CA2205357A1

CA2205357A1 - Stain resistant composition containing sulphonated surfactant

Info

Publication number: CA2205357A1
Application number: CA002205357A
Authority: CA
Inventors: Van Giao Nguyen
Original assignee: Individual
Current assignee: 3M Co
Priority date: 1994-12-15
Filing date: 1995-11-17
Publication date: 1996-06-20
Also published as: NZ296923A; AU4031595A; WO1996018765A1; EP0797699B1; JPH10511434A; AUPN008894A0; EP0797699A1; DE69507719T2; DE69507719D1; AU708303B2

Abstract

A direct application process by spray, pad, foam, flood or roller coating of a chemical composition of Novolak resin, polymethacrylic acid, sulphated or sulphonated surfactants and a fluorochemical to provide stain resistance/release to fibrous material, particularly nylon and wool carpets. The finish offers desirable oil, water and dry soil repellency and acid dye stain release without adverse effect on texture (handle) and pile opening. The invention relates to the use of diethanolamine lauryl sulfate as a foaming surfactant that also has stain release property against artificial coloring material commonly found in food and beverages.

Description

STAIN RESISTANT COMPOSITION CONTAINING
SULPHONATED SURFACTANT

Field of the Invention 5This invention relates to a composition and process for providing stain release/rçsi.~t~nr.e to fibrous m~tçri~l.c, particularly polyamide fibrous m~t~ori~l~ such as nylon and wool carpets, nylon, wool, silk fabrics and natural and synthetic le~ther.s The invention also relates to a direct appli~ation process for providing stain release/rç~ t~nre to fibrous m~teri~
Back~round Fibrous polyamide articles such as nylon and wool carpets, nylon, wool and silk fabrics, natural leather and synthetic fibers are particularly susceptible to st~ining by natural and artificial acid colorants such as are ct mmonly found in many foods and beverages. There has been a long felt need for compositions and processes for economically providing such fibrous polyarnide articles with rç~i~t~nr~e to acidcolorant st~inin~
United States Patent No. 4,081,383 (Warburton, Jr., et al.) discloses an anti-soiling tre~tment for carpets and carpet yarns. The carpet or carpet yarns prior to carpet m~nllf~ctllre are coated with a polymeric m~t~ri~l cn~ either (A) a blend of a methacrylic acid emulsion copolymer having an epoxy resin, or (B) a meth~crylic acid ~mlllsi~n copolymer having epoxy monomer units therein. The copolymer in either case contains 40% to 70% by weight methacrylic acid.
United States Patent No. 4,669,812 (Munk et al.) discloses a method for i~ ing stain rç~i.ct~nce to fibers c. ~ ;ll;llg free amino groups, and especially polyamide fibers by contacting the fiber with a solution of an aliphatic sulphonic acid C()l~tZ~ g 8 to 24 carbons, under acidic conditions. If the fibers are not thoroughly rinsed after application of the aliphatic sl1lrhc)nic acid the product of this method a~er being dried has an undesirable finish due to the deposition of a filmy coating.
United States Patent No. 4,579,762 (Ucci) discloses stain resistant nylon carpet in which the nylon fibers are made from polymers modified to contain, as an CA 0220~3~7 1997-0~-14 integral part of its polymer chain, aromatic sulphonate units and in which the backing adhesive contains a fluorochemical.
United States Patent No. 4,329,391 (McAlister) discloses the tre~tment of synthetic fibers with a sulphon~t~cl polyester stain-releasing finish in an aqueous bath S which includes the addition of water soluble salts to the aqueous fabric treating bath.
United States Patent No. 3,322,488 (Freeman) discloses sulphomethylated contl~n~tion products of bisphenols and aldehydes for use in treating synthetic polyamide and polyurethane fibers to render them resistant to acid and direct dyes.
Australian Patent No. 599427 discloses a method for il~ hlg polyamide 10 m~teri~l~ with stain resistance to natural and synthetic colorants which compri~es cont~r,ting the polyamide m~teri~l with a water-soluble divalent metal salt of apartially sulrhc)n~te-l novolak resin.
Australian Patent No. 632641 (hereafter the "'641 patent") describes a method for illlp~lillg stain resistance to fibrous polyamide m~teri~l~ in which the polyamide 15 m~teri~ are coated with stain resistant agents compri~ing (a) a partially sulphonated novolak resin, and (b) polymethacrylic acid, copolymers of meth~rrylic acid or combinations of said polymethacrylic acid and copolymers of polymethacrylic acid, or combinations of (a) and (b).
Conventional tre~tment processes require thorough washing of the treated 20 polyamide m~teri~l prior to drying in order to remove resin which is not associated with the fibers. Unfixed reagents cause gluing of the fibers. In terms of processing or treating large amounts of m~teri~l, this is inconvenient and costly, as well as environment~lly problematic given the organic waste produced.
Thus, there ~ elllly exists a need for compositions and processes for 25 imparting stain resistance to fibrous materials which do not adversely effect the finish of the treated fiber, which fully treat the fibrous material avoiding "dead spaces", and which do not reduce the performance of fluorochemical tre~tment~ for oil and water repellency.

