Note: Descriptions are shown in the official language in which they were submitted.
,
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1
As originally filed
Thickener comprising at least one polymer based on associative monomers
Description
The present invention relates to a thickener comprising at least one polymer
and at
least one activator where the ratio of activator to polymer is > 10:100 [A) by
weightP/0
by weight]. The polymer is preparable by polymerizing at least one water-
soluble,
ethylenically unsaturated monomer comprising at least one anionic monomer
and/or at
least one nonionic monomer, and at least one ethylenically unsaturated
associative
monomer. Furthermore, the present invention relates to a process for producing
the
thickener according to the invention and also surfactant-containing
formulations
comprising at least one thickener. The invention further provides the use of
the
surfactant-containing formulation, for example as a softener or as a liquid
detergent,
and also the use of the thickener, for example as a viscosity modifier.
WO 03/102043 relates to aqueous formulations comprising a cationic polymer
prepared from (i) a water-soluble, ethylenically unsaturated monomer or a
monomer
mixture comprising at least one cationic monomer, (ii) at least one
crosslinker in an
amount of more than 50 ppm based on component (i), and (iii) at least one
chain
transfer agent. The aqueous formulations can be used as thickeners in
household
formulations.
WO 2009/019225 relates to an aqueous dispersion of an alkali-soluble copolymer
which is suitable as an associative thickener. The copolymer comprises
polymerized-in
units of a) at least one ethylenically unsaturated carboxylic acid, b) at
least one
nonionic ethylenically unsaturated surfactant monomer, c) at least one C1-C2-
alkyl
methacrylate and d) at least one C2-C4-alkyl acrylate, where the alkyl chain
length
averaged over the number of alkyl groups of the alkyl acrylate is 2.1 to 4Ø
The
associative thickeners can be prepared by emulsion polymerization. The
associative
thickeners are suitable for use in detergents and cleaners.
Liquid Dispersion Polymer (LDP) compositions are disclosed in WO 2005/097834.
These LDP compositions comprise a hydrophilic, water-soluble or swellable
polymer
with a neutralization content of approximately 25 to approximately 100%, a
nonaqueous carrier phase and an oil-in-water surfactant. The hydrophilic,
water-soluble
or swellable polymer is preferably obtained by polymerization, for example of
acrylic
acid or methacrylic acid. The LDP dispersions are suitable for producing
microparticulate thickeners, as are used, for example, in aqueous or organic
compositions, in particular in personal care or pharmaceutical formulations.
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WO 2010/078959 relates to cationic polymer thickeners consisting of a
crosslinked
water-swellable cationic polymer comprising at least one cationic monomer and
optionally nonionic or anionic monomers, where the polymer comprises less than
25%
of water-soluble polymer chains, based on the total weight of the polymer.
Furthermore, the polymer comprises a crosslinker in a concentration of 500 to
5000 ppm relative to the polymer. The cationic polymer is prepared by inverse
emulsion polymerization.
WO 2010/079100 discloses fabric softener compositions comprising polymers
according to WO 2010/078959.
US 2008/0312343 relates to inverse latex compositions and to their use as a
thickener
and/or emulsifier, for example for producing cosmetic or pharmaceutical
formulations.
The inverse latex compositions comprise at least 50 to 80% by weight of at
least one
linear, branched or crosslinked organic polymer (P), at least 5 to 10% by
weight of an
emulsifier system of the water-in-oil type, 5 to 45% by weight of at least one
oil and up
to 5% water. The polymer P comprises neutral monomers and optionally cationic
or
anionic monomers. The inverse latex composition can optionally comprise up to
5% by
weight of an emulsifier system of the oil-in-water type. The inverse latex
compositions
can be prepared by inverse emulsion polymerization.
EP-A 172 025 relates to a dispersion in a continuous liquid phase of a polymer
which is
formed by polymerization of an ethylenically unsaturated monomer comprising a
hydrophobic group of at least 8 carbon atoms and an ethylenically unsaturated
monomer copolymerizable therewith. The dispersion is stable, essentially
anhydrous
and comprises at least 40% by weight of polymer. During the polymerization,
anionic
monomers, for example, can be used as copolymerizable, ethylenically
unsaturated
monomer. The polymerization can be carried out as an inverse emulsion
polymerization.
EP-A 172 724 relates to polymers which are prepared by copolymerization of a)
an
ethylenically unsaturated monomer comprising a hydrophobic group having at
least
8 carbon atoms and b) water-solubly ethylenically unsaturated monomers. All
monomers soluble as a mixture in water, and the polymer is prepared by inverse
emulsion polymerization. The polymer particles have a dry size of < 4 pm. As
monomer
component b), it is possible to use anionic monomers such as acrylic acid in
the form of
the free acid or as a water-soluble salt, and also nonionic monomers such as
acrylamide.
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EP-A 172 723 relates to a process for flocculating a suspension using a water-
soluble,
essentially linear polymer with a "single point intrinsic viscosity" of > 3.
The polymer is a
copolymer of two or more ethylenically unsaturated monomers comprising at
least
0.5% by weight of a monomer which comprises hydrophobic groups. The polymer
can
also be a cationic polymer.
The problem underlying the present invention consists in the provision of
novel
thickeners. The object is achieved by the thickeners according to the
invention
comprising
i) at least one polymer preparable by polymerization of
a) at least one water-soluble ethylenically unsaturated monomer
comprising at
least one anionic monomer and/or at least one nonionic monomer,
b) at least one ethylenically unsaturated associative monomer,
c) optionally at least one crosslinker,
d) optionally at least one chain transfer agent,
ii) at least one activator,
where the ratio of activator to polymer is > 10 to 100 [c% by weight/% by
weight].
The thickeners according to the invention are characterized in that they have
advantageous properties with regard to deposition, shear dilution,
stabilization and/or
viscosity (thickening). Deposition is understood as meaning the deposition of
the active
ingredients of, for example, a fabric softener on a fiber during a washing
operation.
Applied to the present invention, this means that, for example, a thickener
according to
the invention comprising at least one polymer (active ingredient) is present
in a fabric
softener and the fabric softener is used during or after the washing
operation. The
thickeners according to the invention promote this deposition of the active
ingredient
during or after the washing operation to a considerable extent. Particularly
good
properties with regard to deposition can be achieved when polymers based on
predominantly neutral monomers are used which are based on at least one
associative
monomer, a nonionic monomer such as acrylamide, and optionally an anionic
monomer.
When assessing the shear dilution, it is important that the thickener or the
corresponding fabric softener in its basic state is viscous and thick whereas
it is thin
upon stirring. The improved shear dilution has a positive effect on the life
and
properties of pumps during the production of the fabric softener, promotes
convenient
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dosage for the consumer and promotes the residue-free use of the fabric
softener,
especially in the washing machines which have an automatic dosing device. The
thickeners according to the invention improve the stability of the thickener
per se and
that of the corresponding formulation. The settling or creaming of particles
is effectively
prevented, irrespective of whether they are within the order of magnitude of
nanometers, micrometers or millimeters. A contributory factor here is the
advantageous
yield point of the thickener according to the invention. Moreover, they have
the
advantage that any redispersion required and the thickening are achieved very
quickly.
Thickeners according to the invention in which a mixture of at least two
activators is
present, where at least one activator has a high HLB value and at least one
activator
has a low HLB value, are associated with an additional advantage. The
combination of
such an activator mixture with polymers comprising at least one ethylenically
unsaturated associative monomer building block leads to spontaneous phase
inversions (within seconds) upon diluting a thickener with water, without
requiring an
input of additional energy, for example in the form of stirring.
