments, R¹ is linear or branched C₁₂-C₂₆ alkyl, or alkenyl groups, or their mixture. Further, R² is linear or branched C₁₁-C₂₅ alkyl, or alkenyl groups, or their mixture. In another embodiment, R³ is a C₁ to C₃ alkyl or benzyl group, and X is a halide or sulfate group. In other embodiments, R⁴ is linear or branched C₁₁-C₂₅ alkyl, or alkenyl groups, or their mixture. The quaternized long-chain imidazolines include but are not limited to 2-(C₁₇ and C₁₇-unsaturated alkyl)-1-[2-(C₁₈ and C₁₈-unsaturated amido)ethyl]-4,5-dihydro-1-methyl, methyl sulfates, 9-octadecenoic acid (Z)-, reaction products with diethylenetriamine, cyclized, diethyl sulfates, 1H-Imidazolium, 1-ethyl-2-(8Z)-8-heptadecen-1-yl-4,5-dihydro-1-[2-[[(9Z)-1-oxo-9-octadecen-1-yl]amino]ethyl]-ethyl sulfate, 1H-Imidazole-1-ethanol, 4,5-dihydro-, 2-nortall-oil alkyl derivatives, and quaternized 1-(2-hydroxyethyl)-2-soya alkylimidazoline chloride. The long-chain fatty acids include, but are not limited to lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, oleic acid, linoleic acid, arachidonic acid, eicosatetraenoic acid, docosahexaenoic acid, erucic acid, and lignoceric acid.

In some embodiments, R¹ is linear or branched alkyl, or alkenyl groups, or their mixture derived from long-chain C₁₆-C₁₈ fatty acids. Further, R² may be C₁₅-C₁₇ alkyl, or alkenyl groups, or their mixture. In another embodiment, R³ is a methyl and X is a sulfate. In some embodiments, R⁴ is long-chain C₁₆-C₁₈ fatty acids.

In another embodiments, the present disclosure provides a release aid composition, said composition comprising quaternized long-chain imidazolines (I) and long chain fatty acids (II), one or more emulsifier agents, one or more lubricant oils, and optionally one or more wetting agents.

In some embodiments, said emulsifier agents comprise anionic emulsifier agents, cationic emulsifier agents, non-ionic emulsifier agents, amphoteric emulsifier agents, natural emulsifier agents, polymeric emulsifier agents, fatty acid derivative emulsifier agents, or phospholipid ester emulsifier agents, and combinations thereof.

The anionic emulsifier agent may be chosen from fatty acid salts derived from natural sources like sodium lauryl sulfate and sodium stearoyl lactylate; from synthetic sulfates and sulfonates like sodium dodecylbenzenesulfonate and linear alkylbenzene sulfonates; from carboxylates like acylglutamates, and from phosphates like sodium lauryl phosphate.

The cationic emulsifier agent may be chosen from quaternary ammonium compounds including cetyltrimethylammonium bromide, distearyldimonium chloride, cetrimonium chloride, and behentrimonium chloride; amidoamine quaternaries including TEGO® Care CE 40 and VARISOFT® PATC.

The non-ionic emulsifier agent may be chosen from polysorbates, fatty alcohol ethoxylates, polyoxyethylene fatty acid esters, sugar esters, glyceryl esters, and sorbitan esters. The amphoteric emulsifier agent may be chosen from betaines like cocamidopropyl betaine and lauramidopropyl betaine, sultaines, and imdazolines.

The natural emulsifier agent may be chosen from lecithin, beeswax, and acacia gum. The polymeric emulsifier agent may be chosen from poloxamers, styrene-maleic acid anhydride copolymers, hydrophilically modified starches, cellulose derivatives, shellac, and soy protein isolates. The fatty acid derivative may be chosen from monoglycerides, diglycerides and sorbitan esters.

