Polymer deposition and attachment process for textile

Abstract

To provide a system and method for applying a polymer surface treatment to carpets and other textiles.SOLUTION: A system and method include the use of a surfactant-free emulsion of a surface treatment polymer. The use of the surfactant-free emulsion of the surface treatment polymer reduces or eliminates the need to use pH adjusting agents and / or ionic salt solutions when applying surface treatment polymers to carpets or other textiles. By reducing the need to remove surfactants, emulsifiers, pH adjusting agents, and / or salts, the total volume of water used in treating carpets or other textiles is reduced.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 138,497, filed January 17, 2021, which is incorporated herein by reference in its entirety.

[0002] This disclosure relates to the application of polymeric surface treatments to carpets and other textiles, and more particularly to the use of surfactant-free emulsion polymeric products to improve the stain resistance and / or liquid repellency of textiles. [Background technology]

[0003] In the carpet and textile industry, stain resistance and liquid repellency are highly desirable properties for carpets and other textiles. As the industry moves away from the use of fluorochemicals, the challenge is to provide improved performance properties at low cost. A typical method for surface treatment of carpets and other textiles involves the application of a surfactant-stabilized polymeric emulsion product to the carpet or other textile during manufacture. While surfactant-stabilized emulsion particles are kept suspended in a continuous phase by various surfactants, the disclosed polymeric surface treatment agents are stabilized by ionic moieties inherent in the polymer that keep them suspended in the continuous phase.

[0004] Most repellent chemicals for carpet applications are surfactant-stabilized emulsions. Surfactant-based emulsion chemicals require surfactants and emulsifiers to keep the emulsion stable. Acidic pH and salt solutions are used to destabilize the surfactant-stabilized emulsion and release the polymer onto the carpet fibers.

[0005] Conventional surfactant-stabilized emulsion surface treatments applied via the standard exhaust method typically require a low pH (approximately pH 2-3) and the use of salt solutions such as magnesium sulfate. A rinsing step may also be required to remove remaining surfactants, emulsifiers, salts, and / or acids before drying. These additional process requirements can pose environmental and safety concerns. Some embodiments of the disclosed surface treatments can be applied via the exhaust method without the need for pH adjustment, salt solutions, or rinsing steps. In some embodiments, the disclosed invention achieves superior repellency performance over other non-fluorochemical options. Summary of the Invention

[0006] FIELD OF THE DISCLOSURE This disclosure relates generally to the application of surfactant-free emulsions of polymeric surface treatments to carpets and other textiles.

[0007] Some disclosed embodiments relate to a method of treating a carpet, comprising applying a surfactant-free emulsion of a surface-treating polymer to the carpet, wherein the surface-treating polymer is formed by solution polymerization, and drying the carpet after applying the surfactant-free emulsion of the surface-treating polymer to the carpet. In some embodiments, the surface-treating polymer comprises (a) repeating units formed from an acrylic monomer having a hydrocarbon group containing 7 to 40 carbon atoms, (b) repeating units formed from an acrylic monomer having a hydrophilic group, and (c) repeating units formed from a monomer having an ion-donating group. In some embodiments, the step of drying the carpet is performed without rinsing the carpet after applying the surfactant-free emulsion to the carpet.

[0008] Some disclosed embodiments relate to methods and process steps for treating carpet that can be used in-line as part of a continuous or semi-continuous manufacturing process.

[0009] The foregoing presents a simplified summary in order to provide a basic understanding of some aspects of the claimed subject matter. This summary is not an extensive overview. It is not intended to identify key or critical elements or to delineate the scope of the claimed subject matter. Its sole purpose is to present some concepts in a simplified form as a prelude to the more detailed description that is presented later. Preferred embodiments of the present disclosure are as follows: Embodiment 1. A method for treating carpet, comprising: applying a surfactant-free emulsion of a surface-treating polymer to the carpet, the surface-treating polymer being formed by solution polymerization; applying a surfactant-free emulsion of the surface treatment polymer to the carpet and then drying the carpet; A method comprising: Embodiment 2. A method for treating a carpet according to embodiment 1, wherein the step of drying the carpet is carried out by heating the carpet. Embodiment 3. A method of treating carpet according to embodiment 2, wherein the carpet is heated to a temperature of at least 60°C or above 93°C (200°F) for a period of from 1 second to 500 minutes. Embodiment 4. The method of treating a carpet according to embodiment 1, wherein the step of drying the carpet is carried out without rinsing the carpet after applying the surfactant-free emulsion to the carpet. Embodiment 5. A method of treating carpet according to embodiment 1, wherein the surfactant-free emulsion is applied to the carpet without the use of a salt solution. Embodiment 6. A method of treating carpet according to embodiment 1, wherein the surfactant-free emulsion is applied to the carpet without the use of a magnesium salt solution. Embodiment 7. A method of treating a carpet according to embodiment 1, wherein the carpet is dried before applying a solution having a conductivity greater than 0.1 mS / cm to the carpet. Embodiment 8. A method of treating carpet according to embodiment 1, wherein the surfactant-free emulsion is applied to the carpet without the use of a separate acidic solution. Embodiment 9. A method of treating carpet according to embodiment 1, wherein the surfactant-free emulsion has a pH greater than 4.0 when applied to the carpet. Embodiment 10. The method of treating carpet according to embodiment 1, wherein the surfactant-free emulsion has a pH between 4.5 and 10.0 when applied to the carpet. Embodiment 11. A method of treating a carpet according to embodiment 1, wherein the carpet is dried before applying a separate pH adjuster to the carpet. Embodiment 12. The method of treating carpet according to embodiment 1, wherein the surfactant-free emulsion is substantially free of emulsifiers. Embodiment 13. A method for treating a carpet according to embodiment 1, wherein the surface treatment polymer does not contain fluorine. Embodiment 14. A method for treating a carpet according to embodiment 1, wherein the surface treatment polymer comprises (a) repeating units formed from an acrylic monomer having a hydrocarbon group containing 7 to 40 carbon atoms, (b) repeating units formed from an acrylic monomer having a hydrophilic group, and (c) repeating units formed from a monomer having an ion-donating group. Embodiment 15. A method for treating carpet according to embodiment 14, wherein the ion-donating groups are cation-donating groups. Embodiment 16. A method for treating carpet according to embodiment 15, wherein the cation donating group is an amino group. Embodiment 17. A method (or system) for treating textiles, comprising: immersing the textile in a treatment bath, the treatment bath containing a surfactant-free emulsion of a surface treatment polymer, the surface treatment polymer containing (a) repeating units formed from an acrylic monomer having a hydrocarbon group, (b) repeating units formed from an acrylic monomer having a hydrophilic group, and (c) repeating units formed from a monomer having a cation donating group; After immersing the textile in the treatment bath, without rinsing the textile, heating the textile to reduce its moisture content; A method comprising: Embodiment 18. The method for treating textiles according to embodiment 17, wherein the treatment bath is substantially free of emulsifiers. Embodiment 19. The method of treating a textile according to embodiment 17, wherein the textile is a continuous or semi-continuous web of carpet. Embodiment 20. The method of treating a textile according to embodiment 17, wherein the textile is a carpet comprising polyethylene terephthalate (PET) or polytrimethylene terephthalate (PTT) fibers. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 shows a summary of the solution grades used in the modified AATCC Liquid Repellency Test Method 193-2017 discussed herein. DETAILED DESCRIPTION OF THE INVENTION

[0011] The embodiments set forth below represent the information necessary to enable those skilled in the art to practice the present disclosure and illustrate the best mode of practicing the disclosure. Upon reading the following description in light of the accompanying drawings, those skilled in the art will understand the concepts of the present disclosure and will recognize applications of these concepts not specifically addressed herein. It is to be understood that these concepts and applications fall within the scope of the present disclosure and the appended claims.

[0012] Unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by those skilled in the art of the present disclosure. Terms, such as those defined in commonly used dictionaries, should be interpreted to have a meaning consistent with the meaning in the context of this specification, and should not be interpreted in an idealized or overly formal sense unless explicitly defined herein. Well-known functions or configurations may not be described in detail for conciseness or clarity.

[0013] The terms "about" and "approximately" generally refer to an acceptable degree of error or variation in the measured quantity, given the nature or precision of the measurement. Typical and exemplary degrees of error or variation are within 20%, preferably within 10%, and more preferably within 5% of a given value or range of values. Numerical quantities given herein are approximate unless otherwise specified, meaning that the term "about" or "approximately" can be inferred if not explicitly stated. Numerical quantities in the claims are exact unless otherwise specified.

[0014] When a feature or element is referred to as being "on" another feature or element, it is understood that it may be directly on the other feature or element, or that intervening features and / or elements may be present. In contrast, when a feature or element is referred to as being "directly on" another feature or element, there are no intervening features or elements present. When a feature or element is referred to as being "connected," "attached," or "coupled" to another feature or element, it is understood that it may be directly connected, attached, or coupled to the other feature or element, or that intervening features or elements may be present. In contrast, when a feature or element is referred to as being "directly connected," "directly attached," or "directly coupled" to another feature or element, there are no intervening features or elements present. Although described or illustrated with respect to one embodiment, features and elements so described or illustrated may be applicable to other embodiments.

[0015] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise.

