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Patent 2829311 Summary

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(12) Patent Application: (11) CA 2829311
(54) English Title: PEROXYGEN CONTAINING CLEANING SUBSTRATES WITH IMPROVED STORAGE STABILITY
(54) French Title: SUBSTRATS DE NETTOYAGE CONTENANT DU PEROXYDE D'HYDROGENE AYANT UNE STABILITE AMELIOREE AU STOCKAGE
Status: Deemed Abandoned and Beyond the Period of Reinstatement - Pending Response to Notice of Disregarded Communication
Bibliographic Data
(51) International Patent Classification (IPC):
  • C11D 17/04 (2006.01)
  • A47L 13/17 (2006.01)
  • C11D 01/62 (2006.01)
  • C11D 03/39 (2006.01)
  • C11D 03/48 (2006.01)
  • C11D 11/00 (2006.01)
(72) Inventors :
  • KASER, MATTHEW (United States of America)
(73) Owners :
  • RECKITT BENCKISER LLC
(71) Applicants :
  • RECKITT BENCKISER LLC (United States of America)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 2012-03-09
(87) Open to Public Inspection: 2012-09-20
Examination requested: 2017-02-07
Availability of licence: N/A
Dedicated to the Public: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/GB2012/050527
(87) International Publication Number: GB2012050527
(85) National Entry: 2013-09-06

(30) Application Priority Data:
Application No. Country/Territory Date
61/451,707 (United States of America) 2011-03-11

Abstracts

English Abstract

Peroxygen containing cleaning substrates, such as wipes and sponges which exhibit improved storage stability, and in preferred embodiments, also exhibit an antimicrobial benefit to hard surfaces treated with the peroxygen containing cleaning substrates.


French Abstract

L'invention concerne des substrats de nettoyage contenant du peroxyde d'hydrogène, tels que des lingettes et des éponges qui présentent une stabilité améliorée au stockage, et dans des modes de réalisation préférés, présentent également un bénéfice antimicrobien pour des surfaces dures traitées par les substrats de nettoyage contenant du peroxyde d'hydrogène.

Claims

Note: Claims are shown in the official language in which they were submitted.


Claims:
1. A peroxygen compound containing cleaning substrates which exhibits good
storage stability, and optionally but preferably also exhibits an anti-
pathogentic
benefit to hard surfaces which are treated with the said peroxygen compound
containing cleaning substrates, which cleaning substrates comprise:
a cleaning substrate pretreated with a finishing composition which
comprises at least one diamidoamine quaternary ammonium compound, and
impregnated in the cleaning substrate;
a largely aqueous composition which includes up to 5%wt. of a peroxygen
compound, and which optionally further includes an acid, a surfactant, an
organic
solvent or further optional constituent.
2. The cleaning substrate according to claim 1 wherein the peroxygen
compound is a
compound containing a dioxygen (O-O) bond.
3. The cleaning substrate according to claim 1 or 2 wherein the peroxygen
compound is selected from peracids, peracid salts, and peroxides.
4. The cleaning substrate according to any preceding claim wherein the
peroxygen
compound comprises, but preferably consists of, hydrogen peroxide.
5. The cleaning substrate according to any preceding claim wherein the
largely
aqueous composition comprises one or more C1-C4 monohydric alcohols.
6. The cleaning substrate according to any preceding claim wherein the
diamidoamine quaternary ammonium compound is selected from methyl-
bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, methyl
bis(oleylamidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and methyl
bis(hydr.tallowamidoethyl)-2-hydroxyethyl ammonium methyl sulfate.
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7. The cleaning substrate according to any preceding claim wherein the
cleaning
substrate comprises one or more aqueous insoluble polymer fibers, preferably
wherein the polymer used to form the fibers are based on polyolefin or
polyester
polymers.
8. A method for the treatment of hard surfaces which comprises the step of:
applying a cleaning substrate according to any preceding claim onto a hard
surface wherein the largely aqueous treatment composition contacts the hard
surface and provides a cleaning benefit, and optionally but preferably, also
provides an anti-pathogenic or antimicrobial benefit thereto.
9. A method for improving the storage stability of a cleaning substrate
containing a
largely aqueous composition which includes a peroxygen compound, the method
comprising the steps of:
pretreating the cleaning substrate with a at least one diamidoamine
quaternary ammonium compound, prior to applying the largely aqueous
composition which includes a peroxygen compound to the cleaning substrate.
10. A cleaning substrate comprising a one diamidoamine quaternary ammonium
compound, and which further comprises a largely aqueous treatment composition
according to one or more of the Examples.
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Description

Note: Descriptions are shown in the official language in which they were submitted.


