WO2006050300A2

WO2006050300A2 - Processes for modifying textiles using ionic liquids

Info

Publication number: WO2006050300A2
Application number: PCT/US2005/039346
Authority: WO
Inventors: Kenneth Nathan Price; Jiping Wang; Nodie Monroe Washington; Stacie Ellen Hecht; Gregory Scot Miracle; Jeffrey John Scheibel
Original assignee: The Procter & Gamble Company
Priority date: 2004-11-01
Filing date: 2005-11-01
Publication date: 2006-05-11
Also published as: US20060090271A1; WO2006050300A3; JP2008516106A; EP1807565A2

Abstract

Processes for modifying a textile to improve its performance which comprise the steps of a) contacting a textile comprising fibers with a treating composition comprising an ionic liquid under conditions sufficient to modify at least surfaces of the fibers, thereby provide a performance improvement to treated textile; b) optionally, contacting a textile comprising fibers with a composition comprising a benefit agent; and c) at least partially removing the treating composition from the textile. In specific embodiments, the surface modification comprises a partial dissolution of at least one outer layer of the fibers and/or crystal structure change in at least surfaces of the fibers. The surface modification can impart improvements to the textile or allow embedding or attachment of a benefit agent in the fibers.

Description

PROCESSES FOR MODIFYING TEXTILES USING IONIC LIQUIDS

FIELD OF THE INVENTION

The present invention is directed to processes for modify ing textiles which comprise fibers. More particularly, the invention is directed to such processes which employ ionic liquid-containing compositions.

BACKGROUND OF THE INVENTION

In recent years, ionic liquids have been extensively evaluated as environmental- friendly or "green" alternatives to conventional organic solvents for a broad range of organic synthetic applications. Ionic liquids offer some unique characteristics that distinguish them from conventional organic solvents, such as no effective vapor pressure, a broad liquid range, high polarity and charge density, can be either hydrophobic or hydrophilic, and unique solvating properties.

One widely studied class of ionic liquids includes imidazolinium salts, such as butylmethylimidazolinium hexafluorophosphate, also known as B3MXM/PF6. Other well known ionic liquids include N-I -ethyl 3-methylimidazolinum chloride aluminum (III) chloride, which is usually referred to as [emim]Cl-AlC13; and N-butyl pyridinium chloride aluminum (III) chloride, which is usually referred to as [Nbupy]Cl-AlC13. A broad range of ionic liquids have also been investigated in the following references: WO 03/029329; WO 03/074494; WO 03/022812; WO 2004/016570; US 2004/0035293 Al; and US 5,827,602.

In addition to chemical processes, ionic liquids have also been used as microbiocides/plant growth regulators, as described in FR 2434156; as antistatic agents, as described in JP10-265674 and U.S. Patent No. 3,282,728; and. as fruit and vegetable produce treating agents, as described in WO 01/19200. Other uses of ionic liquids are disclosed in U.S. Patent No. 6,048,388 as a component of an ink composition; and in J. Am. Chem. Soc, Vol. 124, pp. 4974-4975 (2002), as an agent to dissolve cellulose.

Published PCT Application WO 2004/003120 discloses ionic liquid based products suitable for use in surface or air treating compositions, and ionic liquid cocktails containing three or more different and charged ionic liquid components. The products are particularly useful in various consumer product applications, such as home care, air care, surface cleaning, laundry and fabric care applications.

Owing to various unique properties of ionic liquids, it would be advantageous to employ such materials in additional applications.

Accordingly, it is desirable to employ ionic liquid-containing compositions in textile treating processes. Particularly, the treating process provides improvements to textiles which comprise fibers, and to provide such improvements through the use of ionic liquid-containing compositions. These processes are advantageous in that they allow provision of improved properties to textiles while employing materials recognized as environmentally friendly.

SUMMARY OF THE INVENTION

The present invention is directed to processes for modifying a textile to improve its performance which comprise the steps of a) contacting a textile comprising fibers with a treating composition comprising an ionic liquid under conditions sufficient to modify at least a portion of the surface of the fibers, thereby providing a performance improvement to treated textile; b) optionally, contacting a textile comprising fibers with a composition comprising a benefit agent; and c) at least partially removing the treating composition from the textile. In specific embodiments, the surface modification comprises a partial dissolution of at least one outer layer of the fibers and/or crystal structure change in at least surfaces of the fibers. The surface modification can impart improvements to the textile or allow embedding or attachment of a benefit agent in the fibers.

Additional embodiments and advantages of the processes are described in further detail in the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION

The processes according to the present invention for modifying a textile which comprises fibers include the steps of a) contacting the textile with a composition comprising an ionic liquid under conditions sufficient to modify at least surfaces of the fibers and provide, or facilitate provision of, a performance improvement thereto; and b) at least partially removing the composition from the textile. Within the present context, a textile which comprises fibers refers to any fiber-containing textile material or product and includes, but is not limited to, loose or free fibers, yarns (including threads), woven textiles, nonwoven textiles, knitted textiles, fabric articles, and the like. Fabric articles include, but are not limited to, garments, components used in the manufacture of garments, carpets, upholstery, and the like. Additionally, the textile fibers may be formed of any natural (e.g., cellulose), regenerated (e.g., rayon), or synthetic material, or a combination thereof. In one embodiment, the textile fibers comprise a cellulosic material. In another embodiment, the fibers comprise a synthetic material, for example comprising polyester.

