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CLEANING COMPOSITION COMPRISING
SATURATED DIALKYL CATIONIC SURFACTANTS
Technical Field
The present invention relates to a cleaning composition for
hard surfaces, wherein said composition comprises both a
fully saturated dialkyl cationic surfactant and a nonionic
surfactant .
Background to the Invention
In traditional cleaning of hard surfaces such as wood,
glazed tiles, painted metal and the like, it is known to
follow soil removal using surfactant or solvent based
compositions with the application of a lacquer, wax or
polish as a separate operation so as to seal and protect
the surface and reduce the rate of soil redeposition. This
two-step cleaning and sealing operation is time-consuming
and complex.
It is known to incorporate components into a surfactant-
based composition with the intention that deposition of
such components onto surfaces will provide a protective
layer in a one step cleaning operation.
GB 1528592 (1978) discloses alkaline, floor cleaning
compositions which comprise an organic, polycarboxylic acid
co-polymer having a molecular weight in the range 100,000-
2,500,000 which is soluble in aqueous solutions having a pH
of 8.5 or above. These polymers are readily available in
commercial quantities.
~';!~j'1 ~D H~
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GB 1534722 (1978) discloses granular hard surface cleaning
compositions which comprise surfactant and, as "a soil
removal improvement mixture", a polyvinyl alcohol or
pyrrolidone and a biopolysaccharide. These polymers. have
molecular weights ranging from around 5000 to around'
360,000 and are available in industrially useful
quantities. The compositions form alkaline solutions.
US 07/297807 (EP379256), as described in EP 0467472 A2
(Colgate Palmolive) demonstrates that the incorporation of
2.3% of a 15-20o aqueous solution of the cationic polymer
poly-[beta(methyl diethyl-ammonium) ethyl-methacrylate] in
a mixed nonionic surfactant system for hard surface
cleaning results in significant improvement of ease of
subsequent re-cleaning of previously soiled and cleaned
ceramic tiles.
EP 0467472 A2 discloses that soil release promoting
polymers such as, but not limited to, the cationic poly-
[beta(methyl diethyl-ammonium) ethyl-methacrylate] are also
effective in combination with anionic and cationic
surfactant. In that published application it is stated
that 'said adsorbed polymer forms a residual anti-soiling
hydrophillic layer of said soil release promoting polymer
on said surface, whereby removal of soils subsequently
deposited thereupon requires less work than in the absence
of said residual layer'. The molecular weight range of the
polymers falls into the range 4,000-100,000 although the
use of polymers having a molecular weight above 50,000 is
discouraged for solubility reasons.
EP 0379256 discloses similar compositions to the
above-mentioned document, having up to 2owt of an optional
quaternised, anti-static, polymer of molecular weight in
the range of 2,000 - 500;000, and being characterised by an
a~~~~~~F~ sHF~r
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~ .. ~ ,
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acidic pH of 2-4 and a 2-4~wt of a nonionic surfactant
system. Specific examples relate to compositions having a
( _.
A~VIc~IGEG SHEET
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pH of 2.5 and comprising 2.2%wt of a mixed nonionic system
and 0.07% of the specified cationic polymer. The modified
polymer is again said to function as a soil release agent.
US-A-4065409 discloses a detergent mixture for cleaning
hard surfaces which comprises a low level of nonionic
detergent (which can include ethoxylated alcohol) and a
quat. (such as dimethyl didecyl ammonium chloride: DDAC).
There is no mention of any soil release benefit in this
document.
'~ WO-A-8605199 discloses compositions which comprise
glycoside nonionics. It is noted that the compositions of
the prior art disclosed in this citation are said. to leave
essentially no residues on the surface and it is believed
that the compositions of the reference are also intended to
leave no residues.
w0-A-9406899 also discloses compositions which comprise
quaternised mono and di tallow acid esters in combination
with glycoside nonionics
In addition to the above it is known from US 4606842 to use
low molecular weight polyacrylic resins as a builder in
glass cleaning compositions of the spray-on, wipe-off type.
Baker et al in US 4690779 discloses the use of the
combination of polymers of polyacrylic acid having a
molecular weight below 5000 with certain nonionic
surfactants in hard surface cleaning compositions. The
primary function of the polymer in these systems is as a
builder.
From the above it cari be seen that it is known to include
certain polymers in generally alkaline hard surface
cleaning compositions with so as to obtain either a primary
cleaning benefit when the composition is first used on the
~;:~~~!~~p SHEET
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surface or a secondary cleaning benefit by modification of
the surface so as hinder soil deposition or otherwise
facilitate repeated cleaning.
