Note: Descriptions are shown in the official language in which they were submitted.
-
2~Q~9~3
- 1 - C3402
Deterqent Compositions
Technical Field
The present invention relates to detergent
compositions, particularly to compositions used for
washing fabrics, dishes and household surfaces. The
compositions of the invention, which are especially but
not exclusively suitable for fabric washing, contain one
or more glycolipid biosurfactants.
Backqround and Prior Art
Detergent compositions traditionally contain one or
more detergent active material in addition to various
other ingredients such as detergency builders, bleaches,
fluorescers, perfumes etc. Notable applications of
detergent compositions are to clean fabrics, usually by
washing portable fabric items in a bowF or in a washing
machine, to clean crockery and cooking utensils, again by
washing in a bowl ~hand dishwashing), and to clean hard
surfaces such as glass, glazed surfaces, plastics, metals
and enamels.
~- 2r~ 8
- 2 - C3402
A number of classes of surfactant materials have
been used, some for many years, as detergent active
materials, ineluding anionie and nonionie materials.
Glycolipid biosurfaetants, whieh are deseribed in
more detail below, inelude rhamnolipids, sophoroselipids,
glueoselipids, eellobioselipids and trehaloselipids.
Glyeolipid biosurfaetants ean be produeed by either
baeterial or yeast fermentation. This is inherently
advantageous in that products of fermentation ean
generally be derived from renewable raw materials and are
likely to be biodegradable after use.
JP 63 077 535A (Toyo Beauty) diseloses an emulsion
eomposition eontaining alpha-deeenoic bonded rhamnolipid
or its salt as emulsifying agent. The emulsion is
said to be useful for cosmetics, health-care products,
medicines, toiletries, detergents and foods.
2C DE 3 526 417A (Wella) diseloses a eosmetic agent
containing sophoroselipid laetone used to eombat dandruff
and as a bacteriostatic agent in deodorants.
US 4 216 311 (Kao) diseloses the production of a
glyeolipid methyl ester from sophoroselipid. These
glyeolipid methyl esters are useful as a base or
improving additive for various cleansers and fats and
oils products and for use in painting and printing
processes, fibre processing, metal processing,
stationery, cosmetics, drugs, agricultural chemicals,
luster prevention, synthetic resins, paper manufacturing,
machinery, leather and the like.
C3402 CA1
_ _ 3 _ . 206069 8
We have now found that these glycolipid biosurfactants
can give a synergistic enhancement of oily/fatty soil
detergency when used in certain combinations with each other,
or jointly with other surfactant(s). Enhanced detergency has
been observed even with glycolipids that exhibit poor
detergency when used alone.
Definition of the Invention
The present invention provides a detergent composition
comprising from 1 to 60 wt% in total of:
(i) a first surfactant which is a micellar phase surfactant
(as defined below) which is a glycolipid biosurfactant
selected from sophorose lipids, rhamnolipids, glucose
lipids, cellobiose lipids and mixtures thereof, and
(ii) a second surfactant which is a lamellar phase surfactant
(as defined below) which is a glycolipid biosurfactant
selected from rhamnolipids, glucose lipids, trehalose
lipids and mixtures thereof, or a non-glycolipid
surfactant,
and optionally from 5 to 80 wt% of a detergency builder,
the composition containing more than 5 wt% of glycolipid
biosurfactant.
The invention also provides a method of washing which
comprises contacting fabrics, or an inanimate surface to be
cleaned, with a composition according to the previous
paragraph, or a wash liquor obtainable by adding the
composition to water, notably in an amount ranging from 0.5 to
50 grams of compositions per litre of water.
C3402 CA1
-- 4
~ 2 0 6 0 6 9 8
net~;le~ Descri~tion of the Invention
The detergent composition of the invention contains at
least two different surfactants having different
characteristics, at least one of which must be a glycolipid
biosurfactant.
The two classes of surfactant are referred to herein as
micellar phase and lamellar phase surfactants respectively.
These terms relate to the phase in which the surfactants are
likely to be present under typical wash conditions.
The two types of surfactant may be distinguished by the
behaviour of a 1 % by weight aqueous solution in demineralised
water at pH 7.0 and 25~C. A surfactant solution containing
dispersed lamellar phases exhibits birefringent textures when
viewed under a polarising optical microscope, while a micellar
solution does not.
In general, a micellar phase surfactant will provide a
clear solution when present at a concentration of 1% by weight
in demineralised water at pH 7.0 and 25~C, although the
presence of small amounts of impurities may reduce the
clarity. A lamellar phase surfactant will always provide a
cloudy solution when present at a concentration of 1% by
weight in demineralised water at pH 7.0 and 25~C.
At least the micellar phase surfactant must be chosen
from a specific class of surfactant, the glycolipid
biosurfactants; while the lamellar phase surfactant may or
may not also be a glycolipid biosurfactant. Thus some
glycolipids are micellar phase surfactants and others are
lamellar phase surfactants.
C3402 CAl
2 0 6 0 B ~ 8
Glycolipid surfactants with which the present invention
are concerned include rhamnolipids, glucoselipids,
sophoroselipids, trehaloselipids, cellobioselipids and
mixtures thereof. Within any one class of glycolipids, some
S materials may be micellar and others lamellar.
Micellar phase glycolipid biosurfactants may suitably be
selected from rhamnolipids, glucoselipids, sophoroselipids,
cellobioselipids and mixtures thereof.
Lamellar phase glycolipid biosurfactants may suitably be
selected from rhamnolipids, glucoselipids, trehaloselipids and
mixtures thereof.
The surfactants (i) and (ii) may both be glycolipids.
The micellar phase glycolipid is then most preferably a
rhamnolipid, a sophoroselipid or a cellobiose lipid, while the
lamellar phase glycolipid is most preferably a trehaloselipid,
a glucoselipid or a rhamnolipid.
