Note: Descriptions are shown in the official language in which they were submitted.
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HARD SURFACE CLEANING COMPOSITTONS
The present invention relates to sprayable disinfecting hard surface cleaning
compositions. More particularly the present invention relates tothickened
lavatory
cleaning compositions which provide a cleaning and disinfecting effect to hard
surfaces,
and which include visibly discernible inclusions.
Cleaning compositions which also provide a disinfecting or sanitizing effect
are
commercially important products. Such compositions enjoy a wide field of
utility in
assisting in the removal of stains and grime from surfaces, especially those
characterized
as useful with "hard surfaces". Hard surfaces are those which are frequently
encountered
in lavatories such as lavatory fixtures such as toilets, shower stalls,
bathtubs, bidets,
sinks, etc., as well as countertops, walls, floors, etc. Two types of commonly
encountered stains in lavatories include "hard water" stains and "soap scum"
stains. Such
hard surfaces, and such stains, may also be found in different environments as
well,
including kitchens, hospitals, etc.
Various formulations in compositions of cleaning agents have been produced and
are known to the art which cleaning agents are generally suited for one type
of Main but
not necessarily for both classes of stains. For example, it is known to the
art that highly
acidic cleaning agents comprising strong acids, such as hydrochloric acids,
are useful in
the removal of hard water stains. However, the presence of strong acids is
known to be
an irritant to the skin and further offers the potential of toxicological
danger. Other
classes of cleaning compositions and formulations are known to be useful upon
soap
scum stains, however, generally such compositions comprise an organic and/or
inorganic
acid, one or more synthetic detergents from commonly recognized classes such
as those
described in U.S. Patent No. 5,061,393; U.S. Patent No. ~,008,03fl; U.S.
Patent No.
4,759,867; U.S. Patent No. 5,192,460; U.S. Patent No. 5,039,441. Generally,
the
compositions described in these patents are claimed.to be effective in the
removal of soap
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scum stains from such hard surfaces and may fmd further limited use in other
classes of
stains.
However, the formulations of most of the compositions within the
aforementioned
patents generally have relatively high amounts of acids (organic andJor
inorganic) which
raises toxicological concerns, and further none of the above patents provide
any
disinfecting properties.
While many disinfecting hard surface cleaning compositions are known to the
art,
there is nonetheless a need for further improved compositions in the art.
According to the one aspect of the invention, there is provided a sprayable
hard
surface cleaning and/or disinfecting composition which comprises (preferably
consists
essentially of):
a thickener constituent which comprises both gellan gum and xanthan gum;
at least one nonionic surfactant;
an acid constituent;
suspended inclusions which appear as visibly discernible, discrete particulate
materials, preferably where said discrete particulate materials are based on
alginates;
optionally, at least one further detersive surfactant selected from amphoteric
and
zwitterionic surfactants;
optinally at least one anionic surfactant;
optionally, at least one organic solvent;
optionally, one or more constituents for improving the aesthetic or functional
features of the inventive compositions; and;
water.
In further aspects of the invention there are provided processes for the
production
of the aforesaid compositions.
It is yet a further obj ect of the invention to provide a readily sprayable
cleaning
composition which features the benefits described above.
It is a further object of the invention to provide a process for the
improvement of
the simultaneous cleaning and sanitization of hard surfaces, which process
comprises the
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step of providing a composition as outlined above, and applying an effective
amount to a
haxd surface requiring such treatment.
Particularly preferred compositions according to the invention are acidic in
character, are effective in the removal of both soap scum stains and hard
water stains, and
which compositions provide an effective sanitizing effect to hard surfaces.
Further,
particularly preferred sprayable compositions may be dispensed from a manually
operable trigger pump spray apparatus and the composition provided by such
device has
visibly discernible, visibly discrete particulate materials on a treated hard
surface.
The inventive compositions necessarily comprise a thickener constituent. In
addition to the gellan gum and the xanthan gum, one or more further thickeners
may also
be included in the inventive compositions. By way of non-limiting example such
further
thickeners include one or more of cellulose, alkyl celluloses, allcoxy
celluloses, hydroxy
alkyl celluloses, alkyl hydroxy alkyl celluloses, carboxy alkyl celluloses,
carboxy alkyl
hydroxy alkyl celluloses, and mixtures thereof. Examples of the cellulose
derivatives
include ethyl cellulose, hydroxy ethyl cellulose, hydroxy propyl cellulose,
carboxy
methyl cellulose, carboxy methyl hydroxyethyl cellulose, hydroxypropyl
cellulose,
hydroxy propyl methyl cellulose, and ethyl hydroxy ethyl cellulose.
Preferably, the
thickener constituent is a mixture of xanthan gurn and gellan gum to the
exclusion of
other thickener constituents described herein. Further examples of preferred
thickener
constituents are described in the Examples.
The gellan gum and the xanthan gum may be present in the thickener constituent
in any relative amounts with respect to each other. Desirably however the
ratio of gellan
gum to xanthan gum on a respective parts by weight basis is from 1:1-10,
preferably 1:1-
5 but more preferably from 1:1 to 1:2 parts by weight. These preferred
respective weight
ratios may be used in the presence of further thickeners forming the thickener
constituent,
and especially preferably are used in the absence of further thickeners. The
present
inventors have observed that the combination of gellan gum and xanthan gum,
especially
in the respective weight ratios described above are particularly effective in
providing the
desirable rheological properties to the sprayable compositions. Even minor
amounts of
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gellan gum when combined with xanthan gum may provide surprisingly good
thickening
and desirable rheological properties.
The amount of thickener present in the composition may be any amount which is
effective in suspending the suspended inclusions as hereinafter described.
Desirably the
composition of the present of invention is thickened to a viscosity range of
from about 25
to about 300 centipoise, preferably to a viscosity of from about 100 to about
300
centipoise, more preferably is in the range of about 50-200 centipoise
measured at room
temperature, on a LVTDV IIBrookfield viscometer, spindle #l, at 30 rpm,
measured at
25°C. Generally good thickening has been observed when the total amount
of the
thickeners are present in amount from about 0.001 to about 5% by weight, more
preferably from about 0.001 to about 3% by weight, more preferably from about
0.001-
1.5%wt, still more preferably from about 0.01-O.Sn%wt. and most preferably the
total
amount of the thickeners are present in the inventive compositions in amount
of from
about 0.03%wt. to about 0.20%wt.
1~ Preferably other thickening materials known to the art, particularly those
based on
synthetic polymers such as acrylic acid copolymers, e.g. Carbopol~ materials,
as well as
those based on clays are absent from the inventive compositions.
The inventive compositions further requires at least one nonionic surfactant.
Generally any nonionic surfactant material may be used in the inventive
compositions.
Practically any hydrophobic compound having a carboxy, hydroxy, amido, or
amino
group with a free hydrogen attached to the nitrogen can be condensed with an
alkylene
oxide, especially ethylene oxide or with the polyhydration product thereof, a
polyalkylene glycol, especially polyethylene glycol, to form a water soluble
or water
dispersible nonionic surfactant compound. By way of non-limiting example,
particularly
examples of suitable nonionic surfactants which may be used in the present
invention
include the following:
One class of useful nonionic surfactants include polyalkylene oxide
condensates
of alkyl phenols. These compounds include the condensation products of alkyl
phenols
having an alkyl group containing from about 6 to 12 carbon atoms in either a
straight
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chain or branched chain configuration with an alkylene oxide, especially an
ethylene
oxide, the ethylene oxide being present in an amount equal to 5 to 25 moles of
ethylene
oxide per mole of alkyl phenol. The alkyl substituent in such compounds can be
derived,
for example, from polymerized propylene, diisobutylene and the like. Examples
of
compounds of this type include nonyl phenol condensed with about 9.5 moles of
ethylene
oxide per mole of nonyl phenol; dodecylphenol condensed with about 12 moles of
ethylene oxide per mole of phenol; dinonyl phenol condensed with about 15
moles of
ethylene oxide per mole of phenol and diisooctyl phenol condensed with about
15 moles
of ethylene oxide per mole of phenol.
A further class of usefixl nonionic surfactants include the condensation
products of
aliphatic alcohols with from about 1 to about 60 moles of an alkylene oxide,
especially an
ethylene oxide. The alkyl chain of the aliphatic alcohol can either be
straight or branched,
primary or secondary, and generally contains from about 8 to about 22 carbon
atoms.
Examples of such ethoxylated alcohols include the condensation product of
myristyl
alcohol condensed with about 10 moles of ethylene oxide per mole of alcohol
and the
condensation product of about 9 moles of ethylene oxide with coconut alcohol
(a mixture
of fatty alcohols with allcyl chains varying in length from about 10 to 14
carbon atoms).