Lubricant oils may be mineral oils, vegetable oils, synthetic oils, or biodiesels, or combinations thereof. In some embodiments, said mineral oil may be gear oil, dryer oil, turbine oil, spindle oil, liquid paraffin, isoparaffin, or naphthene. Examples of vegetable oils that may be used include soybean oil, canola oil, sunflower oil, peanut oil, coconut oil, olive oil, palm oil, linseed oil, castor oil, tung oil, tall oil, rapeseed oil, and corn oil. Examples of synthetic oils that may be used include polyalphaolefins, synthetic ester oil, polyalkylene glycol, and synthetic fatty acids.

Turning to the wetting agents, examples of wetting agents that may be used include anionic wetting agents, cationic wetting agents, non-ionic wetting agents, amphoteric wetting agents, or natural wetting agents. In some embodiments, said anionic wetting agents may be sulfonates or sulfates. In other embodiments, said cationic wetting agents are chosen from quaternary ammonium compounds and amine salts. In further embodiments, said non-ionic wetting agents are chosen from ethoxylated alcohol and polyol esters. In yet further embodiments, said amphoteric wetting agents are chosen from betaines and amino acids. In other embodiments, said natural wetting agents are chosen from saponins, Lecithins, and Gemini surfactants.

Another embodiment of the present disclosure pertains to the release aid composition, wherein said composition forms emulsion with an emulsion particle size distribution of about 0.5 to about 5 microns, or about 0.8 to about 3 microns, or about 1 to 2 microns.

The release aid composition may include a composition disclosed herein in a range of about 1% to about 40%, by weight, or in the range of about 1% to about 10%, by weight, or in the range of about 3% to about 5%, by weight.

In some embodiment, the invention pertains to a release aid composition comprising one or more emulsifier surfactants, one or more lubricant oils, and Yankee adhesives. Examples of Yankee adhesives that may be used include PAE resins, PVOH resins, PEI resins, PVAm resins, PA resins, and PVP resins.

Another embodiment of the invention pertains to a method for reducing paper adhesion to surfaces in a papermaking process, wherein said surface is a fabric surface. Said surface may also be a TAD fabric surface, a structured fabric surface, a papermaking belt, Yankee dryer surface, a textured or structured belt, or combinations thereof. In some embodiments, said surface is a TAD fabric surface.

A further embodiment of the invention pertains to a method for reducing paper adhesion between a wet tissue web and the surface of a dryer in a papermaking process, wherein said surface is a Yankee dryer.

A further embodiment of the invention pertains to a method for reducing paper adhesion between a wet tissue web and a surface in a papermaking process, comprising contacting a composition disclosed, wherein paper adhesion between the wet tissue web and said surface is reduced by about 20% to about 95%.

In some embodiments, prior to said contacting, said release aid composition is emulsified into an emulsion.

Another aspect of the invention pertains to a method of making a release aid composition comprising combining, the composition as previously described, one or more emulsifier agent, and optionally, the one or more lubricant oils into a feed line.

In some embodiments, Formula I and Formula II are combined into said feed occurs simultaneously. In other embodiments, Formula I and Formula II are combined into said feed separately.

When Formula I and Formula II are combined into said fed separately, Formula I, one or more emulsifier agents, and optionally, one or more lubricant oils may be combined, followed by combining Formula II, one or more emulsifier agents, and optionally, one or more lubricant oils. After the composition as previously described, the one or more emulsifier agent, and

optionally, the one or more lubricant oils are combined into said feed, the release aid may then be emulsified into an emulsion. In some embodiments, the emulsifying takes places along any point of said feed.

EMBODIMENTS

A non-limiting list of embodiments is provided below:

1. A composition comprising one or more quaternized long-chain imidazolines of Formula (I-A) and/or (I-B) and one or more long chain fatty acids of Formula (II):

wherein

• • R¹ is linear or branched C₁₂-C₂₆ alkyl, or alkenyl groups or their mixture.
  • R² is linear or branched C₁₁-C₂₅ alkyl, or alkenyl groups or their mixture.
  • R³ is a C₁ to C₃ alkyl or benzyl group, and X is a halide or sulfate.
  • R⁴ is linear or branched C₁₁-C₂₅ alky, or alkenyl groups or their mixture.