Disclosure of Inverltion According to a first aspect of the invention there is provided an aqueous treating composition for providing stain release properties to fibrous m~t~ri~l~ which comprlses:
S (a) polymethacrylic acid or copolymers of methacrylic acid or combinations thereof;
(b) a partially s-llphon~ted novolak resin;
(c) a surfactant co~ g a sulphate or sulphonate moiety; and (d) water.
In a pl~r~ d embodiment, the sulphonated surfactant is an aromatic or aliphatic mono- or poly-sl-lrhon~te-l fatty acid. In a still further plefe,l~d embodiment, the sulphonated s~ rt~nt is a sulphonated fatty acid alkanolamine contlen.c~te.
This invention is also directed to a process for providing fibrous m~teri~l and 15 leather with stain release p~up~"ies which compri.ces applying directly to said m~t~.ri~l a composition which comprises:
(a) polymethacrylic acid or copolymers of methacrylic acid or comhin~tions thereof;
(b) a partially sulphonated novolak resin;
(c) a sllrf~c.t~nt cu.ll;~ a sulphate or sulphonate moiety, and (d) water and thereafter drying the m~teri~l.
In a further l.refell~d embodiment the tr~tn ent composition is applied to fibrous m~teri~l~ using a foaming agent as a carrier.
Detailed Description The aqueous treating composition for providing stain release properties to fibrous m~t~n~l~ and leather comprises three key components:
(i) polymethacrylic acid or copolymers of methacrylic acid or combinations thereof, , CA 0220~3~7 1997-0~-14 WO 96tl8765 PCTtUS95/15112 (ii) a partially sulphonated novolak resin, and (iii) a ellrf~r,t~nt co~ )g a sulphate or sulphonate moiety.
Preferably, the treatment composition also includes a volatile orgar~ic acid.
When the composition of the invention is applied to fibrous m~t~ri~l, 5 particularly polyamide fibers, such as nylon and wool carpets, nylon, wool, silk fibers and fabrics, natural and synthetic leathers and the like, stain release properties are imparted without loss of product finish.
The term "stain release" used herein refers to the property of ready release of stains which have been absorbed by fibrous m~teri~l~ or leather. The term "stain10 resistance" used herein refers to anti-wetting properties which result from tre~tment of fibrous m~t~.ri~l~ or leather with fluorochemic~
The polymethacrylic acid, copolymers of methacrylic acid, or combinations thereof are embraced in this disclosure by the term "methacrylic polymer", which is inten(le~l to include polymethacrylic acid homopolymer as well as polymers formed 15 from methacrylic acid and one or more other monomer.~
The monomers useful for copolymeri7~tion with the methacrylic acid are monomers having ethylenic unsaturation. Such monomers include, for example, monocarboxylic acids, polycarboxylic acids, and anhydrides; ~ub~lilul~d and unsubstituted esters and amides of carboxylic acids and anhydrides; nitriles; vinyl 20 monomers; vinylidene monomers; monoolefinic and polyolefinic monomers; and heterocyclic monomers.
Representative monomers include, for example, acrylic acid, itaconic acid, citraconic acid, aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, Cilln~ iC acid, oleic acid, palmitic acid, vinyl sulphonic acid, vinyl phosphoric 25 acid, alkyl or cycloalkyl esters of the foregoing acids, the alkyl or cycloalkyl groups having 1 to 18 carbon atoms such as, for example, ethyl, butyl, 2-ethylhexyl, octadecyl, 2-sulphoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl and hydroxypropyl acrylates and methacrylates, and amides of the foregoing acids, such as, for example, acrylamide, methacrylamide, methylolacrylamide, and 30 1,1-dimethylsulphoethylacrylamide, acrylonitrile, methacrylonitrile, styrene, CA 0220~3~7 1997-05-14 WO 96/18765 PCT/US95/lS112 S
a-methylstyrene, p-hy~o~y~ylene, chlorostyrene, sulphostyrene, vinyl alcohol, N-vinyl pyrrolidone, vinyl acetate, vinyl chloride, vinyl ethers, vinyl slllphides, vinyl toluene, butadiene, isoprene, chloroprene, ethylene, isobutylene, vinylidene chloride, snlph~ted castor oil, slllph~ted sperm oil, snlph~t~l soybean oil, and sulphonated 5 dehydldl~d castor oil. Particularly useful monomers include, for example, ethyl acrylate, itaconic acid, sodium sulphostyrene, and slllph~te~l castor oil. Mixtures of the monomers can be copolymeri7~-1 with the mçth~rylic acid.
The methacrylic polymers useful in the present invention can be prepared using methods well known in the art for polymeri7~tion of ethylenically wlsdLuldLed 1 0 mon-)mer~
Preferably, the methacrylic acid comprises about 30% to 100% by weight, more preferably 60% to 90% by weight, of the methacrylic polymer. The optimum proportion of methacrylic acid in the polymer is dependent on the comonomers used, the molecular weight ofthe copolymer, and the pH at which the m~tP.ri~l is applied.
When water-insoluble comonQmers, such as ethyl acrylate, are copolymeri7~d with the methacrylic acid, they may comprise up to about 40% by weight of the methacrylic polymers. When water-soluble mont~mers, such as acrylic acid or sulphoethyl acrylate are copolymeri7~1 with the methacrylic acid, the water-soluble comonomers preferably comprise no more than 30% by weight of the methacrylic polymer and preferably the methacrylic polymer also comprises up to about 50% byweight water-insoluble monomer.
Generally, the methacrylic polymer should be su~lciently water-soluble that l application and penetration of the polymer into the fiber surface can be achieved.
The glass transition temperature of the methacrylic acid copolymer can be as low as about 35C although high glass transition temperatures are preferred. When polymers having high glass transition temperatures, that is, as high as 230C orhigher, are used, an additional beneflt of improved soil resistance of the fibrous polyamide substrate can be obtained.

