Note: Descriptions are shown in the official language in which they were submitted.
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Self-emulsifiable polyolefine compositions
The present invention is directed to self-emulsifiable polyolefine
compositions, in particular to
self-emulsifiable polyisobutene compositions and the use of said emulsions.
Polyolefines and in particular polyisobutene(s) are useful ingredients in a
lot of technical appli-
cations and contribute to improve the feel properties when applied on surfaces
such as hair or
textile. The formulation of polyisobutene mostly consists in firstly emulsify
the polyisobutene in
an oil-in-water emulsion and then incorporate the emulsion in an aqueous
formulation such as a
hair care or laundry formulation, in order to obtain benefits such as
emollience, hydrophobi-
zation, lubrication or adhesion. Polyisobutene emulsions are exemplified in
PCT/EP2011/057586, which has not yet been published and which discloses an
emulsion com-
prising (a) polyolefines such as polyisobutene, in an amount of from 2 to 75
weight%, (b) poly-
mers Px which are copolymers of non ionic, anionic or pseudocationic monomers
in an amount
of from 0.05 to 40 weight % and (c) water in an amount of from 10 to 97.95
weight %.
WO 2007/042454 Al describes the use of terpolymers of (a) maleic anhydride,
(b) isobutylene
and (c) polyisobutylene for producing aqueous emulsions or dispersions of
hydrophobic sub-
stances such as silicones.
WO 2007/014915 writes on aqueous dispersions comprising (A) a polymer such as
polyisobu-
tene and (B) an emulsifier obtained by the polymerization of isobutylene,
maleic anhydride and
polyethyleneglycol. This dispersion is used for the treatment of leather or as
additive in con-
struction chemicals.
W02004/154216 describes a copolymer containing polyisobutene, maleic anhydride
and poly-
alkylene glycols. These copolymers are used as emulsifiers for the preparation
of oil-in-water
emulsions and find applications e.g. in washing and cleaning formulations, in
the cosmetics or
pharmaceutical sector.
Nevertheless, the preparation of an emulsion as a formulation ingredient has a
number of draw-
backs. Firstly, emulsions have to be prepared at high shear rate stirring,
which is a complex
process in the production scale and involve a high energy input. Secondly,
unlike microemul-
sions, emulsions are not thermodynamically stable, and can segregate by
creaming / sedimen-
tation, aggregation and coalescence (phase separation). Creaming is observed
when emulsion
droplets have a density lower than that of the continuous phase. Such droplets
have the ten-
dency to gather on top of the liquid level to form a layer enriched with
emulsion droplets. In con-
trast, droplets having a density higher than that of the continuous phase have
the tendency to
sink down to the bottom of the liquid, forming a layer enriched with emulsion
droplets. This ef-
fect is called sedimentation. Whereas creaming and sedimentation are
reversible processes,
coalescence is an irreversible effect where individual emulsion droplets merge
until, in the end,
two continuous phases are formed. Creaming, sedimentation and coalescence have
to be
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avoided, at least during the time between production of the emulsion and the
introduction of the
emulsion in the intended formulation. To guarantee the stability of the
emulsion until its applica-
tion, measures like temperature control ¨ avoiding too high as well as too low
temperatures ¨ or
the shipment in stirred containers are needed, which adds to complexity in the
supply chain as
well as to shipping costs.
Besides, the incorporation of an emulsion, which already contains a large
amount of water, in
an aqueous formulation such as a hair care or laundry formulation reduces the
flexibility of the
formulator as to the choice of ingredients and the total concentration of the
final formulation.
The problem to be solved is to identify a polyolefin composition that has a
water content as low
as possible or, even better, is completely free of water and that can be
emulsified in aqueous
formulations and/or water without the need for a high shear emulsification or
any other standard
emulsification process. Ideally, the composition should be able to self-
emulsify only by stirring it
into water or an aqueous formulation.
This goal is surprisingly reached by the composition according to claims 1 to
12. The use of
such a composition according to claim 13 forms an additional aspect of the
present invention.
For the purpose of this invention the prefix (meth) written before a compound
means the re-
spective unsubstituted compound and/or the compound substituted by the methyl
group. For
instance, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid,
(meth)acrylate means
acrylate and/or methacrylate, (meth)acrylamide means acrylamide and/or
methacrylamide.
Thus the present invention is directed to a self-emulsifiable composition
containing
a) polyolefine(s) in an amount of from 5 to 90 weight %,
b) polymeric emulsifier(s) Px in an amount of from 5 to 90 weight %,
c) oil(s) Ox in an amount of from 0 to 40 weight %,
d) surfactant(s) Sx in an amount of from 0 to 40 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range of
from 4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25.
The self-emulsifiable composition can consist of components a) and b), in
which case the
amounts add up to 100 weight %, - such a composition forms a preferred
embodiment of the
present invention. The composition can also contain components a) and b) as
well as additional
components. Compositions, which in addition to components a) and b) also
contain components
c) and/or d) and/or e) form one preferred embodiment of the invention. The
inventive composi-
tion may also contain other components.
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With regard to the amounts, in which the respective compounds are present in
the self-
emulsifiable composition, there exist preferred ranges. Thus a composition
according to the
invention, wherein the components of the self-emulsifiable composition
independently of each
other are present in amounts of:
a) polyolefine(s) in an amount of from 20 to 70 weight %,
b) polymer emulsifier(s) Px in an amount of from 10 to 50 weight %,
c) oil(s) Ox in an amount of from 0 to 40 weight %,
d) surfactant(s) Sx in an amount of from 0.1 to 30 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range of
from 4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25.
Even more preferred is a composition, wherein the components of the self-
emulsifiable compo-
sition independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 30 to 60 weight %,
b) polymer emulsifier(s) Px in an amount of from 20 to 45 weight %,
c) oil(s) Ox in an amount of from 0,1 to 30 weight %,
d) surfactant(s) Sx in an amount of from 0,5 to 25 weight %,
e) additive(s) Ax in an amount of from 0,1 to 10 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from
4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25.
And most preferred is a composition, wherein the components of the self-
emulsifiable composi-
tion independently of each other are present in amounts of:
a) polyolefine(s) in an amount of from 40 to 50 weight %,
b) polymeric emulsifier(s) Px in an amount of from 25 to 40 weight %,
c) oil(s) Ox in an amount of from 5 to 15 weight %,
d) surfactant(s) Sx in an amount of from 5 to 15 weight %,
e) additive(s) Ax in an amount of from 2 to 8 weight %,
f) water in an amount of from 0 to 8 weight %,
based on the total weight of the composition
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from
4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25.
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To maximize the content of polyolefine(s), it is advantageous to reduce the
amount of other
components in the emulsion. Therefore, further preferred emulsions are those,
which comprise:
a) polyolefine(s) in an amount of from 35 to 55 weight%,
b) polymeric emulsifier(s) Px in an amount of from 30 to 45 weight %,
c) oil(s) Ox in an amount of 0,1 to 20 weight %,
d) surfactant(s) Sx in an amount of from 5 to 12 weight %,
e) additive(s) Ax in an amount of from 0 to 10 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from
4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25
a) polyolefine(s) in an amount of from 50 to 65 weight %,
b) polymer(s) Px in an amount of from 25 to 65 weight %,
c) oil(s) Ox in an amount of 0 weight %,
d) surfactant(s) Sx in an amount of from 5 to 12 weight %,
e) additive(s) Ax in an amount of 0 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from
4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25
a) polyolefine(s) in an amount of from 5 to 20 weight %,
b) polymer(s) Px in an amount of from 70 to 90 weight %,
c) oil(s) Ox in an amount of 0 to 15 weight %,
d) surfactant(s) Sx in an amount of from 0 weight %,
e) additive(s) Ax in an amount of 0,5 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
wherein the weight ratio of polyolefine(s) to Px and Sx is in the range from
4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25
or
a) polyolefine(s) in an amount of from 40 to 60 weight %,
b) polymer(s) Px in an amount of from 40 to 60 weight %,
c) oil(s) Ox in an amount of from 0 to 5 weight %,
d) surfactant(s) Sx in an amount of 0 weight %,
e) additive(s) Ax in an amount of from 0 to 8 weight %,
based on the total weight of the composition,
wherein water is not the continuous phase of the composition,
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wherein the weight ratio of polyolefine(s) to P. and S. is in the range from
4:1 to 1:3 and the
weight ratio of Px to Sx is higher than 1.25.
In order to test whether or not water is the continuous phase of the
composition a conductivity
5 measurement is used showing that the compositions have a low conductivity
in the range of the
pure polyolefine(s), oil(s) or surfactant(s), and not a high conductivity as
water.
The composition according to the invention is self-emulsifiable, i.e. when
mixed in an aqueous
formulation, simple stirring is required for the composition to form an
emulsion.
In one embodiment of the invention, the self-emulsifiable composition is a
water-free composi-
tion. Water-free compositions are prepared without added water. Nevertheless,
there might be
minor amounts of residual water originating from the water content of the raw
materials. Self-
emulsifiable water-free compositions contain less than 2 weight% of water,
preferably less than
1 weight% of water, even more preferably, less than 0.5 weight% of water.
In another embodiment of the invention, the self-emulsifiable composition is a
water-reduced
composition. Water-reduced compositions are prepared by adding a reduced
amount of water,
in order to reduce the viscosity of the self-emulsifiable composition, so that
the total amount of
water in the composition lies in the range of from 2 to 8 weight%, preferably
from 2 to 6
weight%, even more preferably from 2 to 5 weight%.
Not only the amount but also the nature of the components of the inventive
composition can be
chosen advantageously:
In general polyolefine(s) as used in the present invention is/are a chemical
compound(s) con-
sisting of carbon and hydrogen atoms. The polyolefine(s) can be linear, e.g.
polyethylene, or
can have side chains, e.g. polypropylene having methyl-side chains, which side
chains may be
that long that comb-like structures are found, or can be co- or ter-polymers,
e.g. eth-
ene/propene-copolymer or ethane/propene/hexane-terpolymer. It is particularly
preferred, when
the polyolefine(s) is/are substantially homopolymers, i.e. the degree of co-
or ter-monomer is
below 10 mass%, preferably below 5 mass% based on the mass of the polymer. It
is particularly
preferred, if the polymer(s) is/are homopolymers, i.e. they consist of only
one kind of monomer.
In particular a composition, wherein the polyolefin(s) a) is/are selected from
the group consisting
of: polyethylene, polypropylene, polybutylene and polyisobutylene is
preferred. The composition
can comprise one or more polyolefine. An emulsion, which only comprises one
polyolefine a) is
preferred. A composition, which only comprises polyisobutylene as polyolefine
a) is particularly
preferred. The polyolefines a) can be prepared by the usual procedures
(Ullmann's Encyclope-
dia of Industrial Chemistry, Polyolefins, Whiteley, Heggs, Koch, Mawer, lmmel,
Wiley-VCH Ver-
lag GmbH & Co. KGaA, Weinheim 2005). The production of polyisobutylene is
described e.g. in
WO 02/06359 and WO 96/40808 in even more detail. The polyolefine(s) a)
preferably has/have
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of molar mass (Mn) of at least 250 g/mol, preferably at least 350 g/mol and
more preferred at
least 500 g/mol. The polyolefin(s) a) have a maximum molar mass Mn of 10.000
g/mol, prefe-
rably 5000 g/mol and more preferred of 2500 g/mol. The most preferred range of
the molar
mass Mn of polyolefins a) is from 550 to 2000 g/mol.
Also the self-emulsifiable composition according to the invention comprises
polymeric emulsifi-
er(s) Px, wherein Px is/are selected from the group consisting of
Pi) polyisobutene derivatives, wherein Pi is polyisobutenamine, polyisobutene
succinic anhy-
dride, a copolymer of polyisobuten succinic anhydride with polyalkylene
glycol, a copolymer of
polyisobuten succinic anhydride with an oligoamine or with an oligoamine
alkoxylate.
