Note: Descriptions are shown in the official language in which they were submitted.
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= = TITLE OF THE INVENTION
LIGHT DUTY LIQUID CLEANING COMPOSITIONS AND METHODS OF
MANUFACTURE AND USE THEREOF
100011 Intentionally left blank.
BACKGROUND OF THE INVENTION
[0002) Light duty liquid cleaning compositions should be designed
with acceptable
foaming and cleaning properties. Such cleaning compositions should maintain
acceptable
cleaning performance, have ease of rinsing, and contain a low level of dye mix
that yields a.
near colorless visual appearance. Light duty liquid cleaning compositions
should include an
ingredient mix that increases utilization of naturally derived ingredients,
results in a cleaned
surface with minimal spotting and is both mild and hypoallergenic. Light duty
liquid
cleaning compositions should also be designed to be biodegrade-able and not to
leave any
harmful residue on surfaces.
100031 Accordingly, the inventors of the invention have developed
light duty liquid
cleaning compositions, which are suitable for disinfecting all types of
surfaces including
animate surfaces (e.g., human skin and/or mouth When used as an oral
preparation or
toothpaste) and inanimate surfaces. This technology is suitable for use on
delicate surfaces
including those surfaces in contact with food in a safe manner, Moreover, the
light duty
liquid cleaning compositions according to the invention reduce the amount of
chemical
residues left on a surface disinfected therewith. Thus, it may be not
necessary to rinse, for
example, a surface after the compositions of the invention have been applied
thereto in
diluted conditions. The inventors have developed compositions and methods that
include
cleaning compositions with enhanced cleaning possessing antibacterial efficacy
and low
toxicity.
BRIEF SUMMARY OF THE INVENTION
[0004] The invention encompasses acidic liquid cleaning compositions
designed for
cleaning surfaces including hard surfaces, which deliver acceptable cleaning
and foaming
performance and exhibit ease of rinsing while leaving low amounts residue.
[0005] The inventors have suiprisingly found that cleaning
compositions including a
combination of one or more of anionic surfactants, a zwitterionic surfactant
and an acid in
specific amounts have antibacterial activity while at the same time having low
toxicity. In
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certain embodiments, the cleaning composition is a colorless liquid.
[00061 In one embodiment the invention encompasses cleaning compositions
including
an. acidic formulation that exhibits ease of rinsing, which assists with the
removal of residue
while exhibiting antibacterial efficacy.
100071 In other embodiments, the invention encompasses cleaning
compositions
including a surfactant based cleaning composition comprising at least one
anionic surfactant,
at least one zwitterionic surfactant, and at least one organic acid, wherein
the composition has
a logio reduction in microbes of at least about 3 when a surface containing
bacteria is
contacted with the composition for about 30 seconds at 25 wherein the
composition is
stable for at least about 1 year at room temperature, and wherein the
composition has a low
toxicity. An exemplary cleaning composition contains up to about 10 wt. % of
an alkyl
benzene sulfonate, between about 5 wt/. % and about 30 wt. % of an alkyl ether
sulfate,
between about 3 wt. % and about 10 wt. A) of a betaine, and between about 1
wt. % and about
3 wt. % of lactic acid, based on the total weight of the composition.
[00081 In certain embodiments, the invention encompasses a cleaning
composition
including a first anionic surfactant wherein the first anionic surfactant is
present in an amount
of about 3 wt. % to about 10 wt. % by weight of the total composition, a
second anionic
surfactant, wherein the second anionic surfactant is present in an amount of
about 2 wt. % to
about 30 wt. % by weight of the total composition, at least one zwitterionic
surfactant,
wherein the zwitterionic surfactant is present in an amount of about 1 wt. %
to about 8 wt. %
by weight of the total composition, and lactic acid, wherein the lactic acid
is present in an
amount of about 1 wt. % to about 2.5 wt. % by weight of the total composition.
[00091 in certain embodiments, the invention encompasses compositions
including a first
anionic surfactant wherein the first anionic surfactant is present in an
amount of about 5 wt.
% to about 10 wt. % by weight of the total composition, a second anionic
surfactant, wherein
the second anionic surfactant is present in an amount of about 5 wt. % to
about 28 wt. % by
weight of the total composition, at least one zwitterionic surfactant, wherein
the zwitterionic
surfactant is present in an amount of about 2 wt. % to about 8 wt. % by weight
of the total
composition., and at least one acid, wherein the acid is present in an am.ount
of about 1 wt. %
to about 3 wt. % by weight of the total composition.
[00101 in certain embodiments, the invention encompasses compositions
including a first
anionic surfactant wherein the first anionic surfactant is present in an
amount of about 5 wt.
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% to about 9 wt. % by weight of the total composition, a second anionic
surfactant, wherein
the second anionic surfactant is present in an amount of about 9 wt. % to
about 20 wt. % by
weight of the total composition, at least one zwitterionic surfactant, wherein
the zwitterionic
surfactant is present in an amount of about I wt. % to about 7 wt. % by weight
of the total
composition, and at least one acid, wherein the acid is present in an amount
of about 2 wt. %
by weight of the total composition.
[00111 In certain embodiments, the invention encompasses compositions
including a first
anionic surfactant wherein the first anionic surfactant is present in an
amount of about 2 wt.
% to about 5 wt. % by weight of the total composition, a second anionic
surfactant, wherein
the second anionic surfactant is present in an amount of about 5 wt. % to
about 8 wt. % by
weight of the total composition, at least one zwitterionic surfactant, wherein
the zwitterionic
surfactant is present in an amount of about 1 wt. (N) to about 3 wt. % by
weight of the total
composition, and at least one acid, wherein the acid is present in an amount
of about 2 wt. %
by weight of the total composition.
[00121 In certain embodiments, the invention encompasses an acidic liquid
cleaning
composition designed for cleaning hard surfaces as well as glass surfaces and
effective in
removing grease soil and/or other soil.
[00131 In other embodiments, the invention encompasses cleaning
compositions
including a first anionic surfactant wherein the first anionic surfactant is
present in an amount
of about 4 wt. % by weight of the total composition, a second anionic
surfactant, wherein the
second anionic surfactant is present in an amount of about 12 wt. % by weight
of the total
composition, at least one zwitterionic surfactant, wherein the zwitterionic
surfactant is
present in an amount of about 3.5 wt. % by weight of the total composition,
and at least one
acid, wherein the acid is present in an amount of about 2 to about 2.5 wt. %
by weight of the
total composition.
[00141 In other embodiments, the invention encompasses cleaning
compositions
including a first anionic surfactant wherein the first anionic surfactant is
present in an amount
of about 6 wt. % by weight of the total composition, a second anionic
surfactant, wherein the
second anionic surfactant is present in an amount of about 20 wt. % by weight
of the total
composition, at least one zwitterionic surfactant, wherein the zwitterionic
surfactant is
present in an amount of about 7 wt. % by weight of the total composition, and
at least one
acid, wherein the acid is present in an amount of about 2 wt. % by weight of
the total
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composition.
[00151 in other embodiments, the invention encompasses cleaning
compositions
including a first anionic surfactant wherein the first anionic surfactant is
present in an amount
of about 8.5 wt. % by weight of the total composition, a second anionic
surfactant, wherein
the second anionic surfactant is present in an amount of about 18 wt. A) by
weight of the total
composition, at least one zwitterionic surfactant, wherein the zwitterionic
surfactant is
present in an amount of about 5.5 wt. % by weight of the total composition,
and at least one
acid, wherein the acid is present in an amount of about 2 wt. % by weight of
the total
composition.
[00161 in another embodiment, the invention encompasses cleaning
compositions
including a first anionic surfactant wherein the first anionic surfactant is
present in an amount
of about 5.7 wt. % by weight of the total composition, a second anionic
surfactant, wherein
the second anionic surfactant is present in an amount of about 19.5 wt. % by
weight of the
total composition, at least one zwitterionic surfactant, wherein the
zwitterionic surfactant is
present in an amount of about 6.5 wt. A) by weight of the total composition,
and at least one
acid, wherein the acid is present in an amount of about 2 wt. % by weight of
the total
composition.
[00171 Another embodiment of the invention encompasses cleaning
compositions
including dodecyl benzene sulfonate is present in an amount of about 5 wt. %
to about 10 wt.
% by weight of the total composition, lauryl ether sulfate with about two EO
units is present
in an amount of about 5 wt. % to about 20 wt. % by weight of the total
composition, a
betaine, wherein the zwitterionic surfactant is present in an amount of about
3 wt. % to about
8 wt. % by weight of the total composition, and lactic acid, wherein the acid
is present in an
amount of about I wt. % to about 3 wt. % by weight of the total composition.
[00181 Another embodiment of the invention encompasses cleaning
compositions
including a sodium salt of dodecyl benzene sulfonate, which is present in an
amount of up to
about 10 wt. %, preferably up to about 7 wt. %, by weight of the total
composition; a sodium
salt of lauryl ether sulfate with about two EO units, which is present in an
amount of about 5
wt. % to about 30 wt. % by weight of the total composition; a betaine, which
is present in an
amount of about 3 wt. % to about 8 wt. % by weight of the total composition;
and lactic acid,
which is present in an amount of about 1 wt. % to about 3 wt. % by weight of
the total
composition.
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[00191 Another embodiment of the invention encompasses cleaning
compositions
including an alkyl ether sulfate, which is present in an amount of about 5 wt.
% to about 40
wt. % by weight of the total composition, and a zwitterionic surfactant, which
is present in an
amount of about I wt. % to about 8 wt. % by weight of the total composition;
and lactic acid,
which is present in an amount of about 1 wt. % to about 3 wt. % by weight of
the total
composition.
[00201 Another embodiment of the invention encompasses cleaning
compositions
including a sodium salt of an alkyl ether sulfate, which is present in an
amount of about 5 wt.
% to about 40 wt. 'Yo by weight of the total composition, and a betaine, which
is present in an
amount of about I wt. % to about 8 wt. % by weight of the total composition;
and lactic acid,
which is present in an amount of about 1 wt. % to about 3 wt. % by weight of
the total
composition.
100211 Another embodiment of the invention encompasses a method of making a
liquid
cleaning composition designed for cleaning surfaces including hard surfaces
and effective in
removing soil, which includes combining a first anionic surfactant wherein the
first anionic
surfactant is present in an amount of about 5 wt. % to about 10 wt. % by
weight of the total
composition, a second anionic surfactant, wherein the second anionic
surfactant is present in
an amount of about 5 wt. % to about 15 wt. % by weight of the total
composition, at least one
zwitterionie surfactant, wherein the zwitterionic surfactant is present in an
amount of about 3
wt. % to about 8 wt. % by weight of the total composition, and at least one
acid, wherein the
acid is present in an amount of about 1 wt. % to about 3 wt. % by weight of
the total
composition.
[00221 Another embodiment of the invention encompasses a method of removing
soil and
killing bacteria, which includes contacting the surface with a composition
including a first
anionic surfactant wherein the first anionic surfactant is present in an
amount of about 3 wt.
% to about 10 wt. % by weight of the total composition, a second anionic
surfactant, wherein
the second anionic surfactant is present in an amount of about 5 wt. % to
about 18 wt. % by
weight of the total composition, at least one zwitterionic surfactant, wherein
the zwitterionic
surfactant is present in an amount of about 2 wt. % to about 8 wt. % by weight
of the total
composition, and at least one acid, wherein the acid is present in an amount
of about 1 wt. %
to about 3 wt. % by weight of the total composition.
[00231 To achieve the foregoing and other embodiments and in accordance
with the
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purpose of the invention, as embodied and broadly described herein the light
duty liquid
detergent of this invention includes at least one anionic surfactant, at least
one zwitterionic
surfactant, and at least one acidic component, which has both good
disinfecting properties on
hard surfaces and good food soil and/or other soil removal and leaves surfaces
with a shiny
appearance.
