Note: Descriptions are shown in the official language in which they were submitted.
' CA 02430682 2003-05-28
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Reactive modified particulate polymers for surface treatment of textile and
nontegtile
materials
This invention relates to a method for surface treating textile and nontextile
materials with
reactive modified particulate polymers, the use of the reactive modified
particulate
polymers, and wrinkleproofmg, washing, rinsing, refreshing and textile
treatment
formulations comprising the reactive modified particulate polymers.
Cellulosic textiles are given easy care properties by treatment with
condensation products
of urea, glyoxal and formaldehyde, for example. The finish is applied during
the
manufacture of textile materials. Softening compounds are frequently further
applied with
the finish. Thus finished textiles are less wrinkled and creased, easier to
iron and softer and
smoother after laundering than untreated cellulosics.
WO 98!04772 discloses a process for pretreating textile materials by applying
a mixture of
a polycarboxylic acid and a cationic softener to the textile materials.
Wrinkle control is
2 0 obtained as a result.
EP-A 0 978 556 describes a mixture of a softener and a crosslinker component
having
cationic properties as a fabric wrinkle and crease control composition and
also a method of
wrinkleproofmg textiles.
Washing, rinsing, cleaning and refreshing processes in aqueous media are
customarily
earned out in a very dilute liquor, and the ingredients of the particular
formulation used
generally do not remain on the substrate, but are disposed of with the
effluent. Sustained
modification of the surface of cellulosic materials with dispersed particles
in the
3 0 hereinbelow mentioned processes is accomplished only to an unsatisfactory
degree.
US 5,476,660 discloses the principle of using polymeric retention aids for
cationic or
zwitterionic dispersions of polystyrene or wax that contain the active
substance embedded
in the dispersed particles. These dispersed particles act as carrier
particles, since they
3 5 adhere to the treated surface where they release an active substance, for
example in the
case of use in surfactant formulations.
CA 02430682 2003-05-28
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US 3,993,830 discloses applying a non-permanent soil-release finish to a
textile material
by treating the textile material with a dilute aqueous solution comprising a
polycarboxylate
and a water-soluble salt of a polyvalent metal. Preferred polycarboxylates are
said to be
water-soluble copolymers of ethylenically unsaturated monocarboxylic acids and
alkyl
acrylates. The mixtures are released in the rinse cycle of a home laundry
process.
It is an object of the present invention to provide a further method for
modifying surfaces
of textile and nontextile materials.
l0 More particularly, it is an object of the present invention to provide a
method for
wrinkleproofing cellulosic textiles.
It is a further object of the present invention to provide a method for
improving the soil
release from textiles and nontextile surfaces.
We have found that this object is achieved in this invention by a method of
treating a
textile material, which comprises applying a reactive modified particulate
polymer having
a particle size from 10 nm to 100 pm from an aqueous dispersion to the surface
of the
textile material and drying the textile material.
The invention further provides for the use of the reactive modified
particulate polymers as
surface-modifying ingredient in rinsing, refreshing or washing compositions
and also
laundry detergent, refreshing and textile treatment formulations comprising
the particulate
polymers.
Reactive modified polymers for the purposes of the invention are particulate
polymers
containing reactive, crosslinking groups. The reactive modified polymers may
contain
units derived from anionic and/or cationic monomers and may have anionic,
cationic or
amphoteric protective colloids or emulsifiers at their surface. The reactive
modified
3 0 polymers may contain units derived from monomers containing reactive
groups and/or
may have at their surface protective colloids or emulsifiers that contain
reactive groups.
Reactive modified polymers of anionic character, i.e., which contain anionic
groups and/or
are dispersed using anionic protective colloids or emulsifiers, may have a
coating with
cationic polymers at their surface.
The reactive groups may also have a postcrosslinking effect, i.e., develop
their crosslinking
effect only on heating or drying of the treated textile surfaces.
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The reactive modified particulate polymers are obtainable by copolymerization
of
ethylenically unsaturated monomers containing no crosslinking reactive groups
with
ethylenically unsaturated monomers which do contain such crosslinking reactive
groups.
But the reactive groups may also be introduced into the polymer by coating the
surfaces of
the polymer particles with colloids having crosslinking reactive groups.
The reactive modified polymers used according to the invention are in one
embodiment of
the invention obtainable by copolymerizing ethylenically unsaturated monomers
containing no reactive groups with ethylenically unsaturated monomers
containing reactive
groups.
Useful monomers containing no reactive groups include for example alkyl esters
of C3-CS
monoethylenically unsaturated carboxylic acids with monohydric C1-C~ alcohols,
hydroxyalkyl esters of C3-CS monoethylenically unsaturated carboxylic acids
with dihydric
C2-C4 alcohols, vinyl esters of saturated C1-Cla carboxylic acids, ethylene,
propylene,
isobutylene, C4-C24 alpha-olefins, butadiene, styrene, alpha-methylstyrene,
acrylonitrile,
methacrylonitrile, tetrafluoroethylene, vinylidene fluoride, fluoroethylene,
chlorotrifluoro-
ethylene, hexafluoropropene or mixtures thereof.
2 o Preferred monomers are methyl acrylate, ethyl acrylate, n-butyl acrylate,
sec-butyl
acrylate, tent-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate,
hydroxypropyl
acrylate, methyl methacrylate, n-butyl methacrylate, vinyl acetate, vinyl
propionate,
styrene, ethylene, propylene, butylene, isobutene, diisobutene and
tetrafluoroethylene, and
particularly preferred monomers are methyl acrylate, ethyl acrylate, n-butyl
acrylate,
2 5 styrene, methyl methacrylate and vinyl acetate.
Useful reactive, crosslinking groups include for example azetidinium, glycidyl
ether,
halohydrin, carboxylic anhydride, carbonyl chloride, isocyanate, vinyl
sulfone,
N-methylol, aldehyde and imine groups.
Preferred unsaturated monomers containing reactive groups are
N-methylol(meth)acrylamide, glycidyl methacrylate,
meths.cryloyloxypropyltrimethylsilane, vinyltrimethoxysilane, m-
isopropenylbenzyl
isocyanate, acrolein, isobutoxymethylacrylamide, isobutoxymethylacrylamide,
3 5 hydroxymethylated diacetoneacrylamide, allyl N-methylolcarbamate, N-formyl-
N'-
acryloyloxymethylenediamine, gamma-methylacryloyloxypropyltrimethoxysilane,
methacryloyloxyethoxytrimethylsilane, epithiopropyl methacrylate, vinyl
chloride,
2-chloroethyl acrylate, 4-chlorobutyl acrylate, 3-chloro-2-hydroxypropyl
acrylate, methyl
1-(chloromethyl)acrylate, 2-(bromomethyl)acrylonitrile, 2-
(chloromethyl)acrylamide,
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6-bromo-2-naphthylenyl acrylate, 2-(4-chloro-2-nitroanilino)ethyl acrylate, 6-
chloro-S-
(trichloromethyl)-2-norbornyl acrylate, 3-chloro-2-
[(dimethylphosphinyl)oxy]propyl
acrylate, 3-chloro-2-[(1-oxo-3-phenyl-2-propenyl)oxy]propyl methacrylate, 2-
phenylallyl
bromide, p-chloromethylstyrene, vinyl monochloroacetate, 2-(4-ethoxyphenyl)-2-
oxazolinyl methacrylate.
The reactive modified polymers used according to the invention may be prepared
by the
conventional methods of solution, precipitation, suspension or emulsion
polymerization
described for example in P. Lovell and M.S. El-Aasser, Emulsion Polymerisation
and
l0 Emulsion Polymers, Wiley, New York, 1997. Preferably, the reactive modified
particulate
polymers used according to the invention are obtained by emulsion
polymerization in an
aqueous medium.
The polymerization is conducted in the presence of polymerization initiators
that
1 S decompose either thermally or photochemically or in the presence of redox
initiators. Of
the polymerization initiators that decompose thermally, preference is given to
those which
decompose in the range from 20 to 180°C, especially from 50 to
90°C.
Preferred polymerization initiators for the emulsion polymerization are water-
soluble
2 0 organic peroxides such as peresters, percarbonates, perketals,
hydroperoxides, inorganic
peroxides such as H2Oz, salts of peroxosulfuric acid and peroxodisulfuric
acid, azo
compounds, boron-alkyl compounds and also hydrocarbons that decompose
homolytically.
The polymerization initiators, which are used in amounts in the range from
0.01 to 15% by
2 5 weight, based on the monomers, can be used individually or in combination.
An emulsion polymerization to prepare the polymers is generally carried out
using
dispersing assistants.
3 0 Useful dispersing assistants include water-soluble macromolecular organic
compounds
having polar groups, such as polyvinylpyrrolidone, copolymers of vinyl
propionate or
acetate and vinylpyrrolidone, partially hydrolyzed copolymers of an acrylic
ester, and
acrylonitrile, polyvinyl alcohols having different residual acetate contents,
cellulose ethers,
gelatin, block copolymers, modified starch, low molecular weight carboxyl-
and/or sulfo-
3 5 containing polymers or mixtures thereof. Useful natural protective
colloids include water-
soluble proteins, partially degraded proteins, water-soluble cellulose ethers,
native
starches, degraded starches and/or chemically modified starches. Examples of
water-
soluble cellulose esters are hydroxyethylcellulose and methylcellulose. Useful
natural
starches include those obtainable by heating in an aqueous medium to above the
' CA 02430682 2003-05-28
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gelatinization temperature. It is also possible to use degraded starches that
are obtainable
by hydrolytic, oxidative or enzymatic degradation.
Particularly preferred protective colloids are polyvinyl alcohols having a
residual acetate
content from 0 to 39, especially from 5 to 39, mol% and vinylpyrrolidonelvinyl
propionate
copolymers having a vinyl ester content of up to 35%, especially from 5 to
30%, by
weight.
