Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ 94/01520 2 1 3 9 3 5 9 PCT/US93/06086
"Concentrated Aqueous Liquid Detergent Comprising Poiyviny!pyrrolidonen
Technical Field
The present invention relates to concentrated aqueous
liquid detergent composi~ions containing polyvinyl-
pyrrolidone, in which the anionic surfactant majorily
consists of an alkyl ethoxy sulfate salt~
Backqround of the inven~
.
It is widely known in the art to use various polymers in
liquid detergent compositions. The use of polyvinyl
pyrrolidone in detergent compositions, mainly for fabric care
properties, has been described for instance in EP 262 897,
EP 327 927 and EP 203 486. These documents encompass the use :-~
of polyvinylpyrrolidone in liquid detergent compositions. .:
A new trend in the field of detergent compositions is the
formulation of so-ca'led concentrated detergents. In the :~
context of liquid aqueous detergents, this refers to products ~:;
comprising less water and a higher total amount of active
ingredients.
i~
SUBSTlTUtE SHEET ~;
WO94/01520 2 ~ 3 9 3 5 ~ PCT/US93/060~
There is a need to provide concentrated detergent
compositions which are able to provide superior color
maintenance to the washed colored fabrics, that is
compositions wherein polyvinylpyrrolidone provides an optimum
efficiency as a dye transfer inhibitor agent.
It has now surprisingly been found that such an optimum
efficiency of polyvinylpyrrolidone can be achieved in the
present concentrated aqueous liquid detergent matrix, when
the anionic surfactant in said matrix majorily consists of-an
alkyl ethoxy sulfate salt.
~ It has also been found that such a surfactant system
improves stability of enzymes such as cellulase, in presence
of protease.
:
; ~ Summary of the Invention
.
r.~:;
The present invention is directed to liquid detergent
compositions comprising an anionic surface-active agent, and
from 2% to 35% by weight of the total composition of water,
characterized in that the anionic surfactant contains at
least 70%, preferably from 75% to 100% by weight of a water-
soluble C~ s alkyl ethoxy sulfate salt containing an
average per mole of from l to 9 ethoxy groups and that the
composition comprises from 0.05% to 5% by weight of the total
composition of polyvinylpyrrolidone.
The compositions preferably contain less than 6% by weight
of the total composition of alkyl benzene sulfonate salt or
non-ethoxylated alkyl sulfate salt.
SUBSTITUTE SHEET
'094/01520 ' 2 1 3 9 3 5 9 PCTIUS93/06086
Detailed DescriPtion of the Invention
The compositions according to the present invention are
concentrated liquid detergents which comprise from 2% to 35
by weight of the total composition of water.
Preferred compositions according to the present invention
comprise from 5% to 25% by weight of the total composition of
water.
The compositions according to the invention contain from
0.05% to 5% by weight of polyvinlypyrrolidone, preferably
from 0.25% to 2%. Preferred polyvinylpyrrolidone for use
herein have a molecular weight of from lO00 to lO0,000,
preferably from 2500 to 30,000, most preferably from 5000 to ~-~
15, 000. '
The compositions according to the present invention
comprise a surfactant, and in particular an anionic surface
active agent.
In the compositions of the present invention, it is '`
essential that the anionic surfactant (hereafter meant as not
including soaps) contains at least 70% by weight of said
anionic surfactant, of a water soluble C~ s alkyl ethoxy ;~
sulfate salt containing an average of from l to 9 ethoxy
groups per mole.
The Cll-Cl5 alkyl ethoxy sulfate salt herein comprises a
primary alkyl ethoxy sulfate derived from the condensation ~ `~
product of a Cll-Cls alcohol with an average of up to 9 ~
ethylene oxide groups. Cl3-Cls alkyl ethoxy sulfate with an t ;`
average of two to three ethoxy groups per mole is preferred.
The Cll-Cl5 alcohol itself can be obtained from natural or
synthetic sources. Thus, Cll-Cls alcohols, derived from
SUBSTITUTE SHEE~
WO94/~1520 ~13 9~3 5 9 PCT/US93/060&
natural fats, or Ziegler olefin build-up, or OXO synthesis
can form suitable sources for the alkyl group. Examples of
synthetically derived materials include Dobanol 23 (RTM) sold
by Shell Chemicals (UK) Ltd., Ethyl 24 sold by the Ethyl
Corporation, a blend of Cl3-Cl5 alcohols in the ratio 67%
Cl3 33% Cl5 sold under the trade name Lutensol by BASF GmbH
and Synperonic (RTM) by ICI Ltd., and Lial 125 sold by
Liquichimica Italiana. Examples of naturally occurring
materials from which the alcohols can be derived are coconut
oil and palm kernel oil and the corresponding fatty acids.