CA 0220~3~7 1997-0~-14 The weight average molecular weight and the number average molecular weight of the methacrylic polymer should be such that satisfactory stain resistance is provided by the polymer. Generally, the higher 90% by weight of the polymer m~t~ri~l preferably has a weight average molecular weight in the range of about 3000 to 100,000. Generally, the lower 90% by weight ofthe polymer material preferablyhas a number average molecular weight in the range of about 500 to 20,000 more preferably in the range of about 800 to 10,000. Generally, more water-soluble comonomers are pl~re,led when the molecular weight of the polymer is high and less water-soluble or water-insoluble comonomers are ~l~rel,~d when the molecular weight of the polymer is low.
Commercially available methacrylic polymers generally useful in the present invention include LeukotanTM 970, LeukotanTM 1027, LeukotanTM 1028 and LeukotanTM QR 1083 available from Rohm and Haas Co~ )~ly.
The partially sulphonated novolak resins useful in this invention include known substances such as those compositions which are cnn-l~n~tion products of formaldehyde with bis (hydroxyphenyl) sulphone and phenylsulphonic acid. Insteadof, or in addition to, form~ hyde, another aldehyde such as, for exarnple, acetaldehyde, furfuraldehyde, or ben7~l~1ellyde, can be used to make the con-l~n~tion product. Also, other phenolic compounds such as, for example, bis(hydroxyphenyl)alkane, for example, 2,2-bis(hydroxyphenyl)propane, and bis(hydroxyphenyl)ether compounds can be used instead of, or in addition to, thebis(hydroxyphenyl)sulphone. The sulphnn~te~l novolak resin is partially sulphonated, that is, has a sulphonic acid equivalent weight of about 300 to 1200, preferably 400 to 900.
Examples of such resins are disclosed in United States Patent No. 4,592,490 (Bly~ et al.). Also commercially available sulphonated novolak products are available such as: FX-369, a stain release product available from Minnesota Mining and M~nllf~ lring Com~ally, St. Paul, Minnesota, U.S.A.; IntratexTM N available from Crompton and Knowles Corp., North Carolina, U.S.A.; ErionalTM PA available from Ciba-Geigy AG, Basle, Switzerland; NylofixanTM P available from Sandoz CA 0220~3~7 1997-0~-14 WO 9611B765 PCT/US95/1~112 Chemicals Ltd., North Carolina, U.S.A., MesitolTM NBS available from Mobay Chemical Corp., Pennsylvania, U.S.A.; ~esist 4TM available from Lyndal Chemical Co., U.S.A.; MakTM 7 available from Allied Signal Inc., New Jersey, U.S.A.; NRD
329 and NRD 332 available from DuPont Co., Delaware, U.S.A.; AmeriolateTM
5 available from American Emulsions Co~ Inc., Georgia, U.S.A.; and SynthabondTM
1938 available from Piedmont Chemical Industries, North Carolina, U.S.A.
Sulphonation of phenolic compounds is taught, for example, in Sulfonation and Related Reactions, E E Gilbert, Interscience Publishers, 1965. Con~len~ation of phenol-formaldehyde resins is taught, for example, in Phenolic Resins, A Knopf et 10 al., Springer-Verlag, 1985.
Other partially sulphonated novolak resins which may be used in place of or in addition to the aforementioned novolak resins include those resins described in ctr~ n Patent No. 599427, that is, a water-soluble divalent metal salt of a partially sulphonated novolak resin, wherein the salt contains less than 1% sulphonic acid moieties. The te~ ingc of Australian Patent No. 599427 are incorporated herein by reference in their entirety.
The s--lph~te~l or sulphon~te-l snrf~t~nt used in l~l~mg the aqueous treating compositions of this invention include alkyl aryl sulphonated and hydroxyethylated fatty amines and their derivatives, such as UnivadineTM PS-AU
20 available from Ciba-Geigy AG, Basle, Switzerland, which comprises an alkyl aryl sulphonate and hydroxyethylated fatty amine of the formulae:

Na 0- 9~R

OIH
"~C~C--C~C~C~C,NH2 OH

CA 0220~3~7 1997-0~-14 WO 96/18765 PCrrUS95/15112 in which R is an alkyl chain of 14 to 18 carbons, and MiltopanTM D503 available from Henkel Australia Pty. Ltd., Victoria, Australia which has the formula:

~So~3Y+ r Rl .
5 in which Y is an alkali, and Rl is a C6 to C18 group which substitutes the phenyl ring at the 1, 2 or 3 position; sodium alkyl diphenyl ether ~ llphonates~ such as PelexTM
SS-L available from Kao Corporation; sodium dodecyl diphenyl oxide fli~lllphon~te with high sulphur bond (co~ ammonium thiosulphate) such as PelexTM SS-H;
dodecyl (sulphophenoxy) benzene sulphonic acid, disodium salt; oxybis 10 (dodecylbenzene slllphonic acid) disodium salt such as RhodacalTM DSB, siponateTM
DSB available from Rhone-Poulenc Pty. Ltd., Victoria, Australia; oxybis (dodecylbenzene sulphonic acid) disodium salt co"l~i"i~.~ xylene, KemmatTM SN18 available from Harcros Chemicals Pty. Ltd., New South Wales, Australia; aryl sulphonates; fatty amine polyglycol ether (slllph-)n~te ethylene oxide contlen~t~) 15 such as TEBANTM ES available from Dr TH Bohme Chemie, Geretsried, Ger~nany;
sodium salts of highly sulphonated oil/ethylene oxide contl~n~te, such as MATEXILTM LA-NS available from ICI, New South Wales, Australia; dodecyl (sulphophenoxy) benzene sulphonic acid, disodium salt oxybis (dodecylbenzene slllphonic acid) disodium salts collli1;";l-~ at least 1% sodium sulphate and at least 20 3% sodium chloride, such as DowfaxTM 2-Al available from Dow Chemicals Pty.
Ltd., New South Wales, Australia; benzene sulphonic acid, dodecyl (sulphophenoxy) disodium salt, monosodium and didodecyl tli~nlphonated diphenyl oxide such as CALFAXTM DB-45 available from Pilot Chemicals Inc., Los Angeles, California, U.S.A.. Other examples of sulphonated surfactants which may be used in the 25 invention are disclosed in McCutcheon's Fm~ ifiers and D~L~1`g~ , Tnt~rn~tional Edition, 1983.
Aromatic or aliphatic mono or poly-sulphonated fatty acids are preferred, such as those co"~ ""g 8 to 20 and more preferably 8 to 16 carbon atoms in the _ 9 fatty acid ~lirh:~tic chains. Examples of alkyl groups which may used in the sulphonated fatty acids include, octyl, nonyl, decyl, dodecyl (lauryl), eicosyl, nicosyl, docosyl, tricosyl and tetracosyl group. The alkanoyl groups which may be used are monounsaturated analogues of those above, that is, octenyl, nonenyl and the like.
Alkanolamine and alkanolamide sulphon~te~l fatty acids are ~-~felled such as those CO.~ g Cl to Cl0 alkyl groups. These compounds are the con~lene~tion products of aliphatic fatty acids and hydroxy alkyl amines. Reference to alkanolamine and alkanolamide sulphonate fatty acids includes the mono-, di- andtri-alkanolamine and alkanolamide con~ne~t~s Fatty acid diethanolamide and diethano1~mines are versatile and widely used s~ ct~nte Examples ofthe fatty acid component of such compounds include ricinoleic, lauric, linoleic, tall oil, coco, lauric, oleic, stearic, capric and isosteric acid, all of which are described inKirk-Othmer Encyclopedia of Chemical Technology 3rd Edition, Volume 22, at Table 24, which reference is incorporated herein in its entirety.
The most ~rerell.,d s~11rhnn~tecl fatty acids according to this invention are the ethanolamine lauryl s1-1rh~tes, particularly diethanolamine lauryl s~11rh~te, a commercially available surfactant which is sold under the trade mark Empicol DA by Albright & Wilson, Victoria, ~uetr~ Diethanolamine lauryl s111rh~1e has the following formula:

Cl IH230S03.NH2(CH2CH20H)2 The fatty acid ethanolamine lauryl s111rh~tes, as well the other sulphonated fatty acid surfactants, can be applied in the form of a foam given their detergent pl~lLies. This is an advantage, as will be hereinafter described in further detail.
~ . .... ~ ..
The respective amounts of the m~th~crylate, novolak resin and sl11phnn~te(1 s11rf~ct~nt used in the compositions of the invention are those which provide the desired degree of stain release from the fibrous m~t~ri~1s, without adversely effecting the finish ofthe fibrous m~t~ri~1e or re-l11cing the effects of fluorochemical tre~tmt?nt.s 30 for water repellency. It has surprisingly been found that sulphonated surfactants can CA 0220~3~7 1997-0~-14 replace to a ~ignifie~nt extent the methacrylate polymer and novolak resin previously thought to be n~ce~ry in significant quantity.
This substitution enhances the effects of the treating composition in a number of unexpected ways. Firstly, the sllbstitlltion provides a greater penetration into the 5 fibrous m~teri~l~, thereby ensuring that the totality of fibers are treated. Secondly, the gluing effect which results from the direct application of high concentrations of methacrylate polymer in the order of 15% to 90% in association with a novolak resin is avoided giving a soft h~nrlling finish to polyamide fibers. This is particularly significant in the carpet industry where a high texture bloom (opening of the yarn 10 ends to give softer feel or hand) is ~l~rn~n~lecl by carpet cll~tomers, particularly in respect of nylon carpets. As treated fibers according to this invention are not washed to remove non-fixed m~teri:~l, significant economic and environment~l benefits apply. Thirdly, methacrylate polymers and novolak resins reduce the effects of fluorochemical tre~tment due to their strong hydrophilic properties and hence the 15 ability to reduce the amounts ofthese m~teri~l~ without tlimini~hing stain release properties is an important advantage.
Generally, the compositions of the invention contain from 20% to 90% by weight of sulphonated sllrf~- t~nt, preferably 30% to 8Q% by weight and more preferably 30% to 60% by weight. The methacrylate polymer and novolak resin are 20 generally provided in ~ oxilllately the same weight ~ut;;lct;ll~ge in the composition, in amounts from about 5% by weight to 30% by weight, preferably 10% to 20% by weight.
The treating compositions according to the invention may contain other ingredients which increase effectiveness, stability of the composition, miscibility, 25 foaming properties and the like. For example, these compositions may contain ingredients which make the composition more suitable for use and less susceptible to degradation.
Minor amounts of additives such as wetting agents improve migration of compositions along fiber tips and improve stability of the compositions. An example CA 0220~3~7 l997-0~-l4 of such a wetting agent is wetting agent NFTM from Hoechst AG which is a modified diestersulphosuccinate acid s~ .t~nt Minor amounts of de-aerating and stabilizing additives may be used in an amount from 1% to 10% by weight. An example of such an ingredient is LeonilTM
S GP-Z from Hoechst AG, which composition is a nonylphenylethoxylate s~ t~nt Divalent metal salts may be used in the treating compositions. Suitable divalent metal salts include water-soluble inorganic and organic salts of metals, such as m~gn~eium, calcium and zinc. Organic metal salts include, for example, acetates and formates of the aforementioned metals. Preferred divalent metal salts are 10 m~gn~eium slllrh~t~, m~gn~eium chloride and calcium chloride. Mixtures of two or more divalent metal salts may be used. When divalent metal salts are added to the treating composition, they are preferably used in an amount of at least 0.5% by weight of solids, based on the weight of the fabric ("owf"), more preferably at least 1% by weight of solid owf, most preferably at least 2% by weight of solid owf.
Preferably, an organic acid, more preferably a volatile aliphatic carboxylic acid, is used in the treatment compositions according to the invention. Examples of volatile carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid and valeric acid, with forrnic acid and acetic acid being particularly pl~f~ d. Acids are believed to assist in fixation of stain release reagents to polyamide fibers.
20 Conventional methods in the art use strong mineral acids and non-volatile acids for fixation of novolak resins and methacrylate polymers. These acids must be removed by washing of the fibers. Volatile acids, in contrast, are simply removed from polyamide fibers during conventional drying procedures, which for carpets is above 120C. Under such conditions, volatile acids are liberated from the fibers leaving no 25 acidic residue. Acids may be used in an amount from 0.1% to 5% by weight of the composition at a pH of about 2.0 to 4Ø Without wishing to be limited to any reaction mech~nieme, it is believed that at low pH the affinity of the stain release reagents and the polyamide fiber is greater, allowing chemical bonding by dipolar attraction as well as covalent bonding to amine groups on the fiber (the sites of dye 30 binding).