Useful dispersing assistants further include nonionic or ionic emulsifiers and
also mixtures
thereof. Preferred emulsifiers are optionally ethoxylated or propoxylated long-
chain
alkanols or alkylphenols having different degrees of ethoxylation or
propoxylation, for
example adducts with from 0 to 50 mol of alkylene oxide, and their
neutralized, sulfated,
sulfonated or phosphated derivatives. Neutralized dialkyl sulfosuccinates or
alkyl diphenyl
oxide disulfonates are particularly useful.
Useful dispersing assistants further include cationic emulsifiers based on C~-
C2s
alkylamines, N,N-dimethyl-N-(C~-Czs-hydroxyalkyl)ammonium salts, mono- and
di-(CrC2s-alkyl)dimethylammonium compounds quatennized with alkylating agents,
ester
goats, such as quaternary esterified mono-, di- or trialkanolamines esterified
with C~-C~
2 o carboxylic acids, and imidazoline goats, such as 1-alkylimidazolinium
salts.
The polymers have for example molar masses from 1 000 to 2 million, preferably
from
5 000 to 500 000, and usually the molar masses of the polymers are in the
range from
10 000 to 1 SO 000.
The molar masses of the polymers can be limited by using customary regulators
in the
polymerization. Examples of typical regulators are mercapto compounds such as
mercaptoethanol or thioglycolic acid.
3 0 To increase the density of the reactive groups at the surface of the
polymer particles, the
monomers containing reactive groups can be added in stages and separately from
the other
monomers. Preferably, the predominant portion of the monomers containing
reactive
groups is not added until toward the end of the total feed time for all
monomers. In a
variant for preparing the polymers used according to the invention, 70% of the
monomers
3 5 containing the reactive groups are added in the last third of the total
feed time.
As well as the polymerization methods mentioned, other methods may also be
used for
preparing the particulate polymers used according to the invention. For
instance,
particulate polymers can be precipitated by lowering the solubility of
dissolved polymers
CA 02430682 2003-05-28
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in a solvent. For example, a polymer containing an acidic group can be
dissolved in a
suitable, water-miscible solvent and the solution metered into an excess of
water in such a
way that the pH of the initial charge is at least 1 lower than the equivalent
pH of the
copolymer. By equivalent pH is meant that pH at which 50% of the acidic groups
of the
copolymer are neutralized. This method may require the use of a dispersing
assistant, pH
regulators and/or salts in order that stable, finely divided aqueous
dispersions may be
obtained.
The reactive modified polymers used in the invention have a particle size from
10 nm to
l0 100 p.m, preferably from 30 nm to 3 ~.m, especially from 50 nm to 800 nm.
The reactive modified polymers used according to the invention may be of
anionic,
cationic, amphoteric or nonionic character.
Reactive modified polymers of anionic character are obtainable by
copolymerizing anionic
monomers such as acrylic acid, methacrylic acid, styrenesulfonic acid,
acrylamido-2-
methylpropanesulfonic acid, vinylsulfonic acid and malefic acid, monomaleates
with C1-C8
alkanols and/or salts thereof, which may be done in the presence of
emulsifiers and
protective colloids. Anionic monomers as the term is used herein also
comprehends
2 0 monomers having acidic groups which are convertible into their salts, even
though these
are not present in ionic form during the polymerization.
The anionic character for the polymers is also obtainable by conducting the
copolymerization in the presence of anionic protective colloids andlor anionic
emulsifiers.
But the anionic character for the polymers may also be obtained by emulsifying
or
dispersing the finished polymers in the presence of anionic protective
colloids and/or
anionic emulsifiers.
3 o Reactive modified polymers of cationic character are obtainable by
including cationic
monomers in the polymerization, which rnay be carned out in the presence of
emulsifiers
and protective colloids. Cationic monomers are herein also to be understood as
meaning
monomers having basic groups which are convertible into their salts, even
though these are
not present in ionic form during the polymerization. Useful cationic monomers
include
3 5 nitrogenous basic ethylenically unsaturated monomers in the form of the
free bases, the
salts with organic or inorganic acids or in quaternized form. Useful
nitrogenous basic
ethylenically unsaturated compounds include for example N,N'-dialkylaminoalkyl
(meth)acrylates, for example dimethylaminoethyl acrylate, dimethylaminoethyl
methacrylate, diethyl aminoethyl acrylate, diethylaminoethyl metha,crylate,
CA 02430682 2003-05-28
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dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate,
diethylaminopropyl
acrylate, diethylaminopropyl methacrylate, dimethylaminobutyl acrylate,
dimethylaminobutyl methacrylate, dimethylaminoneopentyl acrylate,
dimethylaminoneopentyl methacrylate. Useful basic monomers of this group
further
include N,N'-dialkylaminoalkyl(meth)acrylamides, for example N,N'-di-Ci-C3-
alkylamino-C2-C6-alkyl(meth)acrylamides, such as dimethylaminoethylacrylamide,
dimethylaminoethylmethacrylamide, diethylaminoethylacrylamide,
diethylaminoethylmethacrylamide, dipropylaminoethylacrylamide,
dipropylaminoethyl-
methacrylamide, dimethylaminopropylacrylamide,
dimethylaminopropylmethacrylamide,
diethylaminopropylacrylamide, diethylaminopropylmethacrylamide, dimethyl-
aminoneopentylacrylamide, dimethylaminoneopentylmethacrylamide and
dialkylaminobutylacrylamide.
Useful monomers of this group further include 4-vinylpyridine, 2-
vinylpyridine,
1-vinylimidazole, 2-methyl-1-vinylimidazole and/or diallyl(di)alkylamines
where the alkyl
group contains from 1 to 12 carbon atoms. The abovementioned basic monomers
are used
in the copolymerization in the form of the free bases, the salts with organic
or inorganic
acids or in quaternized form. Useful carboxylic acids for salt formation
include for
example carboxylic acids containing from 1 to 7 carbon atoms, for example
formic acid,
2 0 acetic acid or propionic acid, benzenecarboxylic acid, sulfuric acid,
phosphoric acid,
p-toluenesulfonic acid or inorganic acids such as halohydric acids, for
example
hydrochloric acid or bromohydric acid. 'The basic monomers mentioned above by
way of
illustration may also be used in quaternized form. Useful quaternizing agents
include for
example alkyl halides having from 1 to 18 carbon atoms in the alkyl group, for
example
2 5 methyl chloride, methyl bromide, methyl iodide, ethyl chloride, propyl
chloride, hexyl
chloride, dodecyl chloride, lauryl chloride and benzyl halides, especially
benzyl chloride
and benzyl bromide. The nitrogenous basic monomers may also be quaternized by
reacting
these compounds with dialkyl sulfates, especially diethyl sulfate or dimethyl
sulfate.
Examples of quaternized monomers of this group are trimethylammoniumethyl
3 o methacrylate chloride, dimethylethylammoniummethyl methacrylate ethyl
sulfate and
dimethylethylammoniumethylmethacrylamide ethyl sulfate, 3-methyl-1-
vinylimidazolinium chloride.
But the cationic character for the polymers is also obtainable by conducting
the
3 5 copolymerization in the presence of cationic protective colloids and/or
cationic emulsifiers.
But the cationic character for the polymers mentioned is also obtainable by
emulsifying or
dispersing the finished polymers in the presence of cationic protective
colloids and/or
cationic emulsifiers.
CA 02430682 2003-05-28
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An overview of a selection of suitable cationic surfactants may be found in
Ullmanns
Enzyklopadie der Industriellen Chemie, Sixth Edition, 1999, Electronic
Release,
"Surfactants", Chapter 8, Cationic Surfactants.
Reactive modified polymers of amphoteric character are obtainable by including
both
cationic and anionic monomers. Useful monomers include for example the
aforementioned
cationic and anionic monomers.
'The amphoteric character for the polymers is also obtainable by conducting
the
copolymerization in the presence of amphoteric protective colloids and/or
amphoteric
emulsifiers.
But the amphoteric character for the polymers is also obtainable by
emulsifying or
dispersing the finished polymers in the presence of amphoteric protective
colloids and/or
amphoteric emulsifiers.
Reactive modified polymers are obtainable for example by copolymerization of
2 0 (a) from 40 to 99.9% by weight, preferably from 50 to 90% by weight,
particularly
preferably from 60 to 75% by weight, of at least one sparingly water-soluble
or
water-insoluble nonionic monomer,
(b) from 0 to 60% by weight, preferably from 1 to 55% by weight, particularly
2 5 preferably from 5 to 50% by weight, especially from 15 to 40% by weight,
of
carboxyl-containing monomers or salts thereof,
(c) from 0 to 25% by weight, preferably from 0 to 15% by weight, of sulfo-
and/or
phosphono-containing monomers or salts thereof,
(d) from 0 to 30% by weight, preferably from 0 to 15% by weight, of cationic
monomers,
(e) from 0 to 55% by weight, preferably from 0 to 40% by weight, of water-
soluble
3 5 nonionic monomers,
(fj from 0 to 30% by weight, preferably from 0 to 10% by weight, of multiply
ethylenically unsaturated monomers, and
CA 02430682 2003-05-28
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(g) from 0.1 to 30% by weight, preferably from 0.25 to 15% by weight,
particularly
preferably from 0.5 to 10% by weight, of at least one ethylenically
unsaturated
monomer containing reactive, crosslinking groups.
Polymers containing units derived from at least one anionic monomer b) or c)
can be used
without additional anionic emulsifiers or protective colloids. Polymers
containing less than
0.5% by weight of units derived from anionic monomers are usually used
together with at
least one anionic emulsifier or protective colloid.
Preferred monomers a) are methyl acrylate, ethyl acrylate, n-butyl acrylate,
sec-butyl
acrylate, tert-butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate,
hydroxypropyl
acrylate, methyl methacrylate, n-butyl methacrylate, vinyl acetate, vinyl
propionate,
styrene, ethylene, propylene, butylene, isobutene, diisobutene and
tetrafluoroethylene, and
particularly preferred monomers are methyl acrylate, ethyl acrylate, n-butyl
acrylate,
styrene, methyl methacrylate and vinyl acetate.
