Note: Descriptions are shown in the official language in which they were submitted.
CA 02248790 1998-09-11
WO 97/33963 PCT/US97/03388
GLASS CLEANER COMPOSITIONS HAVING GOOD FILMING/STREAKING
CHARACTERISTICS CONTAINING AMINE OXIDE POLYMERS
FUNCTIONALITY
FIELD OF INVENTION
This invention pertains to glass cleaning compositions, preferably liquid
detergent
compositions for use in cleaning glass, especially window glass, and,
preferably, other
hard surfaces. Such compositions typically contain detergent surfactants,
solvents,
builders, etc.
BACKGROUND OF THE INVENTION
The use of, e.g., solvents and organic water-soluble synthetic detergent
surfactants
at low levels for cleaning glass are known. There are several compositions
known that
provide good filming/streaking characteristics so that the glass is cleaned
without leaving
objectionable levels of spots and/or films.
Known detergent compositions comprise certain organic solvents, detergent
surfactants, and optional builders and/or abrasives. The prior art, however,
fails to teach,
or recognize, the advantage of providing an amine oxide polymer material in
glass cleaner
formulations to provide a residual hydrophilicity.
The preferred liquid cieaning compositions have the great advantage that they
can
be applied to hard surfaces in neat or concentrated form so that a relatively
high level of,
e.g., surfactant material and/or organic solvent is delivered directly to the
soil. Therefore,
liquid cleaning compositions have the potential to provide superior soap scum,
grease,
and oily soil removal over dilute wash solutions prepared from powdered
cleaning
compositions. The most preferred compositions are those that provide good
cieaning on
tough soils and yet clean glass without leaving objectionable levels of spots
and/or films.
Liquid cleaning compositions, and especially compositions prepared for
cleaning
glass, need exceptionally good filming/streaking properties. In addition, they
can suffer
problems of product form, in particular, inhomogeneity, lack of clarity, or
excessive
"solvent" odor for consumer use.
SUMMARY OF THE INVENTION
The present invention relates to detergent compositions that can clean glass
3~ without leaving objectionable levels of filming and/or streaking and which
contain an
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WO 97/33963 2 PCT/US97/03388
effective amount of amine -oxide polymer which provides the glass, especially
window
glass. with long lasting higher hydrophilicity. Preferably, said compositions
are in the
form of an aqueous, liquid, hard surface detergent composition having improved
cleaning
and good spotting characteristics after rewetting comprising: (A) an amount of
water
soluble amine oxide polymer effective to provide an improvement in
spotting/filming
after at least three rewettings of the glass; (B) hydrophobic solvent; (C)
detergent
surfactant selected from the group consisting of anionic surfactants,
amphoteric detergent
surfactants including zwitterionic surfactants; and mixtures thereof; and (D)
the balance
being an aqueous solvent system comprising water and, optionally, non-aqueous
polar
solvent with only minimal cleaning action selected from the group consisting
of
methanol, ethanol, isopropanol, ethylene glycol, polypropylene glycol, glycol
ethers
having a hydrogen bonding parameter of greater than 7.7, and mixtures thereof
and any
minor ingredients.
The compositions can be formulated at usage concentrations, or as
concentrates,
1 S either solid, or liquid, and can be packaged in a container having means
for creating a
spray to make application to hard surfaces more convenient.
All percentages, parts, and ratios herein are "by weight" and all amounts are
approximations, unless otherwise stated.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the present invention, it has been found that superior
detergent
compositions for cleaning shiny surfaces such as glass which leave said
surface with a
desirable appearance, i.e., without objectionable levels of filming and/or
streaking, can be
further improved to help maintain said desirable appearance for an extended
period of
time by incorporating an amine oxide polymer which is substantive to said
surfaces and
which provides a more hydrophilic surface. When such surfaces are rewetted,
e.g., as
when windows are wetted by rain, the water "sheets" off the surface and the
surface is
still without objectionable levels of spotting (and/or filming) after the
surface dries. As
anyone who has cleaned windows can attest, one of the most frustrating things
that can
happen after windows have been cleaned is for a rain shower to occur and leave
spots on
the just cleaned window. The present invention meets a long felt need. The
preferred
aqueous liquid detergent compositions for cleaning shiny surfaces such as
glass contain:
(A) an amount of amine oxide polymer effective to provide an improvement in
spotting/filming after at least three rewettings of the glass; (B) hydrophobic
solvent; (C)
detergent surfactant selected from the group consisting of anionic
surfactants, amphoteric
detergent surfactants including zwitterionic surfactants; and mixtures
thereof; and (D) the
CA 02248790 2003-03-07
s
balance being an aqueous solvent system comprising water and, optionally. non-
aqueous
polar solvent with only minimal cleaning action selected from the group
consisting of
methanol, ethanol, isopropanol, ethylene glycol, polypropylene glycol, glycol
ethers
having a hydrogen bonding parameter of greater than 7.7, and mixtures thereof
and any
minor ingredients.