Furthermore, in the case of thickeners according to the invention, it is
advantageous
that the ratio of associative monomer to the total polymer is relatively low.
When using
the thickener in surfactant-containing formulations, the effect of the
associative
monomers is optimal even in amounts of approximately 0.5 % by weight (based on
the
polymer).
If the thickeners according to the invention are prepared by inverse emulsion
polymerization in which the temperature is kept constant at at least 40 C, a
good
uniformity of distribution of the associative monomer building blocks within
the polymer
can be observed. Particularly in the case of small use amounts of, for
example, 0.1 to
1% by weight of associative monomers, this is advantageous with regard to the
overall
aforementioned rheological properties such as thickening, shear dilution,
stabilization,
and also washing and rinsing effects.
Embodiments of the present invention in which the polymers present in the
thickener
are prepared using little or no crosslinker are likewise associated with
advantages. On
account of the relatively high (water-) soluble components of the polymer,
resoiling
during a washing operation is reduced. Consequently, the article to be washed,
even
after repeated washing processes, has clean fibers which have been effectively
freed
from dirt particles, meaning that no graying is detected. No or only very
slight adhesion
and/or redistribution of dirt particles/polymers on the washed articles is
observed.
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Within the context of the present invention, the definitions such as C1-C30-
alkyl, as
defined, for example, below for the radical Rg in formula (I), mean that this
substituent
(radical) is an alkyl radical having a carbon atom number from 1 to 30. The
alkyl radical
can be either linear or branched and also optionally cyclic. Alkyl radicals
which have
5 both a cyclic and a linear component likewise fall within this
definition. The same also
applies to other alkyl radicals, such as, for example, a C1-C4-alkyl radical
or a C16-C22-
alkyl radical. The alkyl radicals can optionally also be mono- or
polysubstituted with
functional groups such as amino, quaternary ammonium, hydroxy, halogen, aryl
or
heteroaryl. Unless stated otherwise, the alkyl radicals preferably do not have
any
functional groups as substituents. Examples of alkyl radicals are methyl,
ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, 2-ethylhexyl, tertiary-butyl (tert-
Bu/t-Bu),
cyclohexyl, octyl, stearyl or behenyl.
The present invention is described in more precise terms below.
The thickener according to the invention comprises, as component i), at least
one
polymer. The polymer is preparable by polymerization of the following
components a)
and b) and also optionally c) and d).
As component a), at least one water-soluble, ethylenically unsaturated
monomer,
comprising at least one anionic monomer and/or at least one nonionic monomer
is
used. Anionic and nonionic monomers per se are known to the person skilled in
the art.
If at least one anionic monomer is present in component a), it is preferably
selected
from acrylic acid, methacrylic acid, itaconic acid, maleic acid or a salt
thereof, in
particular the anionic monomer is Na acrylate.
If at least one nonionic monomer is present in component a), apart from the
nitrogen-
containing monomers described below, such as, for example, the compounds
according to formula (I), esters of the anionic monomers described above are
also
suitable as nonionic monomers. Such nonionic monomers are preferably the
methyl or
ethyl esters of acrylic acid or methacrylic acid such as ethyl acrylate or
methyl acrylate.
Preference is also given to the corresponding dimethylamino-substituted esters
such
as dimethylaminoethyl (meth)acrylate.
Preferably, the nonionic monomer is selected from N-vinylpyrrolidone, N-
vinylimidazole
or a compound according to the formula (I)
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R 0
18 11 /Rs
¨C=C¨C¨N
R7 H
R10 (I)
where
R7 is H or C1-C4-alkyl,
R9 is H or methyl, and
R9 and R10, independently of one another, are H or C1-C30-alkyl.
The nonionic monomer is particularly preferably acrylamide, methacrylamide or
dialkylaminoacrylamide.
In a preferred embodiment of the present invention, in the polymer, component
a)
comprises 30 to 99.5% by weight of at least one anionic monomer and 0.5 to 70%
by
weight of at least one nonionic monomer.
In a further preferred embodiment of the present invention, component a)
comprises
100% by weight of at least one nonionic monomer.
In a further preferred embodiment of the present invention, component a)
comprises
100% by weight of at least one anionic monomer.
Furthermore, within the context of the present invention, it is preferred that
component
a) comprises no cationic monomer.
As component b), at least one ethylenically unsaturated associate monomer is
used in
the polymerization for producing the polymer. Associative monomers per se are
known
to the person skilled in the art. Suitable associative monomers are described,
for
example, in WO 2009/019225. Associative monomers are also referred to as
surfactant
monomers.
Preferably, in the polymer, the ethylenically unsaturated associative monomer
according to component b) is selected from a compound according to formula
(II)
R-0-(CH2-CHR'-0)n-CO-CR"=CH2 (II)
where
R is C6-050-alkyl, preferably Ce-C30-alkyl, in particular C16-C22-alkyl,
R' is H or C1-C4-alkyl, preferably H,
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R" is H or methyl,
n is an integer from 0 to 100, preferably 3 to 50, in particular 25.
As component b), particular preference is given to using a compound according
to
formula (II) in which
R is C16-C22-alkyl,
R' is H,
R" is H or methyl and
n is 25.
Compounds according to formula (II) are commercially available in solution,
for
example under the name Plex 6954 0 from Evonik Rohm GmbH. These are
methacrylates of fatty alcohol ethoxylates, such as the commercially available
Lutensol AT 25 (BASF SE, Ludwigshafen, Germany).
The radical R in the compounds according to formula (II) can also be present
as a
mixture of radicals with different chain lengths, such as C16 and C18. One
example of
this is C16-C18-fatty alcohol (ethylene glycol)26-ether methacrylate, where
both C16 and
C18 fatty alcohol radicals (in non-negligible amounts) are present as a
mixture. In
contrast to this, for example, in the compounds (according to formula (II))
beheny1-25
methacrylate and cety1-25 methacrylate, the respective radical R is not
present as a
mixture but as a C22 or C16 chain. Other chain lengths occur only in the form
of
impurities. The number "25" in these compounds according to formula (II)
represents
the size of the variables n.
In the preparation of the polymer by polymerization, at least one crosslinker
may
optionally be present as component c). Suitable crosslinkers are known to the
person
skilled in the art. Preferably, in the polymer, the crosslinker according to
component c)
is selected from divinylbenzene; tetraallylammonium chloride; ally' acrylates;
allyl
methacrylates; diacrylates and dimethacrylates of glycols or polyglycols;
butadiene;
1,7-octadiene, allylacrylamides or allylmethacrylamides; bisacrylamidoacetic
acid;
N,N'-methylenebisacrylamide or polyol polyallyl ethers such as polyallyl
sucrose or
pentaerythritol triallyl ether. Also suitable as a preferred crosslinker is
dialkyldimethylammonium chloride.
Furthermore, during the preparation of the polymer by polymerization, at least
one
chain transfer agent can be used as component d). Suitable chain transfer
agents are
known to the person skilled in the art. Preferred chain transfer agents
according to
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component d) are selected from mercaptan, lactic acid, formic acid,
isopropanol or
hypophosphites.
Suitable polymerization processes for preparing the polymer or the thickener
according
to the invention comprising at least one polymer, and also any additives or
auxiliaries
used in the polymerization or in the thickener production process are defined
in more
detail below.