Other examples are those C6 -C 11 straight-chain alcohols which are
ethoxylated with
from about 3 to about 6 moles of ethylene oxide. Their derivation is well
known in the
art. Examples include Alfonic~ 810-4.5, which is described in product
literature from
Sasol as a C8-10 having an average molecular weight of 356, an ethylene oxide
content
of about 4.85 moles (about 60 wt.%), and an HLB of about 12; Alfonic~ 810-2,
which is
described in product literature as a C8-C10 having an average molecular weight
of 242,
an ethylene oxide content of about 2.1 moles (about 40 wt.%), and an HLB of
about 12;
and Alfonic~ 610-3.5, which is described in product literature as having an
average
molecular weight of 276, an ethylene oxide content of about 3.1 moles (about
50 wt.%),
and an HLB of 10. Other examples of alcohol ethoxylates are C10 oxo-alcohol
ethoxylates available from BASF under the Lutensol~ ON tradename. They are
available in grades containing from about 3 to about 11 moles of ethylene
oxide
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(available under the names Lutensol~ ON 30; Lutensol~ ON 50; Lutensol~ ON 60;
Lutensol~ ON 65; Lutensol~ ON 66; Lutensol~ ON 70; Lutensol~ ON 80; and
Lutensol~ON 110). Other examples of ethoxylated alcohols include the Neodol~
91
series non-ionic surfactants available from Shell Chemical Company which are
described
as C9-C 11 ethoxylated alcohols. The Neodol~ 91 series non-ionic surfactants
of interest
include Neodol~ 91-2.5, Neodol~ 91-6, and Neodol~ 91-8. Neodol~ 91-2.5 has
been
described as having about 2.5 ethoxy groups per molecule; Neodol 91-6 has been
described as having about 6 ethoxy groups per molecule; and Neodol 91-8 has
been
described as having about 8 ethoxy groups per molecule.Further examples of
ethoxylated
alcohols include the Rhodasurf~ DA series non-ionic surfactants available from
Rhodia
which are described to be branched isodecyl alcohol ethoxylates. Rhodasurf~ DA-
530
has been described as having 4 moles of ethoxylation and an HLB of 10.x;
Rhodasurf~
DA-630 has been described as having 6 moles of ethoxylation with an HLB of
12.5; and
RhodasurfC~ DA-639 is a 90% solution of DA-630. Further examples of
ethoxylated
alcohols include those from Tomah Products (Milton, Wn under the Tomadol~
tradename with the formula RO(CH2CH20)nH where R is the primary linear alcohol
and
n is the total number of moles of ethylene oxide. The ethoxylated alcohol
series from
Tomah include 91-2.5; 91-6; 91-8 - where R is linear C9/C10/C11 and n is 2.5,
6, or 8; 1-
3; 1-5; 1-7; 1-73B; 1-9; where R is linear Cl 1 and n is 3, ~, 7 or 9; 23-1;
23-3; 23-5; 23-
6.5 - where R is linear C12/C13 and n is 1, 3, 5, or 6.5; 25-3; 2~-7; 25-9; 25-
12 - where R
is linear C 12/C 13/C 14/ C 15 and n is 3, 7, 9, or 12; and 45-7; 45-13 -
where R is linear
C14/ C15 and n is 7 or 13.
A further class of useful nonionic surfactants include primaxy and secondary
linear and branched alcohol ethoxylates, such as those based on C6-C18
alcohols which
2~ further include an average of from 2 to 80 moles of ethoxylation per mol of
alcohol.
These examples include the Genapol~ UD (ex. Clariant, Muttenz, Switzerland)
described
under the tradenames Genapol~ UD 030, C11-oxo-alcohol polyglycol ether with 3
EO;
Genapol~ UD, 050 C11-oxo-alcohol polyglycol ether with 5 EO; Genapolfl UD 070,
C11-oxo-alcohol polyglycol ether with 7 EO; Genapol~ UD 080, C11-oxo-alcohol
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polyglycol ether with 8 EO; Genapol~ UD 088, C11-oxo-alcohol polyglycol ether
with 8
EO; and Genapol~ UD 110, C11-oxo-alcohol polyglycol ether with 11 EO.
A further class of useful nonionic surfactants include those surfactants
having a
formula RO(CH2CH20)nH wherein R is a mixture of linear, even carbon-number
hydrocarbon chains ranging from C12H25 to C16H33 and n represents the number
of
repeating units and is a number of from about 1 to about 12. Surfactants of
this formula
are presently marketed under the Genapol~ tradename(ex. Clariant), which
surfactants
include the "26-L" series of the general formula RO(CH2CH20)nH wherein R is a
mixture of linear, even carbon-number hydrocarbon chains ranging from C12H25
to
C 16H33 and n represents the number of repeating units and is a number of from
1 to
about 12, such as 26-L-1, 26-L-1.6, 26-L-2, 26-L-3, 26-L-5, 26-L-45, 26-L-50,
26-L-60,
26-L-60N, 26-L-75, 26-L-80, 26-L-98N, and the 24-L series, derived from
synthetic
sources and typically contain about 55% C12 and 45% C14 alcohols, such as 24-L-
3, 24-
L-45, 24-L-50, 24-L-60, 24-L-60N, 24-L-75, 24-L-92, and 24-L-98N, all sold
under the
Genapol~ tradename.
A further class of useful nonionic surfactants include alkoxy block
copolymers,
and in particular, compounds based on ethoxy/propoxy block copolymers.
Polymeric
alkylene oxide block copolymers include nonionic surfactants in which the
major portion
of the molecule is made up of block polymeric C2-C4 allcylene oxides. Such
nonionic
surfactants, while preferably built up from an alkylene oxide chain staxting
group, and
can have as a starting nucleus almost any active hydrogen containing group
including,
without limitation, amides, phenols, thiols and secondary alcohols.
One group of such useful nonionic surfactants containing the characteristic
alkylene oxide blocks are those which may be generally represented by the
formula (A):
HO-(EO)X(PO)y(EO)rH (A)
where EO represents ethylene oxide,
PO represents propylene oxide,
y equals at least 15,
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(EO)x+y equals 20 to 50% of the total weight of said compounds, and, the total
molecular weight is preferably in the range of about 2000 to 15,000. These
surfactants
are available under the PLURONIC~(ex. BASF) or EMULGEN~ (ex. Kao.)
A further group of such useful nonionic surfactants containing the
characteristic
alkylene oxide blocks are those can be represented by the formula (B):
R-(EO,PO)a(EO,PO)b-H (B)
wherein R is an alkyl, aryl or aralkyl group, where the R group contains 1 to
20 carbon
atoms, the weight percent of EO is within the range of 0 to 45% in one of the
blocks a, b,
and within the range of 60 to 100% in the other of the blocks a, b, and the
total number of
moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50
moles in
the PO rich block and 5 to 100 moles in the EO rich block. Specific nonionic
surfactants
which in general are encompassed by Formula B include butoxy derivatives of
propylene
oxide/ethylene oxide block polymers having molecular weights within the range
of about
2000-5000.
Still further examples of useful nonionic surfactants include those which can
be
represented by formula (C) as follows:
RO-(BO)"(EO)x-H (C)
wherein EO represents ethylene oxide,
BO represents butylene oxide,
R is an alkyl group containing I to 20 carbon atoms,
n is about 5-15 and x is about 5-15.
Yet further useful nonionic surfactants include those which may be represented
by the
following formula (D):
HO-(EO),~(BO)~(EO)y-H (D)
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wherein EO represents ethylene oxide,
BO represents butylene oxide,
n is about 5-15, preferably about 15,
x is about 5-I5, preferably about 15, and
y is about 5-15, preferably about 15.
Still further exemplary useful nonionic block copolymer surfactants include
ethoxylated
derivatives of propoxylated ethylene diamine, which may be represented by the
following
formula:
H(EO)y(PO)~~ / (PO)X(EO)yH
CH2 CH2 ~ (E)
(PO)X(EO)yH
H(EO)y(PO)X
where (EO) represents ethoxy,
(PO) represents propoxy,
the amount of (PO)x is such as to provide a molecular weight prior to
ethoxylation of
about 300 to 7500, and the amount of-(EO)y is such as to provide about 20% to
90% of
the total weight of said compound.
Particularly preferred nonionic block copolymers include those based on a
polymeric ethoxy/propoxy units which may also be used include those presently
commercially available in the PLURAFAC~ series of block copolymers {ex. BASF)
These are described to be nonionic surfactants based on ethoxy/propoxy block
copolymers, conveniently available in a liquid form from its supplier. One
particularly
preferred nonionic block copolymer is PLUR.AFAC~~ SL-62 which is described to
be a
nonionic surfactant based on ethoxy/propoxy block copolymers having an average
of
from about I-3 moles propoxy groups, and ~-12 moles ethoxy groups and having a
total
molecular weight from about 600 - 650. In certain preferred embodiments of the
inventive composition present the sole nonionic surfactant present is a
nonionic
surfactant based on ethoxy/propoxy units, and especially is a nonionic block
copolymer
as described with reference to PLURAFAC~ SL-62.