A. WATER SOLUBLE AMINE OXIDE POLYMER
An essential part of this invention is the substantive material that improves
the
hydrophilicity of the surface being treated, especially glass. This increase
in
hydrophilicity provides improved appearance when the surface is rev~ietted and
then dried.
The water "sheets" off the surface and thereby minimizes the formation of,
e.g.,
"rainspots" that form upon drying. The use of polycarboxylate, polystyrene
sulfonate,
and poiyether based polymers to provide this hydrophilicity is known in the
art. The use
of these polymers is described in u.:>. ~at~nt r~~. ~,53~,19s, granted ,7uly ,
9, 1996.
However, the use of relatively low molecular weight, water soluble amine oxide
polymers
to achieve improved hydrophilicity in a glass cleaner has heretofore not been
disclosed in
the art.
While as not to be limited by theory, it is believed that the partial positive
charge of
the amine oxide group acts to adhere the polymer to the surface of the glass.
It is further
:20 believed that the adhesion of these polymers alters the surface properties
of the glass thus
allowing water to "sheet" more readily, The polymers of this invention have
one or more
monomeric units containing at least one N-oxide group. At least about 10%,
preferably
more than about 50%, more preferably greater than about 90% of said monomers
forming
said polymers contain an amine oxide group. These polymers can be described by
the
:25 general formula:
P
B
a
t
wherein each P is selected from homopolymerizable and copolymerizable moieties
which
attach to form the polymer backbone, preferably vinyl moieties, e.g. C(Rr-
C(R)S.
wherein each R is H, C,-C~2 (preferably C~-C4) alkyl(ene), C6-Ci2 aryl(ene)
and/or H; B is
30 a moiety selected from substituted and unsubstituted, linear and cyclic C,-
C,z alkyl, C,-
C,z alkylene, C,-C,Z heterocyclic, aromatic C6-C~~ groups and wherein at least
one of said
CA 02248790 2003-03-07
4
B moieties has at least one amine oxide p~N-->03 group present: a is from 0 to
about ?:
and t is number such that the average molecular weight of the polymer is from
about
2.000 to about 100.000, preferably from about x.000 to about ?U.000. arid more
preferably from about $.000 to about 12.000.
The preferred palymers of this invention passers the unexpected property of
being
substantive without leaving a visible residue that would render the glass
surface
unappealing to consumers. 'The preferred polymers include poly(4-vinylpyridine
N-oxide)
polymers (PVNO), e.g. those formed by polymerization of monomers that include
the
following moiety:
CHCHz
w
O
t
wherein, for the purposes of this invention, t is a number such that the
average molecular
weight of the polymer is from about 2,000 to about 100,000, preferably from
about 5,000
to about 20,000, and more preferably from about 8,000 to about 12,000. 'The
desirable
l5 moiecular weight range of polymers useful in the present invention stands
in contrast to
that found in the art relating to polycarboxylate, polystyrene sulfonate, and
polyether
based additives which prefer molecular weights in the range of 400,000 to
1,500,000.
'The level of amine axide polymer should normally be from about 0.01 % to
about
1%, preferably from about 0.05% to about 0.5%, more preferably from about 0.1%
to
about 0.3%, by weight of the composition.
B. HYDROPHOBIC SO~
In order to improve cleaning in liquid compositions, one can use a hydrophobic
solvent that has cleaning activity. The solvents employed in the hard surface
cleaning
compositions herein can be any of the well-known "degreasing" solvents
commonly used
in, for example, the dry cleaning industry, in the hard surface cleaner
industry and the
metalworking industry.
A useful definition of such solvents can be derived from the solubility
parameters
as set forth in "The Hoy," a publication of 1,.1'nion Carbide,
CA 02248790 2005-02-02
The most useful parameter appears to be the hydrogen bonding parameter which
is
calculated by the formula:
a - 1 1/2
yH=~yT
a
wherein y H is the hydrogen bonding parameter, a is the aggregation number,
(Log a = 3.39066 Tb / T° - 0.15848 - Log M), and
d
y T is the solubility parameter which is obtained from the formula:
(OH25 - RT)d 1/2
yT-
M
where OH25 is the heat of vaporization at 25°C, R is the gas constant
(1.987 cal/mole/deg),
T is the absolute temperature in °K, Tb is the boiling point in
°K, T~ is the critical
temperature in °K, d is the density in g/ml, and M is the molecular
weight.
For the compositions herein, hydrogen bonding parameters are preferably less
than about 7.7, more preferably form about 2 to about 7, or 7.7, and even more
preferably
from about 3 to about 6. Solvents with lower numbers become increasingly
difficult to
solubilize in the compositions and have a greater tendency to cause a haze on
glass.