[0024] As a particularly desirable embodiment, the cleaning composition
does not
contain ingredients that are not biologically or ecologically favorable. A
preferred cleaning
composition of the invention can be characterized as containing no or no
significant amount
of extraneous preservatives and antimicrobial compounds, other than the acidic
component.
The term "no significant amount" as used herein indicates a content
concentration that is less
than an efficacious amount to achieve the intended purpose. Preferably, the
cleaning
composition contains less than 1 wt. %, preferably 0.5 wt. %, of a magnesium
or ammonium
salt of an anionic surfactant, based on the total weight of the composition.
Particularly
preferred cleaning composition can be characterized as containing only
ecologically
acceptable solvents such as water and one or more of alkanols, e.g., ethanol,
isopropanol and
propanol. The cleaning composition is not an emulsion or microemulsion
composition. A
preferred cleaning composition can also be characterized as colorless or
nearly colorless. A
colorless or nearly colorless composition is highly desirable since the
composition can be
easily rendered to have any desirable color by adding colorants or dyes to the
colorless or
nearly colorless composition.
[0024a] Specific aspects of the invention include:
an acidic surfactant based cleaning composition comprising lactic acid in an
amount of 1 wt. % to 3 wt. % by weight of the total composition, and a
surfactant
combination, wherein the surfactant combination consists of dodecyl benzene
sulfonate in an
amount of 3 wt. % to 10 wt. % by weight of the total composition, lauryl ether
sulfate with
two EO units in an amount of 3 wt. % to 20 wt. % by weight of the total
composition, and
laurylamidopropyl betaine in an amount of 1 wt. % to 8 wt. % by weight of the
total
composition, wherein the composition exhibits at least one of the following:
(i) an acute oral
toxicity of >5000 mg/kg; (ii) an acute dennal toxicity of >5000 mg/kg; (iii)
an acute eye
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irritation of slight corneal opacity and reversible eye irritation within 7
days; and/or (iv) an
acute dermal irritation of moderate irritation at 72 hours that is reversible;
wherein the
composition is dermal non-sensitizer, and wherein the composition is
substantially free of
hydrogen peroxide, with the proviso that if the composition comprises a
magnesium salt of an
anionic surfactant, the magnesium salt of the anionic surfactant is present in
an amount of less
than lwt. % based on the total weight of the composition;
an acidic surfactant based cleaning composition comprising a surfactant
combination and 1 wt. A to 3 wt. % by weight of at least one organic acid,
wherein the
surfactant combination consists of: (i) sodium dodecyl benzene sulfonate,
which is present in
an amount of about 3 wt. % to about 12.7 wt. % by weight of the total
composition; (ii)
sodium lauryl ether sulfate with two E0 units, which is present in an amount
of about 3 wt. %
to about 20 wt. % by weight of the total composition; and (iii)
laurylamidopropyl betaine,
which is present in an amount of about 1 wt. % to about 8 wt. % by weight of
the total
composition; wherein the composition exhibits at least one of the following:
(i) an acute oral
toxicity of >5000 mg/kg; (ii) an acute dermal toxicity of >5000 mg/kg; (iii)
an acute eye
irritation of slight corneal opacity and reversible eye irritation within 7
days; and/or (iv) an
acute dermal irritation of moderate irritation at 72 hours that is reversible;
wherein the
composition is dermal non-sensitizer, and wherein the composition is
substantially free of
hydrogen peroxide, with the proviso that if the composition comprises a
magnesium salt of an
anionic surfactant, the magnesium salt of the anionic surfactant is present in
an amount of less
than lwt. % based on the total weight of the composition;
an acidic surfactant based cleaning composition comprising a surfactant
combination, and 1 wt. % to 3 wt. % by weight of at least one organic acid,
wherein the
surfactant combination consists of: (i) sodium dodecyl benzene sulfonate,
which is present in
an amount of about 2 wt. % to about 9 wt. % by weight of the total
composition; (ii) sodium
lauryl ether sulfate with two EO units, which is present in an amount of about
3 wt. % to
about 20 wt. % by weight of the total composition; and (iii) laurylamidopropyl
betaine, which
is present in an amount of about 1 wt. % to about 8 wt. % by weight of the
total composition;
wherein the composition exhibits at least one of the following: (i) an acute
oral toxicity of
>5000 mg/kg; (ii) an acute dermal toxicity of >5000 mg/kg; (iii) an acute eye
irritation of
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slight corneal opacity and reversible eye irritation within 7 days; and/or
(iv) an acute dermal
irritation of moderate irritation at 72 hours that is reversible; and wherein
the composition is
dermal non-sensitizer, and wherein the composition is substantially free of
hydrogen peroxide,
with the proviso that if the composition comprises a magnesium salt of an
anionic surfactant,
the magnesium salt of the anionic surfactant is present in an amount of less
than 1 wt. % based
on the total weight of the composition;
an acidic surfactant based cleaning composition comprising a surfactant
combination, and 1 wt. % to 3 wt. % by weight of at least one organic acid,
wherein the
surfactant combination consists of: (i) sodium dodecyl benzene sulfonate,
which is present in
an amount of about 3 wt. % to about 12.7 wt. % by weight of the total
composition; (ii)
sodium lauryl ether sulfate with two EO units, which is present in an amount
of about 5 wt. %
to about 30 wt. % by weight of the total composition; and (iii)
laurylamidopropyl betaine,
which is present in an amount of about 1 wt. % to about 8 wt. % by weight of
the total
composition; wherein the composition exhibits at least one of the following:
(i) an acute oral
toxicity of >5000 mg/kg; (ii) an acute dermal toxicity of >5000 mg/kg; (iii)
an acute eye
irritation of slight corneal opacity and reversible eye irritation within 7
days; and/or (iv) an
acute dermal irritation of moderate irritation at 72 hours that is reversible;
and wherein the
composition is dermal non-sensitizer, and wherein the composition is
substantially free of
hydrogen peroxide, with the proviso that if the composition comprises a
magnesium salt of an
anionic surfactant, the magnesium salt of the anionic surfactant is present in
an amount of less
than 1 wt. '9/0 based on the total weight of the composition;
an acidic surfactant based cleaning composition comprising a surfactant
combination, and 1 wt. % to 3 wt. % by weight of at least one organic acid,
wherein the
surfactant combination consists of: (i) sodium dodecyl benzene sulfonate,
which is present in
an amount of about 2 wt. % to about 9 wt. % by weight of the total
composition; (ii) sodium
lauryl ether sulfate with two EO units, which is present in an amount of about
5 wt. % to
about 30 wt. % by weight of the total composition; and (iii) laurylamidopropyl
betaine, which
is present in an amount of about 1 wt. % to about 8 wt. % by weight of the
total composition;
wherein the composition exhibits at least one of the following: (i) an acute
oral toxicity of
>5000 mg/kg; (ii) an acute dermal toxicity of >5000 mg/kg; (iii) an acute eye
irritation of
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slight corneal opacity and reversible eye irritation within 7 days; and/or
(iv) an acute dermal
irritation of moderate irritation at 72 hours that is reversible; and wherein
the composition is
dermal non-sensitizer, and wherein the composition is substantially free of
hydrogen peroxide,
with the proviso that if the composition comprises a magnesium salt of an
anionic surfactant,
the magnesium salt of the anionic surfactant is present in an amount of less
than lwt.% based
on the total weight of the composition;
an acidic surfactant based cleaning composition, comprising lactic acid
present
in an amount of 1 wt. % to 3 wt. % by weight of the total composition and a
surfactant
combination, wherein the surfactant combination consists of: (i) dodecyl
benzene sulfonate
present in an amount of 3 wt. % to 12.7 wt. % by weight of the total
composition; (ii) lauryl
ether sulfate with two E0 units present in an amount of 3 wt. % to 20 wt. % by
weight of the
total composition; and (iii) laurylamidopropyl betaine present in an amount of
1 wt. %
to 8 wt. % by weight of the total composition, wherein the composition is
substantially free of
hydrogen peroxide, with the proviso that if the composition comprises a
magnesium salt of an
anionic surfactant, the magnesium salt of the anionic surfactant is present in
an amount of less
than 1 wt. % based on the total weight of the composition; and
a method of cleaning a surface comprising contacting the surface with a
composition as described herein.
[0025] The compositions have utility in a broad range of applications
including, for
example, in consumer product fluids such as surface cleaners, cleansers and
the like. The
compositions are highly suitable for cleaning surfaces that are designed for
food-contact uses,
such as dishes, silverware, glasses and cups.
DETAILED DESCRIPTION OF THE INVENTION
[0026] As used throughout, ranges are used as a shorthand for describing
each and
every value that is within the range. Any value within the range can be
selected as the
terminus of the range. In the event of a conflict in a definition in the
present disclosure and
that of a cited reference, the present disclosure controls.
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[0027] The cleaning compositions of the invention are useful as ultra and
regular
density dish liquid formulas designed for several key formula characteristics
including, but
not
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limited to, antibacterial efficacy from a naturally-derived organic acid, at
minimum about a 3-
log reduction in about 30 seconds for both Gram-positive (e.g., Staphylococcus
aureus) and
Gram-negative (e.g., Salmonella enterica, E. coil) on surfaces, minimal
toxicity of inert (non-
antibacterial) cleaning materials in the formulation, minimize corrosivity to
processing
equipment, competitive or superior foaming/cleaning performance with existing
commercial
cleaning products, competitive or superior rinsing and/or shine performance
with existing
products, and delivery of both active and aesthetic product stability
performance over product
lifetime.
[0028i Accordingly, the invention encompasses cleaning compositions
including a
surfactant based cleaning composition comprising at least one anionic
surfactant, at least one
zwitterionic surfactant, and at least one organic acid, wherein the
composition has a logio
reduction in bacteria of at least about 3 when a surface containing bacteria
is contacted with
the composition for about 30 seconds at 25 C, wherein the composition is
stable for at least
about 1 year at room temperature, and wherein the composition has a low
toxicity.
According to the invention, a preferred cleaning composition of the invention
can be
characterized as containing no or no significant amount of extraneous
preservatives and
antimicrobial compounds, other than the organic acid. Extraneous preservative
and
antimicrobial compounds that are typically included in a cleaning composition
include
hydrogen peroxide, biguanide, triclosan, chlorophenol, paraben, zinc
compounds,
glutaraldehyde, and formaldehyde. The preferred cleaning composition provides
efficacious
antimicrobial properties without the use of extraneous preservative and
antimicrobial
compounds.
[00291 In certain embodiments, the organic acid is lactic acid.
[00301 In certain embodiments, at least one anionic surfactant is present
in an amount of
about 3 wt. % to about 30 wt. % by weight of the total composition.
[00311 In certain embodiments, at least one zwitterionic surfactant,
wherein the
zwitterionic surfactant is present in an amount of about 1 wt. % to about 8
wt. % by weight of
the total composition.
100321 In certain embodiments, at least one organic acid is present in an
amount of about
I wt. % to about 3 wt. % by weight of the total composition.
[00331 In certain embodiments, the anionic surfactant is a C10-C14. linear
alkyl sulfonate.
[00341 In certain embodiments, the anionic surfactant is sodium lauryl
ether sulfate with
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about two ethylene oxide units.
[00351 In certain embodiments, the zwitterionic surfactant is
laurylamidopropyl betaine.
[00361 In certain embodiments, the anionic surfactants and/or the
zwitterionic surfactants
are derived from a natural source and biodegradable surfactants.
