Canadian Patents Database / Patent 2363741 Summary

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(12) Patent Application: (11) CA 2363741
(54) English Title: COLOR STABLE HYPOCHLOROUS SANITIZER AND METHODS
(54) French Title: DESINFECTANT HYPOCHLOREUX A COULEUR STABLE ET PROCEDES ASSOCIES
(51) International Patent Classification (IPC):
  • C11D 3/395 (2006.01)
  • A01N 25/00 (2006.01)
  • C11D 3/40 (2006.01)
  • C11D 3/48 (2006.01)
  • C11D 7/08 (2006.01)
  • C11D 7/26 (2006.01)
  • C11D 17/00 (2006.01)
(72) Inventors :
  • SOWLE, EDDIE D. (United States of America)
  • BOWLING, DARRYL C. (United States of America)
(73) Owners :
  • KAY CHEMICAL COMPANY (United States of America)
(71) Applicants :
  • KAY CHEMICAL COMPANY (United States of America)
(74) Agent: CASSAN MACLEAN
(74) Associate agent: CASSAN MACLEAN
(45) Issued:
(86) PCT Filing Date: 2000-02-23
(87) Open to Public Inspection: 2000-08-31
Examination requested: 2004-07-21
(30) Availability of licence: N/A
(30) Language of filing: English

(30) Application Priority Data:
Application No. Country/Territory Date
09/257,086 United States of America 1999-02-24
09/501,876 United States of America 2000-02-10

English Abstract




Manual warewashing in common food service locations is typically performed in
a multicompartment sink. In one basin the ware is contacted with an aqueous
detergent. The cleaned ware is rinsed in a subsequent sink and is then
sanitized in a sanitizing solution in a third sink. Hypochlorite bleaches, if
adjusted to an appropriate pH, can maintain substantial sanitizing capacity
while not decolorizing otherwise oxidatively sensitive dyes. In the method of
the invention, the sanitizing solution adjusted to a pH of less than about 7
containing a dye can maintain a stable dye solution for a period of time
greater than the time required to deplete 90 % or more of the OC in solution.
An indication of the existence of active sanitizer in the sanitizer step based
on the presence of color in the aqueous solution is thus obtained.


French Abstract

Dans les entreprises de restauration, la plonge manuelle est généralement effectuée dans un évier à plusieurs compartiments. Dans un bassin la vaisselle est mise en contact avec une solution aqueuse d'un agent tensioactif. La vaisselle est rincée dans un autre bassin, puis désinfectée dans un troisième bassin au moyen d'une solution désinfectante. Des décolorants à base d'hypochlorite fortement oxydant, permettent, lorsque le pH est ajusté à une valeur convenable, de maintenir une capacité sensiblement désinfectante tout en ne décolorant pas des colorants sensibles à l'oxydation. Dans le procédé de l'invention, la solution désinfectante, ajustée à un pH inférieur à environ 7, contenant un colorant, permet de garder une coloration stable durant une période supérieure à la durée requise pour épuiser 90 % ou plus d'ion OCl?-1¿ en solution. Il en résulte une indication satisfaisante de la présence de désinfectant actif sur la base de la couleur de la solution désinfectante.


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




38

WE CLAIM:

1. An active chlorine containing solid unit containing a chlorine
source and an stable source of dye, the solid unit comprising:
(a) about 10 to about 200 parts by weight of a solid active
source of chlorine per each part of dye; and
(b) a source of a dye, the dye comprising a particulate dye
having a minimum particle size of about 200 microns, wherein the
solid unit comprises a major dimension greater than about 2
millimeters and a weight greater than about 2 grams, the solid unit
substantially free of an amount of free water sufficient to act as a
reaction medium between the solid chlorine source and the dye.

2. The solid unit of claim 1 wherein the dye comprises a dye with a
minimum particle size of about 500 microns and a density less than 0.9
gram-cm-3.

3. The solid unit of claim 1 wherein the solid unit comprises a
cylindrical tablet having a diameter of about 4 to 75 millimeters and a
thickness of about 1 to 25 millimeters.

4. The solid unit of claim 1 wherein the solid chlorine source
comprises an alkali metal dichloroisocyanurate dihydrate.

5. The solid unit of claim 1 wherein the solid unit comprises a
spheroid having a major dimension of about 5 to 60 millimeters and a
dimension perpendicular to said major dimension of about 1 to 50
millimeters.

6. The solid unit of claim 4 wherein the solid chlorine source
comprises an encapsulated alkali metal dichloroisocyanurate dihydrate.



39

7. The solid unit of claim 1 wherein the dye comprises a granular dye
having a particle size greater than about 600 microns and a density less than
about
0.85 grams-cm-3.

8. A method of using the solid unit of claim 1 in a cleaning or
sanitizing operation, the method comprises:~
(a) placing the solid unit in a volume of an aqueous liquid in a
container, the weight ratio of the solid to the aqueous solution being
about 0.1 to 20 grams per liter of water to form a dye colored, active-
chlorine solution; and
(b) contacting ware with the aqueous active-chlorine solution
during cleaning or sanitizing operations for a period of up to 4 hours
and after detecting a color change, either replacing the aqueous
solution or replenishing the aqueous solution with additional chlorine
source.

9. A particulate composition forming an aqueous solution having an
active chlorine source and a dye, the powdered concentrate comprising:
(a) about 1 to 90 wt% of an encapsulated source of halogen;
and
(b) an effective amount of dye;
wherein the concentrate has substantially no free water, has an extended
shelf life of greater than one month and when added to an aqueous diluent
provides a dye that indicates the presence of an active halogen
concentration for a predetermined time.

10. The composition of claim 9 wherein the source of halogen
comprises a source of chlorine.

11. The composition of claim 10 wherein the source of chlorine
comprises chloroisocyanurate compound.


40



12. The composition of claim 9 which also comprises an acid source
to obtain a pH less than 7 in the aqueous solution.

13. The composition of claim 9 wherein the indicator comprises
FD&C dye No. 40.

14. The composition of claim 9 wherein the indicator comprises
FD&C dye No. 3.

15. The composition of claim 12 wherein the acid source comprises a
solid acid.

16. The composition of claim 9 wherein the acid salt comprises
sodium dihydrogen phosphate, sodium hydrogen tartrate, sodium hydrogen
sulfate, or mixtures thereof.

17. The composition of claim 9 wherein the builder salt comprises
sodium sulfate, sodium carbonate, trisodium phosphate, sodium bicarbonate
or mixtures thereof.

18. The composition of claim 9 wherein the concentration of dye in
the concentrate is adjusted such that the dye color changes or is depleted
during a useful predetermined period of time during which the sanitizer
solution can be used for its intended purpose and maintain at least 50 ppm
active chlorine.

19. An aqueous liquid cleaning or sanitizing composition containing a
dye that indicates chlorine concentration, the liquid comprising a major
proportion of an aqueous diluent, and
(a) a source of acid;
(b) an effective amount of a dye to obtain a colored solution for
a predetermined period of time;


41



(c) an effective cleaning or sanitizing amount of a halogen
bleach;
wherein the aqueous solution has a pH less than 7 and the dye color is
depleted or changed before the concentration of halogen is depleted to less
than 50 ppm from the solution.

20. The concentrate of claim 19 wherein the source of halogen
comprises a source of chlorine.

21. The composition of claim 20 wherein the source of chlorine
comprises a chloroisocyanurate compound.

22. The composition of claim 19 which also comprises a builder salt.

23. The composition of claim 19 wherein the indicator comprises
FD&C dye No. 40.

24. The composition of claim 21 wherein the chlorine source
comprises an encapsulated alkali metal dichloroisocyanurate dihydrate.

25. The composition of claim 19 wherein the acid source comprises a
solid acid.

26. The composition of claim 19 wherein the acid salt comprises
sodium dihydrogen phosphate, sodium hydrogen tartrate, sodium hydrogen
sulfate, or mixtures thereof.

27. The composition of claim 19 wherein the builder salt comprises
sodium sulfate, sodium carbonate, trisodium phosphate, sodium bicarbonate
or mixtures thereof.

28. The composition of claim 19 wherein the concentration of dye in
the concentrate is adjusted such that the dye color changes or is depleted


42



during a useful period of time during which the sanitizer solution can be used
for its intended purpose.

29. A method of cleaning or sanitizing hard surfaces comprising:
(a) contacting the hard surface with an aqueous solution
comprising the composition of claim 9, forming a surface having the
aqueous liquid comprising a halogen source; and
(b) removing the aqueous liquid halogen source.

30. A method of hand washing ware in a sink having two or more
basins, using a stable dye in an aqueous oxidative chlorine based cleaner or
sanitizer composition, the method comprising:
(a) contacting ware with an aqueous detergent in a first basin
to remove soil, producing cleaned ware; and
(b) contacting the cleaned ware in a subsequent basin with an
aqueous sanitizer solution comprising an effective amount of a
chlorine source, the sanitizer solution additionally comprising a dye
that is sufficiently stable in the aqueous solution to maintain at least
some detectable color in the sanitizing solution after greater than 90%
of the oxidizing species have been consumed.

31. The method of claim 30 wherein the chlorine source comprises
an alkali metal hypochlorite.

32. The method of claim 31 wherein the hypochlorite sanitizer
comprises sodium hypochlorite.

33. The method of claim 30 wherein the chlorine source comprises a
chlorinated isocyanurate compound which generates hypochlorous acid at
the pH.



