Note: Descriptions are shown in the official language in which they were submitted.
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CLEANING COMPOSITION COMPRISING FLUORO-SURFACTANTS
Technical Field
The present invention relates to compositions for cleaning
hard surfaces, wherein said composition comprises both cleans
the surface and prevents or r-etards further soiling of the
surface.
Backqround 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
remova:L using surfactant or solvent based compositions with
the application of a lacquer, wax or polish as a separate
operat:ion so as to seal and protect the surface and reduce the
rate of soil redeposition. This two-step cleaning and sealing
operation is both time-consuming and complex.
It has been proposed to include a range of so-called 'soil
release agents', including polymers, siloxanes and quaternary
cationic surfactants in cleaning compositions so as to provide
a secondary cleaning benefit. It is believed that these soil
release agents function by deposition of a layer of polymer,
siloxane or surfactant on the surface during cleaning. This
layer of material is believe(1 to facilitate further cleaning
operations by reducing the extent to which soil adheres to the
surface. ObviGusly, some care is needed in the choice of
soil-release agents as cleaning compositions typically
comprise surfactants whose primary purpose is to remove
materials from the surface and it is important both that the
cleaning function of the composition is not impaired by the
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presence of the soil-release agent and that the soil release
agent can deposit in the presence of surfactant.
Despite progress in this field there is a need to provide
compositions which further reduce the extent to which soil
adheres to surfaces and provide further formulation
flexihility, especially as regards the possibility of
flocculation of the compositions in the presence of
electrolytes and/or other minor components.
Brief Descri~tion of the Invention
T~e have now devised stable compositions which both clean a
surface and are believed to deposit thereupon a layer of a
cationic fluorosurfactant which assists the release of soil
subsequently deposited upon the said surface.
Accordingly, the present invention provides an aqueous, hard-
surface cleaning composition comprising a surfactant mixture,
wherein said surfactant mixture comprises:
a) a cationic fluorosurfactant, and,
b) a non-fluorinated nonionic surfactant.
It is believed that the cationic flourosurfactants present in
the compositions of the present invention modify the surface
energv of surfaces to which the composition is applied so as
to raise the contact angle of soil subsequently deposited on
the modified surface.
~ypical cleaning compositions falling within the present
invention comprise, in addition to nonionic surfactant, a
level of cationic fluorosurfactant which is effective to lower
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the surface energy of a surface cleaned with the composition
to below 25 mN/m.
Detailed DescriDtion of the Invention
In order that the present invention may be further understood
it wili be described in greater detail below with particular
reference to preferred components and formulation details.
'10
Fluoro surfactants:
It is essential that the compositions of the present invention
comprise a cationic fluorosurfactant. The presence of an
effective amount of the fluorosurfactant is believed to
provide for the deposition of- a 'protective' layer on the
surface being cleaned. This layer prevents or reduces the
adhesion of soil subsequently applied to the surface. The
layer also causes the surface cleaned to exhibit a lower
surface energy and compositions according to the invention
typically reduce the surface energy to less than 25 mN/meter.
Suitable fluorosurfactant compounds can be broadly described
2-5 as compounds which contain al least one CF, moiety and a group
carrying a positive charge. We have determined that
fluorosurfactants which include the CF~ group have a larger
depressive effect on the surface energy than those which
include only CF groups.
Typically the positive charge is borne on a nitrogen atom, and
preferably the said nitrogen atom is quaternary.
Preferably, the fluorosurfactants employed in the present
invention are of the general formula:
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( I ) CFl-L-N R;R R3
wherein L is a linking group which is preferably selected from
linear or branched aliphatic or fluoro-aliphatic chains which
may contain heteroatoms and Rl, R2. and R3 are preferably short
chain alkyl groups, typically Cl-C5 alkyl groups of which
methyl groups are preferred: in an alternative, one of R" R2or
R3 is itself a moiety of the form CF3-L-.
The linking group L typically comprises a backbone which is at
least six carbon or heteroatom units long. This provides
sufficient spacing between the quaternary nitrogen and the -CF3
group to ensure that the molecule exhibits appropriate
surfactant behaviour.
