Technical Field
[0001] The present invention relates to stable liquid detergent compositions inhibiting
dye transfer
Background of the Invention
[0002] Optical brighteners, also known as fluorescent whitening agents, are commonly used
in laundry detergents. Brighteners deposit onto fabrics where they absorb ultraviolet
radiant energy and reemit it as blue light. This reduces or eliminates any yellowish
cast to fabrics and gives them a bright appearance. However, it has been found to
be difficult to create and maintain the brightener dispersed in liquid detergent compositions
containing polymers which exhibit dye transfer inhibiting properties. These polymers
are used to complex or absorb the fugitive dyes washed out of dyed fabrics before
they have the opportunity to become attached to other articles in the wash.
[0003] Such polymers that have been used within detergent compositions to inhibit dye transfer
are disclosed in EP-A-O 102 923, DE-A-2 814 329, FR-A-2 144 721 and EP-265 257.
[0004] Copending EP Patent Application 92202168.8 describes dye transfer inhibiting compostions
comprising polyamine N-oxides containing polymers.
[0005] Surprisingly, it has now been found that improved storage stability of liquid detergent
compositions comprising polyamine N-oxide containing polymers and brightener can be
achieved by adding non-aromatic anionic surfactants.
[0006] According to the present invention, a dye transfer inhibiting composition comprising
a brightener is provided which has improved stability upon storage.
Summary of the Invention
[0007] The present invention relates to inhibiting dye transfer compositions comprising
(a) from 0.01 % to 5% of a polyamine N-oxide containing polymer
(b) from 0.01 % to 1% of a brightener
(c) from 5% to 30% of a non-aromatic anionic surfactant
Detailed description of the invention
[0008] The compositions of the present invention comprise as essential elements
(a) from 0.01 % to 5% of a polyamine N-oxide polymer
(b) from 0.01 % to 1% of a brightener
(c) from 5% to 30% of a non-aromatic anionic surfactant
(a) Polyamine N-oxide containing polymers
[0009] The polyamine N-oxide polymers contain units having the following structure formula
:
wherein
P is a polymerisable unit, whereto the N-O group can be attached to or wherein the
N-O group forms part of the polymerisable unit or a combination of both.
A is
x is or 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups
or any combination thereof whereto the nitrogen of the N-O group can be attached or
wherein the nitrogen of the N-O group is part of these groups.
[0010] The N-O group can be represented by the following general structures :
wherein
R1, R2, R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations
thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can
be attached or wherein the nitrogen of the N-O group forms part of these groups.
[0011] The N-O group can be part of the polymerisable unit (P) or can be attached to the
polymeric backbone or a combination of both.
[0012] Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable
unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic
or heterocyclic groups.
[0013] One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein
the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole,
pyrrolidine, piperidine and derivatives thereof. Another class of said polyamine N-oxides
comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group is
attached to the R-group.
[0014] Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group
is attached to the polymerisable unit.
[0015] Preferred class of these polyamine N-oxides are the polyamine N-oxides having the
general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-0 functional group is part of said R group.
[0016] Examples of these classes are polyamine oxides wherein R is a heterocyclic compound
such as pyrridine, pyrrole, imidazole and derivatives thereof.
[0017] Another preferred class of polyamine N-oxides are the polyamine oxides having the
general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-0 functional group is attached to said R groups.
[0018] Examples of these classes are polyamine oxides wherein R groups can be aromatic such
as phenyl.
[0019] Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble
and has dye transfer inhibiting properties. Examples of suitable polymeric backbones
are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates
and mixtures thereof.
[0020] The amine N-oxide polymers of the present invention typically have a ratio of amine
to the amine N-oxide of 10 : 1 to 1: 1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by appropriate copolymerisation
or by appropriate degree of N-oxidation . Preferably, the ratio of amine to amine
N-oxide is from 3:1 to 1:1000000. The polymers of the present invention actually encompass
random or block copolymers where one monomer type is an amine N-oxide and the other
monomer type is an N-oxide or not.
[0021] The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7,
more preferred PKa < 6. The polyamine oxides can be obtained in almost any degree
of polymerisation. The degree of polymerisation is not critical provided the material
has the desired water-solubility and dye-suspending power.
[0022] Typically, the average molecular weight is within the range of 500 to 1000,000 ;
more preferred 1000 to 500,000 ; most preferred 5000 to 100,000.
[0023] The polyamine N-oxides of the present invention are typically present from 0.01 to
10% , more preferably from 0.05 to 1 %, most preferred from 0.05 to 0.5 % by weight
of the dye transfer inhibiting composition.