Alternatively the lamellar phase surfactant (ii) may be a
non-glycolipid surfactant, preferably an anionic or nonionic
surfactant. Zwitterionic and cationic surfactants are not
preferred, and if present it is desirable that they are at low
levels, such as not more than 10~ by weight of all surfactant
present.
Preferred anionic and nonionic surfactants are listed
below.
The weight ratio of the first surfactant (i) to the
second surfactant (ii) is preferably in the range from 20:1 to
1:20, and may lie in a narrower range, for example from 10:1
to 1:10, more preferably 4:1 to 1:4.
z~Q~
- 6 - C3402
The Glycolipid Biosurfactant
Specific biosurfactants include rhamnolipids,
glucoselipids, sophoroselipids, trehaloselipids,
cellobioselipids and mixtures thereof. Each will now be
described in more detail below:
Rhamnolipids
These biosurfactants have the formula (I):
O
HO O CH - CH2 C O - R
~~\
~ 3 ~ (12)n (I)
OH O R CH3
- a b
where a is 1 or 2; b is 1 or 2, n is 4 to 10. preferably
6; R is H or a cation, preferably H, or a monovalent
solubilising cation, R2 is H or the group
2~ O
CH3(CH2)mCH = CH -,
preferably H; m is 4 to 10; and the values of m and n
need not be the same at each occurrence.
5~3
- 7 - C3402
Rhamnolipids can be produced by bacterial
fermentation. This is inherently advantageous in that
products of bacterial fermentation can generally be
derived from renewable raw materials and are likely to be
biodegradable after use. Another advantage of the
surfactants of formula (I) is that they can be produced
as a by-product of enzyme manufacture.
Rhamnolipids can be produced by bacteria of the
genus Pseudomonas. The bacterial fermentation typically
utilises as substrates a sugar or glycero' or an alkane
- or mixtures thereof.
Appropriate fermentation methods are reviewed in
D Haferburg, R Hommel, R Claus and H P Kleber in
Adv Biochem. Eng./Biotechnol. (1986) 33, 53-90 and by
F Wagner, H Bock and A Kretschmar in Fermentation (ed.
R M Lafferty) (1981), 181-192, Springer Verlag, Vi~nna.
Any sample of rhamnolipid will generally contain a
variety of individual compounds within the general
formula (I) The proportions of individual compounds is
governed by the microorganism species, and the particular
strain employed for fermentation, the substrate materials
~5 supplied to the fermentation, and other fermentation
conditions.
The bacterial fermentation generally produces
compounds in which Rl is hydrogen or a solubilising
cation. Such compounds can undergo conversion between
the salt and the acid forms in aqueous solution,
according to the pH of the solution. Common solubilising
cations are alkali metal, ammonium and alkanolamine.
9~3
-- - 8 - C3402
Glucoselipids
A second class of glycolipid biosurfactant in
accordance with the present invention comprises
glucoselipids of the formula (II).
CH OH ~
1 2 11
~ - O\ O CH CH2 C O R
~ ~ (CIH2)q (II)
HO ~
OH _CH3 ?
where Rl is H or a cation; p is 1 to 4; and q is 4 to
10, preferably 6.
Glucoselipids can be produced by the bacterium
Alcali~enes Sp.MMl. Appropriate fermentation methods
are reviewed by M. Schmidt in his PhD thesis (1990),
Technical University of Braunschweig, and by Schulz et al
(1991) Z. Naturforsch 46C 197-203. The glucoselipids are
recovered from the fermentation broth via solvent
extraction using ethyl ether or a mixture of either
2~ dichloromethane:methanol or chloroform:methanol.
2(~ 8
_ g - C3402
.
Sophoroselipids
A third class of glycolipid biosurfactant in
accordance with the present invention comprises
5sophoroselipids of the formula (III)
CH2~R R5
/,) ~
> O -CH
I\~OH
CH20R3 ~O R6 (III)
~ 0\
~ ~ C=o
oR7 OH R8
where R3 and R4 are individually H or an acetyl group; R5
is a saturated or unsaturated, hydroxylated or
non-hydroxylated hydrocarbon group having 1 to 9 carbon
atoms, preferably being a methyl group; R6 is a saturated
or unsaturated hydroxylated or non-hydroxylated
hydrocarbon group having 1 to 19 carbon atoms; with the
proviso that the total number of carbon atoms in the
groups R5 and R6 does not exceed 20 and is preferably
from 14 to 18.
The sophoroselipid may be incorporated into
detergent compositions of the present invention as either
the open chain free acid form, where R7 is H and R8 is
OH, or in its lactone form, where a lactone ring is
formed between R7 and R8 as shown by formula (I~r).
2~~~98
- 10 - C3402
R4 ~5
\ - O CH
I '~ ~ H ~
CH2OR HO I ~6 (IV)
~0 ~-0
~OH
OH
O C=O
where R3, R4 and R6 are as defined above; with the
proviso that at least one of R and R is an acetyl
group.
Sophoroselipids can be produced by yeast cells, for
example Torulopsis apicola and Torulopsis bombicola. The
fermentation process typically utilises sugars and
alkanes as substrates. Appropriate fermentation methods
are reviewed in A P Tulloch, J F T Spencer and
P A J Gorin, Can. J Chem (1962) 40 1326 and U Gobbert,
S Lang and F Wagner, Biotechnology Letters (1984) 6 (4),
225. The resultant product is a mixture of various
open-chain sophoroselipids and sophoroselipid lactones,
which may be utilised as a mixtures, or the required form
can be isolated. When the glycolipid biosurfactant
comprises sophoroselipids, the weight ratio of
sophoroselipids to additional surfactant is preferably in
the range ~:1 to 3:2 and is more preferably 4:1.
2~ 8
- 11 - C3402
Trehaloselipids
A fourth class of glycolipid biosurfactant in
accordance with the present invention comprises
trehaloselipids of the general formula (V).