Higher numbers require more solvent to provide good greasy/oily soil cleaning.
Hydrophobic solvents are typically used at a level of from about 0.5% to about
30%, preferably from about 2% to about 15%, more preferably from about 3% to
about
8%. Dilute compositions typically have solvents at a level of from about 1% to
about
10%, preferably from about 3% to about 6%. Concentrated compositions contain
from
about 10% to about 30%, preferably from about 10% to about 20% of solvent.
Many of such solvents comprise hydrocarbon or halogenated hydrocarbon
moieties of the alkyl or cycloalkyl type, and have a boiling point well above
room
temperature, i.e., above about 20°C.
The formulator of compositions of the =present type will be guided in the
selection
of cosolvent partly by the need to provide good grease-cutting properties, and
partly by
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WO 97!33963 6 PCTlUS97/03388
aesthetic considerations. For example, kerosene hydrocarbons function quite
well for
grease cutting in the present compositions, but can be malodorous. Kerosene
must be
exceptionally clean before it can be used, even in commercial situations. For
home use,
where malodors would not be tolerated, the formulator would be more likely to
select
solvents which have a relatively pleasant odor, or odors which can be
reasonably
modified by perfuming.
The C6-Cg alkyl aromatic solvents, especially the C6-Cg alkyl benzenes,
preferably octyl benzene, exhibit excellent grease removal properties and have
a low,
pleasant odor. Likewise, the olefin solvents having a boiling point of at
least about
100°CLespecially alpha-olefins, preferably 1-decene or 1-dodecene, are
excellent grease
removal solvents.
Generically, glycol ethers useful herein have the formula R11 O-(R120-)m1H
wherein each R11 is an alkyl group which contains from about 3 to about 8
carbon atoms,
each R12 is either ethylene or propylene, and ml is a number from 1 to about
3. The
most preferred glycol ethers are selected from the group consisting of
monopropyleneglycolmonopropyl ether, dipropyleneglycolmonobutyl ether,
monopropyleneglycolmonobutyl ether, ethyleneglycolmonohexyl ether,
ethyleneglycolmonobutyl ether, diethyleneglycolmonohexyl ether,
monoethyleneglycolmonohexyl ether, monoethyleneglycolmonobutyl ether, and
mixtures
thereof.
A particularly preferred type of solvent for these hard surface cleaner
compositions
comprises diols having from 6 to about 16 carbon atoms in their molecular
structure.
Preferred diol solvents have a solubility in water of from about 0.1 to about
20 g/100 g of
water at 20°C.
Solvents such as pine oil, orange terpene, benzyl alcohol, n-hexanol, phthalic
acid
esters of C 1-4 alcohols, butoxy propanol, Butyl Carbitol~ and 1 (2-n-butoxy-1-
methylethoxy)propane-2-of (also called butoxy propoxy propanol or dipropylene
glycol
monobutyl ether), hexyl diglycol (Hexyl Carbitol~), butyl triglycol, diols
such as 2,2,4-
trimethyl-1,3-pentanediol, and mixtures thereof, can be used. The butoxy-
propanol
solvent should have no more than about 20%, preferably no more than about 10%,
more
preferably no more than about 7%, of the secondary isomer in which the butoxy
group is
attached to the secondary atom of the propanol for improved odor.
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WO 97/33963 ~ PCT/US97_103388
C) THE DETERGENT SURFACTANT
w ( 1 ) The Amphocarboxylate Detergent Surfactant
The aqueous, liquid hard surface detergent compositions (cleaners) herein can
contain from about 0.001 % to about 2%, preferably from about 0.01 % to about
0.5%,
more preferably from about 0.02% to about 0.2%, and even more preferably from
about
0.03% to about 0.08%, of C6_10 short chain amphocarboxylate detergent
surfactant. It
has been found that these amphocarboxylate, and, especially glycinate,
detergent
surfactants provide good cleaning with superior filming/streaking for
detergent
compositions that are used to clean both glass and/or relatively hard-to-
remove soils.
Despite the short chain, the detergency is good and the short chains provide
improved
filming/streaking, even as compared to most of the zwitterionic detergent
surfactants
described hereinafter. Depending upon the level of cleaning desired and/or the
amount of
hydrophobic material in the composition that needs to be solubilized, one can
either use
only the amphocarboxylate detergent surfactant, or can combine it with
cosurfactant,
preferably said zwitterionic surfactants.
