FIELD OF THE INVENTION
[0001] The invention relates to liquid hand dishwashing detergent compositions, which comprise
quaternised acrylic copolymers and provide further improved drying times for the dishware
after rinsing.
BACKGROUND OF THE INVENTION
[0002] Manual dishwashing is a time-consuming task which is considered by many who do it
to be complete when they can put their dishware away. As such, fast drying of dishware
after dishwashing and rinsing is highly desired. Drying is particularly affected by
the water hardness, with reduced sheeting of the water off dishware with water having
lower hardness. With the greater prevalence of in-home water-softeners, there remains
a greater need for improving sheeting and hence drying speed.
[0003] The use of quaternised acrylic copolymers for improving the speed of drying is known.
Such copolymers increase the speed of drying by improving the sheeting of water off
the dishware and improving beading of the water.
[0004] However, it has been found that the performance of such copolymers in liquid detergent
compositions, which do not comprise an alkoxylated alcohol nonionic surfactant, has
been relatively poor, especially under soft water conditions. As such, there remains
a need to further improve the drying time after the manual washing of dishware, without
the need to formulate using high levels of alkoxylated alcohol nonionic surfactant.
[0005] WO201836864A relates to hard surface treatment compositions comprising quaternised acrylic copolymer
and amphoteric modified polysaccharide, wherein the weight ratio of the quaternised
acrylic copolymer to the amphoteric modified polysaccharide is from 0.75:1 to 3:1
and the quaternised acrylic copolymer is different from the amphoteric modified polysaccharide.
EP3835399A1 relates to hard surface cleaning composition comprising a surfactant system; a first
polymer; and a second polymer, the first polymer being a polyethyleneimine, as well
as to the use of the composition to clean a glass surfaces.
US20030134770A relates to liquid detergent compositions comprising a polymeric material which is
a suds enhancer and a suds volume extender, said compositions having increased effectiveness
for preventing re-deposition of grease during hand washing, the polymeric material
being suitable as suds volume and suds endurance enhancers and comprising an effective
amount of a quaternary nitrogen-containing monomeric unit and/or zwitterionic monomeric
unit-containing polymeric suds enhancer.
EP3835399A1 relates to a hard surface cleaning composition comprising a surfactant system; a
first polymer; and a second polymer, the first polymer being a polyethyleneimine.
SUMMARY OF THE INVENTION
[0006] The present invention relates to liquid hand dishwashing detergent composition comprising
a quaternised acrylic copolymer, and from 5.0% to 50% by weight of the liquid hand
dishwashing detergent composition of a surfactant system, wherein the surfactant system
comprises: anionic surfactant; and co-surfactant selected from the group consisting
of: amphoteric surfactant, zwitterionic surfactant, and mixtures thereof; wherein
the anionic surfactant and co-surfactant are present in a weight ratio of less than
1.5:1.
DETAILED DESCRIPTION OF THE INVENTION
[0007] Formulating the liquid cleaning composition with the surfactant system, as described
herein, in addition to a quaternised acrylic copolymer can be used improve the speed
of drying of dishware after hand dishwashing.
[0008] As used herein, articles such as "a" and "an" when used in a claim, are understood
to mean one or more of what is claimed or described.
[0009] The term "comprising" as used herein means that steps and ingredients other than
those specifically mentioned can be added. This term encompasses the terms "consisting
of" and "consisting essentially of." The compositions of the present invention can
comprise, consist of, and consist essentially of the essential elements and limitations
of the invention described herein, as well as any of the additional or optional ingredients,
components, steps, or limitations described herein.
[0010] The term "dishware" as used herein includes cookware and tableware made from, by
non-limiting examples, ceramic, china, metal, glass, plastic (e.g., polyethylene,
polypropylene, polystyrene, etc.) and wood.
[0011] The term "grease" or "greasy" as used herein means materials comprising at least
in part (i.e., at least 0.5 wt% by weight of the grease in the material) saturated
and unsaturated fats and oils, preferably oils and fats derived from animal sources
such as beef, pig and/or chicken.
[0012] The terms "include", "includes" and "including" are meant to be non-limiting.
[0013] The term "particulate soils" as used herein means inorganic and especially organic,
solid soil particles, especially food particles, such as for non-limiting examples:
finely divided elemental carbon, baked grease particle, and meat particles.
[0014] The term "sudsing profile" as used herein refers to the properties of a cleaning
composition relating to suds character during the dishwashing process. The term "sudsing
profile" of a cleaning composition includes initial suds volume generated upon dissolving
and agitation, typically manual agitation, of the cleaning composition in the aqueous
washing solution, and the retention of the suds during the dishwashing process. Preferably,
hand dishwashing cleaning compositions characterized as having "good sudsing profile"
tend to have high initial suds volume and/or sustained suds volume, particularly during
a substantial portion of or for the entire manual dishwashing process. This is important
as the consumer uses high suds as an indicator that enough cleaning composition has
been dosed. Moreover, the consumer also uses the sustained suds volume as an indicator
that enough active cleaning ingredients (e.g., surfactants) are present, even towards
the end of the dishwashing process. The consumer usually renews the washing solution
when the sudsing subsides. Thus, a low sudsing cleaning composition will tend to be
replaced by the consumer more frequently than is necessary because of the low sudsing
level.
[0015] It is understood that the test methods that are disclosed in the Test Methods Section
of the present application must be used to determine the respective values of the
parameters of Applicants' inventions as described and claimed herein.
[0016] All percentages are by weight of the total composition, as evident by the context,
unless specifically stated otherwise. All ratios are weight ratios, unless specifically
stated otherwise, and all measurements are made at 25°C, unless otherwise designated.
Liquid cleaning composition
[0017] The cleaning composition is a liquid cleaning composition, preferably a liquid hand
dishwashing cleaning composition, and hence is in liquid form. The liquid cleaning
composition is preferably an aqueous cleaning composition. As such, the composition
can comprise from 50% to 85%, preferably from 50% to 75%, by weight of the total composition
of water.
[0018] The liquid cleaning composition has a pH greater than 6.0, or a pH of from 6.0 to
12.0, preferably from 7.0 to 11.0, more preferably from 7.5 to 10.0, measured as a
10% aqueous solution in demineralized water at 20 degrees °C.
[0019] The liquid cleaning composition of the present invention can be Newtonian or non-Newtonian,
preferably Newtonian. Preferably, the composition has a viscosity of from 10 mPa·s
to 10,000 mPa·s, preferably from 100 mPa·s to 5,000 mPa·s, more preferably from 300
mPa·s to 2,000 mPa·s, or most preferably from 500 mPa·s to 1,500 mPa·s, alternatively
combinations thereof. The viscosity is measured at 20°C with a Brookfield RT Viscometer
using spindle 31 with the RPM of the viscometer adjusted to achieve a torque of between
40% and 60%.
Quaternised acrylic copolymer
[0020] The liquid hand dishwashing detergent comprises a quaternised acrylic copolymer.
"Copolymer" as used herein refers to a polymer comprising at least two different monomer
compositions. Quaternised polymers comprise quaternary ammonium groups, which are
positively charged polyatomic ions of the structure NR
4+, R being an alkyl group or an aryl group. Unlike the ammonium ion (NH
4+) and the primary, secondary, or tertiary ammonium cations, the quaternary ammonium
cations are permanently charged, independent of the pH of their solution.
[0021] The composition preferably comprises from 0.01% to 3.0%, preferably from 0.05% to
2.0%, more preferably from 0.1% to 1.0% by weight of the composition of the quaternised
acrylic copolymer.
[0022] The quaternised acrylic copolymer can have a weight average molecular weight (Mw),
measured by aqueous gel permeation chromatography (GPC) with light scattering detection
(SEC-MALLS), in the range of from 5,000 to 500,000 Da, preferably from 15,000 to 300,000
Da and even more preferably from 25,000 to 75,000 Da.