2. The composition of embodiment 1, wherein Formula I and Formula II are present in an alternative chemical form based on intermolecular interactions shown below as III and IV:

wherein

• • R¹ is linear or branched C₁₂-C₂₆ alkyl, or alkenyl groups or their mixture.
  • R² is linear or branched C₁₁-C₂₅ alkyl, or alkenyl groups or their mixture.
  • R³ is a C₁ to C₃ alkyl or benzyl group, and X is a halide or sulfate.
  • R⁴ is linear or branched C₁₁-C₂₅ alky, or alkenyl groups or their mixture.

3. The composition of embodiment 1, wherein R¹ is linear or branched C₁₂-C₂₀ alky, or alkenyl groups, or their mixture, R² is linear or branched C₁₁-C₁₉ alky, or alkenyl groups, or their mixture, R³ is a methyl or ethyl group, and X is a halide or sulfate.

4. The composition of embodiment 1, wherein R⁴ is a linear or branched C₁₁ or C₂₁ alkyl, or alkenyl group, or their mixture.

5. The composition of embodiment 1, wherein R¹ is linear or branched C₁₆-C₁₈ alkyl, or alkenyl groups, or their mixture, R² is linear or branched C₁₅-C₁₇ alkyl, or alkenyl groups, or their mixture, R³ is a methyl group, and X is a sulfate group.

6. The composition of embodiment 1, wherein R⁴ is a linear or branched C₁₅-C₁₇ alkyl, or alkenyl group, or their mixture.

7. The composition of embodiment 1, wherein said long-chain fatty acid (II) is chosen from lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, oleic acid, linoleic acid, arachidonic acid, eicosatetraenoic acid, docosahexaenoic acid, erucic acid, and lignoceric acid.

8. The composition of embodiment 1, wherein said quaternized long-chain imidazoline (I) is chosen from 2-(C₁₇ and C₁₇-unsaturated alkyl)-1-[2-(C₁₈ and C₁₈-unsaturated amido)ethyl]-4,5-dihydro-1-methyl, methyl sulfates, 9-octadecenoic acid (Z)-, reaction products with diethylenetriamine, cyclized, diethyl sulfates, and 1H-Imidazolium, 1-ethyl-2-(8Z)-8-heptadecen-1-yl-4,5-dihydro-1-[2-[[(9Z)-1-oxo-9-octadecen-1-yl]amino]ethyl]-ethyl sulfate.

9. The composition of any of the preceding embodiments, wherein the weight ratio of quaternized long-chain imidazoline to long chain fatty acid is in the range of about 10:1 to about 1:10.

10. The composition of any of the preceding embodiments, wherein the weight ratio of quaternized long-chain imidazoline to long chain fatty acid is about 1:1.

11. A release aid composition, said composition comprising:

• • the composition of any of the preceding embodiments;
  • one or more emulsifier agents; and
  • optionally, one or more lubricant oils.

12. The release aid composition of embodiment 11, wherein the one or more emulsifier agents comprise anionic emulsifier agents, cationic emulsifier agents, non-ionic emulsifier agents, amphoteric emulsifier agents, natural emulsifier agents, polymeric emulsifier agents, fatty acid derivative emulsifier agents, phospholipid ester emulsifier agents, and combinations thereof.

13. The release aid composition of any of the preceding embodiments, wherein the anionic emulsifier agent comprises naturally derived fatty acid salts, synthetic sulfates and sulfones, carboxylates, phosphates, and combinations thereof.

14. The release aid composition of any of the preceding embodiments, wherein said naturally derived fatty acid salts are chosen from sodium lauryl sulfate and sodium stearoyl lactylate.

15. The release aid composition of any of the preceding embodiments, wherein synthetic sulfates and sulfones are chosen from sodium dodecylbenzenesulfonate and linear alkylbenzene sulfonates.