In some embodiments, the ionic liquid as used herein refers to a salt that has a melting temperature of about 100°C or less, or, in an alternative embodiment, has a melting temperature of about 60⁰C or less, or, in yet another alternative embodiment, has a melting temperature of about 40⁰C or less. In other embodiments, the ionic liquids exhibit no discernible melting point (based on DSC analysis) but are "flowable" at a temperature of about 100⁰C or below, or, in another embodiment, are "flowable" at a temperature of from about 20 to about 8O⁰C, i.e., the typical fabric or dish washing temperatures. As used herein, the term "flowable" means that the ionic liquid exhibits a viscosity of less than about 10,000 mPa-s at the temperatures as specified above.

It should be understood that the terms "ionic liquid", "ionic compound", and "IL" refer to ionic liquids, ionic liquid composites, and mixtures (or cocktails) of ionic liquids. The ionic liquid can comprise an anionic IL component and a cationic IL component. When the ionic liquid is in its liquid form, these components may freely associate with one another (i.e., in a scramble). As used herein, the term "cocktail of ionic liquids" refers to a mixture of two or more, preferably at least three, different and charged IL components, wherein at least one IL component is cationic and at least one IL component is anionic. Thus, the pairing of three cationic and anionic IL components in a cocktail would result in at least two different ionic liquids. The cocktails of ionic liquids may be prepared either by mixing individual ionic liquids having different IL components, or by preparing them via combinatorial chemistry. Such combinations and their preparation are discussed in further detail in US 2004/0077519Al and US 2004/0097755A1. As used herein, the term "ionic liquid composite" refers to a mixture of a salt (which can be solid at room temperature) with a proton donor Z (which can be a liquid or a solid) as described in the references immediately above. Upon mixing, these components turn into a liquid at about 100°C or less, and the mixture behaves like an ionic liquid.

Some of the properties that ionic liquids possess and make them attractive alternatives to conventional solvents include: a) ionic liquids have a broad liquid range; some ionic liquids can be in the liquid form at a temperature as low as -96°C and others can be thermally stable at temperatures up to 200⁰C; this permits effective kinetic control in many organic reactions and processes; b) ionic liquids have no effective vapor pressure, thus, they are easy to handle and they reduce safety concerns where volatility could be an issue; c) ionic liquids are effective solvents for a broad range of organic and inorganic materials due to their high polarity; d) ionic liquids are effective Bronsted/Lewis acids; and e) ionic liquids can be tuned to the specific application/chemistry desired, for example, they can be selectively made to have properties ranging from hydrophilic to hydrophobic. By virtue of their high polarity and charge density, ionic liquids have unique solvating properties, and may be used in a variety of processing environments and conditions.

Nonlimiting examples of anions and cations suitable for use in the ionic liquids for the present invention are discussed in details below. Anions

Anions suitable for use in the ionic liquids of the present invention include, but are not limited to, the following materials:

(1) Alkyl sulfates (AS), alkoxy sulfates and alkyl alkoxy sulfates, wherein the alkyl or alkoxy is linear, branched or mixtures thereof; furthermore, the attachment of the sulfate group to the alkyl chain can be terminal on the alkyl chain (AS), internal on the alkyl chain (SAS) or mixtures thereof: non-limiting examples include linear Cio- C₂o alkyl sulfates having formula:

CH₃(CH₂)_x+yCH₂OSO₃-M⁺ wherein x+y is an integer of at least 8, preferably at least about 10; M is a cation selected from the cations of the ionic liquids as described in detail herein; or linear Cio-C₂o secondary alkyl sulfates having formula: OSO₃-M⁺

CH₃(CH₂)_x(CH)(CH₂)_yCH₃ wherein x + y is an integer of at least 7, preferably at least about 9; x or y can be 0, M⁺ is a cation selected from the cations of the ionic liquids as described in detail herein; or C10-C20 secondary alkyl ethoxy sulfates having formula:

0(CH₂CH₂O)₂-SO₃-M⁺

CH₃(CH₂)x(CH)(CH₂)yCH₃ wherein x + y is an integer of at least 7, preferably at least about 9; x or y can be O, M⁺ is a cation selected from the cations of the ionic liquids as described in detail herein; non-limiting examples of alkoxy sulfate include sulfated derivatives of commercially available alkoxy copolymers, such as Pluronics® (from BASF);

(2) Mono- and di- esters of sulfosuccinates: non-limiting examples include saturated and unsaturated Ci_2-I8 monoester sulfosuccinates, such as lauryl sulfosuccinate available as Mackanate LO- 100® (from The Mclntyre Group); saturated and unsaturated C₆ - Cj₂ diester sulfosuccinates, such as dioctyl ester sulfosuccinate available as Aerosol OT® (from Cytec Industries, Inc.);

(3) Methyl ester sulfonates (MES);

(4) Alkyl aryl sulfonates, non-limiting examples include tosylate, alkyl aryl sulfonates having linear or branched, saturated or unsaturated C₈-Ci₄ alkyls; alkyl benzene sulfonates (LAS) such as Cn-Ci₈ alkyl benzene sulfonates; sulfonates of benzene, cumene, toluene, xylene, t-butyl benzene, di-isopropyl benzene, or isopropyl benzene; naphthalene sulfonates and C_6-I4 alkyl naphthalene sulfonates, such as Petro® (from Akzo Nobel Surface Chemistry); sulfonates of petroleum, such as Monalube 605® (from Uniqema);

(5) Alkyl glycerol ether sulfonates having 8 to 22 carbon atoms in the alkyl moiety;