Preferably, in the thickener according to the invention, at least one polymer
is present
which is preparable by polymerization of
a) 20 to 99.99% by weight, preferably 95 to 99.95% by weight (based on the
polymer), of at least one water-soluble ethylenically unsaturated monomer
comprising at least one anionic monomer and/or at least one nonionic monomer,
b) 0.01 to 80% by weight, preferably 0.05 to 5% by weight, particularly
preferably
0.1 to 1% by weight (based on the polymer) of at least one ethylenically
unsaturated associative monomer,
c) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the
polymer) of
optionally at least one crosslinker,
d) 0 to 0.3% by weight, preferably 0.01 to 0.1% by weight (based on the
polymer) of
optionally at least one chain transfer agent.
In a further embodiment of the present invention, the water-soluble fractions
of the
polymer are more than 25% by weight (based on the total weight of the
polymer),
particularly when little or no crosslinker is used in addition to the
associative monomer.
Preferably, more than 40% by weight, in particular 70 to 100% by weight, of
the
polymer is soluble in water. The solubility of the polymer is determined by
methods
known to the person skilled in the art, the polymer present in the thickener
according to
the invention being admixed with a defined amount of water (see, for example,
EP-A
343 840 or preferably the determination method of the sedimentation
coefficient in the
unit of Svedberg (sved) according to P. Schuck, "Size-distribution analysis of
macromolecules by sedimentation velocity ultracentrifugation and Lamm equation
modeling, Biophysical Journal 78, (3) (2000), 1606-1619).
Preferably, in this embodiment, the fraction of crosslinker (component c))
used in the
polymerization of the polymer is < 10% by weight (based on the total amount of
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components a) to d)). It is particularly preferred not to use any crosslinker
in the
polymerization of the polymer.
The thickener according to the invention furthermore comprises at least one
activator
as component ii). Activators per se are known in principle to the person
skilled in the
art.
Suitable activators are preferably surfactants, for example anionic, nonionic,
cationic
and/or amphoteric surfactants, which are disclosed, for example, in WO
2009/019225.
Preference is given to using anionic and/or nonionic surfactants.
The nonionic surfactants used are preferably fatty alcohol alkoxylates. Fatty
alcohol
alkoxylates are also referred to as polyalkylene glycol ethers. Preferred
fatty alcohol
alkoxylates are alkoxylated, advantageously ethoxylated, in particular primary
alcohols
having preferably 8 to 18 carbon atoms and on average 1 to 12 mol of ethylene
oxide
(EO) per mole of alcohol, in which the alcohol radical can be linear or
branched,
preferably 2-methyl-branched, or can comprise linear and methyl-branched
radicals in
a mixture, as are usually present in oxo alcohol radicals. Especially
preferred, however,
are alcohol ethoxylates with linear radicals from alcohols of native or
technical origin
having 12 to 18 carbon atoms, for example from coconut alcohol, palm alcohol,
tallow
fatty alcohol or ley' alcohol - or mixtures, as can be derived, for example,
from castor
oil - and on average 2 to 8 EO per mole of alcohol. The preferred ethoxylated
alcohols
include, for example, C12-C14-alcohols with 3 EO, 4 EO or 7 EO, C9-C11-alcohol
with 7
EO, C13-C15-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-C18-alcohols with 3
EO, 5 EO
or 7 EO and mixtures of these, such as mixtures of C12-C14-alcohol with 3 EO
and
C12-C18-alcohol with 7 EO. The stated degrees of ethoxylation are statistical
average
values which may be an integer or a fraction for a specific product. Preferred
alcohol
ethoxylates have a narrowed homolog distribution (narrow range ethoxylates,
NRE). In
addition to these nonionic surfactants, fatty alcohols with more than 12 EO
can also be
used. Examples thereof are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40
EO. It
is also possible to use nonionic surfactants which comprise EO and PO groups
together in the molecule. Here, it is possible to use block copolymers with EO-
P0 block
units or PO-E0 block units, but also EO-PO-E0 copolymers or PO-E0-P0
copolymers.
It is of course also possible to use mixed alkoxylated nonionic surfactants in
which EO
and PO units are not blockwise, but in random distribution. Such products are
obtainable by the simultaneous action of ethylene oxide and propylene oxide on
fatty
alcohols.
Moreover, alkyl glycosides or alkyl polyglycosides can also be used as further
nonionic
surfactants. Alkyl glycosides and alkyl polyglycosides are generally
understood by the
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person skilled in the art as meaning compounds which are composed of at least
one
alkyl fragment and at least one sugar or polysugar fragment. The alkyl
fragments are
preferably derived from fatty alcohols with a carbon atom number of 12 to 22,
and the
sugar fragments are preferably derived from glucose, sucrose or sorbitan.
5 For example, alkyl glycosides of the general formula (1)
R10(G). (1)
can be used, in which R1 is a primary straight-chain or methyl-branched, in
particular
10 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to
18, carbon atoms,
and G is a glycoside unit having 5 or 6 carbon atoms, preferably glucose. The
degree
of oligomerization x, which specifies the distribution of monoglycosides and
oligoglycosides, is any number between 1 and 10; preferably, x is 1.2 to 1.4.
A further class of preferably used nonionic surfactants, which are used either
as the
sole nonionic surfactant or in combination with other nonionic surfactants,
are
alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty
acid alkyl
esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in
particular fatty acid
methyl esters, as are described, for example, in the Japanese patent
application
JP 58/217598, or which are preferably prepared by the process described in the
international patent application WO-A-90/13533.
Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-
N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and
of the
fatty acid alkanolamide type may also be suitable. The amount of these
nonionic
surfactants is preferably not more than that of the ethoxylated fatty
alcohols, in
particular not more than half thereof.
Further suitable surfactants are polyhydroxy fatty acid amides of formula (2),
0
R2/.\ N [Z] (2)
I 3
R
in which R2C(=0) is an aliphatic acyl radical having 6 to 22 carbon atoms, R3
is
hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z]
is a linear
or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10
hydroxyl
groups. The polyhydroxy fatty acid amides are known substances which can
usually be
obtained by reductive amination of a reducing sugar with ammonia, an
alkylamine or an
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alkanolamine, and subsequent acylation with a fatty acid, a fatty acid alkyl
ester or a
fatty acid chloride.
The group of polyhydroxy fatty acid amides also includes compounds of formula
(3)
RLO¨R6
4 I
R N[Z]i (3)
0
in which R4 is a linear or branched alkyl or alkenyl radical having 7 to 12
carbon atoms,
R6 is a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms
or an
arylene radical having 6 to 8 carbon atoms, and R6 is a linear, branched or
cyclic alkyl
radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms,
where
C1-C4-alkyl or phenyl radicals are preferred, and [Z]l is a linear
polyhydroxyalkyl radical
whose alkyl chain is substituted with at least two hydroxyl groups, or
alkoxylated,
preferably ethoxylated or propoxylated derivatives of this radical. [Z]l is
preferably
obtained by reductive amination of a sugar, for example glucose, fructose,
maltose,
lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted
compounds can then be converted to the desired polyhydroxy fatty acid amides,
for
example, according to WO-A-95/07331 by reaction with fatty acid methyl esters
in the
presence of an alkoxide as catalyst.
The anionic surfactants used are, for example, those of the sulfonate and
sulfate type.
Suitable surfactants of the sulfonate type here are alkylbenzenesulfonates,
preferably
C9-C13-alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene- and
hydroxyalkanesulfonates, and also disulfonates, as are obtained, for example,
from
C12-C18-monoolefins with terminal or internal double bond by sulfonation with
gaseous
sulfur trioxide and subsequent alkaline or acidic hydrolysis of the
sulfonation products.