CA 0220~3~7 l997-0~-l4 WO 96/18765 PCTrUS9S/15112 Foaming agents as are well known in the art may be incorporated into the composition of the invention in order to assist application as a foam. ~It~rn~tively, the composition itselfmay form a foam on agitation due to the p~up~lLies ofthe sulphonated ~ r,t~nt or other components.
The aforementioned ingredients may be simply added to the composition of the invention prior to treating fibrous m~tt?ri~l The composition of the invention may be coapplied with a fluoroch~.mir~l composition in order to provide oil, water and soil repellency (that is, stain resi~t~nce) in addition to stain release properties. The fluorochemical composition is 10 added in an ~prop.;ate amount to the treating solution. The r~sult~nt compositions may be referred to as stain release/resistant compositions.
The fluorochemicals which may be used in the present invention for providing oil and water repellency include anionic, cationic, or nonionic fluorochPmic~l~ which are usually provided as aqueous emulsions, such as the 15 fluorochemical alloph~n~tçs disclosed in United States Patent No. 4,606,737 (Stern);
fluorochemical polyacrylates disclosed in United States Patent Nos. 3,574,791 (Sherman et al.) and 4,147,851 (Raynolds); fluorochPmic~l~ urethanes disclosed in United States Patent No. 3,398,182 (Guçnthner et al.); fluorochemical carborliimide~
disclosed in United States Patent No. 4,024,178 (T ~n~llcci); fluorochemical 20 guanidines disclosed in United States Patent No. 4,540,497 (Chang et al.); and fluorochemical potassium salts (which are self curing or cross-link under ambient temperatures).
The fluorochemical, when included in the treating solution, is preferably present in an amount that is sufficient to retain on the fiber of the finished article 25 about 200 to 1000 ppm fluorine based on the.weight of the fiber. This can generally be achieved by using at least about 0.4% product owf? more preferably at least 0.7%
product owf, most preferably 0.8% product owf. Generally, amounts of the fluorochemical in excess of 2% product do not appreciably improve the oil and water repellency.

CA 0220~3~7 l997-0~-l4 The respective components of the treating composition are admixed ~ltili7inp;
standard procedures. Heat and agitation may be applied as neces.~ry. The pH of the treating solutions depends on the fiber being treated. Generally, the pH is acidic in the range of 2.0 to 4.0, more preferably 2.5 to 4.5. pH may be adjusted with acid or 5 base reagents.
The tre~tmen~ composition according to the invention can be conveniently applied directly to a fibrous substrate by spraying, dipping, coating, p~ lin~, foarning or roller coating application, or by a combination of two or more of these methods. Application by way of foarning is particularly pl~r~lled as the amount of 10 composition applied is much decreased compared to other applications, wastage of treating solution is minimi7ed and processing is stre~mlin~l In this regard, the use of alkanolamine and alkanolamide sulphonated fatty acids are particularly pl~r~ d given their d~ ,ell~ o~ ies and the subsequent ease with which foaming p~ dLd~ions can be prepared according- to processes well known in the art. As no15 washing is required to remove non-fixed reagents, overall processing is str~mline~l and waste products minimi7P~l The interaction between the components of the keatment composition of the invention may be regarded as synergistic. ~ltern~tively, the result of the combination may be regarded as unexpected. These considerations arise from a 20 number of perspectives. Sulphonated surfactants have not hitherto been proposed as stain release agents. When applied directly to fibrous m~t~ri~l.c such as carpets at high levels, excess sulphonated surfactants have the disadvantage that they leave a filmy residue after drying and actually atkact dry soil, (such problems are associated with the processes of United States Patent No. 4,699,812 (Munk et al.) described25 earlier in this document). However, when sulphonated surfactants are used in combination with a methacrylate polymer and novolak resin (that is, to substitute a proportion of these components), these problems are overcome, particularly in the situation where the sulphonated surfactant is used to an appreciable extent, such as 15% to 80% by weight of the keatment composition.

CA 0220~3~7 1997-0~-14 The use of a sulphonated s~ ct~nt in the tre~trnent composition of the invention does not adversely effect the actions of the methacrylate polymer and novolak resin and removes disadvantages associated with these agents. For example, methacrylate polymers when applied directly (that is, without washing after S application) to fibrous m~tto.r~ may cause aggregation or a gluing effect which adversely effects the fini.~h.?rl product, giving a hard texture due to the aggregated fibers as well as a poor texture bloom. This is a particular problem in nylon carpets where the weight of the carpet ~le~ es costs. Where standa=rd nylon carpets are treated with methacrylate polymers and novolak resin by direct application, the fiber aggregation is such that the carpet appears to have a much less open bloom and therefore gives the hll~l~s~ion of being of a much lesser quality, that is, less weight per square yard. Utilizing the compositions of this invention, however, carpets are provided with a normal open bloom which gives the impression of a much greater veight carpet, particularly with carpet yarn density below 20 oz/yd2 (ounces/square 1 5 yard).
The interaction between the components of the tre~tment composition of this invention also removes the problems associated with coapplication of fluorochemicals for water and oil repellency. Methacrylate polymers and novolak resins have been found to be hydrophilic in nature and the use of these treatingcompositions as in prior known proposals largely reduces the effects of fluorochemical tre~tment, namely water repellency. In the tre~tment compositions of this invention these problems are overcome with the result that the methacrylatepolymer and novolak resin employed in the composition do not effect the performance of coapplied fluorochemic~l~. This is particularly advantageous.
Fibrous material which may be treated according to this invention include polyamide fibrous materials such as nylon and wool carpets, nylon, wool, silk fabrics and natural and synthetic leathers. .-The following non-limitin~ examples serve to illustrate the invention. All ratios are by weight and percentages are weight percent unless otherwise indicated.

