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Patent 2801285 Summary

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(12) Patent: (11) CA 2801285
(54) English Title: HYPOCHLORITE DENTURE COMPOSITIONS AND METHODS OF USE
(54) French Title: COMPOSITIONS A BASE D'HYPOCHLORITE POUR PROTHESE DENTAIRE ET PROCEDES D'UTILISATION
Status: Granted
Bibliographic Data
(51) International Patent Classification (IPC):
  • A61K 8/02 (2006.01)
  • A61K 8/19 (2006.01)
  • A61K 8/20 (2006.01)
  • A61K 8/36 (2006.01)
  • A61K 8/81 (2006.01)
  • A61Q 11/02 (2006.01)
  • C01B 11/06 (2006.01)
(72) Inventors :
  • SMITH, WILLIAM L. (United States of America)
  • RUMBERGER, EVAN M. (United States of America)
(73) Owners :
  • THE CLOROX COMPANY (United States of America)
(71) Applicants :
  • THE CLOROX COMPANY (United States of America)
(74) Agent: BORDEN LADNER GERVAIS LLP
(74) Associate agent:
(45) Issued: 2017-08-22
(86) PCT Filing Date: 2010-10-13
(87) Open to Public Inspection: 2011-05-26
Examination requested: 2015-09-21
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2010/052487
(87) International Publication Number: WO2011/062707
(85) National Entry: 2012-11-30

(30) Application Priority Data:
Application No. Country/Territory Date
61/351,433 United States of America 2010-06-04

Abstracts

English Abstract

A solid composition including calcium and/or magnesium hypochlorite, a builder (e.g., one or more of carbonate, bicarbonate, sesquicarbonate), an acid, a water- soluble polymer, at least one anionic surfactant, and optionally, a hydrotrope. The composition does not include any potassium hypochlorite, sodium hypochlorite, lithium hypochlorite, N-halogenated compounds, peroxides, persulfates, hydantoins, isocyanurates, or carboxylic acids that also have hydroxyl, amino, amido, imino, or imido groups. Upon dissolution of the composition in water, the calcium and/or magnesium hypochlorite and acid react to form hypochlorous acid. The use of hypochlorous acid, rather than direct use of an alkaline or alkaline earth hypochlorite results in a composition that is typically acidic rather than basic, and that results in improved cleaning. The composition is particularly suited for cleaning and disinfecting dentures.


French Abstract

L'invention porte sur une composition solide comprenant un hypochlorite de calcium et/ou de magnésium, un additif (par exemple, un ou plusieurs parmi carbonate, bicarbonate, sesquicarbonate), un acide, un polymère soluble dans l'eau, au moins un tensioactif anionique et facultativement un hydrotrope. La composition ne comprend pas d'hypochlorite de potassium, d'hypochlorite de sodium, d'hypochlorite de lithium, de composés N-halogénés, de peroxydes, de persulfates, d'hydantoïnes, d'isocyanurates ou d'acides carboxyliques qui ont également des groupes hydroxyles, amino, amido, imino ou imido. Lors de la dissolution de la composition dans l'eau, l'hypochlorite de calcium et/ou de magnésium et l'acide réagissent pour former un acide hypochloreux. L'utilisation d'acide hypochloreux, plutôt qu'une utilisation directe d'un hypochlorite alcalin ou alcalino-terreux conduit à une composition qui est typiquement acide plutôt que basique, et qui conduit à un nettoyage amélioré. La composition est particulièrement appropriée pour nettoyer et désinfecter des prothèses dentaires.

Claims

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


35

CLAIMS:
1. A solid, one-layered composition comprising:
a) a hypochlorite selected from the group consisting of calcium
hypochlorite,
magnesium hypochlorite and mixtures thereof;
b) a builder selected from the group consisting of carbonate, bicarbonate,
sesquicarbonate and mixtures thereof;
c) at least 30% by weight of an acid selected from the group consisting of
a
carboxylic acid, a dicarboxylic acid, a sulfonic acid, an acid sulfate, an
acid phosphate,
and mixtures thereof;
d) a water-soluble polymer selected from the group consisting of a
polycarboxylate, a sulfonated carboxylate, a polysulfonate, a
polyvinylpyrrolidone, a
polypyridinium salt, a polyquaternary ammonium salt, and mixtures thereof;
e) at least one anionic surfactant; and
f) at least one hydrotrope;
wherein the composition excludes potassium hypochlorite, sodium hypochlorite,
lithium hypochlorite, N-halogenated compounds, peroxides, persulfates,
hydantoins,
isocyanurates, and carboxylic acids that also have hydroxyl, amino, amido,
imino, or imido
groups;
wherein the composition contains only one layer.
2. The composition of claim 1, wherein the hypochlorite is the calcium
hypochlorite and
the calcium hypochlorite comprises less than 50% by weight of the composition.
3. The composition of claim 1 or 2, wherein the acid comprises at least 50%
by weight of
the composition.
4. The composition of claim 1, wherein the acid is the dicarboxylic acid.

36

5. The composition of claim 4, wherein the water-soluble polymer is the
polycarboxylate, and where the carboxylate ions for the polycarboxylate are
derived from the
group consisting of maleic acid, acrylic acid, methacrylic acid and mixtures
thereof
6. The composition of claim 5, wherein the hydrotrope is a salt selected
from the group
consisting of a toluene sulfonate, a cumene sulfonate, a xylene sulfonate, a
naphthalene
sulfonate, a methyl naphthalene sulfonate, and mixtures thereof.
7. The composition of claim 6, wherein the composition excludes enzymes,
waxes,
resins, nonionic surfactants, chlorite salts, or chlorine dioxide.
8. A solid, one-layered composition consisting essentially of:
a) a hypochlorite selected from the group consisting of calcium
hypochlorite,
magnesium hypochlorite and mixtures thereof;
b) a builder selected from the group consisting of carbonate, bicarbonate,
sesquicarbonate and mixtures thereof;
c) at least 30% by weight of an acid selected from the group consisting of
a
carboxylic acid, a dicarboxylic acid, a sulfonic acid, an acid sulfate, an
acid phosphate,
and mixtures thereof;
d) a water-soluble polymer selected from the group consisting of a
polycarboxylate, a sulfonated carboxylate, a polysulfonate, a
polyvinylpyrrolidone, a
polypyridinium salt, a polyquaternary ammonium salt, and mixtures thereof;
e) at least one anionic surfactant;
f) at least one hydrotrope; and
g) optionally, a cobuilder selected from the group consisting of a
hydroxide, an
oxide, a silicate, a phosphate, a borate and mixtures thereof and
h) optionally, colorants, perfumes, sequestrants, anti-corrosion agents,
lubricants,
binders, fillers, disintegration aids, preservatives, desiccants, or mixtures
thereof.

37

9. The composition of claim 8, wherein the composition excludes potassium
hypochlorite, sodium hypochlorite, lithium hypochlorite, N-halogenated
compounds,
peroxides, persulfates, hydantoins, isocyanurates, carboxylic acids that have
hydroxyl, amino,
amido, imino, or imido group, enzymes, waxes, resins, and nonionic
surfactants.
10. The composition of claim 9, wherein the hypochlorite is calcium
hypochlorite and the
calcium hypochlorite comprises less than 50% by weight of the composition.
11. The composition of claim 10, wherein the acid is the dicarboxylic acid.
12. The composition of claim 11, wherein the water-soluble polymer is the
polycarboxylate, and where the carboxylate ions for the polycarboxylate are
derived from the
group consisting of maleic acid, acrylic acid, methacrylic acid and mixtures
thereof.
13. The composition of claim 12, wherein the hydrotrope is a salt selected
from the group
consisting of a toluene sulfonate, a cumene sulfonate, a xylene sulfonate, a
naphthalene
sulfonate, methyl naphthalene sulfonate, and mixtures thereof.
14. A solid, one-layered composition consisting of:
a) a hypochlorite selected from the group consisting of calcium
hypochlorite,
magnesium hypochlorite and mixtures thereof;
b) a builder selected from the group consisting of carbonate, bicarbonate,
sesquicarbonate and mixtures thereof;
c) at least 30% by weight of an acid selected from the group consisting of
a
carboxylic acid, a dicarboxylic acid, a sulfonic acid, an acid sulfate, an
acid phosphate,
and mixtures thereof;
d) a water-soluble polymer selected from the group consisting of a
polycarboxylate, a sulfonated carboxylate, a polysulfonate, a
polyvinylpyrrolidone, a
polypyridinium salt, a polyquaternary ammonium salt, and mixtures thereof;
e) at least one anionic surfactant;

38

f) optionally, at least one hydrotrope;
g) optionally, a cobuilder selected from group consisting of a hydroxide,
an
oxide, a silicate, a phosphate, a borate and mixtures thereof; and
h) optionally, colorants, perfumes, sequestrants, anti-corrosion agents,
lubricants,
binders, fillers, disintegration aids, preservatives, desiccants, or mixtures
thereof.
15. The composition of claim 14, wherein the composition excludes potassium

hypochlorite, sodium hypochlorite, lithium hypochlorite, N-halogenated
compounds,
peroxides, persulfates, hydantoins, isocyanurates, carboxylic acids that have
hydroxyl, amino,
amido, imino, or imido group, enzymes, waxes, resins, and nonionic
surfactants.
16. The composition of claim 15, wherein the acid comprises at least 50% by
weight of
the composition.
17. The composition of claim 16, wherein the acid is the dicarboxylic acid.