Polyisobutylene succinic acid is prepared by en-reaction of succinic anhydride
and polyisobutyl-
ene, as described in DE-A 19519042, DE-A 4319671, DE-A 4319672 or H. Mach and
P. Rath in
"Lubrication Science 11(1999), S. 175-185. The preparation of polyisobutene
and polyisobutene
amine is described in EP244616 and references cited therein. Copolymers of
polyisobutene
succinic anhydride with polyalkylene glycol are described in W02007/014915.
Copolymers of
succinic anhydride with oligoamine or with an oligoamine alkoxylate are
described in
PCT/EP2011/057586. For all polyisobutylene derivatives, the polyisobutylene
part has a molar
mass (Ma) of at least 250 g/mol, preferably at least 350 g/mol and more
preferred at least 500
g/mol, and a maximum molar mass Mr, of 10.000 g/mol, preferably 5000 g/mol and
more pre-
ferred of 2500 g/mol. The most preferred range of the molar mass Mr, of the
polyisobutylene part
is from 550 to 2000 g/mol.
Polymer P1 is preferably selected from the group consisting of polyisobutene
derivatives,
wherein Pi is polyisobutenamine, polyisobutene succinic anhydride, a copolymer
of polyisobu-
ten succinic anhydride and polyethylene glycol.
P2) polymeric cationic emulsifiers, wherein P2 is the result of the
polymerization of
A2) one or more cationic ethylenically unsaturated monomers (monomer A2)
B2) one or more linear or branched alkyl(meth)acrylates (monomer B2),
02) from 0 to 30 weight % of one or more 03-08 monoethylenically unsaturated
carboxylic acids
(monomer 02),
Monomer A2 is a cationic monoethylenically unsaturated monomer which is at
least partially
soluble in water of the reaction solvent, or in the other monomers if no water
or solvent is used.
Suitable examples of monomer A are (3-acrylamidopropyI)-trimethylammonium
chloride (AP-
TAO), (3-methacrylamidopropyI)-trimethylammonium chloride (MAPTAC),
dimethylaminopropy-
lacrylat methochlorid, dimethylaminopropylmethacrylat methochlorid, diallyl
dimethyl ammonium
chloride (DADMAC). Monomer A is preferably DADMAC.
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Monomer B2 is a linear or branched alkyl (meth)acrylate, preferably a 010-030
al-
kyl(meth)acrylate, even more preferably a 012-020 alkyl(meth)acrylate.
Suitable monomers B
include linear and branched alkyl esters of (meth)acrylic acid, such as octyl
acrylate, dodecyl
acrylate, lauryl acrylate, cetyl acrylate, octadecyl acrylate, isodecyl
acrylate, 2-ethylhexyl acry-
late. Monomer B is preferably lauryl acrylate (LA).
Monomer 02 is a 03-08 monoethylenically unsaturated carboxylic acid. Suitable
examples of
monomer C include acrylic acid, methacrylic acid, crotonic acid, maleic acid,
maleic anyhyd ride,
fumaric acid, itaconic acid and alkyli and metal salts thereof. Monomer C is
preferably acrylic
acid (AA).
With regard to the amounts in which the respective monomers are present in the
polymer P2,
there are preferred ranges. Thus the polymer Px is preferably the product of
the polymerization
of
A2) from 60 to 95 weight % of monomer A2,
B2) from 5 to 45 weight % of monomer B2,
02) from 0 to 30 weight % of monomer 02.
Even more preferred is a polymer P2 which is the product of the polymerization
of:
A2) from 70 to 90 weight % of monomer A2,
B2) from 10 to 35 weight % of monomer B2,
02) from 5 to 20 weight % of monomer 02.
Another preferred embodiment is a polymer P2 which is the product of the
polymerization of:
A2) from 70 to 90 weight % of monomer A2,
B2) from 10 to 35 weight % of monomer B2,
02) 0 weight % of monomer 02.
Most preferably, polymer P2) is a polymeric cationic emulsifier, wherein P2 is
the result of the
polymerization of
A2) diallyl dimethyl ammonium chloride,
B2) one or more linear or branched alkyl(meth)acrylates,
02) from 0 to 30 weight % of acrylic acid.
P3) being copolymers of polyalkylene(s) of formula 3
R*
R¨K-) l'n r
R R
3
wherein:
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R* = H, CH3,
R = H, methyl,
R' = H, methyl,
n = 1 to 200,
with monoethylenically unsaturated monomers.
With regard to copolymers of polyalkylene(s) of formula 3, there exist
preferred embodiments.
Thus, the polyalkylene(s) of formula 3 is preferrably composed of:
R* = R = R' = CH3,
n = 1 to 200
In another embodiment of the invention, polyalkylene(s) of formula 3 is
preferably composed of:
R* = R = R' = H
n = 1 to 200
The composition can comprise one or more polymers of one or more of the groups
P1), P2) and
P3). If two or more polymers of one group and/or of different groups are
present, they can be
present in equal amounts or in different amounts.
A self-emulsifiable composition, wherein the oil(s) Ox is/are selected from
the group consisting
of:
c1) mineral oils, having a boiling point at atmospheric pressure of 150 C or
higher
c2) esters of Ow- to 026-carboxylic acid with Cs ¨ 024-alcohols and
c3) silicone oils forms a preferred embodiment of the present invention.
Preferred oil(s) Ox are mineral oils available under the names mineral oil
light, mineral oil heavy,
paraffin liquid or Nujol, that are liquid at room temperature. One example is
mineral oil available
from Sigma-Aldrich Chemie GmbH, Munich, under the order number 69808.
Particularly preferred oils are silicone oils. Preferred silicone contents are
less that 5 weight %,
preferably less than 3 weight%, even more preferably less than 1 weight%.
Suitable silicone oils
are, for example, linear polydimethylsiloxanes,
poly(methylphenylsiloxanes), cyclic siloxanes, polyethersiloxanes, dimethicone
copolyols
(CTFA) and amino-functional silicone compounds such as amodimethicones
(CTFA)and mix-
tures thereof. The number-average molecular weight of the polylsiloxanes is
preferably in a ran-
ge from about 1000 to 150 000 g/mol.
A self-emulsifiable composition, wherein the surfactant(s) Sx is/are selected
from the group con-
sisting of:
d1) nonionic surfactants,
d2) anionic surfactants and
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d3) cationic surfactants is preferred.
Surfactants normally consist of a hydrophobic and a hydrophilic part. Thereby
the hydrophobic
part normally has a chain length of 4 to 20 C-atoms, preferably 6 to 19 C-
atoms and particularly
preferred 8 to 18 C-atoms. The functional unit of the hydrophobic group is
generally an OH-
group, whereby the alcohol can be linear or branched. The hydrophilic part
generally consists
substantially of alkoxylated units (e.g. ethylene oxide (EO), propylene oxide
(PO) and/or butyl-
ene oxide (BO), whereby generally 2 to 30, preferably 5 to 20 of these
alkoxylated units are an-
nealed, and/or charged units such as sulfate, sulfonate, phosphate, carbonic
acids, ammonium
und ammonium oxide.
Examples of anionic surfactants are: carboxylates, sulfonates, sulfo fatty
acid methylesters, sul-
fates, phosphates. Examples for cationic surfactants are: guartery ammonium
compounds. Ex-
amples for betaine-surfactants are: alkyl betaines. Examples for non-ionic
compounds are: al-
cohol alkoxylates.
A õcarboxylate" is a compound, which comprises at least one carboxylate-group
in the molecule.
Examples of carboxylates, which can be used according to the present
invention, are
D soaps ¨ e.g. stearates, oleates, cocoates of alkali metals or of
ammonium,
D ethercarboxylates ¨ e.g. Akypo@ RO 20, Akypo@ RO 50, Akypo@ RO 90.
A õsulfonate" is a compound, which comprises at least one sulfonate-group in
the molecule.
Examples of sulfonates, which can be used according to the invention, are
D alkyl benzene sulfonates ¨ e.g. Lutensit@ A-LBS, Lutensit@ A-LBN,
Lutensit@ A-LBA,
Marlon AS3, Maranil@ DBS,
D alkyl sulfonates ¨ e.g. Alscoap OS-14P, BIO-TERGE@ AS-40, BIO-TERGE@ AS-
40
CG, BIO-TERGE@ AS-90 Beads, Calimulse@ AOS-20, Calimulse@ AOS-40, Ca!soft@
AOS-40, Colonial AOS-40, Elfan@ OS 46, Ifrapon AOS 38, Ifrapon AOS 38 P,
Jeenate@ AOS-40, Nikkol@ 05-14, Norfox@ ALPHA XL, POLYSTEP@ A-18, Rhodacal@
A-246L, Rhodacal@ LSS-40/A,
D sulfonated oils such as Turkish red oil,
D olefine sulfonates,
D aromatic sulfonates ¨ e.g. Nekal@ BX, Dowfax@ 2A1.
A õsulfo fatty acid methylester" is a compound, having the following general
formula (I):
SO3Na
R13 OMe (I)
0
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wherein R13 has 10 to 20 C-atoms; preferably 12 to 18 and particularly
preferred 14 to 16 C-
atoms.
A õsulfate" is a compound, which comprises at least one 504-group in the
molecule. Examples
5 of sulfates, which can be used according to the present invention, are
D fatty acid alcohol sulfates such as coco fatty alcohol sulfate (CAS 97375-
27-4) ¨ e.g.
EMAL 10G, Dispersogen SI, Elfan 280, Mackol 100N,
D other alcohol sulfates ¨ e.g. Emal 71, Lanette E,
D coco fatty alcohol ethersulfates ¨ e.g. Emal 200, Latemul E150,
Sulfochem ES-7,
10 Texapon ASV-70 Spec., Agnique SLES-229-F, Octosol 828, POLYSTEP B-23,
Uni-
poi 125-E, 130-E, Unipol ES-40,
D other alcohol ethersulfates ¨ e.g. Avanel 5-150, Avanel S 150 CG,
Avanel S 150
CG N, Witcolate D51-51, Witcolate D51-53.
A õphosphate" is a compound, which comprises at least one PO4-group. Examples
of phos-
phates, which can be used according to the present invention, are
D alkyl ether phosphates ¨ e.g. Maphos 37P, Maphos 54P, Maphos 37T,
Maphos
210T and Maphos 210P,
D phosphates such as Lutensit A-EP,
D alkyl phosphates.
When producing the chemical composition of the present invention the anionic
surfactants are
preferably added as salts. Acceptable salts are e.g. alkali metal salts, such
as sodium-, potassi-
um- and lithium salts, and ammonium salts, such as hydroxyl ethylammonium-,
di(hydroxy-
ethyl)ammonium- and tri(hydroxyethyl)ammonium salts.
One group of the cationic surfactants are the quarternary ammonium compounds.
A õquarternary ammonium compound" is a compound, which comprises at least one
R4N+-group
per molecule. Examples of counter ions, which are useful in the quarternary
ammonium com-
pounds, are
D halogens, methosulfates, sulfates and carbonates of coco fat-, sebaceous
fat- or ce-
tyl/oleyltrimethylammonium.
Particularly suitable cationic surfactants are:
- N,N-dimethyl-N-(hydroxy-C7-C25-alkyl)ammonium salts;
- mono- and di-(C7-C25-alkyl)dimethylammonium compounds, which were
quarternised with
alkylating agents
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- esterquats, especially mono-, di- and trialkanolamines, quarternary
esterified by 08-022-
carbonic acids;
- imidazolinquats, especially 1-alkylimidazoliniumsalts of formula II or
III
R11
I
9 +
R9----N R----___ N)
N+ _______________________________ / N __ /
R10/ \R11 R10/
II III
wherein the variables have the following meaning:
R9 Ci-C25-alkyl or 02-025-alkenyl;
R1 01-04-alkyl or hydroxy-C1-04-alkyl;
R11 01-04-alkyl, hydroxy-C1-04-alkyl or a rest R1-(C0)-X-(0H2)m- (X:-0- or -NH-
; m: 2 or
3),
whereby at least one rest R9 is 07-022-alkyl.