Preferably L is selected from the group comprising:
(II) - (CF ),~- (CH~),nSCH,CHOH-CH - where n + m is 6-22,
( I I I ) - R4CH~CH2CH ( R4. C F3 )NHCOCH2- where R4 i s - ( C F~) n ( CH2 ) m~ ( CO ) ~
and n+m is 6 to 22,
(IV) - (CF ) - (CH )mO(CO)CH -CH - where n + m is 6-22,
(V) -RsCHCH( Rs~ C F~) CH - where Rc is -(CF2)rl(CH2) m~ ( CO ) - and n+m
is 6 to 22,
(VI) -(CF)n-(CH2),n- where n + m is 6-22,
(VII) -(CF)~!-(CH)Il~SO~NH(CH) - where n + m is 6-22,
Particularly preferred fluorosurfactant materials are selected
from the groups comprising:
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(IIa) F3- (CF ) "- (CH.) mSCH2CHOH-CH,,-N RIR,,R3
where n is 5-g and m is 2, and RIR~ and R3 are -CH3. A suitable
material being available as Z.ONYL FSD (TM) ex. Dupont.
(IIIa) CFl-R4CH2CH2CH(R4.CF3)N~lCOCH2-N RIR~R3
where R4 is - (CF~)n(CH2)mO(CO)--~ n is 5-9 and m is 2, and RIR2
and R3 are -CH3. A suitable material being available as
DC-5-8F2L (TM) ex. Sogo Pharmaceuticals of Tokyo.
(IVa) CF~- ( CF~ ) n- ( CH~) m~ ( CO ) CH2-CH ,-N R~R2R3 ~
where RIR~ are -CH3 and R3 is CF3- (CF ,) n~ (CH2) m~ (CO) CH2-CH2- and n
is 5-9 and m is 2. A suitable material being synthesised on
request by Lancaster Synthesis Limited in Lancashire UK.
(Va) F3-RsCHCH( Rc . CF3 ) CH, -N R,R ~R
where Rl,R and R3 are -CH3, R, is - (CF2)n(CH2)mO(CO) - where n is
5-9 and m is 2. A suitable material being synthesised on
request by Lancaster Synthesis Limited in Lancashire UK.
(VIa) F~- (CF )~- (CH ),I,-NRlR~R
where n + m is 6-22 and R, R and R3 are -CH3. Suitable materials
being found in the SURFLON (TM) range of surfactants available
from Asahi Glass of Japan.
30 (VIIa) F,- (CF,) ,- (CH,)~SO"NH (CH,) 3-N R R,R3
where n is 5-9 and m is 0, and RIR and R3 are -CH3. Suitable
materials are a~Jailable as FLUORAD FC135 (TM) ex. Minnesota
Mining and Manufacturing.
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Preferred levels of cationic fluorosurfactant are the range
0.05-5%wt on product. Particularly preferred levels are in
the range 0.1-2%wt on product, with levels of around 0.2%wt
being rnost preferred as a compromise between cost and
efficacy.
Nonionic Surfactants:
It is essential that the compositions of the present invention
comprise a non-fluorinated nonionic surfactant. The presence
of nonionic surfactant is be]ieved to contribute significantly
to the cleaning effectiveness of the compositions of the
invention.
Suitable nonionic detergent active compounds can be broadly
described as compounds produced by the condensation of
alkylene oxide groups, which are hydrophilic in nature, with
an organic hydrophobic compound which may be aliphatic or
alkyl aromatic in nature.