43



34. The method of claim 30 wherein the cleaned ware is contacted
with a potable water rinse to form a rinsed cleaned ware prior to contacting
the rinsed cleaned ware with the sanitizing solution.

35. The method of claim 30 wherein the aqueous sanitizer solution
has a pH of less than about 7, the pH selected such that the concentration of
OCl-1 is minimized and the concentration of HOCl is maximized.

36. The method of claim 34 wherein the cleaned ware is contacted
with the aqueous rinse for approximately 1 to about 30 seconds and the
rinsed cleaned ware is contacted with the aqueous sanitizing solution for
about 1 to 30 seconds.

37. The method of claim 30 wherein the ware is contacted with
mechanical action in the first basin with the aqueous detergent for sufficient
amount of time to substantially remove food soil and the cleaned ware is
contacted with the aqueous sanitizer solution for about 1 to about 30
seconds.

38. The method of claim 30 wherein the concentration of the chlorine
source is about 1 to 100 parts per million in the solution.

39. The method of claim 30 wherein the indicator comprises FD&C
Dye #40.

40. The method of claim 30 wherein the indicator comprises FD&C
Dye #3.

41. The method of claim 30 wherein after the sanitizing step, the
ware is permitted to dry without contact with mechanical action or an
aqueous solution.



44



42. The method of claim 30 wherein the sanitizing solution is made
by diluting a powdered solid comprising:
(a) about 1 to 90 wt% of an encapsulated chlorine source;
(b) about 0.01 to 1.0 wt% of a dye;
(c) about 0.5 to 20 wt% of an acid source; and
(d) a major portion of a builder salt.

43. The method of claim 42 wherein the encapsulated chlorine
source comprises an encapsulated chloroisocyanurate compound.

44. The method of claim 42 wherein the encapsulated chlorine
source comprises a particle of the chlorine source, a first inorganic layer
and
a second organic layer.

45. The method of claim 42 wherein the dye comprises FD&C dye
No. 40.

46. The method of claim 42 wherein the acid salt comprises
potassium dihydrogen phosphate, sodium hydrogen tartrate or mixtures
thereof.

47. The method of claim 42 wherein the builder salt comprises
sodium sulfate.

48. The method of claim 42 wherein the pH of the aqueous sanitizing
solution is adjusted to a pH less than 7 and to a pH at which greater than
about 80% of the oxidative species is in the form of HOCl and less than
about 20% of the oxidative species is in the form of OCl-1.

49. The method of claim 42 wherein the dye color is maintained in
the aqueous sanitizing solution for a period of time of about 3 to 6 hours.




45



50. A sanitizing solution useful in sanitizing a surface, the solution
comprising:
(a) a major proportion of an aqueous medium having a pH less
than 7;
(b) about 1 to 90 wt% of a source of an encapsulated active
chlorine source resulting in at least 100 ppm active chlorine;
(c) an effective amount of a dye; and
(d) a solid diluent or extender salt.

51. The composition of claim 50 wherein the composition additionally
comprises an acid salt selected from the group consisting of sodium acid
phosphate, sodium acid tartrate or mixtures thereof.


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



CA 02363741 2001-08-23
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COLOR STABLE HYPOCHLOROUS SANITIZER AND METHODS
Field of the Invention
The invention relates to a solid concentrate composition which is shelf stable
S for a minimum of two years. The invention also relates to a liquid or solid
composition that combine a dye and a chlorine source resulting in unique
cleaning or
sanitizing properties with controlled, measured, acceptable and useful
chlorine
stability. The invention also relates to methods for cleaning or sanitizing
hard
surfaces and for hand washing ware in a multibasin sink using at least a
washing step
involving an aqueous detergent solution followed by a sanitizing step
involving an
aqueous chlorine based sanitizer solution. The invention further relates to a
spray
bottle application for sanitizing hard surfaces.
Background of the Invention
Active halogen, e.g. chlorine, materials have been available for bleaching,
sanitizing and cleaning purposes for many years. Such materials in the form of
hypochlorite (NaOCI), chlorinated isocyanurate compounds, encapsulated
chlorine
sources, chlorinated tripolyphosphate, etc. have been used in single solutions
or
more commonly in alkaline, aqueous, powdered or solid materials to form active
concentration of chlorine. Such materials are commonly used to bleach
clothing,
clean or sanitize hard surfaces, and other generic destaining, antimicrobial
or soil
removing processes.
Cleaning solutions using surfactants, builders, detergents, etc. for removing
soil or the reduction of microbial populations on hard surfaces have been in
use for
many years. Such hard surfaces include ceramic, metal, plastic composite,
surfaces
that can be walls, floors, countertops, tables, chairs, food surface
apparatus, etc.
Such surfaces come into contact with a variety of soils and can also promote
the
growth of large populations of microorganisms. The removal of such soils and
the
reduction of microbial populations is an important goal in maintaining a high
quality
food service operation.



CA 02363741 2001-08-23
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2
Another important type of hard surface is the surface of ware including
dishware tableware and kitchenware. The hand washing of dish and kitchenware
is
commonly achieved in a multibasin sink by first contacting soiled ware in an
aqueous detergent solution with hand or mechanical agitation for the purpose
of
removing soil from the ware. Such processes can also include other steps such
as a
prescraping step, a deliming step, a stain bleaching step or other
conventional
operations. Once cleaned of soil, the ware is thoroughly rinsed typically with
potable water. Once rinsed, the ware is then submerged in a sanitizing bath in
a
third basin and allowed to drain and permitted to dry. Such a sanitizing step
ensures
that microbial populations are substantially reduced.
One common use for chlorine based sanitizer solutions is in a final sanitizing
step in a hand surface sanitizing or warewashing method using a solution made
by
diluting commonly available aqueous sodium hypochlorite. Dilution ratio of
about 1
part by volume of sodium hypochlorite per 10,000 parts of service water are
used
resulting in an effective bleaching and sanitizing solution at a strength of
greater
than 100 parts per million, or for certain applications, SO parts per million
(ppm)
active chlorine. The conventional solutions typical in the prior art have a
substantial hypochlorite (OCl-~) concentration and an alkaline pH. Such a
sanitizing
solution is highly effective in bleaching stains and is very effective at
reducing
microbial populations. Such solutions can also be used on hard surfaces for
soil,
stain and microbial control.
These sanitizing solutions are used until depleted of an effective chlorine
content and are replaced when the concentration of the oxidizing species drops
below a certain concentration typically below about 50 ppm active chlorine.
Maintaining an effective concentration of the oxidizing species in the final
sanitizing
solution is important to maintain cleanliness, sanitization and a stain free
condition
in the ware. Active chlorine or OCl-1 concentration is typically monitored
using
indicator strips or test kits. Oxidizing solutions are highly active and can
oxidize
and decolorize a dye, used at conventional concentration, contained in the
solution,
rapidly often in an amount of time less than about 15 minutes. Since dyes are
typically used at very low concentrations, the substantial decolorization of
the
solution consumes little hypochlorite but provides little information with
respect to



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
the concentration of the hypochlorite in solution. Dishwashing or kitchen
personnel
cannot know when to change the chlorine depleted solution to maintain at least
SO
ppm active chlorine. As a result, the sanitizing solution is discarded and
replenished
very often resulting in substantial waste of materials, time and money.
Potentially
worse is the situation in which the solution is not changed often enough,
resulting in
inadequate sanitization due to an active chlorine concentrate less than 50
ppm.
Attempts have been made to produce stabilized colored or dye containing
hypochlorite materials. Initial efforts using inorganic insoluble pigments
were
attempted. Other attempts are shown, for example, in Jones et al., U.S. Patent
No.
4,554,091, which discloses a colored polymer latex material. The latex tends
to
form an organic phase separate from the aqueous phase resulting in reduced
decolorization in a hypochlorite bleaching composition. Rapisarda et al., U.S.
Patent
No. 5,089,162, teach a bleach stable dispersible soluble yellow colorant.
Rapisarda
et al. disclose that a granular liquid or gelled warewashing detergent
comprising a
source of alkalinity such as a silicate, a builder, a surfactant and other
warewashing
components can be made stable in the presence of 0.01 to about 5 % of
available
chlorine from a chlorine bleach and a specifically disclosed yellow colorant
or dye.
Choy et al., U.S. Patent No. 5,376,297 disclose thickened aqueous hard surface
cleaning compositions containing a colloidal alumina thickener in combination
with
hard surface cleaner compositions such as a surfactant, a buffer, solvents,
etc. The
thixotropic hard surface cleaner contains a source of oxidative chlorine and
can
contain a dispersible pigment. Wise, U.S. Patent No. 5,384,061, discloses an
aqueous thickened liquid or gel typically automatic warewashing detergent
composition and can contain a dye in the presence of sodium hypochlorite.
However, Choy and Wise fail to disclose the sanitizing of ware in a third sink
basin.
Kitko, U.S. Patent No. 4,248,827, discloses a toilet sanitizing composition
which produces hypochlorite ion in solution and contains a water soluble
bleachable
dye that provides a transitory visual signal. The dye is oxidized to a
colorless state
within 5 seconds to 15 minutes. Cosentino et al., U.S. Patent No. 5,279,735,
discloses a stable colored peracetic acid solution which contains a dye
indicating its
presence. Sumi et al., JP 91-200365, disclose a detergent composition that
cleans
and sanitizes in a single step and develops color upon dilution. Color
duration is