The "amphocarboxylate" detergent surfactants herein preferably have the
generic
formula:
~(R1)(CH2)nN(R2)(CH2)pC(O)OM
wherein R is a C6_10 hydrophobic moiety, typically a fatty acyl moiety
containing from
about 6 to about 10 carbon atoms which, in combination with the nitrogen atom
forms an
amido group, R 1 is hydrogen (preferably) or a C 1-2 alkyl group, R2 is a C 1-
3 alkyl or,
substituted C 1-3 alkyl, e.g., hydroxy substituted or carboxy methoxy
substituted,
preferably, hydroxy ethyl, each n is an integer from 1 to 3, each p is an
integer from 1 to
2, preferably 1, and each M is a water-soluble cation, typically an alkali
metal,
ammonium, and/or alkanolammonium cation. Such detergent surfactants are
available,
for example: from Witco under the trade name Rewoteric AM-V~, having the
formula
C~H15C(O)NH(CH2)2N(CH2CH20H)CH2C(O)O(-) Na(+)~
Mona Industries, under the trade name Monateric 1000~, having the formula
C~H15C(O)NH(CH2)2N(CH2CH20H)CH2CH2C(O)O(-) Na(+);
. and Lonza under the trade name Amphoterge KJ-2~, having the formula
C7,9H 15,19C(O)NH(CH2)2N(CH2CH20CH2C(O)O(-)Na(+))CH2C(O)O(-)
Na(+)~
(2) Zwitterionic Detergent Surfactant
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WO 97/33963 g PCT/US97I03388
The aqueous, liquid hard surface detergent compositions (cleaners) herein can
contain from about 0.001% to about 2% of suitable zwitterionic detergent
surfactant
containing a cationic group, preferably a quaternary ammonium group, and an
anionic
group, preferably carboxylate, sulfate and/or sulfonate group, more preferably
sulfonate.
A more preferred range of zwitterionic detergent surfactant inclusion is from
about 0.02%
to about 1% of surfactant, a most preferred range is from about 0.05% to about
0.2%.
Zwitterionic detergent surfactants, as mentioned hereinbefore, contain both a
cationic group and an anionic group and are in substantial electrical
neutrality where the
number of anionic charges and cationic charges on the detergent surfactant
molecule are
substantially the same. Zwitterionic detergents, which typically contain both
a quaternary
ammonium group and an anionic group selected from sulfonate and carboxylate
groups
are desirable since they maintain their amphoteric character over most of the
pH range of
interest for cleaning hard surfaces. The sulfonate group is the preferred
anionic group.
Preferred zwitterior~ic detergent surfactants have the generic formula:
R3-[C(O)-N(R4)-(CR52)n 1 ~mN(R6)2(+)-(CR52)p 1-Y(-)
wherein each Y is preferably a carboxylate (COO-) or sulfonate (S03-) group,
more
preferably sulfonate; wherein each R3 is a hydrocarbon, e.g., an alkyl, or
alkylene, group
containing from about 8 to about 20, preferably from about 10 to about 18,
more
preferably from about 12 to about 16 carbon atoms; wherein each (R4) is either
hydrogen,
or a short chain alkyl, or substituted alkyl, containing from one to about
four carbon
atoms, preferably groups selected from the group consisting of methyl, ethyl,
propyl,
hydroxy substituted ethyl or propyl and mixtures thereof, preferably methyl;
wherein each
(RS) is selected from the group consisting of hydrogen and hydroxy groups with
no more
than one hydroxy group in any (CR52)pl group; wherein (R6) is like R4 except
preferably not hydrogen; wherein m is 0 or l; and wherein each nl and pl are
an integer
from 1 to about 4, preferably from 2 to about 3, more preferably about 3. The
R3 groups
can be branched, unsaturated, or both and such structures can provide
filming/streaking
benefits, even when used as part of a mixture with straight chain alkyl R3
groups. The
R4 groups can also be connected to form ring structures such as imidazoline,
pyridine,
etc. Preferred hydrocarbyl amidoalkylene sulfobetaine (HASB) detergent
surfactants
wherein m = l and Y is a sulfonate group provide superior grease soil removal
and/or
filming/streaking and/or "anti-fogging" and/or perfume solubilization
properties. Such
hydrocarbylamidoalkylene sulfobetaines, and, to a lesser extent
hydrocarbylamidoalkylene betaines are excellent for use in hard surface
cleaning
CA 02248790 2003-03-07
O
detergent compositions, especially those formulated for use on both Glass and
hard-to-
remove soils. They are even better w°hen used with monoethanolamine
andlor specific
beta-amino alkanol as disclosed herein.
A more preferred specific detergent surfactant is a C 1 p_ l ,~ fatty
acylamidopropylene(hydroxypropylene)sulfobetaine, e.g., the detergent
surfactant
available from the Witco Company as a 40% active product under the trade name
"REWOTERIC AM CAS Sulfobetaine~."
The level of zwitterionic detergent surfactant, e.g., HASB, in the composition
is
typically from about 0.001 % to about 2.0%, preferably from about 0.02% to
about 1.0%.
The level in the composition is dependent on the eventual level of dilution to
make the
wash solution. It is an advantage of the zwitterionic detergent, e.g., HASB,
that
compositions containing it care be more readily diluted by consumers since it
does not
interact with hardness cations as readily as conventional anionic detergent
surfactants.