CH2OH OH
"~o\ ~1~~1 1~ (V~
O-c-Rl ~ ~ O-C-R
O O
C=O
(lCH2)2
COOH
where R , R and Rll are individually a saturated or
unsaturated, hydroxylated or non-hydroxylated hydrocarbon
of 5 to 13 carbon atoms.
Trehaloselipids can be produced by bacteria
fermentation using the marine bacterium Arthrobacter sp.
Ek 1 or the fresh water bacterium Rhodococcus
erythropolis. Appropriate fermentation methods are
provided by Ishigami et al (1987) J. Jpn Oil Chem Soc 36
847-851, Schultz et al (1991), Z. Naturforsch 46C
197-203; and Passeri et al (1991) Z Naturforsch 46C
204-209.
- 12 - C3402
Cellobioselipids
A fifth class of glycolipid biosurfactant in
accordance with the present invention comprises
cellobioselipids of the general formula (VI).
COOR
112
CH OH ¦ (VI)
~ O OR CHOH
1~'' \\ 1 11
~ \ CH2 l H2
HO OH
lS O
\~
C=o ~OH x
~14 OH
CH3
where Rl is H or a cation; R12 is a saturated or
non-saturated, hydroxylated or non-hydroxylated
hydrocarbon having 9 to 15 carbon atoms, preferably 13
carbon atoms; R13 is H or an acetyl group; R is a
saturated or non-saturated, hydroxylated or
non-hydroxylated hydrocarbon having 4 to 16 carbon atoms.
Cellobioselipids can be produced by fungi cells from
the genus ustilaqo. Appropriate fermentation methods
are provided by Frautz, Lang and Wagner (1986) Biotech
Letts 8 757-762.
3~
C3402 CA1
~ - 13 - ~ 2 ~
When the glycolipid biosurfactant comprises
cellobioselipids the weight ratio of cellobioselipids to
additional surfactant is preferably in the range 4:1 to 2:3.
Non-qlYcoli~i~ Surf~ctants
As indicated previously, the detergent composition of the
invention may optionally contains at least one non-glycolipid
surfactant in addition to the glycolipid biosurfactant(s)
described above, provided that at least one micellar phase
glycolipid surfactant is present.
The non-glycolipid surfactant can be chosen from anionic
surfactants, nonionic surfactants, zwitterionic surfactants,
cationic surfactants; but if zwitterionic or cationic
surfactants are present, it is desirable that they are
incorporated at low levels, such as not more than 10% by
weight of all surfactant present.
~n;onic Surfactants
Examples of suitable anionic surfactants that may be used
are alkyl benzene sulphonates, alkyl ether sulphates, olefin
sulphonates, alkyl sulphonates, secondary alkyl sulphonates,
fatty acid ester sulphonates, dialkyl sulphosuccinates, alkyl
orthoxylene sulphonates and other disclosed in the literature,
C
2~5"~3
- 14 - C3402
especially 'Surface Active Agents' Vol. 1, by Schwartz &
Perry, Interscience 1949 and 'Surface Active Agents' Vol.
II by Schwartz, Perry & Berch (Interscience 1958), in the
current edition of "McCutcheon's Emulsifiers &
Detergents" published by the McCutcheon division of
Manufacturing Confectioners Company or in
'Tensid-Taschenbuch', H. Stache, 2nd Edn., Carl Hanser
Verlag, M~nchen & Wien, 1981.
Specific examples of alkyl benzene s~lphonates
include alkali metal, ammonium or alkanolamine salts of
alkylbenzene sulphonates having from 10 to 18 carbon
atoms in the alkyl group.
Suitable alkyl and alkylether sulphates include
those having from 10 to 24 carbon atoms in the alkyl
group, the alkylether sulphates have from 1 to 5 ethylene
oxide groups.
Suitable olefin sulphonates are those prepared by
sulphonation of C10-C24 alpha-olefins and subsequent
neutralisation and hydrolysis of the sulphonation
reaction product.
2~ Specific examples of alkyl sulphates, or sulphated
fatty alcohol salts, include those of mixed alkyl chain
length, in which the ratio of C12 alkyl chains to C18
alkyl chains is in the range of from 9:4 to 1:6. A
suitable material can be obtained from a mixture of
33 synthetic lauryl and oleyl alcohols in appropriate
properties.
- 15 - C3402
Specific examples of fatty acid ester sulphonates
include those of the general formula
Rl CH COOR
-03M
wherein Rl is derived from tallow, palm or coconut oil
and R2 is a short chain alkyl group such as butyl.
Specific examples of dialkyl sulphosuccinates
include those in which both alkyl substituent contains at
least 4 carbon atoms, and together contain 12 to 20
carbon atoms in total, such as di-C8 alkyl
sulphosuccinate.
Specific examples of alkyl orthoxylene sulphonates
include those in which the alkyl group contains from 12
to 24 carbon atoms.
Other anionic surfactants which may be used include
alkali metal soaps of a fatty acid, preferably one
containing 12 to 18 carbon atoms. Typical such acids are
oleic acid, ricinoleic acid and fatty acids derived from
2~ caster oil, rapeseed oil, groundnut oil, coconut oil,
palmkernal oil or mixtures thereof. The sodium or
potassium soaps of these acids can be used. As well as
fulfilling the role of surfactants, soaps can act as
detergency builders or fabric conditioners.
33
Dialkyl sulphosuccinates are of especial interest as
lamellar phase anionic surfactants for use in the present
lnventlon .
2 ~ Q~
- 16 - C3402
Nonionic Surfactants
Nonionic detergent compounds which may be used are
alkyl (C6 22) phenol-ethylene oxide condensates, the
condensation products of linear or branched aliphatic
C8 20 primary or secondary alcohols with ethylene oxide,
and products made by condensation of ethylene oxide with
the reaction products of propylene oxide and
ethylenediamine. Other so-called nonionic detergent
compounds include long-chain tertiary amine oxides, alkyl
sulphoxides C10-C14 alkyl pyrollidones and tertiary
phosphine oxides.
