Note: Descriptions are shown in the official language in which they were submitted.
W094/12599 ~14 9 2 2 7 PCT~S93111293
CLEANING COMPOSITIONS WITH COMBINED HIGHLY HYDROPHILIC AND
HIGHLY HYDROPHOBIC NONIONIC SURFACTANTS
Technical field
The present invention relates to cleaning compositions.
Although the present invention applies primarily to hard
surface cleaning compositions, it may also be of interest
for other cleaning compositions including dishwashing and
laundry detergent compositions.
Backqround
Compositions which can be used in diluted form are known in
the art. In such compositions, the technical problem lies
in sustaining upon dilution an efficient cleaning
performance. Such compositions for dilute cleaning are
described for instance in the European Patent EP-A- 0 503
2l9. In these compositions, the dilute cleaning
performance is obtained by using alkanolamines. This '219
patent application also mentions the use of nonionic
surfactants among which ethoxylated fatty alcohols are
listed.
~_ 2 ~ 1 ~292j ~g~
Hard surface cleaning compositions comprising various
surfactants, including highly ethoxylated nonionic
surfactants, which can be used in diluted form are also
known in the art. Representative of this prior art are
the compositions described in European Application EP
561,103, published September 22, 1993.
There is a constant strive for the development of cleaning
compositions with better performance in several respects.
Better cleaning on all soils, including greasy soils and
soap scum is of course a principal object, both for neat
and diluted compositions which are often used in the
cleaning of for instance hard surfaces. Such greasy soils
are commonly brought by cooking with oils and fatty foods,
and by simple contact with human skin, thus they are
present on most surfaces, particularly in bathrooms and
kitchens.
It is thus an object of the present invention to provide
cleaning compositions which can be effectively used in
diluted form, on various surfaces as well as in laundry
applications, to clean various soils and stains. More
specifically, it is a further object of the present
invention to provide satisfactory shine performance and
surface safety when used as hard surface cleaners.
It has now been found that this object can be efficiently
met by formulating cleaning compositions comprising a
specific nonionic surfactant system. Indeed, it has been
found that cleaning compositions comprising at least a
first nonionic surfactant with an HLB of at least
12(hydrophilic-lipophilic balance) and at least a second
nonionic surfactant with an HLB below 10 and at least 4
less than the HLB of said first surfactant exhibit a great
flexibility in the soils it may clean. These compositions
unexpectedly exhibit outstanding cleaning performance upon
dilution, compared to compositions comprising typical
nonionic surfactants while the cleaning performance of the
neat, i.e. undiluted compositions is similar, regardless
of the presence of said nonionic surfactant system.
,- ~
3 21 4~9 2i
In other words, it has now been found that the cleaning
compositions comprising a nonionic surfactant system of at
least a first surfactant with an HLB of at least 12 and at
least a second surfactant with an HLB below 10 and at
least 4 less than the HLB of said first surfactant exhibit
outstanding cleaning performance when used both neat and
diluted.
Specifically, the compositions according to the present
invention are especially effective on greasy soils, both
when used in hard water and also when used in soft water.
Indeed, a particular advantage of the present invention is
robustness to different usage conditions, e.g. variations
in water hardness used for diluting the product.
This invention is also particularly useful as it allows to
formulate compositions with reduced levels of other
ingredients, yet retaining optimal cleaning performance,
due to said combination of at least a first nonionic
surfactant with an HLB of at least 12 and at least a
second nonionic surfactant with an HLB below 10 and at
least 4 less than the HLB of said first surfactant; also,
the user needs less product to achieve the same task.
This advantage is particularly valuable in terms of
environmental compatibility.