100371 In other embodiments, the invention encompasses a cleaning
composition
comprising a first anionic surfactant wherein the first anionic surfactant is
present in an
amount of about 6 wt. % by weight of the total composition, a second anionic
surfactant,
wherein the second anionic surfactant is present in an amount of about 20 wt.
% by weight of
the total composition, at least one zwitterionic surfactant, wherein the
zwitterionic surfactant
is present in an amount of about 7 wt. % by weight of the total composition,
and lactic acid,
wherein the lactic acid is present in an amount of about 2 wt. % by weight of
the total
composition.
[00381 In other embodiments, the invention encompasses a cleaning
composition
comprising a first anionic surfactant wherein the first anionic surfactant is
present in an
amount of up to about 10 wt. %, preferably up to about 7 wt. %, by weight of
the total
composition, a second anionic surfactant, wherein the second anionic
surfactant is present in
an amount between about 12 wt. % and about 30 wt.% by weight of the total
composition, at
least one zwitterionic surfactant, wherein the zwitterionic surfactant is
present in an amount
between. about 3 wt. % and about 7 wt. % by weight of the total composition,
and lactic acid,
wherein the lactic acid is present in an amount of about 2 wt. % by weight of
the total
composition. For example, a suitable cleaning composition may contain about 6
wt. % of
sodium dodecyl benzene sulfonate, about 20 wt. % of sodium pareth sulfate,
about 7 wt. % of
laurylamidopropyl betaine, and about 2 wt. % of lactic acid, based on the
total weight of the
composition.
[00391 In other embodiments, the invention encompasses a cleaning
composition
comprising a first anionic surfactant wherein the first anionic surfactant is
present in an
amount of about 8 wt. % by weight of the total composition, a second
anionic
surfactant, wherein the second anionic surfactant is present in an amount of
about 18 wt. %
by weight of the total composition, at least one zwitterionic surfactant,
wherein the
zwitterionic surfactant is present in an amount of about 5.5 wt. % by weight
of the total
composition, and lactic acid, wherein the lactic acid is present in an amount
of about 2 wt. %
by weight of the total composition.
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[00401 In other embodiments, the invention encompasses a cleaning
composition
comprising dodecyl benzene sulfonate is present in an amount of about 3 wt. %
to about 10
wt. % by weight of the total composition, lauryl ether sulfate with about two
EU units is
present in an amount of about 3 wt. % to about 20 wt. % by weight of the total
composition,
laurylamidopropyl betaine, preferably a sodium salt, wherein the zwitterionic
surfactant is
present in an amount of about I wt. % to about 8 wt. 1/0 by weight of the
total composition,
and lactic acid, wherein the acid is present in an amount of about 1 wt. % to
about 3 wt. % by
weight of the total composition.
[00411 In a preferred embodiment, the invention encompasses a cleaning
composition
comprising a sodium salt of dodecyl benzene sulfonate is present in an amount
of about 3 wt.
% to about 10 wt. /.9 by weight of the total composition, a sodium salt of
lauryl ether sulfate
with about two EO units is present in an amount of about 3 wt. % to about 20
wt. % by
weight of the total composition, laurylamidopropyl Maine, wherein the
zwitterionic
surfactant is present in an amount of about 1 wt. % to about 8 wt. % by weight
of the total
composition, and lactic acid, wherein the acid is present in an amount of
about 1 wt. % to
about 3 wt. % by weight of the total composition.
[00421 In other embodiments, the invention encompasses a cleaning
composition
including an anionic surfactant, which is present in an amount of about 5 wt.
% to about 40
wt. % by weight of the total composition, and a zwitterionic surfactant, which
is present in an
amount of about 1 wt. % to about 8 wt. % by weight of the total composition,
and lactic acid,
which is present in an amount of about 1 wt. % to about 3 wt. % by weight of
the total
composition.
[00431 in a preferred embodiment, the invention encompasses cleaning
compositions
including a sodium salt of an alkyl ether sulfate, which is present in an
amount of about 5 wt.
% to about 40 wt. % by weight of the total composition, and a betaine, which
is present in an
amount of about 1 wt. % to about 8 wt. % by weight of the total composition,
and lactic acid,
which is present in an amount of about 1 wt. % to about 3 wt. % by weight of
the total
composition.
[00441 The invention also encompasses methods of cleaning a surface
including
contacting the surface with a composition of the invention, diluted or
undiluted. The cleaning
compositions possess antibacterial efficacy from an acid, for example lactic
acid. In certain
embodiments, the acid is a naturally-derived, weak-organic acid manufactured
from
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renewable plant resources via microbial fermentation. In other embodiments,
the acid is
natural and readily biodegradable, non-toxic to the environment, and a natural
product. In
other embodiments, the surfactant is natural and readily biodegradable, non-
toxic to the
environment, and a natural product.
100451 As used herein the phrase "from a natural source" refers to
surfactants that have a
natural origin and are derived from, for example, crops, animal fats and/or
trees. These are
also referred to in the art as oleochemical surfactants and are derived from
sources including
but not limited to plant oils such as palm, palm kernel or coconut oil, or
from animal fats such
as tallow, lard or fish oil. This is in contrast to petroleum or petrochemical
surfactants
derived from, for example, crude oil.
[00461 As used herein, the term "biodegradable surfactants" refers to
surfactant-based
cleaning ingredients that are designed to be used with water and disposed of
down the drain.
There they combine with other wastes for treatment in either a municipal
treatment plant or a
household septic tank system. During treatment, microorganisms biodegrade
surfactants and
other organic materials, ultimately breaking them down into carbon dioxide,
water and
minerals. Any small amounts of surfactants that remain after treatment
continue to
biodegrade in the environment. In certain embodiments, the surfactants of the
invention
biodegrade quickly and thoroughly and do not present a risk to organisms
living in the
environment.
100471 The cleaning compositions of the invention, diluted or undiluted,
result in a
minimum 3-log reduction in about 30 seconds or about one minute of both Gram-
positive
(e.g., Staphylococcus aureus) and Gram-negative (e.g., Salmonella enterica,
E.coli) bacteria,
or run-off solutions. Without being limited by theory, the inventors believe
that the cleaning
compositions of the invention, which include an acid result in the acid
crossing the bacterial
cell membrane in its protonated or charge-neutral form. Lactic acid with a pKa
of about 3.8
(the point at which half of the molecules are protonated and half are not
protonated) is
effective at a pH below 3.5. In certain embodiments, the recommended pH for
the cleaning
compositions of the invention for maximal efficacy balanced against safety is
about 3.25.
Without being limited by theory, the mechanism of action for lactic acid is
thought to be two-
fold: (1) as protonated molecules cross the bacterial membrane they become
deprotonated at
the internal pH of the cell and progressively lower the internal bacterial
cell pH that can lead
to protein deformation and halt critical cellular processes, but (2) this
change in internal pH
can act to collapse the delta psi gradients critical to microbial nutrient and
energy transport
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systems in the bacterial cell membrane -- also leading to a cut-off of
critical nutrients and
energy sources.
Anionic Surfactants
[00481 In certain embodiments, the compositions of the invention include
one or more
anionic surfactants. The anionic surfactants, which may be used in the
compositions of the
invention include water soluble anionic sulfonate surfactants and include
sodium salts of
linear C8-C16 alkyl benzene sulfonates; C10-C20 paraffin sulfonates, alpha
olefin sulfonates
containing about 10 to about 24 carbon atoms and C8-C18 alkyl sulfates and
mixtures thereof.
10049) The anionic surfactant may be any of the anionic surfactants known
or previously
used in the art of aqueous surfactant compositions. Suitable anionic
surfactants include, but
are not limited to, alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates,
alkyl succinates,
alkyl sulfosuccinates, N-allcoyl sarcosinates, alkyl phosphates, alkyl ether
phosphates, alkyl
ether carboxylates, alkylamino acids, alkyl peptides, alkoyl taumtes,
carboxylic acids, acyl
and alkyl glutamates, alkyl isethionates, and alpha-olefin sulfonates,
especially their sodium,
potassium, magnesium, ammonium and mono-, di- and triethanolamine salts.
Preferred are
sodium salts of the surfactants. The alkyl groups generally contain about 8 to
about 18
carbon atoms and may be unsaturated.
100501 In certain embodiments, suitable anionic surfactants include sodium
lauryl ether
sulfate, ammonium lauryl ether sulfate, sodium lauryl sulfate, ammonium lauryl
sulfate,
triethanolamine lauryl sulfate, disodium laureth sulfosuccinate, sodium cocoyl
isethionate,
sodium C12-Cgolefin sulfonate, sodium laureth-6 carboxylate, sodium C12-C15
pareth sulfate,
sodium methyl cocoyl taurate, sodium dodecylbenzene sulfonate, sodium cocoyl
sarcosinate,
triethanolamine monolauryl phosphate, and fatty acid soaps. Preferred are
sodium lauryl
ether sulfate, sodium lauryl sulfate, disodium laureth sulfosuccinate, sodium
cocoyl
isethionate, sodium C12-Cgo1efin sulfonate, sodium laureth-6 carboxylate,
sodium C12-C15
pareth sulfate, sodium methyl cocoyl taiffate. sodium dodecylbenzene
sulfonate, and sodium
cocoyl sarcosinate.
100511 In certain illustrative embodiments, examples of suitable sulfonated
anionic
surfactants include, but are not limited to, alkyl mononuclear aromatic
sulfonates, such as the
higher alkylbenzene sulfonates containing in one embodiment 8 to 18 carbon
atoms, in
another embodiment 11 to 16 carbon atoms, and in another embodiment 14 or 15
carbon
atoms, the higher alkyl group in a straight or branched chain, or C8-15 alkyl
toluene
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sulfonates and C8-C15 alkyl phenol sulfonates. In another embodiment, the
alkylbenzene
sulfonate is a linear alkylbenzene sulfonate having a higher content of 3-
phenyl (or higher)
isomers and a correspondingly lower content (well below 50%) of 2-phenyl (or
lower)
isomers, such as those sulfonates wherein the benzene ring is attached mostly
at the 3 or
higher (for example 4, 5, 6 or 7) position of the alkyl group and the content
of the isomers in
which the benzene ring is attached in the 2 or 1 position is correspondingly
low. Illustrative
materials are described in U.S. Pat. 3,320,174. Of these, preferred are sodium
salts of the
anionic surfactants.
[0052J In another embodiment, examples of suitable sulfonated anionic
surfactants
include, but are not limited to, those surface-active or detergent compounds,
which contain an
organic hydrophobic group containing generally about 8 to about 26 carbon
atoms or 10 to 18
carbon atoms in their molecular structure and at least one water-solubilizing
group including,
but not limited to, sulfonate, sulfate and carboxylate so as to form a water-
soluble detergent.
Usually, the hydrophobic group will include a C8-C22 alkyl, alkyl or acyl
group. Such
surfactants are employed in the form of water-soluble salts and the salt-
forming cation is
sodium, potassium, ammonium, magnesium and mono-, di- or tri-C1-C3
alkanolammoniutn.
In an illustrative embodiment the cations are sodium, magnesium or ammonium
cations, and
preferred is sodium.
[00531 Other suitable anionic surfactants encompassed within the scope of
the invention
include, but are not limited to, the olefin sulfonates, including long-chain
alkene sulfonates,
long-chain. hydroxyalkane sulfonates or mixtures of alkene sulfonates and
hydroxyalkarie
sulfonates. These olefin sulfonate detergents may be prepared in a known
manner by the
reaction of sulfur trioxide (SO3) with long-chain olefins containing 8 to 25,
or 12 to 21
carbon atoms and having the formula RCH=CHR1 where R is a higher alkyl group
of 6 to 23
carbons and RI is an alkyl group of I to 17 carbons or hydrogen to form a
mixture of
sulfones and alkene sulfonic acids which is then treated to convert the
sulfones to sulfonates.