The length of the hydrophilic 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 hydrophilic 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;
condensates of alkylphenols whose alkyl group contains from 6
to 12 carbon atcms with 5 to 25 moles of ethylene oxide per
mole of alkylphenol; condensates of the reaction product of
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ethylenediamine and propylene oxide with ethylene oxide, the
condensates containing from 40 to 80% of polyoxyethylene
radicals by weight and having a molecular weight of from 5,000
to 11,000; tertiary amine oxides of structure R3N0, where one
group R is an alkyl group of 8 to 18 carbon atoms and the
others are each methyl, ethyl or hydroxy-ethyl groups, for
instance dimethyldodecylamine oxide; tertiary phosphine oxides
of structure R3P0, where one group R is an alkyl group of from
10 to 18 carbon atoms, and the others are each alkyl or
hydroxyalkyl groups of I to 3 carbon atoms, for instance
dimethyldodecylphosphine oxide; and dialkyl sulphoxides of
structure R~S0 where the group R is an alkyl group of from 10
to 18 carbon atoms and the ot:her is methyl or ethyl, for
instance methyltetradecyl su]phoxide; fatty acid
alkylolamides; alkylene oxide condensates of fatty acid
alkylolamides and alkyl mercaptans.
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 C~ll nonionic having on average five moles of
ethoxylation and NONIDET 91-6T (TM) a topped C ll nonionic with
an average of six moles of ethoxylation.
Many more nonionic surfactants are known to the skilled
worker, as set forth in M.J.Schick 'Nonionic Surfactants',
Marcel Dekker (lg67) and 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
30%wt, preferably from 2 to 20%wt, and most preferably from 5
to 10%wt.
Anionic surfactant may be present in the composition, but is
preferably present at levels of less than 1% and is more
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preferably absent. 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.
It is particularly preferred that the ratio of nonionic
surfactant to the total of anionic and cationic surfactant is
such that > 75% of the total surfactant present in the
composition is nonionic.
The overall surfactant content of compositions according to
the present invention will generally be 1 to 30%.
Minors and other components:
A plurality of minor components can be present in the
compositions of the present invention. The composition
according to the invention can contain other ingredients which
aid in their cleaning performance and/or improve the physical
properties of the composition. These components are not
essential to the functioning of the invention.
It is preferable that the compositions of the invention
comprise at least 0.5%wt of an organic amine, with a PKa of at
least 8Ø This component is believed to function as ester-
cleavage agent which assists cleaning of recalcitrant soils
such as the pyrolised soils which are produced when fatty
and/or proteinaceous foodstuffs are heated at the surface.
~hen organic amines with a lower pK~ such as aniline are used
they are ineffective in assisting cleaning.
It is preferred that the composition comprises 1-10% of an
alkanolamine, with levels of 2-6%wt being particularly
preferred. Particularly suitable alkanolamines include: 2-
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amino-2-methyl-1-propanol, mono-ethanolamine and di-
ethanolamine. 2-amino-2-methyl-1-propanol is the most
preferred organic amine.
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.
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.
Solvents are optional components of compositions according to
the present invention. Where solvents are present, preferred
solvents are of the form Ri-()-(E0)~-(PO)n-R2, wherein R, and R2
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 suspendinq agents, enzymes, compatible
bleaching agents, gel-control agents, freeze-thaw stabilisers,
bactericides, preservatives, detergent hydrotropes, abrasives,
perfumes and opacifiers.
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- 10 -
It has been found convenient to deliver products according to
the invention in the form of a relatively low dosage of
product in a relatively fine mist. This has the significant
advantage that only low levels of product need be employed.
Preferably compositions according to the invention are
packaged in a container adapted to produce a spray of 0.1-
1.5ml of product per sprayinq operation, said spray having an
average drop si~e in the ranc~e 30-300 microns.
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.
Suitable levels of PVP polymer range upwards from 50ppm.
Levels of 300-2000ppm are particularly preferred.
Preferred compositions according to the invention comprise:
a) 0.05-5% of a cationic fluorosurfactant, and,
b) 1-30% of a nonionic surfactant.
Particularly preferred alkaline cleaning compositions
according to the invention comprise:
a) 0.1-1% of cationic fluorosurfactant IIa, VIa or VIIa as
described above,
b) 2-15% of an alkoxylatecl alcohol, nonionic surfactant,
and,
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c) 1-6% of an alkanolamine
Particularly preferred neutral cleaning compositions according
to the invention comprise:
a) 0.1-1% of a cationic fluorosurfactant as described above,
and,
b) 2-15% of an alkoxylated alcohol, nonionic surfactant.