[0016] Terms such as "first," "second," and the like are used herein to describe various features or elements, but these features or elements should not be limited by these terms. These terms are merely used to distinguish one feature or element from another. Thus, a first feature or element discussed below may be referred to as a second feature or element, and similarly, a second feature or element discussed below may be referred to as a first feature or element, without departing from the teachings of the present disclosure.

[0017] Terms such as "at least one of A and B" should be understood to mean "A only, B only, or both A and B." The same construction should apply to longer lists (e.g., "at least one of A, B, and C").

[0018] As used herein, chemical formulations containing parentheses may or may not include the term contained within the parentheses. For example, the term "(meth)acrylic" means acrylic or methacrylic. As a second example, "(meth)acrylate" means acrylate or methacrylate.

[0019] The term "consisting essentially of" means that in addition to the recited elements, the claimed thing may also contain other elements (steps, structures, ingredients, components, etc.) that do not adversely affect the operability of the claimed thing for its intended purposes as specified in this disclosure. The term excludes other elements that adversely affect the operability of the claimed thing for its intended purposes as specified in this disclosure, even if such elements may enhance the operability of the claimed thing for some other purpose.

[0020] In some places, reference is made to standard methods, including, but not limited to, measurement methods. It should be understood that such standards are revised from time to time and that, unless expressly stated otherwise, references to such standards in this disclosure should be construed as referring to the most recently published standard as of the filing date.

[0021] This disclosure describes embodiments of methods and systems for treating carpets and other textiles to improve their liquid repellency. Although the disclosed embodiments are described in the context of carpet surface treatment, it will be recognized that the disclosed embodiments may be applied to other textiles, including natural and / or synthetic fiber textiles.

[0022] Conventional carpet surface treatment polymers are formed using emulsion polymerization. Emulsion polymerization typically involves an aqueous continuous phase, one or more emulsifiers, a water-soluble initiator, monomers, and / or chain transfer agents. During emulsion polymerization, the monomers diffuse through the aqueous continuous phase until they come into contact with the emulsifier or groups of emulsifiers in the form of micelles. The hydrophobic monomers are contained within the emulsion until the initiator polymerizes the monomers. The product of emulsion polymerization is generally an emulsion of surfactant-stabilized polymer particles in an aqueous continuous phase.

[0023] Embodiments of the disclosed surface-treated polymers are prepared using solution polymerization. Solution polymerization involves combining one or more monomers in a solvent with an initiator. The monomers react with each other in solution to form a polymeric product that can remain in the solvent or can be precipitated or solidified by solvent removal. The polymeric product can also undergo a solvent exchange process in which the continuous phase solvent is transferred from an organic phase to an aqueous phase.

[0024] The disclosed solution polymerization products are colloidal solutions that convert to surfactant-free emulsions upon cooling. In some embodiments, the disclosed products convert from colloidal solutions to surfactant-free emulsions at temperatures around about 45° C. Unlike emulsion polymerization products that are stabilized in an aqueous continuous phase by surfactants and / or emulsifiers, the disclosed surfactant-free emulsions are stabilized in an aqueous continuous phase by ionic moieties inherent in the polymer once they are converted from a solvent to an aqueous continuous phase.

[0025] In some embodiments, the disclosed surface treatment polymers are free or substantially free of fluorine.

[0026] In some embodiments, the disclosed surfactant-free emulsions are free or substantially free of emulsifiers, preferably in an amount of 0 to 0.01 parts by weight, more preferably 0 to 0.001 (or 0 to 0.0001) parts by weight, and especially 0 parts by weight, based on 1 part by weight of the surface-treating polymer.

[0027] (1) Surface-treated polymer An embodiment of the disclosed surface-treated polymer (1) includes (a) a repeating unit formed from an acrylic monomer having a hydrocarbon group containing 7 to 40 carbon atoms, (b) a repeating unit formed from an acrylic monomer having a hydrophilic group, and, in addition to the monomers (a) and (b), (c) a repeating unit formed from a monomer having an ion-donating group.

[0028] In some embodiments, the surface treatment polymer may include, in addition to the (a), (b), and (c) monomers, (d) repeat units formed from another monomer.

[0029] (a) Acrylic monomer having a long-chain hydrocarbon group The long-chain hydrocarbon group-containing monomer has a hydrocarbon group having 7 to 40 carbon atoms. The long-chain hydrocarbon group is preferably a straight-chain or branched-chain hydrocarbon group having 7 to 40 carbon atoms. The number of carbon atoms in the straight-chain or branched-chain hydrocarbon group may be 10 to 40, 12 to 30, or 14 to 22. The straight-chain or branched-chain hydrocarbon group preferably has 12 to 40, more preferably 12 to 30, particularly preferably 14 to 22, and particularly preferably 16 to 20 (or 16 to 22) carbon atoms, and is preferably a saturated aliphatic hydrocarbon group, especially an alkyl group. The long-chain hydrocarbon group is particularly preferably a stearyl group, an icosyl group, or a behenyl group.

[0030] The long chain hydrocarbon group containing monomer preferably has the formula: CH2=C(-X 1 )-C(=O)-Y 1 (R 1 ) k (In the formula, R 1 are each independently a hydrocarbon group having 7 to 40 carbon atoms, X 1 is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, Y 1 is a group consisting of at least one moiety selected from a divalent to tetravalent hydrocarbon group having one carbon atom, —CH—, —O—, —C(═O)—, —S(═O)—, and —NH—; k is an integer from 1 to 3. It is a monomer of

[0031] X 1 X can be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 1 Examples of X include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 1 is preferably a hydrogen atom, a methyl group or a chlorine atom. 1 is particularly preferably a hydrogen atom for high water repellency and high stain resistance.

[0032] Y 1 is a divalent to tetravalent group. Y 1 is preferably a divalent group. 1 is preferably a hydrocarbon group having one carbon atom, a group containing at least one moiety selected from -CH-, -O-, -C(=O)-, -S(=O)2, and -NH-. Examples of hydrocarbon groups having one carbon atom include -CH2-, -CH=, and -C≡.

[0033] Y 1 Examples are -Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'- R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'- and Y'-R'-Y'-R'- (wherein Y′ is a direct bond, —O—, or —NH—; R' is -(CH2) m - (wherein m is an integer of 1 to 5) or -C6H4- (phenylene group) Examples include:

[0034] Y 1 Specific examples of the alkyl group include -O-, -NH-, -OC(=O)-, -C(=O)-NH-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, and -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m-NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -S(=O)2-NH-, -O-(CH2) m -N HS(=O)2-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, and -NH-(CH2) m -NH-C6H4- (wherein m is an integer of 1 to 5, particularly 2 or 4). Examples include:

[0035] Y 1 is more preferably —O—, —NH—, —O—(CH2) m -OC(=O)-, -O-(CH2) m -NH-C(=O)-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -NH-S(=O)2- or -O-(CH2) m -S(=O)2-NH- (wherein m is an integer of 1 to 5, particularly 2 or 4). is.

[0036] Y 1 is particularly preferably —O—, —NH—, —O—(CH2) m -NH-C(=O)-, -O-(CH2) m-OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -NH-C(=O)-NH-, especially -O-(CH2) m -NH-C(=O)- (wherein m is an integer of 1 to 5, particularly 2 or 4). is.

[0037] R 1 is preferably a straight-chain or branched-chain hydrocarbon group. The hydrocarbon group may particularly be a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 15 to 26, particularly 17 to 22.

[0038] k is an integer of 1 to 3, preferably 1.

[0039] Examples of long chain hydrocarbon group-containing monomers include: Formula (a1): CH2=C(-X 4 )-C(=O)-Y 2 -R 2 (In the formula, R 2 is a hydrocarbon group having 7 to 40 carbon atoms, X 4 is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, Y 2 is -O- or -NH-) Acrylic monomers represented by: Formula (a2): CH2=C(-X 5 )-C(=O)-Y 3 -Z(-Y 4 -R 3 ) n (In the formula, R 3 are each independently a hydrocarbon group having 7 to 40 carbon atoms, X 5is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, Y 3 is -O- or -NH-, Y 4 are each independently a direct bond or a group consisting of at least one moiety selected from -O-, -C(=O)-, -S(=O)2-, and -NH-; Z is a direct bond or a divalent or trivalent group having 1 to 5 carbon atoms; (n is 1 or 2) An acrylic monomer represented by:

[0040] (a1) Acrylic monomer The acrylic monomer (a1) is represented by the formula: CH2=C(-X 4 )-C(=O)-Y 2 -R 2 (In the formula, R 2 is a hydrocarbon group having 7 to 40 carbon atoms, X 4 is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, Y 2 is -O- or -NH-) is a compound of

[0041] The acrylic monomer (a1) is Y 2 a long chain acrylate monomer in which Y is -O-; or 2 is a long-chain acrylamide monomer in which is -NH-.

[0042] R 2 is preferably a straight-chain or branched-chain hydrocarbon group. The hydrocarbon group may particularly be a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 16 to 26, particularly 18 to 22.

[0043] X 4X can be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 4 Examples of X include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 4 is preferably a hydrogen atom, a methyl group or a chlorine atom.

[0044] Specific examples of long-chain acrylic acid ester monomers include lauryl meth(acrylate), stearyl (meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate, stearyl a-chloroacrylate, icosyl a-chloroacrylate, and behenyl a-chloroacrylate.