CA 02363741 2001-08-23
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4
controlled by dye concentration, which results in solution color lasting from
2 to 12
minutes depending on solution temperature.
A substantial need exists for sanitizing materials that contain active halogen
sources and a stable dye. In use, the stable dye may act as an indicator of
active
halogen concentration or content. The formulation, dye type and constituent
concentrations can be adjusted such that the presence of color is indicative
of a
proper sanitizing solution. As the bleaching, sanitizing, cleaning properties
of the
sanitizer use solution is consumed over a useful period of time, the solution
loses
color indicating the possible consumption of active chlorine and the need for
a new
sanitizer use solution. A further need for acid powdered materials having a
chlorine
source in a stable dye that can be diluted into a use solution having the
unique
chlorine indicator is a long term goal of the industry. Further, a substantial
need
exists for improving methods using chlorine-containing sanitizing solutions in
such
a way that the solution can contain a stable soluble dye material that is
sufficiently
stable, (i.e.), a detectable color for a period after a substantial portion,
(e.g.) of the
chlorine based species have been depleted from the sanitizing solution but an
effective amount of chlorine remains when the solution is replaced. Restaurant
personnel need to know when a reasonable tune has elapsed, indicating that a
new
solution is needed in order to maintain proper sanitization. Such a time
period to be
useful is no less than 15 to 30 minutes and is typically greater than 2 but
less than 24
hours, preferably greater than 2 but less than 6 hours.
Brief Discussion of the Invention
We have found a unique liquid, solid unit or powdered composition
comprising an encapsulated source of halogen, preferably chlorine, and an
indicator
dye formulated such that a use solution made by diluting the liquid or
powdered
composition results in an aqueous composition containing an active
concentration of
a halogen source that can be gauged, estimated or monitored by the depth of
color in
the solution. We have also found a unique liquid, solid unit or powdered
composition comprising a source of acid, an encapsulated source of halogen,
preferably chlorine, and an indicator dye formulated such that a use solution
made by
diluting the liquid or powdered composition results in an acidic aqueous



CA 02363741 2001-08-23
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composition containing an active concentration of a halogen source that can be
monitored by the depth of color in the solution. In the solid unit, powdered
or solid
concentrate form, effervescing tablet and/or solid block, this composition is
shelf or
storage stable for a minimum of two years. We have also found that the depth
of
color in such aqueous solutions can be used as an indicator of concentration
of the
active halogen species. Lastly, we have found a number of methods using such
solid
unit. powdered and liquid materials.
More specifically, we have found a hard surface cleaning or a hand
warewashing method or process including a sanitizing step in which a chlorine
based
sanitizing solution with a dye used in the sanitizing step. The sanitizer can
be
formulated with an active chlorine source and sufficient dye to survive a
predetermined period. The sanitizing solution made from the composition of the
invention can also be stabilized using a near neutral or an acid pH in such a
way that
a soluble dye added to the sanitizer solution can survive and provide color to
the
1 S sanitizing solution for a predetermined period of time. Such a period of
time is an
amount of time sufficient to deplete greater than 50%, 60%, 75%, 90% or other
predetermined depletion target for the chlorine based oxidant in the sanitizer
solution. This means that after a period of time when the solution goes clear
or
changes color, (i.e.), no original color present, a replenishment of the
active chlorine
or a new sanitizer use solution is required. The loss or change in color
indicates that
the concentration of halogen has been reduced significantly and can be reduced
to
near ineffective levels. This indicates the need for a fresh solution.
Monitoring the
solution color will allow the personnel to know at all times that a proper
sanitizing
solution is present. In the sink sanitizer basin, two to six hours is adequate
and is a
reasonable predetermined period of time. In the other uses including hard
surface
cleaning three to twenty four hours is adequate and is a reasonable
predetermined
period of time. The length of time between the formation of the solution and
the
depletion of color can be adjusted by adjusting dye concentration and other
active
ingredient concentrations in the solid unit, powder or liquid material. The
aqueous
chlorine containing solutions of the invention can be prepared in two specific
embodiments. In a first embodiment, the active chlorine solution can be
prepared
with any arbitrary pH. Often such pH's are mildly or strongly alkaline. In
such a



CA 02363741 2001-08-23
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6
case, an amount of dye is used such that the color of the solution is
maintained, even
in the presence of the active chlorine sanitizes for a predetermined period.
The rates
of reaction between the dye and the chlorine based sanitizes can be easily
measured
at a defined alkaline pH and an amount of dye is added to the composition to
ensure
that the dye survives to the end of the predetermined period. Once the dye in
the
solution is depleted, then the solution can be replaced or refreshed with
additional
chlorine source and dye. We have also found in an alternate mode, that if used
at a
near neutral or an acid pH (pH less than about 7) that the dyes are unusually
stable.
In such a mode, a substantially reduced dye concentration can be used while
maintaining an effective color in the sanitizing solutions for the
predetermined
period of time. We have also found, at active pH, that the active chlorine
species
possess enhanced antimicrobial activity or sanitizing capacity. Whereas, in
alkaline
chlorine species, an effective killing of microorganisms can exist at
concentrations
of between 100 and 1000 ppm, at acid pH's the concentration of the material
can be
reduced as low as 50 ppm with maintaining effective antimicrobial action.
Such materials can be used in a variety of useful processes that use the
unique qualities of the halogen source. Generally such processes involve
removing
stains, removing soil, or killing microbial populations on surfaces that
require
cleaning. In a multiple sink method of warewashing, ware is commonly washed in
a
first sink with aqueous detergent and exposed to mechanical action to remove
soil
resulting in cleaned ware. After the first sink the ware can optionally be
treated in
subsequent sinks for a variety of purposes. Then the cleaned ware is rinsed in
a
potable water rinse and is contacted with the dye containing chlorine
sanitizes in a
subsequent sink or basin for sanitizing purposes.
In a hard surface method, the hard surface is contacted with the oxidative
halogen bleach composition in an overall cleaning method. The hard surface can
be
scraped, washed with a detergent solution, rinsed and sanitized with the
solutions of
the invention. In this method, the solutions are diluted and placed into an
applicator
bottle having the dye visible through a translucent or transparent bottle. The
material is applied preferably with a spray device uniformly contacting the
hard
surface with 50 to 200 ppm of the active halogen sanitizes material. The
sanitizes
can be wiped from the surface or simply allowed to dry.



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7
The preferred oxidative halogen chlorine-based sanitizing solution comprises
a major proportion of an aqueous medium, a soluble oxidative active chlorine
or
chlorine based sanitizer, and a soluble organic dye. In one embodiment said
solution
is maintained at a pH less than about 7, preferably between a pH of 2 to 6.5.
One
S solution that maximizes chlorine activity and user comfort obtains about 90
to 200
ppm active Clz at a pH of about 5.5 to 7. At such a preferred pH, the
concentration
of hypochlorous acid (HOCI) is maximized while the concentration of
hypochlorite
(OCl-l, usually NaOCI) is minimized. Such a solution can be made from a
powdered
or solid concentrate or liquid co-systems comprising a diluent, a dye, a
chlorine
source and other ingredients including an acid or acid salt. We have found
that
hypochlorite not hypochlorous acid is the major oxidative species that
decolorizes
dye in hypochlorite based sanitizers. As a result, the change in pH permits
the dye to
survive a substantial period since the oxidative (OCl-1) species is at reduced
concentrations when compared to alkaline (pH>8) solutions. While the strength
or
capacity for the solution to remove surface stains in the ware is somewhat
reduced,
the ability to sanitize ware surfaces is substantially increased. As a result
of this pH
modification of the sanitizing solution, the dye can survive an extended
period of
time in the sanitizing solution. The dye can be selected and matched with an
appropriate pH such that the dye is depleted of color after a reasonable
amount of
time, roughly simultaneously with the sanitizing solution being substantially
depleted of oxidizing chlorine species. However, preferably the sanitizing
solution
remains at least some detectable color until the oxidative chlorine species is
depleted
or consumed by bleaching or sanitizing processes.
For the purpose of this patent application, the term "ware" indicates
dishware, pots and pans, flatware, glassware, metallic and plastic utensils,
and other
tools and containers common in institutional or commercial kitchen or
restaurant
environments. For the purpose of this patent application, the term "solid
unit" refers
to a circular, cylindrical, pyramidal, rectangular, octangular or other
geometrically
shaped solid block or object having a mass of at least 1 gram, preferably 5 -
25
grams. The term "solid unit" does not refer to a particulate or granulated
solid or
simple high viscosity liquids that retain some shape. The term "subsequent
basin"
means that the basin follows the previous basin. However, one or more basins
can



CA 02363741 2001-08-23
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come between the first basin and a subsequent basin to provide other method
steps
prior to the sanitizing step. Typically, the sanitizing basin is the last
basin in the
process. After ware contact with the sanitizing solution, the ware is
typically not
further contacted with an aqueous solution because even service water can
contain
some level of a microbial population that can contaminate the sanitized
surface.
One aspect of the invention is a method of using a color stable hypochlorous
acid sanitizer material in a mode that permits the operator to gauge the
bleaching or
sanitizing capacity of a hypochlorous acid sink contents using a dyestuff. In
this
aspect the quantity of dye combined with the active chlorine material in the
claimed
compositions is matched to the pH and chlorine concentration to give apparent
or
detectable dye color to the hypochlorite solution for a predetermined time.
After the
dye color disappears or is depleted, the active chlorine can be replaced or
augmented
with an added active chlorine and dye composition.
A second aspect of the invention is a chemical composition that can be used
to form the color stable hypochlorous acid sanitizer materials used in the
method
discussed above. Such compositions comprise an active chlorine source and a
dye in
an amount that can give apparent or detectable dye color to the hypochlorite
solution
for a predetermined time, such time selected to ensure at least 50 ppm active
chlorine is present in the solution. After the dye color disappears or is
depleted, the
active chlorine can be replaced or augmented with added chlorine composition.
A third aspect of the invention is a is a solid unit in the form, for example,
of
a tablet or pellet composition that can be manufactured and used to form the
aqueous
color stable hypochlorous acid sanitizer materials of the compositions and in
the
methods set forth above. Simple solid units such as tablets or pellets can be
formulated to contain the active ingredients of the stable system. In use, to
create an
active chlorine aqueous system or to replenish an aqueous system during
operations,
one or more pellets or tablets of the active materials can be introduced into
the
appropriate sink or container to create the active materials. Surprisingly, we
have
found that certain forms of preferred dyes are compatible in long term storage
in the
presence of highly active chlorine based oxidizing agents or sanitizers. After
the dye
color disappears or is depleted, the active chlorine can be replaced or
augmented
with added chlorine composition.