Also of suitability are alkanesulfonates, preferably secondary
alkanesulfonates, which
are obtained, for example, from C12-C18-alkanes by sulfochlorination or
sulfoxidation
with subsequent hydrolysis or neutralization. The esters of a-sulfo fatty
acids (ester
sulfonates), for example the a-sulfonated methyl esters of hydrogenated
coconut fatty
acids, palm kernel fatty acids or tallow fatty acids, are also likewise
suitable.
Further suitable anionic surfactants are sulfated fatty acid glycerol esters.
Fatty acid
glycerol esters are to be understood as meaning the mono-, di- and triesters,
and
mixtures thereof, as are obtained during the preparation by esterification of
a
monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of
triglycerides
with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters
here are the
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sulfation products of saturated fatty acids having 6 to 22 carbon atoms, for
example of
caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic
acid, stearic
acid or behenic acid.
Further suitable anionic surfactants are fatty alcohol sulfates, for example
alk(en)yl
sulfates. Preferred alk(en)yl sulfates are the alkali metal salts, and in
particular the
sodium salts, of the sulfuric acid monoesters of the C12-C18-fatty alcohols,
for example
of coconut fatty alcohol, tallow fatty alcohol, lauryl alcohol, myristyl
alcohol, cetyl
alcohol or stearyl alcohol, or of the C10-C20-oxo alcohols and those
monoesters of
secondary alcohols of these chain lengths. Further preferred are alk(en)yl
sulfates of
said chain lengths which comprise a synthetic straight-chain alkyl radical
produced on
a petrochemical basis, which have analogous degradation behavior to the
equivalent
compounds based on fatty-chemical raw materials. In the interests of washing
technology, the C12-C16-alkyl sulfates and C12-C16-alkyl sulfates, and also
C14-C16-alkyl
sulfates are preferred. Also 2,3-alkyl sulfates, which are prepared, for
example,
according to the US patent specifications 3,234,258 or 5,075,041 and can be
obtained
as commercial products from Shell Oil Company under the name DAN , are
suitable
anionic surfactants.
The sulfuric acid monoesters of the straight-chain or branched C7-C21-alcohols
ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C9-
C11-
alcohols having on average 3.5 mol of ethylene oxide (EO) or C12-C18-fatty
alcohols
with 1 to 4 EO, are also suitable.
Further suitable anionic surfactants are also the salts of alkylsulfosuccinic
acid, which
are also referred to as sulfosuccinates or as sulfosuccinic acid esters and
which are
monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably
fatty alcohols
and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates
comprise C8-C18-
fatty alcohol radicals or mixtures of these. Particularly preferred
sulfosuccinates
comprise a fatty alcohol radical which is derived from ethoxylated fatty
alcohols. In this
connection, particular preference is given in turn to sulfosuccinates whose
fatty alcohol
radicals are derived from ethoxylated fatty alcohols with a narrower homolog
distribution. It is likewise also possible to use alk(en)ylsuccinic acid
having preferably 8
to 18 carbon atoms in the alk(en)yl chain or salts thereof.
Further suitable anionic surfactants are alkyl carboxylates, for example the
sodium
salts of saturated or unsaturated fatty acids, where the alkyl radical of the
alkyl
carboxylate is preferably linear.
EK10-0898PC "as originally filed"
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Within the context of the present invention, the activator is preferably
selected from
fatty alcohol alkoxylates, alkyl glycosides, alkyl carboxylates,
alkylbenzenesulfonates,
secondary alkanesulfonates and fatty alcohol sulfates, particularly preferably
selected
from fatty alcohol alkoxylates. One example of a preferred fatty alcohol
alkoxylate is
C6-C17(secondary)-poly(3-6)ethoxylate.
Furthermore, it is preferred within the context of the present invention to
use an
activator which has a (relatively) high HLB value (Hydrophilic-Lipophilic
Balance value).
Preferably, the activator has an HLB of 7 to 18, more preferably of 8 to 15
and
particularly preferably of 9 to 13.
Activators with a high HLB value are preferably i) fatty alcohol alkoxylates
formed from
secondary alcohols or mixtures of alcohols having 12 to 18 carbon atoms and
ethylene
oxide or propylene oxide, and ii) alkyl glycosides formed from sucrose and C8
to C22-
fatty alcohols. Examples of such activators are the commercially available
Synperonic
87K from Croda GmbH , Herrenpfad-Siid 33, 41334 Nettetal, Germany; Croduret 40
or
other ethoxylated hydrogenated castor oils (ricinus oils) such as Etocas 40 or
Crodesta
F110, all from Croda.
In a further embodiment of the present invention, it is preferred to use a
mixture of at
least two activators, where at least one activator has a high HLB value and at
least one
activator has a low HLB value. The activator with a high HLB value preferably
has an
HLB value of > 12 to 20 and the activator with a low HLB value preferably has
an HLB
value of 1 to 12. In this embodiment, the activator with a high HLB value and
the
activator with a low HLB value can be present relative to one another in any
desired
ratios known to a person skilled in the art. Preferably, in the mixture, 20 to
50% by
weight of activator with a high HLB value and 50 to 80% by weight of activator
with a
low HLB value are used. Further preferably, this ratio of activator with a
high HLB value
to activator with a low HLB value is adjusted such that the overall HLB value
is 7 to 18,
more preferably 8 to 15 and particularly preferably from 9 to 13.
In these mixtures of at least two activators, the activators with a high HLB
value used
are preferably alkyl glycosides or polyalkyl glycosides or polyalkyl
oligoethylene oxide
glycoside based on sucrose or sorbitan and C8 to C22-fatty alcohols such as
polyethylene glycol sorbitan monostearate or polyoxyethylene sorbitan
monostearate.
Examples of such activators are the commercially available Crillet 1, Crillet
3 or
Crodesta F160, all available from Croda. As activators with a low HLB value,
preference is given to using alkyl glycosides formed from sucrose or sorbitan
and C8 to
C22-fatty alcohols or fatty acids, such as sorbitan laurate or sorbitan
stearate. Examples
EK10-0898PC "as originally filed"
' PF0000070898/We1
CA 02853243 2014-04-23
,
14
of such activators are the commercially available Crill 1, Crill 3 or Crodesta
F10 from
Croda.
According to the invention, the ratio of activator to polymer is > 10:100 [%
by weight/%
by weight], preferably 10.5 to 50:100 [ /0 by weight/% by weight],
particularly preferably
11.5 to 20:100 [% by weight/% by weight].
In the thickeners according to the invention, further components may also be
present in
addition to the polymer and the activator. Suitable further components are
defined in
more detail in the text below within the context of the preparation of the
thickener and
of the polymer. Suitable further components may be, for example, oils and
solvents.
In the thickener according to the invention, the polymer can be present in the
oil phase
in dispersed form, preferably as an inverse dispersion, water-in-oil
dispersion or as a
dispersed anhydrous polymer in oil.
The present invention further provides a process for preparing the thickeners
according
to the invention. Thickener preparation processes per se and processes for
preparing a
polymer are known to the person skilled in the art. Preferably, the polymer is
obtained
by an emulsion polymerization, in particular by an inverse emulsion
polymerization.
Preferably, the polymer is firstly prepared and after the polymerization,
preferably by
means of inverse emulsion polymerization, the activator is added to give the
thickener.
The polymer can be prepared in various ways, preferably by emulsion
polymerization,
in particular by inverse emulsion polymerization. Inverse emulsion
polymerization is
understood by the person skilled in the art generally as meaning
polymerization
processes according to the following definition: the hydrophilic monomers are
dispersed in a hydrophobic oil phase. The polymerization takes place directly
in these
hydrophilic monomer particles by addition of initiator.