(6) Diphenyl ether (bis-phenyl) derivatives: Non-limiting examples include Triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether) and Diclosan (4,4'-dichloro-2- hydroxydiphenyl ether), both are available as Irgasan® from Ciba Specialty Chemicals; (7) Linear or cyclic carboxylates: non-limiting examples include citrate, lactate, tartarate, succinate, alkylene succinate, maleate, gluconate, formate, cinnamate, benzoate, acetate, salicylate, phthalate, aspartate, adipatej, acetyl salicylate, 3 -methyl salicylate, 4-hydroxy isophthalate, dihydroxyfumarate, 1 ,2,4-benzene tricarboxylate, pentanoate and mixtures thereof;

(8) Alkyl oxyalkylene carboxylates: non-limiting examples include Ci_O-Ci₈ alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units;

(9) Alkyl diphenyl oxide monosulfonate: non-limiting examples include alkyl diphenyl oxide monosulfonate of the general formula:

wherein R¹ is Ci_O-C]₈ linear or branched alkyl; R² and R³ are independently SO₃ ^" or H, provided at least one of R² or R³ is not hydrogen; R⁴ is R¹ or H; suitable alkyl diphenyl oxide monosulfonates are available as DOWF AX® from Dow Chemical and as POLY-TERGENT® from OHn Corp.;

(10) Mid-chain branched alkyl sulfates (HSAS), mid-chain branched alkyl aryl sulfonates (MLAS) and mid-chain branched alkyl polyoxyalkylene sulfates ; non-limiting examples of MLAS are disclosed in US 6,596,680; US 6,593,285; and US 6,202,303;

(11) Alpha olefin sulfonates (AOS) and paraffin sulfonates, non-limiting examples include Ci_0-22 alpha-olefm sulfonates, available as Bio Terge AS-40® from Stepan Company;

(12) Alkyl phosphate esters, non-limiting examples include C_8-22 alkyl phosphates, available as Emphos CS® and Emphos TS-230® from Alczo Nobel Surface Chemistry LLC;

(13) Sarcosinates having the general formula RCON(CH₃)CH₂CO₂ ^" , wherein R is an alkyl from about C_8-20; non-limiting examples include ammonium lauroyl sarcosinate, available as Hamposyl AL-30® from Dow Chemicals and sodium oleoyl sarcosinate, available as Hamposyl O® from Dow Chemical;

(14) Taurates, such as C_8-22 alkyl taurates, available as sodium coco methyl tauride or Geropon TC® from Rhodia, Inc.; (15) Sulfated and sulfonated oils and fatty acids, linear or branched, such as those sulfates or sulfonates derived from potassium coconut oil soap available as Norfox 1101® from Norman, Fox & Co. and Potassium oleate from Chemron Corp.;

(16) Alkyl phenol ethoxy sulfates and sulfonates, such as C_8-I4 alkyl phenol ethoxy sulfates and sulfonates; non-limiting examples include sulfated nonylphenol ethoxylate available as Triton XN-45S® from Dow Chemical;

(17) Fatty acid ester sulfonates having the formula:

R^CH(SO₃OCO₂R² wherein R¹ is linear or branched C₈ to Cig alkyl, and R² is linear or branched Ci to C₆ alkyl;

(18) Substituted salicylanilide anions having the formula (I):

- R]_n

[R - (X)a - (T)_b - (X')g]m-

wherein m is an integer from 0 to 4; n is an integer from 0 to 5; the sum of m+n is greater than zero; a is 0 or 1 ; b is 0 or 1 ; g is 0 or 1 ; when b is 0, one of a and g must be 0; Z and Z' are independently selected from O and S; X and X', when present, are selected from O, S, and NR¹, where R¹ is independently selected from the group consisting of H, Ci-Ci₆ linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl, and aryl; T, when present, is selected from C=O, C=S, S=O, and SO₂; when T is S=O or SO₂, X and X' may not be S; when either a, b or g is 1 for a radical R-(X)_a-(T)_b-(X')_g-_> R for that radical is independently selected from the group consisting of H, Ci-Ci₆ linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl, and aryl; when a, b and g are all 0 for a radical, R for that radical may be further selected from the group consisting of F, Cl, Br, I, CN, R₂N- »0, NO₂; when all a, b and g are 0, at least one R must be non-H; further provided that the total number of halogen atoms in the molecule excluding any present in R does not exceed two; R is independently selected from the group consisting OfCi-Ci₆ linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl, and aryl, and mixtures thereof; derivatized substituted salicylanilide anions, wherein one or both aromatic rings comprise additional substituents, are also suitable for use herein; substituted salicylanilide and derivatives thereof are disclosed in US 2002/0068014A1 and WO 04/026821; M⁺ is a cation selected from, the cations of the ionic liquids as disclosed herein; (19) Substituted phenol or thiophenol anions having the formula (II):

wherein m is an integer from 0 to 4; a is 0 or 1 ; b is 0 or 1 ; g is 0 or 1 ; when b is 0, one of a and g must be 0; Z is selected from O and S; X and X', wtien present, are selected from O, S, and NR¹; when either a, b or g is 1 for a radical R-(X)_a-(T)b-(X')_g- , R for that radical is independently selected from the group consisting of H, C₁-C₁₆ linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl, and aryl; when a, b and g are all 0 for a radical, R for that radical may be further selected from the group consisting of F, Cl, Br, I, CN, R₂N→O, NO₂; T, when present, is selected from C=O, C=S, S=O, and SO₂; when T is

