Note: Descriptions are shown in the official language in which they were submitted.
2~31~
23443-447
The present invention relates to low-foaming liquids
or pulverulent detergent formulations for washing machines. More
particularly, the present invention relates to detergents whose
surfactant components are prepared mostly from renewable raw
materials.
Modern liquid detergents consist mostly of anionic
surfactants, in particular alkylbenzenesulphonate, fatty alcohol
oxyethylate and soap, whereas washing powders usually contain
bullder substances, bleaching agents and other electrolytes as
essential active compounds, ln addition to the alkylbenzenesul-
phonate and fatty alcohol oxyethylate surfactants. The common
feature of liquid and pulverulent detergent formulations is that
the surfactants employed are those based on petrochemicals.
In view of the future possible shortages of petroleum
raw materials, this petrochemlcal basi~ is a considerable disad-
vantage. Another disadvantage is that the biological degradabil-
lty of these surfactants does not achieve the corresponding
degradability level of surfactants based on naturally occurring
substances.
The object of the invention is therefore to find a
combination of surfactants for low-foaming detergents, which
surfactants are prepared mostly from renewable raw materials, have
an outstandlng blologlcal degradabllity and achieve very good
washing results.
Thls object may be achieved by a surfactant combinatlon
whlch consists essentlally of alkyl polyglycosldes, ether-
-- 1 --
- 2043~7
23443~447
carboxylates and soap.
The invention therefore relates to a low-foaming, liquid
or pulverulent detergent for washing machines, which is charac-
terized in that the surfactant content consists of
5 to 30% of alkyl polyglycosides,
5 to 30% of alkanol ether-carboxylate,
5 to 30% of soap and
0 to 30% of other surfactants.
Surprisingly, it has been found that very good washing
results are achieved with the combinations according to the
invention.
The use of alkyl polyglycoside in combination with
anionic surfactants is known. Thus, German Published Patent
Application 593,422 mentions the effect of alkylglycoside in inten-
sifying the washing effect of soaps. Later publications, such as
European Published Patent Applications 0.075,99~, 0,105,556 and
0,199,765 or German Published Patent Application 3,702,286,
describe the use of alkyl polyglycosides in combination with a
number of known anionic surfactants in detergents. In each case
the alkylbenzenesulphonate surfactant is most important component
of the disclosed compositions.
The use as detergents of carboxymethylated fatty
alcohol oxyethylates, which are a subgroup of ether-carboxylates
is known from German Published Patent Applications 2,327,234 and
3,320,340. In contrast thereto, the use of bisalkanol alkoxylate-
acetates, which are also a subgroup of ether-carboxylates, is new.
- 2 -
-- 2~43~7
23443-447
Also the use in detergents of the ether-carboxylates in combina-
tion with alkyl polyglycosides is unknown.
Other constituents, according to the state of aggrega-
tion (liquid or pulverulent formulations) are small amounts of
other surfactants, complexing agents, bleaching agents, optical
brlghteners, greylng inhibitors, corrosion inhibitors, foam
regulators, stabilizers, enzymes, enzyme stabilizers, electrolytes,
hydrotropic substances, solubilizing agents and the like.
Alkvl polYglvcosldes
Alkyl polyglycosides employed according to the invention -
are of the general formula I
R~O-Zn I,
ln whlch R represents a linear or branched, saturated or unsatur-
ated aliphatlc alkyl radical having 10 to 18 carbon atoms or
mixtures thereof and Zn represents a polyglycosyl radical, where
n represents 1.0 to 3 hexose or pentose units, or mixtures there-
of.
Alkyl polyglycosides containing fatty alkyl radicals
having 10 to 16 carbon atoms and a polyglycosyl radical of
n = 1.1 to 2 are preferred. Alkyl polyglucosides are particularly
preferred.
The alkyl polyglycosides employed according to the
invention can be prepared by known processes based on renewable
raw materials. For example, dextrose is reacted with n-butanol
; ln the presence of an acld catalyst to glve butyl polyglycoside
mixtures, which are transglycosidated with long-chain alcohols,
31 47
23443-447
in the presence of an acid catalyst, to give the desired alkyl
polyglycoside mixtures. Alternatively, dextrose is reacted
directly with the desired long-chain alcohol.