A õbetain-surfactant" is a compound, which comprises under conditions of use -
i.e. in the case
of textile washing under normal pressure and at temperatures of from room
temperature to 95
C ¨ at least one positive charge and at least one negative charge. An
õalkylbetain" is a betain-
surfactant, which comprises at least one alkyl-unit per molecule. Examples of
betain-
surfactants, which can be used according to the invention, are
Cocamidopropylbetain ¨ e.g. MAFOO CAB, AmonylO 380 BA, AMPHOSOLO CA, AMPHO-
SOLO CG, AMPHOSOLO CR, AMPHOSOLO HOG; AMPHOSOLO HOG-SO, ChembetaineO C,
ChembetaineO CGF, ChembetaineO CL, DehytonO PK, DehytonO PK 45, Emery 6744,
Em-
pigenO BS/F, EmpigenO BS/FA, EmpigenO BS/P, GenagenO CAB, LonzaineO C,
LonzaineO
CO, MirataineO BET-C-30, MirataineO CB, MonatericO CAB, NaxaineO C, NaxaineO
CO,
Norfox CAPB, Norfox Coco Betaine, RalufonO 414, TEGOO-Betain CKD, TEGOO
Betain E
KE 1, TEGOO-Betain F, TEGOO-Betain F 50 and aminoxides such as alkyl dimethyl
amineoxi-
de, i.e. compounds of general formula (IV)
El
1 I
R ¨N-3-0 (IV)
I 1
R
whereby R1 are different or identical and independently from each other
selected from an ali-
phatic, cyclic or tertiary alkyl- or amido alkyl-moiety, e.g. Mazox LDA,
GenaminoxO, Aromox
14 DW 970.
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Non-ionic surfactants are interfacially active substances having a head group,
which is an un-
charged, polar, hydrophilic group, not carrying an ionic charge at neutral pH,
and which head
group makes the non-ionic surfactant water soluble. Such a surfactant adsorbs
at interfaces and
aggregates to micelles above the critical micelle concentration (cmc).
According to the type of
the hydrophilic head group it can be distinguished between (oligo)oxyalkylene-
groups, especial-
ly (oligo)oxyethylene-groups, (polyethyleneglycol-groups), including fatty
alcohol polyglycol
ether (fatty alcohol alkoxylates), alkylphenol polyglycolether and fatty acid
ethoxylates, alkox-
ylated triglycerides and mixed ethers (polyethylene glycolether alkoxylated on
both sides); and
carbohydrate-groups, including e.g. alkyl polyglucosides and fatty acid-N-
methylglucamides.
Alcohol alkoxylates, are based on a hydrophobic part having a chain length of
4 to 20 C-atoms,
preferably 6 to 19 C-atoms and particularly preferred 8 to 18 C-atoms, whereby
the alcohol can
be linear or branched, and a hydrophilic part, which can be alkoxylated units,
e.g. ethylene ox-
ide (EO), propylene oxide (PO) and/or butylene oxide (BuO), having 2 to 30
repeating units.
Examples are besides others Lutensol XP, Lutensol XL, Lutensol ON,
Lutensol AT,
Lutensol A, Lutensol AO, Lutensol TO.
Alcoholphenolalkoxylates are compounds according to general formula (V),
R3
R5
-
R2 lik 0 --..........................---\ -------
- R4
(V)
0 x
R3
which can be produced by addition of alkylene oxide, preferably ethylene oxide
onto alkyl phe-
nols. R4 is selected from C-1C10-alkyl and hydrogen, preferably R4 = H. It is
also preferred, if R5
= H; in the same way it is preferred if R5 = CH3, or, if R5 = CH2CH3. A
compound is especially
preferred, in which octyl- [(R3 are identical and each hydrogen, R2 = 1,1,3,3-
tetramethylbutyl
(diisobutylene)], nonyl- [(R3 are identical and each hydrogen, R2 = 1,3,5-
trimethylhexyl (tripro-
pylene)], dodecyl-, dinonyl- or tributylphenolpolyglycolether (e.g. EO, PO,
BuO), R-C6H4-0-
(E0/PO/BuO)n with R4 = C8 to C12 alkyl and x = 5 to 10, are present. Non-
limiting examples of
such compounds are: Norfox OP-102, Surfonic OP-120, T-Det 0-12.
Fatty acid ethoxylates are fatty acid esters, which have been treated with
different amounts of
ethylene oxide (EO).
Triglycerides are esters of the glycerols (glycerides), in which all three
hydroxy-groups have
been esterified using fatty acids. These can be modified by alkylene oxides.
Fatty acid alkanol amides are compounds of general formula (VI)
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13
,_, _
0 ,-7L/u
_m H
N
R12 .__\
(VI)
------H
0 _t
which comprise at least one amide-group having one alkyl moiety R12 and one or
two alkoxyl-
moiety(ies), whereby R12 comprises 11 to 17 C-atoms and 1 m + n 5.
Alkylpolyglycosides are mixtures of alkylmonoglucosides (alkyl- a-D- and - 8-D-
glucopyranoside
plus small amounts of -glucofuranoside), alkyldiglucosides (-isomaltosides, -
maltosides and
others) and alkyloligoglucosides (-maltotriosides, -tetraosides and others).
Alkylpolyglycosides
are among other routes accessible by acid catalysed reaction (Fischer-
reaction) from glucose
(or starch) or from n-butylglucosides with fatty alcohols. Alkylpolyglycosides
fit general formula
(VII)
OH OH
0 0
H+0 0+CH¨*
OH OH H2 S
(VII),
with
r = 0 to 3 and
s = 4 to 20.
One example is Lutensol GD70.
In the group of non-ionic N-alkylated, preferably N-methylated, fatty acid
amides of general for-
mula (VIII)
0 OH OH
7
R
N OH
I 6
R OH OH (VIII),
R6 is a n-C12-alkyl-moiety, R7 an alkyl-moiety having 1 to 8 C-atoms. R7
preferably is methyl.
A self-emulsifiable composition, wherein the additive(s) Ax is/are selected
from the group con-
sisting of:
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disinfectant, dye, acid, base, complexing agent, biocide, hydrotope,
thickener, builder, cobuild-
er, enzyme, bleaching agent, bleach activator, bleaching catalyst, corrosion
inhibitor, dye pro-
tection additive, dye transfer inhibitor, anti-greying agent, soil-release-
polymer, fiber protection
agent, silicon, bactericide, preserving agent, organic solvent, solubility
adjustor, solubility en-
hancer, perfume, gel formers, dyes, pigments, photoprotective agents,
consistency regulators,
antioxidants, bleaches, care agents, tints, tanning agents, humectants,
refatting agents, colla-
gen, protein hydrolysates, lipids, emollients, softeners, antifoams,
antistats, resins, solvents,
solubility promoters, neutralizing agents, stabilizers, sterilizing agents,
propellants, drying
agents, opacifiers is preferred.
Disinfectants can be: oxidation agents, halogens such as chlorine and iodine
and substances,
which release the same, alcohols such as ethanol, 1-propanol and 2-propanol,
aldehydes, phe-
noles, ethylene oxide, chlorohexidine and mecetroniummetilsulfate.
The advantage of using disinfectants is that pathogenic germs can hardly grow.
Pathogenic
germs can be: bacteria, spores, fungi and viruses.
Dyes can be besides others: Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid
Yellow 73, Pig-
ment Yellow 101, Acid Green 1, Acid Green 25.
Acids are compounds that can advantageously be used to solve or to avoid
scaling. Non-limiting
examples of acids are formic acid, acetic acid, citric acid, hydrochloric
acid, sulfuric acid and
sulfonic acid.
Bases are compounds, which are useful for adjusting a preferable pH-range for
complexing
agents. Examples of bases, which can be used according to the present
invention, are: NaOH,
KOH and amine ethanol.
As inorganic builder the following are especially useful:
- crystalline and amorphous alumino silicates having ion exchanging
properties, such as
zeolites: different types of zeolites are useful, especially those of type A,
X, B, P, MAP and
HS in their Na-modification or in modifications in which Na is partially
substituted by other
cat ions such as Li, K, Ca, Mg or ammonium;
- crystalline silicates, such as disilicates and layer-silicates, e.g. 6-
and 13-Na2Si205. The
silicates can be used as alkali metal-, earth alkali metal- or ammonium salts,
the Na-, Li-
and Mg-silicates are preferred;
- amorphous silicates, such as sodium metasilicate and amorphous
disilicate;
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- carbonates and hydrogencarbonates: These can be used as alkali metal-,
earth alkali
metal- or ammonium salts. Na-, Li- and Mg-carbonates and ¨hydrogen carbonate,
espe-
cially sodium carbonate and/or sodium hydrogen carbonate are preferred;
- polyphosphates, such as pentanatriumtriphosphate.
5
Useful as oligomeric and polymeric cobuilders are:
Oligomeric and polymeric carbonic acids, such as homopolymers of acrylic acid
and aspartic
acid, oligomaleic acid, copolymers of maleic acid and acrylic acid,
methacrylic acid or 02-022-
olefines, e.g. isobutene or long chain a-olefines, vinyl-C1-C8-alkylether,
vinylacetate, vinylpropi-
10 onate, (meth)acryl acid ester of 01-08-alcohols and styrene. Preferred
are the homopolymers of
acrylic acid and the copolymers of acrylic acid with maleic acid. The
oligomeric and polymeric
carbonic acids preferably are used as acids or as sodium salts.
Chelating agents are compounds, which can bind cat ions. They can be used to
reduce water
15 hardness and to precipitate heavy metals. Examples of complexing agents
are: NTA, EDTA,
MGDA, DTPA, DTPMP, IDS, HEDP, 13-ADA, GLDA, citric acid, oxodisuccinic acid
and bu-
tanetetracarbonic acid. The advantage of the use of these compounds lies in
the fact that many
compounds, which serve as cleaning agents, are more active in soft water. In
addition to that
scaling can be reduced or even be avoided. By using such compounds there is no
need to dry a
cleaned surface. This is an advantage in the work flow.
Useful anti greying agents are e.g. carboxymethylcellulose and graft polymers
of vinyl acetate
on polyethylene glycol.
Useful bleaching agents are e.g. adducts of hydrogenperoxide at inorganic
salts, such as sodi-
um perborate-monohydrate, sodium perborate-tetrahyd rate and sodium carbonate-
perhydrate,
and percarbonic acids, such as phthalimidopercapronic acid.
As bleach activators compounds such as N,N,N',N'-tetraacetylethylendiamine
(TAED), sodium-
p-nonanoyloxybenzenesulfonate and N-methylmorpholiniumacetonitrilemethyl-
sulfate are use-
ful.
Useful enzymes are e.g. proteases, lipases, amylases, cellulases, mannanases,
oxidases and
peroxidases.
Useful as dye transfer inhibitors are e.g. homo-, co- and graft-polymers of 1-
vinylpyrrolidone, 1-
vinylimidazol or 4-vinylpyridine-N-oxide. Also homo- and copolymers of 4-
vinylpyridin, which
have been treated with chloro acetic acid are useful dye transfer inhibitors.
Biocides are compounds which kill bacteria. An example of a biocide is
glutaric aldehyde. The
advantage of the use of biocides is that the spreading of pathogenic germs is
counteracted.
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Hydrotropes are compounds which enhance the solubility of the surfactant / the
surfactants in
the chemical composition. An example is: cumolsulfonate.
Thickeners are compounds, which enhance the viscosity of the chemical
composition. Non-
limiting examples of thickeners are: polyacrylates and hydrophobically
modified polyacrylates.
The advantage of the use of thickeners is, that liquids having a higher
viscosity have a longer
residence time on the surface to be treated in the cases this surface is
inclined or even vertical.
This leads to an enhanced time of interaction.
A self-emulsifiable composition, which has a content of organic solvent below
50 mg/kg of
emulsion is particularly preferred.
A self-emulsifiable composition that forms a transparent, homogeneous oil-
phase forms one
preferred embodiment of the present invention.
The self-emulsifiable compositions can be prepared by simply mixing and
stirring the com-
pounds a) to e) with each other until a homogeneous composition is obtained.