[0023] The quaternised acrylic copolymer may be characterized by a cationic charge density.
Cationic charge density is typically expressed as milliequivalents of charge per gram
of compound (mEq/g). The hydrophobically modified cationic polyvinyl alcohols of the
present disclosure may be characterized by a cationic charge density (or "CCD") ranging
from 0.10 mEq/g to 4.0 mEq/g, preferably from 1.0 mEq/g to 3.50 mEq/g, more preferably
from 1.75 mEq/g to 2.75 mEq/g.
[0024] Preferably the different types of monomer units are randomly distributed over the
quaternised acrylic copolymer.
[0025] The quaternised acrylic copolymer is preferably derived from cationic monomer units
and ethylenically unsaturated monomer units.
[0026] The cationic monomer units can be selected from:
CH
2=CR
1-Y-(CH
2)
n-N
+R
2R
3R
4X
- (a);
wherein:
each R1 are independently selected from a hydrogen or a methyl, preferably a methyl;
each R2 is independently selected from a C1 to C4 alkyl(ene), preferably CH2CH=CH2 or methyl, more preferably methyl;
each R3, R4 are independently selected from a C1 to C4 alkyl, preferably C1 to C3 alkyl, more
preferably methyl;
each Y is a linking group independently selected from: CO-NR5-(CH2)n, CO-O-(CH2)n, or (CH2)n, preferably CO-NR5-(CH2)n, or (CH2)n, more preferably CO-NR5-(CH2)n,
wherein:
each R5 is independently selected from hydrogen or methyl, preferably hydrogen,
n is an average of from 1 to 4, preferably 1 or 3, more preferably 3; and
X- is a suitable counterion, preferably X- is independently selected from a halide counterion, more preferably Cl-.
[0027] The choice of linking group Y is dependent on the reaction scheme used to make the
quaternised acrylic copolymer. Preferably, all Y are the same. Preferably, all R
5 are the same.
[0028] The cationic monomer units can be selected from the group consisting of: acrylamidopropyl
trimethylammonium chloride (APTAC), methacrylamidopropyltrimethylammonium chloride
(MAPTAC), diallyl dimethyl ammonium chloride (DADMAC), acryloyloxyethyltrimethylammonium
chloride (AETAC), methyloyloxyethyltrimethyl ammonium chloride (METAC), and mixtures
thereof. Particularly preferred cationic monomers are (meth)acrylamidopropyltrimethylammonium
chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), with methacrylamidopropyltrimethylammonium
chloride (MAPTAC) being most preferred. Two polymeric structures are possible when
polymerizing DADMAC: N-substituted piperidine structure or N-substituted pyrrolidine
structure. The pyrrolidine structure is favored (see John, Wilson; et al. (2002),
Synthesis and Use of PolyDADMAC for Water Purification).
[0029] The ethylenically unsaturated monomers can be selected from the group consisting
of: C3-C8 ethylenically unsaturated acids and/or salts thereof, C3-C8 hydroxyalkyl
acrylates, and mixtures thereof. By C3-C8, it is meant that the ethylenically unsaturated
acids and/or salts thereof, or C3-C8 hydroxyalkyl acrylate comprises from 3 to 8 carbon
atoms.
[0030] Suitable C3-C8 ethylenically unsaturated acids and/or salts thereof include (meth)acrylic
acid and mixtures thereof, with acrylic acid being preferred. Suitable salts include
alkali metal and ammonium salts.
[0031] Suitable C3-C8 hydroxyalkyl acrylates can be selected from the group consisting of:
ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate,
2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate,
with ethyl acrylate being most preferred.
[0032] The quaternised acrylic copolymer can further comprise additional monomers selected
from the group consisting of: ethyl acrylate, 2-acrylamido-2-methylpropane-sulfonic
acid, N-isopropylamide, vinylpyrrolidone, and mixtures thereof, as polymerized monomers,
with ethyl acrylate and/or vinylpyrrolidone being preferred, with ethyl acrylate being
particularly preferred.
[0033] The additional monomer is preferably present at a level of less than 20 mol%, preferably
less than 15 mol%, more preferably less than 10% of the total monomers present in
the quaternised acrylic.
[0034] The quaternised acrylic copolymer can comprise diallyldimethylammonium chloride (DADMAC)
as the cationic monomer with hydroxyethylacrylate as the ethylenically unsaturated
monomer. Such quaternised acrylic copolymers can comprise vinylpyrrolidone as an additional
monomer. Such quaternised acrylic copolymers include those sold under the tradename
of Mirapol
® SURF-S FAST DRY by Solvay.
[0035] More preferably, the quaternised acrylic copolymer can comprise (meth)acrylamidopropyltrimethylammonium
chloride (APTAC or MAPTAC) as the cationic monomer, with acrylate and/or ethyl acrylate
as the ethylenically unsaturated monomer. Such quaternised acrylic copolymers can
comprise ethyl acrylate as an additional monomer. Such quaternised acrylic copolymers
include those sold under the tradename of Polyquart
® by BASF, with Polyquart149A
® being particularly preferred.
Surfactant System
[0036] The liquid cleaning composition comprises from 5.0% to 50%, preferably from 6.0%
to 40%, most preferably from 15% to 35%, by weight of the total composition of a surfactant
system. The surfactant system comprises an anionic surfactant and a co-surfactant
selected from amphoteric surfactant, zwitterionic surfactant, or mixtures thereof.
[0037] The anionic surfactant and co-surfactant are present in a weight ratio of less than
1.5:1, preferably from 0.5:1 to 1.5:1, more preferably from 0.8:1 to 1.2:1.
Anionic surfactant
[0038] The surfactant system comprises an anionic surfactant. The surfactant system can
comprise at least 35%, preferably from 35% to 65%, more preferably from 40% to 60%
by weight of the surfactant system of an anionic surfactant. The surfactant system
is preferably free of fatty acid or salt thereof, since such fatty acids impede the
generation of suds.
[0039] Suitable anionic surfactants can be selected from the group consisting of: alkyl
sulphated surfactant, alkyl sulphonated surfactant, alkyl sulphosuccinate and dialkyl
sulphosuccinate ester surfactants, and mixtures thereof.
[0040] The anionic surfactant can comprise at least 70%, preferably at least 85%, more preferably
100% by weight of the anionic surfactant of alkyl sulphated anionic surfactant.
[0041] The mol average alkyl chain length of the alkyl sulphated anionic surfactant can
be from 8 to 18, preferably from 10 to 14, more preferably from 12 to 14, most preferably
from 12 to 13 carbon atoms, in order to provide a combination of improved grease removal
and enhanced speed of cleaning.
[0042] The alkyl chain of the alkyl sulphated anionic surfactant can have a mol fraction
of C12 and C13 chains of at least 50%, preferably at least 65%, more preferably at
least 80%, most preferably at least 90%. Suds mileage is particularly improved, especially
in the presence of greasy soils, when the C13/C12 mol ratio of the alkyl chain is
at least 57/43, preferably from 60/40 to 90/10, more preferably from 60/40 to 80/20,
most preferably from 60/40 to 70/30, while not compromising suds mileage in the presence
of particulate soils.
[0043] The relative molar amounts of C13 and C12 alkyl chains in the alkyl sulphated anionic
surfactant can be derived from the carbon chain length distribution of the anionic
surfactant. The carbon chain length distribution of the alkyl chains of the alkyl
sulphated anionic surfactants can be obtained from the technical data sheets from
the suppliers for the surfactant or constituent alkyl alcohol. Alternatively, the
chain length distribution and average molecular weight of the fatty alcohols, used
to make the alkyl sulphated anionic surfactant, can also be determined by methods
known in the art. Such methods include capillary gas chromatography with flame ionisation
detection on medium polar capillary column, using hexane as the solvent. The chain
length distribution is based on the starting alcohol and alkoxylated alcohol. As such,
the alkyl sulphated anionic surfactant should be hydrolysed back to the corresponding
alkyl alcohol and alkyl alkoxylated alcohol before analysis, for instance using hydrochloric
acid.