Suitable lamellar phase nor.ionic surfactants include
those with an HLB value below 10.5, preferably below 10
and more preferably in a range of from 8.5 to 9.5. For
ethoxylated nonionic surfactants the HLB value is defined
as one fifth of the mole per cent of ethylene oxide in
the molecule.
Suitable nonionic surfactants may be ethoxylated
materials, especially ethoxylated aliphatic alcohols,
with a relatively low proportion of ethoxylation so as to
give an HLB value below 10.5.
It may be desirable, however, that any ethylene
oxide content of the nonionic surfactant be <5~ by weight
of the surfactant system, or zero, and various
non-ethoxylated nonionic surfactants are also suitable
for use in the present invention.
z~
- 17 - C3402
These include alkyl polyglycosides of general
formula
R15O(R16O) (G) or R15Co(R16o) (G)
in which R15 is an organic hydrophobic residue containing
10 to 20 carbon atoms, R16 contains 2 to 4 carbon atoms,
G is a saccharide residue containing 5 to 6 carbon atoms,
t is in the range 0 to 25 and y is in the range from 1 to
10 .
The hydrophobic group R15 is preferably alkyl,
alkenyl, hydroxyalkyl or hydroxyalkenyl. However, it may i-
include an aryl group for example alkyl-aryl,
alkenyl-aryl and hydroxyalkyl-aryl. Particularly
preferred is that R is alkyl or alkenyl of 10 to 16
carbon atoms, more particularly 12 to 14 carbon atoms.
The value of t in the general formula above is
preferably zero, so that the -(R16O)t- unit of the
general formula is absent.
If t is non-zero it is preferred that R16O is an
ethylene oxide residue. Other likely possibilities are
propylene oxide and glycerol residues. If the parameter
t is non-zero so that R16O is present, the value of t
(which may be an average value) will preferablv lie in
the range from 0.5 to 10.
3~
The group G is typically derived from fructose
glucose, mannose, galactose, talose, gulose, allose,
altrose, idose, arabinose, xylose, lyxose and/or ribose.
2r~9~
- 18 - C3402
Preferably, the G is provided substantially exclusively
by glucose units. Intersaccharide bonds may be from a 1-
position to a 2, 3, 4 or 6-position of the adjoining
saccharide. Hydroxyl groups on sugar residues may be
submitted, e.g. etherified with short alkyl chains of 1
to 4 carbon atoins.
The value which y, which is an average, desirably
lies between 1 and 4, especially 1 and 2.
Alkyl polyglycosides of formula R15O(G)y, i.e. a
formula as given above in which t is zero, are available
from Horizon Chemical Co.
O-alkanoyl glucosides are described in International
Patent Application WO 88/10147 (Novo Industri A/S). In
particular the surfactants described therein are glucose
esters with the acyl group attached in the 3- or 6-
position such as 3-0-acyl-D-glucose or
6-0-acyl-D-glucose. In the present invention we prefer
to use a 6-0-alkanoyl glucoside, especially compounds
having the formula:
2~ ¦!
R17_ ~_ o
- ~~
~- OH "' 18
,,
HO
OH
2060698 ,
- 19 - C3402
wherein R17 is an alkyl or alkenyl group having from 7 to
19 preferably 11 to 19 carbon atoms, and R is hydrogen
or an alkyl group having from 1 to 4 carbon atoms.
Most preferred are such compounds where R18 is an
alkyl group, such as ethyl or isopropyl. Alkylation in
the 1- position enables such compounds to be prepared by
regiospecific enzymatic synthesis as described by
Bjorkling et al. (J.Chem. Soc., Chem. Common. 1989 p934).
While esters of glucose are contemplated especially,
it is envisaged that corresponding materials based on
other reduced sugars, such as galactose and mannose are
also suitable.
Further possible nonionic surfactants are
monoglyceryl ethers or esters of the respective formulae
0
R OCH2f~CH2OH and ~ 9C~c~2cHcH2~H
OH OH
2~ Rl9 is preferably a saturated or unsaturated
aliphatic residue. In particular Rl9 may be linear or
branched alkyl or alkenyl. More preferably, Rl9 is a
substantially linear alkyl or alkenyl moiety having from
9 to 16 carbon atoms, notably a C~-C12 alkyl moiety.
3G Most preferably, ~19 is decyl, undecyl or dodecyl.
The monoglyceryl ethers of alkanols are known
materials and can be prepared, for example by the
condensation of a higher alkanol and glycidol. Glycerol
3~ monoesters are of course well know and available from
various suppliers including Alkyril Chemicals Inc.
X
C3402 CA1
- 20 -
Another class of nonionic surfactants of interest for use
in the present invention is comprised by 1,2- diols of the
general formula
R - CH - CH2OH
I
OH
where R is a saturated or unsaturated hydrocarbon group
containing from 8 to 16 carbon atoms.
~m~l]nts ~nd Pro~ortions of Surfactants
Compositions of this invention will generally contain a
surfactant mixture comprising micellar phase surfactant (i)
and lamellar phase surfactantts) (ii) in an amount which is
from 1 to 60% by weight of the composition; preferably from 2
to 45%; more preferably from 5 to 40~; most preferably from
5 to 35%.
The amount of glycolipid biosurfactant present is more
than 5~ by weight of the overall composition.
The weight ratio range which gives enhanced detergency
will vary depending on the specific surfactants used and can
be determined by experiment. In general the proportion of
glycolipid biosurfactant should be low when its alkyl chains
are shorter, but higher if its alkyl chains are longer.
C3402 CA1
- 21 - ~ 8
The weight ratio of micellar phase surfactant to lamellar
phase surfactant will generally lie within a range of 20:1 to
1:20 and may lie in a narrower range, e.g. from 10:1 to 1:10;
more preferably 4:1 to 1:4.