WO 96/18765 PCT/US9511~112 Te-~t Methods A. Oil Repellency Test (OR) The oil repellency of treated carpet and textile samples is measured by the American Association of Textile Chemists and Colorists (AATCC) Standard Test S Method No. 118-1983, which test is based on the resistance oftreated fabric to penetration by oils of varying surface ten.cion~. Treated fabrics resistant only to KaydolTM, a brand of mineral oil and the least penetrating of the test oils, are given a rating of 1, whereas treated fabrics resistant to heptane (the most penetr~ting of the test oils) are given a value of 8. Other immediate values are ~letermined by use of other pure oils or mixtures of oils, as shown in the following table:

STANDARD TEST LIQUIDS
AATCC Oil Repellency Rating ~omposition Number KaydolTM

2 63:35 KaydolTM: he~lec~ne by volume at 3 n-h~ lec~ne 4 n-tetr~-lec~ne n-dodecane 6 n-decane 7 n-octane 8 n-heptane The rated oil repellency corresponds to the most penetrating oil (or mi~ of oils) which does not penetrate or wet the fabric after ten seconds contact. Higher numbers 15 indicate better oil repellency.
- In the test procedure the test sample is placed on a flat surface. A dropper pipette is used to gently place five drops of the selected oil onto the sample at 5 cm intervals. After ten seconds, if four out of five drops are still visible, the sample passes the test. A rating of "2" is generally considered a minimllm requirement.
-CA 0220~3~7 1997-0~-14 B. Water Repellency Test (WR) The aqueous stain or water repellency of treated samples is measured using a water/iso~lu~yl alcohol test, and the result is ~ lcssed in terms of a water repellency 5 rating ofthe treated fabric. Treated fabrics which are resistant to a 100% water/0%
isu~lv~yl alcohol lllixlule (the least penetrating ofthe test ~ ulcS) are given a rating of W; re~i~t~n~e to a 90% water/10% isopropyl alcohol mixture is given a rating of 1, whereas treated fabrics resistant to 0% water/100% isopropyl alcohol llliXLulc (the most penetrating ofthe test llli~lulcs) are given a rating of 10. Other 10 int~rm~?Ai~te values are ~iet~rrnin~cl by use of other water/isopropyl alcohol llliXlUlCS, in which the pcrcclll~ge amounts of water and isopropyl alcohol are each multiples of ten. Results are reported as an average of replicate testing. The water repellency rating co~lc~onds to the most penetrating llli~lule which does not penetrate or wet the fabric after ten seconds.
The procedure involves placing five small drops of water/alcohol llli~lulc onto the carpet face. After ten seconds, if four out of five drops are still visible, the sample passes the test.
A rating of "1" (90/10 water/iso~.u~anol llli~lulc) is generally considered as aIllillilllUlll requirement.
C. Dry Soil Repellency (~S) This test is intPn-lecl to measure the tendency of a carpet to resist dry soil during the use. The soil contains clay, carbon black, silica and mineral oil. It is deposited on to the carpet via a soil capsule in a tumbler coll~ g seventy steel25 balls. The tumbler rotates for ten min~lt~s and the carpet samples are removed and the excess soil is blown off by an air nozzle at 50 psi. The degree of soiling resistance is measured by comp~ring the soiled area to a standard rating board. A 5.0 rating is the absolute standard of soil repellency and 3.0 is an acceptable soiling degree.

CA 0220~3~7 1997-0~-14 D. Twenty Four Hour ~tain Release Test (SR) This test is designed to evaluate the effectiveness of stain resistant tre~tment.c on carpet against acid staining medium (artificial colourings in food and drink). A
stock solution using 80 mg of FD8C Red 40 is dissolved in one liter of water co~ ;llg citric acid to pH 3.0 ~ 0.2; a 15 ml aliquot ofthe staining medium is deposited on carpet sample via a bottomless staining ring of approximately 50 mminternal diameter. The stained sample was left untouched for 24 ~ four hours in room temperature, on a flat and non-absorbing surface. It is rinsed in luke-warm running water until no more stain is released, then dried and rated against 3M Stain Release 10 Rating Scale - where a score of 8.0 is absolute stain release, 6.0 is average and scores under 5.0 are not acceptable.

E. MRTF Li~ht Fastness (LF) This test d~le. .,.i.~es the colour fastness oftextiles to light, using an artificial 15 light source. A test specimen ofthe textile, together with blue light fastness standards, is exposed to the light from a 500 W mercury vapour, tungsten fil~ment larnp. Fading/colour change is rated against the blue scale standards - while 8.0 as an absolute rating and 5.0 as a minimum industry requirement.

F. Handle of Texture (HAND) ~ses~ment is done by subjectively "feeling" the surface texture and compa~ g the sample to that from a conventional finish. The softness degree of the sample finished by foam co-application must be about the same as the conventional finish which is described as the one accomplished by the hot flood of the stain release 25 and spraying of the ScotchgardTM product.

G. Openin~ of Texture (Bloom) ~ses~ment is done by visual or microscopic close-up observation of the texture for the opening of the individual yarn (made up of a group of filament). An 30 "open" bloom is defined as similar to that of the texture of carpet receiving no -CA 0220~3~7 1997-0~-14 WO 96/18765 PCT/US95/1~112 protective chemical finish, that is, the fil~ment.~ do not bundle closely together. This achievement is particularly significant for lower weight carpets (below about 20 oz =
680 gsm). A carpet with an open bloom has the appearance of an expansion or spread of the carpet fibers, giving a greater a~)pa~ buL~. For a given weight carpet, it is advantageous to provide the appearance of increased bulk.

