Note: Descriptions are shown in the official language in which they were submitted.
~7~ C 538 (R)
This invention relates to a cleaning composition, and
particu~arly to a cleaning composition suitable for use in
the dishwashing area, for washing cups, dishes, glassware,
crockery, pots and pans, glazed objects etc. The invention
is, however, especially concerned with a dishwashing
composition for use in manual dishwashing operations.
In manual dishwashing operations, the objects to be
cleaned are usually washed in a hand-warm aqueous solution
of a suitable dishwashing composition, and subsequently put -~
on a rack and dried with a tea-cloth. During the period
between the cleaning and the cloth-drying some of the wash
liquor may dry up on the objects and leave spots or streaky
films. This can be reduced by rinsing the cleaned objects
with running tap water or immersing them in a bowl with
15 clean water, but the film of water on the objects left on ~ -
the rack may not drain and dry evenly or quickly and t~e
consequence thereof is that they may need to be polished or
cloth-dried to prevent spotting. It has already been
proposed to improve the "drainage" properties of dishwashing
compositions by inclusion of gelatin which allows a "sheeting-
off" effect. Objects cleaned with such compositions may,
after having been rinsed under running tap w~ter, be left to
stand and drain, thus obviating a cloth-drying operation.
It has now been found that the inclusion of a small
amount of casein in dishwashing compositions that comprise
an active detergent system containing a secondary alkyl
sulphonate/sulphate and an alkylethersulphate or a nonionic
detergent provides for a dishwashing composition with improved
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1~764~7 C 538 (R)
"sheeting-off" properties and improved "drain-dry" properties onrinsing.
The effect found must be surprising since casein belongs
to quite a different class of proteins than gelatin. Casein
is a phosphoprotein whereas gelatin is a scleroprotein.
Certainly the drain-dry effect is not a property that can be
attributed to proteins in general. Experiments have shown
that a number of protein-kypes, such as egg-albumin, bovine
albumin, ~-lactoglobulin, pepsin, fibrinogen and various
protein hydrolysates were~found ineffective.
Also, apparently certain compatibility and concerted
action rules between casein and the active detergent system
must be fulfilled in order to provide for a ~,ood drain-
dry effect in conjunction ~ith a good dishwashing performance.
Though other anionic organic sulphonate or sulphate
surface-active compounds e.g. the alkylbenzenesulphonates,
olefinsulphonates, primary alkyl sulphates and the primary
alkyl sulphonates, can be used in replacement of the
secondary alkyl sulphonate, these actives alone, without
the presence of a secondary alkyl sulphonate will not be as
compatible~with the casein to produce positively a good
drain-dry effect as compared to compositîons containing
a secondary alkyl sulphonate, the proportion o~ which may be
as low as 1% by weight, based on the total composition,in
the presence of other anionic organic surface active agents ~;
aæ stated above. However, it has been found that the
secondary alkyl sulphonate can be replaced by the similarly
structured compound, i.e. secondary alkyl sulphate, without
any loss in performance.
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C 538 (R)
The secondary alkyl sulphonate used in the invention can
be obtained by sulphonating C8-C24, preferably C12_18 alkanes
with a suitable sulphonating agent, and subsequently neutral-
izing the sulphonic acids to their suitable salts.
Other methods of obtaining secondary alkyl sulphonates
are by sulphochlorination or sulphoxidation of alkanes, or by
the bisulphite-addition to suitable alkanes. The secondary
alkyl sulphonates to be used in the present invention are the
alkali metal, ammonium and substituted~ammonium salts there-
of, the alkali metal salts, particular y the sodium salts
being preferred. Mixtures of secondary alkyl sulphonates
having dif~erent chain lengthsare also suitable. The second-
ary alkyl sulphate for use in the present invention may be
obtained by reacting C8-C24, preferably C12 18 olefins with
sulphuric acid; or by sulphatlon of the corresponding second-
ary alcohols,followed by neutralization. It is used in the
form of its alkali metal, ammonium or substituted a~monium salts.
The active detergent system further comprises an alkyl-
ethersulphate and/or a nonionic detergent compound.