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Further useful non-ionic surfactants which may be used in the inventive
compositions include those presently marketed under the trade name Piuronics~
(ex.
>3ASF). The compounds are formed by condensing ethylene oxide with a
hydrophobic
base formed by the condensation of propylene oxide with propylene glycol, The
S molecular weight of the hydrophobic portion of the molecule is of the order
of 950 to
4,000 and preferably 200 to 2,500. The addition of polyoxyethylene radicals of
the
hydrophobic portion tends to increase the solubility of the molecule as a
whole so as to
make the surfactant water-soluble. The molecular weight of the block polymers
varies
from 1,000 to 15,000 and the polyethylene oxide content may comprise 20% to
80% by
weight. Preferably, these surfactants are in liquid form and particularly
satisfactory
surfactants are available as those marketed as Pluronics~ L62 and Pluronics~
L64.
Alkylrnonoglyocosides and alkylpolyglycosides which find use in the present
inventive
compositions include known nonionic surfactants which are alkaline and
electrolyte
stable. Alkylinonoglycosides and alkylpolyglycosides are prepared generally by
reacting
a monosaccharide, or a compound hydrolyzable to a monosaccharide with an
alcohol
such as a fatty alcohol in an acid medium. Various glycoside and polyglycoside
compounds including alkoxylated glycosides and processes for making them are
disclosed in U.S. Pat. Nos. 2,974,134; 3,219,656; 3,598,865; 3,640,998;
3,707,535,
3,772,269; 3,839,318; 3,974,138; 4,223,129 and 4,528,106 the contents of which
are
incorporated by reference. .
One exemplary group of such useful alkylpolyglycosides include those according
to the formula:
RO-(CnH2n0)r-(Z)x
wherein:
R is a hydrophobic group selected from alkyl groups, alkylphenyl groups,
hydroxyalkylphenyl groups as well as mixtures thereof, wherein the alkyl
groups may be
straight chained or branched, and which contain from about 8 to about 18
carbon atoms,
n has a value of 2 - 8, especially a value of 2 or 3;
r is an integer from 0 to 10, but is preferably 0,
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Z is derived from glucose; and,
x is a value from about 1 to 8, preferably from about 1.5 to 5.
Preferably the alkylpolyglycosides are nonionic fatty alkylpolyglucosides
which
contain a straight chain or branched chain C8 -C15 alkyl group, and have an
average of
from about 1 to 5 glucose units per fatty alkylpolyglucoside molecule. More
preferably,
the nonionic fatty alkylpolyglucosides which contain straight chain or
branched C8 -C15
alkyl group, and have an average of from about 1 to about 2 glucose units per
fatty
alkylpolyglucoside molecule.
A fiu-ther exemplary group of alkyl glycoside surfactants suitable for use in
the
practice of this invention may be presented by the following formula (A):
RO-(R~ O)y-(G)x Zb (A)
wherein:
R is a monovalent organic radical containing from about 6 to about ~0,
preferably from
1 ~ about 8 to 18 carbon atoms,
Rl is a divalent hydrocarbon radical containing from about 2 to about 4 carbon
atoms,
y is a number which has an average value from about 0 to about 1 and is
preferably 0,
G is a moiety derived from a reducing saccharide containing ~ or 6 carbon
atoms; and,
x is a number having an average value from about 1 to 5 (preferably from 1.1
to ~);
O
I I
Z is OaMI, ~ C R2 , O(CHa), CO2M1, OSO3M1, or O(CHZ)S03M1 ; Ra is
(CHa)COa Ml or CH=CHCOZMI ; (with the proviso that Z can be O~MI only if Z is
in
place of a primary hydroxyl group in which the primary hydroxyl-bearing carbon
atom, --
O
IC-OM ~
CH20H, is oxidized to form a group)
b is a number of from 0 to 3x+1 preferably an average of from 0.5 to 2 per
.glycosal
group;
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p is 1 to 10, Ml is H+ or an organic or inorganic counterion, particularly
cations such as,
for example, an alkali metal cation, ammonium cation, monoethanolamine cation
or
calcium cation. As defined in Formula (A) above, R is generally the residue of
a fatty
alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms.
Examples of such
alkylglycosides as described above include, for example APG 325 CS Glycoside~
which
is described as being a 50% C9 -Cl1 alkyl polyglycoside, also commonly
referred to as D-
glucopyranoside, (commercially available from Henkel I~GaA) and Glucopon~ 625
CS
which is described as being a 50% Cio -C16 alkyl polyglycoside, also commonly
referred
to as a D-glucopyranoside, (ex. Henkel).
Further nonionic surfactants which may be included in the inventive
compositions
include alkoxylated alkanolamides, preferably Cs-Ca4 alkyl di(C2-C3 allcanol
amides), as
represented by the following formula:
R5-CO-N H-R~-O H
wherein RS is a branched or straight chain C8-Ca4 alkyl radical, preferably a
Clo-C16 alkyl
radical and more preferably a Cla-C14 alkyl radical, and R6 is a Cl-C4 alkyl
radical,
preferably an ethyl radical.
The inventive compositions may also include a nonionic amine oxide
constituent.
Exemplary amine oxides include:
(A) Alkyl di (lower alkyl) amine oxides in which the alkyl group has about 10-
20, and preferably 12-16 carbon atoms, and can be straight or branched chain,
saturated
or unsaturated. The lower alkyl groups include between 1 and 7 carbon atoms.
Examples include lauryl dimethyl amine oxide, myristyl dimethyl amine oxide,
and those
in which the alkyl group is a mixture of different amine oxide, dimethyi
cocoamine
oxide, dimethyl (hydrogenated tallow) amine oxide, and myristyl/palinityl
dimethyl
amine oxide;
(B) Alkyl di (hydroxy lower alkyl) amine oxides in which the alkyl .group has
about 10-20, and preferably 12-16 carbon atoms, and can be straight or
branched chain,
saturated or unsaturated. Examples are bis(2-hydroxyethyl) cocoamine oxide,
bis(2-
hydroxyethyl) tallowamine oxide; and bis(2-hydroxyethyl) stearylamine oxide;
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(C) Alkylamidopropyl di(lower alkyl) amine oxides in which the alkyl group
has about 10-20, and preferably 12-16 carbon atoms, and can be straight or
branched
chain, saturated or unsaturated. Examples are cocoamidopropyl dimethyl amine
oxide
and tallowamidopropyl dimethyl amine oxide; and
(D) Alkylmorpholine oxides in which the alkyl group has about 10-20, and
preferably 12-16 carbon atoms, and can be straight or branched chain,
saturated or
unsaturated.
Preferably the amine oxide constituent is an alkyl di (lower alkyl) amine
oxide as
denoted above and which may be represented by the following structure:
R~
R2 ~ ---~O
R~
wherein each:
Rl is a straight chained C1-C4 alkyl group, preferably both Rl are methyl
groups;
and,
RZ is a straight chained C8-C18 alkyl group, preferably is Clo-C14 alkyl
group, most
preferably is a C12 alkyl group.
Each of the alkyl groups may be linear or branched, but most preferably are
linear. Most
preferably the amine oxide constituent is lauryl dimethyl amine oxide.
Technical .grade
mixtures of two or more amine oxides may be used, wherein amine oxides of
varying
chains of the R2 group are present. Preferably, the amine oxides used in the
present
invention include Ra groups which comprise at least 50%wt., preferably at
least 60%wt.
of Cia alkyl groups and at least 2~%wt. of C14 alkyl groups, with not more
than 15%wt.
of Cts, Cis or higher alkyl groups as the R2 group.
Of course the nonionic surfactant constituent, when present, my comprise two
or
more nonionic surfactants. The nonionic surfactant is present in the
compositions of the
present invention in an amount of from about 0.1 to about 10% by weight, more
preferably is present in an amount of from about 0.1- 5%wt., yet snore
preferably in an
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amount of from about 0.25 - 2%wt., and most preferably in an amount of from
about 0.3
-1.5%Wt.
The present inventive compositions necessarily comprise an acid constituent
which be a water soluble inorganic acid, or a water soluble organic acids. By
way of non-
limiting example useful inorganic acids include hydrochloric acid, phosphonic,
and
sulfuric acid. With respect to water soluble organic acids, generally include
at least one
carbon atom, and include at least one carboxyl group (--COON) in its
structure. Preferred
are water soluble organic acids which contain from 1 to about 6 carbon atoms,
and at
least one carboxyl group as noted. Particularly preferred amongst such organic
acids are:
formic acid, citric acid, sorbic acid, acetic acid, boric acid, malefic acid,
adipic acid, lactic
acid, rnalic acid, malonic acid, glycolic acid, and mixtures thereof.