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PEROXYGEN CONTAINING CLEANING SUBSTRATES WITH
IMPROVED STORAGE STABILITY
The present invention relates peroxygen containing cleaning substrates, which
cleaning substrates exhibit improved storage stability, and in preferred
embodiments
exhibit an antimicrobial benefit to hard surfaces which are treated with the
peroxygen
containing cleaning substrates.
A particularly popular class cleaning products are so-called wipes which are
typically a flexible cleaning substrate, such as a substantially planar thin
flexible wipe
article which is preimpregnated with the quantity of a surface treatment
composition, as
well as somewhat thicker, three-dimensional sponge type articles which are
also
preimpregnated with a quantity of a surface treatment composition. Such wipes
are
typically packaged either individually in a sealed, but breachable container
or as a
plurality of such wipes in an openable container but typically resealable or
closable
container. Subsequent to their manufacture and prior to their use such
manufactured
wipes are typically stored for a period of time, which can be weeks or months
prior to
their being used. It is during this storage that the chemical constituents
which are
impregnated into the wipe article are subject to undesirable reactions,
including the
degradation of one or more of the constituents. This is a particularly
notorious problem
wherein such wipe articles include a reactive constituents such as an
oxidizing agent in
particular a peroxygen compound, e.g., hydrogen peroxide. Hydrogen peroxide
provides
many advantages in treatment compositions which are supplied to a surface by
the
application (contact) of a wipe or other cleaning substrate especially in the
reduction or
eradication of undesired microorganisms, such as pathogens (bacteria, viruses,
etc.)
which may be present on services being treated with such wipe articles. Many
oxidizing
agents, and especially peroxygen compounds such as hydrogen peroxide is known
to
undergo degradation when stored for extended periods of time and/or when
stored at
elevated temperatures, e.g., 25'C or more, and especially at even higher
temperatures of
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30 C, 35 C, and 40 C. The degradation of hydroperoxide present within such a
wipe
article which is been packaged, and marketed for use in the treatment of hard
surfaces in
order to provide a cleaning benefit and especially a anti-pathogenic benefits
to treated
hard surfaces is particularly problematic. In order to ensure satisfactory
product
performance, the maximum retention of hydroperoxide or other oxidizing agent
present
within such a wipe article for an extended period of time is essential.
Admittedly, while there are currently widely commercially available a number
of
so-called wipes impregnated with a hard surface treatment composition which
comprise
peroxygen compounds, and especially hydrogen peroxide which are marketed as
providing a hard surface cleaning benefit an concurrently also a anti-
pathogenic benefits,
there is nonetheless a real and urgent need in the relevant order in order to
provide
improved so-called wipes impregnated with a hard surface treatment composition
comprising an a peroxygen compound and particularly hydrogen peroxide, wherein
such
wipes exhibit improved storage stability. It is to this object, as well as to
further objects,
that the present invention is directed. A full understanding of the benefits
of the present
invention will be understood from the following specification.
In one aspect, the present invention provides peroxygen compound containing
cleaning substrates, e.g, wipes, sponges, which cleaning substrates exhibit
improved
storage stability, and in preferred embodiments also exhibit an anti-
pathogentic benefit to
hard surfaces which are treated with the said peroxygen compound containing
cleaning
substrates.
A further aspect, the present invention provides a method for improving the
stability of peroxygen compounds, and especially hydrogen peroxide contained
within
cleaning substrates, e.g, wipes, sponges, over extended periods of time and/or
when the
cleaning substrates are stored at elevated temperatures, e.g., 25 C or more,
and especially
at even higher temperatures of 30 C, 35 C, and 40 C.
According to further aspect, the present invention provides a method for the
manufacture of peroxygen compound containing, cleaning substrates, e.g, wipes,
sponges, which cleaning substrates exhibit improved storage stability, and in
preferred
embodiments also exhibit an anti-pathogentie benefit to hard surfaces which
are treated
with the said hydrogen peroxide containing cleaning substrates.
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These and further aspects of the invention will become apparent from the
following description of the invention and from the several examples of
peroxygen
compound containing cleaning substrates described hereinafter.
The peroxygen compound containing cleaning substrates of the invention
comprise a largely aqueous treatment composition which is impregnated within,
or
applied onto a cleaning substrate. The largely aqueous treatment composition
comprises
at least water, and also comprises at least one or more peroxygen compounds,
and
especially preferably wherein the peroxygen compound comprises, or consists
of,
hydrogen peroxide. The peroxygen compound may be essentially any compound
containing a dioxygen (0-0) bond. Dioxygen bonds, particularly bivalent 0-0
bonds,
are readily cleavable, thereby allowing compounds containing them to act as
powerful
oxidizers. Non-limiting examples of classes of p eroxygen compounds include
peracids,
peracid salts, and peroxides such as hydrogen peroxide. The peroxygen can be
any
aliphatic or aromatic peracid (or peroxyacid) that is functional for
disinfectant pmposes
, 15 in accordance with embodiments of the present invention. While any
functional
peroxyacid can be used, peroxyacids containing from 1 to 7 carbons are the
most
practical for use. These peroxyacids can include, but not be limited to,
peroxyfoimic acid,
peroxyacetic acid, peroxyoxalic acid, peroxypropanoic acid, perlactic acid,
peroxybutanoic acid, peroxypentanoic acid, peroxyhexanoic acid, peroxyadipic
acid,
peroxycitric, and/or peroxyberizoic acid. Exemplary peracid salts include
permanganates,
perborates, perchlorates, peracetates, percarbonates, persulphates, and the
like.
Exemplary peroxide compounds include hydrogen peroxide, metal peroxides and
peroxyhydrates. The metal peroxides that can be used include, but are not
limited to,
sodium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, and/or
strontium peroxide. Other salts (for example sodium percarbonate) have
hydrogen
peroxide associated therewith are also considered to be a source of hydrogen
peroxide,
thereby producing hydrogen peroxide in situ.
Advantageously the peroxygen compound comprises up to about 5%wt.,
preferably up to about 3%wt., yet more preferably up to about 2%wt, still more
preferably up to about 1.5%wt., of the largely aqueous treatment compositions
which is
impregnated within, or applied onto a cleaning substrate. Advantageously also,
the
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peroxygen compound comprises at least about 0.01%wt., yet more preferably at
least
about 0.1%wt, still more preferably an amount of at least about 0.2%wt.,
0.3%wt.,
0.4%wt., 0.5%wt., 0.6%wt., 0.7%wt., 0.8%wt., 0.9%wt. and 1%wt. of the said
largely
aqueous treatment compositions.
As noted the peroxygen compound constituent of the invention comprises, or
consists of, hydrogen peroxide. Advantageously when two or more different
peroxygen
compounds are present in the largely aqueous treatment composition, then it is
preferred
that hydroperoxide or precursor or source thereof comprise at least 50% by
weight of the
peroxygen compound constituent, but more advantageously comprises at least
75%wt.,
and especially preferably comprises at least 80%wt., 85%wt., 90%wt., 95%wt.,
97%wt.,
98%wt., 99%wt. of the largely aqueous treatment composition which is
impregnated
within, or applied onto a cleaning substrate.
As is noted above, the compositions applied to the cleaning substrates are
largely
aqueous in nature. Water is added to order to provide to 100% by weight of the
largely
aqueous treatment compositions. 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 treatment compositions
applied to the wipe
articles according to the invention. Advantageously, water provides at least
90%wt, and
in order of increasing preference at least 91%wt., 92%wt., 93%wt., 94%wt.,
95%wt.,
96%wt., 97%wt. 98%wt., and 99%wt. of the aqueous treatment compositions which
is
impregnated within, or applied onto a cleaning substrate.
While, according to one aspect, the treatment compositions of the invention
comprises (preferably consists essentially of, or consists of) a peroxygen
compound,
especially preferably wherein the peroxygen compound is hydrogen peroxide, and
water,
according to further inventive aspects one or more further constituents are
also
necessarily present as well.
In certain embodiments, the aqueous treatment compositions further necessarily
include an acid constituent. One or more organic or inorganic acids which may
be used
to adjust the pH of the composition to a target range or level, and/or to
impart an
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antimicrobial benefit. The acids may be one or more of a water soluble
inorganic acids,
mineral acids, or organic acids, with virtually all such known materials
contemplated as
being useful in the aqueous treatment compositions. By way of non-limiting
example
useful inorganic acids include mineral acids, hydrochloric acid, phosphoric
acid, sulfuric
acid, and the like.
In certain embodiments, the aqueous treatment compositions may comprise or
necessarily comprise one or more organic acids which may be used to adjust the
pH of
the treatment composition, and which optionally may also provide an
antimicrobial
benefit. Exemplary organic acids are those which generally include at least
one carbon
atom, and include at least one carboxyl group (--COOH) in its structure.
Derivatives of
said organic acids are also contemplated to be useful. Exemplary organic acid
include
linear aliphatic acids such as acetic acid; dicarboxylic acids, acidic amino
acids, and
hydroxy acids such as glycolic acid, lactic acid, hydroxyacrylic acid, alpha-
hydroxybutyric acid, glyceric acid, malic acid, tartaric acid and citric acid,
as well as acid
salts of these organic acids. Of these, citric acid, sorbic acid, acetic acid,
boric acid,
formic acid, maleic acid, adipic acid, lactic acid, malic acid, malonic acid,
glycolic acid,
salicylic acid and/or derivatives thereof, e.g., salicylic acid derivatives
such as esters of
salicylic acid, such as ethylhexyl salicylate, dipropylene glycol salicylate,
TEA salicylate,
salicylic acid 2-ethylhexylester, salicylic acid 4-isopropyl benzylester,
salicylic acid
homomenthylester are preferred. Of course mixtures of one or more acids are
contemplated as being useful.
When present, such one or more acids may be present in any effective amount in
order to impart a desired pH range or level to the largely aqueous treatment
composition
impregnated within the cleaning substrate. Advantageously, the one or more
acids
comprise at least about 0.05%wt., yet more preferably at least about 0.1%wt.,
0.2%wt.,
0.25%wt., 0.3%wt., 0.35%wt., 0.4%wt., and 0.5%wt. of the largely aqueous
treatment
compositions. Similarly advantageously, the one or more acids comprise not
more than
about 2.5%wt, and preferably not more than about 2%wt., 1.9%wt.,
1.8%wt.,1.7%wt.,1.6%wt.,1.5%wt., 1.4%wt.,1.3%wt., 1.2%wt., 1.1%wt., and 1%wt.,
of
the largely aqueous treatment compositions. Preferably, when present, such one
or more
acids are selected from organic acids, and especially preferably why the acids
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demonstrated in one or more of the following Examples. Such organic acids may
be
present to the exclusion of inorganic acids. Citric acid is one such
particularly preferred
acid, and is demonstrated amongst the following Examples.
In certain embodiments the aqueous treatment compositions may comprise or
necessarily comprise, one or more surfactants. Such may be one or more
anionic,
nonionic, cationic, amphoteric or zwitterionic surfactants. The presence of
one or more
such surfactants which are advantageously included to typically provide for
the loosening
of soils or other hydrophobic matter which may be present on a surface being
treated with
the device of the invention. Such surfactants may be selected from one or more
of
anionic, nonionic, cationic, amphoteiic and zwitterionic surfactants. Such are
per se,
known to the art.
Non-limiting examples of usethl anionic surfactants include one or more of:
alcohol sulfates and sulfonates, alcohol phosphates and phosphonates, alkyl
ester sulfates,
alkyl diphenyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, sulfate
esters of an
alkylphenoxy polyoxyethylene ethanol, alkyl monoglyceride sulfates, alkyl
sulfonates,
alkyl ether sulfates, alpha-olefin sulfonates, beta-alkoxy alkane sulfonates,
alkyl ether
sulfonates, ethoxylated alkyl sulfonates, alkylaryl sulfonates, alkylaryl
sulfates, alkyl
monoglyceride sulfonates, alkyl carboxylates, alkyl ether carboxylates, alkyl
alkoxy
carboxylates having 1 to 5 moles of ethylene oxide,
alkylpolyglycolethersulfates
(containing up to 10 moles of ethylene oxide), sulfosuccinates, octoxynol or
nonoxynol
phosphates, taurates, fatty taurides, fatty acid amide polyoxyethylene
sulfates, acyl
glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene
oxide ether
sulfates, paraffin sulfonates, alkyl phosphates, isethionates, N-acyl
taurates, alkyl
succinamates and sulfosuccinates, alkylpolysaccharide sulfates,
alkylpolyglucoside
sulfates, alkyl polyethoxy carboxylates, and sarcosinates or mixtures thereof.
Anionic
soaps may also be used in the inventive compositions. Examples of the
foregoing anionic
surfactants are available under the following tradenames: Rhodapon , Stepanol
,
HostaputO, Surfine , Sandopan , and Biosoft tradenames.
Preferred examples of anionic surfactants include water soluble salts or acids
of
the formula (ROS03)xM or (RS03)õM wherein R is preferably a C6-C24
hydrocarbyl,
preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more
preferably a
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C12-C18 alkyl or hydroxyalkyl, and M is H or a mono-, di- or tri-valent
cation, e. g., an
alkali metal cation (e. g., sodium, potassium, lithium), or ammonium or
substituted
ammonium (e. g., methyl-, dimethyl-, and trimethyl ammonium cations and
quaternary
ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium
cations
and quaternary ammonium cations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like) and x is an
integer,
preferably 1 to 3, most preferably 1. Materials sold under the Hostapur and
Biosoft
trademarks are examples of such preferred anionic surfactants.
Exemplary useful nonionic surfactants are those which include a hydrophobic
base portion, such as a long chain alkyl group or an alkylated aryl group, and
a
hydrophilic chain portion comprising a sufficient number of ethoxy and/or
propoxy
moieties to render the nonionic surfactant at least partially soluble or
dispersible in water.
By way of non-limiting example, such nonionic surfactants include ethoxylated
alkylphenols, alkoxylated fatty alcohols, polyethylene glycol ethers of methyl
glucose,
polyethylene glycol ethers of sorbitol, ethylene oxidepropylene oxide block
copolymers,
ethoxylated esters of fatty (C6¨C24) acids, condensation products of ethylene
oxide with
long chain amines or amides, condensates of alkylene oxides, particularly
ethylene oxide
with sorbitan fatty acid esters, e.g., polyoxyethylene sorbitan monolaurate,
polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan trioleates,
alkoxylated alkanolamides, e.g. Cs-C24 alkyl di(C2-C3 alkanol amide) as well
as mixtures
thereof. Examples of the useful nonionic surfactants include materials are
available under
the Tomadol , Neodol , Rhodasurf , Genapol , Pluronic , Lutensol , Emulgen
and Alfonic tradenames. Further useful nonionic surfactants include
alkylmonoglycosides 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; examples include D-glucopyranoside,
available as
Glucopon 625 CS which is described as being a 50% C10 -C16 alkyl
polyglycoside.
One class of preferred nonionic surfactants include amine oxides. 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
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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, dimethyl cocoamine
oxide,
dimethyl (hydrogenated tallow) amine oxide, and myristyllpalmityl 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;
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) Alkylmmpholine 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:
R2 0
R1
wherein each:
RI is a straight chained CI-C4 alkyl group, preferably both R1 are methyl
groups;
and,
R2 is a straight chained C 8-C 18 alkyl group, preferably is C10-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 R2 groups which comprise at least 50%wt.,
preferably at
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least 60%wt. of C12 alkyl groups and at least 25%1Art. of C14 alkyl groups,
with not more
than 15%wt. of C16, C18 or higher alkyl groups as the R2 group.
The treatment compositions may include one or more amphoteric surfactants,
non-limiting examples of which are: derivatives of secondary and tertiary
amines having
aliphatic radicals that are straight chain or branched, and wherein one of the
aliphatic
substituents contains from about 8 to 18 carbon atoms and at least one of the
aliphatic
substituents contains an anionic water-solubilizing group, e.g., a carboxy,
sulfonate, or a
sulfate group, such as sodium 3-(dodecylamino)propionate, and sodium 3-
(dodecylarnino)propane-1-sulfonate, sarcosinates, taurates, amide
sulfosucchiates, and
betaines including phosphobetaines. Exemplary betaines include dodecyl
dimethyl
betaine, cetyl dimethyl betaine, and dodecyl amidopropyldimethyl betaine.
The treatment composition may also comprise one or more cationic surfactant
constituents, especially preferably one cationic surfactants which provide an
appreciable
germicidal benefit. Non-limiting examples ofpreferred cationic surfactant
compositions
which may be included in the treatment compositions are those which provide an
appreciable germicidal benefit, and especially prefeffed are quaternary
ammonium
compounds and salts thereof, which may be characterized by the general
structural
formula:
R2-N--R3
1=2.4
where at least one of RI, R2, R3 and R4 is a alkyl, aryl or alkylaryl
substituent of from 6 to
26 carbon atoms, and the entire cation portion of the molecule has a molecular
weight of
at least 165. The alkyl substituents may be long-chain alkyl, long-chain
alkoxyaryl, long-
chain alkylaryl, halogen-substituted long-chain alkylaryl, long-chain
alkylphenoxyalkyl,
arylalkyl, etc. The remaining substituents on the nitrogen atoms other than
the
abovementioned alkyl substituents are hydrocarbons usually containing no more
than 12
carbon atoms. The substituents RI, R2, R3 and R4 may be straight-chained or
may be
branched, but are preferably straight-chained, and may include one or more
amide, ether
or ester linkages. The counterion X may be any salt-forming anion which
permits water
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solubility or water miscibility of the quaternary ammonium complex. Preferred
quaternary ammonium compounds which act as germicides according to the
foregoing
formula are those in which R2 and R3 are the same or different C8-C12alkyl, or
R2 is C12-
C8_Balkylethoxy, C8_ isalkylphenolethoxy and R3 is benzyl, and X is a halide,
for
example chloride, bromide or iodide, or is a methosulfate anion. The alkyl
groups recited
in R2 and R3 may be straight-chained or branched, but are preferably
substantially linear.
Particularly useful quaternary germicides include compositions which include a
single quaternary compound, as well as mixtures of two or more different
quaternary
compounds. Such useful quaternary compounds are available under the Bardac ,
Barquat , Hyamine , Lonzabac , and Onyxide trademarks. When one or more
cationic surfactants which provide an appreciable germicidal benefit are
present, they
may be present as a co-antimicrobial agent, with a further antimicrobial agent
described
hereinafter. When one or more cationic surfactants which provide an
appreciable
germicidal benefit are present, preferably anionic surfactants and further
optionally,
amphoteric surfactants are omitted from the treatment compositions of the
invention.
Other surfactants, although not specifically disclosed herein but known to the
art may
also be used within the treatment compositions of the present invention.
When present, such one or more surfactants may be present in any effective
amount in order to impart a desired technical advantage, e.g. cleaning, and in
the case of
certain cationic surfactants, an ancillary antimicrobial benefit to the
largely aqueous
treatment composition impregnated within the cleaning substrate.
Advantageously, the
one or more surfactants comprise at least about 0.05%wt., yet more preferably
at least
about 0.1%wt., 0.2%wt., 0.25%wt., 0.3%wt., 0.35%wt., 0.4%wt., and 0.5%wt. of
the
largely aqueous treatment compositions. Similarly advantageously, the one or
more
surfactants comprise not more than about 5%wt., and preferably not more than
about
2.3%wt., 2.25%wt., 2.2%wt., 2.1%wt., 2%wt., 1.9%wt.,
1.8%wt.,1.7%wt.,1.6%wt.,1.5%wt., 1.4%wt.,1.3%wt., 1.2%wt., 1.1%wt., 1%wt.,
0.9%wt., 0.8%wt., 0.75%wt., 0.6%wt and 0.5%wt. of the largely aqueous
treatment
compositions. Preferably, when present, preferred surfactants are demonstrated
amongst
the following Examples.
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In certain embodiments the aqueous treatment compositions may comprise or
necessarily comprise, one or more organic solvents. By way of non-limiting
example
exemplary useful organic solvents which may be included in the treatment
compositions
include those which are at 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
mono alkylethers of ethylene glycol or propylene glycol (e.g. propylene glycol
monomethyl
ether acetate), and mixtures thereof. Of course, mixtures of two or more
organic solvents
may be used concurrently.
When present, such one or more organic solvents may be present in any
effective
amount in order to impart a technical benefit, e.g., cleaning benefit and/or
ancillary
antipathogentic benefit the largely aqueous treatment composition impregnated
within the
cleaning substrate. Advantageously, the one or more organic solvents comprise
at least
about 0.05%wt., yet more preferably at least about 0.1%wt., 0.2%wt., 0.25%wt.,
0.3%wt., 0.35%wt., 0.4%wt., 0.5%wt. of the largely aqueous treatment
compositions.
Similarly advantageously, the one or more organic solvents comprise not more
than about
5%wt, and preferably not more than about 4.5%wt., 4.25%wt., 4%wt., 3.9%wt.,
3.8%wt.,
3.7%wt., 3.6%wt., 3.5%wt., 3.4%wt., 3.3%wt., 3.2%wt., 3.1%wt., 3.0%wt.,
2.9%wt.,
2.8%wt., 2.7%wt., 2.6%wt., 2.5%wt., 2.4%wt., 2.3%wt., 2.2%wt., 2.1%wt.,
2.0%wt.,
1.9%wt., 1.8%wt.,1.7%wt.,1.6%wt.,1.5%wt., 1.4%wt.,1.3%wt., 1.2%wt., 1.1%wt.,
and
1%wt., of the largely aqueous treatment compositions. Preferably, when
present, such
one or more organic solvents include those demonstrated in one or more of the
following
Examples.
In certain preferred embodiments the organic solvent constituent comprises, or
consists (solely) of a single C1-C4monohydric alcohol or a plurality of CI-
C4monohydlic
alcohols. In certain preferred embodiments the organic solvent constituent
comprises, or
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consists (solely) of at least one monohydric alcohol with at least one glycol
ether. In
further prefen-ed embodiments the organic solvent constituent comprises, or
consists
(solely) of at least two different monohydric alcohols which are preferably
selected from
C1-C4 monohydric alcohols concurrently with at least one glycol ether solvent
constituent. Preferred combinations of organic solvents, including the
respective amounts
of each organic solvents present, are demonstrated in one or more of the
following
Examples.
The largely aqueous peroxygen compound containing treatment compositions
present in the cleaning substrates exhibit a pH in the range of about 1 to
about 3.5,
preferably in the range of about 2 to about 3. Preferably the pH may be
adjusted by the
inclusion of an appropriate amount of one or more acids as described
previously.
Specifically preferred pHs are demonstrated in the following Examples.
The pH of the said largely aqueous peroxygen compound containing treatment
compositions present in the cleaning substrates may also be adjusted by the
addition of
other constituents, such bases, inorganic salts, as well as one or more amine
compounds
such as one or more alkanolamines which in addition to providing an improved
cleaning
benefit may also be used to concurrently adjust the pH of the treatment
composition. By
way of nonlimiting examples such include monoalkanolamines, dialkanolarnines,
trialkanolamines, and alkylalkanolamines such as alkyl-dialkanolamines, and
dialkyl-
monoalkanolamines. The alkanol and alkyl groups are generally short to medium
chain
length, that is, from 1 to 7 carbons in length. For di- and trialkanolamines
and dialkyl-
monoalkanolamines, these groups can be combined on the same amine to produce
for
example, methylethylhydroxypropylhydroxylamine. One of skill can readily
ascertain
other members of this group.
The largely aqueous peroxygen compound containing treatment compositions
may include one or more further optional constituents which may be included to
provide
an improved aesthetic and/or technical benefit to the treatment compositions,
and or the
cleaning substrates impregnated with the said treatment compositions. When
present,
such further optional constituents are generally present in a cumulative
amount of less
than about 25%wt. based on the total weight of the largely aqueous peroxygen
compound
containing treatment compositions wherein one or more such further optional
constituents
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may be present. By way of non-limiting example such further optional
constituents
include one or more of: coloring agents, fragrances and fragrance
solubilizers, viscosity
modifying agents, further oxidizing agents, germicidal agents, further pH
adjusting
agents and buffers including organic and inorganic salts as well as
organic and
inorganic acids, chelating agents, and preservatives, as well as other
optional constituents
known to the skilled artisan. When one or more of the optional constituents is
added, i.e.,
fragrance, the esthetic and consumer appeal of the product is often favorably
improved.
The use and selection of these optional constituents should be based on
imparting a
desired additional aesthetic or technical benefit, as well as to ensure
compatibility with
the further constituents present in the inventive adhesive lavatory treatment
compositions,
especially such that the desirable properties, especially storage stability,
of the cleaning
substrate product impregnated with or containing the largely aqueous peroxygen
compound containing treatment compositions are not deleteriously diminished.
Optionally the inventive compositions may comprise a germicide constituent
(other than the cationic germicidally active quaternary ammonium halide
surfactants
noted above) which has germicidal or antimicrobial efficacy against at least
one of gram-
positive or gram-negative pathogens, e.g., bacteria or other microorganisms.
Such may
be based, for example, on one or more non-cationic antimicrobial compounds or
constituents, e.g., halophenols such 3-trifluoromethy1-4,4'-
dichlorocarbanilide, 3,3',4-
trichlorocarbanilide, as well as 2,4-dichloro-3,5-m-xylenol ("DCMX"). The
phenol
based non-cationic antimicrobials are preferred, of which parachlorometacresol
("PCMC") and especially parachlorometaxylenol ("PCMX").
Alternately such may be based, for example, on one or more phenol derivatives
such as those based on 2-hydroxydiphenyl compounds, including Tiiclosan (ex.
Ciba),
those based on 2,2'-hydroxy-5,5'-dibromo-diphenyl ethers, such as one or more
of
chlorophenols (o-, m-, p-), 2,4-dichlorophenol, p-nitrophenol, picric acid,
xylenol, p-
chloro-m-xylenol, cresols (o-, p-), p-chloro-m-cresol, pyrocatechol,
resorcinol, 4-n-
hexylresorcinol, pyrogallol, phloroglucin, carvacrol, thymol, p-chlorothymol,
o-
phenylphenol, o-benzylphenol, p-chloro-o-benzylphenol, phenol, 4-ethylphenol,
and 4-
phenolsulfonic acid, as well as further diphenol compounds such as
hexachlorophene,
tetrachlorophene, dichlorophene, 2,3-dihydroxy-5,5'-dichlorodiphenyl sulfide,
2,2'-
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dihydroxy-3,31,5,5'-tetrachlorodiphenyl sulfide, 2,2'-dihydroxy-3,51,5,51,
6,61-
hexachlorodiphenyl sulfide, and 3,3'-dibromo-5,51-dichloro-2,21-
dihydroxydiphenylamine, and especially "Triclocarban", 3,4,4"-
trichlorocarbanilide as
well as derivatives thererof.
The optional germicide constituent may also be based on one or more acids,
including organic acids such as salicylic and citric acid, and/or inorganic
acid such as
hydrochloric acid when present in effective amounts in order to sufficiently
acidify the
treatment composition formed from the inventive compositions.
Optionally there may be included a small amount (preferably less than 1%wt.)
of
chelating agents or mixtures to deactivate trace catalytic impurities,
thereof. Such may
have a beneficial effecting improving the storage stability of the peroxygen
compound(s).
Exemplary suitable phosphonate chelating agents for use herein may include
alkali metal
ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate),
as well
as amino phosphonate compounds, including amino aminotri(methylene phosphonic
acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diarnine tetra
methylene phosphonates, and diethylene triamine penta methylene phosphonates
(DTPMP). The phosphonate compounds may be present either in their acid form or
as
salts of different cations on some or all of their acid fimctionalities.
Preferred
phosphonate chelating agents to be used herein are diethylene triamine penta
methylene
phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such
phosphonate
chelating agents are commercially available from Monsanto under the trade name
DEQUEST .
The compositions may also include a small amount of an antifoaming agent;
typically silicone antifoaming agents comprising silicone and siloxane
polymers often
provided as emulsions in water. A particularly suitable antifoam agent is a
polydimethylsiloxane composition. Such silicone antifoaming agents comprising
silicone
and siloxane polymers in aqueous emulsions are widely commercially available.
The total amount of the largely aqueous peroxygen compound containing
treatment compositions applied to a cleaning substrate may vary, but typically
the
treatment composition is applied to the cleaning substrate on a wt:wt ratio
basis of the
former to the latter of about 40-0.5:1, preferably about 15-1:1. It is
preferred, especially
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wherein the cleaning substrate is a wipe formed of substantially polymeric
fibers that the
amount of the largely aqueous peroxygen compound containing treatment
composition be
at least equal to, per preferably in excess of the weight of the wipe.
Particularly
advantageously, the respective weight ratios of the treatment composition:wipe
falls in
the range of about 10-2:1. In such manner the retention of the treatment
composition
within the wipe prior to use in the treatment of a hard surface, as well as
for the effective
delivery of the treatment composition from the wipe onto the hard surface
being released
by the cleaning substrate can be provided.
The cleaning substrates can be of a woven or non-woven nature. Non-limiting
examples of cleaning substrates to which the foregoing compositions may be
applied
include woven or nonwoven wipe articles, nonwoven or woven pouches, sponges,
any of
which may also include a later or part thereof which includes an abrasive
material or
abrasive layer. The cleaning substrates can be resin bonded, hydroentanged,
thermally
bonded, meltblown, needlepunched or any combination of the former. The
cleaning
substrates may also be open celled or closed celled polymers especially foams,
e.g.
sponges.
The cleaning substrates may also be in the form of sponges which are formed
from regenerated cellulose, or formed from other foamed materials such as
foamed
hydrophobic or hydrophilic synthetic polymers.
Nonlimiting examples of wipes useful as the cleaning substrate may also be
nonwoven fabrics formed from a combination of wood pulp fibers and textile
length
synthetic fibers formed by well known dry-form or wet-lay processes. Synthetic
fibers
such as rayon, nylon, orlon and polyester as well as blends thereof can be
employed. The
wood pulp fibers should comprise about 30 to about 60 percent by weight of the
nonwoven fabric, preferably about 55 to about 60 percent by weight, the
remainder being
synthetic fibers. The wood pulp fibers provide for absorbency, abrasion and
soil
retention whereas the synthetic fibers provide for substrate strength and
resiliency.
Further nonlimiting examples of preferred wipes are those which are
substantially
formed of, meaning at least 75%wt., and in order of increasing preference, at
least;
80%wt., 85%wt., 90%wt., 92%wt, 93%wt., 94%wt., 95%wt., 96%wt., 97%wt., 98%wt.,
99%wt. and 100%wt. of one or more aqueous insoluble polymer fibers, preferably