In other embodiments olefin sulfonates contain about 14 to about 16 carbon
atoms in the R
alkyl group and are obtained by sulfonating an alpha-olefin.
[00541 Other examples of suitable anionic sulfonate surfactants encompassed
within the
scope of the invention include the paraffin sulfonates containing about 10 to
about 20, or
about 13 to about 17 carbon atoms. Primary paraffin sulfonates are made by
reacting long-
chain alpha olefms and bisuffites and paraffin sultanates having the sulfonate
group
distributed along the paraffin chain are shown in U.S. Pat. Nos. 2,503,280;
2,507,088;
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3,260,744; 3,372,188; and German Patent 735,096.
[00551 The compositions of the invention may also include alkyl ethoxylated
ether
sulfates or alkyl ether sulfates. Another surfactant utilized in the instant
composition at a
concentration of about 2 to about 15% by weight in one embodiment or about 4
to about 14%
by weight in another embodiment is a metal salt of a C8---Cg alkyl ether
sulfate. The alkyl
ether sulfate (AEOS.xE0) is depicted by the Formula I:
R1-(OCH(CH3)CH2)x OSO3M
Formula I.
[00561 In one embodiment, x is 1 to 22; in another embodiment x is 1 to 10.
In certain
embodiments, R.1 is an alkyl group having 10 to 16 carbon atoms; in other
embodiments R1 is
an alkyl group having 12 to 15 carbon atoms. In other embodiments, RI is
C12¨C14, Cir-C13
and C12-C15 and M is an alkali metal cation such as, for example, lithium,
potassium, sodium
or magnesium, preferably sodium.
[00571 Other examples of anionic ethoxylated sulfates are the Cg-Cg alkyl
ether sulfate
salts having the Formula II:
111(0C1-12012)n OSO3M
Formula II
[00581 wherein RI and M are defined above and n is 1 to 22, preferably 1 to
3.
[00591 In another embodiment, the anionic surfactant is present in an
amount of about 3
wt. % to about 20 wt. Vo. In another embodiment, the anionic surfactant is
present in an
amount of about 5 wt. % to about 15 wt. %. In another embodiment, the anionic
surfactant is
present in an amount of about 8 wt. % to about 13 wt. %. In another
embodiment, the anionic
surfactant is present in an amount of about 12 wt. % to about 13 wt. %.
[00601 In certain embodiments, the compositions include a first surfactant
and a second
surfactant. In certain embodiments, the first anionic surfactant is present in
an amount of
about 8 wt. % to about 18 wt. % based on the weight of the total composition.
In certain
embodiments, the first anionic surfactant is present in an amount of about 8
wt. % to about 13
wt. % based on the weight of the total composition. In certain embodiments,
the first anionic
surfactant is present in an amount of about 8.5 wt. % based on the weight of
the total
composition. In certain embodiments, the first anionic surfactant is present
in an amount of
about 12.5 wt. % based on the weight of the total composition. In certain
embodiments, the
second anionic surfactant is present in an amount of about 5 wt. % to about 20
wt. % based
on the weight of the total composition. In certain embodiments, the second
anionic surfactant
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is present in an amount of about 13 wt. % to about 20 wt. % based on the
weight of the total
composition. Tn certain embodiments, the second anionic surfactant is present
in an amount
of about 13.5 wt. % based on the weight of the total composition. In certain
embodiments,
the second anionic surfactant is present in an amount of about 18 wt. % based
on the weight
of the total composition.
Zwitterionic Surfactants
[00611 The compositions of the invention also include one or more
zvvitterionic
surfactants. In certain embodiment, the zwitterionic surfactant is also an
amphoteric
surfactant. Amphoteric and zwitterionic surfactants are those compounds that
have the
capacity of behaving either as an acid or a base. Suitable zwitterionic or
amphoteric
surfactants include, but are not limited to, alkyl betaines, alkyl amidopropyl
betaines, alkyl
sulphobetaines, alkyl glycinates, alkyl carboxyglycinates, alkyl
amphopropionates, alkyl
amidopropyl hydroxysultaines, acyl taurates and acyl glutamates wherein the
alkyl and acyl
groups have about 8 to about 18 carbon atoms. Examples include cocamidopropyl
betaine,
sodium cocoamphoacetatc, cocamidopropyl hydroxysultaine, lauryl betaine,
myristyl Maine,
laurylamidopropyl betaine, myristamidopropyl betaine, and sodium
cocamphopropionate.
[00621 In another embodiment, suitable zwitterionic surfactants for use
herein contain
both a cationic hydrophilic group (i.e., a quaternary ammonium group) and
anionic
hydrophilic group on the same molecule at a relatively wide range of pHs. The
typical
anionic hydrophilic groups are carboxylates and sulfonates, although other
groups like
sulfates, phosphonates, and the like can be used.
[00631 In certain embodiments, the zwitterionic surfactants also include
hydrophobic
groups including aliphatic or aromatic, saturated or unsaturated, substituted
or unsubstituted
hydrocarbon chains that can contain linking groups such as amido groups, ester
groups. In
another embodiment the hydrophobic group is an alkyl group containing about 1
to about 24
carbon atoms, in another embodiment about 8 to about 18, and in another
embodiment about
to about 16. In certain embodiments, simple alkyl groups are utilized for cost
and stability
reasons.
[0064] Some common examples of betaine/sulphobetaine are described in U.S.
Pat. Nos.
2,082,275, 2,702,279 and 2,255,082.
[00651 Examples of suitable alkyldimethyl betaines include, but are not
limited,
cocodimethyl betaine, lautyl dimethyl betaine, decyl dimethyl betaine, 2(N-
decyl-N, N-
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dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl
dimethyl
betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl
betaine. For
example Coconut dimethyl betaine is commercially available from Seppic under
the trade
name of Amonyl 265 . Lauryl betaine is commercially available from Albright &
Wilson
under the trade name Empigen BBlEt.
100661 Examples of amidobetaines include cocoamidoethylbetaine,
cocoamido-propyl
betaine or C10-C14 fatty acylamidopropylene(hydropropylene)-sulfobetaine. For
example
CorC14 fatty acylamidopropylene(hydropropylene)-sulfobetaine is commercially
available
from Sherex Company under the trade name Warion CAS1' sulfobetaine." A further
example
of betaine is Lauryl-imino-dipropionate. Laurylamido propylbetaine is
commercially
available from Stepan Chemical under tradename AmphoSol LB
100671 In certain embodiments, the zwitterionic surfactant is present in
an amount of
about 2 wt. % to about 7 wt. % based on the weight of the total composition.
In certain
embodiments, the zwitterionic surfactant is present in an amount of about 2.5
wt. % to about
6.5 wt. % based on the weight of the total composition. In certain
embodiments, the
zwitterionic surfactant is present in an amount of about 5.5 wt. % to about
6.5 wt. based on
the weight of the total composition.
100681 The cleaning composition optionally contains minor amounts, up to
3 wt. %, of
other surfactants including nonionic surfactants. Suitable nonionic
surfactants include
alcohol ethoxylates, such as, the primary aliphatic alcohol ethoxylates,
secondary aliphatic
alcohol ethoxylates, and alkylphenol ethoxylates, and ethylene-oxide-propylene
oxide
condensates on primary alkanols, such a PLUR AFACTm surfactants (BASF) and
condensates
of ethylene oxide with sorbitan fatty acid esters such as the TWEENTm
surfactants (ICI). The
nonionic synthetic organic detergents generally are the condensation products
of an organic
aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene
oxide groups.
Acids of the invention
100691 The cleaning compositions of the invention also include an acid
constituent, which
can be a water soluble organic acid. The organic acids of the invention
generally include at
least one carbon atom, and include at least one carboxyl group (--000171) in
its structure. In
certain embodiments, water soluble organic acids contain from 1 to about 6
carbon atoms and
at least one carboxyl group.
100701 in certain embodiments, organic acids include, but are not
limited to, formic acid,
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citric acid, sorbic acid, acetic acid, glycolic acid, propanoic acid,
propionic acid, oxalic acid,
maleic acid, tartaric acid, adipic acid, lactic acid, malic acid, malonic
acid, glycolic acid, and
mixtures thereof. A preferred acid is lactic acid, for example, 1)- and/or L-
lactic acid or
mixtures thereof, and more preferred is L-lactic acid.
100711 The compositions are acidic in nature (pH<:7.0). Accordingly, there
should be
sufficient acid present in the composition such that the pH of the composition
in various
embodiments is less than about 6, or about 2 to about 5, or about 3 to about
4, or about 3.1 to
about 3.5, or about 3.2 to about 3.3. The pH of the composition incorporating
a selected acid
is preferred to be within 10% of the pKa of the selected acid. Mixtures of two
or more acids
may be used, and the acid constituent may be present in any effective amount.
The pH of the
composition after the aging period remains less than about 6.5, or about 2.1
to about 5, or
about 3 to about 4, or about 12 to about 3.8. The pH of the composition after
the aging
period incorporating a selected acid is preferred to be within 10% of the pKa
of the selected
acid. The aging period should be at least about two months, or about 6 months,
or about 1
year or about 2 years.
100721 The acid is present in an amount of less than about of 5% wt. based
on the total
weight of the compositions. In other embodiments, the acid is present in an
amount of about
0.05 to about 4% wt., from about 1 to about 3% wt., and in an amount of about
2% wt. to
about 2.5% wt. The amount of acid present after the aging period should not
differ
substantially from the level of acid in the initial composition.
Sequestering/Chelating Agents of the Invention
[00731 In certain embodiments, the cleaning compositions of the invention
can also
contain an organic or inorganic sequestrant or mixtures of sequestrants.
Organic sequestrants
such as citric acid, the alkali metal salts of nitrilotriacetic acid (NTA),
EDTA or salts thereof,
alkali metal gluconates, polyelectrolytes such as a polyacrylic acid, and the
like can be used
herein. In certain embodiments. sequestrants are organic sequestrants such as
sodium
eluconatc due to the compatibility of the sequestrant with the formulation
base.
100741 The sequestering agent of the invention also includes an effective
amount of a
water-soluble organic phosphonic acid, which has sequestering properties. In
certain
embodiments, phosphonic acids include low molecular weight compounds
containing at least
two anion-forming groups, at least one of which is a phosphonic acid group.
Such useful
phosphonic acids include mono-, di-, tri- and tetra-phosphonic acids which can
also contain
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groups capable of forming anions under alkaline conditions such as carboxy,
hydroxy, thio
and the like.
[0075] The phosphonic acid may also include a low molecular weight
phosphonopolyearboxylic acid such as one having about 2-4 carboxylic acid
moieties and
about 1-3 phosphonic acid groups. Such acids include 1-phosphono-1-
methylsuccinic acid,
phosphonosuccinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid.
[0076] Other organic phosphonic acids include I -hydmxyethylidene-1,1-
diphosphonic
acid (CH3C(P03H2)20H), available from Monsanto industrial Chemicals Co., St.
Louis, Mo.
as Dequese 2010, a 58-62% aqueous solution; amino [tri(methylenephosphonic
acid)]
(N[CII2P0.3112]3), available from Monsanto as Dequest1'2000, a 50% aqueous
solution;
ethylenediamine [tetra(methylene-phosphonic acid)] available from Monsanto as
Dequest1)2041, a 90% solid acid product; and 2-phosphonobutane-1,2,4-
tricarboxylic acid
available from Mobay Chemical Corporation, Inorganic Chemicals Division,
Pittsburgh, Pa.
sita
as Bayhibit AM, a 45-50% aqueous solution. It will be appreciated that, the
above-mentioned
phosphonic acids can also be used in the form of water-soluble acid salts,
particularly the
alkali metal salts, such as sodium or potassium; the ammonium salts or the
alkylol amine salts
where the alkylol has 2 to 3 carbon atoms, such as mono-, di-, or tri-
ethanolamine salts. If
desired, mixtures of the individual phosphonic acids or their acid salts can
also be used.