[0045] Specific examples of long chain acrylamide monomers include lauryl (meth)acrylamide, stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

[0046] In some embodiments, the long chain acrylic ester monomers and / or long chain acrylamide monomers enhance the water repellency imparted by the surface treatment polymer.

[0047] (a2) Acrylic monomer The acrylic monomer (a2) is a compound different from the acrylic monomer (a1). The acrylic monomer (a2) is a (meth)acrylate or (meth)acrylamide having a group consisting of at least one moiety selected from -O-, -C(=O)-, -S(=O)2-, or -NH-.

[0048] The acrylic monomer (a2) is represented by the formula: CH2=C(-X 5 )-C(=O)-Y 3 -Z(-Y 4 -R 3 ) n (In the formula, R 3are each independently a hydrocarbon group having 7 to 40 carbon atoms, X 5 is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom, Y 3 is -O- or -NH-, Y 4 are each independently a direct bond or a group consisting of at least one moiety selected from -O-, -C(=O)-, -S(=O)2-, and -NH-; Z is a direct bond or a divalent or trivalent group having 1 to 5 carbon atoms, and n is 1 or 2. is a compound of

[0049] The acrylic monomer (a2) is Y 3 a long chain acrylate monomer in which Y is -O-; or 3 is a long-chain acrylamide monomer in which is -NH-.

[0050] R 3 is preferably a straight-chain or branched-chain hydrocarbon group. The hydrocarbon group may particularly be a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, especially an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 12 to 30, for example 15 to 26, or 16 to 26, particularly 17 to 22 (or 18 to 24).

[0051] X 5 X can be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a cyano group, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. 5 Examples of X include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, and a cyano group. 5 is preferably a hydrogen atom, a methyl group or a chlorine atom, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom for high water repellency and high soil resistance properties.

[0052] Y 4Examples are -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y'-, -Y'-R'-, -Y'-R'-Y '-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O)-Y'-, -Y'-R'-Y'-C(=O)-Y'-, or -Y'-R'-Y'-R'- (In the formula, each Y' is independently a direct bond, -O-, -NH-, or -S(=O)2-; Each R' is independently -(CH2) m - (wherein m is an integer of 1 to 5), a linear hydrocarbon group of 1 to 5 carbon atoms having an unsaturated bond, a hydrocarbon group of 1 to 5 carbon atoms having a branched structure, or -(CH2) l -C6H4-(CH2) l (wherein each l is independently an integer from 0 to 5, and -C6H4- is a phenylene group). Examples include:

[0053] Y 4 Specific examples include direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -S(=O)2-NH-, - NH-S(=O)2-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C6H4-, -NH-C6H4-, -O-(CH2) m -O-, -NH-(CH2) m -NH-, -O-(CH2) m -NH-, -NH-(CH2) m -O-, -O-(CH2) m -OC(=O)-, -O-(CH2) m -C(=O)-O-, -NH-(CH2) m -OC(=O)-, -NH-(CH2) m -C(=O)-O-, -O-(CH2) m -OC(=O)-NH-, -O-(CH2) m -NH-C(=O)-O-, -O-(CH2) m -C(=O)-NH-, -O-(CH2) m-NH-C(=O)-, -O-(CH2) m -NH-C(=O)-NH-, -O-(CH2) m -O-C6H4-, -NH-(CH2) m -OC(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, and -NH-(CH2) m -NH-C6H4- (wherein m is an integer of 1 to 5, particularly 2 or 4). Examples include:

[0054] Y 4 is more preferably -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S(=O)2-, -S(=O)2-NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, or -O-C6H4- (wherein m is an integer of 1 to 5, particularly 2 or 4).

[0055] Particularly preferably, Y 4 is -NH-C(=O)-, -C(=O)-NH-, -OC(=O)-NH-, -NH-C(=O)-O- or -NH-C(=O)-NH-.

[0056] Z is a direct bond or a divalent or trivalent hydrocarbon group containing 1 to 5 carbon atoms, which may have a linear or branched structure. Preferably, Z has 2 to 4 carbon atoms, particularly 2 carbon atoms. Specific examples of Z include a direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2-, a branched -CH2CH=, a branched -CH2(CH-)CH2-, a branched -CH2CH2CH=, a branched CH2CH2CH2CH2CH=, a branched -CH2CH2(CH-)CH2-, and a branched -CH2CH2CH2CH=. Preferably, Z is not a direct bond, but is a group selected from Y 4 and Z are not simultaneously a direct bond.

[0057] The acrylic monomer (a2) is preferably CH═C(-X 5 )-C(=O)-O-(CH2) m -NH-C(=O)-R 3 , CH2=C(-X 5 )-C(=O)-O-(CH2) m -OC(=O)-NH-R 3 , CH2=C(-X 5 )-C(=O)-O-(CH2) m -NH-C(=O)-OR 3 ,or CH2=C(-X 5 )-C(=O)-O-(CH2) m -NH-C(=O)-NH-R 3 (In the formula, R 3 , X 5 and m is as defined above). The acrylic monomer (a2) is particularly preferably CH2=C(-X 5 )-C(=O)-O-(CH2) m -NH-C(=O)-R 3 (In the formula, R 3 , X 5 and m is as defined above).

[0058] The acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or a hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate, such as lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.

[0059] Alternatively, the acrylic monomer (a2) can be produced by reacting a long-chain alkylamine or long-chain alkylalcohol with a (meth)acrylate having an isocyanate group on the side chain, such as 2-methacryloyloxyethyl isocyanate. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of long-chain alkylalcohols include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

[0060] Specific examples of the acrylic monomer (a2) are as follows: Stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl a-chloroacrylate, behenyl a-chloroacrylate; stearyl (meth)acrylamide, behenyl (meth)acrylamide;

[0061] TIFF2025186545000002.tif21952 TIFF2025186545000003.tif17062 (wherein m is an integer from 1 to 5, and n is an integer from 7 to 40).

[0062] The compound having the above chemical formula is an acrylic compound in which the a-position is a hydrogen atom, and specific examples thereof may be a methacryl compound in which the a-position is a methyl group and an a-chloroacrylic compound in which the a-position is a chlorine atom.

[0063] Typical specific examples of the acrylic monomer (a2) include palmitic acid amidoethyl (meth)acrylate, stearic acid amidoethyl (meth)acrylate (i.e., amidoethyl stearate (meth)acrylate), behenic acid amidoethyl (meth)acrylate, and myristate amidoethyl (meth)acrylate.

[0064] The melting point of the long-chain hydrocarbon group-containing acrylic monomer (a) is preferably at least 10°C, more preferably at least 25°C or at least 40°C.

[0065] The long-chain hydrocarbon group-containing acrylic monomer (a) is preferably X 1 , X 4 and X 5 is an acrylate in which each of the groups is a hydrogen atom.

[0066] The acrylic monomer (a2) particularly preferably has the formula: R 12 -C(=O)-NH-R 13 -OR 11 (In the formula, R 11 is an organic residue having an ethylenically unsaturated polymerizable group, R 12 is a hydrocarbon group having 7 to 40 carbon atoms, R 13 is a hydrocarbon group having 1 to 5 carbon atoms It is an amide group-containing monomer.

[0067] R 11 is an organic residue having an ethylenically unsaturated polymerizable group, and is not limited as long as the group has a carbon-carbon double bond. Specific examples thereof include -C(=O)CR 14 =CH2, -CHR 14 =CH2 and -CH2CHR 14 =CH2(wherein, R 14R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). 11 In addition to the ethylenically unsaturated polymerizable group, R may have any of a variety of organic groups, examples of which include organic groups such as chain hydrocarbons, cyclic hydrocarbons, polyoxyalkylene groups, and polysiloxane groups. For example, these organic groups may be substituted with various substituents. 11 is preferably —C(═O)CR 14 =CH2.

[0068] R 12 R is a hydrocarbon group having 7 to 40 carbon atoms, preferably an alkyl group having 7 to 40 carbon atoms, examples of which include chain hydrocarbons and cyclic hydrocarbons. Among these, chain hydrocarbons are preferred, and linear saturated hydrocarbon groups are particularly preferred. 12 The number of carbon atoms is 7 to 40, preferably 11 to 27, and particularly preferably 15 to 23.

[0069] R 13 R is a hydrocarbon group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms. For example, the hydrocarbon group having 1 to 5 carbon atoms may be linear or branched, and may have an unsaturated bond. The hydrocarbon group is preferably linear. 13 The number of carbon atoms in R is preferably 2 to 4, and particularly preferably 2. 13 is preferably an alkylene group.

[0070] The amide group-containing monomer is R 11 those having a single group as the 11 only compounds with 17 carbon atoms), or R 11 Those having a combination of multiple groups as 11 A compound with 17 carbon atoms and R 12 The compound may be a mixture of compounds having 15 carbon atoms.

[0071] Examples of amide group-containing monomers include carboxylic acid amide alkyl (meth)acrylate.Specific examples of amide group-containing monomers include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristate amide ethyl (meth)acrylate, lauric acid amide ethyl (meth)acrylate, isostearic acid ethyl amide (meth)acrylate, oleic acid ethyl amide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantanecarboxylic acid ethyl amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl (meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether, stearic acid amide ethyl allyl ether and mixtures thereof.