Some attention has been paid to other surface treatment
agents, including specific cationic detergents. WO 91/09930
(Ques Industries) discloses the use 'ETHOQUAT' (TM) on
aluminium e.g. metal surfaces such .as those found on
vehicles.
Brief Description of the Invention
We have devised improved compositions which both clean a
surface and deposit thereupon a layer of
cationic surfactant which assists the release of soil
subsequently, deposited upon the said surface.
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Accordingly the present invention provides an aqueous,
hard-surface cleaning composition comprising a surfactant
mixture, wherein said surfactant mixture comprises:
a) at least 65%wt on total surfactant of nonionic surfactant (more precisely
defined below) produced by the condensation of hydrophilic alkylene oxide
groups with a hydrophobic aliphatic or alkyl aromatic compound,
b) less than 1 %wt on total surfactant of anionic surfactant, and,
c) 0.135%wt on total surfactant of a cationic surfactant (more precisely
defined below) which is an ethyleneically saturated dialkyl quaternary
ammonium
compound.
petailed Descri~tiQn of the Invention
A range of cationic dialkyl quaternary ammonium compounds
find useful application in the compositions of the present
invention. While these can contain moieties such as C=O
the alkyl chains are free of moieties such as C=C, i.e.
they are ethyleneically saturated. Moreover, while it is
important that the molecules contain at least two
moderately long alkyl chains the compounds can have more
than two of said alkyl chains. =Ln the context of the
present invention at least t.wo of these alkyl group: are $
or more carbons long.
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The cationic surfactant is of the general formula I, or II, or III:
R1\
S X- R2-N'- ( CHZ ) ~- ~ H-- ( CH2 ) m- OOCR5
R3 / (Formula I)
OOCR4
wherein Rl, R2 and R~ are independently C1_6 alkyl or
hydrogen, n and m are 0-4, OOCR4 and OOCRS are fatty acid
residues comprising $-2g carbon atoms and x is a
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monovalent anion equivalent. More typically, the cationic
surfactant comprises a ration of the formula given above
wherein m =1 and n=1.
a Preferably, the cationic surfactant comprises a ration of
the formula given above wherein Ri=Rz=R3=CH3. Most
preferably the cationic surfactant comprises a ration of
the formula given <above wherein RQ and RS are independently
Ciz-Czo .
Alternative fully saturated dialkyl quaternary ammonium
compounds include
X- [ CH3 ( CHz ) "CO . NH ( CHz ) m J z - N'RIRz (Formula ~ ~)
1 '_i
wherein R1 and Rz are independently selected from hydrogen,
C1-C4 alkyl, C1-C4 hydroxy alkyl and alkylene glycol
residues or polymers thereof, n is $-2g and m is 1-4 and X
is an monovalent anion equivalent.
2 ()
Preferably R1 is methyl, Rz is - (CHzCH20) XH, or methyl .
Further fully saturated dialkyl quaternary ammonium
compounds include
2 ~;
X- [CH3 (CHz ) COO (CHz ) m] z . N'RIRz (Formula ~~~)
wherein R1 and Rz are independently selected from hydrogen,
C1-C4 alkyl, C1-C4 hydroxy alkyl and alkylene glycol
3C~ residues or palymer.s thereof, n is g-26 and m is 1-4 and
X is an monovalent anion equivalent.
Preferably R1 is methyl , Rz is - (CHZCH20) XH (where x is on
average 1-2), or methyl, and m is 2.
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Further fully saturated dialkyl quaternary ammonium
compounds include
X- [ CH3 ( CHz ) "] 2 . N'RlRz
wherein R1 and Rz are independently selected from hydrogen,
C1-C4 alkyl, C1-C4 hydroxy alkyl and alkylene glycol.
residues or polymers thereof, n is $-2g and X is an
monovalent anion equivalent. Preferably R1 is methyl, Rz
1n is - (CHzCH20) XH (where x is 1-2 1 , or methyl . Preferably n
is selected such that the longer alkyl chains have a chain
length distribution similar to that of tallow.
The pH of the compositions according to the present
invention is acidic,, alkaline or neutral.
Typical compositions according to the present invention
have a pH of less than '7.5 where ester groups are used.
Where ester groups are absent as linkages in the cationic
surfactant the pH c:an be higher than 7.5.
A preferred cationic surfactant is:
X- [ (CH3) 3N-CH2-CH (OOCR4) -CH200CR5]
2 '_~
wherein, RQ and RS are independently Ciz-Czo and the
composition is essentially free of anionic surfactant.