Further useful phosphonic acids are disclosed in U.S. Pat. No. 4,051,051.
In certain embodiments, phosphonic acids useful
in the present invention do not contain amino groups since they produce
substantially less
degradation of the active chlorine source than do phosphonic acids including
amino groups.
[0077) Sequestrants of the invention also include materials such as,
complex phosphate
sequestrants, including sodium tripolyphosphate, sodium hexametaphosphate, and
the like, as
well as mixtures thereof. Phosphates, the sodium condensed phosphate hardness
sequestering
agent component functions as a water softener, a cleaner, and. a detergent
builder. Alkali
metal (M) linear and cyclic condensed phosphates commonly have a M70:P205 mole
ratio of
about 1:1 to 2:1 and greater. Typical polyphosphates of this kind are sodium
tripolyphosphate, sodium hexametaphosphate, sodium metaphosphate as well as
corresponding potassium salts of these phosphates and mixtures thereof. The
particle size of
the phosphate is not critical, and any finely divided or granular commercially
available
product can be employed.
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[0078] In certain embodiments, sodium tripolyphosphate is an inorganic
hardness
sequestering agent for reasons of its ease of availability, low cost, and high
cleaning power.
Sodium tripolyphosphate acts to sequester calcium and/or magnesium cations,
providing
water softening properties. It contributes to the removal of soil from hard
surfaces and keeps
soil in suspension. It has little corrosive action on common surface materials
and is low in
cost compared to other water conditioners. Sodium tripolyphosphate has
relatively low
solubility in water (about 14 wt-%) and its concentration must be increased
using means other
than solubility. Typical examples of such phosphates being alkaline condensed
phosphates
(i.e. polyphosphates) such as sodium or potassium pyrophosphate, sodium or
potassium
tripolyphosphate, sodium or potassium hexameta.phosphate.; carbonates such as
sodium or
potassium carbonate; borates, such as sodium borate.
100791 If utilized, the sequestering or chelating agent(s) will generally
include about
0.00015% to about 15% by weight of the cleaning compositions herein. In other
various
embodiments, if utilized, the sequestering or chelating agent(s) will include
about 0.0003% to
about 3.0% by weight of such compositions or about 0.003% to about 1.0% by
weight of
such compositions or about 0.03% to about 0.1% by weight of such compositions.
Fragrance Agents
10080] The compositions and methods of the invention can also include one
or more
fragrance agents. Fragrance agents useful in the compositions and methods
include a wide
variety of natural and synthetic chemical ingredients, including, but not
limited to, aldehydes,
ketones, esters, and the like. Also included are various natural extracts and
essences, which
can include complex mixtures of ingredients, such as orange oil, lemon oil,
rose extract,
lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar,
and the like.
Finished fragrance agents can include extremely complex mixtures of such
ingredients.
Finished fragrance agents typically include about 0.01% to about 2%, by
weight, of the
detergent compositions herein, and individual fragrance agents can include
about 0.0001% to
about 90% of a finished perfume composition.
100811 In a certain embodiments of the invention, the composition includes
a blooming
perfume. A blooming perfume ingredient is characterized by its boiling point
(B.P.) and its
octanollwater partition coefficient (P). The octanol/water partition
coefficient of a perfume
ingredient is the ratio between its equilibrium concentrations in octanol and
in water. The
fragrance agents of the invention have a B.P., determined at the normal,
standard pressure of
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about 760 mm Ng, of about 260 C or lower, less than about 255 C; and less
than about 250
C, and an octanol/water partition coefficient P of about 1,000 or higher.
Since the partition
coefficients of the fragrance agents of the invention have high values, they
are more
conveniently given in the form of their logarithm to the base 10, logP. Thus
the fragrance
agents have logP of about 3 or higher, or more than about 3.1, or more than
about 3.2.
[00821 In certain embodiments, the compositions can include a combination
of fragrance
agents. In certain embodiments, the composition includes a first perfume
ingredient having
boiling point of 250 "C or less and ClogP of 3.0 or less; and a second perfume
ingredient
having boiling point of 250 C or less and Clog P of 3.0 or more.
Hydrotropes
100831 The compositions of the invention can also include one or more
hydrotrope(s).
Without being limited by theory it is believed that the hydrotropc contributes
to the physical
and chemical stability of the compositions.
100841 Suitable hydrotropes include sulfonated hydrotropes. Any sulfonated
hydrotropes
known. to those skilled in the art are suitable for use herein. In certain
embodiments, alkyl
aryl sulfonates or alkyl aryl sulfonic acids are used. In other embodiments
alkyl aryl
sulfonates include sodium, potassium, calcium and ammonium xylene sulfonates;
sodium,
potassium, calcium and ammonium toluene sulfonates; sodium, potassium, calcium
and
ammonium cumene sulfonates; sodium, potassium, calcium and ammonium
substituted or
unsubstituted naphthalene sulfonates and mixtures thereof, and preferred are
sodium salts
thereof. In other embodiments alkyl aryl sulfbnic acids include xylenesulfonic
acid,
toluenesulfonic acid, cumenesulfonic acid, substituted or unsubstituted
naphthaleriesulfonic
acid and salts thereof. In other embodiments, xylenesulfonic acid or p--
toluene sulfonate or
mixtures thereof are used.
[00851 In various embodiments, the compositions may include hydrotropes in
amounts of
about 0.01 wt. % to 20 wt. %, about wt. 0.05% to 10 wt. % or about 0.1 wt. %
to 5 wt. % or
about 3 wt. % by weight of the total composition.
Solvents of the Invention
100861 The invention in certain embodiments can also include one or more
solvents.
Typical solvents used in the composition are aqueous soluble, miscible or
immiscible.
Solvents can include aliphatic and aromatic hydrocarbons, chlorinated
hydrocarbons,
alcohols, ether compounds, fluorocarbon compounds, and other similar low
molecular weight
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generally volatile liquid materials. Of these, preferred are alkanols; more
preferred are
ethanol, isopropanol, and propanol; and most preferred is ethanol. In a
particularly desirable
embodiment, the solvents of the cleaning composition are of alkanols, and more
preferably
the solvent is ethanol. In various embodiments, the compositions may include
solvents in
amounts of up to about 6 wt. %, preferably at least about wt. 0.1% by weight
of the total
composition.
[0087j in certain embodiments, water is not a solvent but when used acts
as a diluent or
as a dispersing medium for the active materials. In other embodiments, water
is a solvent.
(00881 These materials can be used in solution or as a miscible mixture
or as a dispersion
of the solvent in the aqueous liquid. A solvent or cosolvent can be used to
enhance certain
soil removal properties of this invention. Cosolvents include alcohols and the
mono and di-
alkyl ethers of alkylene glycols, dialkylene glycols, trialkylene glycols,
etc. Alcohols which
are useful as cosolvents in this invention include methanol, ethanol, pmpanol
and
isopropanol. Other suitable solvents include the mono and dialkyl ethers of
ethylene glycol
and diethylene glycol, which have acquired trivial names such as polyglymes,
cellosolves,
and carbitols. Representative examples of this class of cosolvent include
methyl cellosolves,
butyl carbitol, dibutyl carbitol, diglyme, triglyme. Nonaqueous liquid
solvents can be used
for varying compositions of the present invention, These include the higher
glycols,
polyglycols, polyoxides and glycol ethers.
10089] Suitable substances are propylene glycol, polyethylene glycol,
polypropylene
glycol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether,
diethylene
glycol monobutyl ether, tripropylene glycol methyl ether, propylene glycol
methyl ether
(PM), dipropylene glycol methyl ether (DPM), propylene glycol methyl ether
acetate (PMA),
dipropylene glycol methyl ether acetate (CPMA), propylene glycol n-butyl
ether, dipropylene
glycol monobutyl ether, ethylene glycol n-butyl ether and ethylene glycol n-
propyl ether, and
combinations thereof In certain embodiments, the glycol solvent is propylene
glycol n-butyl
ether. In certain embodiments, the glycol solvent is dipropylene glycol
monobutyl ether.
100901 Other useful solvents are ethylene oxide/propylene oxide, liquid
random
copolymer such as Synalox' solvent series from Dow Chemical (e.g., Synalo,e'50-
508).
Other suitable solvents are propylene glycol ethers such as NB, DPnB and TP118
(propylene
glycol mono n-butyl ether, dipropylene glycol and tripropylene glycol mono n-
butyl ethers
sold by Dow Chemical under the trade name Dowanol®). Also tripropylene
glycol mono
methyl ether "Dowanol TPMe," from Dow Chemical is suitable.
10091] The final ingredient in the inventive cleaning compositions is
water. The
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proportion of water in the compositions generally is in the range of about 35%
to about 90%
or about 50% to 85% by weight of the cleaning composition.
Thickening Agents
[00921 In certain embodiments, the compositions of the invention also
include a
thickening or structuring agent. Suitable thickening or structuring agents may
be organic or
inorganic in nature. The agent may thicken the composition by either
thickening the aqueous
portions of the composition, or by thickening the non-aqueous portions of the
composition.
In certain embodiments, the agent is a water soluble polymer. In other
embodiments, the
agent is a cationic water soluble polymer.
[00931 In certain embodiments, the polymeric thickener may be added to the
composition
to achieve two objectives (i) to increase the "flow" viscosity or the yield
stress, and (ii) to
neutralize the anionic detergent carry-over guaranteeing a high level of
softness in washing
conditions where the carry-over is high. The flow viscosity corresponds to the
viscosity
measured with a tlowmeter. The flowability of the tested composition is
expressed as time
needed to a fixed amount of product flowing through a small tube.
[00941 Thickeners can be divided into organic and inorganic thickeners. Of
the organic
thickeners there are (1) cellulosic thickeners and their derivatives, (2)
natural gums, (3)
actylates, (4) starches, (5) stearates, (6) fatty acid alcohols and inorganic
thickeners including
(7) clays, and (8) salts. Some non-limiting examples of cellulosic thickeners
include
carboxymethyl hydroxyethylcellulose, cellulose, hydroxybutyl methylcellulose,
hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropyl methyl cellulose,
methylcellulose, microciystalline cellulose, sodium cellulose sulfate, and the
like. Some non-
limiting examples of natural gums include acacia, calcium carrageenan, guar,
gelatin, guar
gum, hydroxypropyl guar, karaya gum, kelp, locust bean gum, pectin, sodium
carrageenan,
gellan gum, tragacanth gum, xanthan gum, and the like. Some non-limiting
examples of
actylates include potassium aluminum polyacrylate, sodium acrylatelvinyl
alcohol
copolymer, sodium polymethacrylate, and the like. Some non-limiting examples
of starches
include oat flour, potato starch, wheat flour, wheat starch, and the like.
Some non-limiting
examples of stearates include methoxy PEG-22/dodecyl glycol copolymer, PEG-2M,
PEG-
5M, and the like. Some non-limiting examples of fatty acid alcohols include
caprylic
alcohol, cetearyl alcohol, lauryl alcohol, oleyl alcohol, palm kernel alcohol,
and the like.
Some non-limiting examples of clays include bentonite, magnesium aluminum
silicate,
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magnesium trisilicate, stearalkonium bentonite, tromethamine magnesium
aluminum silicate,
and the like. Some non-limiting examples of salts include calcium chloride,
sodium chloride,
sodium sulfate, ammonium chloride, and the like.