Summary of the Invention
The present invention encompasses an aqueous alkaline
cleaning composition comprising, by weight of the total
neat composition, from 0.5% to 30~ of a nonionic
surfactant system and from 0.1~ to 10~ of alkanolamine,
characterized in that said nonionic surfactant system
consists essentially of alkoxylated alcohols, alkoxylated
phenylalcohols, or mixtures thereof and that: - at least
0.1~ by weight of the total neat composition is a first
highly hydrophilic nonionic surfactant of the formula
RO-(C2H40)n(C3H60)mH wherein R is a C822 alkyl chain or a C828
alkyl benzene chain, n and m are each from O to 100 and
n+m is from 6 to 100, said first highly hydrophilic
B~'
4 ~ 2i ~ -
nonionic surfactant having an HLB of from 12 to 20, and
- at least 0.1~ by weight of the total neat composition is
a second highly hydrophobic nonionic surfactant of the
formula RO-(C2H4O)n(C3H6O)mH wherein R is as defined above, n
and m are each from 0 to 5 and n+m is from 0.5 to 5, said
second highly hydrophobic nonionic surfactant having an
HLB of from 2 to 10 and at least 4 less than the HLB of
said first highly hydrophilic nonionic surfactant.
The present invention encompasses both neat compositions
as described hereinabove and diluted compositions.
Diluted compositions are obtained by diluting in water the
above neat compositions comprising from 0.5~ to 30~ by
weight of the total composition of a nonionic surfactant
system. Said diluted compositions comprise from 0.001~ to
5~ by weight of the total composition of said nonionic
surfactant system.
The present invention also encompasses a method of
cleaning hard surfaces wherein a composition comprising a
nonionic surfactant system, whereby said nonionic
surfactant system comprises at least 0.1~ by weight of the
total composition of a first surfactant with an HLB of at
least 12 and at least 0.1~ by weight of the total
composition of a second surfactant with an HLB below 10
and at least 4 less than the HLB of said first surfactant,
is diluted in water and subsequently applied to said hard
surface.
Detailed Description of the Invention
The compositions according to the invention comprise, as
an essential ingredient, a nonionic surfactant system
comprising at least a nonionic surfactant with an HLB of
at least 12, hereinafter referred to as highly hydrophilic
surfactant and at least a nonionic surfactant with an HLB
below 10 and at least 4 less than that of said highly
hydrophilic surfactant, hereinafter referred to as highly
hydrophobic surfactant.
~.
W094/12599 21 ~ 7 PCT~S93/11293
~_ s
Suitable nonionic surfactants for the implementation of
said surfactant system are alkoxylated alcohols or
alkoxylated phenylalcohols which are commercially available
with a variety of alcohol chain lengths and a variety of
alkoxylation degrees. By simply varying the length of the
chain of the alcohol and/or the degree of alkoxylation,
alkoxylated alcohols or alkoxylated phenylalcohols can be
obtained with different HLB values. It is to be understood
to those ordinarily skilled in the art that the HLB value
of any specific compound is available from the literature.
Suitable chemical processes for preparing the highly
hydrophilic and highly hydrophobic nonionic surfactants for
use herein include condensation of corresponding alcohols
with alkylene oxide, in the desired proportions. Such
processes are well known to the man skilled in the art and
have been extensively described in the art. As an
alternative, a great variety of alkoxylated alcohols
suitable for use herein is commercially available from
various suppliers.
The highly hydrophilic nonionic surfactants for use in the
present invention have an HLB of at least 12, preferably
above 14 and most preferably above 15. Those highly
hydrophilic nonionic surfactants have been found to be
particularly efficient for a rapid wetting of typical hard
surfaces covered with greasy soils and to provide effective
soil suspension.
The highly hydrophobic nonionic surfactants for use in the
present invention have an HLB below lO, preferably below 9
and most preferably below 8.5. Those highly hydrophobic
nonionic surfactants have been found to provide excellent
grease cutting and emulsification properties.