[0044] The alkyl sulphated anionic surfactant can be alkoxylated or free of alkoxylation.
When alkoxylated, the alkyl sulphated anionic surfactant can have an average degree
of alkoxylation of less than 3.5, preferably from 0.3 to 2.0, more preferably from
0.5 to 0.9, in order to improve low temperature physical stability and improve suds
mileage of the compositions of the present invention. When alkoxylated, ethoxylation
is preferred.
[0045] The average degree of alkoxylation is the mol average degree of alkoxylation (i.e.,
mol average alkoxylation degree) of all the alkyl sulphated anionic surfactant. Hence,
when calculating the mol average alkoxylation degree, the mols of non-alkoxylated
alkyl sulphate anionic surfactant are included:

wherein x1, x2, ... are the number of moles of each alkyl (or alkoxy) sulphate anionic
surfactant of the mixture and alkoxylation degree is the number of alkoxy groups in
each alkyl sulphated anionic surfactant.
[0046] Preferred alkyl alkoxy sulphates are alkyl ethoxy sulphates.
[0047] The alkyl sulphated anionic surfactant can have a weight average degree of branching
of at least 10%, preferably from 20% to 60%, more preferably from 25% to 45%.
[0048] The alkyl sulphated anionic surfactant can comprise at least 5%, preferably at least
10%, most preferably at least 25%, by weight of the alkyl sulphated anionic surfactant,
of branching on the C2 position (as measured counting carbon atoms from the sulphate
group for non-alkoxylated alkyl sulphate anionic surfactants, and the counting from
the alkoxy-group furthest from the sulphate group for alkoxylated alkyl sulphate anionic
surfactants). More preferably, greater than 75%, even more preferably greater than
90%, by weight of the total branched alkyl content consists of C1-C5 alkyl moiety,
preferably C1-C2 alkyl moiety. It has been found that formulating the inventive compositions
using alkyl sulphated anionic surfactants having the aforementioned degree of branching
results in improved low temperature stability. Such compositions require less solvent
in order to achieve good physical stability at low temperatures. As such, the compositions
can comprise lower levels of organic solvent, of less than 5.0% by weight of the liquid
cleaning composition of organic solvent, while still having improved low temperature
stability. Higher surfactant branching also provides faster initial suds generation,
but typically less suds mileage. The weight average branching, described herein, has
been found to provide improved low temperature stability, initial foam generation
and suds longevity.
[0049] The weight average degree of branching for an anionic surfactant mixture can be calculated
using the following formula:

wherein x1, x2, ... are the weight in grams of each alcohol in the total alcohol
mixture of the alcohols which were used as starting material before (alkoxylation
and) sulphation to produce the alkyl (alkoxy) sulphate anionic surfactant. In the
weight average degree of branching calculation, the weight of the alkyl alcohol used
to form the alkyl sulphate anionic surfactant which is not branched is included.
[0050] The weight average degree of branching and the distribution of branching can typically
be obtained from the technical data sheet for the surfactant or constituent alkyl
alcohol. Alternatively, the branching can also be determined through analytical methods
known in the art, including capillary gas chromatography with flame ionisation detection
on medium polar capillary column, using hexane as the solvent. The weight average
degree of branching and the distribution of branching is based on the starting alcohol
used to produce the alkyl sulphated anionic surfactant.
[0051] Suitable counterions include alkali metal cation earth alkali metal cation, alkanolammonium
or ammonium or substituted ammonium, but preferably sodium.
[0052] Suitable examples of commercially available alkyl sulphated anionic surfactants include,
those derived from alcohols sold under the Neodol
® brand-name by Shell, or the Lial
®, Isalchem
®, and Safol
® brand-names by Sasol, or some of the natural alcohols produced by The Procter & Gamble
Chemicals company. The alcohols can be blended in order to achieve the desired mol
fraction of C12 and C13 chains and the desired C13/C12 ratio, based on the relative
fractions of C13 and C12 within the starting alcohols, as obtained from the technical
data sheets from the suppliers or from analysis using methods known in the art.
[0053] The performance can be affected by the width of the alkoxylation distribution of
the alkoxylated alkyl sulphate anionic surfactant, including grease cleaning, sudsing,
low temperature stability and viscosity of the finished product. The alkoxylation
distribution, including its broadness can be varied through the selection of catalyst
and process conditions when making the alkoxylated alkyl sulphate anionic surfactant.
[0054] If ethoxylated alkyl sulphate is present, without wishing to be bound by theory,
through tight control of processing conditions and feedstock material compositions,
both during alkoxylation especially ethoxylation and sulphation steps, the amount
of 1,4-dioxane by-product within alkoxylated especially ethoxylated alkyl sulphates
can be reduced. Based on recent advances in technology, a further reduction of 1,4-dioxane
by-product can be achieved by subsequent stripping, distillation, evaporation, centrifugation,
microwave irradiation, molecular sieving or catalytic or enzymatic degradation steps.
Processes to control 1,4-dioxane content within alkoxylated/ethoxylated alkyl sulphates
have been described extensively in the art. Alternatively 1,4-dioxane level control
within detergent formulations has also been described in the art through addition
of 1,4-dioxane inhibitors to 1,4-dioxane comprising formulations, such as 5,6-dihydro-3-(4-morpholinyl)-1-[4-(2-oxo-1-piperidinyl)-phenyl]-2-(1-H)-pyridone,
3-α-hydroxy-7-oxo stereoisomer-mixtures of cholinic acid, 3-(N- methyl amino)-L-alanine,
and mixtures thereof.
[0055] Anionic alkyl sulphonate or sulphonic acid surfactants suitable for use herein include
the acid and salt forms of alkylbenzene sulphonates, alkyl ester sulphonates, primary
and secondary alkane sulphonates such as paraffin sulfonates, alfa or internal olefin
sulphonates, alkyl sulphonated (poly)carboxylic acids, and mixtures thereof. Suitable
anionic sulphonate or sulphonic acid surfactants include: C5-C20 alkylbenzene sulphonates,
more preferably C10-C16 alkylbenzene sulphonates, more preferably C11-C13 alkylbenzene
sulphonates, C5-C20 alkyl ester sulphonates especially C5-C20 methyl ester sulfonates,
C6-C22 primary or secondary alkane sulphonates, C5-C20 sulphonated (poly)carboxylic
acids, and any mixtures thereof, but preferably C11-C13 alkylbenzene sulphonates.
The aforementioned surfactants can vary widely in their 2-phenyl isomer content. Compared
with sulfonation of alpha olefins, the sulfonation of internal olefins can occur at
any position since the double bond is randomly positioned, which leads to the position
of hydrophilic sulfonate and hydroxyl groups of IOS in the middle of the alkyl chain,
resulting in a variety of twin-tailed branching structures. Alkane sulphonates include
paraffin sulphonates and other secondary alkane sulfonate (such as Hostapur SAS60
from Clariant).
[0056] Alkyl sulfosuccinate and dialkyl sulfosuccinate esters are organic compounds with
the formula MO3SCH(CO2R')CH2CO2R where R and R' can be H or alkyl groups, and M is
a counter-ion such as sodium (Na). Alkyl sulfosuccinate and dialkyl sulfosuccinate
ester surfactants can be alkoxylated or non-alkoxylated, preferably non-alkoxylated.