The step of combining the components can vary: in one preferred embodiment,
polymer(s) Px is
dissolved in polyisobutene, optionally comprising oil(s) and/or additional
components, and then
optionally combined with surfactants and additional components.
In another preferred embodiment, polymer(s) Px is optionally mixed with
surfactants and/or addi-
tional components, and then combined with polyisobutene phase, comprising
polyisobutene and
optionally oil(s) and/or additional components.
The use of the self-emulsifiable composition as described above in chemical
technical applica-
tions, car wash, cosmetics, plant protection, preparation and treatment of
paper, textiles and
leather, adhesives, dye and pigment formulations, coatings, pharmaceutical
applications, con-
struction, wood treatment forms another aspect of the present invention.
The use of the self-emulsifiable composition as described above in car wash,
forms another
aspect of the present invention.
Aspects of the invention include the use of the self-emulsifiable composition
disclosed herein in
laundry detergent compositions (e.g., TIDETm), hard surface cleaners (e.g., MR
CLEAN TM), au-
tomatic dishwashing liquids (e.g., CASCADETm), and dishwashing liquids (e.g.,
DAWN TM). Non-
limiting examples of cleaning compositions may include those described in U.S.
Pat. Nos.
4,515,705; 4,537,706; 4,537,707; 4,550,862; 4,561,998; 4,597,898; 4,968,451;
5,565,145;
5,929,022; 6,294,514; and 6,376,445. The cleaning compositions disclosed
herein are typically
formulated such that, during use in aqueous cleaning operations, the wash
water will have a pH
of between about 6.5 and about 12, or between about 7.5 and 10.5. Liquid
dishwashing product
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formulations typically have a pH between about 6.8 and about 9Ø Cleaning
products are typi-
cally formulated to have a pH of from about 7 to about 12. Techniques for
controlling pH at rec-
ommended usage levels include the use of buffers, alkalis, acids, etc., and
are well known to
those skilled in the art.
Fabric treatment compositions disclosed herein typically comprise a fabric
softening ac-
tive ("FSA") and a nonionic care agent disclosed herein. Suitable fabric
softening actives, in-
clude, but are not limited to, materials selected from the group consisting of
quats, amines, fatty
esters, sucrose esters, silicones, dispersible polyolefins, clays,
polysaccharides, fatty oils, poly-
mer latexes and mixtures thereof.
Additional Fabric and/or Home care Ingredients
The disclosed compositions may include additional adjunct ingredients. Adjunct
ingredients in-
clude, but are not limited to, deposition aids, bleach activators,
surfactants, builders, chelating
agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme
stabilizers, catalytic
Deposition Aid - In one aspect, the fabric treatment composition may comprise
from about
In one aspect, the deposition aid may be a cationic or amphoteric polymer. In
another aspect,
the deposition aid may be a cationic polymer. Cationic polymers in general and
their method of
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18
ing unit. The positive charges may be located on the backbone of the polymers
and/or the side
chains of polymers.
Non-limiting examples of deposition enhancing agents are cationic or
amphoteric, polysaccha-
rides, proteins and synthetic polymers. Cationic polysaccharides include
cationic cellulose de-
rivatives, cationic guar gum derivatives, chitosan and derivatives and
cationic starches. Cation-
ic polysaccharides have a molecular weight from about 50,000 to about 2
million, or even from
about 100,000 to about 3,500,000. Suitable cationic polysaccharides include
cationic cellulose
ethers, particularly cationic hydroxyethylcellulose and cationic
hydroxypropylcellulose. Exam-
ples of cationic hydroxyalkyl cellulose include those with the INCI name
Polyquaternium10 such
as those sold under the trade names UcareTM Polymer JR 30M, JR 400, JR 125, LR
400 and
LK 400 polymers; Polyquaternium 67 such as those sold under the trade name
Softcat SK TM,
all of which are marketed by Amerchol Corporation, Edgewater NJ; and
Polyquaternium 4
such as those sold under the trade name CelquatTM H200 and CelquatTM L-200
available from
National Starch and Chemical Company, Bridgewater, NJ. Other suitable
polysaccharides in-
clude Hydroxyethyl cellulose or hydoxypropylcellulose quaternized with
glycidyl C12-C22 alkyl
dimethyl ammonium chloride. Examples of such polysaccharides include the
polymers with the
INCI names Polyquaternium 24 such as those sold under the trade name
Quaternium LM 200
by Amerchol Corporation, Edgewater NJ . Cationic starches described by D. B.
Solarek in Mod-
ified Starches, Properties and Uses published by CRC Press (1986) and in U.S.
Pat. No.
7,135,451, col. 2, line 33 ¨ col. 4, line 67. Cationic galactomannans include
cationic guar gums
or cationic locust bean gum. An example of a cationic guar gum is a quaternary
ammonium
derivative of Hydroxypropyl Guar such as those sold under the trade name
Jaguar C13 and
Jaguar Excel available from Rhodia, Inc of Cranbury NJ and N-Hance by
Aqualon, Wilming-
ton, DE.
Another group of suitable cationic polymers includes those produced by
polymerization of eth-
ylenically unsaturated monomers using a suitable initiator or catalyst, such
as those disclosed in
USPN 6,642,200.
Suitable polymers may be selected from the group consisting of cationic or
amphoteric polysac-
charide, polyethylene imine and its derivatives, and a synthetic polymer made
by polymerizing
one or more cationic monomers selected from the group consisting of N,N-
dialkylaminoalkyl
acrylate, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl
acrylamide, N,N-
dialkylaminoalkylmethacrylamide, quaternized N, N dialkylaminoalkyl acrylate
quaternized N,N-
dialkylaminoalkyl methacrylate, quaternized N,N-dialkylaminoalkyl acrylamide,
quaternized N,N-
dialkylaminoalkylmethacrylamide, Methacryloamidopropyl-pentamethy1-1,3-
propylene-24-
ammonium dichloride, N,N,N,N1,N1,N",N"-heptamethyl-N"-3-(1-oxo-2-methyl-2- pro-
penyl)aminopropy1-9- oxo-8-azo-decane-1,4,10-triammonium trichloride,
vinylamine and its de-
rivatives, allylamine and its derivatives, vinyl imidazole, quaternized vinyl
imidazole and diallyl
dialkyl ammonium chloride and combinations thereof, and optionally a second
monomer select-
ed from the group consisting of acrylamide, N,N-dialkyl acrylamide,
methacrylamide, N,N-
dialkylmethacrylamide, C1-C12 alkyl acrylate, C1-C12 hydroxyalkyl acrylate,
polyalkylene glyol
acrylate, C1-C12 alkyl methacrylate, C1-C12 hydroxyalkyl methacrylate,
polyalkylene glycol
methacrylate, vinyl acetate, vinyl alcohol, vinyl formamide, vinyl acetamide,
vinyl alkyl ether,
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vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, vinyl caprolactam, and
derivatives, acrylic acid,
methacrylic acid, maleic acid, vinyl sulfonic acid, styrene sulfonic acid,
acrylamidopropylme-
thane sulfonic acid (AMPS) and their salts. The polymer may optionally be
branched or cross-
linked by using branching and crosslinking monomers. Branching and
crosslinking monomers
include ethylene glycoldiacrylate divinylbenzene, and butadiene. In another
aspect, the treat-
ment composition may comprise an amphoteric deposition aid polymer so long as
the polymer
possesses a net positive charge. Said polymer may have a cationic charge
density of about
0.05 milliequivalents/g. to about 18 milliequivalents/g.
In another aspect, the deposition aid may be selected from the group
consisting of cationic pol-
1 0 ysaccharide, polyethylene imine and its derivatives, poly(acrylamide-co-
diallyldimethylammonium chloride), poly(acrylamide-
methacrylamidopropyltrimethyl ammonium
chloride), poly(acrylamide-co-N,N-dimethyl aminoethyl acrylate) and its
quaternized derivatives,
poly(acrylamide-co-N,N-dimethyl aminoethyl methacrylate) and its quaternized
derivative,
poly(hydroxyethylacrylate-co-dimethyl aminoethyl methacrylate),
poly(hydroxpropylacrylate-co-
dimethyl aminoethyl methacrylate), poly(hydroxpropylacrylate-co-
methacrylamidopropyltrimethylammonium chloride), poly(acrylamide-co-
diallyldimethylammonium chloride-co-acrylic acid), poly(acrylamide-
methacrylamidopropyltrimethyl ammonium chloride-co-acrylic acid),
poly(diallyldimethyl ammo-
nium chloride), poly(vinylpyrrolidone-co-dimethylaminoethyl methacrylate),
poly(ethyl methacry-
late-co-quaternized dimethylaminoethyl methacrylate), poly(ethyl methacrylate-
co-oleyl methac-
rylate-co-diethylaminoethyl methacrylate), poly(diallyldimethylammonium
chloride-co-acrylic
acid), poly(vinyl pyrrolidone-co-quaternized vinyl imidazole) and
poly(acrylamide-co-
Methacryloamidopropyl-pentamethy1-1,3-propylene-2-ol-ammonium dichloride),
Suitable deposi-
tion aids include Polyquaternium-1, Polyquaternium-5, Polyquaternium-6,
Polyquaternium-7,
Polyquaternium-8, Polyquaternium-11, Polyquaternium-14, Polyquaternium-22,
Polyquaterni-
um-28, Polyquaternium-30, Polyquaternium-32 and Polyquaternium-33, as named
under the
International Nomenclature for Cosmetic Ingredients.
In one aspect, the deposition aid may comprise polyethyleneimine or a
polyethyleneimine deriv-
ative. A suitable polyethyleneinine useful herein is that sold under the trade
name Lupasol by
BASF, SE, and Ludwigshafen, Germany
In another aspect, the deposition aid may comprise a cationic acrylic based
polymer. In a fur-
ther aspect, the deposition aid may comprise a cationic polyacrylamide. In
another aspect, the
deposition aid may comprise a polymer comprising polyacrylamide and
polymethacrylami-
dopropyl trimethylammonium cation. In another aspect, the deposition aid may
comprise poly
(acrylamide- N-dimethyl aminoethyl acrylate) and its quaternized derivatives.
In this aspect, the
deposition aid may be that sold under the trade name Sedipur , available from
BTC Specialty
Chemicals, a BASF Group, Florham Park, N.J. In a yet further aspect, the
deposition aid may
comprise poly (acrylamide-co-methacrylamidopropyltrimethyl ammonium chloride).
In another
aspect, the deposition aid may comprise a non-acrylamide based polymer, such
as that sold
under the trade name Rheovis CDE, available from Ciba Specialty Chemicals, a
BASF, SE
group, Florham Park, N.J., or as disclosed in USPA 2006/0252668.
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In another aspect, the deposition aid may be selected from the group
consisting of cationic or
amphoteric polysaccharides. In one aspect, the deposition aid may be selected
from the group
consisting of cationic and amphoteric cellulose ethers, cationic or amphoteric
galactomannan,
cationic guar gum, cationic or amphoteric starch, and combinations thereof
5 Another group of suitable cationic polymers may include alkylamine-
epichlorohydrin polymers
which are reaction products of amines and oligoamines with epichlorohydrin,
for example, those
polymers listed in, for example, USPNs 6,642,200 and 6,551,986. Examples
include dimethyl-
amine-epichlorohydrin-ethylenediamine, available under the trade name Cartafix
CB and
Cartafix TSF from Clariant, Basle, Switzerland.
10 Another group of suitable synthetic cationic polymers may include
polyamidoamine-
epichlorohydrin (PAE) resins of polyalkylenepolyamine with polycarboxylic
acid. The most
common PAE resins are the condensation products of diethylenetriamine with
adipic acid fol-
lowed by a subsequent reaction with epichlorohydrin. They are available from
Hercules Inc. of
Wilmington DE under the trade name Kymene TM or from BASF SE (Ludwigshafen,
Germany)
15 under the trade name Luresin TM . The cationic polymers may contain
charge neutralizing anions
such that the overall polymer is neutral under ambient conditions. Non-
limiting examples of
suitable counter ions (in addition to anionic species generated during use)
include chloride,
bromide, sulfate, methylsulfate, sulfonate, methylsulfonate, carbonate,
bicarbonate, formate,
acetate, citrate, nitrate, and mixtures thereof.