The alkylethersulphates are salts of the monosulphuric
acid esters of C8-C24 primary or secondary, straight or
branched chain alcohols, which have been condensed with 1-10
moles of an alkylene oxide, e.g. ethylene oxide and/or pro-
pylene oxide. Particularly suitable are the C12 C18 primary
alcohols condensed with from 1-5 moles of ethylene oxide,
which have subsequently been sulphated and neutralized.
A typical example thereof is laurylethersulphate
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C 538 (R)
containing ~ moles of ethylene oxide,another typical
example is a secondary C11-C15 alco~oI condensed with 3 moles
of ethylene oxide and subsequently sulphated and neutralized.
The salts of the alkylethersulphates are the alkali
metal, ammonium, and substituted ammonium salts, again the
alkali metal salts, particularly the sodium salts being
preferred.
The nonionic detergent actives which can be used in
the present invention are generally the alkylene oxide
condensat~ion produdts of priLary or secondary, straight or
branched chain C8-C24 alcohols, C8-C18 alkyl or dialkyl
phenols, C8-C24 fatty acld mono- and diamides, and glycols.
In general these condensation products contain from 1-30,
usually from 3-25 moles of ethylene oxide and/or propylene
oxide.
Typical examples of suitable nonionics of the above
group are primary C12-C15 alcohols condensed with 7-12
moles of ethylene oxide and secondary C11-C15 alcohols
condensed with 9-12 moles of ethylene oxide.
Another group of useful nonionic surfactants which can
be used are amine oxides. Amine oxides are reaction products
of tertiary amines and hydrogen peroxide or peroxyacids,
having the general formula R R1 R2 N ~ 0, of whiah R may be
aliphatic,aromatic, heterocyclic, alicyclic or combinations
thereof. The amine oxides of interest in the present
invention have R being a straight or branched chain aliphatic
hydrocarbon radical having 8 to 20 carbon atoms, which may be
J saturated or unsaturated, and R1 and R2 being a methyl-,
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~ 7~47 C 538 (R)
ethyl-, hydroxymethyl or a hydroxyethyl group.
Typical examples are dodecyldimethylamine oxide and the
various fatty acid derived alkyl - R1 R2 ~ amine oxides, such
as coconut dimethylamine oxide.
Mixtures of several of the above nonionic detergents can
also be used, including a mixture of nonionics with a short
and a long alkylene oxide chain.
Accordingly the invention provides a ~is~washing compo-
sition comprising a secondary C8-C24 alkyl sulphonate or
sulphate, a C8-C24 alkylethersulphate having 1-10 alkylene
oxide groups, and/or a nonionic detergent compound, and casein.
The composition of the invention may fu~ther comprise any other -
active detergent materials without departing from the essence
of the invention, such as the water-soluble alkylbenzene-
sulphonates, olefin sulphonates, primary alkyl sulphonates,
and primary alkyl sulphates. - ;
Casein is a known, commercially available, protein
obtained from skim milk by acid or enzyme precipitation, a
general reference of which can be found in Kirk-Othmer, ;~
20 Encyclopaedia of Chemical Technology 1949, Vol. 3, pages
225-237; and the Encyclopaedia of Polymer Science and
Technology 1965, Interscience Publishers, Volume 2, pages
859-871. It has found commercial use in various branches
of industry.
The casein to be included in the dishwashing composition
of the invention can be ~ , y, or whole casein, but
for commercial reasons whole casein is preferred. Both acid
casein and rennet casein can be used. It can be added as
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` 447 C 538 (R)
such, dissolved in a small amount of alkali, or as an aqueous
solution of commercially available sodium caseinate. The
amount of casein to be incorporated in the composition
according to the invention is generally from about 0.25 to
5%, and preferably from about 1 to 3% by weight. ~-
The amounts of secondary alkyl sulphonate or sulphate
and (alkylethersulphate + nonionic detergent) are:
generallypre~erably ~ -
secondary alkyl sulphonate/ 1-40% 5-40% -
10 alkylethersulphate
and/or 1-40% 1-20%
nonionic detergent
It is to be understood that the active detergent system
always comprises a component (a) comprising a secondary a~yl
sulphonate/sulphate, together with a component (b) which is
either an alkylethersulphate or a nonionic detergent or both.