Zwitterionic detergents are also extremely effective at very low levels, e.g.,
below about
1%.
Other zwitterionic detergent surfactants are set forth at Col. 4 of U.S. Pat.
No.
4,287,080, Siklosi. Another detailed listing of suitable
zwitterionic detergent surfactants for the detergent compositions herein can
be found in
U.S. Pat. No. 4,557,853, Collies, issued Dec. 10, 1985.
'10 Commercial sources of such surfactants can be found in MeCutcheon's
EMULSIFIERS
AND DETERGENTS, North American ~ Edition, 1984, McCutcheon Division, MC
Publishing Company.
(3) Anionic an,~ do ~~~li~~l"g~~l~.Su~ac ~n
The detergent compositions, preferably aqueous, liquid hard surface detergent
compositions, herein can contain, as the cosurfa~ctant, less preferred, or as
the primary
detergent surfactant, preferably, from about 0.001 % to about 2.0%, preferably
from about
0.01 % to about 1.0% of suitable anionic detergent surfactant. The anionic
surfactants are
suitably water-soluble alkyl or alkylaryl compounds, the alkyl having from
about 6 to
about 20 carbons, and including a sulfate or sulfonate substituent group.
Depending upon
the level of cleaning desired one can use only the anionic detergent
surfactant, or the
anionic detergent surfactant caa be combined with a cosurfactant, preferably
an
amphoteric cosurfactant.
The anionic detergent surfactants herein preferably have the generic formula:
5 R9_(R 10)0_ 1.503 (-)M(+)
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WO 97/33963 t~ PCT/US97103388
wherein R9 is a C6-C2p alkyl chain, preferably a Cg-C 16 alkyl chain; R 10,
when
present, is a C6-C2p alkylene chain, preferably a Cg-C 16 alkylene chain, a
C6H4
phenylene group, or O; and M is the same as before.
The most preferred compositions herein preferably contain from about 0.001 %
to
about 2%, by weight of the composition, more preferably from about 0.01 % to
about 1 %,
most preferably from about 0.02% to about 0.3%, by weight of the composition,
of one or
more chainlengths of a linear alcohol sulfate detergent surfactant having the
general
formula:
R-O-S03M
wherein M is any suitable counterion, preferably sodium, potassium, etc.; and
wherein R
is an alkyl group with a chainlength of from about Cg to about C 1 g and
mixtures thereof,
preferably from about C 12 to about C 1 g and mixtures thereof, more
preferably from
about C 14 to about C 1 g and mixtures thereof, and wherein R is C 14 in more
than about
30%, preferably more than about 35%, more preferably more than about 40%, by
weight
of the alkyl sulfate. The entire alkyl sulfate surfactant can contain R of C
14 and longer
chainlength(s), but more than 30%, by weight of the alkyl surfactant
preferably must be a
C 14 chainlength. Compositions containing only alkyl sulfate surfactants with
higher
chainlengths, i.e., C16-18 Provide good surface lubricity benefits. However,
these chain
lengths, without the required amount of C 14 chainlengths, exhibit poor
filming/streaking
properties. On the other hand, compositions which are solely made up of lower-
chain
alkyl sulfate surfactants, i.e., Cg_12 alkyl sulfate surfactants, provide
acceptable
filming/streaking properties but show poor surface lubricity properties. The
presence of
the C 14 chainlength at levels of more than about 30%, by weight of the alkyl
sulfate
surfactant, in combination with other chainlengths, or alone, provide a
product with both
excellent surface lubricity properties and excellent filming/streaking
properties.
Particularly preferred compositions contain from about 0.05% to about 0.30%,
by weight
of the composition, of a C 12/ 14 blend in which the C 12 to C 14 weight ratio
is from about
1:10 to about 2:1, preferably from about 1:5 to about 1.5:1, and more
preferably from
about 1:3 to about 1:1. This combination has been found to provide sufficient
surface
lubricity while avoiding objectionable filming/streaking. The alcohol sulfate
detergent
raw materials selected are essentially free from unreacted fatty alcohol
wherein the term
"essentially free" is defined as having less than about 2%, by weight of the
composition,
preferably less than about 1.8%, and more preferably less than about 1.5%, by
weight of
the composition of unreacted fatty alcohol in a nominally 30% active raw
material.
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WO 97/33963 11 PCT/US97J03388
A most preferred alkyl sulfate surfactant is a mixture of Stepanol WA-Extra~,
available from the Stepan Company, with extra C14 alkyl sulfate added such
that the
C 1214 ratio is nearly 1:1.