Preferred monomers b) are acrylic acid, methacrylic acid, malefic acid or
monomaleates
with C,-C8 alkanols.
2 0 Useful monomers c) include for example acrylamido-2-methylpropanesulfonic
acid,
vinylsulfonic acid, methallylsulfonic acid and also their alkali metal and
ammonium salts.
Useful monomers d) include for example dimethylaminoethyl methacrylate,
dimethylaminopropylacrylamide, 1-vinylimidazole, 3-methyl-1-vinylimidazolinium
2 5 chloride and 4-vinylpyridine.
Useful monomers e) include for example acrylamide, methacrylamide, N-
vinylformamide,
N-vinylacetamide, N-vinylpyrrolidone, N-vinyloxazolidone, methyl polyglycol
acrylates,
methyl polyglycol methacrylates, methylpolyglycolacrylamides and
vinylcaprolactam.
Useful polyunsaturated monomers f) include for example acrylic esters,
methacrylic esters,
allyl ethers and vinyl ethers of at least dihydric alcohols. T'he OH groups of
the underlying
alcohols may be wholly or partly etherified or esterified. Crosslinkers
contain at least two
ethylenically unsaturated groups. Examples are butanediol diacrylate,
hexanediol
3 5 diacrylate and trimethylolpropane triacrylate. Useful unsaturated monomers
e) further
include for example allyl esters of unsaturated carboxylic acids,
divinylbenzene,
methylenebisacrylamide and divinylurea.
CA 02430682 2003-05-28
1.~ -
Preferred crosslinking but mainly postcrosslinking unsaturated monomers g)
containing
reactive groups are N-methylol(meth)acrylamide, glycidyl methacrylate,
methacryloyloxypropyltrimethylsilane, vinyltrimethoxysilane, m-
isopropenylbenzyl
isocyanate, acrolein, isobutoxymethylacrylamide, hydroxymethylated
diacetoneacrylamide, allyl N-methylolcarbamate, N-formyl-N'-acryloyloxy-
methylenediamine, gamma-methylacryloyloxypropyltrimethoxysilane,
methacryloyloxyethoxytrimethylsilane, epithiopropyl methacrylate, vinyl
chloride,
2-chloroethyl acrylate, 4-chlorobutyl acrylate, 3-chloro-2-hydroxypropyl
acrylate, methyl
1-(chloromethyl)acrylate, 2-(bromomethyl)acrylonitrile, 2-
(chloromethyl)acrylamide,
6-bromo-2-naphthylenyl acrylate, 2-(4-chloro-2-nitroanilino)ethyl acrylate, 6-
chloro-5-
(trichloromethyl)-2-norbornyl acrylate, 3-chloro-2-
[(dimethylphosphinyl)oxy]propyl
acrylate, 3-chloro-2-[(1-oxo-3-phenyl-2-propenyl)oxy]propyl methacrylate, 2-
phenylallyl
bromide, p-chloromethylstyrene, vinyl monochloroacetate, 2-{4-ethoxyphenyl)-2-
oxazolinyl methacrylate.
One embodiment of the invention comprises using reactive modified particulate
polymers
having an anionic character, i.e., containing anionic groups and/or being
dispersed with
anionic protective colloids or emulsifiers and having a coating of cationic
polymer on their
surface.
These reactive modified particulate polymers which have been cationically
modified are
obtainable by coating the surface of the anionically dispersed, particulate
polymers with
cationic polymers. Useful cationic polymers include all natural or synthetic
cationic
polymers which contain amino and/or ammonium groups and are water soluble.
Examples
2 5 of such cationic polymers are polymers containing vinylamine units,
polymers containing
vinylimidazole units, polymers containing quaternary vinylimidazole units,
condensates of
imidazole and epichlorohydrin, crbsslinked polyamidoamines, ethyleneimine-
grafted
crosslinked polyamidoamines, polyethyleneimines, alkoxylated
polyethyleneimines,
crosslinked polyethyleneimines, amidated polyethyleneimines, alkylated
3 0 polyethyleneimines, polyamines, amine-epichlorohydrin polycondensates,
alkoxylated
polyamines, polyallylamines, polydimethyldiallylammonium chlorides, polymers
containing basic (meth)acrylamide or methacrylate units, polymers containing
basic
quaternary (meth)acrylamide or methacrylate units and/or lysine condensates.
3 5 Cationic polymers also include amphoteric polymers having a net cationic
charge, i.e., the
polymers contain anionic as well as cationic monomers in copolymerized form,
but the
molar fraction of the cationic units present in the polymer is larger than
that of the anionic
units.
CA 02430682 2003-05-28
Polymers containing vinylamine units are prepared for example from open-
chained
N-vinylcarboxamides of the formula (I)
R'
CHZ=CH-N\ 2 (I)
C -R
f
O
where Ri and R2, which may be identical or different, are each selected from
the group
consisting of hydrogen and C,-C6-alkyl. Useful monomers include for example
N-vinylformamide (Rl=R2=H in formula I), N-vinyl-N-methylformamide,
N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinyl-
N-
methylpropionamide and N-vinylpropionamide. The monomers mentioned may be
polymerized either alone or mixed with each other or together with other
monoethylenically unsaturated monomers to prepare the polymers. Preference is
given to
starting from homo- or copolymers of N-vinylformamide. Polymers containing
vinylamine
units are known for example from US 4,421,602, EP-A-0 216 387 and EP-A-0 251
182.
They are obtained by hydrolysis, with acids, bases or enzymes, of polymers
containing
monomers of the formula I in polymerized form.
Useful monoethylenica,lly unsaturated monomers for copolymerization with
N-vinylcarboxamides include all compounds that are copolymerizable therewith.
Examples
thereof are vinyl esters of saturated carboxylic acids of from 1 to 6 carbon
atoms such as
vinyl formate, vinyl acetate, vinyl propionate and vinyl butyrate and vinyl
ethers such as
C1-C6-alkyl vinyl ethers, for example methyl vinyl ether or ethyl vinyl ether.
Useful
comonomers further include ethylenically unsaturated C3-C6-carboxylic acids,
for example
acrylic acid, methacrylic acid, malefic acid, crotonic acid, itaconic acid and
vinylacetic acid
and also their alkali metal and alkaline earth metal salts, esters, amides and
nitrites of the
carboxylic acids mentioned, for example methyl acrylate, methyl methacrylate,
ethyl
2 5 acrylate and ethyl methacrylate.
Useful monoethylenically unsaturated monomers for copolyrnerization with
N-vinylcarboxamides further include carboxylic esters derived from glycols or
polyalkylene glycols where in each case only one OH group is esterified, for
example
3 0 hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate,
hydroxybutyl
acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate and also
monoacrylate
esters of polyalkylene glycols having a molar mass from 500 to 10 000.
Useful comonomers further include esters of ethylenically unsaturated
carboxylic acids
3 5 with amino alcohols such as dimethylaminoethyl acrylate,
dimethylaminoethyl
- 12 -
methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
dimethylamino-
propyl acrylate, dimethylaminopropyl methacrylate, diethylaminopropyl
acrylate,
dimethylaminobutyl acrylate and diethylaminobutyl acrylate. Basic acrylates
can be used
in the form of the free bases, the salts with mineral acids such as
hydrochloric acid, sulfuric
acid or nitric acid, the salts with organic acids such as formic acid, acetic
acid, propionic
acid or sulfonic acids or in quaternized form. Useful quaternizing agents
include for
example dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or
benzyl
chloride.
l0 Useful comonomers further include amides of ethylenically unsaturated
carboxylic acids
such as acrylamide, methacrylamide and also N-alkylmonoamides and -diamides of
monoethylenically unsaturated carboxylic acids with alkyl radicals of from 1
to 6 carbon
atoms, for example N-methylacrylamide, N,N-dimethylacrylamide,
N-methylmethacrylamide, N-ethylacrylamide, N-propylacrylamide and tert-
butylacrylamide and also basic (meth)acrylamides, for example
dimethylaminoethylacrylamide, dimethylaminoethylmethacrylamide,
diethylaminoethylacrylamide, diethylaminoethylmethacrylamide,
dimethylaminopropyl-
acrylamide, diethylaminopropylacrylamide, dimethylaminopropylmethacrylamide
and
diethylaminopropylmethacrylamide.
Useful comonomers further include N-vinylpyrrolidone, N-vinylcaprolactam,
acrylonitrile,
methacrylonitrile, N-vinylimidazole and also substituted N-vinylimidazoles
such as, for
example N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, N-vinyl-5-
methylimidazole, N-vinyl-2-ethylimidazole and N-vinylimidazolines such as
2 5 N-vinylimidazoline, N-vinyl-2-methylimidazoline and N-vinyl-2-
ethylimidazoline.
N-Vinylimidazoles and N-vinylimidazolines are used not only in the form of
their free
bases but also after neutralization with mineral acids or organic acids or
after
quaternization, a quaternization being preferably effected with dimethyl
sulfate, diethyl
sulfate, methyl chloride or benzyl chloride. Also useful are
diallyldialkylammonium
3 0 halides, for example diallyldimethylammonium chlorides.
Useful comonomers further include sulfo-containing monomers, for example
vinylsulfonic
acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, the
alkali metal or
ammonium salts of these acids or 3-sulfopropyl acrylate, and the amphoteric
copolymers
3 5 contain more cationic units than anionic units, so that have a net
cationic charge.
The copolymers contain for example
CA 02430682 2003-05-28
CA 02430682 2003-05-28
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- from 99.99 to 1 mol%, preferably from 99.9 to 5 mol%, of N-vinylcarboxamides
of
the formula I and
- from 0.01 to 99 mol%, preferably from 0.1 to 95 mol%, of other
monoethylenically
unsaturated monomers copolymerizable therewith
in copolymerized form.