100951 Some non-limiting examples of thickeners that thicken the non-
aqueous portions
of the composition include waxes such as candelilla wax, carnauba wax,
beeswax, and the
like, oils, vegetable oils and animal oils, and the like.
100961 The composition may contain one thickener or a mixture of two or
more
thickeners, In certain embodiments the thickeners do not adversely react with
the other
components or compounds of the invention or otherwise render the composition
of the
invention ineffective. It is understood that a person skilled in the art will
know how to select
an appropriate thickener and control any adverse reactions through
formulating.
100971 The amount of thickener present in the composition depends on the
desired
viscosity of the composition. The composition may have a viscosity of about
100 to about
15,000 centipoise, of about 150 to about 10,000 centipoise, and of about 200
to about 5,000
centipoise as determined using a Brookfield DV-1.1.+-rotational viscorneter
using spindle #21
@ 20 rpm @ 7017. Accordingly, to achieve the desired viscosities, the
thickener may be
present in the composition in an amount about 0.001 wt. % to about 5 wt. % of
the total
composition, about 0,01 wt. c.va to about 3 wt. %, and about 0,05 wt. % to
about 2 wt. % of the
total composition.
100981 Thickeners front said classes of substance are commercially
broadly available and
are obtainable, for example, under the trade names Acusol 820 (methacrylic
acid (stearyl
alcohol-20 EO) ester-acrylic acid copolymer, 30% strength in water, Rohm &
Haas),
Daprale-CiT-282-S (alkyl polyalyeril ether, Akzo), Deuterol*polymer-11
(dicarboxylic acid
copolymer, Schoner GmbH), Deuteron' XG (anionic heteropolysaccharide based on
beta-D-
glucose, D-manose, D-glucuronic acid, Schoner GmbH), Deuteron'-XN
(nonionogenic
polysaccharide, Schoner GmbH), Dicrylan" thickener-0 (ethylene oxide adduct,
50%
strength in waterlisopropanol, Pfersse Chemie), EMA - -81 and EMA ---9l
(ethylene-maleic
anhydride copolymer. Monsanto), thickener-OR-1001 (polyurethane emulsion, 19
21%
strength in swaterldiglycol ether, Rohm. & Haas), Nfir0e-AM (anionic acryhe
acid-acrylic
ester copolymer dispersion, 25% strength in water, Stockhausen), SER-AD-FX-
1100
(hydrophobic urethane polymer, Servo Delden), Shelltle-S (high molecular
weight
polysaccharide, stabilized with formaldehyde. Shell) and Shellflo4'-XA
(xanthan biopolymen
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stabilized with formaldehyde, Shell).
100991 The inventors have discovered that xanthan gum is useful as a
thickening agent
for suspending fragrance molecules in a hard surface cleaner. In certain
embodiments, the
thickening agent is xanthan gum. In other embodiments, the thickening agent is
xanthan gum
present in at least about 0.2 weight %.
Additional Optional Ingredients
101001 Examples of additional optional components include, but are not limited
to,
hydrotropes, fluorescent whitening agents, photobleaches, fiber lubricants,
reducing agents,
enzymes, enzyme stabilizing agents, powder finishing agents, builders,
bleaches, bleach
catalysts, soil release agents, dye transfer inhibitors, buffers, colorants,
fragrances, pro-
fragrances, Theology modifiers, anti-ashing polymers, soil repellents, water-
resistance agents,
suspending agents, aesthetic agents, structuring agents, sanitizers, solvents,
fabric finishing
agents, dye fixatives, fabric conditioning agents and deodorizers.
101011 Other surfactants which can be utilized in the present invention are
set forth in more
detail in WO 99121530, U.S. Pat. No. 3,929,678; U.S. Pat. No. 4,565,647; U.S.
Pat, No.
5,720,964; and U.S. Pat. No. 5,858,948, Other suitable surfactants are
described in
McCutcheon's Emulsifiers and Detergents (North American and International
Editions, by
Schwartz, Perry and Beret),
101021 In addition to the previously mentioned. constituents of the
composition, one may also
employ normal and conventional adjuvants, provided they do not adversely
affect the
properties of the detergent. Thus there may be used a cationic antibacterial
agent, coloring
TIC
agents and perfumes; polyethylene glycol, ultraviolet light absorbers such as
the Uvinuls,
which are products of GAF Corporation; pH modifiers; etc. The proportion of
such adjuvant
materials, in total will normally not exceed 15% by weight of the detergent
composition, and
the percentages of illustrative examples of such individual components will be
about 5% by
= MK
weight. Sodium formate or formalin or Quatemium 15 (Dowicil 75) can be
included in the
formula as a preservative at a concentration of about 0.1 to about 4.0 vet. %.
Process of Manufacture
101031 The compositions are readily made by simple mixing methods from readily
available
components which, on storage, do not adversely affect the entire composition,
if a
structuring anent is incorporated in the compositions, a homogenization
process can be added
in the production method. Solubilizing agent such as ethanol, hexylcne glycol,
sodium
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chloride and/or sodium xylene or sodium xylene sulfbnate are used to assist in
solubilizing
the surfactants. The viscosity of the light duty liquid composition desirably
will be at least
100 centipoises (cps) at room temperature, but may be up to 1,000 centipoiscs.
The viscosity
of the light duty liquid composition and the light duty liquid composition
itself remain stable
on storage for lengthy periods of time, without color changes or settling out
of any insoluble
materials.
Methods of Use
[01041 The invention encompasses cleaning compositions useful for cleaning a
surface. The
compositions surprisingly possess antibacterial efficacy and low toxicity.
[01051 By surfaces, it is meant herein any kind of surfaces typically found in
houses like
kitchens, bathrooms, or the exterior surfaces of a vehicle, for example,
floors, walls, tiles,
windows, sinks, showers, shower plastificd curtains, wash basins, WCs, dishes
and other food
contact surfaces, fixtures and fittings and the like made of different
materials like ceramic,
vinyl, no-wax vinyl, linoleum, melamine, glass, any plastics, plastified wood,
metal,
especially steel and chrome metal or any painted or varnished or sealed
surface and the like.
Surfaces also include household appliances including, but not limited to,
refrigerators,
garbage cans, freezers, washing machines, automatic dryers, ovens, microwave
ovens,
dishwashers and so on. The present composition is especially efficacious in
the cleaning of
ceramic, steel, plastic, glass and the exterior painted or othenvise finished
surface of a
vehicle, for example, a car. The cleaning compositions are also safe on the
skin.
101061 The cleaning composition is applied to the surface, undiluted or
diluted, optionally
after a pre-rinse step. The cleaning composition can be diluted with water,
preferably up to a
dilution ratio of 1:20, without significantly affecting its cleaning and
antimicrobial efficacies.
The composition can be applied using a cloth or sponge onto which the
composition has been
applied or by pouring the composition over the surface. Alternatively the
composition may be
applied by spraying the composition onto the surface using a spraying device
as described
above. The cleaning compositions of the invention can be left to sit on a
surface or be wiped
or scrubbed on or from the surface.
[01071 Once the composition has been applied to the surface, the surface can
then be
optionally rinsed, usually with water, and left to dry naturally. Optionally
the user can wait
in between application of the composition and rinsing in order to allow the
composition
maximum working time. .A particular benefit of the composition is that the
surface can be
24
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cleaned as described above with minimal rinsing and the surface left to dry
naturally without
accumulating physiologically hamful deposits, and/or with reduced or no
corrosion.
[0108] The following examples illustrate compositions of the invention. Unless
otherwise
specified, all percentages are by weight. The exemplified compositions are
illustrative only
and do not limit the scope of the invention. Unless otherwise specified, the
proportions in the
examples and elsewhere in the specification are by active weight. The active
weight of a
material is the weight of the material itself excluding water or other
materials that may be
present in the supplied form of the material.
EXAMPLES
10109) The following examples illustrate liquid cleaning compositions of the
invention.
Unless otherwise specified, all percentages are by weight. The exemplified
compositions are
illustrative only and do no limit the scope of the invention. it will be
understood by those of
skill in the art that numerous and various modifications can be made without
departing from
the scope of the present invention. Therefore, it should be clearly understood
that the forms
of the present invention described herein are illustrative only and are not
intended to limit the
scope of the invention.
Example 1
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[0110) Tables la - Id illustrate several non-limiting illustrative embodiments
of the
invention illustrating regular and ultra dishwashing liquids.
Table in
Ingredient Reg 2a Reg 2b Reg la Reg lb Ultra Ultra 2b Ultra
Ultra
(wt. (wt. (wt. (wt. 2a (wt. %) la lb
%) %) %) %) (wt. %) (wt. (WI
%) %)
Na DBSI 3.7 3.7 8.4 8.4 5.8 5.8 8.5 8.5
SLES (2E0) 12 12 9.2 9.2 19.6 19.6 17.9 17.9
C12-C14 .... ...... _
Laurylamido- 3.4 3.4 1.5 1.5 6.6 6.6 5.4 5.4
propyl betaine
Ethanol 3.5 3.5 2.1 2.1 6 6 4.3 4.3
Lactic Acid 2 2 1
- 2 L. 2 2 1
µ..
Mg2SO4 0 0 3.5 3.5 0 0 0.9 0.9
SXS 0.8 0.8 0.8 0.8 2.2 2.2 3 3
NaC1 0 0 0.7 0.7 0 0 0 0
Na4EDIA 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
Color solution 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.2
Fragrance 0.26 0 0.26 0 0.4 0 0.4 0
option A .
Fragrance 0 0.26 0 0.26 0 0.45 0 0.45
option B
Water qs qs qs qs qs qs qs qs
Total 19 19 19 19 32 32 32 32
Surfactant % .
Calculated 4100 4100 3895 3895 4157 4157 3721 3721
LD50
I Sodium dodecyl benzene sulfonate
Table lb
Ingredient Reg. lc Reg. 2e 1 Ultra lc Ultra 2c
NaLAS 8.4 3.7 8.5 5.75
SLES 9.3 12.1 1 17.9 19.6
Betaine 1.5 3.4 5.4 6.6
Lactic 2 2 2 2
Table le
Ingredient Rea Id
.... Reg. 2d
NAAS i 5.3 2.3
SLES i 5.8 7.6
Betaine 0.1 2.2
Lactic 2 2
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Table Id
Ingredient (wt. %)
Na DBS1 12.7
SUS (2E0) CirC14 13.7
Laurylam ido propy I Helaine 5.6
Ethanol 4
Lactic Acid 2
SXS 2.5
Color Solution 0.3
Fragrance 0.35
Water Qs
Example 2
101111 Tables 2a 2d illustrate several non-limiting illustrative embodiments
of the
invention. Amounts added are based on the percent taw amount of ingredient
added.
[01121 In certain illustrative embodiments of the invention, the EPA mandated
antibacterial
efficacy of the cleaning compositions has been validated for independent lots
of dish liquid
manufactured under GMP conditions. The lots were tested on 10 carriers
(replicate surfaces)
against Staphylyeoceus aureus ATCC 6538 and, separately on 10 carriers
(replicate surfaces)
against Salmonella enterica ATCC 10708 as mandated by the EPA. A confirmatory
test, on
independent lots, was also tested on 10 carriers (replicate surfaces) against
Escherichia coil
0157 H7 ATCC 43895 for additional on-pack claims against this specific and
relevant food
pathogen. The tests were conducted on 1:20 use-dilutions with a 30-second
exposure time.
In all cases a minimum 3-log reduction or 99.9% kill rate was attained for
both the surfaces
and the run-off counts, as prescribed for EPA acceptance.
