Note: Descriptions are shown in the official language in which they were submitted.
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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
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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.
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- 3 -
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,
,
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(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,
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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.
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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
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- 7 -
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
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- 8 -
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
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_ 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
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- 10-
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
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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).
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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.
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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.
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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.
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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
21C
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.
-
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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.
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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
-
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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.
EXAMPLE 1
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%
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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.
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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%
EXAMPLE 2
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:
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- 21 -
(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
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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.
EXAMPLE 3
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:
-
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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).
EXAMPLE 4
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:
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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.