According to certain
preferred embodiments however, the acid constituent is a combination of citric
acid in
combination with at least one further acid selected from the group consisting
of sorbic
acid, acetic acid, boric acid, formic acid, malefic acid, adipic acid, lactic
acid, malic acid,
malonic acid, and glycolic acid. Most preferably, the acid constituent is a
combination of
citric acid with lactic acid, glycolic acid or malic acid.
As the inventive compositions are necessarily acidic in nature (pH < 7.0)
there
should be sufficient acid present in the composition such that the pH of the
composition
is desirably less than 6, preferably from about 2 to about 3.5, more
preferably from about
2.8 to about 3.3, and most preferably from about 3.0 to about 3.3. Of course
mixtures of
two or more acids may be used, and the acid constituent may be present in any
effective
amount. Desirably however, the acid constituents is present in an amount not
in excess
of 10%wt. based on the total weight of the compositions; preferably the acid
constituent
is present in an amount of from about 0.05 - 8%wt., more preferably from about
1 -
6°lowt., and most preferably is present in an amount of from about
2%wt. to about ~%wt.
The acid constituent of the inventive formulations provide free acidity within
the cleaning
composition, which free acid reacts with the fatty acid metal salts which are
comprised
within soap scum stains releasing the metal ions and freeing the fatty acid,
which
facilitates the removal of these undesired stains from hard surfaces. These
acids also
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sequester the resulting free metal ions which are released from the soap scum
stains. Also
where the acids are selected to feature disinfecting properties, they
concomitantly provide
anti-microbial activity necessary to disinfect the cleaned surface.
As a necessary constituent, the inventive compositions include suspended
inclusions based on alginates. These suspended inclusions appear as visibly
discernible,
discrete particulate materials to the consumer of the inventive compositions.
These
suspended inclusions desirably appear as small discrete visible particles
suspended within
the composition, particularly by a consumer having normal "20/20" vision. It
is to be
understood however that not all of the particulate materials present in the
inventive
composition need be visibly discernible as a portion of the particulate
materials may be
smaller than the visible threshold of the consumer having normal vision. It is
nonetheless
required that at least a portion of the particulate materials present in the
inventive
composition need be visibly discernible as discrete particles.
Desirably the alginate based particulate materials are supplied to have an
average
particle size in the range of about 50~,m to about 1000~,m, preferably in the
range of
about 350~m to about 700~,m, most preferably in the range of about 5'SOpm to
about
&SOpm, and especially preferably in the range of about 57~~m to about 625~,m.
Desirably the average particle size of these particulate materials represents
that at least
85% of the particles, more preferably at least 90%, still more preferably at
least 92%, and
most preferably at least 95°/~ of the particles present are within a
specified range.
The suspended inclusions present in the inventive compositions are based on
alginates
although other visibly discernible, discrete particulate materials may be used
as well, ~or
in the place of alginate based materials. However tie preferred suspended
inclusions are
based on alginates.
2~ Alginate based particulate materials used for the suspended inclusions in
the
inventive compositions may be formed from an alginate or salts of alginic acid
such as
potassium alginate, calcium alginate or sodium alginate salts, and
advantageously may be
conveniently harvested from naturally occurring seaweed especially of the
species
Laminaria wherein the sodium alginate form predominates. Alginates
typicallyconsist of
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sequences of a-L-guluronic acid and (3-D-mannuronic acid which may be present
in the
alginate in various differing ratios. The term "beads" conveniently describes
the
geometry of the alginate based particulate materials as when these are formed
form an
aqueous slurry containing an alginate such as sodium alginate with one or more
further
constituents and then expelled to form individual particles or droplets, the
coalescing
aqueous slurry may form generally spherical particles, hence the term "beads".
Of course,
other processes for the formation of alginate based suspended inclusions are
also
. contemplated as being useful in conjunction with the present invention such
as processes
wherein the alginate optionally containing one or more further constituents is
comminuted by other methods, such as milling, grinding or other known art
technique.
In such instances the comminuted alginate based suspended inclusions may not
necessarily form generally spherical particles but may form individual
particles of
irregular geometry. In such an instance the largest dimension of such
individual particles
of irregular geometry are used as the basis for determining the average
particle size of the
The alginate based particulate materials may contain from about 0.5%wt. to
100%wt. of an alginate or alginate salt, although quite frequently the amount
of alginate
in the alginate based particulate materials are much less, generally on from
about 0.5%wt.
to about 10%wt., more preferably from about 0.5%wt. to about 5%wt. Such
alginate
based particulate materials may be conveniently referred to as "alginate
beads". Such
alginate beads may be formed by a variety of known art processes including
those
described in the background section of PCT/LjS95/08313 to Thomas et al., as
well as in
US 6,467,699 B1, the contents of which are incorporated by reference.
Alternately such
alginate based particulate materials may be commercially purchased from
various
suppliers, including geniaLab BioTechnologie (Braunschwig, Germany). As noted
the
composition of the alginate based particulate materials may include only a
small
proportion of an alginate or alginate salt, and may include one or more
further non-
alginate materials especially one or more inorganic materials such as titanium
dioxide
which improves the opacity, hence the visibility of the beads, as well as one
or more
coloring agents such as pigments such as ultramarine blue, said coloring
agents which
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also improve the aesthetic appearance of the beads. Other further non-alginate
materials
not recited herein may also be include in the composition of the alginate
based particulate
materials. The alginate based particulate materials may be composed of a major
proportion of water which is entrained within the structure of the discrete
alginate based
particulates and due to the highly porous character of alginates when in an
aqueous
compositions 80%wt., and usually 90%wt. or even greater of the mass of the
discrete
alginate based particulates may be water with the remaining balance to 100%wt.
being
the alginate or alginate salt, and one or more further non-alginate materials.
Conveniently
such alginate based particulate materials may be prepared, stored and sold as
a slurry of
discrete alginate based particulates in an aqueous-based Garner composition
which may
contain a minor amount of one or more further additives such as one or more
salts
especially chloride salts such as calcium chloride, as well as a preservative
for inhibiting
the growth of undesirable microorganisms in the slurry containing the discrete
alginate
based particulates. A preferred commercially available alginate based
particulate material
comprise from about 0.5%wt. to about 5%wt. of a calcium alginate, a pigment
present in
an amount up to about 0.01 %wt., from about 0.1 %wt. to about 5%wt. of TiO~
and the
remaining balance of the mass of the alginate based particulate material
comprised of a
2% calcium chloride solution in water which may also con an a minor amount,
approx.
2% of calcium chloride. Such an alginate based particulate material can be
separated
~0 from its aqueous-based carrier composition by means of a fine sieve or
other means for
decanting the aqueous-based carrier composition from the alginate based
particulate
materials.
By the term "suspended" when referring to inclusions is to be understood that
when the formed inventive compositions are manually shaken and then allowed to
return
to a quiescent state, such as by permitting them to stand on a tabletop or
other surface at
room temperature (approx. ~0°C) for 48 hours, the majority of the
inclusions do not drop
more than 7%, preferably do not drop more than ~%, most preferably do not drop
more
than 2% of their original distance from the bottom of the container in which
the inventive
composition is present when they have returned to a quiescent state following
manual
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shaking. By "majority of inclusions" is meant to convey that at least 90% of,
preferably
at least 95% and most preferably at least 97% of the inclusions physically
present in the
compositions. This is a particularly attractive and characteristic feature of
preferred
embodiments of inventive compositions, as the suspended inclusions do not
appear to
move perceptibly over long periods of time. Desirably, at least 90% of,
preferably at
least 95% and most preferably at least 97% of the inclusions physically
present in the
compositions do not drop more than 5%, most preferably do not drop more than
2% of
their original distance from the bottom of the container in which the
inventive
composition is present when they have returned to a quiescent state following
manual
shaking when measured after 72 hours, more preferably when measured after 168
hours,
still more preferably when measured after 10 days, yet more preferably after
14 days
when left in a quiescent state at room temperature. In certain particularly
preferred
embodiments of the invention at least 90% of, preferably at least 95% and most
preferably at least 97% of the inclusions physically present in the
compositions do not
drop more than 5%, after 3 weeks and especially after 4 weeks, and especially
after 6
months when retained in a quiescent state at room temperature.
Although optional, the compositions according to the present invention may
include one or more further detersive surfactants particularly those selected
from amongst
anionic, amphoteric and zwitterionic surfactants, particularly those which may
provide a
detersive effect to the compositions.
