Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 95/30729 ~ PCT/US95/05069
21~1i36
MANUAL DISHWASHING COMPOSITIONS
Technical field of the Invention
The present invention relates to dishwashing detergent compositions comprising
high levels of hydrotropes.
Backeround of the Invention
The formulator of a manual dishwashing detergent composition is required to
formulate compositions which meet a number of consumer relevant performance
demands.
Firstly, such a composition should be effective at removing soils from dirty
"dishes" when used in a manual dishwashing process. The soils encountered in
dishwashing are largely but not exclusively food based. Particularly difficult
soils to
remove include greasy soils, burnt on food soils, dried on food soils, highly
coloured
soils derived from e.g. highly coloured vegetables, as well as non-food soils
such as
lipstick on the rims of glasses or nicotine stains.
Once the soils have been removed from the dishes the dishwashing detergent
should act such as to suspend these soils in the wash solution and thus
prevent their
redeposition onto the dishes, or onto the surface of the sink.
In addition, the manual dishwashing composition should be high sudsing and the
sudsing should persist throughout the washing process. This is particularly
important as
sudsing is used as an indicator by the consumer that the wash solution still
contains
active detergent ingredients. The consumer usually renews the wash solution
when the
sudsing has subsided .
The manual dishwashing composition should also be mild to the skin, and
particularly to the hands and should not cause skin dryness, chapping or
roughness.
Such skin complaints largely result from the removal of natural oils from the
skin. Thus,
the manual dishwashing composition should desirably be effective at removing
grease
from plates but not natural oils from the skin.
WO 95130729 PCT/US95/05069 -
2i9113b
2
Reflecting the different nature of the performance demands for a manual
dishwashing composition, such compositions are formulated in a distinct way
from, for
example, machine dishwashing, laundry, and hard-surface cleaner compositions.
In addition, due to environmental concerns the detergent manufacturers are
striving
towards producing more concentrated formulations and in order to minimise the
impact
the formulations and their packaging have on the environment.
However, it has been noticed that this concentration results in high active
dishwashing formulations that require an increase in the amount of rinsing in
order to
remove detergent compositions from the dish article once manual agitation is
complete.
For example, in direct application .conditions the dish article is dampened
and the
detergent composition is applied to the dish article in a highly concentrated
form or even
in its undiluted form. After manual agitation by the consumer, the article is
placed under
running water to be rinsed. The article is thus held under the running water
until the
consumer is satisfied that the remaining detergent composition on the dish
article has
been removed. Completion of rinsing is often evaluated by the complete removal
of
suds from the dish article and by the lack of a greasy or slippery feel of the
dish article to
the touch. Under certain consumer washing conditions such as in ambient water
conditions and direct application conditions this problem of complete rinsing
is
particularly noticeable.
It is therefore an aim of the present invention to provide a concentrated
dishwashing detergent composition which exhibits improved rinsing performance.
It has now been found that this objective can be achieved by the incorporation
of
high levels of hydrotropes in the dishwashing formulations.
Hydrotropes are known in the art and have been described for various
applications.
Hydrotropes are typically incorporated into liquid detergent compositions in
order to
increase the aqueous solubility of various slightly soluble organic chemicals,
particularly
surfactants. In order to aid dissolution the art teaches that low levels of
hydrotrope, i.e.
less than 10% are required to deliver the benefit.
For example EP 396340 discloses hard surface cleaning compositions comprising
anionic and nonionic surfactants and hydrotropes. Dishwashing compositions are
also
WO 95/30729 ~ PCT/US95105069
exemplified. EP 467618 discloses liquid hard surface cleaners comprising pine
oil,
chelating agents and hydrotropes. Dishwashing compositions are not mentioned.
Higher levels of hydrotrope have been disclosed in the art. For example EP
200264
discloses concentrated heavy duty liquid detergent compositions comprising
anionic and
nonionic surfactants and 2-50% water soluble dicarboxylic acid monoester (a
hydrotrope). No other hydrotropes or dishwashing compositions are disclosed.
GB 1 380 107 discloses liquid detergent compositions comprising organic
detergents and 1-40% hydrotrope. Dishwashing compositions are not disclosed.
Unpublished US patent application number 07/938978 discloses liquid
dishwashing
compositions comprising polyhydroxy fatty acid amide and 0.001-15%
alkylpolyethoxy
carboxylate (disclosed as a hydrotrope). US patent number 07/938979 discloses
liquid
dishwashing compositions comprising 5-95% alkylamphocarboxylic acid and
calcium or
magnesium ions.
However, the art does not recognise the rinsing performance benefits that are
provided to high active dishwashing detergent compositions by the
incorporation of high
levels of hydrotrope.
Summar,~of the invention
The present invention is a dishwashing detergent composition comprising a
surfactant system, said system comprising a polyhydroxyfatty acid amide and/or
a
alkylpolysaccharide or mixtures thereof and,
greater than 11% hydrotrope selected from lower alkyl aryl sulphonate salts,
C6-C12
alkanols, C 1-C6 carboxylic sulphate or sulphonate salts, urea, C 1-C4
hydrocarboxylates,
C1-C4 carboxylates and C2-C4 diacids and mixtures thereof.
All weights, ratios and percentages are given as a % weight of the total
composition unless otherwise stated.
Detailed description of the invention
Hvdrotropes
WO 95/30729 ~ PCTIUS95/05069
2~9i136
4
According to the present invention an essential feature of the dishwashing
detergent composition is a hydrotrope. Hydrotropes suitable for use herein are
selected
from the group lower alkyl aryl sulphonate salts, C6-C 12 alkanols, C 1-C6
carboxylic
sulphate or sulphonate salts, urea, C 1-C4 hydrocarboxylates, C 1-C4
carboxylates and
C2-C4 diacids and mixtures thereof.
Suitable lower alkyl aryl sulphonates are preferably C~-Cg alkyl aryl
sulphonates
and include sodium, potassium, calcium and ammonium xylene sulphonates,
sodium,
potassium, calcium and ammonium toluene sulphonates, sodium, potassium,
calcium and
ammonium cumene sulphonate, and sodium, potassium, calcium and ammonium
napthalene sulphonates and mixtures thereof.
Suitable C 1-Cg carboxylic sulphate or sulphonate salts are any water soluble
salts
or organic compounds comprising 1 to 8 carbon atoms (exclusive of substituent
groups),
which are substituted with sulphate or sulphonate and have at least one
carboxylic group.
The substituted organic compound may be cyclic, acylic or aromatic, i.e.
benzene
derivatives. Preferred alkyl compounds have from 1 to 4 carbon atoms
substiuted with
sulphate or sulphonate and have from 1 to 2 carboxylic groups. Examples of
suitable
hydrotropes include sulphosuccinate salts, sulphophthalic salts, sulphoacetic
salts, m-
sulphobenzoic acid salts and diesters sulphosuccinates, preferably the sodium
or
potassium salts as disclosed in US 3 915 903.