The weight ratio between the secondary alkyl sulphonate/
sulphate and the alkylethersulphate or noniohic detergent
will generally be from 5~ to 1:2 and pre~erably from 4:1 to
1:1 in the absence of other anionic sulphonate or sulphate
type detergents.
In the presence of other anionic sulphonate or sulphate
detergents of the type as stated above, these detergents can
be grouped in component (a) and the above ratios will apply
25 to component (a) with respect to component (b). ~ ~ ;
The compositions o~ the invention may ~urthermore con- ;
tain the usual ingredients, commonly incorporated in dish-
washing compositions. Such ingredients are hydrotropes,
i such as ethanol, urea, sodium xylene- and toluene~sulphonate,
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~7~,7 C 538 (R)
perfumes, colouring materials, opacifiers, preservatives and
so on.
It has also been found that the further inclusion of an
organo -phosphorus compound as will be defined hereinafterin
the composition of the invention improves drain-drying whilst
providing for an additional benefit in that the rinsability
of these compositions is enhanced, thereby gaining the full
benefit of the invention with less rinsing. The organo-
phosphorus compound used he~re can be a phosphate ester or
a phosphonate, having the general formula R-(EO)n-(O)m-P03X2,
wherein R is a straight or branched chain alkyl having 8-18
carbon atoms, or a phenylalkyl hydrocarbon chain wherein .
the alkyl group has 10-18 carbon atoms; (EO) is an ethylene
oxide or propylene oxide group; n is a number from 0-10;
m = 0-1; and X is hydrogen, or an alkali metal, ammonium or
substituted ammonium cation. Particularly sultable
phosphorus compounds are phosphate esters having the general
formula R(EO)n-OPO3X2, wherein R is a straight chain or
branched chain hydrocarbon radical having 8-18 carbon atoms,
20 preferably 11-15 carbon atoms; (E0) is an ethylene oxide or
propylene oxide group; n is a number from 0-10, preferably
3-7; and X is hydrogen, or an alkali metal, ammonium or
substituted ammonium cation. A typical example is the sodium
salt of the monophosphoric acid ester of a C11-C15 sec.
alcohol, condensed with 3 moles of ethylene oxide. The
amount of organo-phosphorus compound, when incorporated, is
generally small, in the order of 0.5-5%, preferably 0.5-3.0%
by weight Or the total composition.
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C 538 (R)
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Accordingly in one preferred embodiment of the invention ~-
the composition comprising a secondary alkyl sulphonate, an
alkylether sulphate or a nonionic surface active compound
includes casein and the above preferred phosphate ester in
amounts up to 5% of the total composition.
The compositiion of the invention may be made up in any
suitable form, such as powders, aqueous liquids or con-
centrated non-aqueous liquids. They are preferably, however, -
in the form of aqueous liquids.
As stated above, the compositions of the invention are
particularly suitable for manual dishwashing operatiohs, in
which, after cleaning, the cleaned objects are rinsed with
running tap water (either hot or cold), or by immersing them
in a bowl with clean hot or cold water, and then left to ~;
stand to dry. The adhering film of water wlll rapidly drain
or sheet o~f, and the objects will dry without showing
significant spotting or streaking effects.
In the following test the effect of a number of
proteins added to the wash bowl - either as a predissolved
solution or dispersion - on product performance was
examined.
The basic product composition is:
sodium secondarY C12_16 alkyl sulphonate 16.7%
C11_15 alcohol/12 ethylene oxide 8-3%
water to 100%
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Six wash solutions of the above product at a concen-
tration of 0.2% were made. With each wash solution the
following test procedure was followed:
Three plates were washed in the wash solution in the
absence Or soil, rinsed and allowed to dry. Three further
plates were treated in the same wash solution following
sequential addition of protein (3 x 0.2 gms to 5 litres of
wash liquor). Finally 3 more plates were treated ~ th no
further addition of soil.
Each wash lasted for 2 minutes~ followed by a 4
second rinse under the tap and a brief immersion in a
rinse bowl containing the same tap water. The temperature
of both wash and rinse was about 43C.
The types~of protein materials tested were egg~
albumin, bovine albumin, ~-lactoglobulin, pepsin~
fibrinogen and soluble casein.