Furthermore, it is preferred that, after the inverse emulsion polymerization
and before
the activator is added, at least some water and at least some of the low-
boiling
constituents are distilled off from the oil phase, in particular by means of
LDP (liquid
dispersion polymer) technology. LDP technology per se is known to the person
skilled
in the art; it is described for example in WO 2005/097834.
Unless stated otherwise, the details below apply to all types of the emulsion
polymerization, such as, for example, to the emulsion polymerization in water,
which
then also constitutes the continuous phase, and in particular also to the
inverse
emulsion polymerization, in which the hydrophobic oil phase constitutes the
continuous
EK10-0898PC "as originally filed"
PF0000070898NVei CA 02853243 2014-04-23
phase. A suitable polymerization initiator is used for the polymerization.
Redox initiators
and/or thermally activatable free-radical polymerization initiators are
preferred.
Suitable thermally activatable free-radical initiators or the oxidative
component of the
5 redox initiator pair are primarily those of the peroxy and azo type.
These include, inter
alia, hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, di-t-butyl
peroxide,
dibenzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-
dimethy1-
2,5-bis(hydroperoxy)hexane, perbenzoic acid, t-butyl peroxwivalate, t-butyl
peracetate,
dilauroyl peroxide, dicapryloyl peroxide, distearoyl peroxide, dibenzoyl
peroxide,
10 diisopropyl peroxydicarbonate, didecyl peroxydicarbonate, dieicosyl
peroxydicarbonate,
di-t-butyl perbenzoate, azobisisobutyronitrile, 2,2'-azobis-2,4-
dimethylvaleronitrile,
ammonium persulfate, potassium persulfate, sodium persulfate and sodium
perphosphate.
15 The persulfates (peroxodisulfates), in particular sodium persulfate, are
most preferred.
When carrying out the emulsion polymerization, the initiator is used in a
sufficient
amount to initiate the polymerization reaction. The initiator is usually used
in an amount
of about 0.01 to 3% by weight, based on the total weight of the monomers used.
The
amount of initiator is preferably about 0.05 to 2% by weight and in particular
0.1 to 1%
by weight, based on the total weight of the monomers used.
The emulsion polymerization usually takes place at 35 to 100 C. It can be
carried out
either as a batch process or in the form of a feed process. In the feed
procedure, at
least some of the polymerization initiator and optionally some of the monomers
are
introduced as initial charge and heated to the polymerization temperature, and
the
remainder of the polymerization mixture is subsequently introduced, usually
via a
plurality of separate feeds, one or more of which comprise the monomers in
pure or
emulsified form, continuously or stepwise while maintaining the
polymerization.
Preferably, the monomer feed takes place in the form of a monomer emulsion. In
parallel to the monomer feed, further polymerization initiator can be metered
in.
In preferred embodiments, the total amount of initiator is introduced as
initial charge,
i.e. no further metering of initiator parallel to the monomer feed takes
place.
In a preferred embodiment, the thermally activatable free-radical
polymerization initiator
is therefore introduced in its entirety as initial charge, and the monomer
mixture,
preferably in the form of a monomer emulsion, is run in. Before the monomer
mixture
feed is started, the initial charge is brought to the activation temperature
of the
thermally activatable free-radical polymerization initiator or a higher
temperature. The
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
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activation temperature is considered to be the temperature at which at least
half of the
initiator has decomposed after one hour.
According to another preferred preparation method, the polymer is obtained by
polymerization of a monomer mixture in the presence of a redox initiator
system. A
redox initiator system comprises at least one oxidizing agent component and at
least
one reducing agent component, in which case heavy metal ions are preferably
additionally present in the reaction medium as catalyst, for example cerium
salts,
manganese salts or iron(II) salts.
Suitable oxidizing agent components are, for example, peroxides and/or
hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, cumene
hydroperoxide, pinane hydroperoxide, diisopropylphenyl hydroperoxide,
dicyclohexyl
percarbonate, dibenzoyl peroxide, dilauroyl peroxide and diacetyl peroxide.
Hydrogen
peroxide and tert-butyl hydroperoxide are preferred.
Suitable reducing agent components are alkali metal sulfites, alkali metal
dithionites,
alkali metal hyposulfites, sodium hydrogensulfite, Rongalit C (sodium
formaldehyde
sulfoxylate), mono- and dihydroxyacetone, sugars (e.g. glucose or dextrose),
ascorbic
acid and its salts, acetone bisulfite adduct and/or an alkali metal salt of
hydroxymethanesulfinic acid, sodium hydrogensulfite or sodium metabisulfite
are
preferred.
Also suitable as reducing agent component or catalyst are iron(II) salts such
as e.g.
iron(II) sulfate, tin(II) salts such as e.g. tin(II) chloride, titanium(III)
salts such as
titanium(III) sulfate.
The use amounts of oxidizing agent are 0.001 to 5.0% by weight, preferably
from 0.005
to 1.0% by weight and particularly preferably from 0.01 to 0.5% by weight,
based on
the total weight of the monomers used. Reducing agents are used in amounts of
from
0.001 to 2.0% by weight, preferably from 0.005 to 1.0% by weight and
particularly
preferably from 0.01 to 0.5% by weight, based on the total weight of the
monomers
used.
A particularly preferred redox initiator system is the sodium
peroxodisulfate/sodium
hydrogensulfite system, e.g. 0.001 to 5.0% by weight of sodium peroxodisulfate
and
0.001 to 2.0% by weight of sodium hydrogensulfite, in particular 0.005 to 1.0%
by
weight of sodium peroxodisulfate and 0.005 to 1.0% by weight of sodium
hydrogensulfite, particular preferably 0.01 to 0.5% by weight of sodium
peroxodisulfate
and 0.01 to 0.5% by weight of sodium hydrogensulfite.
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
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A further particularly preferred redox initiator system is the t-butyl
hydroperoxide/hydrogen peroxide/ascorbic acid system, e.g. 0.001 to 5.0% by
weight
of t-butyl hydroperoxide, 0.001 to 5.0% by weight of hydrogen peroxide and
0.001 to
2.0% by weight of ascorbic acid, in particular 0.005 to 1.0% by weight of t-
butyl
hydroperoxide, 0.005 to 1.0% by weight of hydrogen peroxide and 0.005 to 1.0%
by
weight of ascorbic acid, particularly preferably 0.01 to 0.5% by weight of t-
butyl
hydroperoxide, 0.01 to 0.5% by weight of hydrogen peroxide and 0.01 to 0.5% by
weight of ascorbic acid.
Preferably, the polymer is prepared by inverse emulsion polymerization by
firstly
preparing an aqueous phase of the water-soluble components and an oil phase
separately from one another. Subsequently, the two phases are mixed with one
another to give a water-in-oil dispersion. The mixture is polymerized by
adding a redox
initiator system; optionally, a thermal initiator can then also be added or,
if already
present, be thermally activated.
In the aqueous phase, preferably a chain transfer agent, a crosslinker, an
anionic
monomer and/or a neutral monomer and also optionally the associative monomer
are
present, and also optionally further components. Suitable further components
are, for
example, complexing agents for salts such as pentasodium diethylene-
triaminepentaacetic acid.
In the oil phase, preferably an emulsifier, a stabilizer, a high-boiling oil,
a low-boiling oil
and/or optionally the associative monomer are present. Furthermore, a nonionic
monomer may optionally be present in the oil phase.