Suitable C1-C4 hydrocarboxylates, C1-C4 carboxylates for use herein include
acetates and propionates and citrates. Suitable CZ-C4 diacids for use herein
include
succinic, glutaric and adipic acids.
Other compounds which deliver hydrotropic effects suitable for use herein as a
hydrotrope include C6-C 12 alkanols and urea.
Preferred hydrotropes for use herein are sodium, potassium, calcium and
ammonium cumene sulphonate, sodium, potassium, calcium and ammonium xylene
sulphonate, sodium, potassium, calcium and ammonium toluene sulphonate and
mixtures
thereof. Most preferred are sodium cumene sulphonate and calcium xylene
sulphonate
and mixtures thereof.
WO 95/30729 PCT/US95/05069
According to the present invention the dishwashing compositions comprise more
than 11% of said hydrotrope, preferably from 11.5% to 40%, more preferably
from 12%
to 25%, most preferably from 12% to 20% of said hydrotrope and mixtures
thereof.
Another essential feature of the present invention is a surfactant system.
Said
surfactant system comprises as an essential feature a alkylpolysaccharide
and/or a
polyhydroxy fatty acid amide or mixtures thereof. The compositions of the
present
invention comprise from 1% to 50%, preferably from 5% to 40%, more preferably
from
10% to 40% of said surfactant system.
Alkylpolysaccharide surfactant
Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent
4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group containing from
about 6
to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms
and a
polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about
1.0 to
about 10, preferably from about 1.0 to about 3, most preferably from about 1.3
to about
2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms
can be
used, e.g., glucose, galactose and galactosyl moieties can be substituted for
the glucosyl
moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-,
etc. positions
thus giving a glucose or galactose as opposed to a glucoside or galactoside.)
The intersaccharide bonds can be, e.g., between the one position of the
additional
saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding
saccharide units.
Optionally, and less desirably, there can be a polyalkyleneoxide chain joining
the
hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide
is
ethylene oxide.
Typical hydrophobic groups include alkyl groups, either saturated or
unsaturated,
branched or unbranched containing from 8 to 18, preferably from 10 to 16,
carbon
atoms. Preferably, the alkyl group is a straight-chain saturated alkyl group.
The alkyl
group can contain up to about 3 hydroxyl groups and/or the polyalkyleneoxide
chain can
contain up to about 10, preferably less than 5, alkyleneoxide moieties.
Suitable alkyl
polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl,
pentadecyl,
hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and
hexaglucosides,
galatoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides
and tallow alkyl tetra-, penta- and hexaglucosides.
2191136
The preferred alkylpolyglyc.osides have the formt:la:
R20(CnH2n0)t(gly~osyl~
wherein RZ is selected from the group c~~nsisting of alkyl, alkylphcnyl,
hydraxyatkyl,
hydroxyalkytphenyl, and mixtures thereof in ~which the aliryl groups contain
from 10 to
8, preferably from 12 to 1~, carbon ata:ns; n is 2 ar 3, preferabiy from about
1.3 to
about 3, vast preferably frart about 1.3 to at~out 2.7. x is from 1.0 to 10,
preferably
front 1.0 to 3, frost preferably fi'a:n 1.3 to ~.7 The glycosyl is preferably
derived from
glucose. To prepare these compounds. tl:e alcohol or alkylpolyetho~cy alcohol
is formed
first and then reacted with glucose, or a source of glucose, to ferrn the
gluc;eside
(attachment at ttse 1-positionj. The additional glyeos511 unis car then be
attached
between their J-positicri and the preceding ,~lycosyl units 2-,3-, ~- and~'or
6-position,
prefer ably predominantly the 2-position. In additiea to the polysacc~tarides
mentioned
obey ~ tha carrespondirg sulphated pc!ysaoct~~arides tray xlxo he used
1~.erein.
According to the present in~~e.~.tion the dislswashing cvmpasitions comprise
from
0°.o to 50%, preferably tom 1°ro to 30°~0, mare
preferably from 1.5% to ?G% ot= said
aiky'polysaccharide surfactant
Po~yll, d~ r~_x_v_ fatty acid a:~~id~ 5tarfa~an~
Poly hydroxy fatty arid amides suitable for use herein are acecrdir;g to the
formula:
R~-~ ~l-Z
R1
wherein R1 is H, a C2_C~ hydracarbyl, 2-hydraxy ethyl, 2-hydroxy propyl or
mixtures
thereof pre:erably a CI-C4 aii:yl, r<:are preferably a C1 ar C:2 alkyl, most
preferably a
C1~ ~d R2 is a CS-C31 hydrocarbyl, preferably- straight cram C7-Cig alkyl or
alkenyl,
most ~referahly strail;ht cEtain C11-C1y alkyl ar alkenyl or mixtures thereof;
and Z is a
polyhydrocarbyl having a linear hydrocarbyl chain with at Ieast 3 hydroxyl
groups
directly connected to the ;;rain ar an alkov,:ylated cler;vative thereof. Z is
preferably
derived from a reducing sugar ira redyactive amination reaction: more
preferably Z is a
glycityl. Suitable reducing sugars inciuda blucose, fruc.'tese, maltase,
lactose, galactose,
mattnose and xylose. As raw materials high d.extrese corn syn:p, high fructose
com syrup
and ?'tip;h tt~~altose corn syrup can be utili>ed as wel! as individual sugars
listed above, It
should be tandarstood that these corn syrups may yield a mixture of sugar
components
fur Z. Z is preferably selected from the group consisting ef
WO 95/30729 . PCT/US95/05069
7
-CH2(CHOH)nCH20H, -CH(CH201-i)-(CHOH)n-1-CH20H, or -CH2-
(CHOH)2(CHOR')(CHOH)-CH20H and alkoxylated derivatives thereof, wherein n is
an
integer from 3 to 5 inclusive and R' is hydrogen or a cyclic or aliphatic
monosaccharide.
Most preferred are the glycityls wherein n is 4, particularly CH2(CHOH)4CH20H.
According to the formula R1 can be for example, N-methyl , N-ethyl, N-propyl,
N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. RS-CO-N< can
be for
example cocamide, stearimide, oleamide, lauramide, myristamide, capricamide,
palmitamide, talloamide etc. Z cacti be 1-deooxyglycityl, 2-deoxyfructityl, 1-
deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-doexymannityl, 1-
deoxymaltotriotityl, etc.