16. The release aid composition of any of the preceding embodiments, wherein phospholipid emulsifier agents are chosen from lecithin, phosphatidylcholine, phosphatidylserine, and phosphatidylinositol.

17. The release aid composition of any of the preceding embodiments, wherein said carboxylates are acylglutamates.

18. The release aid composition of any of the preceding embodiments, wherein said phosphate is sodium lauryl phosphate.

19. The release aid composition of any of the preceding embodiments, wherein the cationic emulsifier agent comprises quaternary ammonium compounds, amidoamine quaternaries, and combinations thereof.

20. The release aid composition of any of the preceding embodiments, wherein said quaternary ammonium compounds are chosen from cetyltrimethylammonium bromide, distearyldimonium chloride, cetrimonium chloride, behentrimonium chloride, and combinations thereof.

21. The release aid composition of any of the preceding embodiments, wherein said amidoamine quaternaries are chosen from TEGO® Care CE 40, VARISOFT® PATC, and combinations thereof.

22. The release aid composition of any of the preceding embodiments, wherein the non-ionic emulsifier agent is chosen from polysorbates, fatty alcohol ethoxylates, polyoxyethylene fatty acid esters, sugar esters, glyceryl esters, sorbitan esters, and combinations thereof.

23. The release aid composition of any of the preceding embodiments, wherein the amphoteric emulsifier agent comprises betaines, sultaines, imdazolines, and combinations thereof.

24. The release aid composition of any of the preceding embodiments, wherein said betaines are cocamidopropyl betaine, lauramidopropyl betaine, and combinations thereof.

25. The release aid composition of any of the preceding embodiments, wherein the natural emulsifier agent is chosen from lecithin, beeswax, acacia gum, and combinations thereof.

26. The release aid composition of any of the preceding embodiments, wherein the polymeric emulsifier agent is chosen from polyvinyl alcohol, poloxamers, styrene-maleic acid anhydride copolymers, hydrophilically modified starches, cellulose derivatives, shellac, soy protein isolates, and combinations thereof.

27. The release aid composition of any of the preceding embodiments, wherein the fatty acid derivative is chosen from monoglycerides, diglycerides, sorbitan esters, and combinations thereof.

28. The release aid composition of any of the preceding embodiments, wherein the one or more lubricant oils are chosen from mineral oils, vegetable oils, synthetic oils, and biodiesels, or combinations thereof.

29. The release aid composition of any of the preceding embodiments, wherein the mineral oils are chosen from gear oil, dryer oil, turbine oil, spindle oil, liquid paraffin, isoparaffin, and naphthene.

30. The release aid composition of any of the preceding embodiments, wherein the vegetable oils are chosen from soybean oil, canola oil, sunflower oil, peanut oil, coconut oil, olive oil, palm oil, linseed oil, castor oil, tung oil, tall oil, rapeseed oil, and corn oil.

31. The release aid composition of any of the preceding embodiments, wherein the synthetic oils are chosen from polyalphaolefin, synthetic ester oil, polyalkylene glycol, and synthetic fatty acids.

32. The release aid composition of any of the preceding embodiments, further comprising one or more wetting agents.

33. The release aid composition of any of the preceding embodiments, wherein the one or more wetting agents may be anionic wetting agents, cationic wetting agents, non-ionic wetting agents, amphoteric wetting agents, or natural wetting agents.

34. The release aid composition of any of the preceding embodiments, wherein the anionic wetting agents are chosen from sulfonates and sulfates.

35. The release aid composition of any of the preceding embodiments, wherein the cationic wetting agents are chosen from quaternary ammonium compounds and amine salts.

36. The release aid composition of any of the preceding embodiments, wherein the non-ionic wetting agents are chosen from ethoxylated alcohol and polyol esters.

37. The release aid composition of any of the preceding embodiments, wherein the amphoteric wetting agents are chosen from betaines and amino acids.

38. The release aid composition of any of the preceding embodiments, wherein the natural wetting agents are chosen from saponins, Lecithins, and Gemini surfactants.