Materials falling within this general class are available
from Hoechst . Most. preferably, R9 and RS are fatty acid
3 G residue alkyl chains having a chain length distribution corresponding
to that of tallow.
Another preferred cationic is:
3 5 X- [CH3 ( CHZ ) NCO . NH ( CH2 ) z ) 2 . N"RlRz
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wherein n is 11-19, R1 is methyl and RZ is - (CH2CH20) X (where
x is 1-2), H, or methyl. Materials falling within this
general description are available in the marketplace as
ACCOSOFT 440/75 (TM) from Stepan.
In the above-mentioned formulations it is preferable that
the ethoxylation number x is close to 1.7, i.e. 1.5-2Ø
It is believed .that the cationic surfactants present in the
compositions of the present invention modify the surface
energy of surfaces to which the composition is applied so
'' as to raise the contact angle of soil subsequently
deposited on the modified surface. Preferred cationics
have a marked effect on the contact angle of test liquids
which are applied to surfaces which have been treated with
said cationics. Thus, for glass microscope slides which
has been untreated the contact angle of a 10 microlitre
dodecane droplet is less than 10 degrees. When treated
with a composition embodying the present invention, i.e. an
aqueous solution of 5% nonionic and 1o cationic, as
described in further detail below: the contact angle of the
dodecane droplet is increased to typically above 20
degrees.
Accordingly, the present invention also extends to a method
for cleaning a hard surface with a net negative charge
which comprises the step of treating said surface with a
composition as described herein.
It is essential that the compositions of the present
invention comprise an alkoxylated alcohol nonionic
surfactant. The presence of nonionic surfactant is
believed to contribute significantly to the cleaning
effectiveness of the compositions of the invention.
~~~;~~vD~D SN~~1
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Suitable nonionic detergent active compounds can be broadly
described as compounds produced by the condensation of
alkylene oxide groups, which are hydrophillic in nature,
with an organic hydrophobic compound which may be aliphatic
or alkyl aromatic in nature.
The length of the hydrophillic or polyoxyalkylene radical
which is condensed with any particular hydrophobic group
can be readily .adjusted to yield a water-soluble compound
having the desired degree of balance between hydrophillic
and hydrophobic elements.
Particular examples include the condensation product of
aliphatic alcohols having from 6 to 22 carbon atoms in
either straight or branched chain configuration with
ethylene oxide, such as a coconut oil ethylene oxide
condensate having from 2 to 15 moles of ethylene oxide per
mole of coconut alcohol and condensates of alkylphenols
whose alkyl group contains from 6 to 12 carbon atoms with 5
to 25 moles of ethylene oxide per mole of alkylphenol.
ys S,a,. I
pwlCPIDL
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Particularly preferred nonionic surfactants are the
ethoxylated alcohols having 6-14 carbons and 2-9 moles of
ethoxylation. Suitable materials include IMBENTIN 91/35
OFA (TM), a Clo nonionic having on average five moles of
'_i ethoxylation.
Many more nonionic surfactants produced by condensation of alkylene oxides
with aliphatic or alkyl-aromatic compounds are known to the skilled worker, as
set forth in M.J.Schick'Nonionic Surfactant', Marcel Dekker (1967) and
1 « subsequent editions of the same work.
The amount of nonionic detergent active to be employed in
the composition of the invention will generally be from 1
to 30owt, preferably from 2 to 20%wt, and most preferably
15 from 5 to 10%wt.
It is particularly preferred that the ratio of nonionic
surfactant to anionic and cationic surfactant is such that
> 75% of the total surfactant present in the composition is
20 nonionic.
It is essential that the compositions of the present
invention only comprise low levels of anionic detergent
,~ actives or that these actives are absent in so far as is
25 practical. It is believed that the presence of anionic
detergents will cause the formation of a complex between
the cationic and anionic detergents which will reduce the
effectiveness of the compositions.
30 The overall surfactant content of compositions according to
the present invention will generally be 1 to 300.
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Hydrophobic oils are optional components of compositions
according to the present invention. Suitable oils include
oils which rapidly dissolve triglyceride. When oils are
present preferred oils include limonene, para-cymene, di-
butyl ether and butyl butyrate.
The composition according to the invention can contain
other ingredients which aid in their cleaning performance.
For example, the composition can contain detergent
builders. Suitable builders include materials such as
carbonates and bicarbonates, nitrilotriacetates,
polycarboxylates, citrates, dicarboxylic acids, water-
soluble phosphates especially polyphosphates, mixtures of
ortho- and pyrophosphate, zeolites and mixtures thereof.