The compositions of the present invention may include at least an anionic
surfactant. Generally any anionic surfactant material may be used in the
inventive
compositions. By way of non-limiting example, particularly suitable anionic
surfactants
include: alkali metal salts, ammonium salts, amine salts, or aminoalcohol
salts of one or
more of the following compounds (linear and secondary): alcohol sulfates and
sulfonates, alcohol phosphates and phosphonates, alkyl sulfates, alkyl ether
sulfates,
sulfate esters of an alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride
sulfates,
alkyl sulfonates, olefin sulfonates, paraffin sulfonates, beta-alkoxy alkane
sulfonates,
alkylamidoether sulfates, alkylaryl polyether sulfates, monoglyceride
sulfates, alkyl ether
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sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkyl benzene
sulfonates,
alkylamide sulfonates, alkyl monoglyceride sulfonates, alkyl carboxylates,
alkyl
sulfoacetates, alkyl ether carboxylates, alkyl alkoxy carboxylates having 1 to
5 moles of
ethylene oxide, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide
sulfosuccinates, alkyl sulfosuccinamates, octoxynol or nonoxynol phosphates,
alkyl
phosphates, alkyl ether phosphates, taurates, N-aryl taurates, fatty taurides,
fatty acid
amide polyoxyethylene sulfates, isethionates, aryl isethionates, and
saxcosinates, aryl
sarcosinates, or mixtures thereof. Generally, the alkyl or aryl radical in
these various
compounds comprise a carbon chain containing 12 to 20 carbon atoms.
Preferred anionic surfactants useful in forming the compositions of the
invention
include alkyl sulfates which may be represented by the following general
formula:
O
I I O+
RO-(CH~CH20)X-S-O M
O
wherein R is an straight chain or branched alkyl chain having from about ~ to
about 1 ~
carbon atoms, saturated or unsaturated, and the longest linear portion of the
alkyl chain is
1 S carbon atoms or less on the average, M is a ration which makes the
compound water
soluble especially an alkali metal such as sodium, or is ammonium or
substituted
ammonium ration, and x is from 0 to about 4. Of these, most preferred are the
non-
ethoxylated C12-C15 primary and secondary alkyl sulfates.
Exemplary commercially available alkyl sulfates include one or more of those
~0 available under the tradenames RHODAPON~ (ex. Rhone-Poulenc Co.) as well as
STEPANOL~ (ex. Stepan Chemical Co.). Exemplary alkyl sulfates which is
preferred
for use is a sodium lauryl sulfate surfactant presently commercially available
as
RHODAPON~ LCP (ex. Rhone-Poulenc Co.), as well a~ a further sodium lauryl
sulfate
surfactant composition which is presently commercially available as STEPANOL~
WA
~5 Extra (ex. Stepan Chemical Co.), which is amongst the most preferred
anionic surfactants
to be used in the inventive compositions. In certain preferred embodiments an
alkyl
sulfate is the sole anionic surfactant present.
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Particularly preferred anionic surfactants useful in forming the compositions
of
the invention include alkyl sulfonate anionic surfactants which may be
represented
according to the following general formula:
O
I I O+
R-(C H2~C H~O)X-S-O M
O
~ wherein R is an straight chain or branched alkyl chain having from about 8
to about 18
carbon atoms, saturated or unsaturated, and the longest linear portion of the
alkyl chain is
15 carbon atoms or less on the average, M is a cation which makes the compound
water
soluble especially an alkali metal such as sodium, or is ammonium or
substituted
ammonium cation, and x is from 0 to about 4. Most preferred are the C 12-C 1 S
primary
and secondary alkyl sulfates.
Exemplary, commercially available alkane sulfonate surfactants include one or
more of those available under the tradename HOSTAPUR~ (ex. Clariant). An
exemplary
and particularly alkane sulfonate which is preferred for use is a secondary
sodium alkane
sulfonate surfactant presently commercially available as HOSTAPUR~ SAS 60.
The anionic surfactant when present in the compositions of the present
invention
is present in an amount of from about 0.1 to about 10% by weight, more
preferably is
present in an amount of from about 0.1-10%wt., and most preferably is present
in an
amount of from about 0.5 to about 4%wt.
For example the compositions according to the invention may optionally further
comprise an allcyl ethoxylated carboxylate surfactant. In particular, the
alkyl ethoxylated
carboxylate comprises compounds and mixtures of compounds which may be
represented
by the formula:
Ri(OC~H4)ri OCH2C00- M+
wherein Rlis a C4-C18 alkyl, n i's from about 3 to about 20, and M is
hydrogen, a
solubilizing metal, preferably an alkali metal such as sodium or potassium, or
ammonium
or lower alkanolammonium, such as triethanolammonium, monoethanolammonium, or
diisopropanolammonium. The lower allcanol of such alkanolammonium will
normally be
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of 2 to 4 carbon atoms and is preferably ethanol. Preferably, Rl is a C12 -
Czs alkyl, n is
from about 7 to about 13, and M is an alkali metal counterion.
Examples of alkyl ethoxylated carboxylates contemplated to be useful in the
present invention include, but are not necessarily limited to, sodium buteth-3
carboxylate,
sodium hexeth-4 carboxylate, sodium laureth-5 carboxylate, sodium laureth-6
carboxylate, sodium laureth-8 carboxylate, sodium laureth-11 carboxylate,
sodium
laureth-13 carboxylate, sodium trideceth-3 carboxylate, sodium trideceth-6
carboxylate,
sodium trideceth-7 carboxylate, sodium trideceth-19 carboxylate, sodium
capryleth-4
carboxylate, sodium capryleth-6 carboxylate, sodium capryleth-9 carboxylate,
sodium
capryleth-13 carboxylate, sodium ceteth-13 carboxylate, sodium C1.2-zs pareth-
6
carboxylate, sodium C12-is par'eth-7 carboxylate, sodium Cla-is pareth-8
carboxylate,
isosteareth-6 carboxylate as well as the acid form. Sodium laureth-8,
carboxylate, sodium
laureth-13 carboxylate, pareth-25-7 carboxylic acid are preferred. A
particularly preferred
sodium laureth-13 carboxylate can be obtained from Finetex Inc. under the
trade name
1~ Surfine~ WLL or from Clariant Corp. under the trade name Sandopan~ LS-24.
When present, the amount of alkyl ethoxylated carboxylate present in inventive
compositions are from about 0.01%wt. -10%wt., preferably from about 0.1-10%wt.
but
most preferably from about 0.5 - 4%wt.
By way of non-limiting example exemplary amphoteric surfactants include one or
~0 more water-soluble betaine surfactants which may be represented by the
.general formula:
C H3
R~-N-R~-C 00-
C H3
2~ wherein: Rl is an alkyl group containing from 8 to 18 carbon atoms, or the
amido radical
which may be represented by the following general formula:
O H
II I
R-C. N-(CH~)a R~
wherein R is an alkyl group having from 8 to 18 carbon atoms,
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a is an integer having a value of from 1 to 4 inclusive, and
Ra is a Cl-C4 alkylene group. Examples of such water-soluble betaine
surfactants include
dodecyl dimethyl betaine, as well as cocoamidopropylbetaine.
When present, any amphoteric surfactants present in the compositions of the
present invention are desirably included in an amount of from about 0.1 to
about 10% by
weight, more preferably is present in an amount of from about 0.3-5%wt., and
most
preferably is present in an amount of from about 0.3%wt. to about 3%wt.
Most desirably, the total amount of detersive surfactants present in the
inventive
compositions, inclusive of the necessary anionic surfactants and any further
optional
surfactants does not exceed about 10%wt., more preferably does not exceed
about 5%wt.
of the total weight of the inventive composition.
Optionally, but in many cases desirably, the inventive compositions comprise
one
or more organic solvents. By way of non-limiting example exemplary useful
organic
solvents which may be included in the inventive compositions include those
which axe at
i 5 least partially water-miscible such as alcohols (e.g., low molecular
weight alcohols, such
as, for example, ethanol, propanol, isopropanol, and the like), glycols (such
as, for
example, ethylene glycol, propylene glycol, hexylene glycol, and the like),
water-
miscible ethers (e.g. diethylene glycol diethylether, diethylene glycol
dimethylether,
propylene glycol dimethylether), water-miscible glycol ether (e.g. propylene
glycol
monomethylether, propylene glycol mono ethylether, propylene glycol
monopropylether,
propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene
glycol
monomethylether, diethyleneglycol monobutylether), lower esters of
monoalkylethers of
ethylene glycol or propylene glycol (e.g. propylene glycol monomethyl ether
acetate),
and mixtures thereof. Glycol ethers having the general structure Ra-Rb-OH,
wherein Ra
is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms,
and Rb is an
ether condensate of propylene glycol and/or ethylene glycol having from one to
ten
glycol monomer units. Of course, mixtures of two or more organic solvents may
be used
in the organic solvent constituent.