Description

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


CA 02801285 2016-12-14
1
HYPOCHLORITE DENTURE COMPOSITIONS AND METHODS OF USE
100011 < This paragraph has been deleted>
BACKGROUND OF THE INVENTION
1. The Field of the Invention
[0002] The present invention relates generally to solid single-layered
cleaning compositions.
These compositions may be used to clean and disinfect dentures, other dental
appliances, or cleaning
other oral surfaces (e.g., as a mouthwash, endodontic root canal
disinfection).
2. Background and Relevant Art
[0003] Solid bleach compositions have progressed for decades and created a
large
chemical industry devoted to cleaning and disinfecting hard and soft surfaces.
N-chloro
hydantoins, N-chloro isocyanurates, sodium hypochlorite, and calcium
hypochlorite
are used quite frequently in bleach compositions for many companies because
they
are cheap to produce and they are highly effective. However, these bleach
compositions

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2
have several disadvantages that limit their usefulness. Sodium hypochlorite is
only
available as a liquid at room temperature. Calcium hypochlorite leaves
residue.
Chlorinated hydantoins and isocyanurates lack long term solution stability and
generate
malodor. All these disadvantages present compositions which consumers may not
prefer.
BRIEF SUMMARY OF THE INVENTION
[0004] The presently claimed invention solves some of these problems in the
art with
compositions and methods related to denture cleaning compounds comprising
hypochlorite in a single-layered composition. It is contemplated that the
composition
may also be useful in other oral care environments, such as a mouthwash and as
an
endodontic root canal disinfectant. Use of calcium and/or magnesium
hypochlorite in a
single-layered composition (e.g., in tablet form) as taught herein minimizes
and/or
eliminates the formation of residues that are associated with other calcium
hypochlorite
compositions. In addition, the compositions do not generate malodors typically

associated with the use of chlorinated isocyanurates. The present invention
also
releases bleach faster than the typical use of halogenated hydantoins. The
present
invention also dissolves faster than typical commercial products based on
calcium
hypochlorite or halogenated hydantoins.
[0005] One embodiment of the present invention comprises a solid single-
layered
composition including: a) a hypochlorite selected from the group consisting of
calcium
hypochlorite, magnesium hypochlorite and mixtures thereof; b) a builder
selected from
the group consisting of carbonate, bicarbonate, sesquicarbonate and mixtures
thereof; c)
an acid selected from the group consisting of carboxylic acid, dicarboxylic
acid,
sulfonic acid, acid sulfate, acid phosphate, and mixtures thereof; d) a water-
soluble
polymer selected from the group consisting of a polycarboxylate, sulfonated

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3
carboxylate, polysulfonate, polyvinylpyrrolidone, polypyridinium salt,
polyquaternary
ammonium salt, and mixtures thereof e) at least one anionic surfactant; f) at
least one
hydrotrope; g) wherein the composition does not contain potassium
hypochlorite,
sodium hypochlorite, lithium hypochlorite, N-halogenated compounds, peroxides,

persulfates, hydantoins, isocyanurates, carboxylic acids that also have one or
more
hydroxyl, amino, amido, imino, or imido group moieties; h) and wherein the
composition contains only one layer.
[0006] Another embodiment of the present invention comprises a solid-layered
one-
layered composition consisting essentially of a) a hypochlorite selected from
the group
consisting of calcium hypochlorite, magnesium hypochlorite and mixtures
thereof; b) a
builder selected from the group consisting of carbonate, bicarbonate,
sesquicarbonate
and mixtures thereof; c) an acid selected from the group consisting of
carboxylic acid
dicarboxylic acid, sulfonic acid, an acid sulfate, an acid phosphate, and
mixtures
thereof; d) a water-soluble polymer selected from the group consisting of a
polycarboxylate, a sulfonated carboxylate, a polysulfonate, a
polyvinylpyrrolidone, a
polypyridinium salt, a polyquaternary ammonium salt, and mixtures thereof; e)
at least
one anionic surfactant; f) at least one hydrotrope; g) optionally, a cobuilder
selected
from the group consisting of a hydroxide, an oxide, a silicate, a phosphate, a
borate, and
mixtures thereof; h) optionally, colorants, perfumes, sequestrants, anti-
corrosion agents,
lubricants, binders, fillers, disintegration aids, preservatives, desiccants,
and mixtures
thereof
[0007] Another embodiment of the present invention is directed to a solid one-
layered composition consisting of: a) a hypochlorite selected from the group
consisting
of calcium hypochlorite, magnesium hypochlorite and mixtures thereof; b) a
builder
selected from the group consisting of carbonate, bicarbonate, sesquicarbonate
and

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4
mixtures thereof; c) an acid selected from the group consisting of a
carboxylic acid, a
dicarboxylic acid, a sulfonic acid, an acid sulfate, an acid phosphate, and
mixtures
thereof; d) a water-soluble polymer selected from the group consisting of a
polycarboxylate, sulfonated carboxylate, polysulfonate, polyvinylpyrrolidone,
polypyridinium salt, polyquaternary ammonium salt, and mixtures thereof; e) at
least
one anionic surfactant; f) optionally, at least one hydrotrope; g) optionally,
a cobuilder
selected from the group consisting of a hydroxide, an oxide, a silicate, a
phosphate, a
borate, and mixtures thereof; h) optionally, colorants, perfumes,
sequestrants, anti-
corrosion agents, lubricants, binders, fillers, disintegration aids,
preservatives,
desiccants, and mixtures thereof
[0008] Because the composition includes calcium and/or magnesium hypochlorite
and an acid, hypochlorous acid is formed upon dissolution of the composition
in water.
As such, the composition derives its disinfection and cleaning properties from
the
hypochlorous acid formed in situ, rather than the hypochlorite alone. The use
of
hypochlorous acid, rather than direct use of an alkaline or alkaline earth
hypochlorite
(e.g., calcium hypochlorite) results in a composition that is acidic rather
than basic, and
which provides improved efficacy.
[0009] Further features and advantages of the present invention will become
apparent to those of ordinary skill in the art in view of the detailed
description of
preferred embodiments below, when considered together with the attached
claims.

CA 02801285 2016-12-14
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
1. Definitions
[0010] Before describing the present invention in detail, it is to be
understood that this invention
is not limited to particularly exemplified systems or process parameters that
may, of course, vary. It is
also to be understood that the terminology used herein is for the purpose of
describing particular
embodiments of the invention only, and is not intended to limit the scope of
the invention in any
manner.
100111 < This paragraph has been deleted>
[0012] It must be noted that, as used in this specification and the
appended claims, the singular
forms "a," "an" and "the" include plural referents unless the content clearly
dictates otherwise.
[0013] Unless defined otherwise, all technical and scientific terms used
herein have the same
meaning as commonly understood by one of ordinary skill in the art to which
the invention pertains.
Although a number of methods and materials similar or equivalent to those
described herein can be
used in the practice of the present invention, the preferred materials and
methods are described herein.
100141 In the application, effective amounts are generally those amounts
listed as the ranges or
levels of ingredients in the descriptions, which follow hereto. Unless
otherwise stated, amounts listed
in percentage (%) are in weight percent (based on 100% active) of the
composition alone, not
accounting for any substrate weight. Each of the noted composition components
and substrates is
discussed in detail below.

CA 02801285 2016-12-14
6
Additionally, the invention also covers method steps of utilizing the
compositions described in
the present application.
[0015] The term "comprising", which is synonymous with "including,"
"containing," or
"characterized by," is inclusive or open-ended and does not exclude
additional, unrecited
elements or method steps.
[0016] The term "consisting essentially of as used herein, limits the scope
of a claim to the
specified materials or steps "and those that do not materially affect the
basic and novel
characteristic(s)" of the claimed invention.
[0017] The term "consisting of as used herein, excludes any element, step,
or
ingredient not specified in the claim.
[0018] The term "surfactant", as used herein, is meant to mean and include
a substance or compound that reduces surface tension when dissolved in water
or water

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7
solutions, or that reduces interfacial tension between two liquids, or between
a liquid
and a solid. The term "surfactant" thus includes anionic, nonionic, cationic,
zwitterionic
and/or amphoteric agents.
II. Introduction
[0019] The present invention is directed to a solid single-layered
composition. The
solid single-layered composition comprises calcium hypochlorite, magnesium
hypochlorite or mixtures thereof, an acid, a water-soluble polymer, and an
anionic
surfactant. Optional ingredients may be added to the composition to enhance
the
efficacy of the solid single-layered composition. Upon dissolution of the
composition
in water, the calcium and/or magnesium hypochlorite and acid react to form
hypochlorous acid. The composition may be particularly suitable for use in
disinfecting
dentures or other dental appliances, although it is contemplated that the
composition
may also be useful in other oral care environments, such as a mouthwash and as
an
endodontic root canal disinfectant.
[0020] The use of hypochlorous acid, rather than direct use of an alkaline
or alkaline
earth hypochlorite (e.g., calcium hypochlorite) results in a composition that
is typically
acidic rather than basic. This lower pH speeds the rate of antimicrobial
activity,
improves the removal of plaque and biofilms including their conditioning
layer, and
increases the removal of stains from food, beverages and tobacco. Complete
removal of
biofilms including their conditioning layer increases the incubation time
required for
bacteria to reattach to the denture to reform a biofilm when subsequently re-
exposed to
bacteria. Furthermore, the lower pH also increases the removal of dental
calculus and
other hard to remove calcium deposits. This is because the solubility of the
calcium is
significantly greater within the acidic environment.