The alkyl ethoxy sulfate salts are preferably present in
the compositions herein at levels of from 75% to 100% by
weight of the anionic surfactant system. The anionic
surfactant system may contain other types of surface-active
agents, although in minor quantities; in particular, the
present detergent compositions should contain less than 6% by
weight of the to~al composition of alkyl benzene sulfonates
and non-ethoxylated alkyl sulfates such as Cl2_l4 primary
alkyl sulfate salts;
Other anionic co-surfactants which may be present in minor
quantities in the present compositions include Cl2-Cl8 s-
alkane sulfonates and alpha-sulphonated methyl-fatty acid
esters in which the fatty acid is derived from a Cl2-Cl8
fatty source.
Other suitable co-anionic surfactants suitable for the
compositions herein are the alkali metal sarcosinates of
formula
R-CON (R) CH2COOM
wherein R is a Cg-Cl7 linear or branched alkyl or alkenyl
group, R' is a Cl-C4 alkyl group and M is an alkali metal
ion. Preferred examples are the lauroyl, Cocoyl (Cl2-Cl4),
myristyl and oleyl methyl sarcosinates in the form of their
sodium salts.
SUBSTITUTE SHEET
~'094/01520 Z~ 3~g PCI/US93/06086
The present compositions preferably also contain a nonionic
surfactant in combination with the alkyl ethoxy sulfate salts
herein;
Preferred nonionic surfactants for use herein are
polyhydroxy fatty acid amides of the formula !.
~2-C - N-Z,
Il I
O Rl
wherein R1 is H, C1_4 hydrocarbyl, 2 hydroxy ethyl, 2-hydroxy
propyl or a mixture thereof, R2 is C5_31 hydrocarbyl, and æ
is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or
~an alkoxylated derivative thereof. Preferably, R1 is methyl,
R2 is a straight C~ 5 alkyl or alkenyl chain or mixtures
thereof, and Z is derived from a reducing sugar such as
glucose, fructose, maltose, lactose, in a reductive amination
reaction. Preferred are C12 or C12-14 glucSamides
Other preferred nonionic surfactants suitable for use
herein include those produced by condensing ethylene oxide
with a hydrocarbon having a reacti~e hydrogen atom, e.g., a
hydroxyl, carboxyl, or amido group, in the presence of an
acidic or basic catalyst, and includ compounds having the
general formula RA(CH2CH20)nH wherein R represents the
hydrophobic moiety, A represents the group carrying the
reactive hydrogen atom and n represents the average number of
ethylene oxide moieties. R typically contains from about 8
to 22 carbon atoms. They can also be formed by the
condensation of propylene oxide with a lower molecular weight
compound. n usually varies from about 2 to about 24.
. . .
A preferred class of such nonionic ethoxylates is ~. ~
represented by the condensation product of a fatty alcohol j ~`
having from 12 to 15 carbon atoms and from about 4 to 10
moles of ethylene oxide per mole or fatty alcohol. Suitable '
species of this class of ethoxylates include : the -~
condensation product of C12-C15 oxo-alcohols and 3 to 9 moles
SUBSrITUTE SHEET
WO94/01~2~ 2 1 3 9 3 ~ 9 PCT/US93/0608t-
of ethylene oxide per mole of alcohol; the condensation
product or narrow cut C14-C15 oxo-alcohols and 3 to g moles
of ethylene oxide per mole of fatty(oxo)alcohol; the
condensation product of a narrow cut Cl2-C13
fatty(oxo)alcohol and 6,5 moles of ethylene oxide per mole of
fatty alcohol; and the condensation products of a C10-Cl4
coconut fatty alcohol with a degree of ethoxylation (moles
EO/mole fatty alcohol) in the range from 4 to 8. The fatty
oxo alcohols while mainly linear can have, depending upon the
processing conditions and raw material olefins, a certain
degree of branching, particularly short chain such as methyl
branching. A degree of branching in the range from 15% to
50% ~weight%) is frequently found in commercial oxo alcohols.
Another class of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
RO(cnH2nO)tzx
wherein Z is a moiety derived from glucose; R is a saturated
hydrophobic alkyl group that contains from 12 to 18 carbon
atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4,
the compounds including less than 10~ unreacted fatty alcohol
and less than 50% short chain alkyl polyglucosides.
Compounds of this type and their use in detergent
compositions are disclosed in EP-B 0 070 074,
0 070 077, 0 075 996 and O 094 118.
The surfactant system herein may also contain types of
surfactants other than anionic and nonionic species.
Suitable cationic surfactants include quaternary ammonium
compounds of the formula R1R2R3R4N+ where R1, R2 and R3 are
methyl groups, and R4 is a C12_1s alkyl group, or where Rl is
an ethyl or hydroxy ethyl group, R2 and R3 are methyl groups
and R4 is a C12-15 alkyl group.
SUBSTITUTE SI~EE~
~094/01520 2 1 3 9 3 5 9 PCT/US93/06086
Zwitterionic surfactants include derivatives of aliphatic 5
quaternary ammonium, phosphonium, and sulfonium compounds in
which the aliphatic moiety can be straight or branched chain
and wherein one of the aliphatic substituents contains from
about 8 to about 24 carbon atoms and another substituent
contains, at least, an anionic water-solubilizing group.