Concentrated compositions can also be used in order to provide a less
expensive
product. When a higher concentration is used, i.e., when the level of alkyl
sulfate
surfactant used is from about 0.10% to about 2.0%, by weight of the
composition, it is
preferable to dilute the composition before using it to clean a hard surface,
especially
glass. Dilution ratios of the alkyl sulfate concentrates) to water can range,
preferably,
from about 1:1 to 1:10, more preferably from about 1:1.5 to 1:5, and most
preferably from
about 1:2 to 1:5.
Some suitable surfactants for use herein in small amounts are one or more of
the
following: sodium linear Cg-C 1 g alkyl benzene sulfonate (LAS), particularly
C 11-C 12
LAS; the sodium salt of a coconut alkyl ether sulfate containing 3 moles of
ethylene
oxide; the adduct of a random secondary alcohol having a range of alkyl chain
lengths of
from 11 to 15 carbon atoms and an average of 2 to 10 ethylene oxide moieties,
several
commercially available examples of which are Tergitol~ 15-S-3, Tergitol~ 15-S-
5,
Tergitol~ 15-S-7, and Tergitol~ 1 S-S-9, all available from Union Carbide
Corporation;
the sodium and potassium salts of coconut fatty acids (coconut soaps); the
condensation
product of a straight-chain primary alcohol containing from about 8 carbons to
about 16
carbon atoms and having an average carbon chain length of from about 10 to
about 12
carbon atoms with from about 4 to about 8 moles of ethylene oxide per mole of
alcohol;
an amide having one of the preferred formulas:
O
R~-C-N(R8)2
wherein R7 is a straight-chain alkyl group containing from about 7 to about 15
carbon
atoms and having an average carbon chain length of from about 9 to about 13
carbon
atoms and wherein each R8 is a hydroxy alkyl group containing from 1 to about
3 carbon
atoms; a zwitterionic surfactant having one of the preferred formulas set
forth hereinafter;
or a phosphine oxide surfactant. Another suitable class of surfactants is the
fluorocarbon
surfactants, examples of which are FC-129~, a potassium fluorinated
alkylcarboxylate
and FC-170-C~, a mixture of fluorinated alkyl polyoxyethylene ethanols, both
available
from 3M Corporation, as well as the Zonyl~ fluorosurfactants, available from
DuPont
Corporation. It is understood that mixtures of various surfactants can be
used.
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WO 97/33963 12 PCT/US97/03388
Nonionic surfactants, e.g., ethoxylated alcohols and/or alkyl phenols, can
also be
used as cosurfactants.
(4) Mixtures
Mixtures of amphocarboxylate, zwitterionic detergent surfactants, and/or
anionic
detergent surfactants as discussed hereinbefore, can be present in the present
invention.
The zwitterionic detergent surfactants can be present at levels from about
0.02% to about
15%. The amphocarboxylate detergent surfactants can be present at levels from
about
0.001% to about 15%. The ratio of zwitterionic detergent surfactant to
amphocarboxylate
detergent surfactant is typically from about 3:1 to about 1:3, preferably from
about 2:1 to
about 1:2, more preferably about 1:1. The ratio of primary detergent
surfactant to
cosurfactant, or cosurfactants, is typically from about 3:1 to about 1:1.
(D) AQUEOUS SOLVENT SYSTEM
The balance of the formula is typically water and non-aqueous polar solvents
with
only minimal cleaning action like methanol, ethanol, isopropanol, ethylene
glycol, glycol
ethers having a hydrogen bonding parameter of greater than 7.7, propylene
glycol, and
mixtures thereof, preferably ethanol. The level of non-aqueous polar solvent
is usually
greater when more concentrated formulas are prepared. Typically, the level of
non-
aqueous polar solvent is from about 0.5% to about 40%, preferably from about
1% to
about 10%, more preferably from about 2% to about 8% (especially for "dilute"
compositions) and the level of water is from about 50% to about 99%,
preferably from
about 75% to about 95%.
(E) OPTIONAL INGREDIENTS
( 1 ) Optional soluble carbonate and/or bicarbonate salts
Water-soluble alkali metal carbonate and/or bicarbonate salts, such as sodium
bicarbonate, potassium bicarbonate, potassium carbonate, cesium carbonate,
sodium
carbonate, and mixtures thereof, are added to the composition of the present
invention in
order to improve the f lming/streaking when the product is wiped dry on the
surface, as is
typically done in glass cleaning. Preferred salts are sodium carbonate,
potassium
carbonate, sodium bicarbonate, potassium bicarbonate, their respective
hydrates, and
mixtures thereof. Solubilized, water-soluble alkali metal carbonate and
bicarbonate salts
are typically present at a level of from about 0% to about 0.5%, preferably
from about
0.005% to about 0.1 %, more preferably from about 0.01 % to about 0.1 %, and
most
preferably from about 0.02% to about 0.05% by weight of the composition. The
pH in
the composition, at least initially, in use is from about 7 to about 11,
preferably from
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WO 97/33963 13 PCT/US97/03388
about 7.5 to about 10.5, more preferably from about 8 to about 10. pH is
typically
measured on the product.