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wherein the polymer used to form the fibers are based on polyolefin or
polyester
polymers, such as polyalkylene terephthalate polymers. Copolymers containing
polyolefin or polyester groups may also be used, preferably wherein at least
about
50%wt, of the polymer is based on polyolefin or polyester polymers. Blends of
different
fibers fonned of different polymers are also useful, preferably at least
50%wt. of fibers
used to form a wipe are based on polyolefin or polyester polymers.
The substrate of such a wipe may also be a film forming material such as a
water
soluble polymer. Such self-supporting film substrates may be sandwiched
between layers
of fabric substrates and heat sealed to form a useful substrate. The free
standing films
can be extruded utilizing standard equipment to devolatilize the blend.
Casting
technology can be used to form and dry films, or a liquid blend can be
saturated into a
carrier and then dried in a variety of known methods.
It is an essential and characterizing feature of the invention that, prior to
the
application of the largely aqueous peroxygen compound containing compositions
described above that the cleaning substrate, preferably a wipe or sponge, or a
part or
element thereof has been pretreated with a finishing composition which
comprises at least
one diamido amine quaternary ammonium compound. Exemplary amidoamine
quatemaiy ammonium compounds that can be used according to the invention are
methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, methyl
bis(oleylamidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and methyl
bis(hydr.tallowamidoethyl)-2-hydroxyethyl ammonium methyl sulfate. Examples of
such
materials which are presently commercially available include those marketed
under the
name Accosoft (ex. Stepan), and Varisoft (ex. Evonik Industries).
Particularly
preferred is methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl
sulfate,
which is commercially available in a preparation marketed as Accosoft 501
(ex. Stepan)
which is described to contain 3%wt. of methyl-bis(tallow amidoethyl)-2-
hydroxyethyl
ammonium methyl sulfate, and 2%wt. of an alkoxylated acid. In preferred
embodiments
of the invention an alkoxylated acid compound is also necessarily present
within the
finishing composition used to pretreat the cleaning substrate.
The inventors have unexpectedly and suiprisingly found that when fibers, and
or
cleaning substrates formed from fibers are pretreated with such a finishing
composition,
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that an appreciable improvement in the storage stability of the cleaning
substrate
containing the largely aqueous peroxygen compound containing compositions
described
above is realized. At the same time, in preferred embodiments, the resultant
articles
provided by the invention, viz., the cleaning substrate the largely aqueous
peroxygen
compound containing compositions described above also provide a useful anti-
pathogenic benefits to hard surfaces treated with the said articles.
As noted above, the finishing composition which comprises at least one
diamidoamine quaternary ammonium compound is applied to the fibers used form a
wipe, and/or to a sponge, and/or to a cleaning substrate which is formed from
fibers
and/or a polymeric foam. The said finishing composition may be applied in a
conventional manner to the cleaning substrate or to any materials, e.g.
fibers, used to
form the cleaning substrate. According to a preferred embodiment, the cleaning
substrate
is formed, and thereafter a largely aqueous composition comprising the
finishing
composition, or alternately a largely aqueous composition comprising at least
the
diamidoamine quaternary ammonium compound is contacted with the cleaning
substrate
or any material part thereof, and thereafter the bulk of the water is
withdrawn.
Concurrently, at least a part of the diamidoamine quaternary ammonium compound
is
retained upon the cleaning substrate or component part thereof, and
advantageously
between 0.001 - 1%wt., preferably between 0.001 ¨ 0.35%wt. of the cleaning
substrate or
component part thereof is the diamidoamine quaternary ammonium compound.
Thereafter the largely aqueous peroxygen compound containing compositions
described
above may be applied.
The largely aqueous peroxygen compound containing compositions of the present
invention are absorbed onto the cleaning substrate, e.g., sponge or wipe to
impregnate
the cleaning substrate. The cleaning wipe can then be sealed individually in a
pouch
which can then be opened when needed or a multitude of wipes can be placed in
a
container for use on an as-needed basis. The container, when closed, is
sufficiently
sealed to prevent evaporation of any components from the compositions.
The articles provided by the present invention are particularly useful in the
treatment of hard surfaces. By way of non-limiting example, hard surfaces
include
surfaces composed of refractory materials such as: glazed and unglazed tile,
brick,
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porcelain, ceramics as well as stone including marble, granite, and other
stones surfaces;
glass; metals; plastics e.g. polyester, vinyl; fiberglass, Formica , Conan
and other hard
surfaces known to the industry, as well as flooring surfaces, e.g., wood,
tile, glass,
ceramic, cement surfaces, grout, linoleum, and the like. Further hard suifaces
include
nonporous surfaces which may be found in areas or spaces found in domestic or
industrial or institutional environments, especially areas used for the
preparation of food,
in nurseries, in child daycare centers, in nursing homes, in clinics, in
hospitals and in
other locations wherein healthcare services or are provided. The cleaning
articles of the
invention may be used in virtually any environment or in any application
wherein the
treatment of hard surfaces in order to provide a cleaning and/or anti-
pathogenic or
antimicrobial treatment benefit is desired.
According to a further aspect of the invention, there is provided a method for
the
treatment of hard surfaces which method comprises the step of applying a
cleaning
substrate which is impregnated or which otherwise contains a quantity of the
largely
aqueous treatment composition as described above onto a hard surface wherein
the
largely aqueous treatment composition contacts the hard surface and provides a
cleaning
benefit, and optionally but preferably, also provides an anti-pathogenic or
antimicrobial
benefit thereto.
Illustrative example compositions which were produced include those set forth
below. The illustrative example compositions demonstrate particularly
preferred
embodiment of the invention as well as preferred weight percentages as well as
preferred
relative weight percentages/weight ratios with regard to the respective
individual
constituents present within the composition.
Examples:
Examples of inventive peroxygen containing hard surface treatment compositions
are described in the following Table 1; the constituents indicated on Table 1
used to
produce the formulations were used on an "as supplied" basis; the identity of
these
constituents are disclosed in more detail on Table 2. The peroxygen containing
treatment
compositions were produced by mixing the constituents into water as outlined
in Table 1
in a beaker at room temperature which was stirred with a conventional magnetic
stirring
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rod or paddle mixer; stirring continued until the formulation was homogenous
in
appearance. It is to be noted that the constituents might be added in any
order, but it is
preferred that a first prmixture is made of any fragrance constituent with one
or more
surfactants in an aliquot of water used in the peroxygen containing hard
suiface treatment
compositions. The order of addition is not critical, but good results are
obtained where
the surfactants (which may be also the premixture of the fragrance and
surfactants) are
produced prior to the addition of the remaining constituents to the water.
Preferably also
the peroxygen compound, viz., hydrogen peroxide constituent is added last. The
amounts
of the named constituents are indicated in %w/w based on a total weight of the
peroxygen
containing hard surface treatment composition of which they form a part.
Table 1
El E2 E3 E4
hydrogen peroxide (5C%) 2 2 2 2
sodium alkylbenzene sulfonate (38%) 1.2 1.2 1.2
lauryl dimethylamineoxide (30%) 0.5
denatured ethanol (95%) 1 1 1 1
isopropanol 0.5 0.5 0.5 0.5
propylene glycol n-prcoyl ether 0.5 0.5 0.5 0.5
anhydrous citric acid 0.5 0.5 0.5 1
silicone emulsion (10%) 0.04
tetrasodium iminodisuccinate 0.5
fragrance#1 0.075 0.075
fragrance#2 0.05
di water q.s. q.s. q.s. q.s.
pH ¨ 2.5 ¨ 2.5 ¨ 2.5 ¨ 2.5
All of the constituents in the compositions on the foregoing Table 1 are
indicated
in weight percent, and each composition comprised 100%wt. The individual
constituents
were used, "as-supplied" from their respective source and unless otherwise
indicated,
each of the constituents are to be understood as being "100%wt. actives".
Deionized
water was added in quantum sufficient, "q.s." to provide the balance to
100%wt. of each
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of the example and comparative example compositions. Further identity of, and
the
sources of the constituents used in the formulations of Tables 1 are described
on the
following Table 2.
Table 2
hydrogen peroxide (50%) hydrogen peroxide, 50%wt. actives,
supplied as
Peroxal 50% Bic (ex. Arkema)
sodium alkylbenzene sulfonate (38%) anionic surfactant, sodium alkylbenzene
sulfonate, 38% wt. active, supplied as Biosoft 0-
40 (ex. Stepan Co.)
lauryl dimethyiamineoxide (30%) nonionic surfactant, bury!
dimethylamineoxide,
30%wt. active, supplied as Ammonyx LC) (ex.
Stepan Co.)
denatured ethanol (95%) denatured ethanol, 95%wt. active, supplied
as
SDA 40B (ex. MGP)
isopropanol anhydrous isopropanol, technical grade,
100%wt. active
propylene glycol n-propyl ether propylene glycol n-propyl ether, 95-
100%wt.
active, supplied as Dowanol PnP (ex. Dow
Chem. Co.)
anhydrous citric acid anhydrous citric acid, 100%wt. active
silicone emulsion (10%) antifoam additive, silicone based emulsion
(10%wt. solids), supplied as DSP Antifoam
Emulsion (ex. Dow Corning)
tetrasodium iminodisuccinate tetrasodium iminodisuccinate, 34%wt.
actives,
supplied as Baypum CX100 (ex. Lanxess)
fragrance#1 proprietary fragrance composition
fragrance#2 proprietary fragrance composition
di water deionized water, 100%wt. actives
Each of the foregoing compositions of Table 1 were applied at a respective
weight
ratio of an example composition:pretreated wipe (cleaning substrate) of 4:1.
The
cleaning substrate used was a nonwoven wipe (having mass of 50 grams/m2)
formed of
spun polyethylene terephalate fiber, which fibers had been treated with a
finishing
composition to coat the fibers prior to the formation of the wipe. The spin
finish was an
aqueous composition, namely Accosoft 501 (ex. Stepan) which is described to
contain
3%wt. of methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate,
and
2%wt. of an alkoxylated oleic acid. The spin finish was applied to the fibers,
which are
then formed into a wipe article, wherein the methyl-bis(tallow amidoethyl)-2-
hydroxyethyl ammonium methyl sulfate and alkoxylated oleic acid comprised
about
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0.03%wt. of the wipe, prior to the application of the example composition at
the
respective weight ratios identified above.
Additionally for use as an "comparative" example of a wipe article, a further
wipe
articles formed from spun finished PET fibers as used in the articles
according to the
invention, however wherein the a different spin finish was applied as the
finishing
composition. This comparative example applied a spin finish which was largely
aqueous,
but included 1.4%wt. of polyethylene glycol, 1%wt. terephtalate ethylene
glycol esters
and 0.1%wt. of an amphoteiic surfactant. Notably, in this comparative example,
methyl-
bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate was not applied
present
in the wipe. Subsequently the composition according to Table 3 was applied at
a
respective weight ratio of an example composition:pretreated wipe (cleaning
substrate) of
4:1. The constituents of the following formula were produced in a manner
similar to that
used in the production of examples El ¨ E4. The constituents were used "as
supplied",
and the identity of these constituents and their respective active weights are
described
with reference to Table 2.
Table 3
E5
hydrogen peroxide (50%) 2
sodium alkylbenzene sulfonate (38%) 1.2
lauryl d methylarnineoxide (30%)
denatured ethanol (95%) 1
isopropanol 0.5
propylene glycol n-propyl ether 0.5
anhydrous citric acid 0.5
silicone emulsion (10%) 0.01
tetrasodium iminodisuccinate
fragrance#1
fragrance#2
di water
pH
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As is discussed in more detail with reference to the following test, the
example
composition "E5" when applied to a clean substrate formed of fibers treated
with a
finishing composition which excluded methyl-bis(tallow amidoethyl)-2-
hydroxyethyl
ammonium methyl sulfate exhibited poor storage stability of the hydrogen
peroxide. It is
hypothesized, believed by the inventors, that the E5 composition would exhibit
improved
store stability when applied to fibrous substrates which had been pretreated
with a
finishing composition which comprises methyl-bis(tallow amidoethyl)-2-
hydroxyethyl
ammonium methyl sulfate.
The wipe articles were tested and evaluated according to one or more of the
following test protocols.
Evaluation of Hydrogen Peroxide Storage Stability
Samples of the compositions from Table 1 and Table 2 as well as wipe articles
formed using these compositions were tested for their retention of hydrogen
peroxide
under storage conditions at a range of temperatures. Plural aliquots of each
of the liquid
compositions were stored in white HDPE sample jars and during the duration of
the test
a small quantity of the aliquot was removed and then analyzed to determine the
%wt. of
hydrogen peroxide present. A single sample jar of each of the compositions was
used
and maintained at each of the temperatures of the test, which are indicated in
the
following Table 4. Additionally a suitable quantity of each of the
compositions of Table
I were applied to a plurality of rolls of pretreated wipe articles formed of
28 contiguous
sheets of 7 inch by 8 inch individual wipes which were joined at opposite
edges by a
perforation, which perforations facilitated the separation of each wipe from
the roll. Each
of the roll ofpretreated wipe articles were formed from 100% polyethylene
terephalate
fibers, having a mass of 50 gram per square meter of area, and one of the
individual
compositions of El ¨ E5 was loaded at a mass ratio of 4:1 of composition:wipe.
It is
noted that the El ¨ E4 compositions had been applied to wipe articles which
had been
pretreated with had been pretreated with a finishing composition which
comprises
methyl-bis(tallow amidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and
which
wipe article had a loading of approx. 0.03%wt. of the wipe, prior to the
application of the
example composition, whereas the "comparative" wipe article was formed by the
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application of the E5 composition at a mass ratio of 4:1 of composition:wipe,
which wipe
substrate had been pretreated with a finishing composition which was largely
aqueous,
but included 1.4%wt. of polyethylene glycol, 1%wt. terephtalate ethylene
glycol esters
and 0.1%wt. of an amphoteric surfactant. Thereafter each of the rolls of wipe
articles
were supplied to individual polymeric canisters having a snap-fit polymeric
cap which
cap included a sealable opening through which the wipes could be withdrawn
from the
roll in a sequential manner.
Sample jars containing aliquots of the compositions as well as a plurality of
sealed canisters congaing the preimpregnated wipe articles as formed above
were stored
at one of several temperature conditions for various time intervals, during
which they
were withdrawn from their storage conditions, allowed to equilibrate to room
temperature
(approx. 20 C) and then tested for their hydrogen peroxide content which was
expressed
as %wt. Tests of the liquid compositions of El ¨ E5 used small samples
withdrawn from
a sample jar. Tests of the El ¨ E5 compositions applied to a wipe were based
on the
liquid "expressed" (manually squeezed) out of a roll of wipes which had been
stored at a
specific temperature for a requisite time period; an individual roll was used
for each test,
and rolls were not retested at a later date or later test but were discarded.
The hydrogen
peroxide content of a test sample was evaluated by a standard quantitative
laboratory
titration method. The test results of this evaluation are set forth in the
following Table 4.
-23-