The surfactant system may comprise further anionic surfactant. However, the composition
preferably comprises less than 30%, preferably less than 15%, more preferably less
than 10% by weight of the surfactant system of further anionic surfactant. Most preferably,
the surfactant system comprises no further anionic surfactant, preferably no other
anionic surfactant than alkyl sulphated anionic surfactant.
Co-Surfactant
[0057] In order to improve surfactant packing after dilution and hence improve suds mileage,
the surfactant system can comprise a co-surfactant. The co-surfactant can be selected
from the group consisting of an amphoteric surfactant, a zwitterionic surfactant and
mixtures thereof.
[0058] The composition preferably comprises from 1.0% to 30%, more preferably from 5.0%
to 25% and especially from 10% to 20% by weight of the cleaning composition of the
co-surfactant.
[0059] The surfactant system of the cleaning composition of the present invention preferably
comprises up to 65%, preferably from 30% to 65%, more preferably from 40% to 60%,
by weight of the surfactant system of a co-surfactant.
[0060] The co-surfactant is preferably an amphoteric surfactant, more preferably an amine
oxide surfactant.
[0061] The amine oxide surfactant can be linear or branched, though linear are preferred.
Suitable linear amine oxides are typically water-soluble, and characterized by the
formula R1 - N(R2)(R3) O wherein R1 is a C8-18 alkyl, and the R2 and R3 moieties are
selected from the group consisting of C1-3 alkyl groups, C1-3 hydroxyalkyl groups,
and mixtures thereof. For instance, R2 and R3 can be selected from the group consisting
of: methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxypropyl,
and mixtures thereof, though methyl is preferred for one or both of R2 and R3. The
linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl
amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
[0062] Preferably, the amine oxide surfactant is selected from the group consisting of:
alkyl dimethyl amine oxide, alkyl amido propyl dimethyl amine oxide, and mixtures
thereof. Alkyl dimethyl amine oxides are particularly preferred, such as C8-18 alkyl
dimethyl amine oxides, or C10-16 alkyl dimethyl amine oxides (such as coco dimethyl
amine oxide). Suitable alkyl dimethyl amine oxides include C10 alkyl dimethyl amine
oxide surfactant, C10-12 alkyl dimethyl amine oxide surfactant, C12-C14 alkyl dimethyl
amine oxide surfactant, and mixtures thereof. C12-C14 alkyl dimethyl amine oxide are
particularly preferred.
[0063] Alternative suitable amine oxide surfactants include mid-branched amine oxide surfactants.
As used herein, "mid-branched" means that the amine oxide has one alkyl moiety having
n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms.
The alkyl branch is located on the α carbon from the nitrogen on the alkyl moiety.
This type of branching for the amine oxide is also known in the art as an internal
amine oxide. The total sum of n1 and n2 can be from 10 to 24 carbon atoms, preferably
from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms for the
one alkyl moiety (n1) is preferably the same or similar to the number of carbon atoms
as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch
are symmetric. As used herein "symmetric" means that | n1 - n2 | is less than or equal
to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt%, more
preferably at least 75 wt% to 100 wt% of the mid-branched amine oxides for use herein.
The amine oxide further comprises two moieties, independently selected from a C1-3
alkyl, a C1-3 hydroxyalkyl group, or a polyethylene oxide group containing an average
of from about 1 to about 3 ethylene oxide groups. Preferably, the two moieties are
selected from a C1-3 alkyl, more preferably both are selected as C1 alkyl.
[0064] Alternatively, the amine oxide surfactant can be a mixture of amine oxides comprising
a mixture of low-cut amine oxide and mid-cut amine oxide. The amine oxide of the composition
of the invention can then comprises:
- a) from about 10% to about 45% by weight of the amine oxide of low-cut amine oxide
of formula R1R2R3AO wherein R1 and R2 are independently selected from hydrogen, C1-C4
alkyls or mixtures thereof, and R3 is selected from C10 alkyls and mixtures thereof;
and
- b) from 55% to 90% by weight of the amine oxide of mid-cut amine oxide of formula
R4R5R6AO wherein R4 and R5 are independently selected from hydrogen, C1-C4 alkyls
or mixtures thereof, and R6 is selected from C12-C16 alkyls or mixtures thereof
[0065] In a preferred low-cut amine oxide for use herein R3 is n-decyl, with preferably
both R1 and R2 being methyl. In the mid-cut amine oxide of formula R4R5R6AO, R4 and
R5 are preferably both methyl.
[0066] Preferably, the amine oxide comprises less than about 5%, more preferably less than
3%, by weight of the amine oxide of an amine oxide of formula R7R8R9AO wherein R7
and R8 are selected from hydrogen, C1-C4 alkyls and mixtures thereof and wherein R9
is selected from C8 alkyls and mixtures thereof. Limiting the amount of amine oxides
of formula R7R8R9AO improves both physical stability and suds mileage.
[0067] Suitable zwitterionic surfactants include betaine surfactants. Such betaine surfactants
includes alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulphobetaine (INCI
Sultaines) as well as the phosphobetaine, and preferably meets formula (I):
R
1-[CO-X(CH
2)
n]
x-N
+(R
2)(R
3)-(CH
2)
m-[CH(OH)-CH
2]
y-Y
-
[0068] Wherein in formula (I),
R1 is selected from the group consisting of: a saturated or unsaturated C6-22 alkyl
residue, preferably C8-18 alkyl residue, more preferably a saturated C10-16 alkyl
residue, most preferably a saturated C12-14 alkyl residue;
X is selected from the group consisting of: NH, NR4 wherein R4 is a C1-4 alkyl residue,
O, and S,
n is an integer from 1 to 10, preferably 2 to 5, more preferably 3,
x is 0 or 1, preferably 1,
R2 and R3 are independently selected from the group consisting of: a C1-4 alkyl residue,
hydroxy substituted such as a hydroxyethyl, and mixtures thereof, preferably both
R2 and R3 are methyl,
m is an integer from 1 to 4, preferably 1, 2 or 3,
y is 0 or 1, and
Y is selected from the group consisting of: COO, SO3, OPO(ORS)O or P(O)(OR5)O, wherein
R5 is H or a C1-4 alkyl residue.
[0069] Preferred betaines are the alkyl betaines of formula (Ia), the alkyl amido propyl
betaine of formula (Ib), the sulphobetaine of formula (Ic) and the amido sulphobetaine
of formula (Id):
R
1-N
+(CH
3)
2-CH
2COO
- (IIa)
R
1-CO-NH-(CH
2)
3-N
+(CH
3)
2-CH
2COO
- (IIb)
R
1-N
+(CH
3)
2-CH
2CH(OH)CH
2SO
3- (IIc)
R
1-CO-NH-(CH
2)
3-N
+(CH
3)
2-CH
2CH(OH)CH
2SO
3- (IId)
in which R1 has the same meaning as in formula (I). Particularly preferred are the
carbobetaines [i.e. wherein Y-=COO- in formula (I)] of formulae (Ia) and (Ib), more
preferred are the alkylamidobetaine of formula (Ib).
[0070] Suitable betaines can be selected from the group consisting or [designated in accordance
with INCI]: capryl/capramidopropyl betaine, cetyl betaine, cetyl amidopropyl betaine,
cocamidoethyl betaine, cocamidopropyl betaine, cocobetaines, decyl betaine, decyl
amidopropyl betaine, hydrogenated tallow betaine / amidopropyl betaine, isostearamidopropyl
betaine, lauramidopropyl betaine, lauryl betaine, myristyl amidopropyl betaine, myristyl
betaine, oleamidopropyl betaine, oleyl betaine, palmamidopropyl betaine, palmitamidopropyl
betaine, palm-kernelamidopropyl betaine, stearamidopropyl betaine, stearyl betaine,
tallowamidopropyl betaine, tallow betaine, undecylenamidopropyl betaine, undecyl betaine,
and mixtures thereof. Preferred betaines are selected from the group consisting of:
cocamidopropyl betaine, cocobetaines, lauramidopropyl betaine, lauryl betaine, myristyl
amidopropyl betaine, myristyl betaine, and mixtures thereof. Cocamidopropyl betaine
is particularly preferred.