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[0021] Since hypochlorous acid is more effective than hypochlorite ion, a
lower
concentration of hypochlorous acid may be used. This largely eliminates the
formation
of unpleasant odors from the reaction of hypochlorite ion and proteins. In
addition, the
hypochlorous acid works more quickly so that shorter contact times with the
cleaning
solution produce the desired results. Hypochlorous acid solutions by virtue of
their
lower effective concentration and their lower pH are also less corrosive to
some
materials used to construct dentures and dental appliances.
[0022] Although the pH of the mixed and prepared composition may be as high as

about 9, preferably, the pH of the hypochlorous acid disinfecting composition
is
between about 5 and about 8. In another embodiment, the pH of the hypochlorous
acid
disinfecting composition is between about 6 and about 7. In one embodiment,
the pH is
preferably acidic (i.e., less than 7), most preferably between about 5.5 and
about 6.5.
[0023] Generally, the concentration of hypochlorous acid will be selected
to remove
stains, biofilms and kill or remove at least 99.9% of bacteria, viruses, and
fungi. The
concentration will depend on the use instructions for the product. For
example, a
product designed for soaking dentures overnight would contain at least 10 ppm,

preferably more than about 20 ppm, more preferably more than about 30 ppm, and
most
preferably more than about 50 ppm of hypochlorous acid. A product designed to
work
in 3 to 5 minutes would contain at least 50 ppm, preferably more than about
100 ppm,
more preferably more than about 150 ppm, and most preferably more than about
300
ppm of hypochlorous acid. In order to minimize the potential to form
unpleasant odors
or damage surfaces if spilled the maximum concentration is about 1500 ppm,
preferably
less than about 1000 ppm, more preferably less than about 600 ppm, and most
preferably less than about 400 ppm of hypochlorous acid.

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III. Oxidants
[0024] The solid single-layered composition contains calcium hypochlorite,
magnesium hypochlorite or mixtures thereof. These hypochlorite salts include
anhydrous varieties as well as the various hydrates, double salts such as
monobasic and
dibasic forms, and triple salts. The hypochlorite salts may be crystalline or
amorphous.
The solid single-layered composition does not contain any other types of
hypochlorite
such as sodium hypochlorite, lithium hypochlorite, or potassium hypochlorite.
Therefore, the composition does not contain any N-halogenated compounds,
peroxides,
persulfates, hydantoins, isocyanurates, or carboxylic acids that also have
hydroxyl,
amino, amido, imino, or imido groups. More specific examples of such excluded
components include hypobromites, hypoiodites, chlorinated trisodium phosphate
dodecahydrates, potassium and sodium dichloroisocyanurates, trichlorocyanuric
acid,
N-chloroimides, N-chloroamides, N-chlorosulfamide, N-
chloroamines,
chlorohydantoins such as dichlorodimethyl hydantoin, chlorobromo
dimethylhydantoin,
and bromo-compounds corresponding to the chloro-compounds above.
[0025] The
compositions of the present invention do not require a bleach activator.
By "bleach activator", it is meant herein a compound which reacts with
peroxygen
bleach like hydrogen peroxide to form a peracid. The peracid thus formed
constitutes
the activated bleach. Bleach activators that are not to be used in the
composition
include, but are not limited to, those belonging to the class of esters,
amides, imides, or
anhydrides. Examples of bleach activators that are not to be used in the
composition
include, but are not limited to, TAED, sodium 3,5,5 trimethyl hexanoyloxy-
benzene
sulphonate, diperoxy dodecanoic acid, nonylamide of peroxyadipic acid,
nonylamide of
peroxyadipic acid, n-nonanoyloxybenzenesulphonate (NOBS), acetyl triethyl
citrate
(ATC), n-alkyl alkyl ammonium acetonitrile activators. Additional examples of
bleach

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activators that are not to be used in the composition include, but are not
limited to, are
N-acyl caprolactams selected from the group consisting of substituted or
unsubstituted
benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, hexanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactam, formyl caprolactam,

acetyl caprolactam, propanoyl caprolactam, butanoyl caprolactam pentanoyl
caprolactam or mixtures thereof
[0026] In one embodiment, the calcium hypochlorite, magnesium hypochlorite or
mixture thereof is present in the composition in an amount of less than about
50%. For
example, the calcium and/or magnesium hypochlorite may be present in the
composition in an amount ranging from about 0.1% to about 50%, about 0.1% to
about
45%, about 0.1% to about 40%, about 0.1% to about 30%, about 0.1% to about
25%,
about 0.1% to about 20%, about 0.1% to about 15%, about 0.1% to about 10%,
about
0.1% to about 5%, about 5% to about 20%, about 5% to about 15%, about 10% to
about
20%, about 10% to about 15% or about 15% to about 20%.
IV. Builders
[0027] The composition may contain a builder. The builder may be present in
the
cleaning composition in an amount ranging from about 10% to about 90%, about
20%
to about 90%, about 20% to about 80%, about 20% to about 60%, about 20% to
about
50%, about 30% to about 60%, about 35 to about 55%, about 40 to about 50%,
about
20% to about 30%, about 30% to about 50%, about 30% to about 45%, about 30% to

about 40%, about 20% to about 60%, about 25% to about 60%, about 20% to about
40%, or about 20% to about 30%. The builder can be selected from inorganic
builders,
such as carbonate, bicarbonate, sesquicarbonate, and mixtures thereof. More
specifically, the builder may comprise a carbonate, bicarbonate, or
sesquicarbonate of

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11
one or more alkali metals. The builder may be in its anhydrous form or any of
its stable hydrates, and
they may be crystalline or amorphous.
0028]
Inclusion of a builder is advantageous, as it can increase the effectiveness
of the
surfactant. The builder can also function as a softener, a sequestering agent,
a buffering agent, or a pH
adjusting agent in the cleaning composition. A variety of builders or buffers
can be used and they
include, but are not limited to, phosphate-silicate compounds, zeolites,
alkali metal, ammonium and
substituted ammonium polyacetates, trialkali salts of nitrilotriacetic acid,
carboxylates,
polycarboxylates, carbonates, bicarbonates, polyphosphates,
aminopolycarboxylates, polyhydroxy-
sulfonates, and starch derivatives. Builders, when used, include, but are not
limited to, organic acids,
mineral acids, alkali metal and alkaline earth salts of silicate,
metasilicate, polysilicate, borate,
sulfates, hydroxide, carbonate, carbamate, phosphate, polyphosphate,
pyrophosphates, triphosphates,
tetraphosphates, ammonia, hydroxide, monoethanolamine, monopropanolamine,
diethanolamine,
dipropanolamine, triethanolamine, and 2-amino-2-methylpropanol. Other suitable
buffers include
ammonium carbamate and acetic acid. Mixtures of any of the above may also be
acceptable. Useful
inorganic buffers/alkalinity sources include ammonia, the alkali metal
carbonates and alkali metal
phosphates, e.g., sodium carbonate, sodium polyphosphate. For additional
buffers see WO 95/07971.
Other preferred pH adjusting agents include sodium or potassium hydroxide. The
term silicate is
meant to encompass silicate, metasilicate, polysilicate, aluminosilicate and
similar compounds.
Preferred builders/buffers of the solid single-layered composition include
carbonate, bicarbonate,
sesquicarbonate and mixtures thereof.