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9
Detailed Discussion of the Invention
The invention resides in a solid unit, liquid or powdered and solid
compositions comprising a source of halogen and a dye. The composition can
contain an acid source to maintain the pH<'7, The invention also resides a
method
for hand washing or cleaning ware in a step-wise fashion with a sanitizing
step as a
last step in the method. Typically, the first step in such a method involves
contacting ware with an aqueous solution of a detergent composition for the
purpose
of removing soil from the surface of the ware. The invention also resides in a
method for cleaning hard surfaces. The cleaning step reduces microbial
population
substantially in a sanitizing fashion. Typically the first step in such a
method
involves rinsing or scraping the hard surface followed by an application of
the
sanitizing material. The sanitizing material can be left in place to dry or
can be
rinsed or wiped from the surface.
The sanitizing solution can contain an effective concentration of one or more
1 S active and inactive ingredients that interacts with the ware and soil to
enhance the
ability of the aqueous medium to remove soil species. The ware can be exposed
to
mechanical action by dishwashing personnel who use pads, brushes, scrapers,
etc. to
remove soil. The aqueous detergent solution can be maintained at a high
temperature (40-80°C) to promote the cleaning action of the aqueous
detergent.
Such solutions are often replaced periodically when the detergent action is
depleted
by the presence of substantial quantities of proteinaceous and oily or fatty
soils.
Prior to contacting the ware in such an aqueous detergent step, the ware is
often
scraped, rinsed or.pretreated to promote soil removal in the detergent step.
Following the initial cleaning step, the ware can be rinsed in a potable water
rinse to
remove the remaining aqueous detergent solution that can contain some small
proportion of soil.
After the rinse step, the ware can be contacted with a variety of different
compositions in subsequent sinks or basins. One common step is a deliming step
for
the purpose of removing hard inorganic calcium or magnesium based coatings
from
the ware comprising hardness, cations and other materials in a film or
coating. Such
a step is often an acid deliming step that can substantially brighten and
clarify the
appearance of glassware. The ware can also be contacted in an aqueous rinse



CA 02363741 2001-08-23
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composition in a rinse station. Such rinse compositions contain organic
polymeric
agents that promote rinsing of the ware. A variety of other stations or steps
can be
used in the method for the purpose of providing enhanced cleaning, brightening
the
appearance of the glass or metal ware, preserving the color or appearance of
plates
and cups, destaining tea stains or coffee stains from coffee mugs or cups or a
variety
of other operational steps.
Halogen Source or Chlorine Sanitizer
The hard surface or the ware is contacted with a sanitizing solution
10 commonly comprising an active halogen or chlorine, based sanitizer
composition.
The sanitizing solution is typically made from a solid unit, solid, powdered
or liquid
concentrate of a chlorine containing product by dissolving the material in
water.
One preferred solid chlorine concentrate of the invention contains a powdered
or
granular dye, a particulate encapsulated chlorine source, an acid or acid salt
dispersed in a substantially neutral alkali metal salt acting as a diluent or
extender.
Useful salts include sodium sulfate, sodium phosphate, sodium chloride, and
other
similar available extender salt materials. Sources of halogen, chlorine, used
in the
methods of the invention include oxidizing compositions capable of liberating
an
active halogen species, typically Clz or OCl-I or equivalent materials.
Suitable
agents for use in the present methods include both liquids and solid forms of
halogen
preferably chlorine sources, for example, chlorine containing compounds such
as
solutions of chlorine, hypochlorite, chloramine, etc. Preferred halogen
releasing
compounds include the alkali metal hypochlorite, alkali metal
dichloroisocyanurate,
chlorinated trisodium phosphate, monochloramine and dichloramine and the like.
Encapsulated chlorine sources may also be used having at least one
encapsulating
layer surrounding a core of a chlorine source. Such encapsulated chlorine
sources
have multiple encapsulating layers. Encapsulated chlorine source are disclosed
in
U.S. Pat. No. 4,618,914 and 5,213,705.
The most common chlorine based sanitizer composition comprises sodium
hypochlorite derived form an encapsulated source or from aqueous hypochlorite
or
other liquid and powdered or solid chlorine sources. Aqueous hypochlorite is
typically sold in the form of an aqueous solution containing approximately 5-
10 wt-



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11
sodium hypochlorate. Solid sources of chlorine include chlorinated
isocyanurate
powder or encapsulate. Such materials, having a high pH, can be diluted with
water
to form an oxidizing aqueous solution containing an oxidative species at a
concentration of about 50 to about 300 ppm, preferably about 60 to 200 ppm
most
preferably 70 to 150 ppm of the oxidative species. Depending on pH, there is
an
equilibrium (see Figure 1) between hypochlorous acid and hypochlorite
according to
the following general equilibration reaction in formula I:
HOCI E---~ OCl-' + H+'. (I)
In a common ion effect, as the acid concentration of the solution. is
increased, the
equilibrium of this reaction is pushed towards producing a substantial
proportion of
hypochlorous acid while minimizing the concentration of hypochlorite. The pH
driven concentration relationship between hypochlorous acid (HOCI) and
hypochlorite (OCl-') is shown is Figure 1. An optimum pH, for conservation of
dye,
is found where the concentration of the hypochlorous acid is maximized while
the
concentration of hypochlorite is minimized. Preferably, the concentration of
(HOCI)
is greater than about 80 percent, while the concentration of (OCI-') is less
than about
percent.
20 The method of the invention uses an aqueous sanitizing composition
containing an oxidative chlorine bleach. The aqueous rinse used in the method
can
be manufactured by diluting a liquid co-system, powdered, pelletized or solid
chlorine bleach containing composition. Preferably, the composition contains a
chlorine source, the soluble dye, optionally an acid source that is typically
diluted by
a liquid or solid diluent or stabilizer. In practicing the process of the
invention,
sufficient amount of a liquid or powdered concentrate is added to the
sanitizing
process basin. The material dissolves in the aqueous liquid, creating an
effective
concentration of HOCI and dye at an appropriate pH. The aqueous solution is
used
until the color is depleted and is replaced when needed.
The oxidative chlorine concentrate of the invention can contain either a
liquid or solid source of halogen, liquid sources of halogen, bleach commonly
comprise alkali metal such as sodium hypochlorite bleach. These materials are



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12
commonly available in aqueous solution in a variety of concentrations. A
variety of
solid chlorine sources are also available such as chlorinated sodium
tripolyphosphate, solid dichloroisocyanurate, calcium hypochlorite and others.
Such
oxidizing agents are disclosed in Kirk-Othmer, Encyclopedia of Chemical
Technology, Second Edition, Volume III, pp. 550-566. A preferred source of
chlorine comprises an encapsulated chlorine source. Such chlorine sources are
shown in Olson et al., U.S. Patent Nos. 4,681,914 and 5,358,635.
The chlorine releasing substances suitable as the core material of the
encapsulated active chlorine compound include chlorine components capable of
liberating active chlorine species such as a free elemental chlorine or OCl- ,
under
conditions normally used in warewashing processes. Useful inorganic sources of
chlorine include solid materials that yield hypochlorite in aqueous
environments
including lithium hypochlorite, calcium hypochlorite, etc. Useful organic
chlorine
releasing compounds must be sufficiently soluble in water to have a hydrolysis
constant (K) of about 10~ or greater. Those with K values below 10~ do not
produce sufficiently high concentration of free available chlorine or other
active
chlorine species for effective bleaching. In general, hydrolysis constants of
the N-
chloro compounds range from 10-'° to approximately 10-3. The principle
N-chloro
compounds used in bleaching are the chlorinated isocyanurates, which are
chlorimides.
Sodium dichloroisocyanurate dihydrate, a preferred chlorine releasing
substance suitable as the core substance of the present encapsulated active
chlorine
compound, is commercially available from Olin Chemicals, Stamford, Conn., as
CDB-56TM; or as ACL-56TM; Monsanto Company, St. Louis, MO. The chemical
structure of this compound is represented by the formula (II) below:
MC12(NCO)3~2H20 (II)
wherein M is an alkali metal such as Na+, K+, etc.
The encapsulate typically has one, two or more coatings sufficient to reduce
chlorine loss. The innermost, chlorine releasing core of the encapsulated
active
chlorine compound of the present rinse aid concentrate is surrounded by an