Preferred highly hydrophilic nonionic surfactants to be
used in the compositions according to the present invention
6 ~ 27 ~
are surfactants having an HLB from 12 to 20 and being
according to the formula RO-(C2H40)n(C3H6O)mH, wherein R is a
C8 to C22 alkyl chain or a C8 to C28 alkyl benzene chain, and
wherein n+m is from 6 to 100 and n is from 0 to 100 and m
is from 0 to 100, preferably n+m is from 21 to 50 and, n
and m are from 0 to 50, and more preferably n+m is from 21
to 35 and, n and m are from 0 to 35. Throughout this
description n and m refer to the average degree of the
ethoxylation/propoxylation. The preferred R chains for
use herein are the C8 to C22 alkyl chains. Examples of
highly hydrophilic nonionic surfactants for use herein are
LUTENSOLR A030 (HLB=17; R is a mixture of C13 and C15 alkyl
chains, n is 30 and m is 0) commercially available from
BASF, CETALOXR 50 (HLB=18; R is a mixture of Cl6 and C18
alkyl chains, n is 50 and m is 0) commercially available
from WITC0 AlfonicR and 810-60 (HLB=12; R is a mixture of
C8 and C10 alkyl chains, n is 6 and m is 0); and MARLIPALR
013/400 (HLB=18; R is a mixture of Cl2 and C14, n is 40 and
m is 0) commercially available from HULS.
Preferred highly hydrophobic nonionic surfactants to be
used in the compositions according to the present
invention are surfactants having an HLB of from 2 to 10
and being according to the formula R0-(C2H4O) n(C3H6~)mH/
wherein R is a C8 to C22 alkyl chain or a C8 to C28 alkyl
benzene chain, and wherein n+m is from 0.5 to 5 and n is
from 0 to 5 and m is from 0 to 5, preferably n+m is from
0.5 to 4 and, n and m are from 0 to 4, more preferably n+m
is from 1 to 4 and, n and m are from 0 to 4. The
preferred R chains for use herein are the C8 to C22 alkyl
chains. Examples of highly hydrophobic nonionic
surfactants for use herein are DOBANOLR 91-2. 5 (HLB=8.1;
R is a mixture of Cg and C11 alkyl chains, n is 2. 5 and m
is 0) commercially available from SHELL~ LUTENSOLR AO3
(HLB=8; R is a mixture of C13 and C1s alkyl chains, n is 3
and m is 0) commercially available from BASF; Neodol~ 23-3
(HLB=7.9; R is a mixture of C12 and C13 alkyl chains, n is 3
and m is 0) and TERGITOLR 25L3
, ~ ~.
~'':
WO94/12599 2 ~ ~ 9 2 2 7 PCT~Sg3/11293
(HLB= 7.7; R is in the range of Cl2 to Cl5 alkyl chain
length, n is 3 and m is 0) commercially available from
UNION CARBIDE.
It is possible to use for each category of nonionic
surfactants (highly hydrophilic or highly hydrophobic)
either one of the nonionic surfactant belonging to said
category or mixtures thereof.
The aqueous cleaning compositions according to the present
invention comprise from 0.5% to 30% by weight of the total
composition of said nonionic surfactant system, preferably
from 2 % to 25 %, more preferably from 4 % to 20 %.
The compositions according ta the present invention
comprise said highly hydrophilic nonionic surfactant in an
amount of at least 0.l %, preferably of at least 0.5 %,
more preferably of at least 2 %, and said highly
hydrophobic nonionic surfactant in an amount of at least
0.1%, preferably of at least 0.5 %, more preferably of at
least 2 %.
In the compositions according to the present invention,
said highly hydrophilic and highly hydrophobic nonionic
surfactants may be used in a weight ratio from one to
another of from 0.l:l to l:0.l, preferably of from 0.2:l to
l:0.2.
The present invention further encompasses diluted
compositions which are obtainable by diluting the
compositions described hereinabove, and said diluted
compositions comprise from 0.00l % to 5 % by weight of the
total composition of the nonionic surfactant mixture
described hereinabove, preferably from 0.0l % to 0.5 %.