Emulsifiers, stabilizers, low-boiling oils and high-boiling oils as such are
known to the
person skilled in the art. These compounds can be used individually or in the
form of
mixtures.
Typical emulsifiers are anionic emulsifiers such as, for example, sodium
lauryl sulfate,
sodium tridecyl ether sulfates, dioctyl sulfosuccinate sodium salt and sodium
salts of
alkylaryl polyether sulfonates; and nonionic emulsifiers such as, for example,
alkylaryl
polyether alcohols and ethylene oxide-propylene oxide copolymers. Sorbitan
trioleate is
likewise suitable as an emulsifier.
Preferred emulsifiers have the following general formula:
R-0-(CH2-CHR'-0)n-X ,
EK10-0898PC "as originally filed"
' PF0000070898/We1 CA 02853243 2014-04-23
18
in which R is C6-C30-alkyl,
R' is hydrogen or methyl,
X is hydrogen or SO3M,
M is hydrogen or an alkali metal, and
n is an integer from 2 to 100.
Suitable stabilizers are described, for example, in EP-A 172 025 or EP-A 172
724.
Preferred stabilizers are copolymers of stearyl methacrylate and methacrylic
acid.
Suitable high-boiling oils are, for example, 2-ethylhexyl stearate and also
hydroheated
heavy naphtha, and suitable low-boiling oils are, for example, dearomatized
aliphatic
hydrocarbons or mineral oils of low viscosity.
In a preferred embodiment of the present invention, during the inverse
emulsion
polymerization, component b) (at least one ethylenically unsaturated
associative
monomer) is added to the oil phase.
During the inverse emulsion polymerization, the temperature can be kept
constant or it
can also increase. The increase in temperature can be carried out continuously
or in
stages. Thus, for example, the temperature during the polymerization can
increase by
0.2 to 10 C per minute, preferably from 1 to 3 C per minute. The temperature
increase
is controlled by the rate at which the initiator is added. The temperature
starting value
can be 0 to 30 C, preferably 10 to 20 C.
In another embodiment of the present invention, the temperature during the
inverse
emulsion polymerization is kept constant (cold procedure), the temperature is
0 to
C, preferably 10 to 20 C. In a further embodiment of the present invention,
the
temperature is kept constant in a higher temperature range (warm procedure).
The
30 temperature during the polymerization is 40 to 150 C, preferably 70 to
120 C.
In a particularly preferred embodiment of the present invention, the
temperature is kept
constant during the inverse emulsion polymerization, the temperature being at
least
C, preferably 50 to 90 C.
If, within the context of the present invention, the temperature is kept
constant during a
polymerization, in particular during an inverse emulsion polymerization, this
means that
the temperature is kept at a constant value from the start of the
polymerization.
Fluctuations of +/-5 C, preferably +/-2 C and in particular +/-1 C during the
polymerization process are considered to be a constant temperature (based on
the
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
19
desired constant temperature value). The temperature is kept constant until
the
polymerization is complete; preferably, this is the case after a conversion of
more than
90% of the monomers used, more preferably more than 95% by weight and
particularly
preferably at complete conversion (100% by weight). The temperature can be
kept
constant by dissipating the heat of reaction which arises by cooling. The
start of the
polymerization is normally the addition of the polymerization initiator,
preferably the
addition of a redox initiator system. Normally, the system is firstly heated
to the desired
temperature and a constant temperature is awaited while stirring. Then, the
polymerization initiator is added, as a result of which the polymerization
process is set
in motion. In one embodiment of the present invention, the temperature is kept
constant at a value above the melting point of the associative monomer used.
The present invention further provides surfactant-containing acidic
formulations
comprising at least one thickener according to the invention as per the
definitions
above. The pH of the formulation is 1 to < 7.
The present invention further provides surfactant-containing alkaline
formulations
comprising at least one thickener according to the invention as per the
definitions
above. The pH of the formulation is 7 to 13.
The surfactant-containing acidic or alkaline formulations according to the
invention can
comprise further ingredients known to the person skilled in the art. Suitable
ingredients
comprise one or more substances from the group of builders, bleachers, bleach
activators, enzymes, electrolytes, nonaqueous solvents, pH modifiers,
fragrances,
perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors,
silicone oils,
antiredeposition agents, optical brighteners, graying inhibitors, antishrink
agents,
anticrease agents, dye transfer inhibitors, antimicrobial active ingredients,
germicides,
fungicides, antioxidants, corrosion inhibitors, antistats, ironing aids,
phobicization and
impregnation agents, swelling and antislip agents, and UV absorbers.
The present invention further provides the use of a surfactant-containing
acidic
formulation according to the invention in hair cosmetics, in hairstyling, as a
shampoo,
as a softener, as a care composition, as a conditioner, as a skin cream, as a
shower
gel, as a fabric softener for laundry, or as an acidic cleaner, preferably for
the toilet or
the bath.
The present invention further provides the use of a surfactant-containing
alkaline
formulation as a care composition, as a liquid detergent or as a dishwashing
detergent
for machine washing or hand washing.
EK10-0898PC "as originally filed"
' PF0000070898NVei CA 02853243 2014-04-23
The present invention further provides the use of the thickener according to
the
invention as a viscosity modifier, for optimizing shear dilution, as a
thickening agent, for
stabilizing suspended ingredients with a size in the range from nanometers to
millimeters and/or in surfactant-containing acidic or alkaline formulations.
5
In the description including the examples, the following abbreviations are
used:
Monomers
ACM Acrylamide
AA Acrylic acid
MAA Methacrylic acid
NaAc Sodium acrylate
BEM Beheny1-25 methacrylate
MBA Methylenebisacrylamide (crosslinker)
TAAC Tetraallylammonium chloride (crosslinker)
NaHP Sodium hypophosphite (chain transfer agent)
C16E025MAc C16-C15-Fatty alcohol-(ethylene glycol)25 ether
methacrylate
Others
pphm Parts per hundred parts of monomers (based
on components a) and b))
demin. Demineralized
The invention is illustrated below by reference to the examples.
Examples
Comparative example Cl
Synthesis of a thickener/polymer starting from anionic monomers without
associative
monomer, but with crosslinker and chain transfer agent and also increasing
polymerization temperature.
An aqueous phase of water-soluble components is prepared by mixing the
following
components:
250.24 g (139.02 pphm) of water,
0.89 g (0.49 pphm) of pentasodium diethylenetriaminepentaacetic acid,
11.05 g (0.06 pphm) of methylenebisacrylamide (1% in water),
180 g (100 pphm) of acrylic acid and
146.8 g (40.78 pphm) of NaOH (50% in water)
EK10-0898PC "as originally filed"
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21
Use NaOH (50% in water) to adjust the water phase to pH 5.5.
An oil phase is prepared by mixing the following components:
20.62 g (8.59 pphm) of sorbitan monooleate (75% in hydroheated heavy naphtha
(petroleum) [Isopar G])
93.19 g (12.27 pphm) of a polymeric stabilizer: stearyl methacrylate-
methacrylic acid
copolymer (23.7% in hydroheated heavy naphtha [lsopar G]),
120.24 g (66.8 pphm) of mineral oil of low viscosity (Kristol M14) and
236.28 g (131.27 pphm) of hydroheated heavy naphtha [lsopar G].
The two phases are mixed in a ratio of 55.6 parts of aqueous phase to 44.4
parts of oil
phase with high shear to produce a water-in-oil emulsion. The resulting water-
in-oil
emulsion is introduced into a reactor equipped with nitrogen spray line,
stirrer and
thermometer. The emulsion is purged with nitrogen, as a result of which the
oxygen is
removed, and is cooled to 20 C.