Other polyhydroxy fatty acid amides suitable for use herein are gemini
polyhydroxy
fatty acid amides having the formula:
Z Z
I I
N-X-N
1 I
0=C C v =0
I t
R R'
wherein: X is a bridging group having from about 2 to about 200 atoms; Z and
Z' are the
same or different alcohol-containing moieties having two or more hydroxyl
groups (e.g.,
glycerol, and units derived from reducing sugars such as glucose, maltose and
the like); or
either one (but not both) of Z or Z' is hydrogen; and R and R' are the same or
different
hydrocarbyl moieties having from about 1 to about 21 carbon atoms and can be
saturated,
branched or unsaturated (e.g., oleoyl) and mixtures thereof.
Preferred X groups are selected from substituted or unsubstituted, branched or
linear alkyl, ether alkyl, amino alkyl, or amido alkyl moieties having from
about 2 to about
15 carbon atoms. Preferred alkyl moieties are unsubstituted, linear alkyl
moieties having
the formula -(CH2)n-, wherein n is an integer from 2 to about 15, preferably
from 2 to
about 10, and most preferably from 2 to about 6; and also unsubstituted,
branched alkyl
moieties having from 3 to about 1 S carbon atoms, preferably from 3 to about
10 carbon
atoms, and most preferably from 3 to about 6 carbon atoms. Most preferred are
ethylene
and propylene (branched or linear) alkyl moieties. Also preferred are
unsubstituted,
branched or linear ether alkyl moieties having the formula -R2-(O-R2)m-,
wherein each R2
is independently selected from C2-Cg branched or linear alkyl and/or aryl
moieties
WO 95/30729
PCTIUS95/05069
8
(preferably ethyl, propyl or combinations thereof) and m is an integer from 1
to about 5. X
may also be unsubstituted, branched or linear amino and/or amido alkyl
moieties having the
formula -R2-(N(R3)-R2)m-, wherein each R2 is independently selected from C2-Cg
branched or linear alkyl and/or aryl moieties (preferably ethyl, propyl or
combinations
thereof), m is an integer from 1 to about 5, and R3 is selected from hydrogen,
C 1-CS alkyl,
and -C(O)R4-, wherein R4 is C 1-C21 alkyl, including -C(O)R. The X moiety may
be
derived from commercially available amine compounds such as, for example,
JeffaminesR
(supplied by Texaco) such as JED600, JEDR148, JEDR192, JED230, JED2000, J-D230
and J-D400.
Preferred X moieties therefore include: -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)S-
, -
(CH2)6-~ -CH2CH(CH3)(CH2)3-~ -(CH2)2-O'(CH2)2-~ -(CH2)3'O-(CH2)3-~ -(CH2)2-O-
(CH2)3'~ -(CH2)2'O-(CH2)2-O-(CH2)2-~ -(CH2)3-O-(CH2)2-O-(CH2)3'~ -(CH2)2-O-
(CH2)3'O'(CH2)2-~ -(CH2)2-~-(CH2)2-~'CH2)3-~-(CH2)3-~ -(CH2)2-~'CH2)3-
-(CH2)2-N(C(O)R)-(CH2)2-~ -(CH2)3-N(C(O)R)-(CH2)3-~ '(CH2)2-N(C(O)R)-
(CH2)3-~ -(CH2)2-~(C6H4)~-(CH2)2-~ -(CH2)3-~(C6H4)~OCH2)3-~ -(CH2)2-
NHCH2(C6H4)CH2~-(CI"i2)2-~ -(CH2)3-NHCH2(C6H4)CH2~-(CH2)3-~ etc.
Preferred Z and Z' groups are independently selected from
polyhydroxyhydrocarbyl
moieties having a linear hydrocarbyl chain with at least 2 hydroxyls (in the
case of glycerol)
or at least 3 hydroxyls ( in the case of other sugars) directly connected to
the chain, or an
alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z and
Z'
preferably will be derived from a reducing sugar, more preferably Z and/or Z'
is a glycityl
moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose,
galactose,
mannose, and xylose, as well as glyceraldehyde. As raw materials, high
dextrose corn
syrup, high fructose corn syrup, and high maltose corn syrup can be utilised
as well as the
individual sugars listed above. These corn syrups may yield a mix of sugar
components for
Z and Z'. It should be understood that it is by no means intended to exclude
other suitable
raw materials. Z and/or Z' preferably will be selected from the group
consisting of -CH2-
(CHOH)-p-CH20H, -CH(CH20H)-(CHOH)p_ 1-CH20H, -CH2-
(CHOH)2(CHORI)(CHOH)-CH20H, where p is an integer from 1 to 5, inclusive, and
RI
is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives
thereof.. Most
preferred are glycityls wherein p is 4, particularly -CH2-(CHOH)4-CH20H.
Preferred R and R' groups are independently selected from C3-C21 hydrocarbyl
moieties, preferably straight or branched chain C3-C 13 alkyl or alkenyl, more
preferably
straight chain C5-C 11 alkyl or alkenyl, most preferably straight chain CS-Cg
alkyl or
WO 95/30729 . : ; PCT/US95/05069
alkenyl, or mixtures thereof. R-CO-N< and/or R'-CO-N< can be, for example,
cocamide,
stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide,
tallowamide, etc.
Examples of such compounds therefore include, but are not limited to:
CH3(CH2)6C(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3; CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-
(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3 (CH2) 1 OC(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)(CH2) 1 OCH3
CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-(CH2)2-O-(CH2)2-O-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3; CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-
CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)gC(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-
[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3;
CH3(CH2)3CH(CH2CH3)C(O)N[CH2(CHOH)4CH20H]-(CH2)2-
[CH2(CHOH)4CH20H]NC(O)CH(CH2CH3)(CH2)3CH3;
CH3(CH2)6C(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-
[CH2(CHOH)4CH20H]NC(O)(CH2)6CH3; CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-
(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NC(O)(CH2)8CH3;
C6HSC(O)N[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-
[CH2(CHOH)4CH20H]NC(O)C6H5; CH3(CH2)4C(O)N[CH2(CHOH)4CH20H]-
(CH2)2-[CH2(CHOH)4CH20H]NC(O)(CH2)gCH3.
These compounds can be readily synthesised from the following disugar
diamines:
HN[CH2(CHOH)4CH20H]-(CH2)2-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-CH2CH(CH3)(CH2)3-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-(CH2)2-O-(CH2)2-O-(CH2)2-[CH2(CHOH)4CH20H]NH;
HN[CH2(CHOH)4CH20H]-(CH2)3-O-(CH2)2-O-(CH2)3-[CH2(CHOH)4CH20H]NH;
and HN[CH2(CHOH)4CH20H]-(CH2)3-[CH2(CHOH)4CH20H]NH.