In a preferred embodiment of the present invention the
compositions according to the present invention further
WO94/12599 PCT~S93/11293
21~9227 8
comprise an anionic surfactant. The prior art extensively
describes anionic surfactants, including alkyl benzene
sulfates and sulfonates, alkyl ether sulfates, paraffin
sulfonates, sulfonates of fatty acids and of fatty acid
esters, sulpho succinates, sarcosinates, all of which are
suitable for use herein. Said anionic surfactants can also
be used in the form of their salts, including sodium,
potassium, magnesium, ammonium and alkanol/alkyl ammonium
salts. The preferred anionic surfactants for use herein
are paraffin sulfonates or alkyl sulfates, preferably in
the form of their sodium or ammonium salt. The aqueous
cleaning compositions according to the present invention
comprise up to 15% by weight of the total neat composition
of anionic surfactant, preferably from 2 % to 6 %.
The cleaning compositions according to the present
invention may further comprise additional surfactants,
including other nonionic surfactants, amphoteric and
zwitterionic surfactants and mixtures thereof. Typical of
these are amine oxides, betaines, sulphobetaines and the
like, which are well-known in the detergency art.
The compositions according to the present invention may
further comprise an alkanolamine, or mixtures thereof, in
amounts ranging from 0.1% to 10% by weight of the total
neat composition, preferably from 0.5% to 5%, most
preferably from 0.8% to 3%. At such levels, the
alkanolamine has a buffering effect for alkaline products
in the undiluted product, as well as an unexpected boosting
effect on the cleaning performance of the diluted
compositions. Suitable alkanolamines for use in the
compositions according to the present include
monoalkanolamines, dialkanolamines, trialkanolamines,
alkylalkanolamines, dialkylalkanolamines and
alkoxyalkanolamines. Preferred alkanolamines to be used
according to the present invention include
monoethanolamine, triethanolamine, aminoethylpropanediol,
WO94112599 214 9 2 ;~ ~ PCT~S93111293
~ g
2-aminomethyl propanol, and ethoxyethanolamine.
Particularly preferred are monoethanolamine,
triethanolamine and ethoxyethanolamine.
The compositions according to the present invention may
further comprise builders. Suitable builders for use
herein include nitrilotriacetates (NTA), polycarboxylates,
dipicolinates, citrates, water-soluble phosphates such as
tri-polyphosphate and sodium ortho-and pyro-phosphates,
silicates, ethylene diamine tetraacetate (EDTA), amino-
polyphosphonates (DEQUEST), ether carboxylate builders such
as in EP-A-286 167, phosphates, iminodiacetic acid
derivatives such as described in EP-A-317 542, EP-262 112
and EP-A-399 133, and mixtures thereof. Preferred
builders/sequestrants for use herein are selected from
tetrapotassium pyrophosphate and citric acid. The aqueous
cleaning compositions according to the present invention
may comprise up to 15~ by weight of the total neat
composition of a builder, preferably from 1% to 10%.
The compositions according to the present invention may
further comprise solvents. Suitable solvents for use
herein include propylene glycol derivatives such as n-
butoxypropanol or n- butoxypropoxypropanol, water-soluble
CARBITOL R solvents or water-soluble CELLOSOLVE R solvents;
water-soluble CARBITOL R solvents are compounds of the 2-
(2-alkoxyethoxy)ethanol class wherein the alkoxy group is
derived from ethyl, propyl or butyl; a preferred water-
soluble carbitol is 2-(2-butoxyethoxy)ethanol also known as
butyl carbitol. Water-soluble CELLOSOLVE R solvents are
compounds of the 2-alkoxyethoxy ethanol class, with 2-
butoxyethoxyethanol being preferred. Other suitable
solvents include benzyl alcohol, and diols such as 2-ethyl-
l, 3-hexanediol and 2,2,4-trimethyl-l,3-pentanediol and
mixtures thereof. Preferred solvents for use herein are n-
butoxypropoxypropanol, BUTYL CARBITOL R and mixtures
thereof. The compositions according to the present
W094/12599 PCT~S93/11293
~14~27
~o
invention comprise up to 15% by weight of the total neat
composition of a solvent, preferably from 3% to 10%.
The compositions according to the present invention may
also comprise minor ingredients to provide aesthetic or
additional product performance benefits. Typical minor
ingredients include perfumes, dyes, optical brighteners,
soil suspendinq agents, detersive enzymes, gel-control
agents, thickeners, freeze-thaw stabilizers, bactericides,
preservatives, hydrotopes like sodium cumene sulfonate and
the like.