The polymerization is achieved by adding a redox pair composed of
13 g (0.014 pphm) of sodium metabisulfite (0.2% in hydroheated heavy naphtha
(petroleum) [lsopar G] and
13 g (0.014 pphm) of tertiary-butyl hydroperoxide (0.2% in hydroheated heavy
naphtha
(petroleum) [lsopar G].
The redox pair is added stepwise such that a temperature increase of 2 C/min
takes
place. Once the isotherm has been reached, a free radical initiator (2,2'-
azobis(2-
methylbutyronitrile), CAS: 13472-08-7) is added in 2 steps (the 2nd step after
45 min)
and the emulsion is kept at 85 C for 75 minutes.
Vacuum distillation is used to remove water and low-boiling constituents of
the oil
phase (lsopar G).
Mineral oil of low viscosity (Kristol M14) is added to this product in order
to achieve a
solids content of 54%. To this product 8% (based on the total mass fraction of
this
product) of a fat-containing alcohol alkoxylate (C12/15 alcohol alkoxylate
[Synperonic
87KTm]) is added to produce a thickener (dispersion) with 50% polymer solids
fraction.
The ratio of activator to polymer is thus 16.0:100 [% by weight/% by weight].
Example 1
Thickeners/polymers starting from anionic monomers with associative monomer
and
constant polymerization temperature:
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
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Example 1.1
An aqueous phase of water-soluble components is prepared by mixing the
following
components:
246.13 g (140.65 pphm) of water,
0.86 g (0.49 pphm) of pentasodium diethylenetriaminepentaacetic acid,
174.13 g (99.5 pphm) of acrylic acid and
154.26 g (44.07 pphm) of NaOH (50% in water)
Use NaOH (50% in water) to adjust the water phase to pH 5.5.
An oil phase is prepared by mixing the following components:
20.05 g (8.59 pphm) of sorbitan monooleate (75 % in hydroheated heavy naphtha
(petroleum) [Isopar G])
90.6 g (12.27 pphm) of polymeric stabilizer: stearyl methacrylate-methacrylic
acid
copolymer (23.7% in hydroheated heavy naphtha [lsopar
119.03 g (68.02 pphm) of mineral oil of low viscosity (Kristol M14) and
229.72 g (131.27 pphm) of hydroheated heavy naphtha [Isopar G]
1.09 g (0.5 pphm) of associative monomer: 60% by weight of C16E025Mac:
comprised
in the commercial product Plex 6954-0 (with 20% by weight of methacrylic acid,
20%
by weight of water).
The two phases are mixed in a ratio of 55.6 parts of aqueous phase to 44.4
parts of oil
phase with high shear to produce a water-in-oil emulsion. The resulting water-
in-oil
emulsion is introduced into a reactor equipped with nitrogen spray line,
stirrer and
thermometer. The emulsion is purged with nitrogen while heating to 50 C, as a
result of
which the oxygen is removed.
The polymerization is achieved by adding a redox pair composed of
13.6 g (0.016 pphm) of sodium metabisulfite (0.2% in water) and
13.6 g (0.016 pphm) of tertiary-butyl hydroperoxide (0.2% in water).
The redox pair is added at 50 C over the course of 2 hours. After this, the
mixture is
heated to 85 C and then, in 2 steps, (the 2nd step after 45 min) a free
radical initiator
(2,2'-azobis(2-methylbutyronitrile), CAS: 13472-08-7) is added and the
emulsion is kept
at 85 C for 75 minutes.
Vacuum distillation is used to remove water and low-boiling constituents of
the oil
phase (lsopar G).
Mineral oil of low viscosity (Kristol M14) is added to this product in order
to achieve a
solids content of 54%. To this product 8% (based on the total mass fraction of
this
product) of a fat-containing alcohol alkoxylate (C12/15 alcohol alkoxylate
[Synperonic
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
23
87KTm]) is added to produce a thickener (dispersion) with 50% polymer solids
fraction.
The ratio of activator to polymer is thus 16.0: 100 [% by weight/% by weight].
The examples below as per table 1 are prepared as in example 1.1 taking into
consideration the stated changes in the monomer composition. The associative
monomer C16E025MAc is added to the oil phase. The commercial product Plex 6954
0 is used; this comprises 60% by weight of associative monomer and, as
solvent,
water and MA A in the ratio of ca. 1 : 1. The weight data in table 1 refers to
the amount
of associative monomer without solvent. The ratio of activator to polymer in
all
examples as per table 1 is in each case 16.0 : 100 [% by weight/% by weight];
unless
stated otherwise, the respective thickeners (dispersion) have 50% polymer
solids
fraction.
Table 1
Examples C16E025MAc Na Acrylamide MBA Remarks
(pphm) acrylate (pphm)
1.1 0.38 99.5
1.2 0.38 99.5 0.06
1.3 (comp.) 100
1.4 0.38 99.5
Example 2
Thickeners/polymers starting from anionic monomers with associative monomer
and
also increasing polymerization temperature:
The following examples as per table 2 are prepared as in comparative example
Cl
taking into consideration the stated changes in the monomer composition. The
associative monomer C16E025MAc is added to the oil phase. The commercial
product
Plex 6954 0 is used; this comprises 60% by weight of associative monomer and,
as
solvent, water and MM in the ratio of ca. 1 : 1. The weight data in table 2
refers to the
amount of associative monomer without solvent. The ratio of activator to
polymer in all
examples as per table 2 is in each case 16.0 :100 [c/o by weight/% by weight];
unless
stated otherwise, the respective thickeners (dispersion) have 50% polymer
solids
fraction.
Table 2
Examples C16E025MAc Na Acrylamide MBA Remarks
EK10-0898PC "as originally filed"
. PF0000070898/Wei CA 02853243 2014-04-23
24
(pphm) acrylate (pphm)
2.1 1.5 98 0.06
2.2 0.38 99.5 0.06
2.3 0.06 Starting
temperature at
1.5 98 14 C
2.4 1.5 98 --
2.6 0.38 99.5 -
2.5 (comp.) - 100 0.2
Cl - 100 0.06
2.7 (comp.) - - 100 -
2.8 0.38 - 99.5 -
General measurement methods:
Unless stated otherwise, the following general measurement methods are used in
the
examples below:
Determination of viscosity
Taking into consideration the procedures according to DIN 51550, DIN 53018,
DIN
53019, the Brookfield model DV II viscometer is used, unless stated otherwise
in the
tables below at a speed of 20 revolutions per minute with spindle No. 6, to
measure the
stated viscosities in mPa*s.
Determination of shear dilution
Measurement is carried out in an ASC (automatic sample changer) rotary
rheometer
from Antonpaar, with the CC27 cylinder geometry, the radius of the measurement
body
of 13.33 mm and the radius of the measurement cup of 14.46 mm. The measurement
temperature is 23 C. The samples are measured at steady-state shear starting
at a low
shear increasing to high shear (0.01 s'l ¨ 1000 s-1) and back again (1000 s-1
¨0.01 s-1).
Example 3
Use of the thickeners/polymers in water
The thickeners are slowly added to distilled water as per table 3 at room
temperature
and stirred until the formulation has homogenized. The aqueous formulations
obtained
as a result comprise, according to table 3, either 1.0% by weight of polymer
to 99.0%
EK10-0898PC "as originally filed"
PF0000070898ANe1 CA 02853243 2014-04-23
by weight of water or 0.5% by weight of polymer to 99.5% by weight of water.