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V. Water-Soluble Polymers
[0029] The composition may contain a water-soluble polymer. Examples of water-
soluble polymers include, but are not limited to, polycarboxylate, sulfonated
carboxylate, polysulfonate, polyvinylpyrrolidone ("PVP"), a polypyridinium
salt, a
polyquaternary ammonium salt, and mixtures thereof
[0030] Examples of polycarboxylates include, but are not limited to
polymers with
sufficient carboxylate ions to achieve water solubility. Carboxylate ions may
be
derived from various monomers including acrylic acid, methacrylic acid, maleic
acid
and maleic anhydride. Copolymers of different carboxylate-containing monomers
are
also suitable as well as copolymers with non carboxylate containing monomers
such as
methacrylate, acrylonitrile, styrene, ethylene, propylene, and many others.
Mixtures of
carboxylate containing polymers can also be used.
[0031] In one embodiment, the molecular weight of the water-soluble polymer
may
be between about 1,000 to about 10,000 daltons, about 1,000 to about 8,000
daltons,
about 1,000 to about 6,000 daltons, about 1,000 to about 5,000 daltons, about
1,000 to
about 4,000 daltons, about 1,000 to about 2,000 daltons, about 2,000 to about
10,000
daltons, about 2,000 to about 8,000 daltons, about 2,000 to about 6,000
daltons, about
2,000 to about 5,000 daltons, about 2,000 to about 4,000 daltons, about 3,000
to about
10,000 daltons, about 3,000 to about 8,000 daltons, about 3,000 to about 6,000
daltons,
about 3,000 to about 5,000 daltons, about 3,000 to about 4,000 daltons, about
4,000 to
about 10,000 daltons, about 4,000 to about 8,000 daltons, about 4,000 to about
6,000
daltons, about 5,000 to about 10,000 daltons, about 5,000 to about 7,500
daltons, or
about 7,500 to about 10,000 daltons.
[0032] The water-soluble polymer may be present in an amount ranging from
about
0.1% to about 60%, about 0.1% to about 50%, about 0.1% to about 40%, about
0.1% to

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about 30%, about 0.1% to about 20%, about 0.1% to about 15%, about 0.1% to
about
10%, about 1% to about 10%, about 1% to about 5%, about 1% to about 3%, about
5%
to about 60%, about 5% to about 50%, about 5% to about 40%, about 5% to about
30%,
about 5% to about 20%, about 5% to about 10%, about 10% to about 60%, about
10%
to about 50%, about 10% to about 40%, about 10% to about 30%, about 10% to
20%,
about 20% to about 60%, about 20% to about 50%, about 20% to about 40%, about
20% to about 30%, about 30% to about 60%, about 30% to about 50%, about 30% to

about 40%, or about 40% to about 60%.
VI. Acids
[0033] The composition may contain an acid. Examples of acids that can be used

with the present invention include, but are not limited to, carboxylic acid,
dicarboxylic
acid, sulfonic acid, an acid sulfate, an acid phosphate, and mixtures thereof.
Specific
examples of acids include, but are not limited to, succinic acid, glutaric
acid, 3-pyridine
sulfonic acid, dodecyl benzene sulfonic acid, and mixtures thereof.
[0034] Notably, the composition does not contain carboxylic acids that have
one or
more hydroxyl, amino, amido, imino, or imido group moieties. Examples of acids
that
are not to be used in the composition include, but are not limited to citric
acid, tartaric
acid, and alanine.
[0035] The acid may be present in an amount of at least 30%, and in one
embodiment at least 50%, of the composition. For example, the acid may be
present in
an amount ranging from about 30% to about 80%, about 30% to about 70%, about
30%
to about 60%, about 30% to about 50%, or about 40% to about 80%, about 40% to
about 70%, about 40% to about 60%, about 40% to about 50%, about 50% to about
80%, about 50% to about 70%, or about 50% to about 60%.

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[0036] In one embodiment, the acid is present in an amount of at least about
50%
(e.g., about 50% to about 60%), and the calcium and/or magnesium hypochlorite
is
present in an amount of about 0.1% to about 5%. This results in the desired
relatively
low, but effective, concentration of hypochlorous acid upon dissolution of the

composition in water.
VII. Cross-Linked Water-Swellable Polymers
[0037] The composition may optionally contain a cross-linked water-
swellable
polymer. Examples of water-swellable polymers include, but are not limited to,
cross-
linked polycarboxylate, cross-linked sulfonated carboxylate, cross-linked
polysulfonate,
cross-linked PVP, cross-linked polypyridinium salt, cross-linked
polyquaternary
ammonium salt, cellulose, cross-linked carboxymethylcellulose, sodium
carboxymethylcellulose, and mixtures thereof.
[0038] The molecular weight of the water-swellable polymer may be between
about
1,000 to about 10,000 daltons, about 1,000 to about 8,000 daltons, about 1,000
to about
6,000 daltons, about 1,000 to about 5,000 daltons, about 1,000 to about 4,000
daltons,
about 1,000 to about 2,000 daltons, about 2,000 to about 10,000 daltons, about
2,000 to
about 8,000 daltons, about 2,000 to about 6,000 daltons, about 2,000 to about
5,000
daltons, about 2,000 to about 4,000 daltons, about 3,000 to about 10,000
daltons, about
3,000 to about 8,000 daltons, about 3,000 to about 6,000 daltons, about 3,000
to about
5,000 daltons, about 3,000 to about 4,000 daltons, about 4,000 to about 10,000
daltons,
about 4,000 to about 8,000 daltons, about 4,000 to about 6,000 daltons, about
5,000 to
about 10,000 daltons, about 5,000 to about 7,500 daltons, and about 7,500 to
about
10,000 daltons.
[0039] The water-swellable polymer may optionally be present in an amount
ranging
from about 0.1% to about 60%, about 0.1% to about 50%, about 0.1% to about
40%,

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about 0.1% to about 30%, about 0.1% to about 20%, about 0.1% to about 15%,
about 0.1% to about
10%, about 0.5% to about 10%, about 0.5% to about 5%, about 0.5% to about 3%),
about 5% to about
60%>, about 5% to about 50%>, about 5% to about 40%>, about 5% to about 30%>,
about 5% to
about 20%, about 5% to about 10%, about 10% to about 60%, about 10% to about
50%, about 10% to
about 40%, about 10% to about 30%, about 10% to 20%, about 20% to about 60%,
about 20% to
about 50%, about 20% to about 40%, about 20% to about 30%, about 30% to about
60%, about 30%
to about 50%, about 30% to about 40%, about 40% to about 60%.
VIII. Surfactants
00401 The composition may contain one or more anionic surfactants. One or
more
additional surfactants selected from nonionic, cationic, ampholytic,
amphoteric and
zwitterionic surfactants and mixtures thereof may be included in some
embodiments,
although in one embodiment no nonionic surfactants are included. A typical
listing of
anionic, ampholytic, and zwitterionic classes, and species of these
surfactants, is given in
U.S. Pat. No. 3,929,678 to Laughlin and Heuring. A list of suitable cationic
surfactants is
given in U.S. Pat. No. 4,259,217 to Murphy. The surfactants may be present at
a level of
from about 0.1% to about 25%, from about 0.1% to about 20%, from about 0.1% to
about
15%), from about 0.1% to about 10%, from about 0.1% to about 5%, from about 5%
to
about 20%), from about 5% to about 15%, from about 5% to about 10%, from about
10% to
about 20%, from about 10% to about 15%, or from about 15% to about 20%.
00411 The composition comprises an anionic surfactant. Essentially any
anionic
surfactants useful for detersive purposes can be used in the cleaning
composition. These can
include salts (including, for example, sodium, potassium, ammonium, and
substituted
ammonium salts such as mono-, di- and tri-ethanolamine salts) of the

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anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic
surfactants
may comprise a sulfonate or a sulfate surfactant. Anionic surfactants may
comprise an
alkyl sulfate, a linear or branched alkyl benzene sulfonate, or an
alkyldiphenyloxide
disulfonate, as described herein.
[0042] Other anionic surfactants include the isethionates such as the acyl
isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl
succinates and
sulfosuccinates, monoesters of sulfosuccinate (for instance, saturated and
unsaturated
C12-C18 monoesters) diesters of sulfosuccinate (for instance saturated and
unsaturated
C6-C14 diesters), and N-acyl sarcosinates. Resin acids and hydrogenated resin
acids are
may also be suitable, such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tallow oil, although in
one
embodiment, no resins are included. Anionic sulfate surfactants suitable for
use herein
include the linear and branched primary and secondary alkyl sulfates, alkyl
ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide
ether sulfates,
the C5-Cracyl-N--(Ci-C4 alkyl) and --N--(C1-C2 hydroxyalkyl) glucamine
sulfates, and
sulfates of alkylpolysacchanides such as the sulfates of alkylpolyglucoside
(the nonionic
nonsulfated compounds being described herein). Alkyl sulfate surfactants may
be
selected from the linear and branched primary C10-C18 alkyl sulfates, the CH-
Cis
branched chain alkyl sulfates, or the C12-C14 linear chain alkyl sulfates.
[0043] Alkyl ethoxysulfate surfactants may be selected from the group
consisting of
the C10-C18 alkyl sulfates, which have been ethoxylated with from 0.5 to 20
moles of
ethylene oxide per molecule. The alkyl ethoxysulfate surfactant may be a Cu-
C18, or a
C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, or from 1
to 5,
moles of ethylene oxide per molecule. One aspect of the invention employs
mixtures of
the alkyl sulfate and/or sulfonate and alkyl ethoxysulfate surfactants. Such
mixtures