[0072] The amide group-containing monomer is preferably stearamidoethyl (meth)acrylate. The amide group-containing monomer may be a mixture containing stearamidoethyl (meth)acrylate. In the mixture containing stearamidoethyl (meth)acrylate, the amount of stearamidoethyl (meth)acrylate may be, for example, 55 to 99% by weight, preferably 60 to 85% by weight, and more preferably 65 to 80% by weight, based on the weight of all amide group-containing monomers, and the other monomer may be, for example, palmitamidoethyl (meth)acrylate.

[0073] (b) Acrylic monomer having a hydrophilic group The hydrophilic group-containing acrylic monomer (b) is a monomer other than the monomer (a), and is a hydrophilic monomer. The hydrophilic group is preferably an oxyalkylene group (the alkylene group has 2 to 6 carbon atoms). In particular, the hydrophilic group-containing acrylic monomer (b) is preferably a polyalkylene glycol mono(meth)acrylate and / or a polyalkylene glycol di(meth)acrylate. The polyalkylene glycol mono(meth)acrylate and the polyalkylene glycol di(meth)acrylate are each represented by the general formula: CH2=CX 2 C(=O)-O-(RO) n -X 3 (b1) and CH2=CX 2 C(=O)-O-(RO) n -C(=O)CX 2 =CH2(b2) (In the formula, X 2 are each independently a hydrogen atom or a methyl group, X 3 is a hydrogen atom or an unsaturated or saturated hydrocarbon group having 1 to 22 carbon atoms, R is independently an alkylene group having 2 to 6 carbon atoms; n is an integer from 1 to 90. where n can be, for example, 1 to 50, particularly 1 to 30, and specifically 1 to 15 or 2 to 15. Alternatively, n can be, for example, 1.

[0074] R is a straight or branched chain alkylene group, for example, -(CH2)x- (where x is 2 to 6) or -(CH2) x1 -(CH(CH3)) x2 -(CH2) (wherein x1 and x2 each represent an integer of 0 to 6, e.g., 2 to 5, and the sum of x1 and x2 represents an integer of 1 to 4). x1 - and -(CH(CH3)) x2 The order of - is not limited to the formula described and can be random. -(RO) nwherein R may be at least two types (e.g., 2 to 4 types, particularly 2 types). n The - group is, for example, -(RO) n1 -and-(R 2 O) n2 - a combination of (wherein R and R 2 are different from each other and are alkylene groups having 2 to 6 carbon atoms, n1 and n2 are independently an integer of at least 1, and the sum of n1 and n2 is 2 to 90).

[0075] R in formulas (b1) and (b2) is particularly preferably an ethylene group, a propylene group, or a butylene group. R in formulas (b1) and (b2) may be a combination of at least two alkylene groups. In this case, at least one R is preferably an ethylene group, a propylene group, or a butylene group. Examples of R combinations include an ethylene / propylene combination, a propylene / butylene combination, and an ethylene / butylene combination. Monomer (b) may be a mixture of at least two types. In this case, at least one monomer (b) preferably has an ethylene group, a propylene group, or a butylene group for R in formula (b1) or (b2). When a polyalkylene glycol di(meth)acrylate represented by formula (b2) is used, it is not preferable to use only monomer (b2) as monomer (b), but it is preferable to use a combination of monomer (b2) and monomer (b1). Even in this case, the amount of the compound represented by formula (b2) is preferably kept below 30% by weight (for example, 1% to 20% by weight) based on the monomer (b).

[0076] Specific examples of the hydrophilic group-containing acrylic monomer (b) include, but are not limited to, the following: CH2=CHCOO-CH2CH2O-H CH2=CHCOO-CH2CH2CH2O-H CH2=CHCOO-CH2CH(CH3)OH CH2=CHCOO-CH(CH3)CH2O-H CH2=CHCOO-CH2CH2CH2CH2O-H CH2=CHCOO-CH2CH2CH(CH3)OH CH2=CHCOO-CH2CH(CH3)CH2O-H CH2=CHCOO-CH(CH3)CH2CH2O-H CH2=CHCOO-CH2CH(CH2CH3)OH CH2=CHCOO-CH2C(CH3)2O-H CH2=CHCOO-CH(CH2CH3)CH2O-H CH2=CHCOO-C(CH3)2CH2O-H CH2=CHCOO-CH(CH3)CH(CH3)OH CH2=CHCOO-C(CH3)(CH2CH3)OH CH2=CHCOO-(CH2CH2O)2-H CH2=CHCOO-(CH2CH2O)4-H CH2=CHCOO-(CH2CH2O)5-H CH2=CHCOO-(CH2CH2O)6-H CH2=CHCOO-(CH2CH2O) 23 -CH3 CH2=CHCOO-(CH2CH2O) 90 -CH3 CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-CH3 CH2=CHCOO-(CH2CH(CH3)O) 12 -CH3 CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=CHCOO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3 CH2=CHCOO-(CH2CH2O)8-(CH2CH(CH3)O)5-CH2CH(C2H5)C4H9CH2=CHCOO-(CH2CH2O) 23 -OOC(CH3)C=CH2 CH2=CHCOO-(CH2CH2O) 20-(CH2CH(CH3)O)5-CH2-CH=CH2CH2=CHCOO-(CH2CH2O)9-H CH2=C(CH3)COO-CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH3)O-H CH2=C(CH3)COO-CH(CH3)CH2O-H CH2=C(CH3)COO-CH2CH2CH2CH2O-H CH2=C(CH3)COO-CH2CH2CH(CH3)O-H CH2=C(CH3)COO-CH2CH(CH3)CH2O-H CH2=C(CH3)COO-CH(CH3)CH2CH2O-H CH2=C(CH3)COO-CH2CH(CH2CH3)O-H CH2=C(CH3)COO-CH2C(CH3)2O-H CH2=C(CH3)COO-CH(CH2CH3)CH2O-H CH2=C(CH3)COO-C(CH3)2CH2O-H CH2=C(CH3)COO-CH(CH3)CH(CH3)O-H CH2=C(CH3)COO-C(CH3)(CH2CH3)O-H CH2=C(CH3)COO-(CH2CH2O)9-H CH2=C(CH3)COO-(CH2CH2O)5-CH3 CH2=C(CH3)COO-(CH2CH2O)9-CH3 CH2=C(CH3)COO-(CH2CH2O) 23 -CH3 CH2=C(CH3)COO-(CH2CH2O) 90 -CH3 CH2=C(CH3)COO-(CH2CH(CH3)O)9-H CH2=CHCOO-(CH2CH(CH3)O)9-H CH2=C(CH3)COO-(CH2CH(CH3)O)9-CH3CH2=C(CH3)COO-(CH2CH(CH3)O)12 -CH3CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)2-H CH2=C(CH3)COO-(CH2CH2O)5-(CH2CH(CH3)O)3-CH3CH2=C(CH3)COO-(CH2CH2O)8-(CH2CH(CH3)O)5-CH2CH(C2H5)C4H9 CH2=C(CH3)COO-(CH2CH2O) 23 -OOC(CH3)C=CH2CH2=C(CH3)COO-(CH2CH2O) 20 -(CH2CH(CH3)O)5-CH2-CH=CH2

[0077] The monomer (b) is preferably X 2 is a hydrogen atom, and particularly preferred are hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxybutyl acrylate.

[0078] (c) Monomers with ion-donating groups The ion-donating group-containing monomer (c) is a monomer other than the monomers (a) and (b). Generally, the monomer (c) is a monomer having an ethylenically unsaturated double bond and an ion-donating group. The ion-donating group is an anion-donating group and / or a cation-donating group.

[0079] The anion-donating group-containing monomer includes a monomer having a carboxyl group, a sulfonic acid group, or a phosphoric acid group. Specific examples of the anion-donating group-containing monomer include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, vinylsulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid, phosphate acrylate, vinylbenzenesulfonic acid, acrylamidotert-butylsulfonic acid, and salts thereof.

[0080] Examples of salts of anion-donating groups include alkali metal salts, alkaline earth metal salts, and ammonium salts such as methylammonium salts, ethanolammonium salts, and triethanolammonium salts.

[0081] In the monomer having a cation donor group, examples of the cation donor group include an amino group, preferably a tertiary amino group and a quaternary amino group. Preferably, in a tertiary amino group, the two groups attached to the nitrogen atom are the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an aromatic aliphatic group (particularly an aralkyl group, e.g., a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. Preferably, in a quaternary amino group, the three groups attached to the nitrogen atom are the same or different and are an aliphatic group (particularly an alkyl group) having 1 to 5 carbon atoms, an aromatic group (an aryl group) having 6 to 20 carbon atoms, or an aromatic aliphatic group (particularly an aralkyl group, e.g., a benzyl group (CH-CH-)) having 7 to 25 carbon atoms. In a tertiary amino group and a quaternary amino group, one remaining group attached to the nitrogen atom may have a carbon-carbon double bond. The cation donating group may be in the form of a salt.

[0082] The cation-donating group is a salt with an acid (organic or inorganic acid). Organic acids such as carboxylic acids having 1 to 20 carbon atoms (particularly monocarboxylic acids such as acetic acid, propionic acid, butyric acid, and stearic acid) are preferred. Dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate and salts thereof are preferred.