The structure of the products can be varied within
certain limits. The alkyl radical R is determined by the choice
of long-chain alcohols. For economic reasons, the surfactant
alcohols which are accessible on a large industrial scale and
have 10 to 18 C atoms are preferred, in particular naturally occur-
ring fatty alcohols from the hydrogenation of fatty acids or fatty
acid derivatives. Zieglar alcohols or Oxo alcohols can also be
used.
The polyglycosyl radical Zn is determined on the one
hand by the choice of carbohydrate and on the other hand by adjust-
ing the average degree of polymerization n, for example in
accordance with German Published Patent Application 1,943,689.
It is known that in principle polysaccharides, for example starch,
maltodextrins, dextrose, galactose, mannose, xylose and the like,
can be employed. The carbohydrates starch, maltodextrins and in
particular dextrose which are available on a large industrial scale
are preferred. Since the alkyl polyglycoside syntheses which are
of economic interest do not proceed regio- and stereo-selectively,
the alkyl polyglycosides are always mixtures of oligomers, which
in turn are mixtures of various isomeric forms. They are present
together with ~- and ~-glycosidic bonds in the pyranose and
furanose form. The linkage points between two saccharide radicals
also vary.
2~3~7
23443-447
Alkyl polyglycosides employed according to the inven-
tion can also be prepared by mixing alkyl polyglycosides with
alkyl monoglycosides. The latter can be isolated or enriched
from alkyl polyglycosides, for example, in accordance with
European Published Patent Application 0,092,355 using polar sol-
vents, such as acetone.
The degree of glycosidation can be advantageously
determined by means of H-NMR.
The detergents according to the invention contain 5 to
30% of alkyl polyglycoside, preferably 7 to 20%.
In contrast to almost all the other surfactants employ- -~
ed in detergents, the alkyl polyglycosides are regarded as being
entirely ecologically safe. The degree of biological degradation
determined by means of a water treatment plant simulation model/
DOC analysis for the alkyl polyglycosides according to the
invention is thus 96 + 3%. This figure should be considered in
view of the fact that a substance showing a degree of degradation
of > 70% is considered as being readily degradable according to
this test method (total degradation).
~ The acute oral toxicity LD50 (rat) of > 10,000 mg/kg
and the aquatic toxicity LC50 (golden orfe) of about 12 mg/l and
; EC50 (Daphnia) of 30 mg/l are also more favourable by a factor
of 3 to 5 than the corresponding values of currently the most
important surfactants. The same applies to the skin and mucosa
tolerance.
; - 5 -
2 ~ 7
23443-447
Fatty alcohol ether-carboxylates
Fatty alcohol ether-carboxylates are compounds of
either the formula II or the formula ~II
(R-_o(cH2-cH2-o)xcH2coo)mM II,
in which R' is a linear or branched, saturated or unsaturated
alkyl radical having 8 to 22, preferably 10 to 18, carbon atoms,
x is 1 to 40, preferably 3 to 30, m is 1 or 2 and M is hydrogen,
an alkali metal, an alkaline earth metal, ammonium or alkanol-
ammonium, or
([R~'-O(CH2-CH2-O)y]2cHcoo)zN III
in which R'' denotes a linear or branched, saturated or unsaturated
alkyl radical having 8 to 22, preferably 10 to 18, carbon atoms,
y denotes 1 to 4, preferably 3 to 30, z denotes 1 or 2 and N
denotes H, an alkali metal, an alkaline earth metal, ammonium or
alkanolammonium.
Compounds corresponding to the formula II are called
carboxymethylated oxyethylates, and those corresponding to the
formula III are called bisalkanol ethoxylateacetates.
The carboxymethylated oxyethylates can be prepared in
accordance with German Published Patent Application 2,418,444 or
European Published Patent Application 0,106,018 by reaction of
oxyethylates of the formula R'-O(CH2-CH2-O)nH with chloroacetic
acid or a salt of chloroacetic acid in the presence of an alkali
metal hydroxide or other ba~es. However, other preparation
processes, for example by means of catalytic oxidation according
to European Published Patent Application 0,018,681 and 0,039,111,
2~31~7
~3443-447
are also suitable.