CA 02801285 2016-12-14
17
have been disclosed in PCT Patent Application No. WO 93/18124.
[0044] Anionic sulfonate surfactants suitable for use herein include the salts
of C5-C2o linear
alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary
alkane sulfonates, C6-C24
olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates,
fatty acyl glycerol
sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
Suitable anionic carboxylate
surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy
polycarboxylate surfactants and
the soaps (alkyl carboxyls), especially certain secondary soaps as described
herein. Suitable alkyl
ethoxy carboxylates include those with the formula:
RO(CH2CH20),CH2C00-M
wherein R is a C6 to C18 alkyl group, x ranges from 0 to 10, and the ethoxy
late distribution is such
that, on a weight basis, the amount of material where x is 0 is less than 20%
and M is a cation.
Suitable alkyl polyethoxypolycarboxylate surfactants include those having the
formula RO--(CHRI¨
CHR2--0),--R3 wherein R is a C6 to C18 alkyl group, x is from 1 to 25, RI and
R2 are selected from the
group consisting of hydrogen, methyl acid radical, succinic acid radical,
hydroxysuccinic acid
radical, and mixtures thereof, and R3 is selected from the group consisting of
hydrogen,
substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms,
and mixtures
thereof.
100451
Suitable soap surfactants include the secondary soap surfactants, which
contain a
carboxyl unit connected to a secondary carbon. Suitable secondary soap
surfactants for use
herein are water-soluble members selected from the
group consisting

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of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-l-decanoic
acid, 2-
propy1-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-penty1-1-heptanoic acid.
Certain
soaps may also be included as suds suppressors.
[0046] Other suitable anionic surfactants are the alkali metal
sarcosinates of formula
R--CON(R1) CH--)COOM, wherein R is a C5-C17 linear or branched alkyl or
alkenyl
group, Rl is a C1-C4 alkyl group and M is an alkali metal ion. Examples are
the
myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
[0047] Other suitable surfactants include fatty acid sarcosinates which
are mild,
biodegradable anionic surfactants derived from fatty acids and sarcosine
(amino acid).
Sarcosine is the N-methyl derivative of glycine. Sarcosine is a natural amino
acid
found in muscles and other tissues. Sarcosine is found naturally as an
intermediate in
the metabolism of choline to glycine. In a preferred embodiment, the
sarcosines are
acyl sarcosines. Examples of acyl sarcosines include, but are not limited to,
cocoyl
sarcosine, lauroyl sarcosine, myristoyl sarcosine, oleoyl sarcosine, stearoyl
sarcosine
which are modified fatty acids. The salts of acyl sarcosines are referred to
acyl
sarcosinates. Acyl sarcosinates useful herein include, for example, those
having a
formula:
RCON(CH3)CH2COOX
wherein R is an alkyl or alkenyl having from 8 to 22 carbon atoms, preferably
from 12
to 18 carbon atoms, more preferably from 12 to 14 carbon atoms; and X is a
sodium,
potassium, ammonium, or triethanolamine.
[0048] Examples of acyl sarcosinates that can be used with the present
invention
include, but are not limited to, sodium coccyl sarcosinate, sodium lauroyl
sarcosinate

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and sodium myristoyl sarcosinate, sodium oleoyl sarcosinate, sodium stearoyl
sarcosinate, ammonium coccyl sarcosinate, ammonium lauroyl sarcosinate and
ammonium myristoyl sarcosinate, ammonium oleoyl sarcosinate and ammonium
stearoyl sarcosinate. Commercially available preferred acyl sarcosinates
include, but are
not limited to, for example, sodium lauroyl sarcosinate having the tradename
HAMPOSYL L30 which is available from Hampshire Chemicals, and sodium cocoyl
sarcosinate having the tradename HAMPOSYL C30 which is also available from
Hampshire Chemicals.
[0049] Other suitable surfactants include fatty alcohol sulfates which
have a higher
alcohol or alkyl group normally in the range of 10 to 18 carbon atoms. The
cation will
almost invariably be sodium or will include sodium, although other cations,
such as
triethanolamine, potassium, ammonium, magnesium or calcium may also be used.
Preferred fatty alcohol sulfates are those wherein the fatty alcohol is
essentially
saturated and is of a carbon content(s) within the 10 to 18 carbon atoms
range,
preferably 10 or 12 to 14 or 16 carbon atoms, such as 12 to 16, or that is
derived from
coconut oil (coco), palm oil, or palm kernel oil. Lauryl sulfates, and
particularly,
sodium lauryl sulfate, are preferred primary detergents but such designation
also may
apply to such detergents wherein the carbon chain length of the alcohol is not
limited to
12 carbon atoms, but is primarily (over 50% and normally over 70 or 75%) of 12
to 14
carbon atoms. Such materials may be obtained from natural sources, such as
coconut
oil and palm kernel oil. In one embodiment, the fatty alcohol sulfate is a C12-
C18 fatty
alcohol sulfate. In another embodiment, the fatty alcohol sulfate is a C12-C16
fatty
alcohol sulfate. In another embodiment, the fatty alcohol sulfate is a C12-C14
fatty
alcohol sulfate. In another embodiment, the fatty alcohol is a C12 fatty
alcohol sulfate.

CA 02801285 2016-12-14
In another embodiment, the fatty alcohol sulfate is sodium lauryl sulfate. In
a specific embodiment, the
fatty alcohol sulfate is a sodium coco fatty alcohol sulfate.
100501 Suitable amphoteric surfactants for use herein include the amine
oxide surfactants and the
alkyl amphocarboxylic acids. Suitable amine oxides include those compounds
having the formula
R3(0R4)NO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl,
acylamidopropyl and
alkylphenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms;
R4 is an alkylene or
hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures
thereof, x is from 0 to 5,
preferably from 0 to 3; and each R5 is an alkyl or hydroxyalkyl group
containing from 1 to 3, or a
polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
Suitable amine oxides are C 1 Cr
C18 alkyl dimethylamine oxide, and C10-C18 acylamido alkyl dimethylamine
oxide. A suitable example
of an alkyl amphodicarboxylic acid is MIRANOLTM C2M Cone, manufactured by
Miranol, Inc.,
Dayton, N.J.
100511 Zwitterionic surfactants may also be incorporated into the cleaning
compositions. These
surfactants can be broadly described as derivatives of secondary and tertiary
amines, derivatives of
heterocyclic secondary and tertiary amines, or derivatives of quaternary
ammonium, quaternary
phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants
are exemplary
zwitterionic surfactants for use herein.
[0052] Suitable betaines are those compounds having the formula
R(R1)2N+R2C00" wherein R is
a C5-C18 hydrocarbyl group, each RI is typically C1-C3 alkyl, and R2 is a C1-
05 hydrocarbyl group.
Suitable betaines are C12-C18 dimethyl-ammonio hexanoate and the C10-C18
acylamidopropane (or
ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also
suitable for use herein.

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21
100531 Suitable cationic surfactants to be used herein include the
quaternary ammonium
surfactants. The quaternary ammonium surfactant may be a mono C6-C16, or a C6-
C10 N-alkyl or
alkenyl ammonium surfactant wherein the remaining N positions are substituted
by methyl,
hydroxyethyl or hydroxypropyl groups. Suitable are also the mono-alkoxylated
and bis-alkoxylated
amine surfactants. Additional suitable cationic surfactants include coco fatty
acid diethanolamine,
hydrogenated palm tea ester quat, and cationic ethyoxylate fatty acids.
[0054] Another suitable group of cationic surfactants, which can be used in
the cleaning
compositions, are cationic ester surfactants. The cationic ester surfactant is
a compound having
surfactant properties comprising at least one ester (i.e. --COO¨) linkage and
at least one cationically
charged group. Suitable cationic ester surfactants, including choline ester
surfactants, have for
example been disclosed in U.S. Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.
The ester linkage and
cationically charged group may be separated from each other in the surfactant
molecule by a spacer
group consisting of a chain comprising at least three atoms (i.e. of three
atoms chain length), or from
three to eight atoms, or from three to five atoms, or three atoms. The atoms
forming the spacer group
chain are selected from the group consisting of carbon, nitrogen, and oxygen
atoms and any mixtures
thereof, with the proviso that any nitrogen or oxygen atom in said chain
connects only with carbon
atoms in the chain. Thus spacer groups having, for example, ¨0-- (i.e.
peroxide), --N--N-- , and --N¨
O-- linkages are excluded, whilst spacer groups having, for example -CH2-0-- ,
CH2-- and --CH2--
NH--CH2-- linkages are included. The spacer group chain may comprise only
carbon atoms, or the
chain may be a hydrocarbyl chain.