The compositions according to the present invention comprise from 0% to 50% ,
preferably from 1% to 20%, most preferably from 3% to 15%, of said polyhydroxy
fatty
acid amide.
Surfactant s stem
WO 95/30729 ~ PCT/US95/05069
2 ~ 9, ~ 13 0
io
According to the present invention the surfactant system may optionally
comprise
other surfactants selected from nonionic, anionic, cationic, zwitterionic, and
amphoteric
surfactants, and any mixtures thereof.
The anionic surfactant may be essentially any anionic surfactant, including
anionic
sulphate, sulphonate or carboxylate surfactant.
Anionic su~hate surfactant
The anionic sulphate surfactant may be any organic sulphate surfactant. It is
preferably selected from the group consisting of C 10-C 16 alkyl sulphate
which has been
ethoxylated with from about 0.5 to about 20 moles of ethylene oxide per
molecule, C9-
C 17 acyl-N-(C 1-C4 alkyl) glucamine sulphated, -N-(C2-C4 hydroxyalkyl)
glucamine
sulphate, and mixtures thereof. More preferably, the anionic sulphate
surfactant is a
C 10-C 16 alkyl sulphate which has been ethoxylated with from about 0.5 to
about 20,
preferably from about 0.5 to about 12, moles of ethylene oxide per molecule.
Alkyl ethoxy sulphate surfactants comprises a primary alkyl ethoxy sulphate
derived from the condensation product of a C 10-C 16 alcohol with an average
of from
about 0.5 to about 20, preferably from about 0.5 to about 12, ethylene oxide
groups.
The C 10-C 16 alcohol itself is commercially available. C 12-C 14 alkyl
sulphate which has
been ethoxylated with from about 3 to about 10 moles of ethylene oxide per
molecule is
preferred.
Conventional base-catalysed ethoxylation processes to produce an average
degree
of ethoxylation of 12 result in a distribution of individual ethoxylates
ranging from 1 to
15 ethoxy groups per mole of alcohol, so that the desired average can be
obtained in a
variety of ways. Blends can be made of material having different degrees of
ethoxylation
and/or different ethoxylate distributions arising from the specific
ethoxylation techniques
employed and subsequent processing steps such as distillation.
Anionic sulphate surfactants include the Cg-C 17 acyl-N-(C 1-C4 alkyl) and -N-
(C 1-
C2 hydroxyalkyl) glucamine sulphates, preferably those in which the Cg-C 17
acyl group
is derived from coconut or palm kernel oil. These materials can be prepared by
the
method disclosed in U.S. Patent 2,717,894, Schwartz, issued September 13,
1955.
- WO 95/30729 ~ ~ ~ ' ; ~ ~ PCT/US95/05069
11
The counterion for the anionic sulphate surfactant component is preferably
selected
from calcium, sodium, potassium, magnesium, ammonium, or alkanol-ammonium, and
mixtures thereof, with calcium and magnesium being preferred for cleaning and
sudsing,
respectively.
Anionic sulphonate surfactant
Anionic sulphonate surfactants suitable for use herein include, for example,
the
salts (e.g. alkali metal salts) of Cg-C2p linear alkylbenzene sulphonates, Cg-
C22 primary
or secondary alkane sulphonates, Cg-C24 olefin sulphonates, sulphonated
polycarboxylic
acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty
oleyl glycerol
sulphonates, paraffin sulphonates, and any mixtures thereof.
Anionic alkyl ethoxy carboxylate surfactant
Alkyl ethoxy carboxylates suitable for use herein include those with the
formula
RO(CH2CH20)x CH2C00-M+ wherein R is a C 12 to C 16 alkyl group, x ranges from
0
to 10, and the ethoxylate distribution is such that, on a weight basis, the
amount of
material where x is 0 is less than 20%, preferably less than 15%, most
preferably less
than 10%, and the amount of material where x is greater than 7, is less than
25%,
preferably less than 15%, most preferably less than 10%, the average x is from
2 to 4
when the average R is C 13 or less, and the average x is from 3 to 6 when the
average R
is greater than C 13, and M is a cation, preferably chosen from alkali metal,
alkaline earth
metal, ammonium mono-, di-, and tri-ethanol-ammonium, most preferably from
sodium,
potassium, ammonium and mixtures thereof with magnesium ions. The preferred
alkyl
ethoxy carboxylates are those where R is a C 12 to C 14 alkyl group.
Anionic al -1 nolyethoxy pol cay rboxylate surfactant
Alkyl polyethoxy polycarboxylate surfactants suitable for use herein include
those
having the formula:
R-O-(CH- CH- O)x-R3
R1 R2
wherein R is a C6 to C 1 g alkyl group, x is from 1 to 25, R1 and R2 are
selected from the
group consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic
WO 95/30729
PCT/US95/05069 _.
12
acid radical, and mixtures thereof, wherein at least one R1 or R2 is a
succinic acid radical
or hydroxysuccinic acid radical, and R3 is selected from the group consisting
of
hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8
carbon
atoms, and mixtures thereof.
Anionic secondary soap surfactant
Secondary soap surfactants (aka "alkyl carboxyl surfactants") useful herein
are
those which contain a carboxyl unit connected to a secondary carbon. It is to
be
understood herein that the secondary carbon can be in a ring structure, e.g.
as in p-octyl
benzoic acid, or as in alkyl-substituted cyclohexyl carboxylates. The
secondary soap
surfactants should contain no ether linkages, no ester linkages and no
hydroxyl groups.
There should be no nitrogen atoms in the head-group (amphiphilic portion). The
secondary soap surfactants usually contain 11-15 total carbon atoms, although
slightly
more (e.g., up to 16) can be tolerated, e.g. p-octyl benzoic acid.
The following general structures further illustrate some of the secondary soap
surfactants
(or their precursor acids) useful herein.
A. A highly preferred class of secondary soaps useful herein comprises the
secondary carboxyl materials of the formula R3 CH(R4)COOM, wherein R3 is
CH3(CH2)x and R4 is CH3(CH2)y, wherein y can be 0 or an integer from 1 to 4, x
is an
integer from 4 to 10 and the sum of (x + y) is 6-14, preferably 7-13, most
preferably 12.
B. Another class of secondary soaps useful herein comprises those carboxyl
compounds
wherein the carboxyl substituent is on a ring hydrocarbyl unit, i.e.,
secondary soaps of
the formula RS-R6-COOM, wherein RS is C~-C 10, preferably C8-C9, alkyl or
alkenyl
and R6 is a ring structure, such as benzene, cyclopentane and cyclohexane.
(Note: RS
can be in the ortho, meta or para position relative to the carboxyl on the
ring.)