The proportions of the surfactants are desirably such as
to give better oily soil detergency than given by the (or
either) glycolipid biosurfactant alone, the total amount of
surfactant being the same.
If a non-glycolipid surfactant is present, the
proportions are desirably such as to give better oily soil
detergency that that given by the non-glycolipid surfactant
alone, the total amount of surfactant being the same.
Deter~encv builders
If the composition of the invention is intended for
fabric washing, it will generally contain one or more
detergency builders, suitably in an amount of from 5 to 80% by
weight, preferably from 7 to 70~ by weight, more preferably
from 20 to 80% by weight. If it is in solid form, the
composition is likely to contain at least 10 or 15% of
builder. This may be any material capable of reducing the
level of free calcium ions in the wash liquor and will
preferably provide the compositions with other beneficial
properties such as the generation of an alkaline pH and the
suspension of soil removed from the fabric.
Preferred builders include alkali metal (preferably
sodium) aluminosilicates, which may suitably be incorporated
in amounts of from 5 to 60~ by weight
2~
- 22 - C3402
(anhydrous basis) of the composition, and may be either
crystalline or amorphous or mixtures thereof, having the
general formula:
0.8-1.5 Na20.A1203Ø8-6 sio2
These materials contain some bound water and are
required to have a calcium ion exchange capacity of at
least 50 mg CaO/g. The preferred sodium aluminosilicates
contain 1.5-3.5 sio2 units (in the formula above). Both
the amorphous and the crystalline materials can be
prepared readily by reaction between sodium silicate and
sodium aluminate, as amply described in the literature.
Suitable crystalline sodium aluminosilicate
ion-exchange detergency builders are described, for
example, in GB 1 429 143 (Procter & Gamble). The
preferred sodium aluminosilicates of this type are the
well-known commercially available zeolites A and X, and
mixtures thereof. Also of interest is the novel zeolite
P described and claimed in EP 384070 (Unilever).
Phosphate-built detergent compositions are also
within the scope of the invention. Examples of
phosphorus-containing inorganic detergency builders
include the water-soluble salts, especially alkali metal
pyrophosphates, orthophosphates, polyphosphates and
phosphonates. Specific examples of inorganic phosphate
builders include sodium and potassium tripolyphosphates,
ortho phosphates and hexametaphosphates.
However, preferred detergent compositions of the
invention preferably do not contain more than 5% by
weight of inorganic phosphate builders, and are desirably
substantially free of phosphate builders.
2~ 8
- 23 - C3402
Other builders may also be included in the detergent
composition of the invention if necessary or desired:
suitable organic or inorganic water-soluble or
water-insoluble builders will readily suggest themselves
to the skilled detergent formulator. Inorganic builders
that may be present include alkali metal (generally
sodium) carbonate; while organic builders include
polycarboxylate polymers such as polyacrylates,
acrylic/maleic copolymers, and acrylic phosphinates;
monomeric polycarboxylates such as citrates, gluconates,
oxydisuccinates, glycerol mono-, di- and trisuccinates,
carboxymethyloxysuccinates, carboxymethyloxymalonates,
dipicolinates, hydroxyethyliminodiacetates; and organic
precipitant builders such as alkyl- and alkenylmalonates
and succinates, and sulphonated fatty acid salts.
Especially preferred supplementary builders are
polycarboxylate polymers, more especially polyacrylates
and acrylic/maleic copolymers, suitably used in amounts
of from 0.5 to 15% by weight, especially from 1 to 10~ by
weight; and monomeric polycarboxylates, more especially
citric acid and its salts, suitably used in amounts of
from 3 to 20~ by weight, more preferably from 5 to 15~ by
weight.
Other Ingredients
It is desirable that fabric washing compositions
according to the invention be approximately neutral or at
least slightly alkaline, that is when the composition is
dissolved in an amount to give surfactant concentration
of 1 g/l in distilled water at 25~C the pH should
desirably be at least 7.5. For solid compositions the pH
will usually be greater, such as at least 9. To achieve
n~3
- 24 - C3402
the required pH, the compositions may include a
water-soluble alkaline salt. This salt may be a
detergency builder (as described above) or a non-building
alkaline material.
The compositions of the invention may contain an
electrolyte, for instance present in such an amount to
give a concentration of at least 0.01 molar, when the
composition is added to water at a concentration of
1 g/litre-. Electrolyte concentration may possibly be
higher such as at least 0.05 or 0.1 molar especially if
the composition is of solid form: liquid compositions
generally limit electrolyte for the sake of stability.
1 g/litre is approximately the lowest level at which
detergent compositions for fabric washing are used in
usual practice. More usual is usage at a level of 4 to
50 g/litre. The amount of electrolyte may be such as to
achieve an electrolyte concentration of 0.01 molar, most
preferably at least 0.1 molar, when the composition is
added to water at a concentration of 4 g/litre.
Further ingredients which can optionally be employed
in the detergent composition of the invention include
polymers containing carboxylic or sulphonic acid groups
in acid form or wholly or partially neutralised to sodium
or potassium salts, the sodium salts being preferred.
Preferred polymers are homopolymers and copolymers
of acrylic acid and/or maleic acid or maleic anhydride.
Of especial interest are polyacrylates, polyalphahydroxy
acrylates, acrylic/maleic acid copolymers, and acrylic
phosphinates. Other polymers which are especially
preferred for use in liquid detergent compositions are
deflocculating polymers such as for example disclosed in
EP 346995.
2~
- 25 - C3402
The molecular weights of homopolymers and copolymers
are generally 1000 to 150 000, preferably 1500 to
100 000. The amount of any polymer may lie in the range
from 0.5 to 5% by weight of the composition. Other
suitable polymeric materials are cellulose ethers such as
carboxy methyl cellulose, methyl cellulose, hydroxy alkyl
celluloses, and mixed ethers, such as methyl hydroxy
ethyl cellulose, methyl hydroxy propyl cellulose, and
methyl carboxy methyl cellulose. Mixtures of different
cellulose ethers, particularly mixtures of carboxy methyl
cellulose and methyl cellulose, are suitable.