The
results are summarized in table 3.
Table 3
5 Rheology of thickeners/polymers starting from anionic monomers in water,
measured 5
minutes after preparing the formulation
Example Formulation Thickener Thickener Brookfield
No. No. concentration spindle 6
(%) (20 rpm)/mPas
3.1 (comp.) Water V1 1.0 13250
3.7 (comp.) Water 2.5 (comp.) 1.0 9600
3.2 Water 2.1 1.0 22000
3.3 Water 2.2 1.0 14050
3.4 Water 2.3 1.0 23000
3.5 Water 1.1 1.0 15600
3.6 Water 1.2 1.0 18300
3.9 (comp.) Water 2.7 (comp.) 2.0 100
3.10 Water 2.8 2.0 250
3.11 (comp.) Water 1.3 (comp.) 2.0 200
3.12 Water 1.4 2.0 450
If an increasing amount of associative monomer is incorporated into the
polymer, then
10 the thickening performance increases more and more considerably compared
with Cl
without associative monomer. The lower the starting temperature during the
polymerization according to example 2, the greater the thickening performance.
The
procedure at a constant polymerization temperature of 50 C produces, for an
otherwise
identical monomer composition, an increased thickening performance. The last
four
15 examples of table 3 relate to
acrylamide-containing polymers.
Example 4.1
Use of the thickeners/polymers in standard formulations of care compositions
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
26
The care composition formulation (P1) comprises the ingredients as in table
4.1. P1 is
prepared by heating phases A and B in each case to 80 C. The two phases are
then
combined and homogenized. Then, with stirring, the mixture is cooled to
approximately
40 C, whereupon phase C is added and the mixture is homogenized.
Table 4.1.1: Ingredients of P1
Phase Trade name INCI name
1,2 Propylene glycol
Care Propylene glycol 5.00
A Water dem. Aqua ad 100
Ceteareth-6,
Cremophor A 6 Stearyl Alcohol 2.00
Cremophor A 25 Ceteareth-25 2.00
Cetearyl
Luvitol EHO Ethylhexanoate 5.00
Paraffin oil thick-liq. Mineral oil 5.00
Lanette 16 Cetyl Alcohol 2.50
Euxyl K 300 Preservative 0.50
Addition of the thickener to the care composition formulation P1:
The thickeners according to the invention listed in table 4.1.2 or thickeners
according to
the comparative examples are slowly added, at room temperature, to the care
composition formulation P1 and stirred until the formulation is homogenized.
The care
composition formulations obtained in this way comprise the stated
concentration of
thickener in % by weight relative to 100% by weight of the resulting care
composition
formulations.
The Brookfield viscosity is measured one day after the preparation. The
results are
summarized in table 4.1.2.
Table 4.1.2: Thickener performance and shear dilution in care compositions
Rheology of fabric softeners comprising thickeners/polymers starting from
anionic
monomers:
Example Formulation Thickener Thickener Brookfield
No. No. concentration spindel 6
(%) (20 rpm)/mPas
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
27
4.1.1 P1 V1 1.6
(comp.) 13600
4.1.2 P1 V1 2.4
(comp.) 19250
4.1.3 P1 V1 3.2
(comp.) 24300
4.1.4 P1 2.1 1.6 17400
4.1.5 P1 2.1 2.4 33700
4.1.6 P1 2.1 3.2 59400
If an increasing amount of associative monomer is incorporated into the
polymer, then
the thickening performance increases more and more considerably compared with
V1
without associative monomer.
Example 4.2
Use of the thickeners/polymers in standard formulations of fabric softener W3
W3: Preparation of a methyltris(hydroxyethyl)ammonium-di-tallow-fatty acid
ester
methosulfate, partially hydrogenated fabric softener (5.5% active fraction):
The fabric softener has a pH of 2.7 and comprises 5.5% by weight of
methyltris(hydroxyethyl)ammonium-di-tallow-fatty acid ester methosulfate
(partially
hydrogenated) and 94.5% by weight of deionized water.
Addition of the thickener to the fabric softener formulation W3:
The thickeners (see table 4.2) according to examples 1 and 2 and the
comparative
examples are slowly added, at room temperature, to the respective fabric
softener
formulation and stirred until the formulation has homogenized.
The Brookfield viscosity is measured one day after the preparation. The
results are
summarized in table 4.2.
Table 4.2. Thickener performance in fabric softener W3
Rheology of fabric softeners comprising thickeners/polymers starting from
neutral
monomers:
Example Formulation Thickener Thickener Brookfield
No. No. concentration spindel 6
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
28
(%) (20 rpm)/mPas
4.2.1 W3 1.3 1.0 400
(comp.) (comp.)
4.2.2 W3 1.4 1.0 1900
4.2.3 W3 2.7 1.0 600
(comp.) (comp.)
4.2.4 W3 2.8 1.0 1100
If associative monomer is incorporated into the polymer, then the thickening
performance increases more and more considerably compared with the comparative
examples without associative monomer.
Example 5
In table 5 below, the storage stability of the thickeners according to the
invention is
investigated. It is found that the thickeners according to the invention are
considerably
more stable.
Table 5:
Storage stability of thickeners/polymers starting from anionic monomers:
Example Thickener Immediate Precipitate after 4
No. precipitate days at 40 C
5.1 (comp.) V1 None Considerable, not
redispersible
5.2 2.1 None None
Significant improvement, i.e. reduction in sediment, by thickeners according
to the
invention.
Example 6
Storage stability of care composition formulation (P1) according to example 4
comprising thickeners/polymers starting from anionic monomers:
Significant improvement, i.e. reduction in sediment, by thickeners according
to the
invention. After almost three months, significant sediment evident for
formulation with
EK10-0898PC "as originally filed"
PF0000070898/Wei CA 02853243 2014-04-23
29
thickener V1 and only minimal sediment evident for formulation with thickener
2.1
(storage at RD.
Example 7
Thickeners/polymers starting from anionic monomers with associative monomer
and
influence of the amount of activator on the thickening rate in aqueous
formulations:
Examples 7.1 to 7.5 listed in table 6 are prepared in accordance with example
2.1, the
amount of activator added after the distillation being varied to correspond to
the
activator concentration (A %) in the thickener given in table 11 (all data in
% by weight
based on the amount of anionic polymer in the thickener). All of the
thickeners
(dispersion) prepared in this way have a polymer solids fraction of 50%. The
thickeners
are then added to the water with stirring. The aqueous formulations obtained
in this
way comprise 1% by weight of the thickener to 99% by weight of water, i.e.
0.5% by
weight of anionic polymer to 99.5% by weight of water. comp. means comparative
example.
EK10-0898PC "as originally filed"
' PF0000070898NVei
CA 02853243 2014-04-23
Table 6
Thickening rate (Brookfield visc. mPas*s)
of the aqueous formulations
Examples A % 1 min 2 min 3 min 5 min 10 min 20 40 1 h
min min
7.1 2.0
128 240 512
1640 9300 20000 27500 30000
(comp.)
_
7.2 6.0
4590 6750 10300 16700 23300 26200 30100 35600
(comp.)
7.3 16.0
17000 18400 19900 22400 26900 35200 40400 40400
7.4 20.0
32000 32800 34000 36400 38400 41200 42000 42000
7.5 34.0
41600 42000 42400 42400 42400 42400 42400 42400
With associative monomer, an amount of activator above 10% is required in
order to
5 achieve a rapid thickening performance (above 40% based on the end
thickening
within 1 minute).+
EK10-0898PC "as originally filed"