Nonionic Surfactant:
[0071] The surfactant system can further comprises less than 3.0% by weight of the composition
of alkoxylated alcohol nonionic surfactant. If present, the surfactant system preferably
comprises at least 0.5%, preferably at least 1.0% more preferably at least 2.0% by
weight of the composition of the alkoxylated alcohol nonionic surfactant. Alternatively
the composition can comprise greater than 3.0%, preferably from 3.5% to 10%, more
preferably from 4.0% to 7.5% by weight of the liquid hand dishwashing detergent composition
of an alkoxylated alcohol nonionic surfactant.
[0072] The anionic surfactant and alkoxylated alcohol nonionic surfactant can be present
in a weight ratio of less than 10:1. The anionic surfactant and alkoxylated alcohol
nonionic surfactant are preferably present in a weight ratio of from 0.8: 1 to 6.0:1,
more preferably from 3.5:1 to 5.5:1.
[0073] The surfactant system of the liquid hand dishwashing detergent composition can comprise
at least 5%, preferably from 5% to 35%, more preferably from 10% to 30%, by weight
of the surfactant system of the alkoxylated alcohol nonionic surfactant.
[0074] Preferably, the alkoxylated alcohol non-ionic surfactant is a linear or branched,
preferably linear, primary or secondary alkyl alkoxylated non-ionic surfactant, preferably
an alkyl ethoxylated non-ionic surfactant, preferably comprising on average from 9
to 15, preferably from 10 to 14 carbon atoms in its alkyl chain and on average from
5 to 12, preferably from 6 to 10, most preferably from 7 to 8, units of alkylene oxide
per mole of alcohol. The alkoxylated alcohol non-ionic surfactant is preferably ethoxylated
and/or propoxylated, more preferably ethoxylated.
[0075] The surfactant system can comprise a further nonionic surfactant such as an alkyl
polyglucoside nonionic surfactant:
A combination of alkylpolyglucoside and anionic surfactant especially alkyl sulfate
anionic surfactant, has been found to improve polymerized grease removal, suds mileage
performance, reduced viscosity variation with changes in the surfactant and/or system,
and a more sustained Newtonian rheology.
[0076] The alkyl polyglucoside surfactant can be selected from C6-C18 alkyl polyglucoside
surfactant. The alkyl polyglucoside surfactant can have a number average degree of
polymerization of from 0.1 to 3.0, preferably from 1.0 to 2.0, more preferably from
1.2 to 1.6. The alkyl polyglucoside surfactant can comprise a blend of short chain
alkyl polyglucoside surfactant having an alkyl chain comprising 10 carbon atoms or
less, and mid to long chain alkyl polyglucoside surfactant having an alkyl chain comprising
greater than 10 carbon atoms to 18 carbon atoms, preferably from 12 to 14 carbon atoms.
[0077] Short chain alkyl polyglucoside surfactants have a monomodal chain length distribution
between C8-C10, mid to long chain alkyl polyglucoside surfactants have a monomodal
chain length distribution between C10-C18, while mid chain alkyl polyglucoside surfactants
have a monomodal chain length distribution between C12-C14. In contrast, C8 to C18
alkyl polyglucoside surfactants typically have a monomodal distribution of alkyl chains
between C8 and C18, as with C8 to C16 and the like. As such, a combination of short
chain alkyl polyglucoside surfactants with mid to long chain or mid chain alkyl polyglucoside
surfactants have a broader distribution of chain lengths, or even a bimodal distribution,
than non-blended C8 to C18 alkyl polyglucoside surfactants. Preferably, the weight
ratio of short chain alkyl polyglucoside surfactant to long chain alkyl polyglucoside
surfactant is from 1:1 to 10:1, preferably from 1.5:1 to 5:1, more preferably from
2:1 to 4:1. It has been found that a blend of such short chain alkyl polyglucoside
surfactant and long chain alkyl polyglucoside surfactant results in faster dissolution
of the detergent solution in water and improved initial sudsing, in combination with
improved suds stability.
[0078] C8-C16 alkyl polyglucosides are commercially available from several suppliers (e.g.,
Simusol
® surfactants from Seppic Corporation; and Glucopon
® 600 CSUP, Glucopon
® 650 EC, Glucopon
® 600 CSUP/MB, and Glucopon
® 650 EC/MB, from BASF Corporation). Glucopon
® 215UP is a preferred short chain APG surfactant. Glucopon
® 600CSUP is a preferred mid to long chain APG surfactant.
[0079] If present, the alkyl polyglucoside can be present in the surfactant system at a
level of from 0.5% to 20%, preferably from 0.75% to 15%, more preferably from 1% to
10%, most preferably from 1% to 5% by weight of the surfactant composition. Alkyl
polyglucoside nonionic surfactants are typically more sudsing than other nonionic
surfactants such as alkyl ethoxlated alcohols.
[0080] In other preferred compositions, the alkyl polyglucoside is present at a level of
less than 2.0%, preferably less than 1.0%, more preferably less than 0.5% by weight
of the composition.
[0081] In even more preferred compositions, the composition is free of any further nonionic
surfactant.
Further ingredients:
[0082] The composition can comprise further ingredients such as those selected from: amphiphilic
alkoxylated polyalkyleneimines, cyclic polyamines, triblock copolymers, hydrotropes,
organic solvents, other adjunct ingredients such as those described herein, and mixtures
thereof.
Amphiphilic alkoxylated polyalkyleneimine:
[0083] The composition of the present invention may further comprise from 0.05% to 2%, preferably
from 0.07% to 1% by weight of the total composition of an amphiphilic polymer. Suitable
amphiphilic polymers can be selected from the group consisting of: amphiphilic alkoxylated
polyalkyleneimine and mixtures thereof. The amphiphilic alkoxylated polyalkyleneimine
polymer has been found to reduce gel formation on the hard surfaces to be cleaned
when the liquid composition is added directly to a cleaning implement (such as a sponge)
before cleaning and consequently brought in contact with heavily greased surfaces,
especially when the cleaning implement comprises a low amount to nil water such as
when light pre-wetted sponges are used.
[0084] A preferred amphiphilic alkoxylated polyethyleneimine polymer has the general structure
of formula (I):

wherein the polyethyleneimine backbone has a weight average molecular weight of 600,
n of formula (I) has an average of 10, m of formula (I) has an average of 7 and R
of formula (I) is selected from hydrogen, a C
1-C
4 alkyl and mixtures thereof, preferably hydrogen. The degree of permanent quaternization
of formula (I) may be from 0% to 22% of the polyethyleneimine backbone nitrogen atoms.
The molecular weight of this amphiphilic alkoxylated polyethyleneimine polymer preferably
is between 10,000 and 15,000 Da.
[0085] More preferably, the amphiphilic alkoxylated polyethyleneimine polymer has the general
structure of formula (I) but wherein the polyethyleneimine backbone has a weight average
molecular weight of 600 Da, n of Formula (I) has an average of 24, m of Formula (I)
has an average of 16 and R of Formula (I) is selected from hydrogen, a C
1-C
4 alkyl and mixtures thereof, preferably hydrogen. The degree of permanent quaternization
of Formula (I) may be from 0% to 22% of the polyethyleneimine backbone nitrogen atoms
and is preferably 0%. The molecular weight of this amphiphilic alkoxylated polyethyleneimine
polymer preferably is between 25,000 and 30,000, most preferably 28,000 Da.