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When present, the organic solvent constituent is present in the compositions
of the
present invention in an amount of from about 0.1 to about 10% by weight, more
preferably is present in an amount of from about 0.3 - 7%wt., and most
preferably is
present in an amount of from about 0.5%wt. to about 4%wt.
According to certain particularly preferred embodiments, the inventive
compositions exclude added organic solvents, particularly as described
immediately
above. It is recognized that organic solvents may be present as carriers for
certain other
constituents essential to the present invention, and these may be present;
generally the
total amount of such organic solvents, if present, is less than about than 0.1
%wt., more
preferably less than 0.05%wt. and most preferably comprise no organic solvents
as
described above.
While optional, the compositions of the invention may further include an
oxidizing agent, which is preferably a peroxyhydrate or other agent which
releases
hydrogen peroxide in aqueous solution. Such materials are per se, known to the
art.
Such peroxyhydrates are to be understood as to encompass hydrogen peroxide as
well as
any material or compound which in an aqueous composition yields hydrogen
peroxide.
Examples of such materials and compounds include without limitation: alkali
metal
peroxides including sodium peroxide and potassium peroxide, alkali perborate
monohydrates, alkali metal perborate tetrahydrates, alkali metal persulfate,
alkali metal
percarbonates, alkali metal peroxyhydrate, alkali metal peroxydihydrates, and
alkali
metal carbonates especially where such alkali metals are sodium or potassium.
Further
useful are various peroxydihydrate, and organic peroxyhydrates such as urea
peroxide.
Desirably the oxidizing agent is hydrogen peroxide.
Desirably the oxidizing agent, especially the preferred hydrogen peroxide is
present in the inventive compositions in an amount of from about 0.01%wt. to
about
10.0%wt., based on the total weight of the composition of which it forms a
part.
Minor amounts of stabilizers such as one or more organic phosphonates,
stannates, pyrophosphates, as well as citric acid as well as citric acid salts
may be
included and are considered as part of the oxidizing agent. The inclusion of
one or more
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such stabilizers aids in reducing the decomposition of the hydrogen peroxide
due to the
presence of metal ions and or adverse pH levels in the inventive compositions.
The compositions of the present invention can also optionally comprise one or
more further constituents which are directed to improving the aesthetic or
functional
features of the inventive compositions. By way of non-limiting example such
further
constituents include one or more coloring agents, fragrances and fragrance
soiubilizers,
viscosity modifying agents, other surfactants, pH adjusting agents and pH
buffers
including organic and inorganic salts, optical brighteners, opacifying agents,
hydrotropes,
antifoaming agents, enzymes, anti-spotting agents, anti-oxidants,
preservatives, and anti-
corrosion agents. When one or more of the optional constituents is added,
i.e., fragrance
and/or coloring agents, the aesthetic and consumer appeal of the product is
often
favorably improved. The use and selection of these optional constituents is
well known
to those of ordinary skill in the art. When present, the total amount the one
or more
optional constituents present in the inventive compositions do not exceed
about 10%wt.,
preferably do not exceed 5%wt., and most preferably do not exceed about 3%wt.
Certain optional constituents which are nonetheless desirably present in the
inventive
compositions are pH adjusting agents and especially pH buffers. Such pH
buffers include
many materials which are known to the art and which are conventionally used in
hard
surface cleaning and/or hard surface disinfecting compositions. By way of non-
limiting
example pH adjusting agents include phosphorus containing compounds,
monovalent and
polyvalent salts such as of silicates, carbonates, and borates, certain acids
and bases,
tartrates and certain acetates. Further exemplary pH adjusting agents include
mineral
acids, basic compositions, and organic acids, which are typically required in
only minor
amounts. By way of further non-limiting example pH buffering compositions
include the
alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates,
tetraphosphates,
silicates, metasilicates, polysilicates, carbonates, hydroxides, and mixtures
of the same.
Certain salts, such as the alkaline earth phosphates, carbonates, hydroxides,
can also
function as buffers. It may also be suitable to use as buffers such materials
as
aluminosilicates (zeolites), borates, aluminates and certain or-ganic
materials such as
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gluconates, succinates, maleates, and their alkali metal salts. When present,
the pH
adjusting agent, especially the pH buffers are present in an amount effective
in order to
maintain the pH of the inventive composition within a target pH range.
As the compositions are largely aqueous in nature, and comprises as the
balance
of the composition water in to order to provide to 100% by weight of the
compositions of
the invention. The water may be tap water, but is preferably distilled and is
most
preferably deionized water. If the water is tap water, it is preferably
substantially free of
any undesirable impurities such as organics or inorganics, especially minerals
salts which
are present in hard water which may thus undesirably interfere with the
operation of the
constituents present in the aqueous compositions according to the invention.
The inventive compositions provide certain technical benefits when used on
hard
surfaces, particularly: satisfactory removal of hard water stains,
satisfactory removal of
soap scum stains, and satisfactory disinfection or sanitization of hard
surfaces. In
preferred embodiments, the compositions are readily pumpable using a manually
operable trigger spray apparatus are be desirably provided as a ready to use
product in a
container package which comprises a manually operable trigger spray apparatus
and a
non-pressurized reservoir or bottle for containing the inventive compositions.
In use, the
consumer generally applies an effective amount of the composition and within a
few
moments thereafter, wipes off the treated area with a rag, towel, brush or
sponge, usually
a disposable paper towel or sponge. In certain applications, however,
especially where
undesirable stain deposits are heavy, the composition according to the
invention may be
left on the stained area until it has effectively loosened the stain deposits
after which it
may then be wiped off, rinsed off, or otherwise removed. For particularly
heavy deposits
of such undesired stains, multiple applications may also be used.
A particularly advantageous feature of the inventive compositions is that as
the
suspended inclusions are visibly discrete and visibly discernible to the
consumer, these
same inclusions are visible to the consumer on hard surfaces to which the
inventive
compositions have been applied. This permits for ready visual inspection of
the coverage
of the hard surface by an inventive compositions immediately after application
of the
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composition by a consumer. Such provides not only an attractive attribute to
commercial
products based on such compositions but also provides a visual indicator to
the consumer
of thorough coverage and contact with hard surfaces. This visual indicator
provides an
important means whereby the consumer may visually inspect a surface,
particularly a
surface wherein the presence of undesired microorganisms is suspected, to
ensure that
thorough coverage and contact with said hard surface is realized. As is known,
physical
contact between the inventive composition and undesired microorganisms is
required in
order to the inventive compositions to provide a disinfecting effect.
An important technical characteristic lies in rheology of the inventive
compositions. The compositions may be described as being rheopectic at lower
shear
rates, an especially upon standing in quiescent state, but are thixotropic at
higher shear
rates. Such dual properties are very advantageous, as when the compositions
are at rest
in a container, e.g., upon standing, their rheopectic behavior provides for
the stable
suspension of the inclusions described herein. When it is desired to dispense
the .
compositions from a container especially through a manually operable trigger
pump
spray apparatus, the thixotropic characteristics of the compositions permit
for their
dispensing through the nozzle of such a pump spray apparatus. An exemplary
manually
operable trigger pump spray apparatus, such as a "Specialty Trigger Pump
Spray/Of~'
(ex. Owens-Illinois Corp.). Ideally, after being dispensed from such a pump
spray
apparatus and onto a surface, especially an inclined surface the compositions
return to a
quiescent state and once again display a rheopectic behavior. Furthermore, as
at least
some of the suspended inclusions are delivered from the composition and onto
the
surface, these inclusions are present on the surface and provide a useful
indicator as to the
coverage of the sprayed composition onto the surface.
Alternatively in certain preferred embodiments the compositions of the
invention
may be provided in a conventional aerosol as well, and a propellant added to
the
constituents making up the composition. However the latter use of the
inventive
compositions in an aerosol dispenser is unlikely to be adopted for practical
use as current
conventional aerosol dispenser are typically metal canisters which do not
readily permit
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for the consumer to enjoy the appearance of the visibly discernible, visibly
discrete
particulate materials as suspended inclusions when the compositions are in a
quiescent
state. Nonetheless, the use of compositions provided in aerosol canisters does
provide
the benefit of pressurized dispensing of the composition, and the composition
applied to a
hard surface does present the visibly discernible, visibly discrete
particulate materials on
a treated surface. Nonetheless, the use of a manually operable trigger pump
spray
apparatus with the inventive compositions is usually preferred.