20 The weight-average molecular weight of the polymer may be from about 500
Daltons to about
5,000,000 Daltons, or from about 1,000 Daltons to about 2,000,000 Daltons, or
from about
2,500 Daltons to about 1,500,000 Daltons, as determined by size exclusion
chromatography
relative to polyethylene oxide standards with RI detection. In one aspect, the
MW of the cation-
ic polymer may be from about 500 Daltons to about 37,500 Daltons.
Surfactants: The products of the present invention may comprise from about
0.11% to 80% by
weight of a surfactant. In one aspect, such compositions may comprise from
about 5% to 50%
by weight of surfactant. Surfactants utilized can be of the anionic, nonionic,
zwitterionic, am-
pholytic or cationic type or can comprise compatible mixtures of these types.
Detergent surfac-
tants useful herein are described in U.S. Patents 3,664,961, 3,919,678,
4,222,905, 4,239,659,
6,136,769, 6,020,303, and 6,060,443.
Anionic and nonionic surfactants are typically employed if the fabric care
product is a
laundry detergent. On the other hand, cationic surfactants are typically
employed if the fabric
care product is a fabric softener.
Useful anionic surfactants can themselves be of several different types. For
example,
water-soluble salts of the higher fatty acids, i.e., "soaps", are useful
anionic surfactants in the
compositions herein. This includes alkali metal soaps such as the sodium,
potassium, ammoni-
um, and alkylolammonium salts of higher fatty acids containing from about 8 to
about 24 carbon
atoms, or even from about 12 to about 18 carbon atoms. Soaps can be made by
direct saponi-
fication of fats and oils or by the neutralization of free fatty acids.
Particularly useful are the so-
dium and potassium salts of the mixtures of fatty acids derived from coconut
oil and tallow, i.e.,
sodium or potassium tallow and coconut soap.
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Useful anionic surfactants include the water-soluble salts, particularly the
alkali metal,
ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium)
salts,
of organic sulfuric reaction products having in their molecular structure an
alkyl group containing
from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid
ester group. (In-
cluded in the term "alkyl" is the alkyl portion of aryl groups.) Examples of
this group of synthetic
surfactants are the alkyl sulfates and alkyl alkoxy sulfates, especially those
obtained by sulfating
the higher alcohols (C8-018 carbon atoms).
Other useful anionic surfactants herein include the water-soluble salts of
esters of a-
sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty
acid group and
from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-
acyloxy-alkane-l-
sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and
from about 9 to
about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin
sulfonates containing
from about 12 to 24 carbon atoms; and R-alkyloxy alkane sulfonates containing
from about 1 to
3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the
alkane moiety.
In another embodiment, the anionic surfactant may comprise a 011-018 alkyl
benzene sul-
fonate surfactant; a 010-020 alkyl sulfate surfactant; a 010-C18 alkyl alkoxy
sulfate surfactant,
having an average degree of alkoxylation of from 1 to 30, wherein the alkoxy
comprises a 01-
04 chain and mixtures thereof; a mid-chain branched alkyl sulfate surfactant;
a mid-chain
branched alkyl alkoxy sulfate surfactant having an average degree of
alkoxylation of from 1 to
30, wherein the alkoxy comprises a 01-04 chain and mixtures thereof; a 010-018
alkyl alkoxy
carboxylates comprising an average degree of alkoxylation of from 1 to 5; a
012-020 methyl
ester sulfonate surfactant, a 010-018 alpha-olefin sulfonate surfactant, a 06-
020 sulfosuccin-
ate surfactant, and a mixture thereof.
In addition to the anionic surfactant, the fabric care compositions of the
present invention
may further contain a nonionic surfactant. The compositions of the present
invention can con-
tain up to about 30%, alternatively from about 0.01% to about 20%, more
alternatively from
about 0.1% to about 10%, by weight of the composition, of a nonionic
surfactant. In one embod-
iment, the nonionic surfactant may comprise an ethoxylated nonionic
surfactant. Examples of
suitable non-ionic surfactants are provided in U.S. Patents. 4,285,841,
6,150,322, and
6,153,577.
. Suitable for use herein are the ethoxylated alcohols and ethoxylated alkyl
phenols of the for-
mula R(002H4)n OH, wherein R is selected from the group consisting of
aliphatic hydrocarbon
radicals containing from about 8 to about 20 carbon atoms and alkyl phenyl
radicals in which
the alkyl groups contain from about 8 to about 12 carbon atoms, and the
average value of n is
from about 5 to about 15.
Suitable nonionic surfactants are those of the formula R1(002H4)n0H, wherein
R1 is a 010 -
C16 alkyl group or a 08-012 alkyl phenyl group, and n is from 3 to about 80.
In one aspect,
particularly useful materials are condensation products of 09-015 alcohols
with from about 5 to
about 20 moles of ethylene oxide per mole of alcohol.
Additional suitable nonionic surfactants include polyhydroxy fatty acid amides
such as N-
methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide and
alkyl poly-
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22
saccharides such as the ones described in US 5,332,528. Alkylpolysaccharides
disclosed in
U.S. Patent 4,565,647.
The fabric care compositions of the present invention may contain up to about
30%, alternative-
ly from about 0.01% to about 20%, more alternatively from about 0.1% to about
20%, by weight
of the composition, of a cationic surfactant. For the purposes of the present
invention, cationic
surfactants include those which can deliver fabric care benefits. Non-limiting
examples of useful
cationic surfactants include: fatty amines; quaternary ammonium surfactants;
and imidazoline
quat materials.
In some embodiments, useful cationic surfactants, include those disclosed in
U.S. Patent Appli-
cation number 2005/0164905 Al and having the general formula (XIII):
Ri
1+
R3¨N¨R4 x
1
R2 (XIII)
wherein:
(a) R1 and R2 each are individually selected from the groups of: 01-04 alkyl;
01-04 hydroxy
alkyl; benzyl; --(CnH2n0)xH, wherein:
i. x has a value from about 2 to about 5;
ii. n has a value of about 1-4;
(b) R3 and R4 are each:
i. a 08-022 alkyl; or
ii. R3 is a 08-022 alkyl and R4 is selected from the group of: C1-010 alkyl;
C1-010 hydroxy
alkyl; benzyl; --(CnH2n0)xH, wherein:
1. x has a value from 2 to 5; and
2. n has a value of 1-4; and
(c) X is an anion.
Fabric Softening Active Compounds- The fabric softening active may comprise,
as the principal
active, compounds of the following formula:
{R4-m- N+ - [X - Y - Rl]m} X- (XIV)
wherein each R may comprise either hydrogen, a short chain 01-06, in one
aspect a 01-03
alkyl or hydroxyalkyl group, for example methyl, ethyl, propyl, hydroxyethyl,
and the like,
poly(C2-3 alkoxy), polyethoxy, benzyl, or mixtures thereof; each X may
independently be
(CH2)n, CH2-CH(CH3)- or CH-(CH3)-CH2-; each Y may comprise -0-(0)C-, -C(0)-0-,
-NR-
0(0)-, or -C(0)-NR-; each m may be 2 or 3; each n may be from 1 to about 4, in
one aspect 2;
the sum of carbons in each R1, plus one when Y is -0-(0)C- or -NR-C(0) -, may
be 012-022,
or 014-020, with each R1 being a hydrocarbyl, or substituted hydrocarbyl
group; and X- may
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comprise any softener-compatible anion. In one aspect, the softener-compatible
anion may
comprise chloride, bromide, methylsulfate, ethylsulfate, sulfate, and nitrate.
In another aspect,
the softener-compatible anion may comprise chloride or methyl sulfate.
In another aspect, the fabric softening active may comprise the general
formula (XV):
[R3N+CH2CH(YR1)(CH2YR1)] X-
Formula (XV)
wherein each Y, R, R1, and X- have the same meanings as before. Such compounds
include
those having the formula (XVI):
[CH3]3 N(+)[CH2CH(CH20(0)CR1)0(0)CR1] C1(-)
(XVI)
wherein each R may comprise a methyl or ethyl group. In one aspect, each R1
may comprise a
015 to 019 group. As used herein, when the diester is specified, it can
include the monoester
that is present.
These types of agents and general methods of making them are disclosed in USPN
4,137,180.
An example of a suitable DEQA (2) is the "propyl" ester quaternary ammonium
fabric softener
active comprising the formula 1,2-di(acyloxy)-3-trimethylammoniopropane
chloride.
In one aspect, the fabric softening active may comprise the formula (XVII):
[R4-m - N+ - R1m] X-
(XVII)
wherein each R, R1, m and X- have the same meanings as before.
In a further aspect, the fabric softening active may comprise the formula
(XVIII):
0
11 R1 _ N - r2
[
\ +
]A-
-
N - CH2 -
R1 - C -G- R2------ \
R
(XVIII)
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wherein each R and R1 have the definitions given above; R2 may comprise a 01-6
alkylene
group, in one aspect an ethylene group; and G may comprise an oxygen atom or
an -NR-
group; and A- is as defined below.
In a yet further aspect, the fabric softening active may comprise the formula
(XIX):
N¨CH2
1=0¨C(/
\
, Ill N¨CH2
R--C¨G¨R.
(XIX)
wherein R1, R2 and G are defined as above.
In a further aspect, the fabric softening active may comprise condensation
reaction products of
fatty acids with dialkylenetriamines in, e.g., a molecular ratio of about 2:1,
said reaction products
containing compounds of the formula(XX):
R1¨C(0)¨NH¨R2¨NH¨R3¨NH¨C(0)¨R1
(XX)
wherein R1, R2 are defined as above, and R3 may comprise a 01-6 alkylene
group, or an eth-
ylene group and wherein the reaction products may optionally be quaternized by
the additional
of an alkylating agent such as dimethyl sulfate. Such quaternized reaction
products are de-
scribed in additional detail in USPN 5,296,622.
In a yet further aspect, the fabric softening active may comprise the formula
(XXI):
[R1¨C(0)¨NR¨R2¨N(R)2¨R3¨NR¨C(0) ________________ R1]+ A-
(XXI)
wherein R, R1, R2 and R3 are defined as above; A- is as defined below;
In a yet further aspect, the fabric softening active may comprise reaction
products of fatty acid
with hydroxyalkylalkylenediamines in a molecular ratio of about 2:1, said
reaction products con-
taining compounds of the formula (XXII):
R1-C(0)-NH-R2-N(R3OH)-C(0)-R1
(XXII)
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wherein R1, R2 and R3 are defined as above;
In a yet further aspect, the fabric softening active may comprise the formula
(XXIII):
_
- 2e
___________ R R _____
\ / \/
N¨R2¨N
N( ) ___________________ N 2Ae
R1 R1
_
(XXIII)
5 wherein R, R1 and R2are defined as above; A- is as defined below.
In yet a further aspect, the fabric softening active may comprise the formula
(XXIV);
Xi
/\
N \N¨X2¨B¨R2
/µ
X3
1
A
1
R1
Formula (XXIV)
10 wherein;
X1 may comprise a 02-3 alkyl group, in one aspect, an ethyl group;
X2 and X3 may independently comprise 01-6 linear or branched alkyl or alkenyl
groups, in one
aspect, methyl, ethyl or isopropyl groups;
R1 and R2 may independently comprise 08-22 linear or branched alkyl or alkenyl
groups;
15 characterized in that;
A and B are independently selected from the group comprising -0-(C=0)-, -(C=0)-
0-, or mix-
tures thereof, in one aspect, -0-(0=0)-.
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Non-limiting examples of fabric softening actives comprising formula (XIV) are
N, N-bis(stearoyl-
oxy-ethyl) N,N-dimethyl ammonium chloride, N,N-bis(tallowoyl-oxy-ethyl) N,N-
dimethyl ammo-
nium chloride, N,N-bis(stearoyl-oxy-ethyl) N-(2 hydroxyethyl) N-methyl
ammonium methyl-
sulfate.