To prepare polymers containing vinylamine units, it is preferable to start
from
l0 homopolymers of N-vinylformamide or from copolymers obtainable by
copolymerization
of
- N-vinylformamide with
- vinyl formate, vinyl acetate, vinyl propionate, acrylonitrile, N-
vinylcaprolactam,
N-vinylurea, acrylic acid, N-vinylpyrrolidone or C1-C6-alkyl vinyl ethers
and subsequent hydrolysis of the homo- or copolymers to form vinylamine units
from the
copolymerized N-vinylformamide units, the degree of hydrolysis being for
example in the
2 0 range from 0.1 to 100 mol%.
The hydrolysis of the hereinabove described polymers is effected according to
known
processes by the action of acids, bases or enzymes. This converts the
copolymerized
monomers of the hereinabove indicated formula I through detachment of the
group
C R? {II)
O
where R2 is as defined for the formula I, into polymers which contain
vinylamine units of
the formula (III)
CH2 CH
(III)
N
H/ R'
where Rt is as defined for the formula I. When acids are used as hydrolyzing
agents, the
units III are present as ammonium salt.
CA 02430682 2003-05-28
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The homopolymers of the N-vinylcarboxamides of the formula I and their
copolymers may
be hydrolyzed to an extent in the range from 0.1 to 100 mol%, preferably to an
extent in
the range from 70 to 100 mol%. In most cases, the degree of hydrolysis of the
homo- and
copolymers is in the range from 5 to 95 mol%. The degree of hydrolysis of the
homopolymers is synonymous with the vinylamine units content of the polymers.
In the
case of copolymers containing units derived from vinyl esters, the hydrolysis
of the
N-vinylformamide units can be accompanied by a hydrolysis of the ester groups
with the
formation of vinyl alcohol units. This is the case especially when the
hydrolysis of the
copolymers is carried out in the presence of aqueous sodium hydroxide
solution.
Copolymerized acrylonitrile is likewise chemically modified in the hydrolysis,
for example
converted into amide groups or carboxyl groups. The homo- and copolymers
containing
vinylamine units may optionally contain up to 20 mol% of amidine units, formed
for
example by reaction of formic acid with two adjacent amino groups or by
intramolecular
reaction of an amino group with an adj acent amide group, for example of
copolymerized
N-vinylformamide. The molar masses of the polymers containing vinylamine units
range
for example from 1 000 to 10 million, preferably from 10 000 to 5 million
(determined by
light scattering). This molar mass range corresponds for example to K values
of from 5 to
300, preferably from 10 to 250 (determined by the method of H. Fikentscher in
5%
2 0 aqueous sodium chloride solution at 25°C and a polymer
concentration of 0.5% by
weight).
The polymers containing vinylamine units are preferably used in salt-free
form. Salt-free
aqueous solutions of polymers containing vinylamine units are preparable for
example
2 5 from the hereinabove described salt-containing polymer solutions by
ultrafiltration using
suitable membranes _having molecular weight cutoffs at for example from 1 000
to
500 000 dalton, preferably from 10 000 to 300 000 dalton. The hereinbelow
described
aqueous solutions of other polymers containing amino and/or ammonium groups
are
likewise obtainable in salt-free form by ultrafiltration.
Useful cationic polymers further include polyethyleneimines.
Polyethyleneimines are
prepared for example by polymerizing ethyleneimine in aqueous solution in the
presence
of acid-detaching compounds, acids or Lewis acids. Polyethyleneimines have for
example
molar masses of up to 2 million, preferably from 200 to 500 000. Particular
preference is
3 5 given to using polyethyleneimines having molar masses of from 500 to 100
000. Useful
polyethyleneimines further include water-soluble crosslinked
polyethyleneimines which
are obtainable by reaction of polyethyleneimines with crosslinkers such as
epichlorohydrin
or bischlorohydrin ethers of polyalkylene glycols containing from 2 to 100
ethylene oxide
and/or propylene oxide units. Also useful are amidic polyethyleneimines which
are
CA 02430682 2003-05-28
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obtainable for example by amidation of polyethyleneimines with C1-C22-
monocarboxylic
acids. Useful cationic polymers further include alkylated polyethyleneimines
and
alkoxylated polyethyleneimines. Alkoxylation is carried out using for example
from 1 to 5
ethylene oxide or propylene oxide units per NH unit in the polyethyleneimine.
Useful polymers containing amino and/or ammonium groups also include
polyamidoamines, which are preparable for example by condensing dicarboxylic
acids
with polyamines. Useful polyamidoamines are obtained for example when
dicarboxylic
acids having from 4 to 10 carbon atoms are reacted with polyalkylenepolyamines
l0 containing from 3 to 10 basic nitrogen atoms in the molecule. Useful
dicarboxylic acids
include for example succinic acid, malefic acid, adipic acid, glutaric acid,
suberic acid,
sebacic acid or terephthalic acid. Polyamidoamines may also be prepared using
mixtures of
dicarboxylic acids as well as a mixture of plural polyalkylenepolyamines.
Useful
polyalkylenepolyamines include for example diethylenetriamine,
triethylenetetramine,
tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine,
dihexamethylenetriamine, aminopropylethylenediamine and bis-
aminopropylethylene-
diamine. The dicarboxylic acids and polyalkylenepolyamines are heated at an
elevated
temperature, for example at from 120 to 220°C, preferably at from 130
to 180°C, to
prepare the polyamidoamines. The water of condensation formed is removed from
the
2 0 system. The condensation may also employ lactones or lactams of carboxylic
acids having
from 4 to 8 carbon atoms. The amount of a polyalkylenepolyamine used per mole
of a
dicarboxylic acid is for example in the range from 0.8 to 1.4 mol.
Amino-containing polymers further include ethyleneimine-grafted
polyamidoamines. They
2 5 are obtainable from the hereinabove described polyamidoamines by reaction
with
ethyleneimine in the presence of acids or Lewis acids such as sulfuric acid or
boron
trifluoride etherates at for example from 80 to 100°C. Compounds of
this kind are
described for example in DE-B-24 34 816.
3 0 Useful cationic polymers also include crosslinked or uncrosslinked
polyamidoamines
which may additionally have been grafted with ethyleneimine prior to
crosslinking.
Crosslinked ethyleneimine-grafted polyamidoamines are water soluble and have
for
example an average molar weight of from 3 000 to 1 million dalton. Customary
crosslinkers include for example epichlorohydrin or bischlorohydrin ethers of
alkylene
3 5 glycols and polyalkylene glycols.
Further examples of cationic polymers that contain amino and/or ammonium
groups are
polyallyldirnethylammonium chlorides. Polymers of this kind are likewise
known.
CA 02430682 2003-05-28
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a
Useful cationic polymers further include copolymers of for example 1-99 mol%,
preferably
30-70 mol%, of acrylamide and/or methacrylamide and 99-1 mol%, preferably
70-30 mol%, of cationic monomers such as dialkylaminoalkylacrylamide,
dialkylaminoalkyl acrylate, dialkylaminoalkylmethacrylamide and/or
dialkylaminoalkyl
methacrylate. The basic acrylamides and methacrylamides are preferably
likewise present
in acid-neutralized form or in quaternized form. Examples are
N-trimethylammoniumethylacrylamide chloride,
N-trimethylammoniumethylmethacrylamide chloride, N-trimethylammoniumethyl
methacrylate chloride, N-trimethylammoniumethyl acrylate chloride,
l0 trimethylammoniumethylacrylamide methosulfate,
trimethylammoniumethylmethacrylamide methosulfate,
N-ethyldimethylammoniumethylacrylamide ethosulfate,
N-ethyldimethylammoniumethylmethacrylamide ethosulfate,
trimethylammoniumpropylacrylamide chloride,
trimethylammoniumpropylmethacrylamide
chloride, trimethylammoniumpropylacrylamide methosulfate, trimethyl-
ammoniumpropylmethacrylamide methosulfate and
N-ethyldimethylammoniumpropylacrylamide ethosulfate. Preference is given to
trimethylammoniumpropylmethacrylamide chloride.
2 0 Further useful cationic monomers for preparing (meth)acrylamide polymers
are
diallyldimethylammonium halides and also basic (meth)acrylates. Useful
examples are
copolymers of 1-99 mol%, preferably 30-70 mol%, of acrylamide and/or
methacrylamide
and 99-1 mol%, preferably 70-30 mol%; of dialkylaminoalkyl acrylates and/or
methacrylates such as copolymers of acrylamide and N,N-dimethylaminoethyl
acrylate or
2 5 copolymers of acrylamide and dimethylaminopropyl acrylate. Basic acrylates
or
methacrylates are preferably present in acid neutralized from or in
quaternized form.
Quaternization may be effected for example with methyl chloride or with
dimethyl sulfate.
Useful cationic polymers containing amino and/or ammonium groups further
include
3 0 polyallylamines. Polymers of this kind are obtained by homopolymerization
of allylamine,
preferably in acid neutralized form or in quaternized form, or by
copolymerization of
allylamine with other monoethylenically unsaturated monomers described above
as
comonomers for N-vinylcarboxamides.
3 5 The cationic polymers have for example K values of from 8 to 300,
preferably from 100 to
180 (determined by the method of H. Fikentscher in 5% aqueous sodium chloride
solution
at 25°C and a polymer concentration of 0.5% by weight). At pH 4.5, for
example, they
have a charge density of at least 1, preferably at least 4, meq/g of
polyelectrolyte.