Particularly preferred zwitterionic materials are the
ethoxylated ammonium sulfonates and sulfates disclosed in
U.S. Patents 3,92S,262, Laughlin et al., issued December 9,
1975 and 3,929,678, Laughlin et al., issued December 30,
197S. ~
: ' :
Semi-polar nonionic surfactants include water-soluble amine
oxides containing one alkyl or hydroxy alkyl moiety of from
about 8 to about 28 carbon atoms and two moieties selected ~-
from the group consisting of alkyl groups and hydroxy alkyl
groups, containing from 1 to about 3 carbon atoms which can
optionally be joined into ring structures.
The present concentrated detergent compositions typically i
contain from 25% to 45%, preferably 30% to 40% by weight of
surfactant of which the weight ratio of anionic surfactant to
nonionic surfactant is typically of 3:1 to 1:1, more
preferably 2:1 to 1:1.
The ccmpositions according to the present invention may
further comprise a builder. Any conventional builder system i~
is suitable for use herein including polycarboxylates and
fatty acids, materials such as ethylenediamine tetraacetate,
metal ion sequestrants such as aminopolyphosphonates,
particularly ethylenediamine tetramethylene phosphonic acid
and diethylene triamine pentamethylenephosphonic acid.
Though less preferred for obvious environmental reasons,
phosphate builders can also be used herein.
SUBSTITUTE SHEET
W094tO1~20 - 2 1 ~ 9 3:~ 9 PCT/US93/06081 -
Suitable polycarboxylates builders for use herein include
citric acid, preferably in the form of a water-soluble salt,
derivatives of succinic acid of the formula R-
CH(COOH)CH2(COOH) wherein R is C10_20 alkyl or alkenyl,
preferably C12_16, or wherein R can be substituted with
hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific
examples include lauryl succinate, myristyl succinate,
palmityl succinate, 2-dodecenylsuccinate, 2-tetradecenyl
succinate. Succinate builders are preferably used in the
form of their water-soluble salts, including sodium,
potassium, ammonium, and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and
mixtures of tartrate monosuccinic and tartrate disuccinic
acid such as described in US 4,663,071.
Suitable fatty acid builders for use herein are saturated
or unsaturated C10_18 fatty acids, as well as the
corresponding soaps. Preferred saturated species have from
12 to 16 carbon atoms in the alkyl chain. The preferred
unsaturated fatty acid is oleic acid.
A preferred builder system for use herein consists of a
mixture of citric acid, fatty acids and succinic acid
derivatives described hereinabove. The builder system
according to the present invention preferably represents from
5% to 35~ by weight of the total composition.
The compositions according to the invention preferably
comprise enzymes. Suitable enzymes for use herein are
protease, lipases, cellulases, and amylases and mixtures
theréof.
SUBSTIT~JTE SHEEr
` 094/01520 2 1 3 9 3 5 9 PCT/US93/06086 '
The compositions according to the present invention may
still advantageously comprise an enæyme stabilizing system,
although at reduced levels as compared to compositions where
alkyl benzene sulfonate and/or non-ethoxylated alkyl sulfate
salts are present in majority. Any conventional enzyme
stabilizing system is suitable for use herein, and preferred
enzyme stabilizing systems are based on boric acid or
derivatives thereof, 1,2-propanediol, carboxylic acids such
as formic acid/formate, and mixtures thereof.
It has been found that the anionic surfactant system of the
present invention provides improved stability of enzymes such
as cellulase in presence of a protease.
~ .
The compositions~herein can also advantageously contain a
terephthalate-based soil release polymer at levels of from
0.05% to 2~ of the total composition.
Such soil release polymers have been extensively described
in the art, for instance in US 4,116,885, `
US 4,132,680, EP 18S 427, EP 199 403, EP 241 985 and EP 241
984.~
The compositions herein can contain a series of further
optional ingredients. Examples of the like additives include
solvents, alkanolamines, pH adjusting agents, suds regulants,
opacifiers, agents to improve the machine compatibility in
relation to enamel-coated surfaces, perfumes, dyes,
bactericides, brighteners, softening agents and the like.
The present invention is further illustrated in the
following examples.
.
S~JBSTIT-JTE SHEET
_,,," .,,, ,,.,~
WO 94/01520 ` . , PCI`/US93/0608f
2139359
~o
Examples
The following compositions were prepared :
(weight % in formula) exam~le 1 ~3mE
C13-15 Alkyl 3 ethoxylated sulfate23 18
C13-15 alcohol 7 ethoxylated 6 5
C12-14 N-methyl glucosamide 9 9
Builders 16 17
Ethanol 2 2
1,2 Propane diol 13 10
Mono ethanolamine 13 13
Protease 1.8 0.8
C~!llulase 0.15 0.15
Sodium Formate - 1~0
Boric acid 2.5 ~.o
Polyvinylpyrrolidone* 0.5 0.5
Water 8 18
Minors to 100 %
* Molecular weight 5000 - 15000, marketed under name GAFTEX
AE K15, by ISP
SUBSTIT~TE SHEEl-