S=O or SO₂, X and X' may not be S; Y is a radical comprising at least 1 but no more than 20 carbon atoms and containing a substituent -X" -H, where XL" is selected from O, S, and N~(T')_b,-(X"')_a,-R², where a¹ is 0 or 1, b¹ is 0 or 1, and X"¹, when present, is selected from O, S, and NR²; R² is independently selected from the group consisting of H, C]-Ci₆ linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl, and aryl; T¹, when present, is selected from C=O, C=S, and SO₂; when T' is SO₂, X"' may not be S; R³ is independently selected from the group consisting OfCi-Ci₆ linear or branched, substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkaryl, aralkyl, and aryl, and mixtures thereof. The substituted phenol or thiophenol anions are disclosed in US 2002/0068014Al and WO 04/026821; M⁺ is a cation selected from the cations of the ionic liquids as disclosed herein;

(20) Polyamino polycarboxylates: non-limiting examples include ethylene ethylene- diamine tetraacetate (EDTA), diamine tetracetates, N-hydroxy ethyl ethylene diamine triacetates, nitrilo-tri-acetates, ethylenediamine tetraproprionates, triethylene tetraamine hexacetates, diethylene triamine pentaacetates, and ethanol diglycines;

(21) Aminopolyphosphonates: such as ethylenediamine tetramethylene phosphonate and diethylene triamine pentamethylene-phosphonate;

(22) Sweetener derived anions: saccharinate and acesulfamate;

saccharinate acesulfamate

wherein M+ is a cation selected from the cations of the ionic liquids as described herein;

(23) Ethoxylated amide sulfates; sodium tripolyphosphate (STPP); dihydrogen. phosphate; fluroalkyl sulfonate; bis-(alkylsulfonyl) amine; bis- (fluoroalkylsulfonyl)amide; (fluroalkylsulfonyl)(fluoroalkylcarbonyl)amide; bis(arylsulfonyl)amide; carbonate; tetrafluorborate (BF₄ ^"); hexaflurophospliate (PF₆ ^");

(24) Anionic bleach activators having the general formula:

R¹ - CO - O - C₆H₄ -R² wherein R¹ is C₈-Ci₈ alkyl, C₈-Ci₈ amino alkyl, or mixtures thereof, and R² is sulfonate or carbonate; non-limiting examples such as:

4-nonanoyloxybenzene sulfonate

4-dodecanoyloxybenzene sulfonate

4-decanoyloxybenzoate

4-[N-(nonanoyl)aminohexanoyloxy]hexanoyloxybenzenesulfonate are disclosed in US 5,891,838; US 6,448,430; US 5,891,838; US 6,159,919; US 6,448,430; US 5,843,879; US 6,548,467.

Cations

Cations suitable for use in the ionic liquids of the present invention include, but are not limited to, the following materials:

(a) Cations (i.e., in the protonated, cationic form) of amine oxides, phosphine oxides, or sulfoxides: non-limiting examples include amine oxide cations containing one C_8-I8 alkyl moiety and 2 moieties selected from the group consisting of Ci_-3 alkyl groups and Ci_-3 hydroxyalkyl groups; phosphine oxide cations containing one Cio-is alkyl moiety and 2 moieties selected from the group consisting of C_L3 alkyl groups and C_1-3 hydroxyalkyl groups; and sulfoxide cations containing one C₁O_-1S alkyl moiety and a moiety selected from the group consisting of C_1-3 alkyl and Ci_-3 hydroxyalkyl moieties; in some embodiments, the amine oxide cations have the following formula:

wherein R³ is an C_8-22 alkyl, C_8-22 hydroxyalkyl, C_8-22 alkyl phenyl group, and mixtures thereof; R⁴ is an C_2-3 alkylene or C_2-3 hydroxyalkylene group or mixtures thereof; x is from 0 to about 3; and each R⁵ is independently an Ci_-3 alkyl or Ci_-3 hydroxyalkyl group or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups; the R⁵ groups may be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure; other exemplary amine oxide cations include Ci₀-Ci₈, Cio, Ci₀-Ci₂, and C_{I 2}-C_H alkyl dimethyl amine oxide cations, and C₈-Ci₂ alkoxy ethyl dihydroxy ethyl amine oxide cations;

(b) Betaines having the general formula:

R-N⁽⁺⁾(R¹)₂-R²COOH

wherein R is selected from the group consisting of alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkyl aryl and aryl alkyl groups containing a similar number of carbon atoms with a benzene ring treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R¹ is an alley 1 group containing from 1 to about 3 carbon atoms; and R² is an alkylene group containing from 1 to about 6 carbon atoms; non-limiting examples of betaines include dodecyl dimethyl betaine, acetyl dimethyl betaine, dodecyl amidopropyl dimethyl betaine, tetradecyl dimethyl betaine, tetradecyl amidopropyl dimethyl betaine, dodecyl dimethyl ammonium hexanoate; and amidoalkylbetaines which are disclosed in U.S. Pat. Nos. 3,950,417; 4,137,191; and 4,375,421; and British Patent GB No. 2,103,236; in another embodiment, the cation may be a sulfobetaine, which are disclosed in US Patent 4,687,602;

(c) Amphodiacetates, such as disodium cocodiacetate, available as Mackam 2C® from Mclntyre;

(d) Diester quaternary ammonium (DEQA) cations of the type:

R(^ - N⁺ - [(CH₂),, - Y - R¹],,, wherein each R substituent is selected from hydrogen; Ci-C₆ alkyl or hydroxyalkyl, preferably methyl, ethyl, propyl, or hydroxyethyl, and more preferably methyl; poly(Ci-C₃ alkoxy), preferably polyethoxy; benzyl; or a mixture thereof; m is 2 or 3; each n is from 1 to about 4; each Y is -0-(O)C-, -C(O)-O-, -NR-C(O)-, or -C(O)- NR-; with the proviso that when Y is -0-(O)C- or -NR-C(O) -, the sum of carbons in each R¹ plus one is Ci₂-C₂₂, preferably Ci₄-C_2O, with each R¹ being a hydrocarbyl, or substituted hydrocarbyl group; in one embodiment, the DEQA cation is an alkyl dimethyl hydroxy ethyl quaternary ammonium as discussed in US 6,004,922; in another embodiment, the DEQA cation has the general formula:

R₃N⁺CH₂CH(YR¹ )(CH₂ YR¹) wherein each Y, R, R¹ have the same meanings as before; in yet another embodiment, the DEQA cation is [CH₃J₃ N(⁺) [CH₂CH(CH₂O(O)CR¹ P(O)CR*] wherein each R¹ is in the range of Ci₅ to C₁₉;

(e) Alkylene quaternary ammonium cations having the formula:

R, (4,-m) , - N⁺ - R¹ m wherein each m is 2 or 3; each R is independently an alkyl or hydroxyalkyl Ci-C₆ moiety, preferably methyl, ethyl, propyl or hydroxyethyl, and more preferably methyl; each R¹ is independently a linear or branched, saturated or unsaturated C₆-C₂₂ alkyl or alkoxy moiety, preferably Ci₄-C₂O moiety, but no more than one R¹ being less than about Ci₂ and then the other R¹ is at least about Ci₆; or hydrocarbyl or substituted hydrocarbyl moiety, preferably Ci₀-C_2O alkyl or alkenyl, most preferably C]₂-Ci₈ alkyl or alkenyl; in one embodiment, the cation is dialkylenedimethyl ammonium, such as dioleyldimethyl ammonium available from Witco Corporation under the tradename Adogen® 472; in another embodiment, the cation monoalkenyltrimethyl ammonium, such as monooleyltrimethyl ammonium, monocanolatrimethyl ammonium, and soyatrimethyl ammonium;

(f) Difatty amido quaternary ammonium cations such as:

[R¹— C(O)- NR- R²— N(R)₂- R³— NR- C(O)-R¹J⁺ wherein R and R are as defined in cation (e) above, R and R are Ci-C₆ alkylene moieties; for example, difatty amido quats are commercially available from Witco under the Varisoft® tradename;

(g) C_8-22 quaternary surfactants such as isostearyl ethyl imidonium available in its ethosulfate salt form as Schercoquat IIS® from Scher Chemicals, Inc., quaternium-52 obtainable as Dehyquart SP® from Cognis Corporation, and dicoco dimethyl ammonium available in its chloride salt form as Arquad 2C-75® from Akzo Nobel Surface Chemistry LLC;

(h) Cationic esters such as discussed in US 4,228,042, US 4,239,660, US 4,260,529 and US 6,022,844;

(i) 4,5-dichloro-2-n-octyl-3-isothiazolone, which is obtainable as Kathon® from Rohm and Haas;

(j) Quaternary amino polyoxyalkylene derivatives (choline and choline derivatives);

(k) Alkyl oxyalkylene cations;

(1) Alkoxylate quaternary ammoniums (AQA) as discussed in US 6,136,769;

(m) Substituted and unsubstituted pyrrolidinium, imidazolium, benzimidazolium, pyrazolium, benzpyrazolium, thiazolium, benzthiazolium, oxazolium, benzoxazolium, isoxazolium, isothiazolium, imdazolidenium, Guanidinium, indazolium, quinuclidinium, triazolium, isoquinuclidinium, piperidinium, morpholinium, pyridazinium, pyrazinium, triazinium, azepinium, diazepinium, pyridinium, piperidonium, pyrimidinium, thiophenium; phosphonium; in one embodiment, the cation is an substituted imidazolium cation having the formula:

wherein each R and R¹ are as defined in cation (e) above; each R² is a Ci-C₆ alkylene group, preferably an ethylene group; and G is an oxygen atom or an -NR- group; for example, the cation 1 -methyl- l-oleylamidoethyl-2-oleylimidazolinium is available commercially from the Witco Corporation under the trade name Varisoft® 3690; in another embodiment, the cation is alkylpyridinium cation having the formula:

wherein R¹ is an acyclic aliphatic C₈-C₂₂ hydrocarbon group; in another embodiment, the cation is an alkanamide alkylene pyridinium cation having the formula:

wherein R¹ is a linear or branched, saturated or unsaturated C₆-C₂₂ alkyl or alkoxy moiety, or a hydrocarbyl or substituted hydrocarbyl moiety, and R² is a Ci-C₆ alkylene moiety;

(n) Cationic bleach activators having a quaternary ammonium moiety including but not limited to

hexahydro-N,N,N-trimethyl-ζ,2-dioxo- 1 H-azepine- 1 -hexanaminium

N,N,N-triethyl-4-[(hexahydro-2-oxo- lH-azepin- 1 -yl)carbonyl]benzenemethanaminium

N,N-dimethyl-2-[(phenoxycarbonyl)oxy]-N-[2- [(phenoxycarbonyl)oxy] ethyl] ethanaminium