Table 4
El composition El on wipe E2 composition E2 wipe E5
composition E5 wipe 0
(comparative)
=
1--,
%H202 conc. %H202 conc. %1-1202 conc. %H202
conc. %H202 conc. %H202 conc. 1--,
initia11 20 C 1.247 -- 1.222 1.009
1.003 --4
1--,
2 weeks, 5 C -- - -- - 1.016
0.976
2 vfteks, 25"C 1.25 1.231 -- -- 1.01
0.915
2 weeks, 40 C 1.228 1.208 -- -- 0.997
0.732
2 weeks, 50 C 1.222 1.169 -- 0.991
0.508
4 weeks, 5 C - -- 1.253 1.254 --
-
r)
4 weeks, 25 C 1.28 1.269 1.244 1.244 --
- 0
I.)
4 weeks, 40 C 1.232 1.171 1.235 1.199 --
-- co
I.)
l0
4 weeks, 50 C 1.214 1.05 1.232 1.094 --
-- LO
F-,
H
6 weeks, 5 C -- -- 1.276 1.268 1.004
0.957 I.)
0
H
6 weeks, 25 C 1.25 1.251 1.279 1.253 0.997
0.807 u.)
1
0
6 weeks, 40 C 1.258 1.142 1.259 1.186 0.978
0.365 ko
1
0
6 weeks, 50 C 1.202 0.964 1.239 0.998 0.957
0.082 (5)
12 weeks, 5 C - -- 1.294 1.279 --
-
12 weeks, 25 C 1.298 1.269 1.292 1.243 --
-
12 weeks, 40 C 1.274 1.085 1.259 1.024 --
--
12 weeks, 50 C 1.197 0.769 1.200 0.596 --
-- 1-d
n
1-i
" - " indicates not tested
w
t..)
o
,-,
t..)
O-
u,
o
u,
t..)
-4
- 24 -