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13
intermediate coating or spacer layer. This intermediate coating is preferably
inorganic and can comprise a filler or builder compound (or mixtures thereof)
and
provides a protective barrier or spacing between the innermost chlorine core
and the
organic or inorganic outer layer(s). The outer layer can comprise inorganic
builders
or organic surfactants.
The encapsulated halogen source is present in the concentrate at a
concentration of about 1 to 90 wt-%, preferably about 5 to 70 wt-%.
Acid Source
The chlorine concentrate compositions of the invention are typically
combined with an acid source to provide in the final sanitizing solution a pH
of less
than about 7 to control and minimize the concentration of OCl-~ and maximize
the
concentration of HOCI. Generally, any normally liquid or normally solid acid
source
which will facilitate the formation of such low pH may be used in the
composition of
1 S the invention. A liquid aqueous material can contain either solid or
liquid acid.
Both organic and inorganic acids have been found to be generally useful in the
present composition. Organic acids useful in accordance with the invention
include
hydroxyacetic (glycolic) acid, citric acid, formic acid acetic acid, propionic
acid,
butyric acid, valeric acid, caproic acid, gluconic acid, and itaconic acid,
trichloroacetic acid, benzoic acid, among others. Organic dicarboxylic acids
such as
oxalic acid, malonic acid succinic acid, glutaric acid, malefic acid, fumaric
acid,
adipic acid, terephthalic acid among others are also useful in accordance with
the
invention. Any combination of these organic acids may also be used intermixed
or
with other organic acids which allow adequate formation of the composition of
the
invention. Inorganic acids useful in accordance with the invention include
phosphoric acid, sulfuric acid, sulfamic acid, methylsulfamic acid,
hydrochloric acid,
hydrobromic acid, and nitric acid among others. Powdered acid salts can also
comprise a source of acid for the invention. Such acid salts can comprise
sodium
hydrogen sulfate, sodium dihydrogen phosphate, monosodium citrate, monosodium
tartrate, monosodium succinate and other similar powdered acid salt
compositions.
These acids may also be used in combination with other inorganic acids or with
those organic acids mentioned above. Preferred acids for a powdered
composition



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14
are solid or powdered inorganic or organic acid. The acid source is present in
the
concentrate at a concentration of about 0 to 30 wt-%, preferably about 0.5 to
30 wt-
%, most preferably 5 to 15 wt-%. The chlorine concentrate of the invention can
also contain common builders in an acid form such as sodium sulfate (NaZS04),
sodium carbonate (Na2C03), trisodium phosphate, sodium bicarbonate (NaHC03)
and other acid builder salts such as sodium dihydrogen phosphate, disodium
hydrogen phosphate, potassium hydrogen tartrate, monosodium nitrilo triacetic
acid
and other such acid salts that can aid in forming an appropriate acid pH,
provide
mild buffering action and aid in sanitization. The acid builder salts are
present in
the concentrate at a concentration of about 0 to 90 wt-%, preferably about 5
to 75
wt-%.
Dye or Indicator
The sanitizing solution and the chlorine containing concentrate of the
invention include a dye. Such dyes can comprise common ordinary dyes or can
also
include indicator dye materials. Dyes are typically intensely colored
substances used
at low concentration with a coloration of various substances. The visual
properties
of dyes are determined by their electronic transitions within the dye
molecule. The
shade or hue of the dye is determined by energy differences between states in
the
molecular orbitals. A large number of dyes of varying properties are known.
Dyes
useful in this invention are typically acid compatible dyes that are stable in
the
presence of HOCI at the pH disclosed in the invention. Dyes that may have
utility in
the invention include anthraquinone dyes. Useful dyes include such species as
blue
tetrazolium dye, brilliant blue G, brilliant blue R, brilliant cresol blue,
brilliant
sulfone red, brilliant yellow, bromcresol green, reactive blue No. 2, reactive
red No.
2, reactive yellow No. 2, FD&C No. 40, FD&C No. 3, etc. Preferably the dye is
selected for ease in blending with the powdered chlorine source, the acid
salts and
the diluent or extender of the invention. However, the dye should be used at a
concentration such that the dye begins to fade as the concentration of the OC1-
1
begins to be depleted from the sanitizing solution, while the HOC1
concentration
remains. We have found that the particle size of the dye material is important
to
maintain dye stability in the tablet or solid concentrates of the invention.
We have



CA 02363741 2001-08-23
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found that the dye particle having a particle size greater than 200 microns,
preferably
greater than about 400 microns, most preferably greater than 600 microns, can
be
made in the form of a solid, powder or a solid unit concentrate and is
stabilized to
contact with the encapsulated chlorine source. Such a result is surprising in
light of
S the highly active oxidizing capacity of the chlorine source and the
sensitive nature of
typical organic dye molecules.
The sanitizing solution can contain an organic indicator dye. Such
substances reveal through color changes the degree of acidity or basicity of a
solution. Most indicators are weak organic acids or bases which exist in one
or more
10 structural form (tautomers) of which at least one form is colored. In the
case the
indicator dye has two colored species, the colors are substantially different
and can
be detected in solution. Intense colors are desirable so that the minimum
concentration of indicator can be used. Depending on the nature of the
equilibration
reaction between colored species and the uncolored species or between species
of
15 different color, the color can occur at a characteristic pH for each
indicator. Care
must be taken to use an indicator having an appropriate pH change. Indicator
dyes
that can be used in the context of this invention include methyl violet,
metacresol
purple, thimole blue, tropeoline 00 (orange roman IV), bromphenol blue, methyl
orange, bromcresol green, methyl red, orthophenol red, bromcresol purple and
others
that have substantial color within the pH of about 3 to about 7. Typically,
the
sanitizing solution is free of any component that can react with the oxidizing
species.
However, the sanitizing solution can contain other materials that can enhance
the
antimicrobial properties or the bleaching properties of the sanitizing
solution. Such
materials include other oxidative species, oxidation promoters, etc.
The dye is present in the concentrate at a concentration of about 0.001 to 0.5
wt-%, preferably about 0.05 to 0.3 wt-%. Depending on the type of system used,
the
amount of dye is selected to ensure that the dye provides detectable color for
the
predetermined period, which period typically ensures that the solution contain
at
least 50 ppm active chlorine or, depending on circumstances, greater than
about 100
ppm active chlorine. One of ordinary skill in the art will have no trouble in
formulating these materials with the appropriate amount of dye since the rate
of
reaction of dye with the chlorine species selected can be easily determined
for the



CA 02363741 2001-08-23
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16
purpose of selecting dye concentrations for the concentrate materials. We have
found that the amount of dye needed for acid based sanitizer materials is
roughly
10% of the amount required to maintain color in neutral or alkaline systems.
Aqueous Detergent
The ware is contacted, in the method of the invention, in a first basin or
sink
containing an aqueous detergent composition. The aqueous detergent solution
can
comprise a variety of ingredients including anionic, nonionic or cationic
surfactant
materials, other ingredients, etc.
One anionic surfactant useful for detersive purposes can also be included in
the compositions hereof. These can include salts (including, for example,
sodium,
potassium, ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, C9-CZO linear alkylbenzenesulfonates, C8-C2z
primary
or secondary alkanesulfonates, Cg-Cz4 olefinsulfonates, sulfonated
polycarboxylic
acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal
citrates. C8-Cz4 alkylpolyglycolethersulfates (containing up to 10 moles of
ethylene
oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerols
sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates,
alkyl
phosphates, isethionates such as the acyl isethionates, acyl laurates, fatty
acid amides
of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinates (especially saturated and unsaturated C12-C1g monoesters) and
diesters of sulfosuccinates (especially saturated and unsaturated C6-C12
diesters),
acyl sarcosinates; sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucosode (the nonionic nonsulfated compounds being described below),
branched primary alkyl, sulfates, and fatty acids esterified with isethionic
acid and
neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids
are
also suitable, such as rosin, hydrogenated rosin, and resin acids and
hydrogenated
resin acids present in or derived from tall oil.
Another type of anionic surfactant which can be utilized encompasses alkyl
ester sulfonates. Alkyl ester sulfonate surfactants hereof include linear
esters of C8-
CZO carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous S03
according to "The Journal of the American Oil Chemists Society" 52 (1975), pp.