The inventive compositions are desirably provided as a ready to use product
which may be directly applied to a hard surface. By way of example, hard
surfaces
suitable for coating with the polymer include surfaces composed of refractory
materials
such as: glazed and unglazed tile, brick, porcelain, glazed ceramics, vitreous
ceramics
such as china; glass; metals; plastics, e.g. polyester, vinyl, fiberglass,
Formica~,
Corian~; and other hard surfaces known to the industry. Such known hard
surfaces are
usually non-porous. Hard surfaces which are to be particularly denoted are
lavatory
fixtures such as shower stalls, bathtubs and bathing appliances (racks,
curtains, shower
doors, shower bars) toilets, bidets, wall and flooring surfaces especially
those which
include refractory materials and the like. Further hard surfaces which are to
be denoted
are those associated with kitchen environments and other environments
associated with
food preparation, including cabinets and countertop surfaces as well as walls
and floor
surfaces especially those which include refractory materials, plastics, and
glass. Still
further hard surfaces include those associated with medical facilities, e..g.,
hospitals,
clinics as well as laboratories, e.g., medical testing laboratories.
The compositions according to the invention are easily produced by any of a
number of known art techniques. Conveniently, a part of the water is supplied
to a
2~ suitable mixing vessel further provided with a stirrer or agitator, and
while stirring, the
remaining constituents are added to the mixing vessel, including any final
amount of
water needed to provide to 100%wt. of the inventive composition. The order of
addition
is often not critical but preferably, under constant stirring, to a portion of
the water is first
added the thickener constituent, thereafter stirring is allowed to continue
until the
CA 02516731 2005-08-19
WO 2004/074421 PCT/GB2004/000609
thickener constituent is homogenously distributed in the water. Preferably a
homogenizer
or other high shear mixing device is used however so to ensure the uniform
mixing of the
thickener constituent in the compositions taught herein. Subsequently the
nonionic
surfactant is added, then the organic solvent if present, then the anionic
surfactant
followed by the remaining constituents, including optional constituent.
Thereafter, the
suspended inclusions are introduced, desirably as an aqueous slurry containing
the
alginate based inclusions in an aqueous carrier, and finally the remaining
quantity of
water needed to provide 100%wt. of the composition. While the process may be
practiced at room temperature (approx. 20°C) it may be advantageous to
heat the initial
charge of water to an elevated temperature, e.g., even in excess of
90°C to facilitate the
incorporation of one or more of the constituents, particularly the thickener
constituents
into the water.
The following examples below illustrate exemplary formulations and preferred
formulations of the inventive composition. It is to be understood that these
examples are
presented by means of illustration only and that further useful formulations
fall within the
scope of this invention and the claims may be readily produced by one skilled
in the art
and not deviate from the scope and spirit of the invention. Throughout this
specification
and in the accompanying claims, weight percents of any constituent are to be
understood
as the weight percent of the active portion of the referenced constituent,
unless otherwise
indicated.
Examales
Exemplary formulations illustrating certain preferred embodiments of the
inventive compositions and described in more detail in Table I below were
formulated
generally in accordance with the following protocol.
Into a suitably sized vessel, a measured amount of water was provided at a
temperature of between about 5°C-30°Cand under stirring using a
laboratory scale
homogenizer device, the thickener constituents were 'first added, and
homogenization was
permitted to continue for about 30 - 90 minutes until the thickened mixture
became
_~g_
CA 02516731 2005-08-19
WO 2004/074421 PCT/GB2004/000609
homogenous. The thickened mixture was then removed from the homogenizer device
and introduced into a laboratory beaker provided a motor driven propeller as a
stirrer.
Thereafter under constant uniform stirring the remaining constituents were
added in the
following sequence: surfactants, organic solvent (when present), acid, caustic
(sodium
hydroxide) and then the remaining constituents, with the suspended inclusions,
e.g.,
alginate beads in a slurry being added as the last constituent. Thereafter the
remaining
amount of water needed to provide 100%wt. of the composition. Mixing of the
constituents in the laboratory beaker took from about 30 - 90 minutes, and the
total time
of mixing generally lasted from about 60 minutes to about 180 minutes. In each
case,
mixing was maintained until the particular composition appeared to be
homogeneous, and
the suspended inclusions well dispersed. The exemplary compositions were
pourable,
readily pumpable using a manually operable trigger spray apparatus and
retained
exceptionally well mixed characteristics (i.e., stable mixtures) upon
standing.
Notwithstanding the above preferred protocol, other sequences of mixing and
orders of
addition of the constituents may be practiced.
Examples of inventive formulations are shown in Table 1 below (unless
otherwise
stated, the components indicated are provided as "100% active") wherein the
amounts of
the named constituents are indicated in %wlw. Deionized water was added in
"quantum
sufficient" to provide the balance to 100 paxts by weight of the compositions.
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WO 2004/074421 PCT/GB2004/000609
Table 1
Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 Ex.8
.
ellan um 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05
xanthan um 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10
linear primary 1.0 1.0 -- -- 1.0 1.0 1.0 1.0
C$-C,o
alcohol ethoxylated,
avg. 4.5 moles
etho lation~a~
fatty alcohol -- -- 1.0 -- -- -- -- --
etho late~b~
linear alcohol -- -- -- 1.0 -- -- -- --
alko latet~~
sodium lauryl 2.75 -- -- -- -- -- -- --
sulfate~d~
decyl (sulfophenoxy)-- 2.75 -- -- -- -- -- --
benzenesulfonic
acid, disodium
saltier
2-hydroxy-1,2,3-3.5 3.5 3.5 3.5 3.5 3.5 -- --
propanetricarbolic
acid
h drox acetic -- -- -- -- -- -- 3.5 --
acid
hydroxypropionic-- -- -- -- -- -- -- 3.5
acid
caustic soda 0.42 0.44 0.46 0.53 0.39 0.45 0.43 0.34
fra rance 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20
al inate beads 0.41 0.41 0.41 0.41 0.41 0.41 0.41 0.41
di water .s. .s. .s. .s. .s. .s. .s. .s.
pH 3.1 3.14 3.12 3.28 3.20 3.09 3.09 3.10
~
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WO 2004/074421 PCT/GB2004/000609
The identity of the individual constituents indicated above is listed on the
following table:
Table 2
ellan um Kelco e1 AFT 100% ex. Kelco
xanthan um Kelzan ASXT 100% ex. Kelco
linear primary C8-C~oAlfonic 810-4.5 (100%) (ex. Sassol)
alcohol
ethoxylated, avg.
4.5 moles
ethox lationta~
fatt alcohol etho Gena of 26-L-80 100% ex. Clariant
later
linear alcohol alleo Plurafac SL-62 100% ex. BASF
late ~
sodium lau I sulfate Ste anol WAC 30% ex. Ste an Co.
decyl (sulfophenoxy) Hostapur SAS 60 (60%) (ex. Clariant)
benzenesulfonic acid,
disodium saltte~
2-hyroxy-1,2,3- citric acid (100%) (ex. ADM)
ro anetricarbolic
acid
h drox acetic acid I colic acid 70% ex. DuPont
h drox ro ionic acid lactic acid 88%
caustic soda sodium h droxide 25% "ra on rade"
fra rance ro rieta com osition
alginate beads an aqueous suspension of alginate
beads
in an aqueous carrier containing
a 2%
concentration of calcium chloride;
the
drained weight of the beads comprises
73% of the total ~nieight of
the aqueous
suspension of alginate beads
(ex.
eniaLabs Biotechnolo ie, German
di water deionized water
Certain of the compositions described on Table 1 above were tested to evaluate
certain technical characteristics of the compositions.
Evaluation of viscositv:
The viscosity of certain of the compositions were evaluated utilizing using an
LVTDV II Brookfield Viscometer, #1 spindle at 30 rpm and 25°C. The
viscosity of
certain of the exemplary compositions is reported in the following table:
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Table 3
Exam 1e formulation: Viscosit
Ex.1 143 c s
Ex.2 86.8 c s
Ex.3 91.2 c s
Ex.4 84.8 c s
Ex.S 98.2 c s
Ex.6 88.2 c s
Ex.7 95.9 c s
_ 88.2 cps
Ex.8
Evaluation of spra aby_ ility:
A quantity of a sample composition was placed into the interior of a non-
pressurized bottle to which was affixed a manually operable "Specialty Trigger
Pump
Spray/OfP' hex. Cwens-Illinois Corp.) trigger spray device. A vertical glass
panel was
used with the device to evaluate the sprayability characteristics of a sample
composition.
At varying distances from as little as 4 inches to as far as 24 inches, a
composition was
dispensed from the trigger spray device which was held perpendicularly to the
vertical
glass panel. The delivery of the composition from the trigger spray device,
and the
wetting characteristics of the composition were observed and evaluated. To be
considered a "pass" the composition need be dispensed in a generally uniform
spray from
the trigger spray device within the range of 4 - 24 inches, and especially at
about 18 from
the vertical .glass panel, and to generally even wet out the surface and not
form a
preponderance of beads or droplets which clung to the vertical glass panel
without
dispersing after contact.