CA 02829311 2013-09-06
WO 2012/123721 PCT/GB2012/050527
As is evident from the foregoing the wipe articles which had been pretreated
with
the finishing composition which comprises methyl-bis(tallow amidoethyl)-2-
hydroxyethyl ammonium methyl sulfate (viz., Accosoft 501) and to which were
thereafter applied the El or E2 compositions retained a significant proportion
of the
hydrogen peroxide even following 6 weeks, and particularly following 12 weeks
of
storage at elevated temperatures. In contrast the E5 composition, while
demonstrating
good retention of its original concentration of hydrogen peroxide when in its
liquid form,
the same composition which was applied to the wipe article exhibited a drastic
loss of
hydrogen peroxide content even at short storage times at higher temperature,
particularly
when compared to the wipe which comprised the El or E2 compositions.
The percentage of the hydrogen peroxide "lost" (reduction of hydrogen peroxide
as compared to initial levels in wipe, or of initial liquid) from the various
wipes of Table
4 is quantified in the following Table 5.
Table 5
El E2 E5
wipe wipe (comparative)
initial level of hydrogen peroxide (%wt.) 1.25 1.22 1.0
final level of hydrogen peroxide (%wt.) 1.14 1.19 0.37
% change in hydrogen peroxide level -9% -3% -63%
"¨" indicates not tested
The foregoing results reported on Table 5 confirm the earlier reported results
of
Table 4 wherein the wipe articles which had been treated with a diamido amine
quaternary ammonium compound and which had been produced with the compositions
El and E2 exhibited superior storage stability than the wipe article produced
using
composition E5 which wipes had been pretreated with a finishing composition
other than
a diamidoamine quaternary ammonium compound.
- 25 -