CA 02430682 2003-05-28
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Examples of preferred cationic polymers are polydimethyldiallylammonium
chloride,
polyethyleneimine, polymers containing vinylamine units, copolymers of
acrylamide or
methacrylamide that contain basic monomers in copolymerized form, polymers
containing
lysine units or mixtures thereof. Examples of cationic polymers are:
~ copolymers of 50% of vinylpyrrolidone and 50% of trimethylammoniummethyl
methacrylate methosulfate, MW 1 000-500 000;
~ copolymers of 30% of acrylamide and 70% of trimethylammoniummethyl
methacrylate methosulfate, MW 1 000-1 000 000;
~ copolymers of 70% of acrylamide and 30% of dimethylaminoethylmethacrylamide,
MW
1 000-1 000 000;
~ copolymers of 50% of hydroxyethyl methacrylate and 50% of
2-dimethylaminoethylmethacrylamide, MW 1 000-500 000;
~ copolymer of 70% of hydroxyethyl methacrylate and 50% of
2-dimethylaminoethylmethacrylamide; copolymer of 30% of vinylimidazole
2 0 methochloride, 50% of dimethylaminoethyl acrylate, 15% of acrylamide, 5%
of acrylic
acid;
~ polylysines of MW 250-250 000, preferably 500-100 000, and also lysine
cocondensates
having MW molar masses from 250 to 250 000, the cocondensable component being
2 5 selected for example from amines, polyamines, ketene dimers, lactams,
alcohols,
alkoxylated amines, alkoxylated alcohols and/or nonproteinogenic amino acids,
~ vinylamine homopolymers, 1-99% hydrolyzed polyvinylformamides, copolymers of
vinylformamide and vinyl acetate, vinyl alcohol, vinylpyrrolidone or
acrylamide
3 0 having molar masses of 3 000-500 000,
~ vinylimidazole homopolyrners, vinylimidazole copolymers with
vinylpyrrolidone,
vinylformamide, acrylamide or vinyl acetate having molar masses of from 5 000
to
500 000 and also their quaternary derivatives,
~ polyethyleneimines, crosslinked polyethyleneimines or amidated
polyethyleneimines
having molar masses of from 500 to 3 000 000,
CA 02430682 2003-05-28
1$
~ amine-epichlorohydrin polycondensates which contain imidazole, piperazine C1-
C$-
alkylamines, C,-C8-dialkylamines and/or dimethylaminopropylamine as amine
component and have a molar mass of from 500 to 250 000, and
~ polymers containing basic (meth)acrylamide or (meth)acrylate ester units,
polymers
containing basic quaternary (meth)acrylamide or (meth)acrylate ester units
having
molar masses of from 10 000 to 2 000 000.
It is also possible to include a minor amount (<10% by weight) of anionic
comonomers, for
example acrylic acid, methacrylic acid, vinylsulfonic acid or alkali metal
salts of the acids
mentioned.
Anionically dispersed particles of reactive modified polymers may be
additionally
cationically modified, if necessary, by treatment with polyvalent metal ions
and/or cationic
surfactants as well as treatment with cationic polymers. Coating of the
particles with
polyvalent metal ions is obtained when, for example, an aqueous dispersion of
an
anionically dispersed reactive modified polymers is admixed with an aqueous
solution of at
least one water-soluble polyvalent metal salt or a water-soluble polyvalent
metal salt is
dissolved therein, the modification of the anionically dispersed reactive
modified particles
2 0 with cationic polymers being effected either before, concurrently with or
after this
treatment. Useful metal salts include for example the water-soluble salts of
Ca, Mg, Ba, Al,
Zn, Fe, Cr or mixtures thereof. Other water-soluble heavy metal salts derived
for example
from Cu, Ni, Co and Mn are useful in principle, but not desired in all
applications.
Examples of water-soluble metal salts are calcium chloride, calcium acetate,
magnesium
2 5 chloride, aluminum sulfate, aluminum chloride, barium chloride, zinc
chloride, zinc
sulfate, zinc acetate, iron(II) sulfate, iron(III) chloride, chromium(III)
sulfate, copper
sulfate, nickel sulfate, cobalt sulfate and manganese sulfate. Cationization
is preferably
effected using the water-soluble salts of Mg, Ca, A1 and Zn.
3 o There are many industrial uses and uses in the home where the modification
of the
properties of the textile and nontextile surfaces with polymer dispersions is
important. It is
not always possible to effect the modification of the surfaces by
impregnating, spraying
and brushing processes involving concentrated dispersions. It is frequently
desirable to
effect the modification by rinsing the surface to be treated with a very
dilute liquor that
3 5 contains an active substance. It is frequently desirable in this context
to combine the
modifying treatment of the surface with a wash, clean and/or conditioning or
impregnation
of the surface. Useful surfaces here are in particular surfaces of textile
materials such as
cotton and cotton blend fabrics. In addition, installed carpeting and
furniture covers can be
treated according to the invention. The surfaces of textile materials may be
modified for
CA 02430682 2003-05-28
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example to provide them with water resistance, soil release properties, soil
resist
properties, improved integrity of the fiber assemblage and protection against
chemical or
mechanical effects and damage.
The reactive modified particulate polymers are used for modifying surfaces of
the
hereinabove exemplified materials as an ingredient in rinsing or care
compositions,
washing or cleaning compositions, for textile and further, nontextile
surfaces. Especially
contemplated uses are in washing, cleaning and aftertreating of textiles,
leather, wood,
floor coverings, glass, ceramics and other-surfaces in the home and in the
industrial sector.
to
The reactive modified particulate polymers are used in the form of a dilute,
predominantly
aqueous, dispersion. The use takes the form of a treatment of the surfaces in
washing,
cleaning and rinsing liquors to which the polymers are added either directly
or by means of
a liquid or solid formulation, or in the form of a finely divided application
of a liquid
formulation, for example by spraying.
The reactive modified particulate polymers can be used for example as sole
active
component in aqueous rinsing and care compositions and, depending on the
composition of
the polymer, provide for example for easier soil release in subsequent wash,
reduced soil
2 0 attachment in the use of the textiles, improved structural integrity of
fibers, improved
shape retention and structural integrity for fabrics, water repellency on the
surface of the
washed material and also hand improvement.
The concentration of the reactive modified particulate polymers when used in a
rinse or
2 5 care bath, a washing liquor or cleaning bath is for example in the range
from 0.0002 to 1
by weight, preferably 0.0005 to 0.25% by weight, particularly preferably from
0.002 to
0.05% by weight.
The abovementioned applications can in principle be carried out using all
reactive
3 0 modified particulate polymers. Depending on the embodiment, it can be
advantageous to
select a certain monomer composition to obtain particularly advantageous
modifications.
In a preferred embodiment of the invention, the polymers used contain units
derived from
cationic monomers and as a result possess enhanced affinity for the surfaces
to be treated.
In a further preferred embodiment, the polymers used contain units derived
from anionic
monomers and are used together with the cationic polymers, cationic
surfactants and/or
polyvalent metal cations. The surfaces, for example textile surfaces, are
treated with
aqueous liquors containing for example from 2.5 to 300 ppm, preferably from 5
to
CA 02430682 2003-05-28
- 20 -
200 ppm, especially from 10 to 100 ppm, of at least one cationic polymer, up
to 5 mmol/1,
preferably up to 3.5 mmol/1, of water-soluble salts of polyvalent metals,
especially salts of
Ca, Mg or Zn, and/or up to 2 mmol/1, preferably up to 0.75 mmol/1, of water-
soluble Al
salts, and/or up to 600 ppm, preferably up to 300 ppm, of cationic
surfactants.
A further preferred embodiment comprises using alkali-swellable, particularly
preferably
alkali-soluble; reactive modified polymers. Such polymers are particularly
useful for
example for improving the soil release of textile and nontextile surfaces.
Suitable reactive
modified alkali-soluble polymers contain for example
l0
(a) from 30 to 80% by weight, preferably from 40 to 75% by weight,
particularly
preferably from 50 to 70% by weight, of at least one sparingly water-soluble
or
water-insoluble nonionic monomer,
(b) from 20 to 70% by weight, preferably from 25 to 60% by weight,
particularly
preferably from 30 to 50% by weight, of at least one carboxyl-containing
monomer
or salts thereof,
(c) from 0 to 25% by weight, preferably from 0 to 15% by weight, of one or
more
2 0 sulfo- and/or phosphono-containing monomers or salts thereof,
(d) from 0 to 30% by weight, preferably from 0 to 15% by weight, of one or
more
cationic monomers,
2 5 (e) from 0 to 55% by weight, preferably from 0 to 40% by weight, of one or
more
water-soluble nonionic monomers,
(f) from 0 to 30% by weight, preferably from 0 to 10% by weight, of one or
more
multiply ethylenically unsaturated monomers, and
(g) from 0.1 to 30% by weight, preferably from 0.1 to 10% by weight, of at
least one
ethylenically unsaturated monomer containing reactive groups.
Compositions for treating surfaces may have the following composition for
example:
(a) from 0.05 to 40% by weight of a reactive modified particulate polymer
whose
particle size is from 10 nm to 100 pm,
(b) from 0 to 10% by weight of one or more cationic polymers,
CA 02430682 2003-05-28
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(c) from 0 to 30% by weight of one or more water-soluble salts of Mg, Ca, Zn
or Al
andlor of one or more cationic surfactants,
(d) from 0 to 80% by weight of one or more customary ingredients such as acids
or
bases, inorganic builders, organic cobuilders, further surfactants, polymeric
dye
transfer inhibitors, polymeric soil antiredeposition agents, soil release
polymers,
enzymes, complexing agents, corrosion inhibitors, waxes, silicone oils, light
stabilizers, dyes, solvents, hydrotropes, thickeners and/or alkanolamines.
The invention also provides laundry aftertreatment and laundry refreshing
compositions
and also solid and liquid laundry detergent formulations that contain the
reactive modified
particulate polymers.
Laundry aftertreatment and laundry refreshing compositions contain for example
(a) from 0.1 to 40% by weight of a reactive modified particulate polymer
having a
particle size from 10 nm to 100 ~,m and present as a dispersion in water,
2 0 (b} from 0 to 20% by weight of one or more organic acids such as formic
acid, citric
acid, adipic acid, succinic acid, oxalic acid or a mixture thereof,
(c) from 0 to 10% by weight of a cationic polymer,
2 5 (d) from 0 to 30% by weight of one or more water-soluble salts of Mg, Ca,
Zn or Al
and/or of one or more cationic surfactants,
(e) from 0 to 30% by weight of one or more nonionic surfactants,
3 0 (f) from 0 to 30% by weight of further customary ingredients such as
perfume, silicone
oils, other lubricants, film-forming polymers, stabilizers, corrosion control
additives, preservatives, bactericides, light stabilizers, dye, complexing
agents, soil
antiredeposition agents, soil release polyesters, color transfer inhibitors,
nonaqueous solvent, hydrotropes, thickeners and/or alkanolamines, and
(g) water ad 100% by weight.