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Table 2a
Organism Lot Number Dilution Replicate CFUleanier Average
logic,
reduction
1 5.4 x 101 3.41
1:20 2 1.8 x 102 3.89
la 3 3.0 x 101 4.67
1 8.0 x 101 4.54
1:50 2 3.7 x 102 3.58
3 1.9 x 102 4.15
1. 4.7 x 102 347
1:20 2 5.9x 101 3.38
2a 3 7.3 x 101 3.28
1 8.8 x 101 3.20
1:50 2 6.1 x 102 3.36
S. aureus 3 5.5 x 101 3.41
1 1.0 x101 5.51
1:20 2 5.0 x 101 4.45
3a 3 2.0 x 101 4.85
1 1.0 x 101 5.51
1:50 2 5.0 x 101 4.45
3 5.0 x 101 4.45
1 3.4x 101 3.61
1:20 2 3.6 x 101 3.59
3 1.2 x 101 4.07
4a 1 5.1 x 10/ 3.44
1:50 2 3.0x 101 3.67
3 2.4 x 101 3.77
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Table 2b
Organism Lot Number Dilution Replicate CFUicanier Average
logic,
reduction
1 4.5 x 101 3.99
1:20 2 4.7 x 102 3.97
lb 3 3.7 x 101 4.08
1 9.3 x 102 3.67
1:50 2 8.1 x 102 3.73
3 7.6 x 102 3.76
1. 1.5 x 103 3.47
1:20 2 1.1 x 103 3.60
2b 3 1.4 x 103 3.50
1 1.7 x 103 3.41
1:50 2 2.4x 103 3.26
S. aureus 3 2.1 x 103 3.32
1 1.2 x102 4.56
1:20 2 1.1 x 101 4.60
3b 3 4.2 x 101 4.02
1 5.0 x 101 4.94
1:50 2 9.0 x 101 4.69
3 7.0x 101 4.80
1 3.2x 102 4.14
1:20 2 4.9x 102 3.95
3 4.4x 102 4.00
4b 1 1.1 x 103 3.60
1:50 2 1.5 x 103 3.47
3 6.7 x 102 3.82
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Table 2c
Organism Lot Number Dilution Replicate CFUicanier Average
logjo
reduction
1 1.9 x 102 4.17
1:20 2 2.5x 102 4.04
1 c 3 8.3 x 102 3.53
1 3.3 x 102 3.93
1:50 2 2.0 x 102 4.15
3 1.5 x 102 4.27
1. 6.3 x 102 3.65
1:20 2 5.0x 102 3.75
2c 3 5.1 x 102 3.74
1 1.6 x 102 4.24
1:50 2 2.2x 102 4.10
E. calf 3 3.0 x 10 4.97
1 6.2x104 1.65
1:20 2 6.6x 103 2.63
3c 3 6.0x 104 1.67
1 6.3 x 104 1.65
1:50 2 6.8x 103 2.61
3 6.2 x 103 2.65
1 4.0x 102 3.85
1:20 2 7.3 x 102 3.58
3 1.4 x 102 4.30
3d 1 2.0 x 101 5.15
1:50 2 2.0 x 1W 5.15
3 2.8 x 102 4.00
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Table 2d
Organism Lot Number Dilution Replicate CFIJ/carrier
Average
logio
reduction
1 9.0 x 101 4.74
1:20 2 <1.0 x 10i >5.70
Id 3 <1.0 x 10' >5.70
1 6.0 x 102 3.92
1:50 2 4.4x 102 4.06
3 2.4 x 102 4.32
1 1.0 x 101 5.70
1:20 2 <1.0 x 10i >5.70
2c1 3 4.0x 102 4.10
1 7.0 x 101 4.85
1:50 2 5.0 x 101 5.00
E. call 3 2.6x 102 4.28
1 1.8x104 2.44
1:20 2 4.4x 103 3.06
3d 3 1.1 x 104 2.66
1 4.2 x 103 3.08
1:50 2 1.7x 103 3.47
3 1.7x 104 2.47
1 2.0x 101 5.40
1:20 2 9.0 x 10' 4.74
3 2.0 x 101 5.40
4d 1 1.0 x 102 4.70
1:50 2 <1.0 x 10! >5.70
3 3.8 x 102 4.12
Example 3
[01131 In certain embodiments, the cleaning compositions of the invention
include inert
ingredients. The inert ingredients include the surfactants that provide
surface cleaning
benefits, viscosity modifiers, salts, hydrotropes, chelants that deliver
conventional and
consumer parameters such as dispensing and clarity, and color/fragrance to
provide a
consumer-delightful product use experience. The inerts are shown in Table 3
with its status
on the EPA Inert List.
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Table 3
Ingredient EPA Inert List
Na DBS1 3
SLES (2E0) C12-C14 4B
Laurylamidopropyl Betaine 3
Ethanol 4B
Lactic Acid 4B
Mg2SO4 4A
SXS 3
NaC1 4A
Na4EDTA 4B
Gellan gum 4A
Water n/a
I Sodium dodecyl benzene sulfonate
Example 4
101141 The cleaning compositions of the invention were designed for minimal
corrosivity for
processing equipment. In Tables 4a, 4b and 4c, high salt, Sample 1, and low
salt, Sample 2,
versions of formulas were tested by both short-term, accelerated
electrochemical polarization
tests at 100 F, and longer-term (6 weeks) immersion tests at 100 F and at 140
F with
crevice d-corrosion coupons made of varying grades of stainless steel.
Table 4a
Ingredient Ingredient % Weipt in Formulation
Sample I Sample 2 Surfactant 3% NaCI
Control solution
Na DBSI 8.5 8.5 8.2 0
SLES (2E0) C1-2-C14 17.9 17.9 0 0
NI-L4AEOS (1.3 EU) 0 0 11.3 0
Laurylamidopropyl 5.4 5.4 0 0
betaine
Amine Oxide 0 0 3.5 0
__ Lactic Acid 2.0 2.0 0 0
____ MgSO4 0.9 0.9 L31 0
Alcohol 3.0 4.3 1.4 0
NaCI (added) 3.3 ........ 0 0.8 3.0
SXS 3.0 ........ 3.0 0.65 0
Chealant 0.1 0.1 0..1 0
Color Solution 0.2 0.2 0.1 0
Fragrance A 0.4 0.4 0 0
Fragrance B 0 0 0.3 0
1 Sodium dodecyl benzene sulfonate
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Table 4b
Formula pH Cond.' Cond. Cl- SO4- Ac0- LPR I LPR 2
Description _______ (1. D (2nd) (PPIn) (PP1n) (ppin) (InPY)
(ITIPY)
Sample 1 3.04 39.3mS _ 41.7mS 23.980
7.999 14.138 0.248 0.223
Sample 2 2.89 25.6mS 25.4mS 6.190 10.496 15.726 0.081
0.068
Surfactant 6.60 28.2mS 28.5mS 4.494 11.648 BDL 0.059 0.050
Control
3% NaCI 3.00 40.6mS 0.083 0.122
Solution
first conductivity reading was taken and then a second conductivity reading
was taken.
Electrochemical testing was done at 40 C.
Table 4c
Alloy 404"C 60 ()C
Formula Surfactant Sample
Sample 1 Surfactant Sample Sample I
Control 2 Control 2
Attribute High pH Low pH
Low pH High pH Low pH Low pH
Description Low Cl- Low Cl- High Cl- Low Cl- Low Cl- High Cl-
pH 6.6 3.0 3.0 6.6 3.0 3.0
Chloride (ppm) 4500 6200 24000 4500 6200 24000
Stainless Steel =No Attack No Crevice No
Attack Crevice Crevice
Attack Attack Attack Attack
Stainless Steel Not Tested Not Not No Attack No Crevice
Tested Tested Attack Attack
2 Types of Stainless steel were tested (316L and AL6XN)
Example 5
[01151 The cleaning compositions of the invention provide competitive
foaming/cleaning
performance with existing commercial products. Traditional performance tests
were
completed to assess the flash foam profile with and without soil (shake-foam),
the foam
mileage (miniplate), and typical/dynamic (Baumgartner) grease soil removal for
both the
ultra and regular density dishliquids. The resulting performance profiles
against in-market
products are shown in the tables below. These results indicate an unexpectedly
higher
performance profile that should be more acceptable to the consumer.
(I) Baumgartner Grease Removal
[01161 The Baumgartner test measures grease removal in every day cleaning
situations.
Plastic tubes covered with solidified lard, tallow, or mixed greasy soil are
dipped in a warm
LDL solution 100 times; the concentration of the solution is 0.0667%. The
total dipping time
is approximately 1 minute. The tubes are weighed before and after grease is
applied. After
the tubes dry, the % grease removal is calculated.
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(2) Shake-foam Test
101 171 100 ml of a diluted (0.033%) test solution in 150 ppm hardness water
at RT is filled
into a 500 ml graduated cylinder with a stopper. The stoppered cylinder is
placed on an
agitating machine, which rotates the cylinder for 40 cycles at 30 rpm. The
height of the foam
in the cylinder is observed. A milk soil is then introduced (about 175 nL)
into the cylinder.
The cylinder is then inserted 40 times more, and the height after soil
addition is recorded.
[0118] The number of miniplates is measured using an automated miniplate test.
The
procedure is described in detail in U.S. patent number 4,556,509.
The test is used to determine the number of theoretical plates that can be
washed in a cleaning solution until the foam disappears. This test is used to
demonstrate the
improvement in cleaning efficiency as gauged by foam volume and foam
stability. Foam is
generated in a detergent solution by the action of an agitating brush. The
foam is
electronically measured by reflectance of the solution surface (with an added
dye) as a mixed
soil (potato, milk, olive oil, crisco) is added to the detergent solution at a
steady rate. The
disappearance. of the foam determines the endpoint of the test and the number
of miniplates is
then calculated based on foam duration and the rate of soil addition. For
these, tests the
detergent solution was an illustrative cleaning composition of the invention
at 3.3 wt. % with
150 ppm Mg/CaCO3 hardness and was initially heated to 47 'C at the start of
soil addition.
Table 5a
Ingredient Ingredient % Weight in Formulation
Sample I Sample 2 Sample 3 Sample 4 In-
market
1 Control
Na DBS1 8.4 4 4 4 0
Mg DBS2 0
1 0 0 11,2
SLES (2E0) Ci 2-C14 9.3 13 13 13 0
NH4 AEOS (1.3 E0) 0
0 0
Laurylamidopropyl 1.5 3.7
1 3.7 3.7 0
betaine
Amine Oxide 0 0 0 0
MgSO4 0.9 I 0.9 0 0 0.5
NaCI (added) 1.85 3.25 2.1 0 0
Antibacterial Lactic acid I Lactic Lactic acid
Lactic acid Triclosan
Evict
Total % Surfactant 19.2 20.7 10.7 20.7 20.2
Sodium dodecyl benzene sulfimate
Magnesium dodecyl benzene sultanate
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Table 5b
Sample Total % Baumgartner SFI Mean SFS Mean
Miniplate
Surfactant ___________________________________
1 19.2% 75.83 391.67 128.33 14
2 20.7% I 81.13 391.67 130.00 20
__ 3 20.7% ..... i 76.17 391.67 136.37 19.5
4 20.7% 80.27 408.33 138.33 23 __
In-market 20.2 % 88.32 383.33 123.33 17
Control
Table Sc
Ingredient Ingredient % Weight in
Formulation _______ ........