Polyethylene glycol of molecular weight from 400 to
50 000, preferably from 1000 to 10 000, and copolymers of
polyethylene oxide with polypropylene oxide are suitable
as also are copolymers of polyacrylate with polyethylene
glycol. Polyvinyl pyrrolidone of molecular weight of
10 000 to 60 000, preferably of 30 000 to 50 000 and
copolymers of polyvinyl pyrrolidone with other poly
pyrrolidones are suitable. Polyacrylic phosphinates and
related copolymers of molecular weight 1000 to 100 000,
in particular 3000 to 30 000, are also suitable.
It may also be desirable to include in the detergent
composition of the invention an amount of an alkali metal
silicate, particularly sodium ortho-, meta- or preferably
neutral or alkaline silicate. The presence of such
alkali metal silicates at levels, for example, of 0.1 to
10% by weight, may be advantageous in providing
protection against the corrosion of metal parts in
washing machines, besides providing some measure of
building and giving processing benefits.
2~
- 26 - C3402
Further examples of other ingredients which may be
present in the composition include fabric softening
agents such as fatty amines, fabric softening clay
materials, lather boosters such as alkanolamides,
particularly the monoethanolamides derived from palm
kernel fatty acids and coconut fatty acids; lather
depressants; oxygen-releasing bleaching agents such as
sodium perborate and sodium percarbonate; peracid bleach
precursors; chlorine-releasing bleaching agents such as
trichloroisocyanuric acid; heavy metal sequestrants such
as EDTA; fluorescent agents; perfumes including
deodorant pefumes; enzy~mes such as cellulases,
proteases, lipases and amylases; germicides; pigments,
colourants or coloured speckles; and inorganic salts
such as sodium and magnesium sulphate. Sodium sulphate
may if desired be present as a filler material in amounts
up to 40% by weight of the composition; however, as
little as 10~ or less by weight of the composition of
sodium sulphate, or even none at all, may be present.
The detergent compositions according to the
invention may be in any suitable form including powders,
bars, liquids and pastes. For example suitable liquid
compositions may be non-aqueous or aqueous, the latter
being either isotropic or lamellar structured. The
compositions may be prepared by a number of different
methods according to their physical form. In the case of
granular products they may be prepared by dry-mixing,
coagglomeration, spray-drying from an aqueous slurry or
3Q any combination of these methods. One preferred physical
form is a granule incorporating a detergency builder
salt. This may be prepared by conventional granulation
techniques or spray-drying.
zr~
- 27 - C3402
EXAMPLES
The following non-limiting examples illustrate the
invention. Parts and percentages are by weight unless
otherwise stated.
Rhamnolipids
-
Example 1
This example used as the micellar phase surfactant
(i) a rhamnolipid produced as a by-product during
fermentation using Pseudomonas qlumae with glucose and
glycerol as substrates. Partial characterisation of the
dried material obtained from the ,ermentation showed that
it contained one or more compounds of formula I above, in
which the value of n was 10. The lamellar phase
surfactant (ii) was an ethoxylated aliphatic alcohol.
23 Aqueous wash liquors were prepared containing the
following materials in deionised water:
Rhamnolipid (as dried material }
from the fermentation) } 1 g/litre
Ethoxylated dodecyl alcohol with }
average 3 ethylene oxide residues }
Sodium metaborate 0.05 molar
These quantities would be typical of using 6 g/litre
of a particular detergent product containing 16.7% by
weight surfactant.
The wash liquor had pH about 10.7 resulting from the
presence of the metaborate.
3~
Z~F ~5n~3
- 28 - C3402
Wash liquors were prepared with various ratios of
the two surfactants and used to wash polyester test
cloths soiled with radiolabelled triolein. Washing was
carried out at 40~C for 20 minutes in a Tergotometer.
S
The removal of triolein was determined using
radiotracer techniques and the results are set out in
Table 1.
Table 1
Rhamnolipid weight %C12E3 weight % % Triolein
of active materialof active material Removal
100 0 28
42
63
73
72
0 100
Clearly all the mixtures of the rhamnolipid and the
ethoxylate nonionic surfactant gave better detergency
than either surfactant alone.
Example 2
Example 1 was repeated, replacing the ethoxylate
nonionic surfactant with an anionic surfactant, di-C8
33 alkyl sulphosuccinate, as the lamellar surfactant (ii).
The results are set out in Table 2.
2~ 8
- 29 - C3402
Table 2
di-C8
5Rhamnolipid weight %Sulphosuccinate ~ Triolein
of active materialof active material Removal
100 o 28
38
~o 45
46
0 100 35
15Example 3
Example 1 was repeated, using as the micellar
surfactant (i) a rhamnolipid available under the
designation BioEm-LKP (trade mark) from Petrogen Inc,
Illinois. It was a mixture of compounds of formula I
above in which n = 6 and b = 2, Rl = H, R = H.
Compounds with a = 1 and a = 2 were present in
approximately equal weight ratio.
Results are set out in Table 3, which shows a very
considerable synergistic effect.
2~
- 30 - C3402
-
Table 3
Petrogen Rhamnolipid
5weight % of active C12E3 weight % Triolein
material of active Removal
100 ~ 4 59
8020 4.20
6040 36.51
1040 60 55.78
2080 43.0].
0100 1.55
Examples 4-10
23The Test System
Detergency performance of biosurfactants was studied
using the test fabrics described in Table 4 and test
conditions described below.