C. Still another class of secondary soaps comprises secondary carboxyl
compounds of
the formula CH3(CHR)k-(CH2)r,.l-(CHR)n-CH(COOM)(CHR)o-(CH2)p-(CHR)q-CH3,
wherein each R is C1-C4 alkyl, wherein k, n, o, q are integers in the range of
0-8,
provided that the total number of carbon atoms (including the carboxylate) is
in the range
of 10 to 18.
- WO 95/30729 PCTlUS95/05069
13
In each of the above formulas A, B and C, the species M can be any suitable,
especially water-solubilizing, counterion, e.g., H, alkali metal, alkaline
earth metal,
ammonium, alkanolammonium, di- and tri- alkanolammonium, and C 1-CS alkyl
substituted ammonium. Sodium is convenient, as is diethanolammonium.
Preferred secondary soap surfactants for use herein are water-soluble members
selected from the group consisting of the water-soluble salts of 2-methyl-1-
undecanoic
acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic
acid, 2-
pentyl-1-heptanoic acid and isopentadecanoic acid.
Other anionic surfactants useful for detersive purposes can also be included
in the
compositions hereof. These can include salts (including, for example, sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, fatty oleyl glycerol sulphates, alkyl phenol
ethylene oxide
ether sulphates, alkyl phosphates, isethionates such as the acyl isethionates,
N-aryl
taurates, fatty acid amides of methyl tauride, alkyl succinates, N-acyl
sarcosinates,
branched primary alkyl sulphates, alkyl polyethoxy carboxylates such as those
of the
formula RO(CH2CH20)kCH2C00-M+ wherein R is a C8-C22 alkyl, k is an integer
from 0 to 10, and M is a soluble salt-forming cation, and fatty acids
esterified with
isethionic acid and neutralised with sodium hydroxide. Resin acids and
hydrogenated
resin acids are also suitable, such as rosin, hydrogenated rosin, and resin
acids and
hydrogenated resin acids present in or derived from tall oil. Further examples
are given
in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry
and Berch).
A variety of such surfactants are also generally disclosed in U.S. Patent
3,929,678,
issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through
Column 29,
line 23.
According to the present invention the dishwashing compositions may comprise
from 3% to 50%, preferably from 3% to 40%, more preferably from 3% to 30% of
said
anionic surfactant.
Nonionic surfactant
According to the present invention the surfactant system of said dishwashing
detergent composition may comprise nonionic surfactants.
WO 95/30729
j PCT/US95/05069 -
14
Nonionic condensates of alkyl phenols
Nonionic condensates suitable for use herein include polyethylene,
polypropylene,
and polybutylene oxide condensates of alkyl phenols. In general, the
polyethylene oxide
condensates are preferred. These compounds include the condensation products
of alkyl
phenols having an alkyl group containing from about 6 to about 12 carbon atoms
in
either a straight chain or branched chain configuration with the alkylene
oxide.
Nonionic ethoxylated alcohol surfactant
Alkyl ethoxylate condensation products of aliphatic alcohols with from about 1
to
about 25 moles of ethylene oxide are suitable for use herein. The alkyl chain
of the
aliphatic alcohol can either be straight or branched, primary or secondary,
and generally
contains from 6 to 22 carbon atoms. Particularly preferred are the
condensation
products of alcohols having an alkyl group containing from 8 to 20 carbon
atoms with
from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most
preferred
are the condensation products of alcohols having an alkyl group containing
from 8 to 14
carbon atoms with from about 6 to about 10 moles of ethylene oxide per mole of
alcohol.
Examples of commercially available nonionic surfactants of this type include
TergitoITM
15-S-9 (the condensation product of C 11-C 15 linear alcohol with 9 moles
ethylene
oxide), TergitolTM 24-L-6 NMW (the condensation product of C 12-C 14 Pnmary
alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both
marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product
of
C 14-C 15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the
condensation product of C 12-C 13 linear alcohol with 6.54 moles of ethylene
oxide),
NeodoITM 45-7 (the condensation product of C 14-C 15 linear alcohol with 7
moles of
ethylene oxide), NeodolTM 45-4 (the condensation product of C 14-C 15 linear
alcohol
with 4 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C
12-13
linear alcohol with 3 moles of ethylene oxide) marketed by Shell Chemical
Company, and
KyroTM EOBN (the condensation product of C 13-C 15 alcohol with 9 moles
ethylene
oxide), marketed by The Procter & Gamble Company and Dobanol 91 marketed by
the
Shell Chemical Company and Lial 111 marketed by Enichem.
Nonionic EO/PO condensates with propylene glycol
The condensation products of ethylene oxide (EO) with a hydrophobic base
formed by the condensation of propylene oxide (PO) with propylene glycol are
suitable
15
2i 91 136
for use herein. Examples of compounds of this type include certain of the
commercially-
available PluroniG~M surfactants, marketed by BASF.
Iy'onio~nic EO condensation B~~oduc~ith urqpyle a oxidelethvle a dia 'pe
acts
The condensation products of ethylene oxide with the product resulting from
the
reaction of propylene oxide and ethylenediamine are suitable for use herein.
Examples of
this type of nonionic surfactant include certain of the commercially available
TttronicT~'i
compounds, marketed by BASF.
According to the present invention the dishwashing compositions may comprise
nom 0°~o to 30%, preferably from 0.1°ii; to 25'/0. rr~ore
preferably from 0.5% to 20% of
said nonionic surfactants.
Am~tt~teri~surfa
Suitable amphoteric surfactants for use herein include the all'yl
amphocarboxylic
acids of the formula:
C
RC-NHCH2CH2Ri
wherein I~ is a Cg-Clg alkyl group, and Ri is of the general formula
FIL)xCOC- ~H2)xC00-
N or ''~+)-CF'l2CH20H
1 R1
R
wherein R1 is a (CH2)xC00hi or CH2CHZOI~, and x is 1 or 2 and M is preferabiy
chosen from alkali metal, alkaline earth metal, ammonium, mono-, di-, and tri-
ethanolammonium, most preferably from sodium, potassium, ammonium and mixtures
thereof with magnesium ions. The preferred R alkyl chain length is a C10 to
Clq, alkyl
group. A preferred amphocarboxylic acid is produced from fatty imidazolines
wherein
WO 95/30729
PCT/U595/05069
16
the dicarboxylic acid functionality of the arnphodicarboxylic acid is diacetic
acid and/or
dipropionic acid. A suitable example of an alkyl aphodicarboxylic acid for use
herein in
the amphoteric surfactant Miranol(TM) ~.2M Conc. manufactured by Miranol,
Inc.,
Dayton, NJ.