The stain release and other test properties outlined above were compared using sulphonated surfactants only, a combination of novolak resin and polymethacrylate polymer, and the combination of sulphonated surfactant, novolakresin and polymethacrylate polymer according to this invention.
In this example, 108 grams of each product were dissolved in one liter of water. The solution was applied to a 19 oz/yd2 cut pile nylon 6,6 ca~pet in an amount of 15% by weight of the carpet resllltin~ in a minimum application level of 1.6%product on carpet (POC). The solution also c- nt~in~l 4 g of m~gne~ium slllph~tedihydrate and 47 g of an anionic fluorochemical (0.7% POC) in order to test for water and oil resi~t~nee, and soil repellency. The tre~tment compositions were applied by direct spray, foam and pad methods. For the test results described in this example, spray application was used. After application, the carpet was subjected to drying in an oven at between 120C to 130C until dry. The parameters assessed were oil repellency (OR), water repellency (WR), dry soil repellency (DS), twenty four hour stain release (SR), MBTF of light f~tne~.~ (LF), handle of texture (HAND) and opening of texture (Bloom). The tre~tment composition of the invention contained the following components:
1. methacrylate polymer F-7867 15%
2. novolak resin FX-369 14%
3. sulphonated surfactant Empicol DA 50%
4. wettingagent NF 1%
5. de-aerator Leonil GP-Z 7%

6. formic acid 3%

7. water 10%
The tre~tment composition was applied at 1.6% product owf.

Components (1 ) and (2) are comrnercially available products of Minnesota 5 Mining and Manufacturing Co~npally, St. Paul, Minnesota, U.S.A. Component (1) is a polymethacrylic acid polymer formed from methacrylic acid and one or more monomers having ethylenic unsaturation. The molecular weight of the polymer is preferably in the range of 800 to 10,000 daltons. The partially sulphonated novolak resin (2) has a s-llphc nic equivalent weight of preferably 400 to 900.
Component (3) is from Albright & Wilson Australia Ltd., St. Marys, New South Wales, Australia, and comprises diethanolamine lauryl slllphAt~. Component(4) is a non-flAmmAble (NF) wetting agent from Hoechst AG, Frankfilrt, Gerrnany which comrri.~es a modified diester sllll hosl~cinic acid sllrfArt~nt, which component improves stability of the composition at low temperature (below 5C). Component 15 (5) is from Hoechst AG and comprises a nonyl phenol ethoxylate and alkane sulphonate surf~t~nt~ in iso~r~pallol, and is used as a de-aerator as well as to assist in solubilization and stabilization of F-7867 and FX-369.
The test results obtained from the above treatments are set forth in Table 1 below:

OR WR DS SR LFHAND BLOOM
Surfactant/FC 4 3 2 6 6Soft Filmy Open NovolaklFC 4 1 3 7 2ModeratePartial gluing Methacrylate/FC 4 0-1 4 7 6 Harsh Gluing Novolak/methacrylate/FC 4 0-1 4 8 6 Harsh Gluing Combination 4 3 3.5 8 6 Sofl[ Open These results clearly show the Im~ti~f~t~ry results obtained with the application of surfactant, novolak resin, me~acrylate polymer, and the combination of methacrylate polymer and novolak resin when using the direct application 25 method.

CA 0220~3~7 1997-0~-14 The application of s-lrf~rt~nt alone at an elevated level gave a poor dry soil repellency, that is, it has a soil attraction defect due to residual surfactant left on the carpet. The use of sllrf~ct~nt alone in the tre~tment of fibrous materials is l me~ti ef~r,tory.
Tre~tment of the carpet sarnple with the methacrylate polymer gave similar results to that of the novolak resin. A ei~nific~nt gluing of the fibers occurred with a resultant hard texture. The water reeiet~n~e ofthe fluorochemical tre~tment was adversely affected.
In distinct contrast to the coml)~d~ e tre~tmpnte-~ the combination according 10 to the invention of methacrylate polymer, novolak resin and sulphonated eurf~t~nt gave a treated product with excellent properties. Particularly notable is the open bloom of the treated m~teri~l, soft texture, excellent stain release properties and no effect on the oil and water repellency of the fluorochemical tre~tment The treiqtment composition showed excellent penetration into the carpet pile.
When sllrf~t~nt was present in an amount from 5% to 90%, excellent stain release properties were observed. When the combined amount of novolak resin and polymethacrylate exceeds about 40% by weight, the test product shows poor water repellency and handle texture. Such an effect was not observed, however, in the presence of a sulphonated sllrf~rt~nt where the novolak resin and methacrylate polymer were used in amounts up to about 40% by weight.
In a specific group of tests the amounts of surfactant, novolak resin and polymethacrylic acid evaluated in the composition were as follows:
Surfactant 0% to 100%
Novolak resin 0% to 17%
.
Polymethacrylic acid: 0% to 88%

A series of sulphonated sllrf~.t~nt.e were tested in place of diethanolarnine lauryl sulphate ntili~ing the test methods and procedures of Example 1. Examples of 30 surf~.t~nt~ invçstig~te~and the results obtained are set forth below:

(1) UNIVADINE PS-AU
Supplier: Ciba-Geigy Australia Pty. Ltd., Thomastown, Victoria, Australia Composition: alkyl aryl slllrhon~te(l and hydroxyethylated fatty arnine Use ofthis product gave acceptable p~lrOlmance in the treatment composition ofthe 5 invention (2) LANKROPOL WN
Supplier: Lankro Chemicals Ltd., Manchester, United Kingdom Composition: alkylated diphenyl oxide disulphonates, slllrh~te~ monoester of fatty acid, cor~ sodium salt.
Use of this product gave an acceptable result in the treatment composition of the invention.