Preferred cationic surfactants are selected from the group of the quaternary
diesterammonium salts, the quaternary tetraalkylammonium salts, the quaternary
CA 02430682 2003-05-28
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diamidoammonium salts, the amidoamine esters and imidazolium salts. These are
preferably present in an amount of from 3 to 30% by weight in the laundry
refreshers.
Examples are quaternary diesterammonium salts which have two C11- to
C22-alk(en)ylcarbonyloxy(mono- to pentamethylene) radicals and two C1- to C3-
alkyl or -
hydroxyalkyl radicals on the quaternary nitrogen atom and, for example,
chloride,
bromide, methosulfate or sulfate as counterion.
Quaternary diesterammonium salts further include in particular those which
have a C1,- to
C22-alk(en)ylcarbonyloxytrimethylene radical bearing a C11- to C22-
alk(en)ylcarbonyloxy
l0 radical on the central carbon atom of the trimethylene group and three C1-
to C3-alkyl or
-hydroxyalkyl radicals on the quaternary nitrogen atom and, for example,
chloride,
bromide, methosulfate or sulfate as counterion.
Quaternary tetraalkylammonium salts are in particular those which have two C1-
to
C6-alkyl radicals and two C8- to C24-alk(en)yl radicals on the quaternary
nitrogen atom
and, for example, chloride, bromide, methosulfate or sulfate as counterion.
Quaternary diamidoammonium salts are in particular those which bear two C8- to
C24-alk(en)ylcarbonylaminoethylene radicals, a substituent selected from
hydrogen,
2 o methyl, ethyl and polyoxyethylene having up to 5 oxyethylene units and as
fourth radical a
methyl group on the quaternary nitrogen atom and, for example, chloride,
bromide,
methosulfate or sulfate as counterion.
Amidoamino esters are in particular tertiary amines bearing a Cll- to
2 5 C~-alk(en)ylcarbonylamino(mono- to trimethylene) radical, a C 1 i- to
C~-alk(en)ylcarbonyloxy(mono- to trimethylene) radical and a methyl group as
substituents on the nitrogen atom.
Imidazolinium salts are in particular those which bear a Ci4- to CI8-alk(en)yl
radical in
30 position 2 of the heterocycle, a Ci4- to Clg-alk(en)ylcarbonyl(oxy or
amino)ethylene
radical on the neutral nitrogen atom and hydrogen, methyl or ethyl on the
nitrogen atom
carrying the positive charge, while counterions here are for example chloride,
bromide,
methosulfate or sulfate.
3 5 Solid laundry detergent formulations according to the invention contain
(a) from 0.05 to 20% by weight of a reactive modified particulate polymer
having a
particle size from 10 nm to 100 Vim,
CA 02430682 2003-05-28
- 23 -
(b) from 0.1 to 40% by weight of at least one nonionic and/or anionic
surfactant,
(c) from 0 to 50% by weight of one or more inorganic builders,
(d) from 0 to 20% by weight of one or more organic cobuilders,
(e) from 0 to 60% by weight of other customary ingredients such as cationic
surfactants, standardizers, enzymes, perfume, complexing agents, corrosion
inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer
inhibitors, soil
antiredeposition agents, soil release polyesters, dyes, dissolution improvers
andlor
disintegrants,
said components (a) to (e) adding up to 100% by weight.
The solid laundry detergent formulations of the invention are customarily
present as a
powder, granules, an extrudate or in tablet form.
Liquid laundry detergent formulations of the invention contain
2 0 (a) from 0.05 to 20% by weight of a reactive modified particulate polymer
having a
particle size from 10 nm to 100 ~,m,
(b) from 0.1 to 40% by weight of at least one nonionic andlor anionic
surfactant,
2 5 (c) from 0 to 20% by weight of one or more inorganic builders,
(d) from 0 to 10% by weight of one or more organic cobuilders,
(e) from 0 to 40% by weight of other customary ingredients such as cationic
3 0 surfactants, sodium carbonate, enzymes, perfume, complexing agents,
corrosion
inhibitors, bleaches, bleach activators, bleach catalysts, dye transfer
inhibitors, soil
antiredeposition agents, soil release polyesters, dyes, nonaqueous solvents,
hydrotropes, thickeners and/or alkanolamines, and
3 5 (fj from 0 to 99.85% by weight of water,
components (a) to (f) adding up to 100% by weight.
Useful anionic surfactants are in particular:
CA 02430682 2003-05-28
- 24 -
- (fatty) alcohol sulfates of (fatty) alcohols having from 8 to 22, preferably
from 10 to
18, carbon atoms, for example C9- to C,1-alcohol sulfates, C12- to C14-alcohol
sulfates,
C12- to C1g-alcohol sulfates, lauryl sulfate, cetyl sulfate, myristyl sulfate,
palmityl
sulfate, stearyl sulfate and tallow fatty alcohol sulfate;
- sulfated alkoxylated C8- to C22-alcohols (alkyl ether sulfates). Compounds
of this kind
are prepared for example by first alkoxylating a C8- to Czz-alcohol,
preferably a Clo- to
C18-alcohol, for example a fatty alcohol, and then sulfating the alkoxylation
product.
The alkoxylation is preferably carried out using ethylene oxide;
l0 - linear Cg- to C2o-alkylbenzenesulfonates (LAS), preferably linear C9- to
Ci3-alkylbenzenesulfonates and -alkyltoluenesulfonates;
- alkanesulfonates such as Cg- to C24-alkanesulfonates, preferably Clo- to
C 18-alkanesulfonates;
- soaps such as, for example, the sodium and potassium salts of C8- to C24-
carboxylic
acids.
The anionic surfactants mentioned are preferably included in the laundry
detergent in the
form of salts. Suitable cations in these salts are alkali metal ions such as
sodium, potassium
and lithium and ammonium ions such as hydroxyethylammonium,
2 0 di(hydroxyethyl)ammonium and tri(hydroxyethyl)ammonium.
Useful nonionic surfactants are in particular:
- alkoxylated C8- to C22-alcohols such as fatty alcohol alkoxylates or oxo
alcohol
2 5 alkoxylates. These may have been alkoxylated with ethylene oxide,
propylene oxide
and/or butylene oxide. Useful surfactants here include all alkoxylated
alcohols which
contain at least two molecules of one of the aforementioned alkylene oxides.
Here it is
possible to use block polymers of ethylene oxide, propylene oxide and/or
butylene
oxide or addition products which contain the aforementioned alkylene oxides in
3 0 random distribution. Nonionic surfactants generally contain from 2 to 50,
preferably
from 3 to 20, mol of at least one alkylene oxide per mole of alcohol. The
alkylene
oxide component is preferably ethylene oxide. The alcohols preferably have
from 10
to 18 carbon atoms. Depending on the type of alkoxylation catalyst used to
make
them, alkoxylates have a broad or narrow alkylene oxide homolog distribution;
35 - alkylphenol alkoxylates such as alkylphenol ethoxylates having C6- to C14-
alkyl chains
and from 5 to 30 alkylene oxide units;
- alkylpolyglucosides having from 8 to 22, preferably from 10 to 18, carbon
atoms in
the alkyl chain and generally from 1 to 20, preferably from 1.1 to 5,
glucoside units;
CA 02430682 2003-05-28
' - 25 -
- N-alkylglucamides, fatty acid amide alkoxylates, fatty acid alkanolamide
alkoxylates
and also block copolymers of ethylene oxide, propylene oxide and/or butylene
oxide.
Useful inorganic builders are in particular:
- crystalline or amorphous aluminosilicates having ion-exchanging properties
such as
zeolites in particular. Useful zeolites include in particular zeolites A, X,
B, P, MAP
and HS in their sodium form or in forms in which sodium has been partly
replaced by
other cations such as lithium, potassium, calcium, magnesium or ammonium;
l0 - crystalline silicates such as in particular disilicates or sheet-
silicates, for example
S-Na2Si205 or (3-Na2Si205. Silicates can be used in the form of their alkali
metal,
alkaline earth metal or ammonium salts, preferably as sodium, lithium and
magnesium
silicates;
- amorphous silicates such as for example sodium metasilicate or amorphous
disilicate;
- carbonates and bicarbonates. These can be used in the form of their alkali
metal,
alkaline earth metal or ammonium salts. Preference is given to sodium, lithium
and
magnesium carbonates or bicarbonates, especially sodium carbonate and/or
sodium
bicarbonate;
- polyphosphates such as for example pentasodium triphosphate.
Useful organic cobuilders include in particular low molecular weight,
oligomeric or
polymeric carboxylic acids.
- Useful low molecular weight carboxylic acids include for example citric
acid,
2 5 hydrophobic modified citric acid such as for example agaric acid, malic
acid, tartaric
acid, gluconic acid, glutaric acid, succinic acid, imidodisuccinic acid,
oxydisuccinic
acid, propanetricarboxylic acid, butanetetracarboxylic acid,
cyclopentanetetracarboxylic acid, alkyl- and alkenylsuccinic acids and
aminopolycar-
boxylic acids such as for example nitrilotria.cetic acid, (3-alaninediacetic
acid,
3 o ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic
acid,
N-(2-hydroxyethyl)iminodiacetic acid, ethylenediaminedisuccinic acid and
methyl-
and ethylglycinediacetic acid;
- useful oligomeric or polymeric carboxylic acids include for example
homopolymers of
acrylic acid, oligomaleic acids, copolymers of malefic acid with acrylic acid,
3 5 methacrylic acid, C2-C22-olefins such as for example isobutene or long-
chain
a-olefins, vinyl alkyl ethers having C1-C8-alkyl groups, vinyl acetate, vinyl
propionate, (meth)acrylic esters of C1- to C8-alcohols and styrene. Preference
is given
to using the homopolymers of acrylic acid and copolymers of acrylic acid with
malefic
CA 02430682 2003-05-28
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acid. Polyaspartic acids are also useful as organic cobuilders. Oligomeric and
polymeric carboxylic acids are used in acid form or as sodium salt.