A non-limiting example of fabric softening actives comprising formula (XVI) is
1, 2 di (stearoyl-
oxy) 3 trimethyl ammoniumpropane chloride.
Non-limiting examples of fabric softening actives comprising formula (XVII)
may include dial-
kylenedimethylammonium salts such as dicanoladimethylammonium chloride,
di(hard)tallowdimethylammonium chloride dicanoladimethylammonium
methylsulfate,. An ex-
ample of commercially available dialkylenedimethylammonium salts usable in the
present inven-
tion is dioleyldimethylammonium chloride available from Witco Corporation
under the trade
name Adogen 472 and dihardtallow dimethylammonium chloride available from
Akzo Nobel
Arquad 2HT75.
A non-limiting example of fabric softening actives comprising formula (XVIII)
may include 1-
methyl-1-stearoylamidoethy1-2-stearoylimidazolinium methylsulfate wherein R1
is an acyclic
aliphatic C15-C17 hydrocarbon group, R2 is an ethylene group, G is a NH group,
R5 is a methyl
group and A- is a methyl sulfate anion, available commercially from the Witco
Corporation under
the trade name Varisoft .
A non-limiting example of fabric softening actives comprising formula (XIX) is
1-
tallowylamidoethy1-2-tallowylimidazoline wherein R1 may comprise an acyclic
aliphatic C15-C17
hydrocarbon group, R2 may comprise an ethylene group, and G may comprise a NH
group.
A non-limiting example of a fabric softening active comprising formula (XX) is
the reaction prod-
ucts of fatty acids with diethylenetriamine in a molecular ratio of about 2:1,
said reaction product
mixture comprising N,N"-dialkyldiethylenetriamine having the formula (XXV):
R1-C(0)-NH-CH2CH2-NH-CH2CH2-NH-C(0)-R1
Formula (XXV)
wherein R1 is an alkyl group of a commercially available fatty acid derived
from a vegetable or
animal source, such as Emersol 223LL or Emersol 7021, available from Henkel
Corporation,
and R2 and R3 are divalent ethylene groups.
A non-limiting example of Compound (XXI) is a difatty amidoamine based
softener having the
formula (XXVI):
[R1-C(0)-NH-CH2CH2-N(CH3)(CH2CH2OH)-CH2CH2-NH-C(0)-R1]+ CH3SO4-
Formula (XXVI)
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wherein R1 is an alkyl group. An example of such compound is that commercially
available
from the Witco Corporation e.g. under the trade name Varisoft 222LT.
An example of a fabric softening active comprising formula (XXII) is the
reaction products of
fatty acids with N-2-hydroxyethylethylenediamine in a molecular ratio of about
2:1, said reaction
product mixture comprising the formula (XXVII):
R1-C(0)-NH-CH2CH2-N(CH2CH2OH)-C(0)-R1
Formula (XXVII)
wherein R1-C(0) is an alkyl group of a commercially available fatty acid
derived from a vegeta-
ble or animal source, such as Emersol 223LL or Emersol 7021, available from
Henkel Cor-
poration.
An example of a fabric softening active comprising formula (XXIII) is the
diquaternary compound
having the formula (XXVIII):
CH 3 cH3\ , __
\ / /
N¨C H2 CH2 ¨N 2CH3 S049
N( )_ __ N
R1 R1
_
Formula (XXVIII)
wherein R1 is derived from fatty acid. Such compound is available from Witco
Company.
A non-limiting example of a fabric softening active comprising formula (XXIV)
is a dialkyl imid-
azoline diester compound, where the compound is the reaction product of N-(2-
hydroxyethyl)-
1,2-ethylenediamine or N-(2-hydroxyisopropyI)-1,2-ethylenediamine with
glycolic acid, esterified
with fatty acid, where the fatty acid is (hydrogenated) tallow fatty acid,
palm fatty acid, hydro-
genated palm fatty acid, oleic acid, rapeseed fatty acid, hydrogenated
rapeseed fatty acid or a
mixture of the above.
It will be understood that combinations of softener actives disclosed above
are suitable for use
herein.
Anion A
In the cationic nitrogenous salts herein, the anion A-, which comprises any
softener compatible
anion, provides electrical neutrality. Most often, the anion used to provide
electrical neutrality in
these salts is from a strong acid, especially a halide, such as chloride,
bromide, or iodide. How-
ever, other anions can be used, such as methylsulfate, ethylsulfate, acetate,
formate, sulfate,
carbonate, and the like. In one aspect, the anion A may comprise chloride or
methylsulfate.
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The anion, in some aspects, may carry a double charge. In this aspect, A-
represents half a
group.
In one aspect, the fabric care and/or treatment composition may comprise a
second softening
agent selected from the group consisting of polyglycerol esters (PGEs), oily
sugar derivatives,
and wax emulsions. Suitable PGEs include those disclosed in USPA 61/089,080.
Suitable oily
sugar derivatives and wax emulsions include those disclosed in USPA 2008-
0234165 Al.
In one aspect, the compositions may comprise from about 0.001% to about 0.01%
of an unsatu-
rated aldehyde. In one aspect, the compositions are essentially free of an
unsaturated alde-
hyde. Without being limited by theory, in this aspect, the compositions are
less prone to the
yellowing effect often encountered with amino-containing agents.
Builders - The compositions may also contain from about 0.1% to 80% by weight
of a builder.
Compositions in liquid form generally contain from about 1% to 10% by weight
of the builder
component. Compositions in granular form generally contain from about 1% to
50% by weight
of the builder component. Detergent builders are well known in the art and can
contain, for ex-
ample, phosphate salts as well as various organic and inorganic nonphosphorus
builders. Wa-
ter-soluble, nonphosphorus organic builders useful herein include the various
alkali metal, am-
monium and substituted ammonium polyacetates, carboxylates, polycarboxylates
and polyhy-
droxy sulfonates. Examples of polyacetate and polycarboxylate builders are the
sodium, potas-
sium, lithium, ammonium and substituted ammonium salts of ethylene diamine
tetraacetic acid,
nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene
polycarboxylic acids, and citric
acid. Other suitable polycarboxylates for use herein are the polyacetal
carboxylates described
in U.S. 4,144,226 and U.S. 4,246,495. Other polycarboxylate builders are the
oxydisuccinates
and the ether carboxylate builder compositions comprising a combination of
tartrate monosuc-
cinate and tartrate disuccinate described in U.S. 4,663,071, Builders for use
in liquid detergents
are described in U.S. 4,284,532, One suitable builder includes may be citric
acid. Suitable
nonphosphorus, inorganic builders include the silicates, aluminosilicates,
borates and car-
bonates, such as sodium and potassium carbonate, bicarbonate, sesquicarbonate,
tetraborate
decahydrate, and silicates having a weight ratio of 5i02 to alkali metal oxide
of from about 0.5
to about 4.0, or from about 1.0 to about 2.4. Also useful are aluminosilicates
including zeolites.
Such materials and their use as detergent builders are more fully discussed in
U.S. 4,605,509.
Dispersants ¨ The compositions may contain from about 0.1%, to about 10%, by
weight of dis-
persants Suitable water-soluble organic materials are the homo- or co-
polymeric acids or their
salts, in which the polycarboxylic acid may contain at least two carboxyl
radicals separated from
each other by not more than two carbon atoms. The dispersants may also be
alkoxylated de-
rivatives of polyamines, and/or quaternized derivatives thereof such as those
described in US
4,597,898, 4,676,921, 4,891,160, 4,659,802 and 4,661,288.
Enzymes ¨ The compositions may contain one or more detergent enzymes which
provide
cleaning performance and/or fabric care benefits. Examples of suitable enzymes
include hemi-
cellulases, peroxidases, proteases, cellulases, xylanases, lipases,
phospholipases, esterases,
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cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases,
lipoxygenases, lig-
ninases, pullulanases, tannases, pentosanases, malanases, R-glucanases,
arabinosidases,
hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A
typical combina-
tion may be a cocktail of conventional applicable enzymes like protease,
lipase, cutinase and/or
cellulase in conjunction with amylase. Enzymes can be used at their art-taught
levels, for ex-
ample at levels recommended by suppliers such as Novozymes and Genencor.
Typical levels in
the compositions are from about 0.0001% to about 5%. When enzymes are present,
they can
be used at very low levels, e.g., from about 0.001% or lower; or they can be
used in heavier-
duty laundry detergent formulations at higher levels, e.g., about 0.1% and
higher. In accord-
ance with a preference of some consumers for "non-biological" detergents, the
compositions
may be either or both enzyme-containing and enzyme-free.
Dye Transfer Inhibiting Agents - The compositions may also include from about
0.0001%, from
about 0.01%, from about 0.05% by weight of the compositions to about 10%,
about 2%, or even
about 1% by weight of the compositions of one or more dye transfer inhibiting
agents such as
polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone
and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or
mixtures thereof.
Chelant ¨ The compositions may contain less than about 5%, or from about 0.01%
to about 3%
of a chelant such as citrates; nitrogen-containing, P-free aminocarboxylates
such as EDDS,
EDTA and DTPA; aminophosphonates such as diethylenetriamine
pentamethylenephosphonic
acid and, ethylenediamine tetramethylenephosphonic acid; nitrogen-free
phosphonates e.g.,
HEDP; and nitrogen or oxygen containing, P-free carboxylate-free chelants such
as compounds
of the general class of certain macrocyclic N-ligands such as those known for
use in bleach cat-
alyst systems.
Brighteners ¨ The compositions may also comprise a brightener (also referred
to as "optical
brightener") and may include any compound that exhibits fluorescence,
including compounds
that absorb UV light and reemit as "blue" visible light. Non-limiting examples
of useful brighten-
ers include: derivatives of stilbene or 4,4'-diaminostilbene, biphenyl, five-
membered heterocy-
cles such as triazoles, pyrazolines, oxazoles, imidiazoles, etc., or six-
membered heterocycles
(coumarins, naphthalamide, s-triazine, etc.). Cationic, anionic, nonionic,
amphoteric and zwit-
terionic brighteners can be used. Suitable brighteners include those
commercially marketed
under the trade name Tinopal-UNPA-GX by Ciba Specialty Chemicals Corporation,
a BASF,
SE group; (High Point, NC).
Bleach system ¨ Bleach systems suitable for use herein contain one or more
bleaching agents.
Non-limiting examples of suitable bleaching agents include catalytic metal
complexes; activated
peroxygen sources; bleach activators; bleach boosters; photobleaches;
bleaching enzymes;
free radical initiators; H202; hypohalite bleaches; peroxygen sources,
including perborate
and/or percarbonate and combinations thereof. Suitable bleach activators
include perhydrolyz-
able esters and perhydrolyzable imides such as, tetraacetyl ethylene diamine,
octanoylcaprolac-
tam, benzoyloxybenzenesulphonate, nonanoyloxybenzene-isulphonate,
benzoylvalerolactam,
dodecanoyloxybenzenesulphonate. Suitable bleach boosters include those
described in US
Patent 5,817,614. Other bleaching agents include metal complexes of
transitional metals with
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ligands of defined stability constants. Such catalysts are disclosed in U.S.
4,430,243,
5,576,282, 5,597,936 and 5,595,967.
Stabilizer - The compositions may contain one or more stabilizers and
thickeners. Any suitable
level of stabilizer may be of use; exemplary levels include from about 0.01%
to about 20%, from
5 about 0.1% to about 10%, or from about 0.1% to about 3% by weight of the
composition. Non-
limiting examples of stabilizers suitable for use herein include crystalline,
hydroxyl-containing
stabilizing agents, trihydroxystearin, hydrogenated oil, or a variation
thereof, and combinations
thereof. In some aspects, the crystalline, hydroxyl-containing stabilizing
agents may be water-
insoluble wax-like substances, including fatty acid, fatty ester or fatty
soap. In other aspects, the
10 crystalline, hydroxyl-containing stabilizing agents may be derivatives
of castor oil, such as hy-
drogenated castor oil derivatives, for example, castor wax. The hydroxyl
containing stabilizers
are disclosed in US Patents 6,855,680 and 7,294,611. Other stabilizers include
thickening sta-
bilizers such as gums and other similar polysaccharides, for example gellan
gum, carrageenan
gum, and other known types of thickeners and rheological additives. Exemplary
stabilizers in
15 this class include gum-type polymers (e.g. xanthan gum), polyvinyl
alcohol and derivatives
thereof, cellulose and derivatives thereof including cellulose ethers and
cellulose esters and
tamarind gum (for example, comprising xyloglucan polymers), guar gum, locust
bean gum (in
some aspects comprising galactomannan polymers), and other industrial gums and
polymers.