CA 02829311 2013-09-06
WO 2012/123721
PCT/GB2012/050527
Evaluation of Antimicrobial Efficacy
Certain of the largely aqueous peroxygen compound containing treatment
compositions similar to those described above were also subjected to testing
in order to
evaluate their anti-pathogenic benefits (antimicrobial efficacy) against
Rhinovirus and
against Staphylococcus aureus.
The following compositions, E6 and E7, were produced and which were
substantially similar to composition El except that the amount of hydrogen
peroxide was
slightly reduced relative thereto; in the following Table 6 the content of
hydrogen
peroxide is expressed on the basis of "100 %wt. active", while all other
constituents are
as described as on Table 2.
Table 6
E6 E7
hydrogen peroxide (100%) 0.75 0.94
sodium alkylbenzene sultanate (38%) 1.2 1.2
lauryl dimethylamineoxide (30%)
denatured ethanol (95%) 1 1
isopropanol 0.5 0.5
propylene glycol n-propyl ether 0.5 0.5
anhydrous citric acid 0.5 0.5
silicone emulsion (10%) 0.01 0.01
tetrasodium iminodisuccinate
fragrance#1
fragrance#2
di water q.s. q.s.
pH ¨ 2.5 --2.5
-26-

CA 02829311 2013-09-06
WO 2012/123721
PCT/GB2012/050527
The compositions according to E6 exhibited excellent activity, ('complete
inactivation') against sample of Rhinovirus when tested according to an
accepted
protocol.
The compositions according to E7 were applied at a respective weight ratio of
an
example composition:pretreated wipe (cleaning substrate) of 4:1. The cleaning
substrate
used was a nonwoven wipe (having mass of 50 grams/m2) formed of spun
polyethylene
terephalate fiber, which fibers had been treated with a finishing composition
to coat the
fibers prior to the formation of the wipe. The spin fmish was an aqueous
composition,
namely Accosoft 501 (ex. Stepan) which is described to contain 3%wt. of
methyl-
bis(tallow arnidoethyl)-2-hydroxyethyl ammonium methyl sulfate, and 2%wt. of
an
alkoxylated oleic acid. Such wipe articles impregnated with the E7 composition
were
tested according to a protocol generally in conformance with the "Standard
Operating
Procedure for Disinfectant Towelette Test Against Staphylococcus aureus,
Pseudomonas
aueruginosa, and Salmonella enterica", SOP Number: MB-09-04, Date Revised: 02-
26-
10, issued by the US Environmental Protection Agency, Office of Pesticide
Programs.
The said wipe article containing the E7 composition demonstrated a result of
"1/60"
positive samples, which corresponded to excellent antimicrobial efficacy
pursuant that
test protocol.
While the invention is susceptible of various modifications and alternative
forms,
it is to be understood that specific embodiments thereof have been shown by
way of
example in the drawings which are not intended to limit the invention to the
particular
forms disclosed; on the contrary the intention is to cover all modifications,
equivalents
and alternatives falling within the scope and spirit of the invention as
expressed in the
appended claims.
- 27 -