(2) Optional tartaric acid / monoethanolamine salt
Detergent builders that are efficient for hard surface cleaners and have
reduced
filming/streaking characteristics at the critical levels can also be employed
in the present
invention. Addition of the specific detergent builder tartaric acid at
critical levels to the
present composition improves cleaning without the problem of filming/streaking
that
usually occurs when detergent builders are added to hard surface cleaners.
Through the
present invention there is no longer the need to make a compromise between
improved
cleaning and acceptable filming/streaking results which is especially
important for hard
surface cleaners which are also directed at cleaning glass. These compositions
containing
the detergent builder herein at the levels herein, have exceptionally good
cleaning
properties. They also have exceptionally good shine properties, i.e., when
used to clean
glossy surfaces, without rinsing, they have much less tendency than, e.g.,
carbonate built
1 S products to leave a dull finish on the surface and filming/streaking.
The tartaric acid detergent builder is present at levels of from about 0.001 %
to
about 0.1 %. more preferably from about 0.01 % to about 0. I %, and most
preferably from
about 0.01 % to about 0.05%. The salts are preferably compatible and include
ammonium,
sodium, potassium and/or alkanolammonium salts. The alkanolammonium salt is
preferred. The preferred alkanolammonium salt is that formed by the addition
of
monoethanolamine (MEA) at a level of from about 0.005% to about 0.2%,
preferably
from about 0.01 % to about 0. I %, more preferably from about 0.02% to about
0.1 % by
weight of the composition.
(F) OPTIONAL MINOR INGREDIENTS
The compositions herein can also contain other various adjuncts which are
known
to the art for detergent compositions. Preferably they are not used at levels
that cause
unacceptable filming/streaking. Non-limiting examples of such adjuncts are:
Hvdrotropes such as sodium toluene sulfonate, sodium cumene sulfonate and
potassium xylene suIfonate; and
Aesthetic-enhancing ingredients such as colorants and perfumes, providing they
do
not adversely impact on filming/streaking in the cleaning of glass. Most hard
surface
cleaner products contain some perfume to provide an olfactory aesthetic
benefit and to
cover any "chemical" odor that the product may have. The main function of a
small
fraction of the highly volatile, low boiling (having low boiling points),
perfume
components in these perfumes is to improve the fragrance odor of the product
itself,
CA 02248790 2005-10-17
14
rather than impacting on the subsequent odor of the surface being cleaned.
However,
some of the less volatile, high boiling perfume ingredients can provide a
fresh and clean
impression to the surfaces, and it is sometimes desirable that these
ingredients be
deposited and present on the dry surface. The perfumes are preferably those
that are more
water-soluble and/or volatile to minimize streaking and filming. The perfumes
useful
herein are described in more detail in U.S. Patent 5,108,660, Michael, issued
April 28.
1992, at col. 8 lines 48 to 68, and col. 9 lines I to 68, and col. 10 lines 1
to 24, said
patent, and especially said specific portion. '
Antibacterial agents can be present, but preferably only at low levels to
avoid
filming/streaking problems. More hydrophobic antibacterial/germicidal agents,
like
orthobenzyl-para-chlorophenol, are avoided. If present, such materials should
be kept at
levels below about 0.1 %.
Stabilizin."g in redients can be present typically to stabilize more of the
hydrophobic
ingredients, e.g., perfume. The stabilizing ingredients include acetic acid
and propionic
acids, and their salts, e.g., NH4, MEA, Na, K, etc., preferably acetic acid
and the C2-C6
alkane diols, more preferably butane diol. The stabilizing ingredients do not
function in
accordance with any known principle. Nonetheless, the combination of amido
zwitterionic detergent surfactant with linear acyl amphocarboxylate detergent
surfactant,
anionic detergent surfactant, nonionic ~ detergent surfactant, or mixtures
thereof, and
stabilizing ingredient can create a microemulsion. The amount of stabilizing
ingredient is
typically from about 0.01% to about 0.5%, preferably from about 0.02% to about
0.2%.
The ratio of hydrophobic material, e.g., perfume that can be stabilized in the
product is
related to the total surfactant and typically is in an amount that provides a
ratio of
surfactant to hydrophobic material of from about 1:2 to about 2:1.
Other deterggnt builders that are efficient for hard surface cleaners and have
reduced filminglstreaking characteristics at the critical levels can also be
present in the
compositions of the invention.
Suitable additional optional detergent builders include salts of
ethylenediaminetetraacetic acid (hereinafter EDTA), citric acid,
nitrilotriacetic acid
(hereinafter NTA), sodium carboxymethylsuccinic acid, sodium N-(2-
hydroxypropyl)
iminodiacetic acid, and N-diethyleneglycol-N,N-diacetic acid (hereinafter
DIDA). The
salts are preferably compatible and include ammonium, sodium, potassitun
and/or
alkanolammonium salts. The alkanolammonium salt is preferred as described
hereinafter.