All plates washed in the wash solution without
protein and with protein other than casein, showed slow
draining of the water film and water-hardness spotting
and streaks after drying.
Only soluble casein showed a marked beneficial
effect on drain-dry performance, even after the first
- addition to the wash bowl.
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~76~7 C 538 (R)
The plates washed with the casein-containing wash
solution showed an appearance marked].y distinct from that of
the plates treated otherwise, in that they were substantially
free of spotting a~d streaks.
The invention will now be further illustrated by way of
examples.
Exam~le I
The following composition was made: % by weight
sodium C12-C16 secondary alkyl sulphonate 16.67
secondary Cll-C15 alcohol, condensed with
12 moles ethylene oxide 8.33
soluble casein (sodium caseinate) 1.25
water to 100 -`
Dark -plates and glasses, both soiled (milk, ~i
potato~ rice pudding and meat soil) and unsoiled, were -~
cleaned in a wash bowl at a temperature between 40~45C
with a product concentration of 0.05 and 0.2% in water of
40 FH. After washing, the objects were immediately rinsed
for at least 4 seconds with water of 40-45C and 40FH.
The drainage effects without soil were good, particu-
larly at 0.2% and on glasses, and with soil there was a
good overall drainage effect at both concentrations,
with substantially no spotting and no streaky films.
Example II
The following liquid compositlons were made:
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~0~6~7 C 538 (R)
% by weight
sodium sec. C12-C16 alkyl sulphonate20 22.5
sodium laurylethersulphate (containing
3 moles of ebhylene-oxide) 5
sec. C11-C15 alcohol condensed with 12
moles ethylene oxide - 7.5
sodium salt of the~monophosphoric acid
ester of C 1-C alcohol condensed with
3 moles ethyle~e oxide 1 1.2
10 alkali-soluble casein 1.5 1.5
lemon juice 1.0 1.0
~ .
preservative ~ 0.02 0.02
colouring agent 0.002 0.002
perfume o.3 o.3
15 water up to 100 up to 100
pH 8.35 8.4
These products showed good washing performance and good drain- -
dry effects, with less rinsing, as compared to a similar
product without a phosphate ester.
Example III
The following composition exemplifies an~ther formulation
according to the invention: ~
% by weight
sodium sec. C12-C16 alkyl sulphonate (as
100% active detergent) 26.5
sodium laurylethersulphate (containing 3 moles 6 5
of ethylene oxide)
urea 1.1
denatured ethyl alcohol 4.5
30 sodium caseinate 1.6
perfume, colourants etc. and water up to 100
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Example IV
The follo~ring composition was tested in 24FH at a
concentration 0.15% on plates. The plates were washed for
2 minutes, then given a tap rinse followed by a brief bowl
rinse in 24FH water.
% by weight
sodium secondary alkyl sulphonate 22.0
secondary C11-C15 alcohol condensed with 12 11
moles of et~hylene oxide
jcasein 1.65
rest water
~ood drain-dry effects and end result scores were
observed. ~-
Examples V-VIII
` The followi~ng compositions within the invention were
tested and used at a concentration of 1.5 g/l in water of ~-~
40FH. Plates were immersed in the wash liquor (at 40-45C)
for 30 seconds, then rinsed thoroughly in water of the
same hardness and temperature, either under running tap
water for 4 seconds, or in a separate rinse bowl (dipped
three times into the clean water). All samples gave a
good drain-dry effect.
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~07~7
% by wei ght
Compositi ons V VI VII VIII
_ _
sodium C10 12 alkylbenzenesulphonate Ll, 3
sodium sec. C12_18 allcyl sulphonate 21.2 26.4
sodium sec. Cll-C17a~{yl sulphate - ~ 22.0 26.5
sodium lauryl-3 EO-sulphate 10.2 6.6 ~ 6 5
coconut dimethylaTrline oxide - 8 . O
C11_15 sec. alcohol/12 ethylene oxide - - 11. 0
urea !....... '~ ' 3. 0 9. 0 - - ~ -
ethanol 6 . 2 7 . 0 5 . 0 4 . 5
sodium aaseinate 1.5 1.5 1.65 1.65
water to 100. 0 10~0. 0 100. 0 100. 0
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