- 31 - C3402
Table 4
Test cloth: EMPA 104 WFK20D
Supplier: EMPA St-Gallen Wschereiforschung
Krefeld
Test cloth type: Polyester/Cotton Polyester/Cotton
Soil composition: 50 ml Indian Ink 1.72 g/l Kaolin
100 ml Olive Oil 0.16 g/1 Carbon
850 ml Water 0.08 g/1 Iron
oxide (black)
0.04 g/l Iron
oxide (yellow)
14.00 g/l Sebum
sprayed on the
cloth as CC14
solution
Reflectance of
unwashed test
cloth: 14.7 Reflectance 42.6 Reflectance
Units Units
Wasn Liquors
Aqueous wash liquors were prepared containing the
following materials in deionised water:
glycolipid biosurfactant(s) as dried }
material from the fermentation) } 0.5 g/litre
any non-glycolipid surfactant }
sodium metaborate 0.05 molar
Z~ 9~3
-
- 32 - C3402
The wash liquor had a pH of about 10 resulting from
the presence of metaborate.
Test Conditions
The tests were performed in 100 ml polyethylene
bottles with 30 ml/bottle wash liquor, 1 piece of
6 x 6 cm text cloth and 1 piece of 6 x 6 cm white (clean)
cotton as a redeposition cloth. The cloth:liquor
ratio/bottle was 1:30. A maximum of 50 of these bottles
were agitated for 30 minutes in a Miele TMT washing
machine at 40~C. Afterwards, the washed test fabrics
were rinsed 3 times with cold water before drying.
Monitorinq Method
Detergency performance was assessed by calculating
the increase in reflectance at 460 nm (with incident
light <400 nm filtered out) (del~a R460*). [Delta R =
reflectance of the washed cloth (Rw) - the reflectance of
the unwashed cloth (Ri).]
Example 4
2~ Different rhamnolipid samples (micellar phase) were
tested in combination with the nonionic surfactant C12E03
(ethoxylated dodecyl alcohol having an average of 3
ethylene oxide residues) (lamellar phase) in the
described wash liquor. The rhamnolipid RL-BNS was
produced by bacteria of the genus Pseudomonas glumae
which consists of pure rhamnolipid of formula I where
a = 2, b = 2, n = 10, R = H, R = H. BioEm-LKP (trade
mark) (Petrogen Inc, Illinois) is a mixture of
rhamnolipids from Pseudomonas as described in Example 2.
Results are shown in Table 5.
2~ 98
- 33 - C3402
Table 5
delta R(460)*
Rhamnolipid weight BioEm-LKP RL-BNS
5% of active mixtureEMPA 104 WFK20DEMPA 104 WFK20D
100 5.8 10.7 4.2 12.8
17.2 14.4 10.8 14.9
17.7 19.8 14.7 16.5
14.1 20.9 10.2 19.5
10.4 16.8 5.7 17.7
0 6.2 14.2 6.8 15.3
Sophoroselipids
15 Example 5
The sophoroselipids SOL-TUBS (micellar phase) was
tested in combination with several lamellar phase
surfactants in the described wash liquor. Cosurfactants
tested were Synperonic A3, C12-1,2-diol and
C10-mono-glycerolether. Results are shown in Table 6.
SOL-TUBS is a sophoroselipid from Technical
University of Braunschweig, Germany. It is produced by
the yeast strain Torulopsis bombicola. It consists of a
mixture of four sophoroselipids of formula (III) and (IV)
with at least 80% being the 1',4"-lactone-6',6"-diacetate
lipid where in formula (IV) R3 & R4 = acetyl groups; R
= 1 and R6 = 15. As described by the literature in
JAOCS 65 (9) (1990) 1460, the main fatty acid chain
length in SOL-TUBS is C18 ~ie, in formula (IV) R5 + R6 =
C16 ) .
Z~~~9~3
OO ~D ~0 ~ ~D
h 1' ~7 <~1~O
O
a
O ~
~ ~ O
O
ol
~1 C)~
o
o ~0 ~ 0
a~ ~ ~o
h a
oO 0~
Xt~ a~ d' N O O
~
O '1:5
-,~ I
.
I ~
~:~1~
*C~l ~ . . .. .
o ~ ~ ~ ~ ~ O
~r ~ ~
,~ _
R P:;
E~
a) ~
o o o 0~ ~ O
X t' ~ ~
-
o
S~
~ o
~~ ~ 0 ~ ~ o
c
c
aJ
Q ~ ~ ~ ~5
-~ ~ O
o\~ .~
~ O o o o o o c
O I o 0 ~ ~ ~ 11
O O ~J >
Q -- qJ ~ ~5
0 3 0
C
2~59~3
- 35 - C3402
Example 6
The sophoroselipid SOL-CH (micellar phase) was
tested as described in Example S. Results are shown in
Table 7.
SOL-CH is a sophoroselipid produced by the yeast
strain Torulopsis bombicola. It consists of a mixture
of at least 8 sophoroselipids of formula (III) and (IV).
2C~ 9~3
h ~; ~ ~ ~ /:
O
~ a~
O
~ ~ O
O
~ ol a
c~ 01 ~ ~
~ ~ ~ . .
~ O Oa~ d~
X
FL3
u
a
o ~ o ~ o ~ In
V~~ . . . . . .
~ ~o O ~ ~ C~ 00
o
~,
o
.
~1
I ~
~1~
C~l ~ . . . . .
t-- O ~ r~ ~ ~1
~O
~o a) ~
,~ _,
E~
o ~ ~ 7 o
. . . . .
o
o
.
R ~i
-~ ~ O ~
X
a) u o\~ -,~
~ I ~; O O o o o o
O ~ ~) o CO
O ~ O ~J
o u~
~ a~ ~
O ~ V
2C~
- 37 - C3402
Example 7
The sophoroselipid (SOL-COO ) (micellar phase) was
tested as described in Example 5. Results are shown in
Table 8.
SOL-COO is a sophoroselipid produced by the yeast
strain Torulopsis bombicola and is partially hydrolysed,
ie has the structure (III) where R3 and R4 are H; R5 is
1; R6 is 15; R7 is H and R8 is OH.