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17
323-329. Suitable starting materials would include natural fatty substances as
derived from tallow, palm oil, etc. Alkyl sulfate surfactants hereof are water
soluble
salts or acids of the formula ROS03M wherein R preferably is a C1o-Cza
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Clo-C-zo alkyl
component,
S more preferably a Clz-C1$ alkyl or hydroxyalkyl, and M is H or a 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 tetramethylammonium and dimethyl
piperdinium cations and quaternary ammonium cations derived from alkylamines
such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the
like).
Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids
of the
formula RO(A)mS03-M+ wherein R is an unsubstituted Coo-Cz4 alkyl or hydroxy
alkyl group having a C1o-Cz4 alkyl component, preferably Clz-Czo alkyl or
hydroxyalkyl, more preferably Clz-C1g alkyl or hydroxyalkyl, A is an ethoxy or
1 S propoxy unit, m is greater than zero, typically between about 0.5 and
about 6, more
preferably between about 0.5 and about 3, and M is H or a cation which can be,
for
example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium,
etc.). ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as
well as alkyl propoxylated sulfates are contemplated herein. Specific examples
of
substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium
cations and quaternary ammonium canons such as tetramethyl-ammonium and
dimethyl piperdinium canons and those derived from alkylamines such as
ethylamine, diethylamine, triethyl-amine, mixtures thereof, and the like.
Conventional, nonionic detersive surfactants for purposes of this invention
include the polyethylene, polypropylene, and polybutylene oxide condensates of
alkyl phenols. In general, the polyethylene oxide condensates are preferred.
These
compounds include the condensation products of alkyl phenols having an alkyl
group containing from about 6 to about 12 carbon atoms in either a straight
chain or
branched chain configuration with the alkylene oxide. In a preferred
embodiment,
the ethylene oxide is present in an amount equal to from about 5 to about 25
moles
of ethylene oxide per mole of alkyl phenol. Commercially available nonionic
surfactants of this type include IgepalTM CO-630, marketed by the GAF
Corporation;



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18
and TritonTM X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas
Company. Nonionic surfactants also include the condensation products of
aliphatic
alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl
chain of
the aliphatic alcohol can either be straight or branched, primary or
secondary, and
generally contains from about 8 to about 22 carbon atoms. Particularly
preferred are
the condensation products of alcohols having an alkyl group containing from
about
to about 20 carbon atoms with from about 2 to about 10 moles of ethylene oxide
per mole of alcohol. Examples of commercially available nonionic surfactants
of
this type include TergitolTM 15~5~9 (the condensation product of CSI-Cls
linear
10 alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW (the
condensation
product of Cl2-Cia primary alcohol with 6 moles ethylene oxide with a narrow
molecular weight distribution), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-Cis linear alcohol with 9 moles
of
ethylene oxide), NeodolTM 23-6.5 (the condensation product Of C12-Ci3 linear
alcohol with 6.5 moles of ethylene oxide), NeodolTM 45.7 (the condensation
product
of C~4-Cls linear alcohol with 7 moles of ethylene oxide), NeodolTM 45.4 (the
condensation product of C14-Cis linear alcohol with 4 moles of ethylene
oxide),
marketed by Shell Chemical Company, and KyroTM EOB (the condensation product
of C13-Cis alcohol with 9 moles ethylene oxide), marketed by The Procter &
Gamble
Company. The condensation products of ethylene oxide with a hydrophobic base
formed by the condensation of propylene oxide with propylene glycol can also
be
used. The hydrophobic portion of these compounds preferably has a molecular
weight of from about 1500 to about 1800 and exhibits water insolubility. The
addition of polyoxyethylene moieties to this hydrophobic portion tends to
increase
the water solubility of the molecule as a whole, and the liquid character of
the
product is retained up to the point where the polyoxyethylene content is about
50%
of the total weight of the condensation product, which corresponds to
condensation
with up to about 40 moles of ethylene oxide. Examples of compounds of this
type
include certain of the commercially available PluronicTM surfactants, marketed
by
BASF.
Cationic detersive surfactants can also be included in detergent compositions
of the present invention. Cationic surfactants include the ammonium
surfactants



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19
such as alkyldimethylammonium halogenides, and those surfactants having the
formula:
[Rz(OR3)y][R4(OR3)X~3R3N+X ;
wherein RZ is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon
atoms in the alkyl chain, each R3 is selected from the group consisting of:
-CH3CH2-, -CHZCH(CH3)-, -CHCH(CHZOH)-, -CHZCHzCH2-
and mixtures thereof; each R4 is selected from the group consisting of C1-C4
alkyl,
Ci-C4 hydroxylalkyl, benzyl ring structures formed by joining the two R4
groups,
CHZCHOH--CHOHCOR6CHOHCHzOH wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and hydrogen when y is
not O; RS is the same as R'~ or is an alkyl chain wherein the total number of
carbon
atoms of Rz plus RS is not more than about 18; each y is from 0 to about 10
and the
sum of the y values is from 0 to about 15; and X is any compatible anion.
The detergent compositions of the present invention comprises a liquid
carrier, e.g., water, preferably a mixture of water and a C1-C4 monohydric
alcohol
(e.g., ethanol, propanol, isopropanol, butanol, and mixtures thereof), with
ethanol
being the preferred alcohol.
A wide variety of other ingredients useful in detergent compositions can be
included in the compositions hereof, including other active ingredients,
carriers,
processing aids, dyes or pigments, perfumes, solvents for liquid formulations,
hydrotropes (as described below), etc.
Liquid detergent compositions can contain water and other solvents. Low
molecular weight primary or secondary alcohols exemplified by methanol,
ethanol,
propanol, and isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those containing from about 2 to
about 6
carbon atoms and from about 2 to about 6 hydroxy groups (e.g., propylene
glycol,
ethylene glycol, glycerin, and 1,2-propanediol) can also be used.



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The detergent compositions hereof will preferably be formulated such that
during use in aqueous cleaning operations the wash water will have a pH of
between
about 6.5 and about 1 l, preferably between about 7.5 and about 10.5. Liquid
product formulations preferably have a (10% dilution) pH between about 7.5 and
5 about 10.0, more preferably between about 7.5 and about 9.0 Techniques for
controlling pH at recommended usage levels include the use of buffers, alkali,
acids,
etc:, and are well known to those skilled in the art.
Solid Unit
10 A chlorine containing bath having an indicator dye can be made by
introducing into water, a solid unit such as a tablet, a pellet or other small
compressed solid cast unit or extruded material. The unit containing a
chlorine is
formulated to contain solid active chlorine material and the indicator dye.
The solid
unit can be configured with sufficient material to treat an appropriate amount
of
15 water to form the indicated chlorine containing aqueous solution. The size
of the
tablet, pellet or solid unit can range from greater than 200 milligrams to
include sizes
that can be as much as 100 grams depending on the amount of water. Typically,
the
materials are used such that a unit has about 1 to 50 grams preferably 1 to
20,
typically 4 to 8 grams of material in a single unit and can be used to treat
about 1
20 liter of water or more, a typical sink volume of 1 to 100 preferably 10 to
50 liters.
The preferred solid units of the invention typically contain a solid chlorine
source and a dye. Typical solid chlorine sources include sodium
dichloroisocyanurate dihydrate, chlorinated sodium phosphate, calcium
hypochlorite,
chloramines and other well known and available sources of chlorine and solid
particulate or granular form. Useful dyes include those set forth above in the
application. The solid pellets of the invention can also contain solid organic
or
inorganic components that can control pH of the chlorine solution.
In the solid unit aspect of the invention, the physical form of the dye is
important to the stability of the dye in contact with the chlorine source.
Most dyes
comprise complex organic molecules that are easily oxidized by compounds such
as
active chlorine sources. We have found that a dye composition, in the form of
a
particle or granule, having a particle size greater than about 200 microns,
preferably



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WO 00/50554 PCT/US00/04595
21
greater than about 500 microns, most preferably greater than about 700 microns
can
be used in the solid unit and remain stable for indefinite periods. We believe
the
particle size of a granular dye reduces the tendency of the dye to react with
the active
chlorine material in the solid unit. This is particularly true in the dry
systems made
in this invention.
The solid units of the invention are typically made with little or no free
water
or water added. Free water within the solid unit can provide a medium for
reaction
between the chlorine source and the dye material, even if formulated or formed
from
a granular dye. Accordingly, the solid units of the invention have little or
no free
water present. Water can be present in the solid unit in the form of water of
hydration as long as such water is not released from the hydration location
into the
solid unit for the purpose of providing a medium for reaction. Water of
hydration,
for example, of the sodium dichloroisocyanurate dihydrate remains securely
bonded
to the chlorinated molecule and does not typically act to reduce
compatibility. Other
hydrated materials can be used in the solid unit of the invention. For
example,
extender salt hydrates may be present in the solid unit for the purpose of
diluting the
chlorine source, modifying dissolution rates, changing the size of the solid
unit for
the purpose of acting as a binder for the solid unit or further purposes.
In the typical solid units of the invention, the weight ratio between the
chlorine source and the dye will be typically about 1 to about 200 grams of
chlorine
source per gram of dye.
The solid units of the invention can be made using a variety of solids forming
technology. The only limitation on such technology is the need to avoid
forming
substantial quantities of free water remaining in the solid unit. Accordingly,
preferred modes for forming the solid unit of the invention include casting
the solid
units from a castable, typically non-aqueous liquid, or by forming pellets or
tablets
by compressing powder mixture in tablet or pelletizing equipment under
sufficient
pressure and in the pressure of optional binders to form a useful solid unit.
In
forming the solid units of the invention, a mold, a tablet or pellet press
equipment
can be used to form a tablet having dimensions of about 2 to 50 millimeters in
diameter, preferably S to 25 millimeters in diameter. Tablet thicknesses can
range



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
22
from about 2 to 20 millimeters. Most preferred diameters range from about 10
to 25
millimeters.
A useful 20 millimeter tablet can be made using a tablet press that can exert
2 tons force to particulates in a tableting dye. In such a process, a quantity
of a
S mixture of the solid chlorine source and granular dye can be placed manually
or in
an automated mode into the tablet dye and compressed for dwell time of 1 to 30
seconds to a pressure of 1/2 to 15 tons per square inch. The tableting dyes
can be
entirely cylindrical or can have a concave or opaque top or bottom surface to
obtain
a desired tablet shape. Sufficient pressure is placed on the particulate to
achieve a
hardness of greater than about 50 psi, typically 60 to 100 psi.
The tablets of the invention can be made using conventional tableting
technology. In manufacturing the tablets of the invention, dry, granular or
powder
material are combined in typical powder blending equipment to ensure any
uniform
mixture of ingredients that typically include the granular
dichlorodiisocyanurate
chlorine source, the dye in a granular form and often a processing aid or dye
release
material. Any conventional tableter can be used that can form a table of the
appropriate dimensions. The preferred tablet dimensions is about 1.5 to 2.5
centimeters in diameter with a thickness of about 1 to 2 centimeters. Typical
processing conditions involve a tableting pressure of at least 5 tons or more,
tablet
formation occurring in 1 to 5 seconds, typically 2 to 3 seconds.
The compositions and tablets of the invention can be used in a variety of
ways. The material can simply be added directly to a sink when the color is
depleted. Further, the materials can be added from a dispenser that can
dispense
either a measured portion of the powdered material or a single tablet of the
tableted
materials. The tablets can be shaped to fit in a tablet dispenser with a lock-
out
feature. The shape of the tablets can be such that only the tablet shapes can
fit the
dispenser profile. In such a way, only the appropriate tablets can be placed
into the
dispenser to avoid either waste of material or hazardous combinations of
ingredients.