When the reactive modified particulate polymers are to be cationically
modified, this is
preferably effected before use in the aqueous treatments, but can also be
effected in the
course of the manufacture of the aqueous treatments or the use of anionically
dispersed
particulate polymers having a particle size from 10 nm to 100 ~m by for
example mixing
aqueous dispersions of the contemplated particulate polymers with the other
ingredients of
the particular treatment in the presence of cationic polymers and optionally
of water-
soluble salts of polyvalent metals and/or cationic surfactants.
In a particular embodiment, reactive modified polymers of anionic character,
or
formulations containing same, can be added directly to the rinsing, washing or
cleaning
liquor, provided it is ensured that the liquor contains suffcient amounts of
cationic
polymers and optionally polyvalent metal ions and/or cationic surfactants in
dissolved
form. It is possible, for example, to use polymers of anionic character, or
formulations
containing same, in liquors containing from 2.5 to 300 ppm of cationic
polymers and
optionally above 0.5 mmoln, preferably above 1 mmol/1, particularly preferably
above
2 mmol/1, of water-soluble salts of Ca, Mg or Zn. When the cationic
surfactants are used,
2 0 they are used for example in concentrations from 50 to 100 ppm, preferably
from 75 to
500 ppm, especially from 100 to 300 ppm, in the aqueous liquor.
The reactive modified polymers of anionic character, or the formulations
containing same,
may also be added before, after or concurrently with a formulation containing
cationic
2 5 polymers and optionally cationic surfactants.
Alkali-soluble or alkali-swellable reactive modified particulate polymers
provide in
particular on cotton and cellulosic fibers a substantially higher soil release
performance
than known water-soluble soil release polymers.
The invention also provides for the use of reactive modified polymers in
finishes for
wrinkleproofmg cellulosic textiles. Finishes are any liquid formulations which
contain the
reactive modified polymer, especially in the form of an aqueous polymer
dispersion, in
dissolved or dispersed form for application to the textile material. The
finishes of the
3 5 invention can be present for example as finishes in the narrower sense in
the manufacture
of textiles or in the form of an aqueous washing liquor or as a liquid textile
treatment. It is
thus possible for example to treat textiles with the finish in the course of
their manufacture.
Textiles which have not been adequately finished, if at all, may be treated
with a textile
treatment that contains the polymer dispersion for example before or after
home
CA 02430682 2003-05-28
~, - 2 7 -
laundering, for example during ironing. But it is also possible to treat the
textiles with
reactive modified polymers in the main wash cycle or after the main wash cycle
in the
refresher or rinse cycle of the washing machine, for example using the above-
described
formulations.
The present invention also provides for the use of the reactive modified
polymers, in the
manufacture of textiles, textile treatment before and after laundering, main
laundry cycle,
laundry conditioning rinse cycle and ironing. Different formulations are
needed in each
case. Examples are the hereinabove described liquid and solid laundry
detergents, laundry
l0 aftertreatments and laundry refreshers.
The textiles treated with the reactive modified polymers in the main wash
cycle of a
washing machine not only wrinkle substantially less than untreated textiles,
they are also
easier to iron, softer and smoother, more dimensionally and shape stable and,
because of
the fiber and color protection, look less used, i.e., exhibit less fluff and
fewer knots and
less color damage or fading, after repeated washing.
Textiles treated with reactive modified polymers in the rinse or refresher
cycle following
the main wash cycle and then dried on the line or preferably in a tumble dryer
likewise
2 0 exhibit a very high level of crease resistance and are easier to iron.
Crease resistance can be
substantially enhanced by briefly ironing the textiles once after drying. The
treatment in
the conditioning or refresher rinse cycle also has a favorable effect on the
shape retention
of the textiles. It further inhibits the formation of knots and fluff and
suppresses color
damage.
The present invention also provides for the use of the highly branched
polymers, especially
the highly branched polyurethanes, in the manufacture of textiles, textile
treatment before
and after laundering, main laundry cycle, laundry conditioning rinse cycle and
ironing.
Different formulations are needed in each case.
The treatment before or after laundering may utilize a textile treatment
which, as well as
the reactive modified polymer dispersed form, contains a surfactant. In this
treatment, the
cellulosic textiles are for example sprayed with the reactive modified
polymers with an
add-on which is generally in the range from 0.01 to 10% by weight, preferably
in the range
3 5 from 0.1 to 7% by weight, particularly preferably in the range from 0.3 to
4% by weight,
based on the weight of the dry textile material. But the finish may also be
applied to the
textile material by dipping the textiles into a bath which contains generally
from 0.1 to
10% by weight, preferably from 0.3 to 5% .by weight, based on the weight of
the dry textile
material, of the reactive modified particulate polymer in dissolved or
dispersed form. The
CA 02430682 2003-05-28
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textile material is either dipped only briefly into the bath or else allowed
to dwell therein
for a period of from 1 to 30 min for example.
Cellulosic textiles which have been treated with the finish either by spraying
or by dipping
are if necessary squeezed off and dried. Drying may take place in air or else
in a dryer or
else by subjecting the treated textile material to hot ironing. The finish
becomes fixed on
the textile material in the course of drying. The best conditions in each case
are readily
ascertainable by experimentation. The temperatures for drying, including
ironing, are for
example in the range from 40 to 150°C preferably from 60 to
110°C. For ironing, the
cotton program of the iron is suitable in particular. Textiles treated with
the reactive
modified polymers in dispersed form according to the above-described process
exhibit an
excellent level of wrinkle and crease resistance that is durable to multiple
laundering.
There is frequently no longer any need to iron the textiles.
The invention also provides a textile treatment comprising
a) from 0.1 to 40% by weight, preferably from 0.5 to 25% by weight, of at
least one
reactive modified particulate polymer,
b) from 0 to 30% by weight of silicones,
2 0 c) from 0 to 30% by weight of one or more cationic and/or nonionic
surfactants,
d) from 0 to 60% by weight of further ingredients such as further wetting
agents,
softeners, lubricants, water-soluble, film-forming and adhesive polymers,
scents,
dyes, stabilizers, fiber and color protection additives, viscosity modifiers,
soil
release additives, corrosion control additives, bactericides, preservatives
and
2 5 spraying assistants, and
e) from 0 to 99.9% by weight of water,
components a) to e) adding up to 100% by weight.
Preferred silicones are amino-containing silicones, which are preferably
present in
3 0 microemulsified form, alkoxylated, especially ethoxylated, silicones,
polyalkylene oxide-
polysiloxanes, polyalkylene oxide-aminopolydimethylsiloxanes, silicones having
quaternary ammonium groups (silicone quats) and silicone surfactants. Useful
softeners or
lubricants include for example oxidized polyethylenes or paraffinic waxes and
oils. Useful
water-soluble, film-forming and adhesive polymers include for example
(co)polymers
CA 02430682 2003-05-28
- 29 -
based on acrylamide, N-vinylpyrrolidone, vinylformamide, N-vinylimidazole,
vinylamine,
N,N'-dialkylaminoalkyl (meth)acrylates, N,N'-
dialkylaminoalkyl(meth)acrylamides,
(meth)acrylic acid, alkyl (meth)acrylates and/or vinylsulfonate. The
aforementioned basic
monomers may also be used in quaternized form.
A pretreatment formulation to be applied to the textile material by spraying
may
additionally include a spraying assistant. In some cases, it can also be of
advantage to
include in the formulation alcohols such as ethanol, isopropanol, ethylene
glycol or
propylene glycol. Further customary additives are scents, dyes, stabilizers,
fiber and color
l0 protection additives, viscosity modifiers, soil release additives,
corrosion control additives,
bactericides and preservatives in customary amounts.
The textile treatment may generally also be applied by spraying in the course
of ironing
after laundering. This not only substantially facilitates the ironing, but
also imparts
sustained wrinkle and crease resistance to the textiles.
The examples hereinbelow illustrate the invention.
Examples
The emulsifiers used in the examples have the following composition:
Emulsifier 1: 15% by weight solution of sodium lauryl sulfate;
2 5 Emulsifier 2: 40% by weight solution of an ethoxylated and quaternized
oleylamine
(Lipamine~ OK from BASF)
'The particle size distribution was determined using an Autosizer~ 2C from
Malvern,
England. The measurement was carried out at 23°C. Solutions are aqueous
solutions,
3 o unless otherwise stated. The pphm reported in the examples denotes parts
by weight based
on 100 parts by weight of total monomer.
Preparation of polymers
3 5 Inventive example 1
A glass reactor equipped with anchor stirrer, thermometer, gas inlet tube,
dropping funnel
and reflux condenser is charged with 12 g of 0.1 % by weight sodium persulfate
solution
initiator, 6 g of a 15% by weight solution of emulsifier 1 and 402 g of water.
The contents
A
CA 02430682 2003-05-28
- 30 -
are heated in a heating bath with stirring while at the same time the air is
displaced by the
introduction of nitrogen. As soon as the heating bath has reached 75°C,
the introduction of
nitrogen is discontinued and 4 g of 0.1 % by weight sodium persulfate solution
and an
emulsion of 177 g of ethyl acrylate, 69 g of methacrylic acid, 39 g of acrylic
acid, 15 g of
glycidyl methacrylate and 22 g of a 15% by weight solution of emulsifier 1 in
400 ml of
water are added dropwise over 2 hours. This is followed by 1 hour of
supplementary
polymerization at 75°C. The batch cooling down to room temperature is
admixed with 0.75
g of 30% by weight hydrogen peroxide solution, added all at once, and with a
solution
containing 0.3 g of ascorbic acid and 0.3 g of iron(II) sulfate in 29.7 g of
water, added over
15 minutes.