Such builders (particularly the phosphates and the
carbonates) can additionally function as abrasives if
present in an amount in excess of their solubility in
water: although it is preferable that the compositions of
the present invention are essentially free of abrasive
particles. In general, the builder, will form from 0.1 to
25% by weight of the composition.
Metal ion sequestrants such as
ethylenediaminetetraacetates, amino-polyphosphonates
(DEQUESTR) and phosphates and a wide variety of other poly-
functional organic acids and salts,.can also optionally be
employed.
A further optional ingredient for compositions according to
the invention is a suds regulating material, which can be
employed in those compositions according to the invention
which have a tendency to produce excessive suds in use.
Examples of suds regulating materials are organic solvents,
hydrophobic silica and silicone oils or hydrocarbons.
p,'~IiEND cD SH~~~
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Solvents are optional components of compositions according
to the present invention. L~lhere solvents are present,
preferred solvents are of the form R1-0- (E0 ) m- ( PO) n-R2,
wherein R1 and RZ are independently C2-6 alkyl or H, but
not both hydrogen, m and n are independently 0-5. More
preferably, the solvent is selected from the group
comprising di-ethylene glycol mono n-butyl ether, mono-
ethylene glycol mono n-butyl ether, propylene glycol n-
butyl ether, isopropanol, ethanol, butanol and mixtures
thereof. Alternative solvents include the
pyrrolid(in)ones, for example N-methyl pyrrolidinone.
Compositions according to the invention can also contain,
in addition to the ingredients already mentioned,. various
other optional ingredients such as pH regulants,
colourants, optical brighteners, soil suspending agents,
detersive enzymes, compatible bleaching agents, gel-control
agents, freeze-thaw stabilisers, bactericides,
preservatives, detergent hydrotropes, perfumes and
opacifiers.
In embodiments where the cleaning of burnt on or otherwise
crosslinked soils is envisaged, it is particularly
!~ preferred that the composition comprises 1-10% of an
alkanolamine, with levels of 2-6~wt being particularly
preferred. Particularly suitable alkanolamines include: 2-
amino-2-methyl-1-propanol(AMP), mono-ethanolamine and di-
ethanolamine.
We have determined that it is particularly advantageous to
include a polymer in the compositions of the present
invention so as to reduce the level of formation of
exceptionally fine droplets when the composition is sprayed
as a relatively fine mist. Suitable polymers include
polyvinyl pyrrolidone, available in the marketplace as
Polymer PVP K-90.
I~'~~Fi~IDED SH~tT
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Suitable levels of PVP polymer range upwards from 50ppm.
Levels of 300-2000ppm are particularly preferred.
While the compositions of the present invention can be
_'i alkaline, acidic or neutral, it is preferred for kitchen
soils that the compositions are generally alkaline, having
a preferred pH >6.
Particularly preferred compositions have a pH of >10 and
comprise, in admixture with water,:
a) 3-15o alkoxylated alcohol nonionic surfactant
(preferably, C'9-C12 EU5-8 nonionic surfactant)
b) 2-loo solvent (preferably, diethylene glycol mono-n-
butyl ether)
c) 2-6o alkanolamine (preferably, 2-amino-2-methyl-1-
propanol)
d) 0-5% buffer/alkali (preferably, an alkali metal
carbonate),
e) 0-2000ppm polymer (preferably, PVP), and
f) 0.1-20 of a cationic. surfactant comprises a cat:ion of
the general formula:
X- ~CH3 (CH2 ) ~,CO. NH ( CH? ) m) z ~ N'RlRz
wherein R1 and RZ are independently selected from hydrogen,
C1-C4 alkyl, C1-C4 hydroky alkyl and alkylene glycol
residues or polymers thereof, n is g_2g and m is 1-~~ and
X is an monovalent anion equivalent, said composition being
packaged in a container adapted to produce a spray of 0.1-
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1.5m1 of product per spraying operation, said spray having
an average drop size in the range 30-300 microns.
In order that the present invention may be better
understood it will be described hereinafter by way of
example.
Aqueous compositions comprising nonionic surfactant, and a
' relatively low level of cationic surfactant were prepared
as in Tables 1 and 2 below: using the following materials
(all compositions a.re given in terms of wto unless
otherwise stated):
NONI: IMBENTIN 91/35 OFA (TM),
CTAB: Cetyl trimethyl ammonium bromide,
HEQ: [ (CHs) 3N-CH. OOCR4-CH2. OOCR5]+C1- wherein OOCR4
2 0 and OOCR5 are fatty acid residues having a -
fatty acid chain length corresponding to
tallow (manufac:tured by Hoechst).