[0083] Specific examples of the monomer having a cation donor group are as follows: CH2=CHCOO-CH2CH2-N(CH3)2 and its salts (acetate, etc.)CH2=CHCOO-CH2CH2-N(CH2CH3)2 and its salts (acetate, etc.)CH2=C(CH3)COO-CH2CH2-N(CH3)2 and its salts (acetate, etc.)CH2=C(CH3)COO-CH2CH2-N(CH2CH3)2 and its salts (acetate, etc.) CH2=CHC(O)N(H)-CH2CH2CH2-N(CH3)2 and its salts (e.g. acetate salt) CH2=CHCOO-CH2CH2-N(-CH3)(-CH2-C6H5) and its salts (acetate, etc.) CH2=C(CH3)COO-CH2CH2-N(-CH2CH3)(-CH2-C6H5) and its salts (acetate, etc.) CH2=CHCOO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH2-N + (-CH3)2(-CH2-C6H5)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Cl - CH2=CHCOO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (CH3)3Cl - CH2=C(CH3)COO-CH2CH(OH)CH2-N + (-CH2CH3)2(-CH2-C5Hs)Cl - CH2=C(CH3)COO-CH2CH2-N + (CH3)3Br - CH2=C(CH3)COO-CH2CH2-N + (CH3)3I - CH2=C(CH3)COO-CH2CH2-N + (CH3)3O - SO3CH3CH2=C(CH3)COO-CH2CH2-N + (CH3)(-CH2-C6H5)2Br -

[0084] The ion-donating group-containing monomer is preferably methacrylic acid, acrylic acid, and dimethylaminoethyl methacrylate, more preferably methacrylic acid and dimethylaminoethyl methacrylate.

[0085] (d) Another monomer The other monomer (d) is a monomer other than the monomers (a), (b), and (c). Examples of the other monomer (d) include ethylene, vinyl acetate, vinyl chloride, vinyl halides, styrene, a-methylstyrene, p-methylstyrene, (meth)acrylamide, diacetone (meth)acrylamide, methylolated (meth)acrylamide, N-methylol (meth)acrylamide, alkyl vinyl ether, alkyl halide vinyl ether, alkyl vinyl ketone, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, aziridinyl (meth)acrylate, benzyl (meth)acrylate, isocyanatoethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, short-chain alkyl (meth)acrylate, maleic anhydride, (meth)acrylates having a polydimethylsiloxane group, and N-vinylcarbazole.

[0086] In some embodiments, the disclosed surface treatment polymers include, but are not limited to, the following: Monomer (a) + Monomer (b) + Monomer (c) Monomer (a) + Monomer (b) + Monomer (c) + Monomer (d) It includes a combination of monomers that constitute the above.

[0087] The amount of repeating units formed from monomer (a) is 30 to 95% by weight, preferably 40 to 88% by weight, and more preferably 50 to 85% by weight, based on the surface-treated polymer. Alternatively, the amount of repeating units formed from monomer (a) can be at least 20% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, or at least 70% by weight, based on the total of monomers (a), (b), and (c), and can be 97% by weight or less, 95% by weight or less, 90% by weight or less, 85% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less.

[0088] The amount of repeating units formed from monomer (b) can be 5 to 70% by weight, preferably 6 to 50% by weight, and more preferably 8 to 25% by weight, based on the surface-treated polymer. Alternatively, the amount of repeating units formed from monomer (b) can be at least 3%, at least 5%, at least 10%, or at least 15% by weight, based on the total of monomers (a), (b), and (c), and can be 70% by weight or less, 60% by weight or less, 50% by weight or less, 40% by weight or less, 30% by weight or less, 25% by weight or less, or 20% by weight or less.

[0089] The amount of repeating units formed from monomer (c) may be 0.1 to 30% by weight, preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight, based on the total of monomer (a), monomer (b), and monomer (c).

[0090] The weight ratio of repeat units formed from monomer (b) to repeat units formed from monomer (c) may be from 5:1 to 0.5:1, for example from 4:1 to 1:1, especially from 3.5:1 to 2.5:1.

[0091] The amount of repeating units formed from the monomer (d) may be 0 to 20% by weight, for example 1 to 15% by weight, particularly 2 to 10% by weight, based on the surface-treated polymer.

[0092] The weight average molecular weight of the surface treatment polymer may be 1,000 to 10,000,000, preferably 5,000 to 8,000,000, and more preferably 10,000 to 4,000,000. The weight average molecular weight is the value obtained for polystyrene by gel permeation chromatography.

[0093] (2)Aqueous medium The aqueous medium may be water alone or a mixture of water and a (water-soluble) organic solvent (such as an alcohol, ester, or ketone). The amount of the organic solvent may be up to 30% by weight, for example, up to 10% by weight, based on the aqueous medium. The aqueous medium is preferably water alone. The amount of the aqueous medium may be 0.2 to 100 parts by weight, for example, 0.5 to 50 parts by weight, particularly 1 to 20 parts by weight, based on 1 part by weight of the surface-treating polymer.

[0094] The surface treatment polymer polymerization can be carried out by various polymerization methods, such as bulk polymerization, solution polymerization, or radiation polymerization. For example, it is generally solution polymerization using an organic solvent. Preferably, after polymerization, water is added, and then the organic solvent is removed to disperse the polymer in water. Self-dispersing products can be produced without the need to add an emulsifier.

[0095] Furthermore, a chain transfer agent such as a mercapto group-containing compound may be used to adjust the molecular weight. Specific examples of the chain transfer agent include 2-mercaptoethanol, thiopropionic acid, and alkyl mercaptans. The chain transfer agent such as a mercapto group-containing compound may be used in an amount of 10 parts by weight or less, for example, 0.01 to 5 parts by weight, based on 100 parts by weight of the monomer.

[0096] Specifically, some embodiments of the surface-treated polymer can be prepared as follows. When solution polymerization is used, a method is adopted in which a monomer is dissolved in an organic solvent, the surrounding atmosphere is replaced with nitrogen, a polymerization initiator is added, and the mixture is heated and stirred at a temperature of, for example, 40 to 120°C for 1 to 10 hours. Generally, the polymerization initiator can be an oil-soluble polymerization initiator.

[0097] The organic solvent is inert to the monomer and dissolves the monomer. Examples of organic solvents include ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and methyl acetate; glycols such as propylene glycol, dipropylene glycol monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene glycol, and low-molecular-weight polyethylene glycol; alcohols such as ethyl alcohol and isopropanol; and hydrocarbon solvents such as n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane, cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane, isoparaffinic hydrocarbons, liquid paraffin, decane, undecane, dodecane, mineral spirits, mineral terpene, and naphtha. Preferred examples of organic solvents include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, N-methyl-2-pyrrolidone (NMP), and dipropylene glycol monomethyl ether (DPM). The organic solvent is used in an amount of 50 to 2,000 parts by weight, for example, 50 to 1,000 parts by weight, based on 100 parts by weight of the total monomers.

[0098] Surfactant-stabilized emulsion polymeric surface treatments are typically applied to carpets or other textiles in a multi-step process that requires the use of acidic, ionic, and / or heat conditions to destabilize the emulsion and release the polymer onto the material fibers. Metal salt solutions are typically used to create the ionic conditions to destabilize the surfactant-stabilized emulsion. An acidic pH is also typically used to destabilize the surfactant-stabilized emulsion. Once the surfactant-stabilized emulsion is destabilized, the polymer is then deposited onto the carpet or other textile fibers. The physical and chemical conditions used to destabilize the surfactant-stabilized emulsion can have negative environmental impacts, creating a potentially harmful environment for operators.

[0099] In some embodiments, the ionic and / or salt solutions may have a conductivity of greater than about 0.1 mS / cm, greater than about 0.2 mS / cm, greater than about 0.3 mS / cm, or greater than about 0.5 mS / cm. In some embodiments, solutions greater than 0.1 mS / cm may be applied to the carpet to destabilize the surfactant-stabilized emulsion. In some embodiments, the treatment bath containing the surfactant-free emulsion of the surface-treating polymer has a conductivity of less than about 0.1 mS / cm, less than about 0.08 mS / cm, less than about 0.06 mS / cm, less than about 0.05 mS / cm, or less than about 0.04 mS / cm.

[0100] When the destabilized surfactant-stabilized emulsion is applied to carpet, surfactants, emulsifiers, acidic agents, and / or salts remain on the fibers in addition to the polymeric surface treatment. Therefore, an additional rinsing step is required to remove these surfactant, emulsifier, acid, and / or salt compounds. In this case, the rinsate must undergo a water treatment process to reduce the environmental damage of this process.

[0101] Embodiments of the disclosed aqueous surfactant-free emulsion surface treatment methods save both time and energy because they do not require strong acidic or ionic conditions to apply the polymeric surface treatment to carpet, textiles, or other substrates. In some embodiments, the pH of the surfactant-free emulsion (before dilution into a treatment bath) is between about 3.0 and about 6.0. In some embodiments, the pH of the surfactant-free emulsion is between about 4 and about 5. Once the surface treatment surfactant-free emulsion is diluted into a treatment bath to be applied to carpet or other textiles, the treatment bath can have a pH between about 5.0 and about 7.5, depending on the local water conditions. In some embodiments, the treatment bath has a pH between about 6.0 and about 7.0. In some embodiments, the surfactant-free emulsion has a pH greater than 4.0 when applied to carpet. In some embodiments, the surfactant-free emulsion has a pH between 4.5 and 10.0 when applied to carpet.