Sample 1 Sample 2 Sample 3 Sample 4 In-
market
Control
Na DBS1 5.7 5.7 8.5 8.5 0.9
Mg DBS2 0 0 0 0 13.1
SLES (2E0) C12-C14 18.9 18.9 17.9 17.9 0
NH4 AEOS (1.3 BO) 0 , 0 0 , 0 16.2
Laurylamidopropyl 5.4 5.4 5.4 5.4 0
betaine
Amine Oxide 0 0 0 0 5.9
MgSO4 0 0 0.85 0.85 0
NaC1 (added) 3.5 0 3.0 0 0.4
Antibacterial Lactic acid Lactic acid Lactic acid Lactic acid
Triclosan
Total % Surfactant 30 30 31.8 31.8 35.6
I Sodium dodecyl benzene sulfonate
2 Magnesium dodecyl benzene sulfonate
Table 5d
Sample Total % Baumgartner SFI Mean SFS Mean
Miniplate
Surfactant
1 30% 68.267 390 141.67 20.4
2 30% 67.75 398.33 146.67 I 19
3 31.8% 71.12 403.33 145.00 21.4
4 31.8% 75.85 395.67 163.33 ' 21.4
In-Market 35.6% 84.03 380 161.67 23.4
Control
Example 6
[01191 The cleaning compositions of the invention provide superior rinsing
and/or shine
performance with existing products. Studies showed that the acidic formula can
deliver
advantages on rinsing attributes versus in-market formulas. This is likely to
be especially
noticeable in hard water environments.
101201 The rinsing benefits of the compositions of the invention were
demonstrated by actual
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in lab rinsing measurements. This method involves applying an illustrative
cleaning
composition of the invention to a plate and recording the time it takes for
full rinsing of the
product. The illustrative cleaning compositions of the invention were nearly
twice as fast to
rinse.
Table 6
Composition of the Invention Control
Rinsing Time 6.5 sec 11.8 sec
Example 7
Tables 7a - 7e illustrate properties including good Foam Volume, good Grease
Redeposition,
and good rinsibility of illustrative embodiments of the invention.
Table 7a
Ingredient Sample 1 Sample 2 Sample 3 Sample 4 In-
market Control
Na DBS1 10 10 6.4 0
Mg DBS2 0 0 0 14
SLES (2E0) C12-C14 21 21 24.6 0
NH4 AEOS (1.3 EO) 0 0 0 16.1
Laurylamidopropyl 3.6 3.6 3.6 0
betaine
Amine Oxide 0 0 0 5.9
MgSO4 0 1.7 1.6 0
NaCl (added) 0 0.25 1.3 0.4
Antibacterial Lactic acid Lactic acid Lactic acid
Triclosan
Total % Surfactant 34.7 34.6 34.6 36
I Sodium dodecyl benzene sulfonate
2 Magnesium dodecyl benzene sulfonate
Table 7b
Neat I Neat2
Product ini soil re-en Foam l Foam2
0.423 0.55 0.51 0.70 0.73
Sample 1 6.5 4 4.0 4.1 7.4 3.7
Sample 2 6.7 4.5 4.7 7.0 3.6
Sample 3 6.6 4.5 4.7 7.1 3.6
Sample 4 6.7 4.5 4.8 5.7 2.6
I Neat foam without soils - 15 squeezes.
2 Neat foam with soils added - 10 additional squeezes.
3 Minimum significant difference.
4 Means having the same letter are not significantly different (alpha=0.10).
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Table 7e
Or on Or on Cr on Cr on
Product glass plate plastic knife tub
0.32 0.17 0.29 0.22 0.40
Sample 1 1.1 0.3 0.8 0.4 1.7
Sample 2 0.9 0.3 0.8 0.5 1.3
Sample 3 0.9 0.4 0.8 0.4 1.4
Sample 4 0.7 0.2 0.6 0.3 1.0
Table 7d
DLR1N (Ease of Ease of Rinse Amount of Neat4 Neat4
Product rinse) 1 Glass Plate (sec) 2 water film (%)3 Glass
Plate
0.495 1.04 10.73 0.74 0.70
Sample 1 6.26 8.3 46.9 1.9 1.2
Sample 2 6.2 10.0 42.4 2.1 1.9
Sample 3 6.3 9.7 50.2 2.6 1.7
Sample 4 6.8 13.0 48.0 2.6 1.8
'Number of rinses till no foam.
'Seconds needed to rinse detergent off plate.
3 Percent water film on plate.
4Detergent residue remaining on dishes.
'Minimum significant difference.
64eans having the same letter are not significantly different (alpha=0.10).
Table 7e
Product Fat soils remaining
Sample 1 2.4
Sample 2 2.5
Sample 3 2.3
Sample 4 1.58
Example 8
[01211 The compositions exhibit stability at reduced and increased
temperatures. More
specifically, such compositions remain clear and stable in the range of about
0 `)C to about 50
C.
101221 Creep Yield Stress Test (static test) - This rheological test was
conducted on the TA
Instruments ARG2 rheometer. It uses the high surface area vane geometry that
is very
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sensitive and can measure very low yield stresses. The test is run in a 50-
gram water-jacketed
sample holder at a constant temperature of 25 C. The test runs a creep test
(strain vs. stress)
at stresses ranging from 0.01 Pa to 0.6 Pa. Custom software then calculates
yield stress from
the family of curves generated for each sample. A yield stress above 0.5
dyn,'cm2 is ideal for
supporting particulates, but a yield stress above 0.15 dyn/cm2 is sufficient
to justify product
positioning as a gel or dish gel.
[01231 Brookfield Yield Stress Test (dynamic test) - This test was developed
to approximate
the creep analysis above, but with much more rapid output to provide rapid
feedback when
processing formulas at manufacturing conditions. It also uses the high surface
area vane
geometry that is very sensitive and can measure very low yield stresses. The
test is run in a
400-milliliter glass beaker. The test runs a torque sweep at decreasing RPMs,
or revolutions
per minute, ranging from 50 to 0.3 rpm. Once the torques are recorded, custom
software then
calculates yield stress for each sample. A yield stress above 0.5 dyn/cm2 is
ideal for
supporting particulates, but a yield stress above 0.2 dyn/cm2 is sufficient to
justify product
positioning as a gel or dish gel.
[01241 ARG2 Viscosity Test - This rheological test was conducted on the ARG2
rhcometer.
It simply measures viscosity at a constant shear rate of 21 s-1 with a
constant temperature of
25 C. This test simulates the shear rate of the product coming out of the
bottle when the
consumer dispenses the product under normal conditions. If the value is above
2000 cP, the
cap orifice may need to be modified to assure consumer-friendly dispensing.
Table 8a
Ingredient Ex. Ultra acidic Ex. Ultra acidic Ex. Ultra
acidic
LDL gel 41 (wt.%) LDL gel 42 LDL gel 43
(Iv t.%)._
Na DBS 5.75 5.75 5.75
SLES (2E0) Cp-C14 19.6 19.6 19.6
Laurylarnidopropylbetaine 6.6 6.6 6.6
Alcohol 4 4 4
Lactic Acid 2 2 2
SXS 2.5 2.5 2.5
Gellan Gum 0.075 0.094 0.125
Na4EDTA 0.83 0.83 0.83
Water qs qs qs
1 Sodium dodecy1 benzene sulfortate
Table 8b
Ultra Brookfield ARG2 Viscosity ARG2 Creep Brookfield
Acidic Viscosity (cP) (cP) Yield Stress Yield Stress
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I..DL Gel (dynicm) dyn/cm2)
#1 773 1472 0.16 0.231
#2 768 1388 0.40 0.859
#3 905 1778 1.046
Surface skinning over testing creep test timing cycle yielded invalidated data
[01251 The liquid compositions are readily pourable and exhibit a viscosity in
the range of 6
to 300 milliPascal second (mPas or mps) as measured at 25 "C with a Brookfield
RVTDV-II.
Viscometer using a #21 spindle rotating at 20 RPM. In certain embodiments, the
viscosity is
maintained in the range of 10 to 200 mPas.
Example 9
[01261 The compositions of the invention are nearly colorless. The relative
amount of a
coloring agent to deliver near-colorless aesthetics is mainly dependent on the
color of the
dodecyl benzene sulfortate being used. Color is measured on a Klett scale
where the higher
the Klett the more yellow a particular material used. The next table gives an
approximate
amount of color needed to deliver the aesthetic according to Kieft of NaLAS.
The
formulation uses a mixture of violet and pink dyes to yield the final color
aesthetic. The
colors are chosen based on the color wheel. Violet dye is added to offset the
light yellow
color present in the base. Because it may be an imperfect match a slight green
color can be
generated which is accounted for with a pink colorant. The net result is a
product that has an
appearance of a colorless material.
Table 9
Dodecyl Benzene Sulfonate Color Wt. % Coloring Agent Added
0-5 <0.0035
6-10 ......................................... 0.0035
10-15 0.006
15-20 0.008
20-25 0.01
Example 10
[01271 Toxicity Testing was conducted using animal studies and alternative
tests. Animal
studies were completed using Table la formula Ultra 2a/b (with or without
fragrance).
101281 The alternate test methodologies (human testing) were done for the
inventive formula
as listed in Table Id. Studies were completed with 4 different
formula/fragrance options, but
the base formula is Id. The Toxicity Testing was conducted using the following
test
protocols:
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[01291 (1) Acute Oral Toxicity - Exposure is via a single, limit dose of dish
liquid at the
maximum required upper limit dose of 5000mg/kg. The Acute Oral Toxicity was
conducted
using opp.rs Guideline Study 870.1100, EPA Publication # 98-190. The 1.,D50
was not
reached and was greater than 5000mg/kg. As a comparison, two dish liquid
compositions
were prepared and tested. One composition contained about 0.5 wt. % of
betaine, about 13
wt. % each of Na DBS, Mg DBS, and NTI4AEOS, The other composition contained
about
0.5 wt. % of betaine, about 26 wt. % of Na DBS and about 13 wt. % of NH4AEOS.
The LD50
values for the two compositions were less than 5000mg/kg.
[01301 (2) Acute Dermal Toxicity - Exposure is via a single, limit dose of
dish liquid at the
upper limit dose of 5000mg/kg. The Acute Dermal Toxicity was conducted using
OPPTS
Guideline Study 870.1200, EPA Publication # 98-192. The LD50 was not reached
and was
greater than 5000mg/kg.
[01311 (3) Acute Eye Irritation ¨ Exposure is via a single 10 j.il dose, with
scoring for
irritation at fixed intervals after exposure. The Acute Eye Irritation was
conducted using a
lower volume of test material placed directly on the eye. The amount of test
material used in
the LVET is 1/10th of that used in the Draize eye irritation test. There was
some initial
irritation that fully reversed within the 7 day scoring endpoint, and no
corneal opacity.
101321 (4) Acute Dermal Irritation ¨ Exposure is via repeated, occluded,
prolonged exposure
to concentrated (undiluted) dish liquid. The Acute Dermal irritation was
conducted using
OPPTS Guideline Study 870.2500, EPA Publication # 98-196. Results showed
irritation
within the 72 hour period that fully reversed with seven days. A more relevant
measure skin
irritation uses the standard 21-day Cumulative Irritation study methodology
(applied
commonly in the cosmetic industry) on humans. This method is a semi-occluded
exposure at
a relevant product use-dilution, although it is still clearly an
extreme/maximal exposure
scenario. This method shows no significant irritation for lactic acid based
formulations.
[01331 (5) Skin Sensitization ¨ Exposure is via three weekly induction doses
and then a
challenge dose (following a 2 week intervening rest period). The Skin
Sensitization was
conducted using OPPTS Guideline Study 870.2600, EPA Publication # 98-197. A
naïve
control group is used as a comparison for the group receiving the challenge
dose. Result is
that the formula is a non-sensitizer. A more relevant measure of sensitization
potential uses
the Human Repeat Insult Patch Test methodology (applied commonly in the
cosmetic
industry) on humans. This is an occlusive patch exposure method at a relevant
product use-
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dilution. This method also documents no skin sensitization for the sample.
41