20 For the purposes of the present invention, the non-limiting list of
adjuncts illustrated hereinafter
are suitable for use in the instant compositions and may be desirably
incorporated in certain
embodiments of the invention, for example to assist or enhance performance,
for treatment of
the substrate to be cleaned, or to modify the aesthetics of the composition as
is the case with
perfumes, colorants, dyes or the like. It is understood that such adjuncts are
in addition to the
25 components that are supplied via Applicants' perfumes and/or perfume
systems. The precise
nature of these additional components, and levels of incorporation thereof,
will depend on the
physical form of the composition and the nature of the operation for which it
is to be used. Suit-
able adjunct materials include, but are not limited to, surfactants, builders,
chelating agents, dye
transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers,
catalytic materials,
30 bleach activators, polymeric dispersing agents, clay soil removal/anti-
redeposition agents,
brighteners, suds suppressors, dyes, additional perfume and perfume delivery
systems, struc-
ture elasticizing agents, fabric softeners, carriers, hydrotropes, processing
aids and/or pig-
ments. In addition to the disclosure below, suitable examples of such other
adjuncts and levels
of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1
that are incor-
porated by reference.
Silicones - Suitable silicones comprise Si-0 moieties and may be selected from
(a) non-
functionalized siloxane polymers, (b) functionalized siloxane polymers, and
combinations there-
of. The molecular weight of the organosilicone is usually indicated by the
reference to the vis-
cosity of the material. In one aspect, the organosilicones may comprise a
viscosity of from
about 10 to about 2,000,000 centistokes at 25oC. In another aspect, suitable
organosilicones
may have a viscosity of from about 10 to about 800,000 centistokes at 25oC.
Suitable organo-
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silicones may be linear, branched or cross-linked. In one aspect, the
organosilicones may be
linear.
The present invention will be disclosed further by the following non-limiting
examples:
The present invention will be disclosed further by the following non-limiting
examples:
Examples:
Examples of Polyisobutene Premixes (PM):
Assessment of the Premixes and Formulations:
The premixes or formulations are assessed "clear", when the transmittance of
the formulation,
measured with a CADAS 200 spectrophotometer (Dr. Lange Company) at 650 nm in a
1cm cu-
vette is higher than 90%. The premix or formulations are assessed
"homogeneous", when upon
visual inspection no creaming / sedimentation or phase separation can be
observed after one
day. The premixes or formulations are assessed "phase separated" when the
mixture separated
into clearly recognizable organic and aqueous phases, or if droplets of
organic phase could be
observed on top of the aqueous phase.
Example: Polyisobutene Premix PM1
Polyisobutene (6.0 g, 60 parts per weight, molecular weight 1000 g/mol) and
polyisobutene
succinic anhydride (3.0 g, 30 parts per weight) were mixed in a 25m1 glass
vial and stirred at low
shear with a magnetic stirrer bar. The mixture was heated to 80 C to reduce
viscosity and thus
simplify mixing. Nonionic surfactant C10-Guerbetalcohol alkoxylate (HLB 12.5)
(1.0 g, 10 parts
per weight) was added and the resulting mixture was stirred for 5 min,
yielding an emulsifiable
polyisobutene composition PM1 in the form of a homogeneous, clear and stable
solution.
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Example: Polyisobutene Premixes PM2 ¨ PM5
The mixture is prepared in the same way as Example PM1, applying the ratios
given in the table
below. All examples formed homogeneous, clear and stable solutions.
Example PIB PIBSA Surfactant Solution properties
[wt.- /0] [wt.- /0] [wt.- /0]
PM1 60 30 10 Homogeneous, clear, stable
PM2 70 20 10 Homogeneous, clear, stable
PM3 40 35 25 Homogeneous, clear, stable
PM4 40 45 15 Homogeneous, clear, stable
PM5 40 55 5 Homogeneous, clear, stable
Example: Polyisobutene Premix PM6
Polyisobutene (6.0 g, 60 parts per weight, molecular weight 1000 g/mol) and
polyisobutene
succinic anhydride (3.0 g, 30 parts per weight) were mixed in a 25m1 glass
vial and stirred at low
shear with a magnetic stirrer bar. The mixture was heated to 80 C to reduce
viscosity and thus
simplify mixing. A surfactant mixture of nonionic surfactants C13-oxoalcohol +
3 EO (H LB 9)
(0.5 g, 5 parts per weight) and C13-oxoalcohol + 8 EO (HLB 13) (0.5 g, 5 parts
per weight) was
added and the resulting mixture was stirred for 5 min, yielding an
emulsifiable polyisobutene
composition PM6 in the form of a homogeneous, clear and stable solution.
Example: Polyisobutene Premixes PM7 ¨ PM10:
The following examples were done analogous to example PM3, taking the
composition given in
the table.
Example PIB PIBSA Surfactant Mix Solution properties
[wt.- /0] [wt.- /0] [wt.- /0]
PM6 60 30 10 Homogeneous, clear, stable
PM7 70 20 10 Homogeneous, clear, stable
PM8 40 35 25 Homogeneous, clear, stable
PM9 40 45 15 Homogeneous, clear, stable
PM10 40 55 5 Homogeneous, clear, stable
The following comparative examples were done analogous to example PM3, taking
the compo-
sition given in the table below. All emulsions resulted in an unstable premix
solution that
showed turbidity or phase separation when the amount of surfactant was equal
to or higher than
the amount of polymeric emulsifier (PIBSA):
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Comparative Example PIB PIBSA Surfactant Mix Solution properties
[wt.- /0] [wt.- /0] [wt.- /0]
Comp.Ex.4 70 5 25 Phase Separation
Comp.Ex.5 80 5 15 Phase Separation
Comp.Ex.6 90 5 5 Phase Separation
Example: Polyisobutene Premix PM11
Polyisobutene (5.0 g, 50 parts per weight, molecular weight 1000 g/mol) ,
polyisobuteneamine
(3.25 g, 32.5 parts per weight) and n-paraffin C5-C20 (1.75 g, 17.5 parts per
weight) were
mixed in a 25m1 glass vial and stirred at low shear with a magnetic stirrer
bar. The composition
is a homogeneous, clear and stable solution.
Example: Polyisobutene Premix PM12
Polyisobutene (4.0 g, 40 parts per weight, molecular weight 1000 g/mol) ,
polyisobuteneamine
(3.9 g, 39.0 parts per weight) and n-paraffin C5-C20 (2.1 g, 21.0 parts per
weight) were mixed in
a 25m1 glass vial and stirred at low shear with a magnetic stirrer bar. The
composition is a ho-
mogeneous, clear and stable solution.
Example: Polyisobutene Premix PM13
Polyisobutene (1.0 g, 10 parts per weight, molecular weight 1000 g/mol) ,
polyisobuteneamine
(5.85 g, 58.5 parts per weight) and n-paraffin C5-C20 (3.15 g, 31.5 parts per
weight) were
mixed in a 25m1 glass vial and stirred at low shear with a magnetic stirrer
bar. The composition
is a homogeneous, clear and stable solution.
Example: Polyisobutene Premix PM14
Polyisobutene (24.0 g, molecular weight 1000 g/mol) and polyisobutene succinic
anhydride (
12.0 g) were mixed in a 25m1 glass vial and stirred at low shear with a
magnetic stirrer bar. The
mixture is heated to 80 C to reduce viscosity and thus simplify mixing. A
mixture of nonionic
surfactant C10-Guerbetalcohol alkoxylate (H LB 12.5) (4.0 g) and water (2.0 g)
is added and the
mixture is stirred for 30 min, yielding an emulsifiable polyisobutene
composition in the form of a
homogeneous clear stable solution.
Example: Polyisobutene Premix PM15
Polyisobutene (24.0 g, molecular weight 1000 g/mol) and polyisobutene succinic
anhydride
(12.0 g) were mixed in a 25m1 glass vial and stirred at low shear with a
magnetic stirrer bar. The
mixture is heated to 80 C to reduce viscosity and thus simplify mixing.
Nonionic surfactant C10-
Guerbetalcohol alkoxylate (HLB 12.5) (4.0 g) is added and the mixture is
stirred for 5min. Sub-
sequently, water (2 g) is added and the mixture is stirred for another 5 min,
yielding an emulsifi-
yable polyisobutene composition in the form of a homogeneous clear stable
solution.
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Examples of Formulations (F) of Polyisobutylene Premixes in Liquid Detergents
The cleaning and/or treatment compositions of the present invention can be
formulated into any
suitable form and prepared by any process chosen by the formulator, non-
limiting examples of
which are described in U.S. 5,879,584; U.S. 5,691,297; U.S. 5,574,005; U.S.
5,569,645; U.S.
5,565,422; U.S. 5,516,448; U.S. 5,489,392; U.S. 5,486,303 all of which are
incorporated herein
by reference.
Preparation of a Standard Liquid Detergent Formulation (A):
Liquid detergent fabric care compositions of Example A were made by mixing
together the in-
gredients listed in the proportions shown;
Ingredient (wt%) A
C12-C15 alkyl polyethoxylate (1.8) sulfatel 20.1
C12 alkyl trimethyl ammonium chloride4 2.0
C12-C14 alcohol 9 ethoxylate3 0.8
Monoethanolamine 2.5
Na cumenesulfonate 1.8
Cu_Cis Fatty Acid5 1.0
Citric acid8 3.4
Protease (52g/L) 0.35
Fluorescent Whitening Agent8 0.08
Diethylenetriamine pentaacetic acid8 0.5
Ethoxylated polyamine8 0.6
Water, perfumes, dyes, buffers, solvents and other optional com- to 100%
ponents pH 8.0-8.2
1 Available from Shell Chemicals, Houston, TX.
2 Available from Sasol Chemicals, Johannesburg, South Africa
4 Available from Evonik Corporation, Hopewell, VA.
5 Available from The Procter & Gamble Company, Cincinnati, OH.
6 Available from Sigma Aldrich chemicals, Milwaukee, WI
7 Available from Genencor International, South San Francisco, CA.
8 Available from Ciba Specialty Chemicals, High Point, NC
9 600 g/mol molecular weight polyethylenimine core with 20 ethoxylate groups
per -NH and
available from BASF (Ludwigshafen, Germany)
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Example F1:
Liquid detergent formulation A (97.80 g) was placed in a 150 ml glass beaker
and stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene Premix PM1 (2.20 g) was
slowly added
to the detergent formulation upon stirring. The resulting turbid polyisobutene
containing formula-
5 tion was stirred for another 30 min to form a homogeneous, clear and
stable formulation.
Examples F2 ¨F8:
The following examples, summarized in Table 1 were prepared in the same way as
described in
Example F1, applying the polyisobutene premixes and amounts given in the
table. The charac-
10 teristics of the formulation are also described in table 1.
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Table 1
75i
o <
c
E
o c D
-5 O - "E) 0) µ= -...