In order that the present invention may be better understood
it will be described hereinafter by way of non-limiting
examples.
EXAMPLES
Aqueous compositions comprising nonionic surfactant, and a
relatively low level of cationic surfactant were prepared as
in Tables 1 below: using the following materials (all
compositions in Table 1 are given in terms of wt% unless
otherwise stated):
NON: NONIDET 91-6T (TM: ex. Nippon Shell): a C9-C11
ethoxylated alcohol with 6 moles of
ethoxylation, and topped to reduce the quantity
of low ethoxylates,
IMB: IMBENTIN 91-35 OFA (TM: ex. Kolb): a C9-C11
ethoxylated alcohol with 5-6 moles of
ethoxylation, and topped to reduce the quantity
of low ethoxylates,
ZON: ZONYL FSD (TM) ex. Dupont,
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SUR: SURFLON S121 (TM) ex. Asahi Glass of Japan,
FC1: FLUORAD FC135 (TM) ex. 3M
DC5: DC-5-8F2L (TM) ex. Sogo Pharmaceuticals,
LS1: Material (IVa) as specified above with n~7, ex.
Lancaster Synthesis.
LS2: Material (Va) as specified above with n-7, ex.
Lancaster Synthesis.
Solvent: Butyl Digol (TM): diethylene glycol mono
n-butyl ether,
NMP N-methyl pyrrolidinone,
AMP: 2-amino-2-methyl-1-propanol,
HEQ: [~CH) N-CH.COOR~-CH2.COORs] Cl wherein OOR4 and
OOR~ are fatty acid residues having a fatty
acid chain length corresponding to tallow
(manufactured by Hoechst).
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Table 1
Ex. Cati Lvl Non Lvl Post ETh EPh Con CSE
(%) (%)
Series #l
ZON 1 IMB 5 A1639 855 49 17.4
2 ZON 0.1 IMB 5 A41411738 - -
3* ZON 0.01 IMB 5 Afail - - -
4 FCl 1 IMB 5 A - 9 67
5* none - IMB 5 A fail 2634 <10 >25
Series #2
6 DC5 1 IMB 5 C 87 - 74 11.2
7* none - IMB 5 C2788 - <10 >27.6
8* HEQ 1 IMB 5 C 364 - 38 22.2
Series #3
9 LSl 1 IMB 5 C 78
0 LS2 1 IMB 5 C 99
11 DC5 1 IMB 5 C 87
12* HEQ 1 IMB 5 C 94
13* none - IMB 5 C 509 - - -
Series #4
14* SUR 0.01 NON 10 B1308 - <10 >27.6
15* SUR 0.02 NON 10 B1040 - ~10 >27.6
16 SUR 0.05 NON 10 B1003 - <10 >27.6
17 SUR 0.1 NON 10 B 473 - <10 >27.6
18 SUR 0. 2 NON 10 B 322 - 32 23.6
19 SUR 0. 5 NON 10 B 221 - 31 23.7
SUR 1 NON 10 B 158 - 32 23.5
21* non - NON 10 B 795 - <10 >27.6
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- :14 -
The compositions were prepared at room temperature by mixing
except where HEQ was used, this latter material being dissolved
in three parts propylene glycol at 70 celcius and added to
water, also at 70 celcius, while stirring.
Results were obtained in four series over a period of time as it
is commonly found that results should be only compared with
those obtained by the same operator on the same day. These
series of results are indicated as Series #1-4 in Table 1. The
first five columns of table 1, give the identity of the fluoro
and nonionic surfactants and their levels in the numbered
examples. Examples whose number is followed by a star (*) are
comparatives.
L5 In all experiments soiled tiles were cleaned with the
composition given in Table 1 and subsequently cleaned with a
second composition (which did not contain the fluorosurfactant)
as indicated in the column 'Post' in table 1. Compositions A-C
are given below.