A preferred detergent builder is NTA (e.g., sodium), a more preferred builder
is citrate
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WO 97/33963 15 PCT/US97_/03388
(e.g., sodium or monoethanolamine), and a most preferred builder is EDTA
(e.g.,
sodium).
These additional optional detergent builders, when present, are typically at
levels of
from about 0.05% to about 0.5%. more preferably from about 0.05% to about
0.3%, most
preferably from about 0.05% to about 0.15%. The levels of these additional
builders
present in the wash solution used for glass should be less than about 0.2%.
Therefore,
typically, dilution is highly preferred for cleaning glass, while full
strength is preferred
for general purpose cleaning, depending on the concentration of the product.
Typically the best filming/streaking results occurs most when the builder is
combined with amphoteric and/or zwitterionic detergent surfactant compositions
although
an improvement is also seen with the less preferred anionic or
anionic/nonionic detergent
surfactant compositions.
The invention is illustrated by the following nonlimiting Examples.
End Result Wipe Test
Procedure:
Five sprays of the product to be tested are applied to a 2ft. x aft. glass
window
(which can be soiled with body oils from a handprint) and wiped with two paper
towels
to near dryness, simulating actual consumer usage of the product.
Gradine:
Expert judges are employed to evaluate the specific areas of product
application
for amount of filming/streaking, with the aid of a floodlight to simulate a
sunbeam. A
numerical value describing the quality of the end result is assigned to each
product. For
the test results reported here a 0-6 scale is used, in which 0 = good end
result with no
film/streak, and 6 = very poor end result.
EXAMPLE
I
Formula
INGREDIENT _1 _2
Wt.% Wt.%
Butoxypropanol 2.8 2.8
Ethanol 2.8 2.8
Sodium Dodecyl Sulfate 0.13 0.20
-
Sodium Tetradecyl Sulfate0.11 0.08
-
NaHC03 0.02 0
NaC03 0.02 0
PVNO (avg MW ~ I0,000)0.20 0
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WO 97!33963 16 PCT/US97/03388
The above formulas were tested according to the above methods for end result
wipe, with the results as follows (average of 7 different wiping habits):
Wining Film/Streak Test
(avg. of 7 different wiping habits)
Formula Rating
(0 = good, 6 = poor)
1 1.15
2 I .39
These results show that the inclusion of the polymer does not harm
film/streak. In fact, it
is directionally better than the comparison formula.
Sheeting Test
The following test is used to determine the lasting effects of preventing
water
spots upon rewetting.
The windows, or mirrors, from the Filming/Streaking Test are rewetted by
spraying with water containing about 0.02% household dust to simulate rain and
dried, .
and this cycle is repeated twice more for a total of three cycles. The
windows, or mirrors,
are graded while wet using a scale in which 0 = No Sheeting and 6 = Heavy
Sheeting.
The sheeting is indicative of the hydrophilicity and the resulting lack of
spotting/filming
when dry.
Formula No. Average Sheeting Grade
cycle 1 circle 2 cycle 3
1 6.0 6.0 5.3
2 3.7 0.5 0.0
Blank Glass 0.5 0.0 0.0
The above demonstrates the benefit of the polymer, when used at this level, in
providing the sheeting (anti-spotting/filming) benefit upon rewetting.
The formulas are tested as in the above test for sheeting, but the samples are
dried
and graded for "rainspots" using the grading scale of the Filming/Streaking
Test. -
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WO 97/33963 1 ~ PCT/US97/03388
Formula No. Averaee pot" (0 ood 6 = poor)
"RainsGrade =
g
cycle c_, cycle
1 c~ 3
1 0.0 0.0 0.1
2 1.0 3.1 4.2
Blank Glass 2.8 4.1 5.2
These results show the benefit of ping
the polymer in hel prevent
spots
on
windows
even
after 3 simulated rainstorms.
EXAMPLE
II
Formula
Component 3 4 5 6 7
Isopropanol 2.00 4.00 2.00
Ethanol 2.00 5.00
Butoxypropanol 3.00 1.50 2.50 1.004.00
C,2 Alkyl Sulfate 0.20
C,4 Alkyl Sulfate 0.08 0.10
Cocoamidopropylbetaine 0.20 0.10
Linear Alkyl (Cg-C~8) Benzene 0.10
Sulfonate
Sodium Laureth Sulfate 0.25
Alcohol Ethoxylate 0.04
(Neodol~ 91-6)
Sodium Bicarbonate 0.02 0.060.04
Monoethanolamine 0.1
Tartaric Acid 0.03
PVNO (avg MW ~ 10,000) 0.10 0.15 0.25 0.300.20