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[0055] The cleaning composition may comprise cationic mono-alkoxylated amine
surfactants, for instance, of the general formula: R1R2R31\rApR4X- wherein Rl
is an
alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, or
from 6 to
about 16 carbon atoms, or from about 6 to about 14 carbon atoms; R2 and R3 are
each
independently alkyl groups containing from one to about three carbon atoms,
for
instance, methyl, for instance, both R2 and R3 are methyl groups; R4 is
selected from
hydrogen, methyl and ethyl; X- is an anion such as chloride, bromide,
methylsulfate,
sulfate, or the like, to provide electrical neutrality; A is a alkoxy group,
especially a
ethoxy, propoxy or butoxy group; and p is from 0 to about 30, or from 2 to
about 15, or
from 2 to about 8. The ApR4 group in the formula may have p=1 and is a
hydroxyalkyl
group, having no greater than 6 carbon atoms whereby the --OH group is
separated
from the quaternary ammonium nitrogen atom by no more than 3 carbon atoms.
Suitable ApR4 groups are --CH2CH2--OH, --CH2CH2CH2--OH, --CH2CH(CH3)--OH
and --CH(CH3)CH2--OH. Suitable Rl groups are linear alkyl groups, for
instance, linear
Ri groups having from 8 to 14 carbon atoms.
[0056]
Suitable cationic mono-alkoxylated amine surfactants for use herein are of the
formula Ri(CH3)(CH3)1\r(CH2CH20)2_5HX- wherein Rl is Cio-C18 hydrocarbyl and
mixtures thereof, especially C10-C14 alkyl, or C10 and C12 alkyl, and X is any
convenient
anion to provide charge balance, for instance, chloride or bromide.
[0057] As noted, compounds of the foregoing type include those wherein the
ethoxy
(CH2CH20) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and
[CH2CH(CH3)0] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or
Pr
and/or i-Pr units.
[0058] The
cationic bis-alkoxylated amine surfactant may have the general formula:
Riic X R4
- wherein Rl is an alkyl or alkenyl moiety containing from about 8
- 2¨cs4 +ApR3A,

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to about 18 carbon atoms, or from 10 to about 16 carbon atoms, or from about
10 to
about 14 carbon atoms; R2 is an alkyl group containing from one to three
carbon atoms,
for instance, methyl; R3 and R4 can vary independently and are selected from
hydrogen,
methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate,
sulfate, or the
like, sufficient to provide electrical neutrality. A and A' can vary
independently and are
each selected from C1-C4 alkoxy, for instance, ethoxy, (i.e., --CH2CH20¨),
propoxy,
butoxy and mixtures thereof, p is from 1 to about 30, or from 1 to about 4 and
q is from
1 to about 30, or from 1 to about 4, or both p and q are 1.
[0059] Suitable cationic bis-alkoxylated amine surfactants for use herein
are of the
formula RiCH3N '(CH2CH2OH)(CH2CH2OH) X-, wherein Rl is C10-C18 hydrocarbyl and

mixtures thereof, or C10, C125 C14 alkyl and mixtures thereof, X- is any
convenient anion
to provide charge balance, for example, chloride. With reference to the
general cationic
bis-alkoxylated amine structure noted above, since in one example compound Rl
is
derived from (coconut) C12-C14 alkyl fraction fatty acids, R2 is methyl and
ApR3 and
A'qR4 are each monoethoxy.
[0060] Other cationic bis-alkoxylated amine surfactants useful herein
include
compounds of the formula: R1R21\r--(CH2CH20)pH¨(CH2CH20)qH X- wherein Rl is
C10-C18 hydrocarbyl, or C10-C14 alkyl, independently p is 1 to about 3 and q
is 1 to about
3, R2 is Cl-C3 alkyl, for example, methyl, and X- is an anion, for example,
chloride or
bromide.
[0061] Other compounds of the foregoing type include those wherein the ethoxy
(CH2CH20) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH20] and
[CH2CH(CH3)0] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or
Pr
and/or i-Pr units.

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24
100621 In one embodiment, the inventive compositions may include at least
one fluorosurfactant
selected from nonionic fluorosurfactants, cationic fluorosurfactants, and
mixtures thereof which are
soluble or dispersible in the aqueous compositions taught herein, sometimes
compositions which do
not include further detersive surfactants, or further organic solvents, or
both. Suitable nonionic
fluorosurfactant compounds are found among the materials presently
commercially marketed under
the tradename FLUORAD (ex. 3M Corp.) Exemplary fluorosurfactants include those
sold as
FLUORAD FC-740, generally described to be fluorinated alkyl esters; FLUORAD FC-
430, generally
described to be fluorinated alkyl esters; FLUORAD FC-431, generally described
to be fluorinated
alkyl esters; and, FLUORAD FC-170-C, which is generally described as being
fluorinated alkyl
polyoxyethlene ethanols.
100631 An example of a suitable cationic fluorosurfactant compound has the
following structure:
CnF2,,,ISO2NHC3H6N+(CH3)3I- where n is about 8. This cationic fluorosurfactant
is available under the
tradename FLUORAD FC-135 from 3M. Another example of a suitable cationic
fluorosurfactant is
F3--(CF2)õ--(CH2)SCH2CHOH--CH2--WRIR2R3C1- wherein: n is 5-9 and m is 2, and
R', R2 and R'
are --CH3. This cationic fluorosurfactant is available under the tradename
ZONYLP" FSD (available
from DuPont, described as 2-hydroxy-3-((gamma-omega-perfluoro-05-2o-
alkyl)thio)-N,N,N-trimethy-
1-1-propyl ammonium chloride). Other cationic fluorosurfactants suitable for
use in the present
invention are also described in EP 866,115 to Leach and Niwata. The
fluorosurfactant selected from
the group of nonionic fluorosurfactant, cationic fluorosurfactant, and
mixtures thereof may be present
in amounts of from 0.001 to 5% wt., preferably from 0.01 to 1% wt., and more
preferably from 0.01 to
0.5% wt.

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[0064] Some embodiments of the invention may comprise a nonionic surfactant.
Essentially any alkoxylated nonionic surfactants are suitable herein, for
instance,
ethoxylated and propoxylated nonionic surfactants. Alkoxylated surfactants can
be
selected from the classes of the nonionic condensates of alkyl phenols,
nonionic
ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols,
nonionic
ethoxylate/propoxylate condensates with propylene glycol, and the nonionic
ethoxylate
condensation products with propylene oxide/ethylene diamine adducts.
[0065] The condensation products of aliphatic alcohols with from 1 to 25
moles of
alkylene oxide, particularly ethylene oxide and/or propylene oxide, are
suitable for use
herein. The alkyl chain of the aliphatic alcohol can either be straight or
branched,
primary or secondary, and generally contains from 6 to 22 carbon atoms. Also
suitable
are the condensation products of alcohols having an alkyl group containing
from 8 to 20
carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
[0066] Polyhydroxy fatty acid amides suitable for use herein are those
having the
structural formula R2CONR1Z wherein: Rl is H, C1-C4 hydrocarbyl, 2-
hydroxyethyl, 2-
hydroxypropyl, ethoxy, propoxy, or a mixture thereof, for instance, Ci-C4
alkyl, or C1
or C2 alkyl; and R2 is a C5-C31 hydrocarbyl, for instance, straight-chain C5-
C19 alkyl or
alkenyl, or straight-chain C9-C17 alkyl or alkenyl, or straight-chain C11-C17
alkyl or
alkenyl, or mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear

hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain,
or an
alkoxylated derivative (for example, ethoxylated or propoxylated) thereof Z
may be
derived from reducing a sugar in a reductive amination reaction, for example,
Z is a
glycityl.
[0067] Suitable fatty acid amide surfactants include those having the
formula:
RiCON(R2)2 wherein Rl is an alkyl group containing from 7 to 21, or from 9 to
17

CA 02801285 2016-12-14
26
carbon atoms and each R2 is selected from the group consisting of hydrogen, C1-
C4 alkyl, CI-CI
hydroxyalkyl, and --(C2H40)xH, where x is in the range of from 1 to 3.
[0068] Suitable alkylpolysaccharides for use herein are disclosed in U.S.
Pat. No. 4,565,647 to
Llenado, having a hydrophobic group containing from 6 to 30 carbon atoms and a
polysaccharide, e.g.,
a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.
Alkylpolyglycosides
may have the formula: R20(Cn112,0),(glycosyl), wherein R2 is selected from the
group consisting of
alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in
which the alkyl groups
contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and xis
from 1.3 to 8. The glycosyl
may be derived from glucose.
[0069] Other suitable nonionic surfactants are food safe nonionic
surfactants. Examples of food
safe nonionic surfactants are sucrose esters, such as sucrose cocoate
available from Croda, and
sorbitan esters, such as polyoxyethylene (20) sorbitan monooleate from J. T.
Baker and
polyoxyethylene (20) sorbitan monolaurate from Uniquema. Other examples of
food safe nonionic
surfactants are given in Generally Recognized As Safe (GRAS) lists, as
described below.
[0070] In one embodiment, the compositions may specifically contain alkyl
polyglucoside
("APG") surfactant. Suitable alkyl polyglucoside surfactants are the
alkylpolysaccharides that are
disclosed in U.S. Pat. No. 5,776,872 to Giret et at; U.S. Pat. No. 5,883,059
to Furman et at; U.S. Pat.
No. 5,883,062 to Addison et al; and U.S. Pat. No. 5,906,973 to Ouzounis et al.
Suitable alkyl
polyglucosides for use herein are also disclosed in U.S. Pat. No. 4,565,647 to
Llenado, describing
alkylpolyglucosides having a hydrophobic group containing from about 6 to
about 30 carbon atoms, or
from about 10 to about 16 carbon atoms and polysaccharide, e.g., a
polyglycoside, hydrophilic group