[0087] Alternatively, the compositions can be free of amphiphilic polymers.
Cyclic Polyamine
[0088] The composition can comprise a cyclic polyamine having amine functionalities that
helps cleaning. The composition of the invention preferably comprises from 0.1% to
3%, more preferably from 0.2% to 2%, and especially from 0.5% to 1%, by weight of
the total composition, of the cyclic polyamine.
[0089] The cyclic polyamine has at least two primary amine functionalities. The primary
amines can be in any position in the cyclic amine but it has been found that in terms
of grease cleaning, better performance is obtained when the primary amines are in
positions 1,3. It has also been found that cyclic amines in which one of the substituents
is -CH3 and the rest are H provided for improved grease cleaning performance.
[0090] Accordingly, the most preferred cyclic polyamine for use with the cleaning composition
of the present invention are cyclic polyamine selected from the group consisting of:
2-methylcyclohexane-1,3-diamine, 4-methylcyclohexane-1,3-diamine and mixtures thereof.
These specific cyclic polyamines work to improve suds and grease cleaning profile
through-out the dishwashing process when formulated together with the surfactant system
of the composition of the present invention.
[0091] Suitable cyclic polyamines can be supplied by BASF, under the Baxxodur tradename,
with Baxxodur ECX-210 being particularly preferred.
[0092] A combination of the cyclic polyamine and magnesium sulphate is particularly preferred.
As such, the composition can further comprise magnesium sulphate at a level of from
0.001 % to 2.0 %, preferably from 0.005 % to 1.0 %, more preferably from 0.01 % to
0.5 % by weight of the composition.
Triblock Copolymer
[0093] The composition of the invention can comprise a triblock copolymer. The triblock
co-polymers can be present at a level of from 1% to 20%, preferably from 3% to 15%,
more preferably from 5% to 12%, by weight of the total composition. Suitable triblock
copolymers include alkylene oxide triblock co-polymers, defined as a triblock co-polymer
having alkylene oxide moieties according to Formula (I): (EO)x(PO)y(EO)x, wherein
EO represents ethylene oxide, and each x represents the number of EO units within
the EO block. Each x can independently be on average of from 5 to 50, preferably from
10 to 40, more preferably from 10 to 30. Preferably x is the same for both EO blocks,
wherein the "same" means that the x between the two EO blocks varies within a maximum
2 units, preferably within a maximum of 1 unit, more preferably both x's are the same
number of units. PO represents propylene oxide, and y represents the number of PO
units in the PO block. Each y can on average be from between 28 to 60, preferably
from 30 to 55, more preferably from 30 to 48.
[0094] Preferably the triblock co-polymer has a ratio of y to each x of from 3:1 to 2:1.
The triblock co-polymer preferably has a ratio of y to the average x of 2 EO blocks
of from 3:1 to 2:1. Preferably the triblock co-polymer has an average weight percentage
of total E-O of between 30% and 50% by weight of the tri-block co-polymer. Preferably
the triblock co-polymer has an average weight percentage of total PO of between 50%
and 70% by weight of the triblock co-polymer. It is understood that the average total
weight % of EO and PO for the triblock co-polymer adds up to 100%. The triblock co-polymer
can have an average molecular weight of between 2060 and 7880, preferably between
2620 and 6710, more preferably between 2620 and 5430, most preferably between 2800
and 4700. Average molecular weight is determined using a 1H NMR spectroscopy (
see Thermo scientific application note No. AN52907).
[0095] Triblock co-polymers have the basic structure ABA, wherein A and B are different
homopolymeric and/or monomeric units. In this case A is ethylene oxide (EO) and B
is propylene oxide (PO). Those skilled in the art will recognize the phrase "block
copolymers" is synonymous with this definition of "block polymers".
[0096] Triblock co-polymers according to Formula (I) with the specific EO/PO/EO arrangement
and respective homopolymeric lengths have been found to enhances suds mileage performance
of the liquid hand dishwashing detergent composition in the presence of greasy soils
and/or suds consistency throughout dilution in the wash process.
[0097] Suitable EO-PO-EO triblock co-polymers are commercially available from BASF such
as Pluronic
® PE series, and from the Dow Chemical Company such as Tergitol
™ L series. Particularly preferred triblock co-polymer from BASF are sold under the
tradenames Pluronic
® PE6400 (MW ca 2900, ca 40wt% EO) and Pluronic
® PE 9400 (MW ca 4600, 40 wt% EO). Particularly preferred triblock co-polymer from
the Dow Chemical Company is sold under the tradename Tergitol
™ L64 (MW ca 2700, ca 40 wt% EO).
[0098] Preferred triblock co-polymers are readily biodegradable under aerobic conditions.
[0099] The composition of the present invention may further comprise at least one active
selected from the group consisting of: i) a salt, ii) a hydrotrope, iii) an organic
solvent, and mixtures thereof.
Salt:
[0100] The composition of the present invention may comprise from about 0.05% to about 2%,
preferably from about 0.1% to about 1.5%, or more preferably from about 0.5% to about
1%, by weight of the total composition of a salt, preferably a monovalent or divalent
inorganic salt, or a mixture thereof, more preferably selected from: sodium chloride,
sodium sulphate, and mixtures thereof. Sodium chloride is most preferred.
Hydrotrope:
[0101] The composition of the present invention may comprise from about 0.1% to about 10%,
or preferably from about 0.5% to about 10%, or more preferably from about 1% to about
10% by weight of the total composition of a hydrotrope or a mixture thereof, preferably
sodium cumene sulphonate.
Organic Solvent:
[0102] The composition can comprise from about 0.1% to about 10%, or preferably from about
0.5% to about 10%, or more preferably from about 1% to about 10% by weight of the
total composition of an organic solvent. Suitable organic solvents include organic
solvents selected from the group consisting of: alcohols, glycols, glycol ethers,
and mixtures thereof, preferably alcohols, glycols, and mixtures thereof. Ethanol
is the preferred alcohol. Polyalkyleneglycols, especially polypropyleneglycol, is
the preferred glycol, with polypropyleneglycols having a weight average molecular
weight of from 750 Da to 1,400 Da being particularly preferred.
Adjunct Ingredients
[0103] The cleaning composition may optionally comprise a number of other adjunct ingredients
such as builders (preferably citrate), chelants, conditioning polymers, other cleaning
polymers, surface modifying polymers, structurants, emollients, humectants, skin rejuvenating
actives, enzymes, carboxylic acids, scrubbing particles, perfumes, malodor control
agents, pigments, dyes, opacifiers, pearlescent particles, inorganic cations such
as alkaline earth metals such as Ca/Mg-ions, antibacterial agents, preservatives,
viscosity adjusters (e.g., salt such as NaCl, and other mono-, di- and trivalent salts)
and pH adjusters and buffering means (e.g. carboxylic acids such as citric acid, HCl,
NaOH, KOH, alkanolamines, carbonates such as sodium carbonates, bicarbonates, sesquicarbonates,
and alike).
Packaged product
[0104] The hand dishwashing detergent composition can be packaged in a container, typically
plastic containers. Suitable containers comprise an orifice. Typically, the container
comprises a cap, with the orifice typically comprised on the cap. The cap can comprise
a spout, with the orifice at the exit of the spout. The spout can have a length of
from 0.5 mm to 10 mm.
[0105] The orifice can have an open cross-sectional surface area at the exit of from 3 mm
2 to 20 mm
2, preferably from 3.8 mm
2 to 12 mm
2, more preferably from 5 mm
2 to 10 mm
2, wherein the container further comprises the composition according to the invention.
The cross-sectional surface area is measured perpendicular to the liquid exit from
the container (that is, perpendicular to the liquid flow during dispensing).