39. The release aid composition of any of the preceding embodiments, wherein said composition forms emulsion with an emulsion particle size distribution of about 0.5 to about 5 microns.

40. The release aid composition of any of the preceding embodiments, wherein said composition is present in the range of about 1% to about 40% by weight.

41. The release aid composition of any of the preceding embodiments, wherein said composition is present in the range of about 1% to about 10% by weight.

42. The release aid composition of any of the preceding embodiments, wherein said composition is present in the range of about 3% to about 5% by weight.

43. The release aid composition of any of the preceding embodiments, wherein said composition further comprises one or more Yankee adhesives.

44. The release aid composition of any of the preceding embodiments, wherein said one or more Yankee adhesives comprises PAE resins, PVOH resins, PEI resins, PVA resins, PA resins, and PVP resins.

45. A method for reducing paper adhesion to surfaces in a papermaking process, said method comprising contacting said surface with a release aid composition of any of the preceding embodiments.

46. The method of any of the preceding embodiments, wherein, prior to said contacting, said release aid composition is emulsified to obtain an emulsion.

47. The method of any of the preceding embodiments, wherein said surface is a fabric surface.

48. The method of any of the preceding embodiments, wherein the surface is a TAD fabric surface, a structured fabric surface, a papermaking belt, Yankee dryer surface, a textured or structured belt or combinations thereof.

49. The method of any of the preceding embodiments, wherein the surface is a TAD fabric surface.

50. The method of any of the preceding embodiments, wherein, after said contacting of said release aid, paper adhesion between the wet tissue web and said surface is reduced by about 20% to about 95%.

51. A method of making a release aid composition of any of the preceding claims, said method comprising combining, the composition of any of the preceding embodiments, the one or more emulsifier agent, and optionally, the one or more lubricant oils into a feed line.

52. The method of embodiment 51, wherein said composition of any of the preceding embodiments, said emulsifier agent, and optionally, said lubricant oil are co-fed into said feed line (e.g., simultaneously or separately) and combined to obtain said release aid composition.

53. The method of any of the preceding embodiments, wherein said method comprises the step of forming an emulsion when said composition of any of the preceding embodiments, said emulsifier agent, and optionally, said lubricant oil are combined in said feed line.

54. The method of any of the preceding embodiments, wherein said composition of any of the preceding embodiments, said emulsifier agent, and optionally, said lubricant oil are co-fed along any point of said feed line.

EXAMPLES

The fabric release formulations, methods of producing, and application are provided herein. The release formulations are oil/surfactants blends, which are made by mechanically mixing each composition to generate a homogeneous blend. The application of the release formulas is through emulsified form which can be done either through batch or in-line emulsification process. The emulsion is then diluted by water and applied onto a fabric surface to provide the release function to separate the wet paper web from the fabric surface more easily and efficiently during the tissue manufacturing process.

To evaluate the effectiveness of fabric release aids in reducing the adhesion between the tissue web and the TAD fabric, tack measurements were conducted using an Anton Parr MCR302 modular compact rheometer in parallel plate geometry at 25° C. Wet lab handsheets with a consistency of 15-20% and a basis weight of 80 g/m² were gently pressed onto a TAD fabric to ensure good contact. The samples were then hot-air-dried to a target consistency of 35-45%. To facilitate tack measurement, the TAD fabric with the adhered handsheet was mounted between double-sided tape on the bottom and top plates of the rheometer. The top plate was then lowered onto the handsheet, applying a constant normal force of 1 N for 20 seconds. Subsequently, the top plate was pulled up at a speed of 5,000 μm/s with a separation gap of 50 mm. The maximum pull-up force was recorded and compared between samples with and without the application of TAD fabric release aid. The release aid was applied as an emulsion at a dosage of 80 mg/m² to the TAD fabric.

The foregoing may be better understood by reference to the following examples, which are presented for purposes of illustration and are not intended to limit the scope of the invention.