Bisalkanol ethoxylate-acetates can be prepaxed, for
example, in accordance with German Published Patent Application
3,902,663 from oxyethylates and dichloroacetic acid.
Corresponding alcohols for the preparation of the
fatty alcohol ether-carboxylates are preferably fatty alcohols
or Ziegler alcohols, and in exceptional cases also Oxo alcohols.
The carboxymethylation which follows the oxyethylation can be
complete in the case of an appropriate procedure, so that the
fatty alcohol ether-carboxylates are purely anionic surfactants.
Alternatively, if the carboxymethylation is not complete, the
products contain certain amounts of unreacted oxyethylate. The
formulae II and III therefore usually mean a mixture containing
varying amounts of unreacted oxyethylates. A degree of conversion
can accordingly be defined. A degree of conversion of between 70
and 100% is preferred.
The fatty alcohol ether-carboxylates are also very
ecologically-safe surfactants. Biological degradation rates of
above 90% have thus been determined by means of a water treatment
plant simulation model/DOC analysis. The acute oral toxicity
LD50 (rat) and the aquatic toxicity hC50 (golden o_fe) are about
as favourable as those of the alkyl polyglucosides. The same
applies to the skin and mucosa tolerance.
The detergents according to the invention contain 5 to
30% of fatty alcohol ether-carboxylates, which can also be
mixtures. A content of 7 to 20% of fatty alcohol ether-
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'
.~
;
~ 0 ~ 7
23443-447
carboxylate is preferred.
Soap
Fatty acid salts according to the invention and their
acids correspond to the formula IV
R'l'COOP IV,
in which R'l' denotes a saturated or unsaturated alkyl radical
having 8 to 22 C atoms and P denotes hydrogen, an alkali metal,
ammonium or alkanolammonium.
The detergents according to the inventisn contain 5 to
30%, preferably 7 to 20% of soap, which will usually be a mixture
of various components.
Other surfactant constituents
Up to 3% of other anionic, nonionic, zwitter-ionic and
ampholytic surfactants is to be employed according to the inven-
tion. These are, in particular, alkanesulphonates, olefinsulphon-
ates, alkylbenzenesulphonates, ~-sulpho-fatty acid esters, fatty
alcohol sulphates, fatty alcohol ether-sulphates, sulphosuccinic
acid esters, alkanol oxyethylates, fatty acid alkanolamides,
ammine oxides, betains, sulphobetains and the like.
Other non-surfactant constituents
Non-surfactant constituents which may be mentioned are
above all builders. Water-soluble buildersj such as various
polyphosphates, phosphonates, carbonates, polycarboxylates,
citrates, polyacetates, such as NTA and DETA, and the like or mix-
tures thereof are used according to the invention. These compounds
are usually employed as the alkali metal salts, preferably as the
-- 8 --
2~431~7
23443-447
sodium salts. Although it is not a complexing agent, sodium sul-
phate may also be mentioned here. Water-insoluble builders, such
as aluminosilicates of suitable particle size (compare European
Published Patent Application 0.075,994) can also be used. The
concentration of the builders in the detergent is 0 to 70%,
preferably 0 to 50~.
Bleaching agents, such as sodium perborate, if
appropriate combined with bleaching activators, such as tetra-
acetylethylenediamine and the like, or percarbonate, are further-
more employed according to the invention; other bleaching agents
are of course also possible (compare K. Engel, Tenside Surfactants
25, page 21 (1988)). The concentration of the bleaching agent
is 0 to 40%, preferably 0-30%.
If appropriate, standardizing agents, such as low
molecular weight 1- or 2-hydric alcohols, alkyl ethers of poly-
hydric alcohols, hydrotropic agents, such as alkylbenzenesulphon-
ates having 1 to 3 C atoms in the alkyl radical, alkanolamines
or ureas, enzymes, such as, in particular, proteases, and enzyme
stabilizers, corrosion inhibitors, such as alkali metal silicates,
optical brighteners, in particular those based on stilbene and
pyrazolene, foam regulators, greying inhibitors, such as, for
example, carboxymethylcellulose, perfume oils, dyestuffs and other
contents customary for liquid or pulverulent detergents, may also
be employed according to the invention.