B) Brightener
[0024] Preferred brighteners according to the present invention are hydrophobic brighteners
which have the general formula:
wherein R
i, R
2, R
3 and R
4 represent, selected independently, anilino, cyclohexylamino, piperazino, phenylenediamino,
toluenediamino, morpholino, aminophenol, N-2-hydroxyethyl-N-methylamino, N-2-Bis-
hydroxyethyl.
[0025] Suitable brightener species include any combination of the possible Ri-4. moieties.
Examples of preferred brightener species are the tetra-anilino, tetra-piperazino,
tetra-cyclohexylamino and combinations thereof such as for example the di-anilinodipiperazino;
and the dianilino-dicyclohexylamino species.
[0026] Highly preferred for reasons of minimizing brightener staining are the tetraanilino
derivatives, having the following formula : 4,4' -bis (4-anilino-6-anilino-s-triazin-2-yl)amino)-2,2'-
stilbe ne disulfonic acid sodium salt (A). A preferred brightener system in the context
of this invention contains at least 40% (by reference to the total amount of the detergent
brightener) of the specific hydrophobic brightener referred to hereinbefore in combination
with a conventional detergent brightener, e.g., a di-sulfonated dianilino, dimorpholino
stilbene brightener.
[0027] Conventional detergent brighteners for use in combination with the hydrophobic species
described hereinabove embrace common detergent brighteners inclusives of:
4,4(2H-naphtho(1,2-d)triazol-2-yl)-2-stilbenesulfonic acid, sodium salt; (i)
4,41-bis((4-anilino-6(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino)-2,21-stilbenedisulfonic acid disodium salt; (ii)
4,41-bis((4-anilino-6-morpholino-s-triazine-2-yl)amino)-2,21-stilbenedisulfonic acid, sodium salt; (iii)
2,2-(4,41-biphenylene divinylene)-dibenzenesulfonic acid, disodium salt; (ivi)
4,41-bis(4-phenyl-2H-1,2,3-triazol-2-yl) disodium salt (vi)
4,41-bis(4-anilino-6-morpholino-1 ,3,5-triazin-2-yl)amino)-2-stilbene sulfonate sodium
salt. (vii)
C) Non-aromatic anionic surfactants
[0028] Non-aromatic anionic surfactants suitable for the present invention are generally
disclosed in US-A-3,929,678.
[0029] Classes of non-aromatic anionic surfactants include the classes are :
1. Ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium
salts of higher fatty acids containing from 8 to 24 carbon atoms, preferably from
10 to 20 carbon atoms.
2. Water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium
salts, of organic sulfuric reaction products having in their molecular structure an
alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric
acid ester group.
[0030] Examples of this group of anionic surfactants are the sodium and potassium alkylsulfates,
especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such
as those produced by reducing the glycerides of tallow or coconut oil; in straight
chain or branched configuration.
[0031] Other anionic surfactants suitable for the present invention are the alkyl polyethoxylate
sulfates, particulary those in which the alkyl group contains from 10 to 22, preferably
from 12 to 18 carbon atoms, and wherein the polyethoxylate chain contains from 1 to
15 ethoxylate moieties.
[0032] Other anionic surfactants suitable for the present invention include sodium alkyl
glyceryl ether sulfonates, especially those ethers of higher alcohols derived from
tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and
sulfates; sodium or potassium salts of alkyl ethylene oxide ether sulfates containing
1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains
from 10 to 20 carbon atoms.
[0033] Mixtures of anionic surfactants are particularly suitable herein, especially mixtures
of sulphonate and sulphate surfactants in a weight ratio of from 5:1 to 1:2, preferably
from 3:1 to 2:3, more preferably from 3:1 to 1:1. Preferred sulphonates include alpha-sulphonated
methyl fatty acid esters in which the fatty acid is derived from a C
12-Cl8 fatty source preferably from a C
16-C
18 fatty source. In each instance the cation is an alkali metal, preferably sodium.
Preferred sulphate surfactants are alkyl sulphates having from 12 to 18 carbon atoms
in the alkyl radical, optionally in admixture with ethoxy sulphates having from 10
to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree
of ethoxylation of 1 to 6. Examples of preferred alkyl sulphates herein are tallow
alkyl sulphate, coconut alkyl sulphate, and C14 -15 alkyl sulphates. The cation in
each instance is again an alkali metal cation, preferably sodium.
Detergent ingredients
[0034] In another embodiment of the present invention, a liquid detergent composition is
provided comprising the dye transfer inhibiting composition mixed with detergent ingredients.
A wide range of surfactants can be used in the detergent composition of the present
invention.
[0035] A typical listing of anionic, nonionic, ampholytic and switterionic classes, and
species of these surfactants, is given in US Patent 3,664,961 issued to Norris on
May 23, 1972.