Example 1

Four TAD fabric release aid formulations were compared for their effectiveness in reducing adhesion between a tissue web and a TAD fabric surface. The release aid formulations were made by combining a lubricant oil (composition 1), a mixture of emulsifiers (compositions 3 and 4), and the oil anchor molecule (composition 2), and is summarized in Table 1. Formulas A to D were made by combining mineral white oil #150 with the mixture of Tween 81 and Span 80 as well as four different oil anchor molecules at the same weight ratio.

TABLE 1
Release aid formulation.

Composition 1

Composition 2

Composition 3

Composition 4

Sample ID	Chemistry	wt %	Chemistry	wt %	Chemistry	wt %	Chemistry	wt %

Formula A	Mineral white oil, #150	84.8	AM_1	4.8	Tween 81	9.6	Span 80	0.8
Formula B	Mineral white oil, #150	84.8	AM_2	4.8	Tween 81	9.6	Span 80	0.8
Formula C	Mineral white oil, #150	84.8	AM_3	4.8	Tween 81	9.6	Span 80	0.8
Formula D	Mineral white oil, #150	84.8	AM_2 + AM_3	4.8	Tween 81	9.6	Span 80	0.8

The composition 2 which was tested involved the following chemistries: isopropyl nitrate, long chain quaternized imidazoline, tall oil fatty acid, and the mixture of quaternized long-chain imidazoline and long-chain fatty acid at a 1:1 weight ratio. This information is summarized in Table 2.

TABLE 2
Chemistry and commercial names of Composition 2.

Composition 2	Commercial Name	Chemistry
AM_1	TEGP XP 11077	Isopropyl myristate
AM_2	Arosurf PA 842	Long Chain quaternized
		imidazoline
AM_3	Pinchem 100	Tall oil fatty acid
AM_2 +	Arosurf PA 842 +	Long-chain fatty acid + long-chain
AM_3	Pinchem 100	quaternized imidazoline

As shown in FIG. 1, among four different fabric release formulas, formula D which contains the mixture of quaternized long chain imidazolines and long-chain fatty acids (AM_2+AM_3) provides the most adhesion reduction comparing to formula A, B, and C under otherwise identical conditions.

Example 2

Wetting agents were then added to the release aid formulations to evaluate differences in adhesion reduction. Two wetting agents marked as composition 5, WA_1 and WA-2, were tested versus a control which had no wetting agent. These wetting agents represent two chemistry families: ethoxylated fatty alcohol (WA_1) and ethoxylated fatty acid (WA_2), respectively. The commercial names of these wetting agents are Tergitol 15-S-7 for WA_1 and Tween-85 for WA_2, as shown in Table 3. For this series evaluation, the rest of the compositions in the formulas remains identical. Formulation details are summarized in Table 4.

TABLE 3
Chemistry and commercial names of two wetting agents.

Wetting Agent	Commercial Name	Chemistry
WA_1	Tergitol 15-S-7	Ethoxylated fatty alcohol
WA_2	Tween-85	Ethoxylated fatty acid

TABLE 4
Release aid formulations with different wetting agents

Composition 1

Composition 2

Composition 3

Composition 4

Composition 5

Formula ID	Chemistry	wt %	Chemistry	wt %	Chemistry	wt %	Chemistry	wt %	Chemistry	wt %

Formula E	Mineral white oil, #150	88	AM_2 + AM_3	5.4	Tween 81	5.3	Span 80	1.3	None	0
Formula F	Mineral white oil, #150	88	AM_2 + AM_3	5.4	Tween 81	4.9	Span 80	1.3	WA-1	0.4
Formula G	Mineral white oil, #150	88	AM_2 + AM_3	5.4	Tween 81	4.9	Span 80	1.3	WA-2	0.4

FIG. 2 shows that fabric release formulas F and G containing a wetting agent provided additional release or adhesion reduction in comparison with formula E that did not contain a wetting agent. In this case, WA_2 provided higher adhesion reduction than WA 1.