4-(cyanomethyl)-4-methylmorpholinium ; 1 -cyano-N,N,N-trimethylmethanaminium

1 -methyl-3 -( 1 -oxoheptyl)- 1 H-Imidazolium

these and other cationic bleach activators suitable for use herein as cations of the ionic liquids are disclosed in US 5,599,781, US 5,686,015, US 5,686,015, WO 95/29160, US 5,599,781, US 5,534,179, EP 1 253 190 Al, US 6,183,665, US 5,106,528, US5,281,361, and Bulletin de Ia Societe Chimique de France (1973), (3)(Pt. 2),

1021-7; (o) Cationic anti-microbial agents, such as cetyl pyridinium, chlorohexidine and domiphen. (p) Alkylated caffeine cations, such as

wherein Ri and R₂ are Cl to C12 alkyl or alkylene groups, (q) Alkyl poly amino carboxylates, such as

wherein R is C₈ to C₂₂ alkyl or alkylene groups or is coco, tallow or oleyl; non- limiting examples include Ampholak® 7CX/C, Ampholak® 7TX/C, and Ampholak® XO7/C from Akzo Nobel.

Thus, the ionic liquids suitable for use herein may have various anionic and cationic combinations. The ionic species can be adjusted and mixed such that properties of the ionic liquids can be customized for specific applications, so as to provide the desired solvating properties, viscosity, melting point, and other properties, as desired. These customized ionic liquids have been referred to as "designer solvents".

The ionic liquids can be present in various compositions suitable for use in the processes disclosed herein in any desired effective amount. Typically, the ionic liquids are present in an amount ranging from about 0.1% to about 100%, preferably from about 1% to about 85%, and more preferably from about 5% to about 75%, by weight of the textile treating composition. In some embodiments, the ionic liquids comprise at least about 50% by weight of the textile treating composition. In further embodiments, the ionic liquids comprise at least about 80% by weight of the textile treating composition, and in yet further embodiments, the ionic liquids comprise at least about 90% by weight of the textile treating composition.

Many ionic liquids are hygroscopic, thus, may contain appreciable amounts of water (referred to herein as the "innate" or "bound" water) ranging from about 0.01% to less than about 50% by weight of the ionic liquid. It should be noted that "free water" may be added in making the treating composition of the present invention. A person of ordinary skill in the art would recognize that once the components (e.g., innate water and free water) are mixed in a composition, the components can no longer be distinguished by their origin and will be reported in totality as percentage of the overall composition. Thus, the textile treating compositions of the present invention may comprise water, regardless of its origin, ranging from about 0.01% to about 50%, preferably from about 1% to about 40%, more preferably from about 5% to about 30% by weight of the composition. The treating compositions may optionally include a co-solvent. Typical examples of co- solvents include, but are not limited to, linear or branched Cl-ClO alcohols, diols, and mixtures thereof. In specific embodiments, co-solvents such as ethanol, isopropanol, propylene glycol are used in some of the compositions of the present invention. In additional specific embodiments, the ionic liquid textile treating composition is substantially free of free water and/or other organic solvents. These compositions will contain less than about 10 weight percent, more specifically less than about 5 weight percent, even more specifically less than about 1 weight percent, free water and/or other organic solvents.

In some embodiments, the textile treating compositions containing ionic liquids or cocktails of ionic liquids (undiluted with adjuncts, co-solvents or free water) employed herein have viscosities of less than about 2000 mPa-s, preferably less than about 750 mPa-s, as measured at 2O⁰C. In other embodiments, the viscosity of undiluted ionic liquids are in the range from about 0.1 to about 500 mPa-s, preferably from about 0.5 to about 400 mPa-s, and more preferably from about 1 to about 300 mPa-s at 20⁰C. In still another embodiment, the viscosity of textile treating composition containing ILs lowers to less than about 2000 mPa-s, preferably less than about 500 mPa-s, and more preferably less than about 300 mPa-s, when heated to a temperature in the range of about 40⁰C to 60⁰C.

The viscosities of the ionic fluids and compositions containing them can be measured on a Brookfield viscometer model number LVD VII+ at 20⁰C, with spindle no. S31 at the appropriate speed to measure materials of different viscosities. Typically, the measurement is done at a speed of 12 rpm to measure products of viscosity greater than about 1000 mPa-s; 30 rpm to measure products with viscosities between about 500 mPa-s to about 1000 mPa-s; and 60 rpm to measure products with viscosities less than about 500 mPa-s. The undiluted state is prepared by storing the ionic liquids or cocktails in a desiccator containing a desiccant (e.g. calcium chloride) at room temperature for at least about 48 hours prior to the viscosity measurement. This equilibration period unifies the amount of innate water in the undiluted samples.

According to the present processes, the textile comprising fibers is contacted with the composition containing an ionic liquid (which, as noted above, may comprise a mixture or cocktail of ionic liquids) under conditions sufficient to modify surfaces of the fibers and provide, or facilitate provision of, a performance improvement thereto. A performance improvement is any physical property which is improved by the ionic liquid treatment. In one embodiment wherein the textile fibers are in contact with the ionic liquid-containing composition for a sufficient time such that the polarity and/or ionic charges, attributable to presence of IL, may interrupt hydrogen bondings between fibers, thereby crystal structure changes in at least the surfaces of the fibers may result. In another embodiment, the textile fibers are contacted by the ionic liquid-containing composition for a sufficient time such that partial dissolution of at least one outer layer of the surfaces of the fibers may result.

Dissolution of the surface layer(s) and/or changes in crystal structure can provide various improvements in physical properties of the fibers, including, but not limited to, improvements in one or more of the textile's wrinkle resistance, smoothness, softness, shape retention properties, and the like.