[0102] As noted above, the disclosed surface treatment polymers contain ionic moieties that stabilize the surface treatment polymer in an aqueous continuous phase without the use of surfactants or emulsifiers.

[0103] In one embodiment, the surface treatment polymer is applied to the carpet during manufacturing while the carpet is in continuous or semi-continuous web form. The disclosed surfactant-free emulsion polymer surface treatment is applied to the carpet web, thereby allowing the surfactant-free emulsion to soak into the carpet. After saturation, the carpet web enters a steam chamber or other heating device, where the carpet, saturated with the surfactant-free emulsion surface treatment, is heated to a temperature of 60°C to 200°C or 80°C to 150°C for, for example, 1 second to 500 minutes, or 2 seconds to 100 minutes, e.g., 10 seconds to 50 minutes, or 1 minute to 10 minutes. The surface treatment polymer is in a surfactant-free emulsion rather than a surfactant-stabilized emulsion, allowing the polymer to readily adhere to the carpet fibers upon exposure to heat. The surface treatment polymer adheres to the carpet fibers both chemically and physically.

[0104] The adhesion of the surface treatment polymer to the carpet fiber is caused by both van der Waals forces and dipole-dipole interactions between the surface treatment polymer and the polymeric carpet fiber. Film formation on the surface of the fiber can also occur.

[0105] In some embodiments, once the carpet web exits the steam chamber, the carpet is subjected to a vacuum (e.g., 0.0001 atm to 0.5 atm) at 0°C to 80°C or 10°C to 50°C (e.g., room temperature, such as 20°C) to reduce the total moisture to approximately 0% to 70% or 30% to 50%, and then dried for 10 seconds to 24 hours or 10 minutes to 2 hours. In some embodiments, the carpet is heated to above about 100°C or 212°F to dry the carpet. In some embodiments, the carpet is heated to above about 200°F (93°C) to dry the carpet. The carpet heating temperature can be at least 60°C, e.g., 60°C to 200°C or 80°C to 150°C, e.g., 90°C to 120°C. Heating can be carried out for 1 second to 500 minutes, or 2 seconds to 100 minutes, e.g., 10 seconds to 50 minutes, or 1 minute to 10 minutes.

[0106] Because the disclosed surface treatment polymers are maintained in surfactant-free emulsions without the use of surfactants, emulsifiers, acids, or salts, no rinsing step or other post-treatment other than drying is required after the surface treatment polymers are applied to the carpet. The amount of surfactant (or emulsifier) ​​is preferably 0 to 0.01 parts by weight, more preferably 0 to 0.001 (or 0 to 0.0001) parts by weight, and particularly 0 part by weight, based on 1 part by weight of the surface-treated polymer, but the amount of surfactant (and / or emulsifier) ​​may also be 0 to 0.1 parts by weight based on 1 part by weight of the surface-treated polymer.

[0107] In some embodiments, the step of drying the carpet is performed without rinsing the carpet after applying the surfactant-free emulsion to the carpet.

[0108] After applying the surfactant-free emulsion surface treatment and drying the treated carpet, the finished primary-backed carpet roll can be sent to a coater, which is typically a separate line where a secondary backing is applied to the back of the carpet along with a latex composition that bonds the layers together and locks in the tufts, creating a more structurally sound substrate.

[0109] In some embodiments, rather than immersing the carpet or textile in a treatment bath, the surface treatment polymer may be applied in the form of a spray or foam. In such embodiments, it is recognized that the carpet or textile may not be completely saturated, but the surface treatment polymer contacts the carpet or textile fibers through a similar process.

[0110] In some embodiments, a foaming agent is mixed with the aqueous surfactant-free emulsion surface treatment. The surface-treated polymeric foam can be generated by a static or dynamic foaming device and applied to the carpet surface. The surface-treated polymeric foam can then be pressed into the carpet using a press roll before the carpet is heated and dried.

[0111] In some embodiments, the surfactant-free emulsion surface treatment is applied to the carpet using a spray nozzle, which reduces the total volume of liquid required to apply the surface treatment polymer to the carpet or textile fibers.

[0112] The majority of modern rugs are made from polymeric fibers, including, for example, polyethylene terephthalate (PET), nylon 6, nylon 6,6, polytrimethylene terephthalate (PTT), and polypropylene (PP). Carpet surface weight is defined as the ounces of fiber per square yard (osy). Surface weight is the weight of the fiber alone, without latex backing or other components. Carpet surface weights range from less than 20 osy to 100 osy, but are typically about 20 osy to about 60 osy.

[0113] Carpet surface treatment formulations can include many components. Typically, the formulation contains the disclosed surface treatment polymer, adjuvants, and performance chemicals, such as water. Performance chemicals can include, but are not limited to, repellents, stain-resistant additives, odor control additives, antimicrobial additives, and stain blockers. Adjuvants can include, but are not limited to, acids, salt solutions, and foaming agents. Water is typically the continuous phase of the surface treatment formulation. The other components of the formulation are dispersed in the aqueous continuous phase. As noted above, in some embodiments, the disclosed surface treatment polymer is applied to a carpet, and the carpet is then dried. Once the carpet is dry, the surface treatment polymer remains attached to the fibers. In a typical exhaust application, the adjuvants, surfactants, and / or emulsifiers are rinsed from the carpet fibers before the carpet dries.

[0114] When treating carpet, there is a target amount of surface treatment polymer that is desired to be present on the finished carpet to achieve a desired level of performance. The amount of polymer deposited on the carpet fibers is stated as a percentage of polymer by weight of fiber ("owf% polymer").

[0115] The percent polymer on weight of fiber (owf % polymer) is the amount of surface treatment polymer deposited on the carpet once all the liquid has been removed from the carpet by the drying process. The owf% polymer value may be 0.001 to 200 or 0.01 to 100, for example, 0.05 to 20 or 0.1 to 10.

[0116] The performance of surface treatment polymers on various carpet samples can be measured in a number of ways. AATCC Test Method 193-21017 is used to determine the degree of liquid repellency (non-wetting) of fabrics based on liquids with various surface tensions. A modified version of this test can be used to test carpets. As shown in Figure 1, several grades of standardized solutions are used to perform the modified AATCC Test Method 193-2017. First, three drops of Grade W solution (deionized water) are applied to the pile of the carpet sample and observed for 30 seconds. The traditional AATCC Test Method 193-2017 for testing fabric substrates requires the droplets to be observed for 10 ± 2 seconds. In the modified version of this test for carpet testing, the observation period is 30 seconds. If two (or more) of the three drops are absorbed into the carpet sample in less than 30 seconds, the carpet sample is considered to have failed the Grade W solution. If two (or more) drops remain on the surface of the carpet sample in a generally spherical form, the carpet sample passes the Grade W solution and the test is repeated with the Grade 1 solution. This process is repeated until the carpet sample is finally unable to maintain at least two drops of a particular solution on the surface of the carpet sample. The highest grade of solution that the carpet sample passes is recorded. If the carpet fails Grade W, it is assigned an F, indicating that the carpet sample fails deionized water and, consequently, all solution grades.

[0117] A float test is also used to determine the performance of surface treatment polymers. The float test is performed by placing a carpet sample, pile side down, in a container of water so that the carpet sample floats on the surface of the water for a period of time. The amount of time the carpet sample remains afloat is measured. When a significant portion of the carpet sample begins to sink, the test is terminated and the total float time is recorded.

[0118] In the following examples, carpet samples are prepared in a manner that approximates a commercial exhaust treatment process. Multiple surface treatment baths are prepared and applied to the carpet samples. One of two surface treatment solutions is used to make the surface treatment baths. Sample A refers to an embodiment of the disclosed aqueous surfactant-free emulsion polymer surface treatment agent before dilution to form the surface treatment bath. Sample A is made of the surface treatment polymer in an aqueous continuous phase. In the exemplary embodiment referred to herein, Sample A contains 20% surface treatment polymer and 80% water by weight. Sample A is used to make both a low-concentration treatment bath and a standard-concentration treatment bath. The low-concentration treatment bath is referred to as Sample A1, and the standard-concentration treatment bath is referred to as Sample A2.

[0119] Sample B refers to a conventional surfactant-stabilized polymeric surface treatment agent before dilution to form a surface treatment bath. Sample B contains 30% surface treatment polymer, with the remaining 70% being a combination of water and surfactant or emulsifier. Both low-concentration and standard-concentration treatment baths were made using Sample B. Additionally, Sample B formulations were applied to carpet samples in two different ways. First, Sample B formulation was applied to the carpet samples without an adjuvant or rinsing step. Second, Sample B formulation was applied to the carpet samples with an adjuvant and rinsing step. The low-concentration treatment bath applied without an adjuvant or rinsing step is referred to as Sample B1. The standard-concentration treatment bath applied without an adjuvant or rinsing step is referred to as Sample B2. The low-concentration treatment bath applied with an adjuvant and rinsing step is referred to as Sample B3. The standard-concentration treatment bath applied with an adjuvant and rinsing step is referred to as Sample B4.

[0120] Sample A1 is a low concentration treatment bath containing 0.1% emulsion (surfactant-free) by weight of fiber of Sample A ("owf% emulsion"). Sample A2 is a standard concentration treatment bath containing 0.4 owf% emulsion (surfactant-free) of Sample A. Samples B1 and B3 are low concentration treatment baths containing 0.067 owf% emulsion (surfactant-stabilized) of Sample B. Samples B2 and B4 are standard concentration treatment baths containing 0.267 owf% emulsion (surfactant-stabilized) of Sample B.