Example 3

The spatial distribution of fabric release aid on a PET TAD fabric surface was studied by Nile Red, a hydrophobic florescence probe. Nile Red preferentially binds to hydrophobic components, such as lubricant oil, the major component in the release aid. After treating the TAD fabric with 100 ppm Nile Red dye and exciting the treated fabric with a 488 nm laser, strong fluorescence observed with a 495 nm long pass filter from the areas of the fabric indicates the presence of the release aid. By using CLSM, both fluorescence images and transmission images were collected simultaneously. FIG. 3 shows the overlaid images of the fluorescence image shown in green and the transmission image shown in grey. The brighter the green color, the stronger the fluorescence signal. The left image is for a new TAD fabric sample with no fabric release treatment and the right image is for a TAD fabric sample treated with a fabric release aid. The sanded area for the fabric release treated sample exhibited strong fluorescence, suggesting that the fabric release aid was preferentially distributed over sanded areas for the treated sample.

This Nile Red method can also be used for comparing retention efficiency of different release aid formulations. FIG. 4 shows the overlaid images of the fluorescence and transmission images for three TAD fabric samples treated with formula H, formula I and formula J, respectively. When the TAD fabric was treated with 0.5 wt % emulsion of each release formula under the same condition, more release aid was observed to stay on the sanded fabric surface with the formula containing the mixture of quaternized long-chain imidazolines and long-chain fatty acids (Formula I) than long-chain fatty acid (Formula H) and this is further improved when a wetting agent was used (Formula J), evidenced by the brighter color of the fluorescence signal. Such an improved retention impact leads to the improved adhesion reduction as shown in Table 5.

TABLE 5
TAD fabric release formula used in the CLSM
imaging test and their performance in reducing
adhesion between paper sheets and fabrics.

Formula ID	Composition 2	Composition 5	Adhesion Reduction %
Formula H	AM_3	None	34 ± 1
Formula I	AM_2 + AM_3	None	59 ± 25
Formula J	AM_2 + AM_3	WA_2	66 ± 22

All references, including publications, patent applications, and patents, cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.

Embodiments of the present disclosure are described herein, including the best mode known to the inventors for carrying out the invention. Variations of these embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

While this invention may be embodied in many different forms, there are described in detail herein specific preferred embodiments of the invention. The present disclosure is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated. All patents, patent applications, scientific papers, and any other referenced materials mentioned herein are incorporated by reference in their entirety. Furthermore, the invention encompasses any possible combination of some, or all the various embodiments mentioned herein, described herein and/or incorporated herein. In addition, the invention encompasses any possible combination that also specifically excludes any one or some of the various embodiments mentioned herein, described herein and/or incorporated herein.

Any information in any material (e.g., a United States patent, United States patent application, book, article, etc.) that has been incorporated by reference herein, is only incorporated by reference to the extent that no conflict exists between such information and the other statements and drawings set forth herein. In the event of such conflict, including a conflict that would render invalid any claim herein, then any such conflicting information in such incorporated by reference material is specifically not incorporated by reference herein.

The above disclosure is intended to be illustrative and not exhaustive. This description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the claims where the term “comprising” means “including, but not limited to”. Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims.

All ranges and parameters disclosed herein are understood to encompass any and all subranges subsumed therein, and every number between the endpoints. For example, a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more, (e.g. 1 to 6.1), and ending with a maximum value of 10 or less, (e.g. 2.3 to 9.4, 3 to 8, 4 to 7), and finally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10 contained within the range. All percentages and proportions herein are by weight unless otherwise specified.

The recitation of any numerical range by endpoints is meant to include the endpoints of the range, all numbers within the range, and any narrower range within the stated range (e.g. 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.8, 4, and 5). Unless otherwise indicated, all numbers expressing quantities or ingredients, measurement of properties and so forth used in the specification and embodiments are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached listing of embodiments can vary depending upon the desired properties sought to be obtained by those skilled in the art utilizing the teachings of the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claimed embodiments, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

This completes the description of the preferred and alternate embodiments of the invention. Those skilled in the art may recognize other equivalents to the specific embodiment described herein which equivalents are intended to be encompassed by the claims attached hereto.