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WO 00/50554 PCT/US00/04595
23
Generic Formulae Chlorine Solid Unit or Powdered Concentrate
Ingredient Useful Preferred
Weight Weight
PercentagePercentage


Chlorinated encapsulate 5 to 99.950 to
ACP 96


FD&C red dye No. 40 0.001 0.5 to
to S 0.09


Source of acid 0 to 10 0.01 to
5


tableting aid 0 to 0.1 0 to 0.01



The above discussion of the components of the invention provides a basis for
understanding the compositions of the invention and the useful process steps.
The
following example and data illustrate the utility of the invention and contain
a best
mode.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
24
Example I
Powdered Acidic Formulations
Component #1 #2 #3 #4 #5 #6
wt-% wt-% wt-% wt-% wt-% wt-


ACP' 33.60 34.90 9.50 0 67.20 27.57


SAPP' 14.10 56.40 25.70 14.1 28.24 0


anhydrous 2.11 8.40 0 26.6 4.20 5.97
citric acid


FD&C Dye' 0.14 0.20 0.04 0.07 0.28 0.20


propylene 0.17 0.10 1.00 0.11 0.08 0.10
glycol


sodium sulfate49.88 0 46.46 9.12 0 0


MSP" 0 0 17.30 0 0 66.16


chlorinated0 0 0 50.0 0 0
TSPS


1. Encapsulated sodium dichloro-s-triazinetrione dehydrate.
2. Sodium acid pyrophosphate.
3. FD&C red #40, FD&C blue #l, etc.
4. Monosodium phosphate.
5. Chlorinated trisodium phosphate.
Formulations 1 and 3 listed above were made and placed into a 120°F
(49°C)
oven for long term stability testing. The formulations were monitored weekly
for
available chlorine levels and for color stability. Duplicates were made of
formulations and 3 which differed only in using non-encapsulated sodium
dichloro-
s-triazinetrione as the chlorine source. After 8 weeks, all of the
formulations having
encapsulated chlorine sources retained acceptable active levels. The two
formulations lacking an encapsulated chlorine source lost their efficacy after
only 1
week. The active chlorine source bleached the dye.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
Example II
Powdered Chlorine Concentrate
Ingredient Percentage


Chlorinated encapsulate 33.6
ACP


FD&C red dye No. 40 0.14


Citric acid 2.1


Sodium acid pyrophosphate 14.1


(SAPP)


Sodium sulfate 49.9


Using Example II, a sanitizing solution containing 30 ppm chlorine and 10
5 ppm dye at pH about 7 provided active sanitizing with solution color lasting
about
two hours. At a lower pH, between 5 and 6, a sanitizing solution containing 30
ppm
chlorine and 10 ppm dye lasted approximately four hours. In both cases,
substantial
sanitizing activity was observed without corrosion or chlorine gassing.
Example III
10 A dye and chlorine stability test was performed using an initial solution
containing 100 ppm chlorine and 1 ppm of FDBr.C Red #40 dye. CDB (Sodium
dichloroisocyanurate dihydrate) was used as the chlorine source and the tests
were
conducted with an initial temperature of 80°F (26.7°C). The
following data
demonstrate the effects of pH on dye and chlorine stability:



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
26
Results
pH bufferedTime (hours)Color / AppearanceAvailable
at Chlorine m


2 0.0 color gone immediately10 - 50


4 2.5 color gone 80 -100


6 5.0 slightly visible 100


8 0.25 color gone 100


0.0 color gone immediately100


12 0.0 color gone immediately100


2 175 no color 0


4 175 no color 0


6 175 no color 80 - 100


8 175 no color 50 - 100


10 175 no color 10


12 175 no color 10


Additional formulations were tested at an active chlorine level of 100 ppm
and at pH levels which were buffered to between 2 and 12. Each formulation
included 1 ppm FD&C Red #40 dye and began at 80°F (27°C).
pH bufferedInitial Time needed for
at Color / Appearancesolution to become
colorless hours


2 colorless none


4 visible color 2.5


6 visible color 4.0


8 visible color 0.25


10 colorless none


12 colorless none


5.8 visible color 5.0


5.4 visible color 15





CA 02363741 2001-08-23
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27
Several conclusions can be drawn from the data above:
With a pH range of 5.8 to 6.3, the color lasts 4.5 to S.0 hours in the sink.
With a pH
range of 5.3 to 5.6, the color lasts 14 to 16 hours in a bulk container which
can be
used through spray bottle in a daily sanitizing regimen. The sanitizer
materials are to
be replaced daily. A chlorine encapsulate like ACP or Enforcer RC is required
for
dye stability in the powder. In the first table, which indicates time needed
for the
color to disappear, several additional comments can be made. At low pH, pH 2
to
pH 4, the dye is destroyed because of the pH. Additionally, the solution is a
skin
irntant. Conversely, at high pH, that is pH 8 and greater, the dye is
destroyed by the
OCl-1 ion.
Example IV
A test was conducted with several solutions at active levels ranging from 10
ppm to 100 ppm active chlorine. Each solution started with 1 ppm FD&C red #40
and was buffered to a pH of 5.8.
ppm availableInitial Color/appearanceTime needed for solution
chlorine to
become colorless (hours)


10 Visible more than 6.0


30 Visible 6.0


50 Visible 5.0


80 Visible 4.5


100 Visible 3.0


A test was also conducted with 4 solutions by varying the level of dye
(FD&C red #40) from 0.1 to 0.4 wt-%. Each solution was buffered to a pH of 5.8
and had an initial active level of 100 ppm available chlorine. As expected,
there is a
linear relationship between dye concentration and color longevity.
As a result, a sanitizing solution can be made visible based on the
composition of the concentrate. The length of time that the visibility or
color of the
solution lasts can be controlled by varying the percentages of the dye, the
level of
active and the pH/buffer component. The pH/buffer component has the greatest
effect, while the dye and active can be used for fine-tuning.



CA 02363741 2001-08-23
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28
Example V
Example V involves a liquid co-system. This is a two-part system. The first
solution contains sufficient NaOCI into the sink to produce 100 ppm available
chlorine and sufficient H3P04 to produce a pH between 5 and 6, 1.0% of FD&C
RED Dye #40 and color lasting between 2 and 6 hours. The second solution
contains sufficient NaOCI in the sink to produce 100 ppm available chlorine,
20.0%
of a 75% active aqueous H3P04, 1.0% of FD&C RED Dye #40 and 79.0% of water.
The color lasts for at least one hour.
These formulations show that non-encapsulated liquid sources of chlorine
can be used with useful results.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
29
Examples VI-IX
A variety of formulations have been found to be useful in both these methods
in which the formulations are diluted with water and used. These formulations
are
disclosed in the tables below.
Sink Formula with a 3 to 6 hour life
Formula Raw Material % m use ap koz.


Ex VI Encapsulated chlorine33.600 100 1.0
ACP


SAPP 1 14.100


Citric Acid (anh) 2.110


Panodan2 0.166


FD&C RED #40 0.140


NaCI (diluent also 49.884
NaZS04)


Ex VII Encapsulated chlorine67.20 100 0.5
ACP


SAPP 28.20


Citric Acid (anh) 4.22


Panodan 0.10


FD&C RED #40 Gran 0.28


Ex VIII Encapsulated chlorine10.100
ACP


SAPP 14.100


Citric Acid (anh) 2.110


Panodan 0.166


FD&C RED #40 0.140


NaCI flake 73.384


Ex IX Encapsulated chlorine ACP 20.200


SAPP 28.200


Citric Acid (anh) 4.220


Panodan 0.166


FD&C RED #40 0.280


NaCI flake 46.934


Sodium acid pyrophosphate.
Diace 1 tartaric acid ester of lon chain C
ty g ,6_,8 fatty acid mixed monoglycerides and
diglycerides.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
Spray Bottle Formula
with 3 to 18 hour life


Formula Raw Material % m use ap koz.