[0106] The container can typically comprise from 200 ml to 5,000 ml, preferably from 350
ml to 2000 ml, more preferably from 400 ml to 1,000 ml of the liquid hand dishwashing
detergent composition.
Method of Washing
[0107] The invention is further directed to a method of manually washing dishware with the
composition of the present invention. The method comprises the steps of delivering
a composition of the present invention to a volume of water to form a wash solution
and immersing the dishware in the solution. The dishware is be cleaned with the composition
in the presence of water.
[0108] Optionally, the dishware can be rinsed. By "rinsing", it is meant herein contacting
the dishware cleaned with the process according to the present invention with substantial
quantities of appropriate solvent, typically water. By "substantial quantities", it
is meant usually about 1 to about 20 L, or under running water.
[0109] The composition herein can be applied in its diluted form. Soiled dishware is contacted
with an effective amount, typically from about 0.5 mL to about 20 mL (per about 25
dishes being treated), preferably from about 3 mL to about 10 mL, of the cleaning
composition, preferably in liquid form, of the present invention diluted in water.
The actual amount of cleaning composition used will be based on the judgment of the
user and will typically depend upon factors such as the particular product formulation
of the cleaning composition, including the concentration of active ingredients in
the cleaning composition, the number of soiled dishes to be cleaned, the degree of
soiling on the dishes, and the like. Generally, from about 0.01 mL to about 150 mL,
preferably from about 3 mL to about 40 mL of a cleaning composition of the invention
is combined with from about 2,000 mL to about 20,000 mL, more typically from about
5,000 mL to about 15,000 mL of water in a sink. The soiled dishware are immersed in
the sink containing the diluted cleaning compositions then obtained, before contacting
the soiled surface of the dishware with a cloth, sponge, or similar cleaning implement.
The cloth, sponge, or similar cleaning implement may be immersed in the cleaning composition
and water mixture prior to being contacted with the dishware, and is typically contacted
with the dishware for a period of time ranged from about 1 to about 10 seconds, although
the actual time will vary with each application and user. The contacting of cloth,
sponge, or similar cleaning implement to the dishware is accompanied by a concurrent
scrubbing of the dishware.
[0110] Alternatively, the composition herein can be applied in its neat form to the dish
to be treated. By "in its neat form", it is meant herein that said composition is
applied directly onto the surface to be treated, or onto a cleaning device or implement
such as a brush, a sponge, a nonwoven material, or a woven material, without undergoing
any significant dilution by the user (immediately) prior to application. "In its neat
form", also includes slight dilutions, for instance, arising from the presence of
water on the cleaning device, or the addition of water by the consumer to remove the
remaining quantities of the composition from a bottle. Therefore, the composition
in its neat form includes mixtures having the composition and water at ratios ranging
from 50:50 to 100:0, preferably 70:30 to 100:0, more preferably 80:20 to 100:0, even
more preferably 90: 10 to 100:0 depending on the user habits and the cleaning task.
METHODS:
A) Molecular weight determination by Gel Permeation Chromatography:
[0111] Gel Permeation Chromatography (GPC) with Multi-Angle Light Scattering (MALS) and
Refractive Index (RI) Detection (GPC-MALS/RI) is a well known system to directly measure
the weight average molecular weight, M
w, and number average molecular weight, M
n, of a polymer without the need for comparisons with known reference standards.
[0112] The true number-average molecular weight, M
n, of polymers can be obtained by GPC coupled with light-scattering detection and refractive
index detection even if the composition and therefore the refractive index increment
varies with elution volume, provided slices taken are sufficiently monodisperse with
respect to molecular weight and composition.
[0113] For example, the molecular weight distribution of polymer can be measured using a
Liquid Chromatography system such as an Agilent 1260 Infinity pump system with OpenLab
Chemstation software (from Agilent Technology, Santa Clara, CA, USA) provided with
two ultrahydrogel linear columns, 7.8mm ID x 300 mm length used in series (S/N 002C180181
VE077 and 005C180181 VE084, supplied by Waters Corporation of Milford, Mass., USA)
and an ultrahydrogel guard column (6mm ID x 40mm length, S/N2016260401BE105, also
supplied Waters Corporation of Milford, Mass., USA) installed between the injector
and the analytical column to prevent any impurities and suspended solids from reaching
the analytical column, operated at 40°C. A multiangle light scattering (MALS) detector
DAWN
® and a differential refractive index (RI) detector (Wyatt Technology of Santa Barbara,
Calif., USA) controlled by Wyatt Astra
® software can be used for the detection.
[0114] Since the analytes are spread over a relatively narrow time window, an isocratic
rather than gradient elution method can be used. Isocratic means that the mixture
of your mobile phase is consistent over the complete testing time. Using a gradient
implies that the compounding of the eluent mixture is changed during measurement and
so influences the retention of analytes. The separation can be either accelerated
or decelerated when using a gradient method.
[0115] 0.1M sodium nitrate in water containing 0.02% sodium azide is used as the mobile
phase. Samples are prepared by dissolving the polymer in the mobile phase at ~1.0
mg per ml and by mixing the solution overnight at room temperature to ensure full
hydration of the polymer. The sample is then filtered through a 0.8 µm Versapor membrane
filter (AP4189, supplied by PALL, Life Sciences, NY, USA) into the LC autosampler
vial using a 3-ml syringe. The sample is then pumped into the columns at a flow rate
of 1.0 mL/min.
[0116] The number average and weight average molecular weights of the polymer are calculated
from the dn/dc (differential change of refractive index with concentration) measurements,
as provided by the Astra detector software.
B) Water-sheeting:
[0117] The speed of drying is related to the degree of water-sheeting. The higher the water-sheeting,
the less water retained on the wet article.
[0118] The water sheeting behaviour is evaluated by washing grey ceramic plates ("Dinera"
plates, 26 cm diameter, sourced form IKEA) with the hand dishwashing detergent test
compositions, followed by scoring the amount of water sheeting observed on the plate
when leaving them vertically on a drying rack. More particularly:
A sponge (Scotch-Brite
® Classic-schuurspons van cellulose - supplied by 3M Belgium-dimension: 7cm * 10cm)
is homogeneously wetted with water of hardness 0.36 mmol/l CaCO
3 equivalence, at 25 °C, by saturating the sponge with water, and subsequently manually
squeezing until no further water is squeezed out).
[0119] 1ml of the hand dishwashing composition is homogeneously distributed over the sponge.
The sponge is manually squeezed with full force 4 times above the ceramic plate using
one hand to create foam, followed by washing the plate in 10 circular clockwise motions
covering the edges as well as the center part of the plate, so that the full plate
is treated with the foam.
[0120] The plate is then rinsed for 30 seconds under a running tap (25 °C water of having
the same water hardness as before (0.36 mmol/l CaCO, equivalence) at a sufficient
flow rate to enable full foam removal and full coverage with water after which the
plate is placed vertically on a drying rack under standard room conditions (20 +/-1
°C).
[0121] The water running down the plate is then visually evaluated and a score of between
0 - 100% is given depending on the amount of water that has run down the plate in
the first 30 sec, and therefore leaving an area of the plate already dry. 0% corresponds
to water remaining on the full plate, 50% indicates that the half of the plate is
covered with a film of water, and 100% indicating that no water film is visibly present.
EXAMPLES
[0122] The following compositions were prepared and evaluated for their water-sheeting behaviour,
using the method described herein. Rapid water-sheeting is an indicator of quick drying
after rinsing.