[0036] One class of nonionic surfactants useful in the present invention are condensates
of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average
hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5
to 13.5, more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may
be aliphatic or aromatic in nature and the length of the polyoxyethylene group which
is condensed with any particular hydrophobic group can be readily adjusted to yield
a water-soluble compound having the desired degree of balance between hydrophilic
and hydrophobic elements.
[0037] Especially preferred nonionic surfactants of this type are the C
9-C
15 primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol,
particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oxide per
mole of alcohol and the C
12-C14 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
[0038] Another class of nonionic surfactants comprises alkyl polyglucoside compounds of
general formula
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 are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
[0039] Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants
of the formula
wherein R
1 is H, or R
1 is C
1 -
4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R
2 is C
s-
31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative
thereof. Preferably, R
1 is methyl, R
2 is a straight C11
1 -
15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived
from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive
amination reaction.
[0040] The compositions according to the present invention may further comprise a builder
system. Any conventional builder system is suitable for use herein including aluminosilicate
materials, silicates, 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.
[0041] Suitable builders can be an inorganic ion exchange material, commonly an inorganic
hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite
such as hydrated zeolite A, X, B or HS. Another suitable inorganic builder material
is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate
consisting of sodium silicate (Na
2Si
20
s). 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.
[0042] Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-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.
[0043] Especially for the liquid execution herein, 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. Another preferred builder system
for liquid compositions is based on dodecenyl succinic acid. Other suitable water-soluble
organic salts are the homo-or co-polymeric acids or their salts, in which the polycarboxylic
acid comprises at least two carboxyl radicals separated from each other by not more
than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples
of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride,
such copolymers having a molecular weight of from 20,000 to 70,000, especially about
40,000.
[0044] Detergency builder salts are normally included in amounts of from 10% to 80% by weight
of the composition preferably from 20% to 70% and most usually from 30% to 60% by
weight.
[0045] Other components used in detergent compositions may be employed, such enzymes and
stabilizers or activators therefore, soil-suspending agents soil-release agents, optical
brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents, and perfumes.
Especially preferred are combinations with enzyme technologies which also provide
a type of color care benefit. Examples are cellulase for color maintenance/ rejuvenation.
Other examples are the polymers disclosed in EP 92870017.8 filed January 31,1992 and
enzyme oxidation scavengers disclosed in EP 92870018.6 filed January 31, 1992.
[0046] Also particulary suitable are amine base catlyst stabilizers disclosed in EP 92870019.4
filed January 31, 1992.
[0047] These components, particularly the enzymes, optical brighteners, coloring agents,
and perfumes, should preferably be chosen such that they are compatible with the bleach
component of the composition.
[0048] The liquid compositions according to the present invention can also be in "compact
form", i.e. they may have a relatively higher density than conventional liquid detergents,
i.e. from 550 to 950 g/I; in such case, the liquid detergent compositions according
to the present invention will contain a lower amount of water, compared to conventional
liquid detergents.
[0049] The following examples are meant to exemplify compositions of the present inventions,
but are not necessarily meant to limit the scope of the invention.
Test procedure
[0050] To assess the stabilizing effect of the non-aromatic anionic surfactants , the stability
of the brightener and polyamine N-oxide containing polymer incorporated in liquid
detergent compositions were compared in the absence and presence of non-aromatic anionic
surfactants. More in particular, the stability of polyamine N-oxide polymer/brightener
was determined in the absence of ethoxylated surfactant and in the presence of ethoxylated
surfactant.
[0051] Similar measurements were made for samples wherein the polyamine N-oxide was replaced
by another dye transfer inhibiting polymer known in the art e.g polyvinylpyrrolidone.
[0052] The stability was determined by visual inspection of the samples after one month
of storage at room temperature/at 35
° C/50
° C and at 4
° C.
[0053] The following liquid detergent compositions were made :
[0054] Liquid detergent compositions according to the present invention, containing the
brightener/polyamine N-oxide/non-aromatic anionic surfactant system have a translucent
appearance.
[0055] In the abscence of non-aromatic anionic surfactants, the brightener starts to bind
with the polyamine N-oxide containing polymer resulting in a complex, which in turn
flocculates and changes the visual appearance of the bulk solution from translucent
to transparent. In the presence of non-aromatic anionic surfactant the brightener
remains homogeneously dispersed in the liquid, resulting in a translucent liquid even
after long periods of storage. Liquid detergent compositions containing the brigh-
tener/polyvinylpyrrolidone/non-aromatic anionic surfactant system have a transparent
appearance both in the presence or abscense of non-aromatic anionic surfactant.