.~0
A- 5% IMB, 5% NMP, 3.4% AMP and 0.2Molar Na CO~
B- 10% NON, 8% Solvent, 4% AMP, 1.25% K~CO3, 0.1% polymer (PVP
K90) and 0.2% perfume.
:~5
C- 5% IMB.
In order to measure cleaning in Series #1-3, 100g dehydrated
castor oil (ex. UNICHEMA) was weighed into a glass jar. To this
was added 0.2g Fat Red (TM) clye (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.
In order to measure cleaning in Series #4, 100g of 1.5 poise
dehydrated castor oil (ex. SE~ATONS) was weighed into a glass
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jar. To this was added 0.2g Eat Red (TM) dye (ex. SIMGA) and the
mixture was stirred vigorous:Ly (2000 RPM) for 6 hours using a
Heidolph stirrer. The stirred mixture was refrigerated when not
in use.
s
In all series of examples, vitreous enamel tiles (380x300mm)
were cleaned using a fresh damp J-CLOTH (TM) using, in sequence,
JIF cream (TM), then a commercially available brand of hand
dishwashing liquid and finally calcite powder. After drying
residual calcite was removed by buffing with a paper towel.
To determine 'ETh', lml 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 215xl5Omm 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 laid
horizontally in an oven at 85 Celcius and thermally aged for 1.5
hours in Series #4 and otherwise for 2.0 hours before being
stored overnight. Soiled tiles were cleaned by hand using damp
J-cloths and the compositions indicated in table 1. The effort
required to clean the tiles is given as 'ETh' in table 1. ETh
measurements are expressed in Newton.seconds, higher values
indicate that more effort was required to clean the tile. Where
cleaning was not possible with 2 minutes the value is given as
'fail~.
To determine 'EPh' the protocol given above was followed except
the tiles were not laid in the oven but the soil was aged
photochemically by exposure to daylight for 3-6 days at room
temperature. The effort required to clean the tiles is given as
'EPh' in table 1. EPh measurements are expressed in
Newton.seconds, higher values indicate that more effort was
required to clean the tile.
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- 16 -
The surface energy gammaS/mN.m~ was measured by the method of
Grifalco, Good, Fowkes and Young (see Physical chemistry of
Surfaces, A. A. Adamson, Wiley, New York [1990])), using the
contact angle of hexadecane :in Series #2 and Series #4 and
dodecane in Series #1. Contact angles are given as 'Con' (in
degrees) in Table 1 and calculated surface energies as 'CSE' (in
mN/meter) in Table 1. For most household surfaces the surface
energy after cleaning with conventional products is >25 mN/m.
From the results in Series #L of the examples it can be seen
that significantly lower cleaning effort is required for
compositions according to the invention than those which either
contain no fluorosurfactant or only a very low and ineffective
level of fluorosurfactant.
The result of the examples in Series #2 show that the same
benefit is obtained for a different fluorosurfactant and that
the effect obtained is bette:r than that obtained with the non-
fluorosurfactant cationic 'HEQ'.
Series #3 provides further examples illustrated with reference
to the prior known cationic 'HEQ'. It can be seen that with the
fluorosurfactants used essentially the same results were
obtained as with the 'HEQ' material but it is believed that
compositions according to the invention would not suffer from
the preparation and or stability problems which have been
encountered with compositions comprising the HEQ material.
Series ~4 illustrates the effect of varying the level of one
particular fluorosurfactant. It can be seen that for this
particular material, little or no benefit is obtained at
inclusion levels of below 0.05%wt but that an increasing benefit
as compared with the control is found as the level of
fluorosurfactant is increased.
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From the examples as a whole it can be seen that the
formulations of the invention in which there is a 1%wt solution
of cationic fluorosurfactant give a calculated surface energy
below 25 mN/m, as determined from the measurements of contact
angles with hexadecane or dodecane droplets. This also
demonstrates that the compositions of the invention apply an
anti-resoiling benefit to surfaces cleaned with them.