Further, modifications obtained according to the present processes, including, but not limited to, partial dissolution of at least one outer layer of the fibers and/or changes in crystal structure, can enable embedding and/or attachment of at least one benefit agent in the surfaces of the fibers, for example, by further contacting the textile with a composition comprising a benefit agent, either simultaneously with or subsequent to the contact with the ionic liquid-containing composition. Alternatively, the benefit agent may be present, either as an adjunct or as an ionic liquid active, in the IL-containing composition.

In one embodiment, the embedded or attached benefit agent is released from the fibers in a controlled manner (e.g., a slow and sustained release over time). In another embodiment, the benefit agent can be protected or stabilized by the ionic liquids such that the benefit agent is delivered in a controlled manner (e.g., by triggering factors, such as copious amount of water, pH change, heat).

Suitable benefit agents include, but are not limited to, perfumes, dyes, dye fixative agents, sizings, skin conditioning actives, vitamins, enzymes, surfactants, anti-abrasion agents, wrinkle resistant agents, stain resistant agents, water resistant agents, flame retardants, antimicrobial agents, metal bleach catalysts, bleaching agents, fabric softeners, anti-pilling agents, water repellant agents, ultraviolet protection agents, brighteners, mixtures thereof (i.e., of two or more of these types of benefit agents). Additional examples of suitable benefit agents are disclosed in U.S. Patent No. 6,488,943, Beerse et al; U.S. Patent No. 6,548,470, Buzzaccarini et al.; U.S. Patent No. 6,482,793, Gordon et al.; U.S. Patent No. 6,573,234, Sivik et al.; U.S. Patent No. 6,525,012, Price et al.; U.S. Patent No. 6,566,323, Littig et al.; U.S. Patent No. 6,090,767, Jackson et al.; U.S. Patent No. 6,420, 326, Sherry et al.; U.S. Patent No. 6,733,538, Panandiker et al.; U.S. Patent Publication No. 2003/0166495A1, Wang at al; and U.S. Patent Publication No. 2004/0121929A1, Wang at al.

The benefit agents may be included in a textile treating composition in any desired amount. Typical textile treating compositions may contain from about 0.001 to about 20 percent by weight of the benefit agent(s). In more specific embodiments, such compositions may comprise from about 0.01 to about 10 percent by weight, and more specifically, from about 0.1 to about 5 percent by weight, of the benefit agent(s). One skilled in the art will recognize in view of the foregoing therefore that the modification may be conducted to any desired depth in the textile fibers and is not limited to surface modifications.

The processes according to the invention may be conducted in any one or combination of continuous, semi-continuous or batch processing techniques. The contacting step may be achieved in a manner known in the art, for example, including, but not limited to, by immersion techniques, or by non-immersion techniques such as spraying, misting, foaming, padding, or the like. In one embodiment, the composition is provided in the form of droplets and the textile fibers are contacted using a non- immersion technique.

Additionally, the process may be conducted during textile mill manufacture or processing, for example in a separate treatment step or during a conventional processing step, for example during a treatment such as sizing, desizing, bleaching, scouring, mercerization, dyeing, printing, finishing, coating, combinations thereof, or the like. Exemplary textile mill processes which may be employed are disclosed, for examp Ie, in U.S. Patent Application Publication No. US 2003/0226213; and in "Textile Processing and Properties: Preparation, Dyeing, Finishing and Performance", by Vigo, Elsevier, 1994. Alternatively, the process may be conducted by a consumer on a garmeαt, for example during home laundering or drying, or other in-home textile/garment treating processes. The specific physical conditions under which the contacting is conducted, may be varied based on the particular textile fiber to be treated, the treating composition used and the desired physical property improvement thereof.

In one embodiment, energy may be applied to the textile fibers, either prior to, simultaneous with and/or subsequent to the contact with the ionic liquid-containing composition, in order to facilitate achievement and/or durability of the desired improvement. Energy may be applied in the form of heat and/or radiation, including, but not limited to microwave, infrared, ultrasonic, or combinations thereof, and the like. Additionally, the contacting step may be conducted under increased pressure, at anϊbient pressure, or under a reduced pressure vacuum.

The time which will be sufficient to obtain modification according to the invention will be dependent on process specifics. In one embodiment, the contact time is at least about one minute. In an alternate embodiment, the contact time is at least about five minutes. After the contacting step has been conducted for a time sufficient to modify surfaces of the fibers and provide or facilitate provision of a performance improvement thereto, the composition is at least partially removed from the textile. In one embodiment, the composition is substantially fully removed, whereby the textile comprises less than about 5 weight percent, more specifically less than about 1 weight percent, and more specifically less than about 0.1 weight percent of the ionic liquid after the removal step. The composition may be removed from the textile by any technique known in the art, including, but not limited to, rinsing with water, pressing, squeezing, padding, centrifugation, vacuum extraction, combinations thereof, and the like. In one embodiment, the composition is collected after it is removed from the textile, for example for recycle and reuse in the process.

All documents cited in the Detailed Description of the Invention are, in relevant part, incorporated herein by reference; the citation of any document is not to be construed as an admission that it is prior art with respect to the present invention.

While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims

What is claimed is:

1. A process for modifying a textile to improve performance of the textile, the process comprising: a) contacting a textile comprising fibers with a treating composition comprising an ionic liquid under conditions sufficient to modify at least a portion o>f the surface of the fibers; b) optionally, contacting a textile comprising fibers with a composition comprising a benefit agent; and c) at least partially removing the treating composition from the textile.