CA 02801285 2012-11-30
WO 2011/062707 PCT/US2010/052487
27
containing from about 1.3 to about 10, or from about 1.3 to about 3, or from
about 1.3
to about 2.7 saccharide units. Optionally, there can be a polyalkyleneoxide
chain joining
the hydrophobic moiety and the polysaccharide moiety. A suitable alkyleneoxide
is
ethylene oxide. Typical hydrophobic groups include alkyl groups, either
saturated or
unsaturated, branched or unbranched containing from about 8 to about 18, or
from
about 10 to about 16 carbon atoms. The alkyl group may contain up to about 3
hydroxy
groups and/or the polyalkyleneoxide chain can contain up to about 10, or less
than
about 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl,
nonyldecyl,
undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and
octadecyl,
di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides,
glucoses,
fructosides, fructoses and/or galactoses. Suitable mixtures include coconut
alkyl, di-, tri-
, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and
hexaglucosides.
[0071] Suitable alkylpolyglycosides (or alkylpolyglucosides) have the
formula:
R20(CõH2õ0)t(glucosyl)x wherein R2 is selected from the group consisting of
alkyl,
alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which
the alkyl
groups contain from about 10 to about 18, preferably from about 12 to about 14
carbon
atoms; n is about 2 or about 3, preferably about 2; t is from 0 to about 10,
preferably 0;
and x is from about 1.3 to about 10, preferably from about 1.3 to about 3,
most
preferably from about 1.3 to about 2.7. The glycosyl is preferably derived
from
glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is
formed
first and then reacted with glucose, or a source of glucose, to form the
glucoside
(attachment at the 1-position). The additional glycosyl units can then be
attached
between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-
position,
preferably predominantly the 2-position.

CA 02801285 2016-12-14
28
[0072] A
group of alkyl glycoside surfactants suitable for use in the practice of this
invention
may be represented by formula I below:
RO--(R20)y-(G),ZbI
wherein R is a monovalent organic radical containing from about 6 to about 30
(preferably from about
8 to about 18) carbon atoms; R2 is a divalent hydrocarbon radical containing
from about 2 to about 4
carbon atoms; 0 is an oxygen atom; 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 reducing a saccharide
containing 5 or 6 carbon atoms;
and x is a number having an average value from about 1 to 5 (preferably from
1.1 to 2); Z is 02MI,
02CR3, 0(CH2), CO2M1, OSO3M1, or 0(CH7)S03M1; R3 is (CH7)CO2M1
or CH=CHCO2M1; (with the proviso that Z can be 02M1 only if Z is in place of a
primary hydroxyl
group in which the primary hydroxyl-bearing carbon atom, --CH2OH, is oxidized
to form a--CONI
group); b is a number from 0 to 3x+1 preferably an average of from 0.5 to 2
per glycosal group; p is 1
to 10, MI is H+ or an organic or inorganic cation, such as, for example, an
alkali metal, ammonium,
monoethanolamine, or calcium. As defined in Formula I, R is generally the
residue of a fatty alcohol
having from about 8 to 30 or 8 to 18 carbon atoms. Suitable alkylglycosides
include, for example,
APG 325 (a C9-C11 alkyl polyglycoside available from Cognis Corporation), APG
625 (a C10-C16alkyl
polyglycoside available from Cognis Corporation), Dow TRITONTm CG110 (a C8-C10
alkyl
polyglycoside available from Dow Chemical Company), AG6202 (a C8 alkyl
polyglycoside available
from Akzo Nobel) GLUCOPONTM 425N (a C8-C16 alkyl polyglycoside available from
Cognis
Corporation), GLUCOPONTm 215 (a C8-C10 alkyl polyglycoside available from
Cognis Corporation),

CA 02801285 2012-11-30
WO 2011/062707 PCT/US2010/052487
29
GLUCOPON 225 (a C8-C10 alkyl polyglycoside available from Cognis Corporation)
and ALKADET 150 (a C8-C10 alkyl polyglycoside available from Huntsman
Corporation). A C8 to C10 alkylpoly-glucoside includes alkylpoly-glucosides
wherein
the alkyl group is substantially C8 alkyl, substantially C10 alkyl, or a
mixture of
substantially C8 and C10 alkyl. Additionally, short chain APGs such as C4
and/or C6 or
mixtures thereof may be suitable for use with the present invention.
[0073] In one embodiment, the composition contains no enzymes, waxes, resins,
nonionic surfactants, chlorite salts, or chloride dioxide.
IX. Hydrotropes
[0074] The composition may include one or more hydrotropes for solubilizing
the
other components of the composition upon addition of water. The hydrotrope
solubilizing materials, when used, include, but are not limited to water
soluble salts of
low molecular weight organic acids such as the alkali metal (sodium and/or
potassium)
salts of aromatic sulfonic acids. Specific exemplary materials include, but
are not
limited to, toluene sulfonate, cumene sulfonate, xylene sulfonate, naphthalene
sulfonate,
methyl naphthalene sulfonate, and combinations thereof
[0075] The hydrotropes may be present at a level of from about 0.1% to about
25%,
from about 0.1% to about 20%, from about 0.1% to about 15%, from about 0.1% to

about 10%, from about 0.1% to about 5%.
X. Additional Adjuncts
[0076] In some embodiments, the compositions may optionally contain one or
more
of the following adjuncts: colorants, perfumes, sequestrants, anti-corrosion
agents,
lubricants, binders, fillers, disintegration aids, preservatives, or
desiccants. Other
adjuncts include, but are not limited to, acids, electrolytes, stabilizers,
thickeners,
defoamers, cloud point modifiers, stain and soil repellants, odor control
agents,

CA 02801285 2016-12-14
brighteners, fluorescent whitening agents, and solid processing aids. Binders,
when used, include, but
are not limited to, celluloses, starches, gums, and synthetic polymers. Solid
processing aids, when
used, include, but are not limited to, flow aids, lubricants, anti-static
agents, and glidants. Electrolytes,
when used, may include, but are not limited to, calcium, sodium and potassium
chloride. Thickeners,
when used, include, but are not limited to, xanthan gum, calcium carbonate,
cellulose, aluminum
oxide, alginates, guar gum, methyl, ethyl, clays, and/or propyl
hydroxycelluloses. Defoamers, when
used, include, but are not limited to, silicones, aminosilicones, silicone
blends, and/or
silicone/hydrocarbon blends.
[0077]
Preservatives, when used, include, but are not limited to, mildewstat or
bacteriostat,
methyl, ethyl and propyl parabens, phosphates such as trisodium phosphate,
short chain organic acids
(e.g. acetic, lactic and/or glycolic acids), bisguanidine compounds (e.g.
DANTAGARD and/or
GLYDANTI") and/or short chain alcohols (e.g. ethanol and/or isopropyl
alcohol). The mildewstat or
bacteriostat includes, but is not limited to, mildewstats (including non-
isothiazolone compounds)
including KATHONI" GC, a 5-chloro-2-methyl-4-isothiazolin-3-one, KATHON'" ICP,
a 2-methyl-4-
isothiazolin-3-one, and a blend thereof, and KATHON`" 886, a 5-chloro-2-methy1-
4-isothiazolin-3-
one, all available from Rohm and Haas Company; BRONOPOL, a 2-bromo-2-
nitropropane 1, 3 diol,
from Boots Company Ltd., PROXELTM CRL, a propyl-p-hydroxybenzoate, from ICI
PLC; NIPASOL
M, an o-phenyl-phenol, Na salt, from Nipa Laboratories Ltd., DOWICIDE A, a 1,2-

Benzoisothiazolin-3-one, from Dow Chemical Co., Nipacides from Clariant, and
IRGASANTM DP 200,
a 2,4,4'-trichloro-2-hydroxydiphenylether, from Ciba-Geigy A.G.
XL Forms and Uses