(3) TEBAN ES
15 Supplier: Dr TH Bohme Chernie GmbH & Co. Geretsried, Germany Composition: Aryl slllrhon~te~, fatty amine polyglycol ether (sulphonate ethylene oxide Con-l~n~t~?).
This composition gave treatment compositions at the lower end of effectiveness. The product showed some propensity to attract soil and gave a barely acceptable texture 20 bloom after tre~tm~n~

(4) MILTOPAN D 503 PASTE/LIQUID
Supplier: Henkel Australia Pty. Ltd., Broadmeadows, Victoria, Australia Composition: Neutralizedalkyllaurylsulphonate. CASNo.7732-18-5 25 This compound produced a very satisfactory tre~tnlent compound when combined with the novolak resin and methacrylate polymer. Minor problems were noticed with texture bloom.

(5) KEMMAT SN 18 CA 0220~3~7 1997-0~-14 W O96/18765 PCTrUS95/15112 Supplier: Swift Watts Winter Pty. Ltd., Sil~ lel, New South Wales, tr~
Composition: Dimethyl benzene sulphonic acid, sodium salt, cont~ining xylene (generally called sodium xylene slllphon~te) 5 Resulting tre~tment composition was at the lower end of effectiveness, particularly in relation to stain release ~lOp~ Iy.

Tre~tme~t by Direct Foam Application Followed bv a Dryin~/Curin~ Step 10 Nylon 6,6 carpet was treated on a commercial scale using the combination of the invention particlll~ri7e~i in Example 1, namely cont~ining 50% sulphonated s-lrf~(~t~nt,l4% methacrylate polymer and 15% sulphonated novolak resin.
The product was applied by foam via a Texicon Autofoamer with a 1 mm applicator slot. The composition of the invention was dosed at 1.6% product on 15 carpet in conjunction with an anionic aliphatic fluorochemical at 0.7%. The following parameters were recorded:
Stain release composition: 108 g/L
Fluorochemical: 47 g/L
Magnesium sulphate dihydrate: 4 g/L
20 Wet pick-up: 15% add-on based on dry carpet weight Blow ratio: 60:1 Gap setting:
Liquor back pressure: 45 pSi Foam back pressure: 50pSi 25 Foam quality: continuous fine lather The application was on wet carpet afl[er dyeing and steam washing. The carpet was dried at 130C and was later latex backed. Performance achieved was as follows:
-CA 0220~3~7 1997-0~-14 ORWR DSSR LF HAND BLOOM
Sample 43 3.5 8 6 Soft Open Desirable ~ ~lnlance 2 1 3.0 7 5 Soft Open Large scale carpet tre~tment using coapplication of the treatment composition and the fluorochemical in the form of a foam followed directly by drying the carpet gave a product of excellent finish and performance. The Handle and the texture is superior to conventional tre~tment~ applied directly (that is, without a post-tr~tment washing step).

Treatment by Direct Spray Application Followed by Air Dry;r~/Cur;n~
This example indicates that the composition of the invention can be applied in conjunction with a fluorochemical directly to installed carpets to give similar properties of stain release and stain resistance to carpets treated commercially during the m~nllf~c~ling stage.
In this example, the compound and fluorochemical were applied via an airless sprayer at 25 pSi ple~ e, 7 m/minute speed, at 15% wet add-on to a wet/precleaned nylon 6,6 carpet of 680 g (19 oz/yd2).
The solution contained the following ingredients per liter:
108 g (1.6% product on carpet) ofthe trc~tment composition of Example 1.
100 g (1.5% product on carpet) of a fluorochemical potassium salt, which comprises a C6/C8 hybrid potassium salt of a fluoro~liph~tic acid in butyl cellosolve and isopropanol.
792 g water.
The carpet was allowed to air dry at ambient temperature at 23 ~ 2C
overnight. Standard tests of stain release and stain resistance were carried out with the following performance:

CA 02205357 l997-05-l4 WO 96/18765 PCT/US95/lS112 OR WR DS SR HAND BLOOM
Sample 2 1 to 2 4.07.5 to 8.0 SoftOpen Desirable p~ lr(" ,Il~ e 2 1 3.0 7 SoftOpen The composition of the invention is therefore also suitable for application to installed carpet and other polyamide fabrics. Heat tre~tment is llnnecess~ry when fluorochemicals which self-cure or cross-link under arnbient conditions are used.

Claims

CLAIMS:

1. An aqueous treating composition for providing stain release properties to fibrous materials which comprises:
(a) an acrylic polymer selected from the group consisting of:
polymethacrylic acid, copolymers of methacrylic acid, and combinations thereof, (b) a partially sulphonated novolak resin, (c) a surfactant comprising , and (d) water.

a mono-, di- or tri-ethanolamine lauryl sulphate.

2. The composition of claim 1 which comprises:
(a) 5% to 30% by weight of a methacrylate polymer, (b) 5% to 30% by weight of a partially sulphonated novolak resin, and (c) 10% to 90% by weight of a sulphonated surfactant.

3. The composition of claim 1 which additionally includes a fluorochemical for providing oil and water repellency.

4 . The composition of claim 1 which additionally includes a volatile organic acid, which can be removed after application of the composition to a substrate by drying at temperatures above 120°.

5. A process for providing a substrate material selected from fibrous material and leather with stain release which comprises applying to said material a composition according to claim 1 and thereafter drying the material.

6. A process according to claim 5 wherein the fibrous material is a carpet, textile fabric or synthetic leather.

7. A process according to claim 5 wherein a fluorochemical is coapplied or applied separately to the composition according to claim 1 in order to provide oil and water repellency.

8. A process according to claim 7 wherein drying of the treated material takes place under ambient conditions in the presence of a fluorochemical which self cures or cross-links under ambient conditions.