2. The process according to claim 1, wherein the surface modification comprises a partial dissolution of at least one outer layer of the fibers.

3. The process according to any of the preceding claims, wherein the surface modification results in crystal structure change in at least the surfaces of the fibers .

4. The process according to any of the preceding claims, wherein the treated textile exhibits improved property selected from the group consisting of : wrinkle resistance, smoothness, softness, shape retention, and combinations thereof.

5. The process according to any of the preceding claims, wherein the surface modification enables embedding and/or attachment of at least one benefit agent in. the surfaces of the fibers.

6. The process according to any of the preceding claims, wherein the benefit agent is selected from the group consisting of perfumes, dyes, dye fixative agents, sizings, skin conditioning actives, vitamins, enzymes, surfactants, anti-abrasion agents, wrinkle resistant agents, stain resistant agents, water resistant agents, flame retardants, antimicrobial agents, metal bleach catalysts, bleaching agents, fabric softeners, anti- pilling agents, water repellant agents, ultraviolet protection agents, brighteners, and mixtures thereof.

7. The process according to any of the preceding claims, wherein the benefit agent is adapted for controlled release from the surface of the fiber.

8. The process according to any of the preceding claims, wherein the treating composition comprises at least about 50% by weight of the composition of the ionic liquid.

9. The process according to any of the preceding claims, wherein the contacting step is conducted during an additional treatment selected from the group consisting of sizing, desizing, bleaching, scouring, mercerization, dyeing, printing, finishing, coating, and combinations thereof.

10. The process according to any of the preceding claims, wherein the ionic liquid includes an anionic component comprising one or more anions selected from the group consisting of alkyl sulfates, alkoxy sulfates, alkyl alkoxy sulfates, monoesters of sulfosuccinates, diesters of sulfosuccinates, methyl ester sulfonates, alkylaryl sulfonates, alkyl glycerol ether sulfonates, diphenyl ethers, linear carboxylates, cyclic carboxylates, alkyl oxyalkylene carboxylates, monosulfonates of diphenyl oxides, mid-chain branched alkyl sulfates, mid-chain branched alkylaryl sulfonates, mid-chain branched alkyl polyoxyalkylene sulfates, alpha-olefm sulfonates, paraffin sulfonates, alkyl phosphate esters, sarcosinates, taurates, sulfated oils and fatty acids, sulfonated oils and fatty acids, alkyl phenol ethoxy sulfates, alkyl phenol ethoxy sulfonates, fatty acid ester sulfonates, substituted salicylanilides, substituted phenol anions, substituted thiophenol anions, polyamino polycarboxylates, aminopolyphosphates, sweetener-derived anions, ethoxylated amide sulfates, sodium tripolyphosphate; dihydrogen phosphate; fluroalkyl sulfonate; bis-(alkylsulfonyl) amine; bis-(fluoroalkylsulfonyl)amide; (fluroalkylsulfonyl) (fluoroalkylcarbonyl)amide; bis(arylsulfonyl)amide; carbonate; tetrafluorborate (BF₄ ^"); hexaflurophosphate (PF₆ ^"); and anionic bleach activators having the general formula: Ri - CO - O - C₆H₄ -R₂, wherein R, is C8-C 18 alkyl, C8-C 18 amino alkyl, or mixtures thereof, and R₂ is sulfonate or carbonate, and mixturees thereof.

11. The process according to any of the preceding claims, wherein the ionic liquid includes a cationic component comprising one or more cations selected from the group consisting of amine oxide cations, phosphine oxide cations, sulfoxide cations, betaines, diester quaternary ammonium (DEQA) cations, alkylene quaternary ammonium cations, difatty amido quaternary ammonium cations, C_8-22 quaternary surfactants, cationic esters, 4,5-dichloro-2-n-octyl-3-isothiazolone, quaternary amino polyoxyalkylenes, alkyl oxyalkylene cations, alkoxylate quaternary ammoniums, substituted and unsubstituted pyrrolidinium, imidazolium, benzimidazolium, pyrazolium, benzpyrazolium, thiazolium, benzthiazolium, oxazolium, benzoxazolium, isoxazolium, isothiazolium, imdazolidenium, guanidinium, indazolium, quinuclidinium, triazolium, isoquinuclidinium, piperidinium, morpholinium, pyridazinium, pyrazinium, triazinium, azepinium, diazepinium, pyridinium, piperidonium, pyrimidinium, thiophenium; and phosphonium, cationic bleach activators having a quaternary ammonium moiety, cationic anti-microbial agents, alkylated caffeine cations, alkyl poly amino carboxylates, and mixtures thereof.

12. The process according to any of the preceding claims, wherein the textile comprises loose fibers, a yam, a woven textile, a nonwoven textile, a knitted textile, or a fabric article.

13. The process of according to any of the preceding claims, wherein the contacting step is performed by a non-immersive method selected from the group consisting of spraying, misting, foaming, and combinations thereof.

14. The process according to any of the preceding claims, wherein the composition is in the form of droplets.

15. The process according to any of the preceding claims, wherein the composition is removed from the textile by rinsing with water, pressing, squeezing, padding, centrifugation, vacuum extraction, or combinations thereof.

16. The process according to any of the preceding claims, wherein the process further comprises the step of collecting the composition removed from the textile.

17. The process according to any of the preceding claims, wherein energy is applied to the composition prior to or during the contacting step.

18. The process according to any of the preceding claims, wherein energy is selected from heat, microwave, infrared, ultrasonic, and combinations thereof.

19. The process according to any of the preceding claims, wherein pressure is applied during the contacting step.