The present invention further encompasses a method for the
cleaning of hard surfaces. According to the present
invention, an aqueous cleaning composition comprising from
0.5 % to 30 % by weight of the total composition of a
nonionic surfactant system, whereby said nonionic
surfactant system comprises at least O.l % by weight of the
total composition of a first surfactant with an HLB of at
least 12 and at least O.l % by weight of the total
composition of a second surfactant with an HLB below lO and
at least 4 less than said first surfactant's HLB, is
diluted in water so as to obtain from O.OOl % to 5 % by
weight of the total composition of said nonionic surfactant
system and subsequently applied to said hard surface.
In the method according to the present invention, said
composition is diluted into lO to 200 times its weight of
water, more preferably 50 to 150 times, before it is
applied to said hard surface.
The present invention is further illustrated by the
following examples.
WO94/12599 ~ 2 ~ PCT~S93/11293
11
Example I
The following compositions were tested for their cleaning
performance when used diluted on greasy soil.
The following compositions were made by mixing the listed
ingredients in the listed proportions:
Compositions: #l #2 ~3
Ingredients: Weight %
Sodium paraffin sulfonate 3 3 3
Alcohol ethoxylate 7EO (l) 4 - -
Alcohol ethoxylate 30EO (2) - 3 2
Alcohol ethoxylate 3EO (3) - l 2
Sodium Citrate , 3 3 3
Butylcarbitol R 4 4 4
Triethanolamine
water & minors up to 100%
These compositions were evaluated for their grease removal
efficiency. A high index is correlated to a high
performance.
Dilute cleaning performance (index)
Compositions #l #2 #3
Hard water lO0 370 350
Soft water lO0 200 220
In the examples hereinabove, (l) is an ethoxylate nonionic
surfactant representative of the prior art with an HLB of
12. Compounds (2) and (3) are ethoxylate nonionic
surfactants according to the present invention. (2) is a
highly hydrophilic nonionic surfactant with an HLB of 17,
wherein R is a mixture of Cl3 and Cl5 alkyl chains and n is
WO94/12599 PCT~S93/11293
2I49227
12
30. (3) is a highly hydrophobic nonionic surfactant with
an HLB of 8, wherein R is a mixture of C13 and C15 alkyl
chains and alkyl chains and n is 3.
Compositions 1-3 described hereinabove can be used neat or
diluted. In the present cleaning performance test these
compositions are diluted in 64 times their weight of water
and subsequently applied to a hard surface.
Typical dilute grease cleaning results obtained for such
compositions are given for the examples hereinabove.
Composition #l which comprises a nonionic surfactant with
an moderate HLB (12) gets a cleaning index of 100 and is
used as a reference.
According to the present invention, the compositions #2 and
#3 which comprise a nonionic surfactant system comprising
alcohol ethoxylate 30EO (an highly hydrophilic nonionic
surfactant) and alcohol ethoxylate 3E0 (an highly
hydrophobic nonionic surfactant) exhibit outstanding
cleaning performance upon dilution both in hard and soft
water. Indeed, when used with hard water the compositions
#2 and #3 are almost four times more efficient than the
composition #1 and when used with soft water the
compositions #2 and #3 are two times more efficient than
the composition #1.
The above results surprisingly show that the use of diluted
compositions according to the present invention provides a
significant benefit in grease cleaning compared to the
composition comprising only nonionic surfactant with a
moderate HLB (for example 12), both in hard and soft water.
WO94/12599 214 9 2 2 7 PCT~S93/11293
~ 13
Example II
A concentrated composition is prepared with the following
composition:
Ingredients Weight %
Alfonic 810-60 (Cg-ClO E6) 20.0
Neodol 23-3 (Cl2-Cl3 E3) 4.0
Coconut fatty acid 0.6
Monoethanolamine l.0
Sodium cumene sulfonate l.5
Minors and water Balance
This composition provides good performance while requiring
less packaging.