5


Ex X Enforcer RC3 (encapsulated11.20 100 1.0
Clz)


SAPP 14.10


Citric Acid (anh) 00.80


FD&C RED #40 00.40


10 NaCI flake 73.36


Panodan 00.50


Ex XI Enforcer RC 22.40 100 0.5


SAPP 28.20


1 Citric Acid (anh) O l
S .60


FD&C RED #40 00.08


Panodan 00.75


Fill (powder diluent) 46.97


20 Ex XII Enforcer RC 03.40 30 1.0


SAPP 14.10


Citric Acid (anh) 00.08


FD&C RED #40 00.04


Panodan 00.50


25 Fill (powder diluent) 81.88


Surprisingly, we have found, under the conditions of use shown in the
Examples above, that a dye, typically considered to be unstable in the
presence of
30 strong oxidants such as halogen bleaches, can remain stable for a
sufficient period of
time to be used as an indicator of an oxidative quality of the solution and/or
the
efficacy of a sanitizer solution. The use of an encapsulated chlorine source
in a
powdered concentrate appears to be important in maintaining and extending the
stability. The stability permits the use of such a dye with such an oxidative
halogen
bleach in a hard surface sanitizing method and a hand warewashing method. In
hand
ware washing, the ware is first washed with a typical surfactant system and
then
sanitized in the dye containing halogen solution. We have found that the
indicator
can be used to show the effective concentration of the chlorine source and can
suggest the appropriate time for replacing the chlorine bleach solution at
intervals
See U.S. Patent No. 5,213.705 for a disclosure of the encapsulated chlorine
source.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
31
which results in the efficient use of the sanitizer solution. If the solutions
were
replaced too early, the chlorine bleach materials can be wasted. If the
solutions were
replaced after too long an interval, solutions would be depleted of active
chlorine
species and would not bleach or sanitize the ware. The overall process of the
invention produces clean bleached and sanitized ware in a handwashing system
without wasted chlorine bleach materials.
Example XIII
Experimental work was conducted in order to demonstrate antimicrobial or
sanitizing activity of the materials having the dye indicator content. Testing
was
conducted in accordance with the official methods of analysis fox the
"available
chlorine germicidal equivalent concentration" test, AOAC, Fifteenth Edition,
1990,
Chapter 6, Section 955.16, pp. 137-138, per TEC-TM-001. Following the
provisions of that test, five sanitizer solutions were formulated having a
chlorine
concentration that ranged from about 9.8 to about 110 ppm active chlorine. The
solutions were made from concentration mixed at about 0.75 gram per liter of
water
or about one ounce per ten gallons. The sanitizers were formulated with a pH
between 6 and 7. The solutions were prepared for the purpose of determining
chlorine longevity and sanitizing efficacy. The following table shows the
formula
and the chlorine concentration. The test organism used was Staphylococcus
auras,
ATCC No. 6538.
Formulae and C1 concentration
FORMULATION CIZ Conc. m


A 100


B 78


C 48


D 31


E 9.8


Following the protocol set forth above, the following results were obtained:



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
32
Microbiolo~ical test results
m 1 2 3 4 5 6 7 8 9 10


Chlorine 52 - - + + + + + + + +
Std.


A 110 - - - + + + + + + +


B 78 - - - + + + + + + +


C 48 - - + + + + + + + +


D 31 - + + + + + + + + +


E 9.8 + + + + + + + + + +


Results: ( + means positive growth, - means negative growth)
Results were recorded after approximately 48 hours incubation at
37°C.
The bacterial efficacy of a sample must be equivalent to, or greater than, the
SO ppm chlorine standard to be certified by the USDA. Equivalency is met when
the
sample tubes have an absence in growth in as many tubes as the chlorine
standard.
The five experimental sanitizers exhibited bactericidal efficacy approximating
the
expected results from chlorine standards prepared at those concentrations.
Thus,
while passing the Available Chlorine test against S. aureus, the sanitizer
formulations showed no enhancement of antibacterial properties over those of
our
current formula as expected with this test.
Example XIV
A similar set of chlorine base sanitizer solutions were made using
compositions made from chlorinated isocyanurate or chlorinated trisodium
phosphate. The chlorine concentration ranged from 10 to 30 ppm. These
solutions
were tested for sanitizing capacity and chlorine stability. The following test
shows
the results:



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
33
ACID SANITIZER MICROBIOLOGY TEST
Chlorine


Based


Sanitizer


ChlorineSource % pH Chlorine Chlorin Chlorine
of


ppm Chlorine Reduction (ppm) a (ppm) (ppm)


Conc.O Conc.4 Conc.24


Time Hours Hours


CDB 100.0000 4.559.9 8.5 5.67


Chlorinated


Isocyanurate


10 CDB 99.9999 4.559.9 8.5 5.67


Chlorinated


Isoc anurate


30 CDB 100.0000 4.7826.9 22.69 19.85


Chlorinated


Isoc anurate


30 CDB 100.0000 4.7826.9 22.69 19.85


Chlorinated


Isocyanurate


12 Chlorinated100.0000 5.1312.7 9.93 5.67


TSP


12 Chlorinated100.0000 5.1312.7 9.93 5.67


TSP



Inoculum2.2E+9


Control 21.8E+6


This table demonstrates that the chlorine concentration can last more than 24
hours and provide adequate microbial control.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
34
Example XV
The formulations listed below were submitted for microbiological efficacy
testing according to the AOAC Germical and Detergent Sanitizers Method.
Component #13 #14 #15 #16 #17
~wt_%) ~wt_%) ~wt_%) ~wt_%) ~wt_%)


sodium sulfate49.90 56.58 66.68 50.00 0


SAPP' 14.10 14.10 14.10 28.20 56.40


anhydrous citric2.11 2.11 2.11 2.00 8.40
acid


propylene glycol0.15 0.17 0.17 0.56 0.10


FD&C red #40 0.14 0.14 0.14 0.10 0.20


ACP' 33.60 26.90 16.80 19.14 34.90


1. Encapsulated sodium dichloro-s-triazinetrione dehydrate.
2. Sodium acid pyrophosphate.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
The following results were obtained using both S. aureus (ATCC 6538) and
E. coli (ATCC 11229).
FormulationTest CultureAverage SurvivorsPercent
# (cfu/ml) Reduction


13 S. aureus 20 99.999


14 S. aureus 5 99.999


15 S. aureus <10 >99.999


16 S. aureus <10 >99.999


17 S. aureus <10 >99.999


13 E. coli <10 >99.999


14 E. coli <10 >99.999


15 E. coli <10 >99.999


16 E. coli <10 >99.999


17 E. coli <10 >99.999


5 Example XVII
In an appropriate mixing container, 113.3 grams of sodium dichloro-
isocyanurate dihydrate is combined with about 1 gram of a FD&C Red # 40
granular
dye having a powder size of about 700 microns. The blended powder was
introduced into an automated tablet press forming a tablet 3/4 inch (19 mm) in
10 diameter. About 6.86 grams of the blended powdered material was introduced
into
the dye and compressed into the tablet using about 2 tons pressure. The tablet
formed quickly and was hard and not fryable. The hardness was measured within
a
range of about 60 to about 90 psi.
The tableted product produced in the Example was used in forming an active
15 chlorine containing aqueous solution in a sink. The solution is used over a
period of
4 hours. The solution is discarded after the dye disappears indicating that
the typical
lifetime of the solution has ended.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
36
Examples XVIIIA and XVII)B
Tablet Examples
Using the procedure of Example XVII, a 10 gram tablet was made using the
following formulas.
In redients A wt% B (wt%)


Granular sodium 99.56 97.57
dichloroisocyanurate
dehydrate


FD&C #40 (Granular)0.44 1.43


Sodium Stearate 0.0 1.0


Examples XIXA and XIXB
Tablet Examples
Using the procedure of Example XVII, a 6.8 gram tablet was made using the
following formulas.
In redients A wt% B wt%)


Granular sodium 99.56 97.57
dichloroisocyanurate
dehydrate


FD&C #40 (Granular)0.44 1.43


Sodium Stearate 0.0 1.0


The tableted products of Example XVIII and XIX were used in a sanitizing
solution
at a ratio of one tablet in a 10 gallon volume of water. The pH was about 6.0
and
produced at least 100 ppm of active chlorine in the water until the dye color
was
depleted. The tablet was also tested for stability. At ambient temperature,
the
materials lost no chlorine or dye activity over a six month period of storage
at typical
ambient conditions at ambient temperature of about 70-75°F with ambient
relative
humidity. In a five month extreme environment test, the tablets had no
substantial
loss of chlorine or dye activity over five months held at a temperature
between 112°-
127°F.



CA 02363741 2001-08-23
WO 00/50554 PCT/US00/04595
37
The above specification provides the basis for understanding compositions
that can be used in formulating the materials used in the process of the
invention.
The example and data also provide a basis to understand a specific embodiment
of
the invention and disclose the best mode. Since many embodiments can be made
without departure from the spirit and scope of the invention, the invention is
found
in the claims hereinafter appended.

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Title Date
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(86) PCT Filing Date 2000-02-23
(87) PCT Publication Date 2000-08-31
(85) National Entry 2001-08-23
Examination Requested 2004-07-21
Dead Application 2008-10-30

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Current owners on record shown in alphabetical order.
Current Owners on Record
KAY CHEMICAL COMPANY
Past owners on record shown in alphabetical order.
Past Owners on Record
BOWLING, DARRYL C.
SOWLE, EDDIE D.
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