[0123] In the compositions of Table 1, inventive example 1 comprised both anionic surfactant
and a co-surfactant in a weight ratio of 1:1, in addition to a quaternised acrylic
copolymer. Comparative example A comprises the same surfactant system, but did not
comprise a quaternised acrylic copolymer. By comparing the water-sheeting results
of example 1 with that from example A, the improvement in water-sheeting from the
addition of the quaternised acrylic copolymer into compositions comprising anionic
surfactant and co-surfactant in the desired ratio can be seen. In contrast, from the
water-sheeting results of comparative examples B to D, it can be seen that the water-sheeting
benefit is substantially reduced when the anionic surfactant to co-surfactant ratio
is above the desired range.
Table 1: Comparative and inventive liquid hand dishwashing detergent compositions:
wt% (100% active basis) |
Ex 1 |
Ex A* |
Ex B* |
Ex C* |
Ex D* |
C1213AE0.6S (33.43% branching) |
14.00 |
14.00 |
18.67 |
27.00 |
22.62 |
C12-14 dimethyl amine oxide |
14.00 |
14.00 |
9.33 |
7.00 |
5.38 |
Anionic:co-surfactant surfactant ratio |
1:1 |
1:1 |
2:1 |
3:1 |
4.2:1 |
NaCl |
0.8 |
0.8 |
0.8 |
0.8 |
0.8 |
PPG (MW2000) |
0.45 |
0.45 |
0.45 |
0.45 |
0.45 |
Ethanol |
4.0 |
4.0 |
4.0 |
4.0 |
4.0 |
MIT preservative |
0.0075 |
0.0075 |
0.0075 |
0.0075 |
0.0075 |
Phenoxyethanol |
0.11 |
0.11 |
0.11 |
0.11 |
0.11 |
Acrylate/ethyl acrylate/ methacrylamidopropyl trimethyl ammonium chloride copolymer1 |
0.5 |
- |
0.5 |
0.5 |
0.5 |
Water and minors (perfume, dye) |
bal. |
bal. |
bal. |
bal. |
bal. |
|
|
|
|
|
|
pH (10% solution in demi water) |
9.0 |
9.0 |
9.0 |
9.0 |
9.0 |
|
|
|
|
|
|
Water sheeting % |
35 |
5 |
10 |
10 |
10 |
* Comparative
1 a quaternised acrylic copolymer of use in the present invention, sold under the tradename
of Polyquart® 149A, supplied by BASF |
[0124] The dimensions and values disclosed herein are not to be understood as being strictly
limited to the exact numerical values recited. Instead, unless otherwise specified,
each such dimension is intended to mean both the recited value and a functionally
equivalent range surrounding that value. For example, a dimension disclosed as "40
mm" is intended to mean "about 40 mm."
1. A liquid hand dishwashing detergent composition comprising a quaternised acrylic copolymer,
and
from 5.0% to 50% by weight of the liquid hand dishwashing detergent composition of
a surfactant system, wherein the surfactant system comprises:
a. anionic surfactant; and
b. co-surfactant selected from the group consisting of: amphoteric surfactant, zwitterionic
surfactant, and mixtures thereof;
wherein the anionic surfactant and co-surfactant are present in a weight ratio of
less than 1.5:1.
2. The composition according to claim 1, wherein the composition comprises from 0.01%
to 3.0%, preferably from 0.05% to 2.0%, more preferably from 0.1% to 1.0% by weight
of the composition of the quaternised acrylic copolymer.
3. The composition according to any preceding claim, wherein the quaternised acrylic
copolymer has a weight average molecular weight (Mw), measured by aqueous gel permeation
chromatography (GPC) with light scattering detection (SEC- MALLS), in the range of
from 5,000 to 500,000 Da, preferably from 15,000 to 300,000 Da and even more preferably
from 25,000 to 75,000 Da.
4. The composition according to any preceding claim, wherein the quaternised acrylic
copolymer has an average cationic charge density of from 0.01 to 2.8, preferably from
0.1 to 2.75, more preferably from 0.75 to 2.25 mEq/g.
5. The composition according to any preceding claim, wherein the quaternised acrylic
copolymer is derived from:
a. cationic monomer units selected from:
i.
CH2=CR1-Y-N+R2R3R4X- (a);
wherein:
each R1 are independently selected from a hydrogen or a methyl, preferably a methyl;
each R2 is independently selected from a C1 to C4 alkyl(ene), preferably CH2CH=CH2 or methyl, more preferably methyl;
each R3, R4 are independently selected from a C1 to C4 alkyl, preferably C1 to C3 alkyl, more
preferably methyl;
each Y is a linking group independently selected from: CO-NR5-(CH2)n, CO-O-(CH2)n, or (CH2)n, preferably CO-NR5-(CH2)n, or (CH2)n, more preferably CO-NR5-(CH2)n,
wherein:
each R5 is independently selected from: hydrogen or methyl, preferably hydrogen,
n is an average of from 1 to 4, preferably 1 or 3, more preferably 3; and
X- is a suitable counterion, preferably a halide counterion, more preferably Cl-; and
b. ethylenically unsaturated monomer units.
6. The composition according to claim 5, wherein the cationic monomer unit is selected
from the group consisting of: acrylamidopropyl trimethylammonium chloride (APTAC),
diallyl dimethyl ammonium chloride (DADMAC); acryloyloxyethyltrimethylammonium chloride
(AETAC); methacrylamidopropyltrimethylammonium chloride (MAPTAC); methyloyloxy ethyl
trimethyl ammonium chloride (METAC), and mixtures thereof, preferably (meth)acrylamidopropyltrimethylammonium
chloride (APTAC or MAPTAC) or diallyldimethylammonium chloride (DADMAC), more preferably
methacrylamidopropyltrimethylammonium chloride (MAPTAC).
7. The composition according to claim 5 or 6, wherein the ethylenically unsaturated monomer
units are selected from the group consisting of: C3-C8 ethylenically unsaturated acids
and/or salts thereof, C3-C8 hydroxyalkyl acrylates, and mixtures thereof.
8. The composition according to claim 7, wherein the ethylenically unsaturated monomer
units comprise C3-C8 ethylenically unsaturated acids and/or salts thereof, wherein
the C3-C8 ethylenically unsaturated acids and/or salts thereof are selected from the
group consisting of: (meth)acrylic acid, or salt thereof, more preferably is selected
from acrylic acid, or salt thereof.
9. The composition according to claim 7 or 8, wherein the ethylenically unsaturated monomer
units comprise C3-C8 alkyl acrylates selected from the group consisting of: ethyl
(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy-2-methylethyl (meth)acrylate,
2-hydroxy-1-methylethyl (meth)acrylate, and mixtures thereof, preferably ethyl (meth)acrylate,
2-hydroxyethyl (meth)acrylate, and mixtures thereof, more preferably ethyl (meth)acrylate,
most preferably ethyl acrylate.
10. The composition according to any of the preceding claims, wherein the anionic surfactant
and co-surfactant are present in a weight ratio of from 0.5:1 to 1.5:1, preferably
from 0.8:1 to 1.2:1.
11. The composition according to any preceding claims, wherein the composition comprises
from 6.0% to 40%, preferably from 15% to 35%, by weight of the total composition of
the surfactant system.
12. The composition according to any of the preceding claims, wherein the surfactant system
comprises at least 35%, preferably from 35% to 65%, more preferably from 40% to 60%
by weight of the surfactant system of an anionic surfactant.
13. The composition according to any of the preceding claims, wherein the anionic surfactant
comprises at least 70%, preferably at least 85%, more preferably 100% by weight of
the anionic surfactant of alkyl sulphated anionic surfactant.
14. The composition according to any of the preceding claims, wherein the co-surfactant
comprises an amphoteric surfactant, preferably an amine oxide surfactant.
15. The composition according to any of the preceding claims, wherein the surfactant system
comprises less than 10.0%, preferably less than 5.0% by weight of the surfactant system
of alkoxylated alcohol nonionic surfactant, more preferably is free of alkoxylated
alcohol nonionic surfactant.