Each of the formulations according to the invention described on Table 1 were
considered to "pass" the spray test described above.
Evaluation of Efficacy a.~ainst Soap Scum:
The efficacy of inventive compositions in removingsoap scum from a hard
surface was evaluated in accordance with CSMA Methods DCC-16 (iVlay 1995)
titled
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WO 2004/074421 PCT/GB2004/000609
"Guidelines for Evaluating the Efficacy of Bathroom Cleaners - Part 2:
'Scrubber Test for
Measuring the Removal of Lime Soap". This test is described .generally as
follows:
First, a "paxent" soil is made, based on the following formulation:
~~~"Parent"~soij.....................................................olo~~w/w..
..
..
.....y.... .......
~bar~~soa ~...................................................................
: 3.90'.
..................................................................;........~
. ................................;
sham oo 0.35
: ........
~ .........
...........................................................................
...
.
_ ,
~cla 0.06
..~............................................................................
......q.....:..............................<
:artificial sebum............................................
........... 0.15
...
....
'.
.
~hard~~water 95.54
The parent soil was produced according to the following steps: First, the bar
soap
was shaved into a suitable beaker. Afterward the remaining constituents were
added in
the order given above and stirred with three-blade propeller mixer. Next, the
contents of
the beaker was heated to 45-50°C and mixed until a smooth, lump-free
suspension was
achieved. This usually required about two hours with moderate agitation.
Subsequently,
the contents of the beaker were filtered through a Buchner funnel fitted with
Whatman #1
filter paper or equivalent. The filtrate was then resuspended in clean,
deionized water,
using the same amount of water used to make the soil, and this was filtered
again. The
(re-filtered) filtrate was uniformly dried.overnight at 45°C to form a
~.lter cake.
Thereafter, the filter cake was pulverized and was suitable for immediate use,
or may be
stored in a sealed container for up to six months.
The test substrates (tiles) were prepared in the following manner: each tile
was
thoroughly washed (using a commercially available hand dishwashing detergent
such as,
Dove~) and scrubbed using a non-metallic scouring pad (such as a Chore Boy~
Long
Last scrubbing sponge). The washed tiles were then permitted to dry in an oven
at
40.5°C overnight, then withdrawn and allowed to cool to room
temperature ~approx.
20°C) before being provided with the standardized "hard water" test
soil. It is to be noted
that for each test, new tiles were utilized, namely, the tiles were not
reused.
In preparation for supplying the tiles with an amount of the test soil, a test
soil was
prepared based on the following formulation:
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WO 2004/074421 PCT/GB2004/000609
Test~~soil'..'.................................................................
...................%w/w
.. ~......
.....a..... ........
...........<
.......anent"soij..............................................................
...4.50
. p
...............................................................................
...........................................................
~~
~
water 9.0
hard
.~....~rochloric~~acid...o.........Ø77........
~~N....................................................................<
..
:.....Y...................................................~.................?..
...................................
.acetone.......................................................................
............................85:
73.............
The test soil was produced according to the following steps: The constituents
indicated
were introduced into a clean beaker, with the acetone being added prior to the
water, and
the 'parent' soil being added last. The contents of the beaker were mixed
using a
standard three blade laboratory mixer until the contents formed a uniform
mixture, and
the color changed from white to gray. This typically required 20-40 minutes,
during
which time the beaker was covered as much as possible to avoid excessive
solvent loss.
Next, a suitable quantity of the contents of the test soil from the beaker was
provided to
an artist's airbrush while the beaker was swirled to ensure soil uniformity.
(If testing
required more than one day, a fresh amount of test soil was prepared daily and
used for
that day's testing.)
Soil was applied to a number of clean, dry tiles placed into rows and columns
in
preparation for depositing of the test soil. The airbrush was operated at 40
psi, and the
test soil was sprayed to provide a visually uniform amount of soil onto the
tiles.
(Uniform soil suspension during application was maintained by continuous brush
motion
and/or swirling of test soil in the airbrush.) In this manner, approximately
O.lOg-O.lSg
test soil were applied per tile.
The tiles were then allowed to air dry for approximately 30 minutes, during
which
time the a laboratory hotplate was preheated to approximately 320°C.
Each tile was
sequentially placed on the hotplate until the test soil began to melt, thereby
"aging" the
test soil. The melting of the test soil was observed carefully, and each tile
was removed
shortly before the soil began to coalesce into large droplets. This process
was repeated for
each tile, allowing the hotplate to recover to 320°C between tiles.
Subsequently each tile
was permitted to cool for at least about 30 minutes.
To evaluate cleaning, a treated test tile was placed in a Gardner Apparatus
and
secured. A dry 10 cm by 7.6 cm sponge was first rrioistened with 100 g of tap
water, and
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WO 2004/074421 PCT/GB2004/000609
the excess wrung out from the sponge. The sponge was then fitted into a
suitably sized
holder in the Gardner Apparatus. A 4-5 gram aliquot of a test formulation was
then
deposited directly onto the soiled surface of a tile, and allowed to contact
the tile for 15
seconds. Thereafter, the Gardner Apparatus was cycled for from 3 - 6 strokes.
The tile
was then rinsed with tap water, and dried with compressed air from an airbrush
compressor. This test was repeated several times for each formulation, using
new treated
test tile for each evaluation.
The tested tiles were evaluated by either reflective means, i.e., using a
Minolta
Chromameter in order to determine the change in reflectance between an
unsoiled,
untreated tile which was~used as a "control", and the reflectance of a soiled
tile which
was cleaned using a quantity of an inventive composition in accordance with
the test
protocol described above. According to the reflective means, the percentage of
hard
water soil removal was determined utilizing the following equation:
1 ~ % Removal = RC - RS X 100
RO - RS
where
RC = Reflectance of tile after cleaning with test product
RO = Reflectance of original soiled tile
RS = Reflectance of soiled tile
For each tile, a number of readings were taken and the results averaged to
provide a
median reading for each tile. Five tiles were used to evaluate each of the
tested
compositions and the average reading for each tile, as well as the averaged
reflectance
reading for all five tiles treated using a particular composition described in
Table 1 are
reproduced below. These results may be compared to the reflectance of an
unsoiled,
untreated tile which exhibited an averaged reflectance of 93.3% which was used
as a
"control". The tested tiles were evaluated, and the results are indicated on
the Table 4,
below.
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WO 2004/074421 PCT/GB2004/000609
Table
4
Tile: 1 2 3 4 5 Averaged
reflectance
readin
Ex. 63.9% 72.4% 69.3% 76.2% 71.8% 70.72%
1 '
Ex. 59.6% 50.0% 64.2% 63.1 60.8% 59.54%
%
Control:93.3% -- -- -- -- 93.3%
Evaluation of Antimicrobial Efficacy:
Several of the exemplary formulations described in more detail on Table 1
above
were evaluated in order to evaluate their antimicrobial efficacy against
Staphylocoecus
S aureus (gram positive type pathogenic bacteria) (ATCC 6538), Salmonella
choleraesuis
(gram negative type pathogenic bacteria) (ATCC 10708), Pseudomouas ae~csginosa
(ATCC 15442). The testing was performed in accordance with the protocols
outlined in
AOAC Official Method 961.02 "Germicidal Spray Products as Disinfectants", as
described in AOAC Official Methods of Analysis, 16th Ed., (1995).
As is appreciated by the spilled practitioner in the art, the results of the
AOAC
Germicidal Spray Test indicates the number of test substrates wherein the
tested
organism remains viable after contact for 10 minutes with a test disinfecting
composition
/ total number of tested substrates (slides) evaluated in accordance with the
AOAC
Germicidal Spray Test. Thus, a result of "0/15" indicates that of 15 test
substrates
bearing the test organism and contacted for 10 minutes in a test disinfecting
composition,
0 test substrates had viable (live) test organisms at the conclusion of the
test. Such a
result is excellent, illustrating the excellent disinfecting efficacy of the
tested
composition.
Results of the testing are indicated on Table 5, below. The reported results
indicate the number of test cylinders with live test organisms/nurnber of test
cylinders
tested for each example formulation and organism tested.
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Table 5
Test ResultsConclusion
Sta h lococcus aureus 0/15 ass
Salmonella choleraesuis0/15 ass
Pseudomonas aeruginosa 0/15 pass
~
As may be seen from the results indicated above, the compositions according to
the invention provide excellent cleaning benefits to hard surfaces, including
hard surfaces
with difficult to remove stains. These advantages are further supplemented by
the
excellent antimicrobial efficacy of these compositions against known bacteria
commonly
found in bathroom, kitchen and other environments. Such advantages clearly
illustrate
the superior characteristics of the compositions, the cleaning and
antimicrobial benefits
attending its use which is not before known to the art.
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