Amine oxide surfactant
The compositions of the present invention preferably further comprise from 1%
to
20%, preferably from 2% to 20% by weight of an amine oxide.
Amine oxides useful in the present vvention include those compounds having the
formula
O
R3 (OR4)xN(RS )2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl
phenyl
group, or mixtures thereof, containing from 8 to 26 carbon atoms, preferably 8
to 16
carbon atoms; R4 is an alkylene or hydrox~~alkylene group containing from 2 to
3 carbon
atoms, preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3,
preferably 0; and
each RS is an alkyl or hydyroxyalkyl group containing from 1 to 3, preferably
from 1 to 2
carbon atoms, or a polyethylene oxide group containing from 1 to 3, preferable
1,
ethylene oxide groups. The RS groups can be attached to each other, e.g.,
through an
oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C 10-C 1 g alkyl dimethyl
amine
oxides and Cg-C 12 alkoxy ethyl dihydroxyethyl amine oxides. Examples of such
materials include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,
dipropyltetradecylamine
oxide, methylethylhexadecylamine oxide, dodecylamidopropyl dimethylamine oxide
and
dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C l0-C 1 g alkyl
dimethylamine
oxide, and C 10-18 acylamido alkyl dimethylamine oxide.
Zwitterionic surfactant
WO 95/30729 ' ; PCT/US95/05069
17
Zwitterionic surfactants can also be incorporated into the detergent
compositions
herein.
Betaine surfactants
According to the present inventior the compositions may comprise betaines. The
betaines useful as zwitterionic surfactants in the present invention are those
compounds
having the formula R(R1)2N+R2C00- wherein R is a C6-Clg hydrocarbyl group,
preferably a C 1 p-C 16 alkyl group or C 1 p_ 16 acylamido alkyl group, each
R1 is typically
C 1-C3 alkyl, preferably methyl, and R2 is a C 1-CS hydrocarbyl group,
preferably a C 1-
C3 alkylene group, more preferably a C 1-C2 alkylene group. Examples of
suitable
betaines include coconut acylamidoprops idimethyl betaine; hexadecyl dimethyl
betaine;
C12-14 acylamidopropylbetaine; Cg_l~, acylamidohexyldiethyl betaine; 4[C14-16
aeylmethylamidodiethylammonio]-1-carbo~..ybutane; C 16-18
acylamidodimethylbetaine;
C12-16 acylamidopentanediethyl-betaine; [C12-16
acylmethylamidodimethylbetaine.
Preferred betaines are C 12-18 dimethyl-ammonio hexanoate and the C 10-18
acylamidopropane (or ethane) dimethyl (oT diethyl) betaines.
The complex betaines for use herein have the formula
R - (A)n - ~ - (C~1)x]y - N - Q (I)
B B
wherein R is a hydrocarbon group having from 7 to 22 carbon atoms, A is the
group
(C(O)), n is 0 or 1, R1 is hydrogen or a lo~rer alkyl group, x is 2 or 3, y is
an integer of 0
to 4, Q is the group -R2COOM wherein R2 is an alkylene group having from 1 to
6
carbon atoms and M is hydrogen or an ion from the groups alkali metals,
alkaline earth
metals, ammonium and substituted ammonium and B is hydrogen or a group Q as
defined.
Sultaines
The sultaines useful in the present invention are those compounds having the
formula (R(R1 )2N+R2S03- wherein R is a C6-C 1 g hydrocarbyl group, preferably
a
C 10-C 16 alkyl group, more preferably a C 12-C 13 alkyl group, each R 1 is
typically C 1-
C3 alkyl, preferably methyl, and R2 is a C 1-C6 hydrocarbyl group, preferably
a C 1-C3
alkylene or, preferably, hydroxyalkylene group. Examples of suitable sultaines
include
WO 95/30729 y:191 13 6
PCT/US95/05069
18
C 12-C 14 dimethylammonio-2-hydroxypropyl sulfonate, C 12_ 14 amido propyl
ammonio-
2-hydroxypropyl sultaine, C I 2-14 dihydroxyethylammonio propane sulfonate,
and C 16-
1 g dimethylammonio hexane sulfonate, with C 12-14 amido propyl ammonio-2-
hydroxypropyl sultaine being preferred.
The zwitterionics described herein above may also be presen tin small
quantities to
deliver suds enhancing benefits to the compositions.
Enzymes
Compositions according to the present invention may additionally comprise
enzymes. Suitable enzymes for use herein include lipolytic, proteolytic and
amyloyltic
enzymes. A preferred lipase is derived from Pseudomonas pseudoalcaligenes
described
for example in EP-B-0218272. Preferred commercially available proteolytic
enzymes
include Alcalase and Savinase (Novo Industries A/S) and Maxatase
(International Bio-
Synthetics, Inc.). Preferred amyiases include for example alpha-amylases
obtained from a
special strain of B licheniforms, described for example in GB 1 269 839.
Preferred
commercially available amylases include Termamyl (Novo Industries A/S). The
compositions according to the present invention may comprise from 0.001% to
1%,
more preferably from 0.01% to 0.1% of active enzyme. In addition the
composition may
comprise an enzyme stabilizing system.
Lime Soap Dispersants
The compositions of the present invention are particularly useful when
formulated
to contain a lime soap dispersant compound which acts to disperse any
insoluble lime
soap salts formed. Lime soaps prevent the deposition of these salts as spots
or films on
the articles in the wash, or as an unseemly ring around the rim of the sink.
Certain lime
soap dispersant compounds may also provide improved product stability
particularly
where the product is formulated as a liquid product containing calcium ions.
A lime soap dispersant compound herein is defined as a compound, which has a
lime soap dispersing power (LSDP), as defined hereinafter of no more than 8,
preferably
no more than 7, most preferably no more than 6. The lime soap dispersant
compound is
typically present at a level of from 0.1% to 40% by weight, more preferably 1%
to 20%
by weight, most preferably from 2% to 10% by weight of the compositions.
WO 95130729 ~. - PCT/US95/05069
~~'~~1 ~Jb
19
A lime soap dispersant is a material that prevents the precipitation of alkali
metal,
ammonium or amine salts of fatty acids by calcium or magnesium ions. A
numerical
measure of the effectiveness of a lime soap dispersant is given by the lime
soap dispersing
power (LSDP) which is determined using the lime soap dispersion test as
described in an
article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., volume 27,
pages
88-90, (1950). The LSDP is the % weight. ratio of dispersing agent to sodium
oleate
required to disperse the lime soap deposits formed by 0.025g of sodium oleate
in 30m1 of
water of 333ppm CaC03 (Ca:Mg=3:2) equivalent hardness.
Thus in accord with the test method described above a material with a lower
LSDP is a more effective lime soap dispersant than one with a higher LSDP.