CA 02801285 2012-11-30
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31
[0078] The compositions of the present invention may be used in the
disinfection of
dentures, although other uses of the composition (e.g., as a mouthwash, or for
endodontic root canal disinfection) are also contemplated. The
one-layered
composition of the present invention is preferably in the form of a single-
layer
substantially homogenous tablet, although it may alternatively take the form
of a
powder or granules. The present invention is directed to composition claims
and
methods of using the composition. Generally, methods steps of using the
composition
include contacting a specific surface (e.g., dentures) with the composition in
water so as
to clean the specific surface with the composition.
XII. Examples
[0079] Without limitation, the following examples illustrate exemplary
implementation of the present invention:
Table 1-Example Compositions 1-4
Example 1 Example 2 Example 3 Example 4
Ingredient Wt.% active Wt.% active Wt.% active Wt.% active
Calcium hypochlorite 1.65 4.75 1.65 0.34
Succinic acid 56.64 54.37 56.64 57.60
Sodium carbonate 36.28 34.83 36.28 36.90
Maleic acid / acrylic acid
copolymer 2.09 2.01 2.09 2.13
Sodium carboxymethyl
cellulose 0.11 0.11 0.11 0.11
Sodium xylene sulfonate 1.39 1.34 1.39 1.42
Sodium lauryl sulfonate 1.39
Sodium linear alkylbenzene
sulfonate 1.34 1.39 1.42
Weight per use, g 2.726 2.840 2.726 2.680
HOC1, ppm when dissolved in
150 mL of water 211 634 211 42
[0080] The
compositions in Table 1 were initially prepared as powders. The
powders in the above table were prepared and dissolved in 150 mL of water to
make a
cleaning solution for dentures and dental appliances. All of the powders
displayed

CA 02801285 2012-11-30
WO 2011/062707 PCT/US2010/052487
32
effervescence and created foam to signal cleaning power. They also released
the
indicated amount of hypochlorous acid to disinfect and remove stains, plaque
and
biofilms. The pH of the cleaning solution was between pH 5.5 and pH 6.5.
[0081] Each of the powders in Table 1 were compressed into single-layer
tablets to
deliver the desired weight per use. All the tablets dissolved within 5 minutes
with
effervescence and foam. They all released the targeted concentration of
hypochlorous
acid when added to 150 mL of water and had a pH between 5.5 and 6.5.
[0082] Additional exemplary compositions 5-19 are described in Tables 2-4,
below.
Table 2-Example Compositions 5-9
Example 5 Example 6 Example 7 Example 8
Example 9
Ingredient Wt. % active Wt. % active Wt. % active Wt. % active Wt.
% active
Calcium hypochlorite, 79 %
wt 49.88 32.34 2.11 1.03 0.87
Sodium polyacrylate
(MW=5,100) 2.43
adipic acid 31.42 53.20 41.52
Sodium polyacrylate
(MW=2800) 0.95
Sodium polyacrylate; maleic
copolymer (MW=4,500) 2.11 1.97
Sodium polyacrylate; maleic
copolymer (MW=2,800) 1.96
Hydroxypropyl cellulose 0.05
Microcrystalline cellulose 0.10
Sodium linear alkylbenzene
sulfonate 5.78 1.41 1.31
Sodium xylene sulfonate 0.63 0.88 0.36 0.34 1.31
Polyvinylpyrrolidone (PVP)
grade K-13/19 0.19
Sodium carbonate 16.44 22.85 36.63 34.22
Sodium carboxmethyl
cellulose 0.07 0.10
Sodium sesquicarbonate 42.06
Sodium lauryl sulfate 0.63 1.32
Succinic acid 35.65 57.19 18.69
Weight per use, g 6.02 4.33 2.70 2.90 2.89
HOC1, ppm when dissolved
in 150 mL of water 11147 5259 216 114 95

CA 02801285 2012-11-30
WO 2011/062707 PCT/US2010/052487
33
Table 3-Example Compositions 10-14
Example 10 Example 11 Example 12
Example 13 Example 14
Ingredient Wt.
% active Wt. % active Wt. % active Wt. % active Wt. % active
Calcium hypochlorite, 79 %
wt 8.78 0.52 2.99 8.56 0.26
3-pyridinesulfonic acid 46.23
sodium polyacrylate
(MW=5,100) 1.95
Adipic acid 39.56
Sodium polyacrylate
(MW=2800) 1.48 1.71
Alkyldiphenyloxide
disulfonate 1.30 5.12
Alkylnapthalene sulfonate 2.56
Sodium polyacrylate, maleic
copolymer (MW=4,500) 1.46
Crosslinked sodium
carboxymethylcellulose 0.07
Glutaric acid 52.89
Hydroxypropyl cellulose 0.08
Linear alkyl benzene
sulfonic acid 31.21
Sodium linear alkylbenzene
sulfonate 1.14
Sodium xylene sulfonate 0.83 0.99
Polyacrylic acid
(MW<=6000) 33.89
Polyvinylpyrrolidone (PVP)
grade K-13/19 0.10
Sodium bicarbonate 46.70
Sodium bisulfate 12.81
Sodium carbonate 21.71 25.72 33.90 25.34
Sodium carboxymethyl
cellulose 0.08 0.09
Sodium sulfate 33.89 39.01
Sodium xylene sulfonate 1.30
Sodium lauryl sulfate 0.83 0.99 1.14
Succinic acid 12.81
Weight per use, g 4.56 3.85 3.34 2.92 3.90
HOC1, ppm when dissolved
in 150 mL of water 1500 75 378 948 38

CA 02801285 2012-11-30
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34
Table 4-Example Compositions 15-19
Example 15 Example 16 Example 17
Example 18 Example 19
Ingredient Wt.
% active Wt. % active Wt. % active Wt. % active Wt. % active
Magnesium hypochlorite,
52% wt 49.88 1.53 1.29 22.79 0.74
Calcium hypochlorite, 79 %
wt 25.73 1.14 0.74
Adipic acid 31.42 57.67 25.73 22.79 29.52
Alkyl diphenyloxide
disulfonate 0.96 0.87 1.12
Alkylnapthalene sulfonate 1.29 1.14 1.48
Crosslinked sodium
carboxylmethyl cellulose 0.09
Hydroxypropyl cellulose 0.05
Microcrystalline cellulose 0.07 0.09
Polyvinylpyrrolidone (PVP)
grade K-13/19 0.08
Sodium bisulfate 10.29 9.12 11.81
Sodium carbonate 16.44 30.18 25.44 22.54 29.20
Sodium lauryl sulfate 1.16
Sodium linear alkylbenzene
sulfonate 0.63
Sodium polyacrylate
(MW=2800) 0.95 1.47 1.30 1.68
Sodium polyacrylate
(MW=5,100) 1.74
Sodium sesquicarbonate 11.40 14.76
Sodium xylene sulfonate 0.63 1.53
Succinic acid 6.10 7.72 6.84 8.86
Weight per use, g 6.02 3.28 3.89 4.39 3.39
HOC1, ppm when dissolved
in 150 mL of water 8248 140 3906 2966 164
[0083]
Without departing from the spirit and scope of this invention, one of ordinary
skill can make various changes and modifications to the invention to adapt it
to various
usages and conditions. As such, these changes and modifications are properly,
equitably, and intended to be, within the full range of equivalence of the
following
claims.

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Administrative Status

Title Date
Forecasted Issue Date 2017-08-22
(86) PCT Filing Date 2010-10-13
(87) PCT Publication Date 2011-05-26
(85) National Entry 2012-11-30
Examination Requested 2015-09-21
(45) Issued 2017-08-22

Abandonment History

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Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Application Fee $400.00 2012-11-30
Maintenance Fee - Application - New Act 2 2012-10-15 $100.00 2012-11-30
Maintenance Fee - Application - New Act 3 2013-10-15 $100.00 2013-09-20
Maintenance Fee - Application - New Act 4 2014-10-14 $100.00 2014-09-18
Request for Examination $800.00 2015-09-21
Maintenance Fee - Application - New Act 5 2015-10-13 $200.00 2015-09-23
Maintenance Fee - Application - New Act 6 2016-10-13 $200.00 2016-09-20
Final Fee $300.00 2017-07-05
Maintenance Fee - Patent - New Act 7 2017-10-13 $200.00 2017-10-09
Maintenance Fee - Patent - New Act 8 2018-10-15 $200.00 2018-10-08
Maintenance Fee - Patent - New Act 9 2019-10-15 $200.00 2019-10-04
Maintenance Fee - Patent - New Act 10 2020-10-13 $250.00 2020-10-09
Maintenance Fee - Patent - New Act 11 2021-10-13 $255.00 2021-10-11
Maintenance Fee - Patent - New Act 12 2022-10-13 $254.49 2022-10-07
Maintenance Fee - Patent - New Act 13 2023-10-13 $263.14 2023-10-06
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE CLOROX COMPANY
Past Owners on Record
None
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 2012-11-30 34 1,440
Claims 2012-11-30 6 145
Abstract 2012-11-30 1 59
Cover Page 2013-02-05 1 40
Claims 2015-10-07 4 140
Description 2016-12-14 34 1,330
Claims 2016-12-14 4 134
Final Fee 2017-07-05 1 31
Cover Page 2017-07-20 1 40
PCT 2012-11-30 7 354
Assignment 2012-11-30 4 87
PCT 2012-11-30 1 40
Request for Examination 2015-09-21 1 38
Amendment 2015-10-07 6 194
Examiner Requisition 2016-06-14 4 257
Amendment 2016-12-14 24 858