The polymer dispersion obtained has the following properties:
solids content: 25.8% by weight
average particle size: 70 nm
2 0 coagulum content: < 1 g
pH: 2.2
Inventive example 2
2 5 A glass reactor equipped with anchor stirrer, thermometer, gas inlet tube,
dropping funnel
and reflux condenser is charged with 12 g of 0.1 % by weight sodium persulfate
solution
initiator, 2.3 g of a 40% by weight solution of emulsifier 2 and 402 g of
water. The
contents are heated in a heating bath with stirring while at the same time the
air is
displaced by the introduction of nitrogen. As soon as the heating bath has
reached 85°C,
3 0 the introduction of nitrogen is discontinued and 4 g of 0.1 % by weight
sodium persulfate
solution and an emulsion of 178 g of butyl acrylate, 114 g of methacrylic
acid, 1 S g of
glycidyl methacrylate and 22 g of a 15% by weight solution of emulsifier 1 in
400 ml of
water are added dropwise over 2 hours. This is followed by 1 hour of
supplementary
polymerization at 75°C. The batch cooling down to room temperature is
admixed with 0.75
3 5 g of 30% by weight hydrogen peroxide solution, added all at once, and with
a solution
containing 0.3 g of ascorbic acid and 0.3 g of iron(II) sulfate in 29.7 g of
water, added over
15 minutes.
The polymer dispersion obtained has the following properties:
CA 02430682 2003-05-28
- 31 -
solids content: 25.9% by weight
average particle size: 100 nm
coagulum content: < 1 g
pH: 2.2
Inventive ezample 3
A glass reactor equipped with anchor stirrer, thermometer, gas inlet tube,
dropping funnel
and reflux condenser is charged with 12 g of a 0.1% by weight solution of 2,2'-
azobis(2-
amidinopropane) dihydrochloride (Wako V 50 from Wako Chemie) as initiator, 2.3
g of a
40% by weight solution of emulsifier 2 and 402 g of water. The contents are
heated in a
heating bath with stirring while at the same time the air is displaced by the
introduction of
nitrogen. As soon as the heating bath has reached 85°C, the
introduction of nitrogen is
discontinued and 4 g of the initiator solution and an emulsion of 178 g of
butyl acrylate,
114 g of methacrylic acid, 15 g of glycidyl methacrylate and 8.3 g of a 40% by
weight
solution of emulsifier 1 in 400 ml of water are added dropwise over 2 hours.
This is
followed by 1 hour of supplementary polymerization at 85°C. The batch
cooling down to
room temperature is admixed with 0.75 g of 30% by weight hydrogen peroxide
solution,
2 0 added all at once, and with a solution containing 0.3 g of ascorbic acid
and 0.3 g of iron(II)
sulfate in 29.7 g of water, added over 15 minutes.
The polymer dispersion obtained has the following properties:
2 5 Solids content: 25.5% by weight
Average particle size: 120 nm
Coagulum content: < 1 g
pH: 4.0
3 0 Inventive easmple 4
A glass reactor equipped with anchor stirrer, thermometer, gas inlet tube,
dropping funnel
and reflux condenser is charged with 5.2 g of a 3.8% by weight solution of
2,2'-azobis(2-
amidinopropane) dihydrochloride (Wako V SO from Wako Chemie) as initiator,
37.5 g of a
3 5 40% by weight solution of emulsifier 2 and 370 g of water. The contents
are heated in a
heating bath with stirring while at the same time the air is displaced by the
introduction of
nitrogen. As soon as the heating bath has reached 90°C, the
introduction of nitrogen is
discontinued and 46.8 g of the initiator feed and an emulsion of 265 g of n-
butyl acrylate,
14.5 g of acrylic acid, 135 g of glycidyl methacrylate 85.5 g of
dimethylaminopropyl
CA 02430682 2003-05-28
' - 32 -
acrylamide, 52 g of 50% by weight sulfuric acid and 37.5 g of 40% by weight
solution of
emulsifier 2 in 280 ml of water are added dropwise over 2 hours. This is
followed by
1 hour of supplementary polymerization at 85°C. The batch cooling down
to room
temperature is admixed with 25 g of 4% by weight aqueous solution of sodium
formaldehyde sulfoxylate (Rongalitc~ C) and 25 g of a 10% by weight aqueous
solution of
tert-butyl hydroperoxide over 90 min.
The polymer dispersion obtained has the following properties:
l0 Solids content: 40.6% by weight
Average particle size: 120 nm
Coagulum content: < 1 g
pH: 4.0
Testing of soil release properties of polymers
Inventive examples 5-7 and comparative ezample C1
The soil release properties of the polymer dispersions were tested by
conducting washing
2 0 trials:
Cotton fabrics were prewashed with the anionic polymer dispersions of
inventive examples
1 to 3, which contained the polymer in a concentration of 400 ppm, at a pH of
4 in water of
3.0 mmol water hardness and subsequently dried.
In comparative example C1, the fabric was prewashed at pH 4 in the absence of
reactive
modified particles.
In inventive example 7, the fabric was washed with a liquor which contained
the reactive
3 0 modified polymers of inventive example 1 with a coating of
polyethyleneimine having a
molar mass of 25 000. For this, the polyethyleneimine was dissolved in water
of 3.0 mmol
hardness and the solution adjusted to pH 4Ø This solution was admixed with a
20% by
weight polymer dispersion of inventive example 1 having a pH of 4Ø The
concentration
of the polymer particles in the liquor was 400 ppm and the concentration of
the
3 5 polyethyleneimine was 40 ppm.
The prewashed fabrics, after drying, were stained with lipstick material and
subsequently
washed with a commercially available heavy-duty detergent.
CA 02430682 2003-05-28
- 33 -
Washing conditions:
washer: Launder-O-meter
water hardness: 3.0 mmol/1
Ca2+/Mg2+ ratio: 3:1
Prewash:
liquor pH: 4.0
prewash temperature: 20°C
prewash time: 15 min
liquor ratio 12.5:1
Main wash:
washing temperature: 40°C
washing time: 30 min
liquor ratio 12.5:1
After drying, the cotton fabrics were visually rated on a scale from 1 to 5, a
rating of 1
denoting an unchanged stain and a rating of 5 being awarded for complete
detachment of
2 0 the lipstick stain.
Table 1
Exam 1e Addition t prewash Ratin
C 1 without addition 1
Inv. 5 1 er of inventive exam 1e 2 3
Inv. 6 0l er of inventive exam 1e 1 3.5
Inv. 7 polymer of inventive example 1 with 4
coating of
of eth leneimine
2 5 The results of the washing trials show that the use of commercially
available heavy duty
detergent under the conditions chosen provides virtually no improvement in
lipstick soil
removal from cotton fabric. Use of the reactive modified polymers, in
contrast, provides
for a substantial improvement in soil release.
3 0 Testing of hydrophobicizing properties of polymers
Inventive examples 8-10 and comparative example C2
7
CA 02430682 2003-05-28
- 34 -
The hydrophobicizing properties of the reactive modified polymers were tested
by
conducting rinsing trials on glass.
Glass platelets measuring 2.5 x 7.5 cm in area were prerinsed at room
temperature with an
aqueous solution of a nonionic surfactant (200 ppm of C13/Cas oxo alcohol,
alkoxylated
with 7 mol of ethylene oxide), after-rinsed with pure water of 3 mmol/1
hardness and air
dried.
A dispersion of reactive modified polymers as per inventive examples 1 and 2
was
1 o prepared, the polymer concentration being 200 ppm, the water hardness 3
mmol and the
pH 6Ø
In inventive example 10, an additional 20 ppm of polyethyleneimine having a
molar mass
of 25 000 were present.
The glass platelets were dipped into this dispersion for 10 seconds, then
withdrawn and
dried at 60°C for 30 minutes.
The glass platelets thus treated each had applied to them a drop of deionized
water and the
2 o contact angle was measured. Table 2 shows the contact angles measured.
Table 2
Example Addition to rinse liquor Contact
an 1e
C2 without addition 23.9
Inv. 8 0l er of inventive exam 1e 4 42.4
Inv. 9 0l er of inventive exam 1e 3 55.3
Inv.lO polymer of inventive example 3 coated 61.2
with
1 eth leneimine of molar mass 25 000
2 5 Wrinkleproofing of fabric samples
Inventive examples 11-14 and comparative ezampte C3
Cotton fabrics having the size reported in Table 3 and a basis weight of 160
g/m2 were
3 o sprayed on both sides with the polymers of inventive examples 1 to 3 in
such a way that
the add-on was 2%, based on the weight of the dry textile material, and then
hot pressed
while still slightly moist.
CA 02430682 2003-05-28
~5
The fabric samples thus treated and, for comparison, untreated fabric samples
of the same
size were washed in the presence of ballast fabric with a liquid laundry
detergent at 40°C
in an automatic domestic machine (load in the range from 1.5 to 3.0 kg) and
then tumble
dried. A standard washing program and a standard drying program (respectively
40°C
colored wash and the cupboard dry program) were used. After drying, the
sheetlike fabric
samples were visually rated on the lines of AATCC test method 124, where a
rating of 1
indicates that the fabric is highly wrinkled and has many creases and a rating
of 5 is
awarded to wrinkle- and crease-free fabric. The fabric samples pretreated with
the finishes
(inventive examples 1 to 3) received ratings between 2.5 and 3.5. In contrast,
the untreated
fabric samples each received a rating of 1.
Table 3
Example Finish Cotton Cotton
(40 cm x 40 cm) (40 cm x 40 cm)
load 1.5 k load 3 k
C3 Untreated 1 1
Inv. 11 Polymer of 2.5 2
inventive
exam 1e 1
Inv. 12 Polymer of 3 2.5
inventive
exam 1e 2
Inv. 13 Polymer of 3 3
inventive
exam 1e 3
Inv. 14 Polymer of 3.5 3
inventive
exam 1e 4