WO 95/30729
.~ ~ X91 i 3 6 PCT/US95/05069
Calcium
According to the present invention the dishwashing compositions may comprise
from 0.01% to 3%, more preferably from 0.15% to 1% of calcium ions may be
included
in the detergent compositions herein. It has been found for compositions
containing
polyhydroxy fatty acid amide that the presence of calcium greatly improves the
cleaning
of greasy soils. This is especially true when the compositions are used in
softened water,
which contains few divalent ions.
The calcium ions can, for example, be added as a chloride, hydroxide, oxide,
formate or acetate, or nitrate salt. If the anionic surfactants are in the
acid form, the
calcium can be added as a calcium oxide or calcium hydroxide slurry in water
to
neutralise the acid.
The calcium ions may be present in the compositions as salts. The amount of
calcium ions present in compositions of the invention may be dependent upon
the amount
of total anionic surfactant present herein. The molar ratio of calcium ions to
total anionic
surfactant is preferably from 1:0.1 to 1:25, more preferably from 1:2 to 1:10,
for
compositions of the invention.
Calcium stabilising agent
Malic, malefic or acetic acid or certain lime soap dispersant compounds may be
added to a composition formulated to contain calcium to provide good product
stability,
and in particular to prevent the precipitation of insoluble calcium salts.
Malic, malefic or
acetic acid may, where calcium is present, preferably be added at levels of
from 0.05% to
10% of the composition and a molar ratio with calcium of from 10:1 to 1:10.
Ma nesium
From 0.01% to 3%, most preferably from 0.15% to 2%, by weight, of magnesium
ions are preferably added to the liquid detergent compositions of the
invention for
improved product stability, as well as improved sudsing.
If the anionic surfactants are in the acid form, then the magnesium can be
added by
neutralization of the acid with a magnesium oxide or magnesium hydroxide
slurry in
water. Calcium can be treated similarly. This technique minimises the addition
of chloride
2191I3~
fans, which reduces corrosive properties The neutralised surfactant salts and
the
hydrotrope are then added to the f nil mixing tank and any optional
ingredients are added
before adjusting the pH.
Qreanic solvent
The compositions of the im:enzic~n will mast preferably contain an organic
solvent
system present at levels of from I% to 30°I° by weight,
preferably from 1% to 20% by
weight, more preferably form 2°.~o to 15°~o by' weight of the
composition. The organic
solvent system may be a mono, or mL~ced solvent system; but is preferably in
mixed
solvent system. Preferably, at least the major component of ahe solaent system
is of loin
volatility. Suitable organic solvents for use herein has the general formula:
CH3
RO(CH2CH0)nH
wf~erein R is an alkyl, askenyl, or alkyl aryl group having from I to 8 carbon
atoms, and n
is an integer from 1 to 4. Prcferab:y, A is an alkyl group containing 1 to 4
carbon atoms,
and n is I or 2. Especially preferred R groups ar a n-butyl or isobutyi.
Preferred solvents
of this type are 1-n-butoxypropane-2-of (n=1); and 1(2-n-butoxy-1-
methylethoxy)propane-2-of (n=Z), and mixtures thereof.
Other solvents useful herein include the water soluble C ARBrTOL or
CELLOSOLV~ solvents. These solvents are compounds of the 2-(2-
alkoxyethoay)ethanol class wherein the alkoxy group is derived from ethyl,
propyl or
butyl.
Other suitable salv2nts are benzyl alcohol, and dials such as 2-ethy!-1,3-
hexanediol and 2,2,4-trimethl-1,3-pentanediol.The low molecular weight, water-
soluble,
liquid polyethylene glycols are also suitable :~alvents for use herein.
The alkane mono and dials, especially the C 1-Cb alkane mono and dials are
suitable for use herein. C I -C~ monohydric alcohols (ey ethanol, prapanol,
isopropanot,
butanol and mixtures thereof) are preferred, with ethanol particularly
preferred. The C1-
C4 dihydric alcohols, including prcpylene glycol, are also preferred.
T'hickg ing aagtL
TO'flL P . 0p4
WO 95/30729 ~ ' 2 ~ 91 7 3 6 pCT/US95/05069
22
The compositions according to the present invention may addditionally comprise
thickening agents, such as polyquaterium cellulose cationic polymer, for
example
QuatrisoftR available from the Americhol Corporation.
pH of the Composition
The compositions according to the present invention formulated for use in
manual
dishwashing applications are preferably formulated to have a pH at 20 C of
from 3 to 12,
preferably from 6 to 9, most preferably from 7 to 8.5.
In another aspect of the present invention the composition may be formulated
for
use as in pre-treatment applications whereby the composition is applied in
essentially the
concentrated from onto the dishes. Preferably the composition is allowed to
remain on
the dishes for a period of time. Compositions for use in such applications
preferably have
a pH of from 3 to 14, more preferably from 3 to 5 or greater than 8.
Deterrent compositions
According to the present invention the compositions may be liquid or gel
compositions.
Liauid compositions
In a preferred embodiment, the detergent compositions of the present invention
are
liquid detergent compositions. In one preferred embodiment of the present
invention the
compositions are high active formulations such that said compositions comprise
75% to
50% by weight, preferably from 70% to 55% by weight, most preferably from 65%
to
55% by weight of a liquid carrier, e.g., water, preferably a mixture of water
and a C1-C4
monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and
mixtures thereof),
with ethanol being the preferred monohydric alcohol or a mixture of water and
C1-C4
dihydric alcohol (e.g.: propylene glycol). In another preferred embodiment of
the present
invention the detergent composition may be in a concentrated form, such that
the
composition is diluted in water prior to usage.
Gels
WO 95/30729 _ - ~ PCT/US95/05069
23
The detergent compositions of the present invention may also be in the form of
a
gel. Such compositions are typically formulated in polyakenyl polyether and
having a
molecular weight of from about 750,000 to about 4,000,000.
Highly preferred examples of these polycarboxylate polymer thickeners are the
Carbopol 600 series resins available from B.F. Goodrich. Especially preferred
are
Carbopol 616 and 617. It is believed that these resins are more highly cross-
linked than
the 900 series resins and have molecular weights between about 1,000,000 and
4,000,000. Mixtures of polycarboxylate polymers as herein described may also
be used in
the present invention. Particularly preferred is a mixture of Carbopol 616 and
617 series
resins.
The polycarboxylate polymer thickener is utilised preferably with essentially
no
clay thickening agent. In fact, it has been found that if the polycarboxylate
polymers of
the present invention are utilised with clay in the composition of the present
invention, a
less desirable product, in terms of phase instability, results. In other
words, the
polycarboxylate polymer is preferably used instead of clay as a
thickening/stabilising
agent in the present compositions.