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Administrative Status

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Event History

Description Date
Inactive: Dead - No reply to s.30(2) Rules requisition 2019-07-11
Application Not Reinstated by Deadline 2019-07-11
Deemed Abandoned - Failure to Respond to Maintenance Fee Notice 2019-03-11
Inactive: Abandoned - No reply to s.30(2) Rules requisition 2018-07-11
Inactive: S.30(2) Rules - Examiner requisition 2018-01-11
Inactive: Report - QC passed 2018-01-08
Letter Sent 2017-02-09
All Requirements for Examination Determined Compliant 2017-02-07
Request for Examination Requirements Determined Compliant 2017-02-07
Request for Examination Received 2017-02-07
Change of Address or Method of Correspondence Request Received 2015-01-15
Letter Sent 2013-11-14
Inactive: Single transfer 2013-10-30
Inactive: Cover page published 2013-10-29
Inactive: Notice - National entry - No RFE 2013-10-11
Inactive: IPC assigned 2013-10-11
Inactive: IPC assigned 2013-10-11
Inactive: IPC assigned 2013-10-11
Inactive: IPC assigned 2013-10-11
Inactive: IPC assigned 2013-10-11
Inactive: IPC assigned 2013-10-11
Application Received - PCT 2013-10-11
Inactive: First IPC assigned 2013-10-11
National Entry Requirements Determined Compliant 2013-09-06
Application Published (Open to Public Inspection) 2012-09-20

Abandonment History

Abandonment Date Reason Reinstatement Date
2019-03-11

Maintenance Fee

The last payment was received on 2018-01-09

Note : If the full payment has not been received on or before the date indicated, a further fee may be required which may be one of the following

  • the reinstatement fee;
  • the late payment fee; or
  • additional fee to reverse deemed expiry.

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Please refer to the CIPO Patent Fees web page to see all current fee amounts.

Fee History

Fee Type Anniversary Year Due Date Paid Date
Basic national fee - standard 2013-09-06
Registration of a document 2013-10-30
MF (application, 2nd anniv.) - standard 02 2014-03-10 2014-02-18
MF (application, 3rd anniv.) - standard 03 2015-03-09 2015-02-18
MF (application, 4th anniv.) - standard 04 2016-03-09 2016-02-22
MF (application, 5th anniv.) - standard 05 2017-03-09 2017-01-09
Request for examination - standard 2017-02-07
MF (application, 6th anniv.) - standard 06 2018-03-09 2018-01-09
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
RECKITT BENCKISER LLC
Past Owners on Record
MATTHEW KASER
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 2013-09-05 27 1,305
Abstract 2013-09-05 1 52
Claims 2013-09-05 2 64
Notice of National Entry 2013-10-10 1 206
Reminder of maintenance fee due 2013-11-12 1 111
Courtesy - Certificate of registration (related document(s)) 2013-11-13 1 102
Courtesy - Abandonment Letter (R30(2)) 2018-08-21 1 167
Reminder - Request for Examination 2016-11-09 1 117
Acknowledgement of Request for Examination 2017-02-08 1 175
Courtesy - Abandonment Letter (Maintenance Fee) 2019-04-22 1 180
PCT 2013-09-05 3 78
Correspondence 2015-01-14 2 58
Request for examination 2017-02-06 2 81
Examiner Requisition 2018-01-10 4 246