_a
- 5, E S
o E = ¨
o E a) E
co
x TD 2 E t E 2 2- t
L LI Ci_ Ci_ <u- <O- < U-
F1 PM1 97.8 2.2 Clear, homogeneous
F2 PM2 97.8 2.2 Clear, homogeneous
F3 PM3 97.7 2.3 Clear, homogeneous
F4 PM4 97.8 2.2 Clear, homogeneous
F5 PM5 97.9 2.1 Clear, homogeneous
F6 PM6 97.8 2.2 Clear, homogeneous
F7 PM7 97.8 2.2 Clear, homogeneous
F8 PM8 97.7 2.3 Clear, homogeneous
F9 PM9 97.8 2.2 Clear, homogeneous
F10 PM10 97.9 2.1 Clear, homogeneous
F12 PM11 98.0 2.0 Slightly turbid, Transmittance = 82%
F13 PM12 98.0 2.0 Clear, homogeneous
F14 PM13 98.0 2.0 Clear, homogeneous
Comparative Example CF1:
Liquid detergent formulation A (98.0 g) was placed in a 150 ml glass beaker
and stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene (2.0 g, molecular
weight = 1000 g/mol)
was slowly added to the detergent formulation upon stirring. The resulting
turbid polyisobutene
containing formulation was stirred for another 30 min to form a phase-
separated turbid mixture
with a ring of polyisobutene on top of the liquid level.
Examples of Formulations (F) of Polyisobutylene Premixes in Liquid Fabric
Enhancers:
Preparation of a Standard Liquid Fabric Enhancer Formulation (B):
Rinse-Added fabric care compositions were prepared by mixing together
ingredients shown
below:
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Ingredient B
Fabric Softener Activel 11.0
Lutensol XL-702 1.0
Quaternized polyacrylamide4 0.25
Calcium chloride3 0.15
Ammonium chloride3 0.1
Alkyl siloxane polymer6 1.5
Perfume 1.75
Perfume microcapsule5 0.69
Water, suds suppressor, stabilizers, pH control agents, buffers, to 100% pH
= 3.0
dyes & other optional ingredients
1 N,N-di(tallowoyloxyethyl) ¨ N,N dimethylammonium chloride available
from Evonik Corpora-
tion, Hopewell, VA.
2 Available from BASF (Ludwigshafen, Germany)
3 Available from Sigma Aldrich chemicals, Milwaukee, WI
4 Cationic polyacrylamide polymer such as a copolymer of acrylamide/[2-
(acryloylamino)ethyl]tri-methylammonium chloride (quaternized dimethyl
aminoethyl acry-
late) available from BASF, AG, Ludwigshafen under the trade name Sedipur 544.
5 Available from Appleton Paper of Appleton, WI
6 Aminofunctional silicone available from Shin-Etsu Silicones, Akron, OH
Example F15:
Fabric softener formulation B (98.0 g) was placed in a 100 ml glass beaker and
stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM11 (2.0 g) was
slowly added
to the fabric softener formulation upon stirring. The resulting polyisobutene
containing fabric
softener formulation was stirred for another 30 min to form a homogeneous
stable formulation
that did not show any signs of phase separation.
Example F16:
The example is prepared analogous to Example F15, with the difference that the
Polyisobutene
premix PM11 is colored with a red, oil-soluble and water-insoluble dye (Sudan
Red 7B, Sigma-
Aldrich, 20 ppm) and the liquid fabric enhancer is colored with a blue, water-
soluble and oil-
insoluble dye (Liquitint Blue, Milliken, 20 ppm). The resulting polyisobutene
containing formula-
tion exhibited a homogeneous, violet color as a result of the perfect
emulsification of the water
phase and the oil phase, showing not sign of creaming / sedimentation (i.e. no
clear blue aque-
ous phase on top or bottom), as well as not sign of phase separation (i.e. no
red oil phase or
red oil droplets observable).
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Example F17:
Fabric softener formulation B (98.0 g) was placed in a 100 ml glass beaker and
stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (2.0 g) was
slowly added
upon stirring. The resulting polyisobutene containing fabric softener
formulation was stirred for
another 30 min to form a homogeneous stable formulation that did not show any
signs of phase
separation.
Example F18:
The example was prepared analogous to Example F17, with the difference that
the Polyisobu-
tene premix PM5 is colored with a red, oil-soluble and water-insoluble dye
(Sudan Red 7B,
Sigma-Aldrich, 20 ppm) and the liquid fabric enhancer is colored with a blue,
water-soluble and
oil-insoluble dye (Liquitint Blue, Milliken, 20 ppm). The resulting
polyisobutene containing formu-
lation exhibited a homogeneous, violet color as a result of the perfect
emulsification of the water
phase and the oil phase, showing not sign of creaming / sedimentation (i.e. no
clear blue aque-
ous phase on top or bottom), as well as not sign of phase separation (i.e. no
red oil phase or
red oil droplets observable).
Comparative Example CF2:
Fabric softener formulation B (98.0 g) that is colored with a blue, water-
soluble and oil-insoluble
dye (Liquitint Blue, Milliken, 20 ppm) was placed in a 100 ml glass beaker and
stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene (2.0 g, 1000 g/mol),
colored with a red,
oil-soluble and water-insoluble dye (Sudan Red 7B, Sigma-Aldrich, 20 ppm) was
slowly added
to the fabric softener formulation upon stirring. The resulting polyisobutene
containing formula-
tion was stirred for another 30 min to form a clearly phase-separated product
consisting of a
polyisobutene phase forming a red-colored ring at the top of the liquid level
and a liquid fabric
enhancer phase forming a blue aqueous phase.
Examples of Formulations (F) of Polyisobutylene Premixes in Hand Dishwash
Formulations:
Standard Liquid Hand Dishwash Formulation:
The following are non-limiting examples of Liquid Hand Dish Wash formulation
compositions
prepared by mixing together ingredients shown below.
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Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Ex. 9
Lial AE0.6S 25.4 25.4 25.4
AE3S 12.0 28.7
Lial 31.7
39.6 44.4 52.3
AExS 13.0 13.0 13.0 16.3
20.4 22.8 26.9
AO 3.2 3.2 3.2 4.0 3.3 3.8 4.7 5.3
6.3
TMBA 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06
HEDP 0.1 0.1 0.1 0.1 0.1 0.1 0.1
0.1
Ethanol 3.0 3.0 3.0 3.0 3.0 2.5 2.5 2.5
2.5
NaCI 1.0 1.0 1.0 1.0 1.0 1.0 1.0
1.0
Polypropyleneglycol 0.4 0.5 0.5 0.5
0.5
Sodium citrate 5
Water, suds suppressor, stabilizers, pH control agents,
buffers, dyes & other optional ingredients
To 100%
Lial AE0.6S - anionic alkyl(ether)0.6sulphate surfactant and amine oxide
AE3S - anionic alkyl(ether)3sulphate surfactant and amine oxide
Lial - commercially available light duty liquid paste from Sasol containing
anionic AES surfac-
tant and amphoteric amine oxide
AExS - 010-018 alkyl alkoxy sulphate surfactants wherein preferably x is from
1-30
AO - total quantity of amine oxides in final product
TMBA is trim ethoxy benzoic acid
HEDP is 1-hydroxyethylidene 1,1-diphosphonic acid
Example F19:
The hand dishwash formulation (50 g) was placed in a 100 ml glass beaker and
stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 (1.1 g) was
slowly added
upon stirring. The resulting polyisobutene containing formulation was stirred
for another 30 min
to form a slightly turbid, homogeneous liquid.
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Example F20:
The hand dishwash formulation (50 g) was placed in a 100 ml glass beaker and
stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM2 (1.1 g) was
slowly added
5 upon stirring. The resulting polyisobutene containing formulation was
stirred for another 30 min
to form a turbid, homogeneous liquid.
Example F21:
The hand dishwash formulation (50g) was placed in a 100 ml glass beaker and
stirred with a
10 mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (1.54
g) was slowly added
upon stirring. The resulting polyisobutene containing formulation was stirred
for another 30 min
to form a clear homogeneous liquid.
Comparative Example CF3:
15 The hand dishwash formulation (50g) was placed in a 100 ml glass beaker
and stirred with a
mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular weight 1000
g/mol, 1.0 g)
was slowly added upon stirring. The resulting polyisobutene containing
formulation was stirred
for another 30 min to form a turbid liquid with clearly phase separated
droplets of polyisobutene
on top of the liquid.
Examples of Formulations (F) of Polyisobutylene Premixes in Cosmetic
Formulations:
Standard Shampoo and Bodywash Formulation:
Cocoamidopropylbetaine (12.5 g, 29.5 % active in water) and sodium laureth
sulfate (35.7 g, 29
% active) were mixed with demineralized water (51.8 g) to form a standard
shampoo or body-
wash formulation. The product can be thickened with 1.0 g of sodium chloride.
Example F22
The standard shampoo and bodywash formulation (50 g) was placed in a 100 ml
glass beaker
and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene
premix PM1 (1.1 g)
was slowly added upon stirring. The resulting polyisobutene containing
formulation was stirred
for another 30 min to form a turbid, homogeneous liquid.
Example F23
The standard shampoo and bodywash formulation (50 g) was placed in a 100 ml
glass beaker
and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene
premix PM2 (1.1 g)
was slowly added upon stirring. The resulting polyisobutene containing
formulation was stirred
for another 30 min to form a turbid, homogeneous liquid.
Example F24
The standard shampoo and bodywash formulation (50 g) was placed in a 100 ml
glass beaker
and stirred with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene
premix PM13 (1.54 g)
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was slowly added upon stirring. The resulting polyisobutene containing
formulation was stirred
for another 30 min to form a slightly turbid liquid that shows slight creaming
upon storage.
Comparative Example CF4:
The standard body wash formulation (50 g) was placed in a 100 ml glass beaker
and stirred
with a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular
weight 1000, 1.0 g)
was slowly added upon stirring. The resulting polyisobutene mixture was
stirred for another 30
min to form a turbid inhomogeneous liquid that instantaneously shows creaming.
Examples of Formulations (F) of Polyisobutylene Premixes in Car Wash
Formulations:
Standard Car Wash Shampoo for Home Use:
Dodecylbenzenesulfonate amine salt (20 g, 55% active in water), C10-
Guerbetalcohol+7E0
(HLB 12.5) (2 g, 100% active) and alkylpolyglucoside (2 g, 70% active) were
mixed with water
(76 g) to form a standard car shampoo formulation for home users.
Example F25:
The standard car wash formulation (50 g) was placed in a 100 ml glass beaker
and stirred with
a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM1 (1.1 g)
was slowly added
upon stirring. The resulting polyisobutene containing formulation was stirred
for another 30 min
to form a slightly turbid, homogeneous liquid.
Example F26:
The standard car wash formulation (50 g) was placed in a 100 ml glass beaker
and stirred with
a mechanical cross-bar stirrer at 325 rpm. Polyisobutene premix PM13 (1.54 g)
was slowly add-
ed upon stirring. The resulting polyisobutene containing formulation was
stirred for another 30
min to form an opaque homogenous liquid.
Comparative Example CF5:
The standard car wash formulation (50 g) was placed in a 100 ml glass beaker
and stirred with
a mechanical cross-bar stirrer at 325 rpm. Polyisobutene (molecular weight
1000 g/mol, 1.54 g)
was slowly added upon stirring. The resulting polyisobutene containing
formulation was stirred
for another 30 min to form an inhomogenous, turbid liquid that instantaneously
showed cream-
ing and phase separation.
Conductivity measurememts:
Conductivity is measured at room temperature with a conductometer "LF 320" of
"Wis-
sentschaftlich-Technische Werkstatten GmbH". The measurement probe is a
TetraCon 325 with
a cell constant of 0.466 cm-1.
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Sample
Conductivity [p5/cm]
Distilled Water (Lab) 8.0
C10-Guerbetalcohol alkoxylate (HLB 12.5) 0.4
C13-oxoalcohol + 3 BO (HLB 9) 0.4
C13-oxoalcohol + 8 BO (HLB 13) 0.4
Polyisobutene amine (PIBA) 0.1
Polyisobutene (PIB, MW 1000) 0.2
Polyisobutene Succinic Anhydride (PIBSA) 0.2
Premix PM1 0.2
Premix PM2 0.2
Premix PM5 0.2
Premix PM5 + 5% Water 0.2
Premix PM5 + 10% Water 0.2
As can be seen from the measurements, all premixes display the same
conductivity as the hyd-
rophobic components such as PIB or PIBA, showing that water is not the
continuous phase in
these premixes.