If the polycarboxylate polymer is used as a thickening agent in the
compositions of
the present invention, it is typically present at a level of from about 0.1%
to about 10%,
preferably from about 0.2% to about 2% by weight.
The thickening agents are preferably used to provide a yield value of from
about 50
to about 350 and most preferably from about 75 to about 250. The yield value
is an
indication of the shear stress at which the gel strength is exceeded and flow
is initiated. It
is measured herein with a Brookfield RVT model viscometer with a T-bar B
spindle at
25°utilizing a Helipath.
Other desirable ingredients typically used in the compositions herein include
dyes,
perfumes and opacifiers.
Opacifiers such as Lytron (Morton Thiokol, Inc.), a modified polystyrene
latex, or
ethylene glycol distearate can be added, preferably as a last step. Lytron can
be added
directly as a dispersion with mixing. Ethylene glycol distearate can be added
in a molten
state with rapid mixing to form pearlescent crystals. Opacifiers useful
herein, particularly
WO 95/30729 '
j ~ PCT/US95/05069
24
for light duty liquids, are typically present at levels from about 0.2% to
about 10%,
preferably from about 0.5% to about 6% by weight.
Manual dishwashing process
According to the manual dishwashing process aspect of this invention, soiled
dishes are contacted with an effective amount, typically from about 0.5 ml. to
about 20
ml. (per 25 dishes being treated), preferably from about 1 ml. to about 10
ml., of the
composition of the present invention. The actual amount of liquid detergent
composition
used will be based on the judgement of user, and will depend upon factors such
as the
particular product formulation of the composition, the concentration of the
composition,
the number of soiled dishes to be cleaned, the degree of soiling of the dishes
and the
process used by the consumer.
The process by which the soiled dishes are contacted with the effective amount
of
the composition of the invention may be essentially any of the processes for
manual
dishwashing commonly known and encompasses the dilute solution in sink
process,
commonly used in Northern Europe and the US ; the solution in bowl process,
commonly used in Latin America, and the direct application process, commonly
used in
Southern Europe, Japan, and developing countries.
Dilute solution in sink process
In the typical dilute solution in sink process from about 3 ml. to 15 ml.,
preferably
from 5 ml. to 10 ml. of a liquid detergent composition is combined with from
1,000 ml.
to, 10,000 ml., more typically from 3,000 ml. to 5,000 ml. of water in a sink
having a
volumetric capacity in the range of from 5,000 ml. to 20,000 ml., more
typically from
10,000 ml. to 15,000 ml. The detergent composition has a surfactant
concentration of
from about 10 % to about 60 % by weight, preferably from about 45 % to about
50
by weight. The soiled dishes are immersed in the sink containing the detergent
composition and water, where they are cleaned by contacting the soiled surface
of the
dish with a cloth, sponge or similar article. The cloth, sponge or similar
article may be
immersed in the detergent composition and water mixture prior to being
contacted with
the dish surface and is typically contacted with the dish surface for a period
of time
ranging from about 1 to about 10 seconds, although the actual time will vary
with each
WO 95/30729 < ' PCT/US95/05069
21~11~6
application and user. The contacting of the cloth, sponge or similar article
to the dish
surface is preferably accompanied by a concurrent scrubbing of the dish
surface.
Solution in bowl process
In a typical solution in bowl process from 1 ml. to 50 ml., preferably from 2
ml. to
10 ml. of a detergent composition is combined with from 50 ml. to 2,000 ml.,
more
typically from 100 ml. to 1,000 ml. of water in a bowl having a volumetric
capacity in the
range of from 500 ml. to 5,000 ml., more typically from 500 ml. to 2,000 ml.
The
detergent composition has a surfactant concentration of from about 10 % to
about 60
by weight, preferably from about 15 % to about 50 % by weight. The soiled
dishes are
cleaned by contacting the soiled surface of the dish with a cloth, sponge or
similar article.
The cloth, sponge or similar article may be immersed in the detergent
composition and
water mixture prior to being contacted with the dish surface and is typically
contacted
with the dish surface for a period of time ranging from about 1 to about 10
seconds,
although the actual time will vary with each application and user. The
contacting of the
cloth, sponge or similar article to the dish surface is preferably accompanied
by a
concurrent scrubbing of the dish surface.
Direct Application Process
The direct application process will typically comprise as a first step
immersing the
soiled dishes into a water bath without any liquid dishwashing detergent or
holding the
dishes under running water. A device for absorbing liquid dishwashing
detergent, such as
a sponge, is then placed directly into a separate quantity of undiluted liquid
or gel
detergent composition for a period of time typically ranging from about 1 to
about 5
seconds. Alternatively, the dishwashing detergent is dosed directly onto the
absorbing
devicefor about 0.1 to 0.5 seconds. The absorbing device, and consequently the
undiluted detergent composition, is then contacted individually to the surface
of each of
the soiled dishes to remove said soiling. The absorbing device is typically
contacted with
each dish surface for a period of time range from 1 to 10 seconds, although
the actual
time of application will be dependent upon factors such as the degree of
soiling of the
dish. The contacting of the absorbing device to the dish surface is preferably
accompanied by concurrent scrubbing.
WO 95/30729 ~ j ~ i ~ 3 PCT/US95/05069
26
EXAMPLES
The following compositions in accord with the invention were prepared.
by weight
I II III IV V VI
C 12/ 13 alkyl ethoxy (ave. 25. 5 21 18 23 20.0 3 .7
2.2) sulphate
C12/14 Alkyl - - 2.0 - 7.0 5
polyglucoside 600
C12/14 alkyl amine oxide 5.5 1.E 2.1 4.0 2.0 -
C12/14 alkyl di methyl - - 1.3 1.6 - 1.0
betaine
C 10 Alkyl Ethoxylate - - 3 .7 4.4 - 3.0
(ave. 8)
C 12 alkyl N-methyl 5.5 7.0 8.0 4 - -
glucamide
C 11 Alkyl Ethoxylate (ave. 0.9 1. 5 - - 3 .8 -
9)
Mgr ion 0.7 0.6 ~ 0.6 0.7 0.3 -
Ca~ion 0.35 0.1 - - - -
Sodium cumene sulphonate 11.0 13 11.5 15 18 11.2
Calcium xylene sulphonate 3.4 - - - - -
Lipoiase(TM) 0.05 - 0.1 - - -
The compositions are prepared by mixing all of the surfactants with the
exception of the
glucamide. The magnesium/ calcium salts are then pre-dissolved into solution
together
with the malefic acid and added to the surfactant mixture with the remaining
components.
Finally the pH was trimmed to 7.3 using hydrochloric acid.