[0121] For clarity, owf% emulsion represents the amount of polymeric emulsion (Sample A surfactant-free emulsion or Sample B surfactant-stabilized emulsion) expressed as a percent of the weight of the carpet sample fibers being treated. This number is determined prior to preparing the treatment bath.

[0122] The percent polymer by weight of fiber ("owf% polymer") is the amount of surface treatment polymer deposited on the carpet once all liquid has been driven off from the drying process. This number is closely related to the owf% emulsion. The owf% emulsion can be converted to or determined from the owf% polymer using a known amount of solid polymer in a given polymer treatment emulsion, such as Sample A or Sample B.

[0123] Prior to preparing the treatment bath, the percent wet pickup (wpu%) was first determined. The moisture content represents the amount of treatment bath liquid absorbed by the carpet sample. The moisture content is determined prior to preparing the surface treatment bath and influences the preparation of the treatment bath. In commercial applications, the target wpu% will vary depending on the water usage limitations of a given application and the capacity of the drying equipment, etc.

[0124] For the exemplary embodiment described below, the preparation of the surface treatment bath is described as follows.

[0125] 1) Cut a 12.25" x 8.25" carpet sample.

[0126] 2) Weigh the carpet sample. In this particular example, the carpet sample weighs 51.56 grams. The weight of the carpet sample combined with the desired moisture content will inform the weight of all of the treatment bath components that will be applied to the carpet sample.

[0127] 3) Using the predetermined moisture content, calculate the weight (in grams) of the treatment bath. In this example, the moisture content was set at 400%. Therefore, the weight of the treatment bath is 206.24 grams (51.56 x 400%). The weight (in grams) of the treatment bath represents the total weight of the bath applied to the carpet sample. In some embodiments, the treatment bath contains only water and a surfactant-free emulsion surface treatment. In some embodiments, the treatment bath contains water, a surfactant-stabilized emulsion surface treatment, and adjuvants such as a salt solution.

[0128] 4) Calculate percent by weight of bath (owb%). Percent by weight of bath represents the percent of the bath that consists of surface treatment emulsion. To calculate percent by weight of bath (owb%), divide the percent of emulsion by weight of fiber by the moisture content; then multiply by 100 to convert the value to a percentage. One exemplary embodiment of calculating percent by weight of bath is shown below:

[0129] TIFF2025186545000004.tif47160

[0130] 5) Calculate the amount (in grams) of surfactant-free emulsion surface treatment (or surfactant-stabilized emulsion) to add to the treatment bath: Determine the amount (in grams) of surfactant-free emulsion surface treatment (or surfactant-stabilized emulsion) to add to the treatment bath and multiply the weight (in grams) of the treatment bath by the percent of weight of the bath (owb%) as shown in the example calculation below.

[0131] TIFF2025186545000005.tif40160

[0132] 6) Determine the amount of water (grams) needed in the treatment bath. The amount of water in the treatment bath refers to the amount of additional water, other than the other treatment bath components, needed to reach the target treatment bath weight. To determine how much additional water is needed, subtract the amount of surfactant-free emulsion surface treatment (or surfactant-stabilized emulsion) in the treatment bath from the total bath size. An exemplary calculation is shown below:

[0133] TIFF2025186545000006.tif54161

[0134] Once the desired amount of water has been calculated, combine the water, surfactant-free emulsion surface treatment (or surfactant-stabilized emulsion) and any adjuvants. Mix the treatment bath components until thoroughly incorporated.

[0135] Once the treatment bath is prepared, the carpet samples can be treated. In the examples described below, the carpet samples are treated according to the following exemplary process.

[0136] 1) Immerse a carpet sample of known dry weight in water.

[0137] 2) The carpet sample is pre-steamed for 90 seconds. In a typical carpet mill setup, before the carpet is treated, the carpet goes through a steam process to apply dye to the fibers. This dyeing process typically occurs before the carpet sample goes through an exhaust application to apply a surface treatment. In the exemplary embodiment described below, the carpet sample is not dyed. The pre-steaming is used to mimic the dyeing process.

[0138] 3) After pre-steaming, vacuum extract the carpet sample to remove excess moisture and achieve approximately 50%-70% moisture content. Determine the weight of the carpet sample plus remaining liquid to achieve approximately 50%-70% moisture. The weight of the dry carpet sample was measured at the beginning of the bath preparation process. Once the carpet sample has been vacuum extracted to approximately 50%-70% moisture, the carpet will weigh 50%-70% more than the dry carpet sample due to the remaining moisture content. An exemplary calculation is shown below:

[0139] TIFF2025186545000007.tif33160

[0140] 4) Once the carpet sample has reached approximately 50% to 70% moisture, a surface treatment bath is applied to the carpet. In this exemplary embodiment, this is done by pouring the surface treatment bath into a clean tray and placing the carpet sample, pile side down, into the tray. In a traditional carpet mill, the carpet is mounted on a conveyor system. The carpet passes through a delivery system containing the treatment bath, with the pile side of the carpet facing the liquid. In the described example, this is mimicked using a tray containing the treatment bath as described above.

[0141] 5) The treatment bath is then massaged into the carpet fibers. This massage mimics the delivery system in the application process in a carpet manufacturing setting. In the example described, the carpet samples were massaged by hand to thoroughly incorporate the treatment bath into the fibers.

[0142] 6) Once the treatment bath is applied, the carpet samples are steamed for 90 seconds. This step replicates the carpet mill's exhaust process. With traditional surface treatment surfactant-stabilized emulsions, this steaming step may also be necessary to release the surface treatment polymer from the surfactant or emulsifier.

[0143] For treatment baths containing conventional surfactant-stabilized emulsion surface treatments, it is necessary to rinse carpet samples to remove residual surfactant or emulsifier from the surface of the fibers. When using embodiments of the described surfactant-free emulsion surface treatment, the rinsing step is eliminated because no surfactant or emulsifier is used. Eliminating this rinsing step saves carpet manufacturers time, water, and energy.

[0144] 7) After the treated carpet samples have been steamed and / or rinsed, the carpet samples are vacuum extracted to approximately 30% to 50% moisture content. In a conventional mill setting, excess moisture is removed to allow for reduced oven drying times.

[0145] 8) Finally, the carpet sample is dried. In the exemplary embodiment described, the carpet sample is placed pile-side up in a conveyor oven. The carpet sample is dried at approximately 114°C (238°F) for 10 minutes. After the drying process is complete, excess moisture is removed from the carpet sample, leaving only the dried surface treatment polymer on the carpet fibers. [Example]

[0146] The surface treatment examples described below are carried out on carpet samples made from three different materials: polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polyamide (nylon). Carpet surface weight is defined as ounces of fiber per square yard (osy). Surface weight is the weight of only the fiber portion of the carpet sample. Carpet surface weight can range from less than 20 osy to a maximum of 100 osy. A typical range is 20 osy to 60 osy.

[0147] Examples 1-3 focus on the repellency performance of carpet samples treated with Samples A1, A2, B1, and B2 described above. In Examples 1-3, each of these samples is tested on PET, PTT, and nylon carpet samples without pH adjustment, salt addition, or a final rinse step after steaming the treated carpet samples. For Examples 1-3, treatment bath Samples A1 and A2 contained only surfactant-free emulsion surface treatment polymer and water. For Examples 1-3, treatment bath Samples B1 and B2 contained only surfactant-stabilized emulsion and water. No adjuvants were used. After applying the surface treatment bath to the carpet samples, the carpet samples were steamed for 90 seconds, vacuum extracted to reduce the moisture content, and then dried. No rinse step was performed after applying the surface treatment polymer to the carpet samples.

[0148] PET, PTT, and nylon carpets were cut into 8.25" x 12.25" carpet samples and individually weighed. The total weight of each treatment bath was determined by multiplying the weight of the associated carpet sample by the predetermined moisture content of 400%. Low-concentration treatment bath samples A1 and B1 were each formulated to contain 0.02% polymer by weight of fiber. For clarity, this means that the amount of dry surface treatment polymer in each treatment bath was equal to 0.02% of the weight of the associated carpet sample. Standard-concentration treatment bath samples A2 and B2 were each formulated to contain 0.08 owf% polymer.

[0149] The surface treatment bath was applied to the carpet according to the process described above. [Example]

[0150] PET carpet sample In Example 1, 20 osy to 25 osy cut pile PET carpets were treated according to the method described above. The aqueous liquid repellency (modified AATCC Test Method 193-2017) and flotation performance of carpet samples treated with A1, A2, B1, and B2 were determined and compared. The aqueous liquid repellency tests for carpet samples treated with Samples A1 and A2 demonstrated better ability to repel low surface tension liquids than carpet samples treated with Samples B1 and B2. The flotation tests showed that carpet samples treated with Sample A1 floated longer than carpet samples treated with Sample B1, indicating that at lower-than-typical treatment levels, the surfactant-free emulsion of Sample A performed better than the surfactant-stabilized emulsion of Sample B. The flotation performance for carpet samples treated with Samples A2 and B2 appeared generally comparable. The test results are shown in Table 1 below.