ACCO: ACC:OSOFT 440/75 ex. Stepan.
AMP: amino-2-methyl--1-propanol
digol: Butyl Digol (TM)
The compositions were prepared at room temperature by
mixing except where HEQ and AC:CO were used, these latter
material being dissolved in three parts propylene glycol at
70 celcius and added to water, also at 70 cel.cius, while
stirring.
Results 'ETh' and 'EPh' are explained below. CTAB, a
typical mono-alkyl. cationic surfactant was selected as a
control as it has a significantly lower effect on the
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contact angle of a dodecane droplet placed on a glass
(microscope) slide which has been treated with a 1%
r
f_
a ~~L~u~~ s~s~r
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solution of the dialkyl cationic in a 5~ aqueous solution
of NONI.
The surface energy gammas/mN.iri 1 of the CTAB treated glass
(microscope slide) surface is believed to be of the order
of 25 mN.nl1 (as measured by the method of Grifalco, Good,
Fowkes and Young (see Physical chemistry of Surfaces, A. A.
Adamson, Wiley, New York [1990])), whereas the surface
energy of surfaces treated with similar solutions of the
cationics used in the compositions of the present invention
was less than 25 mN.iri 1.
TABLE 1
EXAMPLE:
Comp: 1 2 3 4 5
NONI 50 5% 50 5% 5%
CTAB - 1% - - -
HEQ - - .01% 0.1% 1/0o
ETh * * * 2140 2119
EPh 2634 1697 - 896 776
Gammas >25 25 - - 23.1
* indicates that the tile was not clean in less than 2
minutes i.e. the cleaning effort was believed to be of the
order of 10000 Ns.
Ar~~r~~F~ su~~z
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Table 2
Example
Comp: 6 7 8 9
NONI 10a 100 100 100
AMP 4% 4% 4% 4%
KZC03 1.2% 1.2% 1.20 1.2%
Digol 8% 8% 80 80
Prop - - 0.60 3.0o
G
CTAB - 1% - -
ACCO - - 0.20 1.0%
ETh 930 469 189 137
100g dehydrated castor oil (ex. UNICHEMA) was weighed into
a glass jar. To this was added 0.2g Fat Red (TM) dye (ex.
SIMGA) and the mixture was stirred vigorously (2000 RPM)
for 6 hours using a Heidolph stirrer. The stirred mixture
was refrigerated when not in use.
Vitreous enamel times (380x300mm) were cleaned using a
fresh damp J-CLOTH (TM) using, in sequence, JIF LAC (TM), a
commercially available brand of hand dishwashing liquid and
calcite powder. After drying residual calcite was removed
by buffing with a paper towel.
1m1 of the compositions listed in Table 1 was wiped onto
the cleaned tiles using a fresh damp J-CLOTH. The tiles
were rinsed with tap water for 15 seconds to remove excess
composition and allowed to drain. Tiles were soiled over a
215x150mm area using a DeVilbiss (TM) gravity feed spray
gun (MODEL MPS-514/515) using compressed air at 25 psi, by
spraying from 27 cm for 35 seconds. The soiled tiles were
either laid horizontally in an oven at 85 Celsius and
a~YA~~,~~r~ s~~~~
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thermally aged for 2 hours and then stored overnight, or
aged photochemically by exposure to daylight for 3-6 days.
Tiles were cleaned by hand using damp J-cloths and for the
examples cited in table 1, 1-2 ml of a control composition
which comprised the formulation given in table 3 below:
Table 3 control formulation
5 % NONI
t~ 3 . 4 % AMP
0.2M KZC03
5% N-methyl pyrollidon
The effort required to clean the tiles was determined as
~ETh~ in table 1 for thermally aged tiles and ~EPh~ for
photochemically aged tiles.
2m1 of the compositions listed in Table 2 were wiped onto
the cleaned tiles using a fresh damp J-CLOTH. The tiles
were soiled and aged as described above and cleaned with
same formulation as used in pre-treatment rather than the
control formulation.
From the results presented in tables 1 and 2 it can be seen
that the compositions according to the present invention,
show a marked reduction in the cleaning effort required as
compared with comparable compositions which either contain
no cationic surfactant or contain a cationic surfactant
which is not a saturated dialkyl cationic.
A"p=l~ju~~ S~~tT