The total use concentration of the surfactant content
in the machine detergents according to the invention is 0.3-20
g/l. 0.5-10 g/l is preferred.
2 0 ~ 7
23443-447
Examples
The invention is illustrated by the following examples.
The liquid detergent formulations listed in Tables 1 and 2 each
contain 6% of triethanolamine, 12% of ethanol, 6% of 1,2-propylene-
glycol and water to 100%, in addition to the surfactant
constituents mentioned which are used according to the invention.
The foaming capacity was determined in accordance with
DIN 53 902, part 1. The concentration of detergent substance was
in each case 1 g/l, and the volume of foam was recorded after 5
minutes. The washing power was measured both in a Linitest*
laboratory washing machine (that is to say under moderate mechani-
cal stress) and in a normal domestic machine. The model fabric
used was cloth 11 x 18 cm in size of WFK test fabric with skin
grease-pigment soiling: polyester ~PE), mixed fabric (MF) and
cotton (C), the water used was drinking water (13 dH). The
polyester was washed at 30C and the mixed fabric and cotton at
60C. The active compound concen~ration was 1 g/1 in the
Linitest* laboratory washing machine and 5 g/l in the domestic
washing machine, the pH was in each case about 7, the liquor ratio
was about 1:60 and 1:4 respectively and the washing times in both
cases were about 30 minutes.
; In the Linitest* machine, the washing operation was
repeated twice, each time after rinsing. The washing values
after drying of the fabric were - as is customary - measured by
spectrophotometry relative to a white standard (Datacolor*, 560
nm).
;:
*Trade-mark
-- 10 --
2~3147
23443-447
~gLid formulations:
Tables 1 and 2 show the comparison of the properties
of the detergents according to the invention as a liquid
formulation with those of other known combinations and of a
liquid brand detergent, for which optimization of the recipe can
be assumed.
-- 11 --
~31~7
O.Z.4491 23443-447
Table 1: Liquid detergent based on carboxymethylated
oxyethylate/alkyl polyglucoside/~oap
_
E~mple
~o.
Surf~nt l(V) 2~V) 3 4 5 6 7 8~V)
.
~oC~ AES-Na 15 - _ _ _ _ _ ~ d
C~, PS-Na _ 15 _ _ _ _ _ braDd
C~(EO); cm~O0 _ _ 15 - - 15 - ~r-
C~(E0)sc~ 0 _ _ _ 15 - ~ 15 gent
C~ 0)3 CmO.SII _ _ _ _ 15
C~i.2*~ 15 15 15 15 15 -
C~.7 _ _ - - - 15 15
Soap**~ 10 10 10 10 10 10 10 _
Pe~lts .
Cl ;~rif~:atiorl
point (-C)s~1 -2 2 1 3 -1 -1 _
ViKx~ity at
25-C (mPa~)-68 55 68 72 71 66 70 90
Foamingcap~ y
(60-C) DINs 120 150 50 55 45 S0 40 30
~hinq pa~
(refleGu~xe (~))
llnitest~
P~ 30-C 6 8 15 11 11 15 }5 11
NY 60-C 11 12 26 27 24 24 22 17
C 60-C 22 26 46 4S 45 46 50 39
Washing m~nes
MF 60-C _ 31 29 58 54 - 53 55 IS4
A~S-Na - alkylbenzene sulphonate Na salt
PS-Na - paraffinsulphonate Na salt
(V) s comparison example
- abbreviated formula for carboxymethylated C12-
C,~ fatty alcohol oxyethylates contalning 4 mol
of ethylene oxide/mol, degree of con~lrersion 93%
= C,2C1~-alkyl polyglucoside having a degree of
glucosidation of 1.2
*~ - coconut fatty acld (neutralized with trlethanol-
amine)
- - not measured
- 12 -
2 ~ 7
O.Z.4491 23443-447
able 2~ Liquid detergent based on bisalkanoloxy-
ethylateacetate/alkyl polyglucoside/coap
E~pla
N~.