[0151] [Table 1]

[0152] For clarity, "bath dosage (grams / liter)" refers to grams of surfactant-free emulsion of Sample A or surfactant-stabilized emulsion of Sample B per liter of water in the treatment bath. [Example]

[0153] PTT carpet sample In Example 2, 35 osy to 40 osy cut pile PTT carpets were treated and dried according to the above method. The water repellency (modified AATCC Test Method 193-2017) and flotation performance of carpet samples treated with A1, A2, B1, and B2 were determined and compared.

[0154] The water repellency of the carpet samples, as indicated by the modified AATCC Test Method 193-2017 rating, showed that Sample A had a better ability to repel low surface tension liquids than Sample B. Floatation tests showed that carpet samples treated with Samples A1 and A2 floated longer than carpet samples treated with Samples B1 and B2, indicating that Sample A performed better than Sample B at both low and standard concentrations of surface treatment. The test results are shown in Table 2 below.

[0155] [Table 2] [Example]

[0156] Nylon carpet sample In Example 3, 20 osy to 25 osy cut pile nylon carpets were treated and dried using the method described above. The water-liquid repellency (modified AATCC Test Method 193-2017) and flotation performance of carpet samples treated with Samples A1, A2, B1, and B2 were determined and compared. In this example, a rating of "W" indicates that at least two out of three drops of 100% deionized water remained on the carpet sample's surface for at least 30 seconds, and an "F" indicates failure of the test using 100% deionized water. The water-liquid repellency test demonstrated that Sample A1 had a better ability to repel deionized water on nylon than Sample B1. Furthermore, the water-liquid repellency test demonstrated that Sample A2 had a better ability to repel low surface tension liquids than Sample B2. Carpet samples treated with Samples A1 and B1 did not float for a measurable amount of time, indicating that none of the low-concentration surface treatment baths were able to provide flotation performance on nylon carpet samples. Only the nylon carpet sample treated with Sample A2 floated for a measurable amount of time. The test results are shown in Table 3 below.

[0157] [Table 3]

[0158] In Examples 4-6, repellency tests were performed on PET, PTT, and nylon carpet samples treated with Sample B at low (Sample B3) and high (Sample B4) application rates. These examples represent a typical method for carpet exhaust treatment. In Examples 4-6, the pH of each treatment bath was adjusted to pH 2 using sulfuric acid solution. A 30% magnesium sulfate solution was added to each treatment bath to create a 1.4% magnesium sulfate bath. After the carpet samples were treated with the polymer surface treatment and steamed, they were thoroughly rinsed with water to remove any residual adjuvants, surfactants, or emulsifiers. Other than these modifications, carpet sample preparation and application of the surface treatment polymer were the same as those described above and used in Examples 1-3. Repellency performance was determined using the modified AATCC Test Method 193-2017 and flotation tests described above. [Example]

[0159] PET carpet sample In Example 4, 20 osy to 25 osy cut pile PET carpets were treated and dried according to the above method. The water repellency (modified AATCC Test Method 193-2017) and flotation performance of carpet samples treated with Samples B3 and B4 were determined and compared. The test results are shown in Table 4 below.

[0160] [Table 4] [Example]

[0161] PTT carpet sample In Example 5, 35 osy to 40 osy cut pile PTT carpet was treated and dried according to the method described above. The water repellency and flotation performance of carpet samples treated with Samples B3 and B4 were determined. The test results are shown in Table 5 below.

[0162] [Table 5] [Example]

[0163] Nylon carpet sample In Example 6, 20 osy to 25 osy cut pile nylon carpet was treated and dried according to the method described above. The water repellency and flotation performance of carpet samples treated with Samples B3 and B4 were determined. The test results are shown in Table 6 below.

[0164] [Table 6]

[0165] For Tables 7-9 below, carpet samples treated with Samples A1 and A2 without pH adjustment, salt solution, or rinsing are compared to carpet samples treated with Samples B3 and B4 with pH adjustment, magnesium salt, and rinsing.

[0166] [Table 7]

[0167] [Table 8]

[0168] [Table 9]

[0169] As can be seen from a comparison of the data in Tables 7-9, the polymeric surface-treated surfactant-free emulsion of Sample A is an improvement over conventional carpet exhaust processes that utilize a surfactant-stabilized emulsion treatment similar to that of Sample B. In addition to improved repellency, the surfactant-free emulsion of Sample A does not require pH adjustment, salt solutions, or a final rinse step. These improvements offer carpet manufacturers the opportunity to save time, water, and energy in their processes by reducing the amount of surface treatment required to achieve acceptable results and by reducing the amount of water used in the treatment process. Other cost-saving, safety, and environmental benefits include protecting equipment by eliminating corrosive auxiliary chemicals and reducing the amount of water used by eliminating the rinse step.

[0170] Those skilled in the art will recognize improvements and modifications to the preferred embodiments of the present disclosure. All such improvements and modifications are considered to be within the scope of the concepts disclosed herein and the following claims. It should be understood that any given element of the disclosed embodiments of the present invention may be embodied in a single structure, step, material, etc. Likewise, any given element of the disclosed embodiments may be embodied in multiple structures, steps, materials, etc.

[0171] The foregoing description illustrates and describes the processes, machines, manufactures, compositions, and other teachings of the present disclosure. Furthermore, while the present disclosure shows and describes only certain embodiments of the processes, machines, manufactures, compositions, and other teachings disclosed, it should be understood that, as noted above, the teachings of the present disclosure are capable of use in various other combinations, modifications, and environments, and are capable of changes or modifications within the scope of the teachings expressed herein, commensurate with the skill and / or knowledge of those skilled in the relevant art. The above-described embodiments of the present specification describe certain best modes known for carrying out the processes, machines, manufactures, compositions, and other teachings of the present disclosure, and are further intended to enable those skilled in the art to utilize the teachings of the present disclosure in such or other embodiments, with various modifications dictated by a particular application or use. Accordingly, the processes, machines, manufactures, compositions, and other teachings of the present disclosure are not intended to limit the precise embodiments and examples disclosed herein. Any section headings herein are provided solely for consistency with the recommendations of 37 CFR § 1.77 or to provide organizational cues. These headings are not intended to limit or characterize the invention presented herein.

Claims

1. 1. A method of treating carpet, comprising: applying a surfactant-free emulsion of a surface-treating polymer to the carpet, the surface-treating polymer being formed by solution polymerization; applying the surfactant-free emulsion of the surface treatment polymer to the carpet and then drying the carpet; A method comprising:

2. 10. The method of treating carpet of claim 1, wherein the step of drying the carpet is carried out by heating the carpet.

3. 3. The method of treating carpet of claim 2, wherein the carpet is heated to a temperature of at least 60°C or greater than 93°C (200°F) for a period of from 1 second to 500 minutes.

4. 10. The method of treating carpet of claim 1, wherein the step of drying the carpet is performed without rinsing the carpet after applying the surfactant-free emulsion to the carpet.

5. 10. The method of treating carpet of claim 1, wherein the surfactant-free emulsion is applied to the carpet without the use of a salt solution.

6. 10. The method of treating carpet of claim 1, wherein the surfactant-free emulsion is applied to the carpet without the use of a magnesium salt solution.

7. 10. The method of treating carpet of claim 1, wherein the carpet is dried before applying a solution having a conductivity greater than 0.1 mS / cm to the carpet.

8. 10. The method of treating carpet of claim 1, wherein the surfactant-free emulsion is applied to the carpet without the use of a separate acidic solution.

9. 10. The method of treating carpet of claim 1, wherein the surfactant-free emulsion has a pH greater than 4.0 when applied to the carpet.

10. 10. The method of treating carpet of claim 1, wherein the surfactant-free emulsion has a pH between 4.5 and 10.0 when applied to the carpet.

11. 10. The method of treating carpet of claim 1, wherein the carpet is dried before a separate pH adjuster is applied to the carpet.

12. 10. The method of treating carpet of claim 1, wherein the surfactant-free emulsion is substantially free of emulsifiers.

13. The method of treating carpet according to claim 1 , wherein the surface treatment polymer is fluorine-free.

14. 2. The method for treating a carpet according to claim 1, wherein the surface treatment polymer comprises: (a) repeating units formed from an acrylic monomer having a hydrocarbon group containing 7 to 40 carbon atoms; (b) repeating units formed from an acrylic monomer having a hydrophilic group; and (c) repeating units formed from a monomer having an ion-donating group.

15. 15. The method of treating carpet according to claim 14, wherein the ion donating groups are cation donating groups.

16. 16. The method of treating carpet according to claim 15, wherein the cation donating groups are amino groups.

17. 1. A method of treating textiles, comprising: immersing the textile in a treatment bath, the treatment bath containing a surfactant-free emulsion of a surface treatment polymer, the surface treatment polymer containing (a) repeating units formed from an acrylic monomer having a hydrocarbon group, (b) repeating units formed from an acrylic monomer having a hydrophilic group, and (c) repeating units formed from a monomer having a cation donor group; after immersing the textile in the treatment bath, without rinsing the textile, heating the textile to reduce its moisture content; A method comprising:

18. 20. The method of treating textiles of claim 17, wherein the treatment bath is substantially free of emulsifiers.

19. 20. The method of treating a textile of claim 17, wherein the textile is a continuous or semi-continuous web of carpet.

20. 20. The method of treating a textile of claim 17, wherein the textile is a carpet comprising polyethylene terephthalate (PET) or polytrimethylene terephthalate (PTT) fibers.

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