2(~~~Ç5~3
a ~
o 0
o
o ~
o
o
~, ol ~
C~l ~ o
~ ~ ~ ~~7 ~ o
JJ
o
o 0 0 ~n ~ o
-_,
C
.
~1
I ~
~1~
Vl ~. . . . .
0 0 ~~ ~ 0 In d'
0 a)~
Q~;
a
o 0
o
Q ~
~ o
U~ ~. . .
Q --I '~ ~
-~ I I O
O
~}o o\~ -~
U~ U ~ O o o o o O
O I ~ o 0
s a
O O
S U~ -,1 ~~
Q '- O
0 3 U
Z~ 8
- 39 - C3402
Cellobioselipids
Example 8
Cellobioselipids (CELL-TUBS) (micellar phase), which
are produced by fungi of the strain Ustilaqo maydis were
tested in combination with several lamellar phase
surfactants in the described wash liquor. Cosurfactants
tested were Synperonic A3, C12-1,2-dio and
C10-mono-glycerolether. Results are shown in Table 9.
CBL-TUBS consists of approximately 4
cellobioselipids of formula (IV). In the main component
R is H; R is 15; Rl is acetyl; R 4 is 4.
'2~ 9~3
a
o 1~ a~ o
. . . .
o ~ ~ ~ oD ~ ~ o ~1
.C 3
O
O ~
O
o
~1 ~
~I ~ ~
~~ ~ o o
~: ~ ~ . . .
X
J
~a
~1
a
ot~ ~ ~ ~ ~ a~
u~ ~ . . . . .
~;~DO Oa~ ao
0 3
,C ~,
.,,
I
~1~
Ul ~ . ~ t' ~ ~ U~
~ o
o E~
~ o t' t' U~ ~ o
a ~ . . . . . .
~ 3 ~/ ~ ~ ~ ~
o
~, ~
o
~n ~ . . . ~ .
o ~ t'
-.
__~ IJ
.,~ _ O
U~ ~
n ~-,1 o O
O I ~ ~ O O O O O O
o m -~ :,
~ -- 3 ~ ~
ZC~ 9~3
- 41 - C3402
Example 9
Cellobioselipids as described in Example 8 were
partially hydrolysed such that in Formula (VI) Rl = H,
R = H; R is 15; Rl3 is H; also the ester-linked
fatty acid group containing Rl4 is absent. These
cellobioselipids (micellar phase) were studied with
different lamellar phase cosurfactants as described in
Example 8. Results are shown in Table lO.
o ~oo o~'
r~ ~ ~ ~ ~ . .
o ~ ~ ~ ~ ~ ~ ~oul
O
~l
~11 r~~
C~l ~ O
JJ
a
o ~. ~ ~ 00
~ . . . .
,~ 0 3
O
-,~
'
,~ ,1
I ~
o
Vl ~ o o co a~ o
~ ~ ~ o o o
o
~1 o
a) ~
,~ _
Q~;
~ a
al o ~ ~ o ~ 1-- ~o
a ~ . . . . . .
X U- ~ ~. ~ o t~
.'I 3
O
-
h
~L d'
C: o
U~ ~ .. . . .
ol~
~ ~ h
-,~ ~ O
~I ~
~ O ~ X
U7 O ''~
O ~ o o o o o O
,, I ,~ o ~ ~ ~ ~
Q ~ ~ a) ~1
o m ,1 ~
-- 3 ~
C) O
C~ ~
C3402 CA1
- 43 -
~x~le 10
Trehaloselipid (THL-4) (lamellar phase) was tested in
combination with rhamnolipid BioEm-LKP as described in Example
2 (micellar phase).
The trehaloselipid THL-4 was produced by the bacterium
Arthroh~cter s~.~k1 and consists of trehaloselipid of formula
(V) in which R9, R10, R11 have an average of 7-9 carbon atoms.
Results are shown in Table 11.
Table 11
TrehaloseliDid Rhamnoli~id Delta R(460)*
weiqht weiqht
% of active % of active ~PA 104 WFK 20D
mixture mixture
100 0 5.8 9.8
8.9 10.7
lO.g 13.6
7.2 14.8
8.2 12.9
0 100 4.5 9.5
~xam~les 11 to 12
The test sYstem
Detergency performance of biosurfactants was studied
using the test fabric WFK 2OD as described in Table 4, and
test conditions described below.
~ r~9~
- - 44 - C3402
Wash Liquors
Aqueous wash liquors were prepared containing the
following materials in deionised water:
glycolipid biosurfactant(s) (as dried material from
the fermentation)
any non-glycolipid surfactant
detergent base powder as shown in Table 12.
Total surfactant concentration was 0.5 g/litre.
The detergent base powder was incorporated at
5 g/litre. Test conditions and monitoring methods
were as described for Examples 4 to 10.
Table 12 - Deterqent Base Powder
Parts
Zeolite 4A (anhydrous basis) 27.62
Maleic/acrylic acid copolymer 4.15
Sodium carbonate 10.15
Alkaline silicate 0.46
Sodium carboxymethylcellulose 0.81
Fluorescer 0.22
Moisture plus salts 12.85
Example 12
The sophoroselipids SOL-TUBS as described in Example
5 (micellar phase) was tested in combination with
3G Synperonic A3 (lamellar phase!. Results are shown in
Table 13.
2~
- 45 - C3402
Table 13
_ Sophoroselipid Weiqht
% of Active Mixture Delta R(460)*
100 14.4
18.1
20.3
16.8
14.2
o 14.3
Example 12
The cellobioselipid CBL-TUBS as described in Example
8 ~micellar phase) was tested in combination with
Synperonic A3 (lamellar phase). Results are shown in
Table 14.
Table 14
Cellobioselipid Weight
% of Active Mixture Delta R(460~*
100 14.5
16.9
18.2
17.2
16.2
0 14.3