~ nt 9 10 11 ~ 13 14
_ . . .
eis(Cl2C~(EO)~*o.s~ 15 _ _ 15 _ 7.5
Els~C~(EO)s)~o.s3 - 15 - _ _ 7.5
1~8(C~oc~(Eo)s)aco~82 _ _ 15 - - _
ais(c~a(l~))8)ac ~ 15 _
~ .2~* 15 1515 - - _
C~ .7 - - - 15 15 15
Soap*** 10 1010 10 10 10
R~
_
Clarification
point (-C)s 2 1 2 -1 0 1
Vi~K~ity at
25-C (mPa~)~ 100 90140 120 150110
P~ng capaci~y
(60-C) : 20 3020 30 20 20
Wb~hing power
(reflecuuLe (%))
Linite~t~
PS 30-C 11 1211 16 13 15
MF 60-C 21 2622 19 17 18
C 60-C 40 4041 40 39 40
~s
MP 60-C _ 5954 59 - 58
- - - -
* = -abbreviated formuls for bl~ C~C~alkanol oxy-
ethylate-acetate containing 6 mol of ethylene
oxid~/mol, degree of conversion 84%
** 3 C~C1~-alkyl polyglucoside having a degree of
glucosidation of 1.2
*** - coconut fatty acid (neutralized with triethanol-
amine~
- ~ not measured
- 13 -
2~431~7
O.Z.4491 23443-44
The clarification point and vlscosity entirely comply
with the u~ual market standard for liquid detergents. The
foaming capacity of the formulation~ according to the
Lnvention show~ very favourable value~ - without other
regulating additives. This particularly applie~ to the
washing power. The formulation~ according to the inven-
tion are far more effective here than other known com-
binations in which the surfactant content likewise
con~ists of an anionic surfactant, alkyl polyglucoside
and ~oap (Comparison Examples 1 and 2).
Powde ~ fQrmulationss
Table 3 shows the comparison of the properties of pul-
verulent detergent formulations according to the inYen-
tion with ~ho~e of a known combination and of a brand
detergent. The bulk den~ity, angle of repose and foaming
capacity were determined by DIN methods. The solubility
is estimated by mean~ of a plot of the electrical conduc-
tivity against time, the measurement value being taken at
80% of an average final conductivity when 1 g of powder
L~ dissolved ln 800 ml of drinking water ~13 dH). $he
measurement values include an error of ~ 5~.
- 14 -
2 0 ~ 7
o.z.4491 23443-447
able 3s Powder detergent based on carboxymethylated
oxyethylate/alkyl polyglucoside/soap
_
E~ple
No.
S~ nt lS(V) 20(V1 16 17 18 19
. .
C~ o~* - Pul- 3 - -
C~(EO)~.0~ - veru- - 3 - -
oy~ol~80/85(EO)~b.s - lent - - 3 3
C~ .2~ 4 ~rand 4 4 4 -
C~F~.7~ - d~ - 4
C~Cu-AES-Na 3 genS - - - -
Soap*~ 5 5 5 5 5
_
P~ll.'cs .
_
Eblk ~ ty g/l~ 760 460 780 820 790 800
Angle of nq~xe
(ctg~) 1.5 1.5 1.4 1.5 1.4 1.4
Solubility (mln.)~14 14 16 17 14 16
F~ng cyx~ity (ml)~
(60-C) DDN a~r
30 ~ec. 120 160 150 140 100 100
300 sec. 30 20 30 30 40 20
~q E~
(~ (%))
~$~:~
Pe 20-C 8 9 10 11 9 12
MF 60-C 14 17 18 18 17 19
C 60-C 31 37 38 39 38 40
Wad~nq ma~es
NF 60-C 33 42 43 45 42 ~3
ABS-Na - alkylbenzenesulphonate Na salt
(V) - comp~ri~on example
* ~ compare T~ble 1
** - 90 part- of beef tallow, 10 parts of coconut
oil hydrolyzed with NaOH
20~3:L47
o.z.4491 23443-447
Apart from a considerably higher bulk density, which is
typical of agqlomerated washing powder~, in compari~on
with the spray-dried brand product (Example 20), the
powders according to the invention are very ~imilar and
better in their washing values. The greatly improved
washing effects in compari~on with known formulations of
Example 15 containing anionic surfactant~ are aqain also
clearly to be ~een here.
- 16 -
.
., . - :
.
.
