U.S. patent application number 13/209719 was filed with the patent office on 2011-12-08 for method of reducing corrosion using a warewashing composition.
This patent application is currently assigned to ECOLAB USA INC.. Invention is credited to Michael J. Bartelme, Michael E. Besse, Keith E. Olson, Kim R. Smith.
Application Number | 20110301072 13/209719 |
Document ID | / |
Family ID | 39939966 |
Filed Date | 2011-12-08 |
United States Patent
Application |
20110301072 |
Kind Code |
A1 |
Smith; Kim R. ; et
al. |
December 8, 2011 |
METHOD OF REDUCING CORROSION USING A WAREWASHING COMPOSITION
Abstract
A warewashing composition includes a cleaning agent having a
detersive amount of a surfactant, an alkaline source in an amount
effective to provide a use composition having a pH of at least
about 8 when the use composition is measured at a solids
concentration of about 0.5 wt %, and a corrosion inhibitor in an
amount sufficient for reducing corrosion of glass when the
warewashing composition is combined with water of dilution at a
dilution ratio of at least about 20:1 water of dilution to
detergent composition o form a use composition. The corrosion
inhibitor includes a salt of calcium, magnesium, or a mixture of
calcium and magnesium. The salt has a water solubility of less than
about 0.5 wt % in water at about 20.degree. C. and atmospheric
pressure so that the salt precipitates to form a protective layer
on a substrate in contact with the use composition.
Inventors: |
Smith; Kim R.; (Woodbury,
MN) ; Olson; Keith E.; (Apple Valley, MN) ;
Besse; Michael E.; (Golden Valley, MN) ; Bartelme;
Michael J.; (Eden Prairie, MN) |
Assignee: |
ECOLAB USA INC.
ST. PAUL
MN
|
Family ID: |
39939966 |
Appl. No.: |
13/209719 |
Filed: |
August 15, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
12114385 |
May 2, 2008 |
8021493 |
|
|
13209719 |
|
|
|
|
60927575 |
May 4, 2007 |
|
|
|
Current U.S.
Class: |
510/227 |
Current CPC
Class: |
C23F 11/18 20130101;
C23F 11/124 20130101; C02F 2303/22 20130101; C02F 5/02 20130101;
C11D 7/10 20130101; C11D 3/10 20130101; C23G 1/20 20130101; C02F
5/06 20130101; C23F 11/08 20130101; C11D 3/046 20130101; C02F
2303/14 20130101; C11D 3/044 20130101; C11D 11/0023 20130101; C23G
1/22 20130101 |
Class at
Publication: |
510/227 |
International
Class: |
C11D 3/60 20060101
C11D003/60 |
Claims
1. A warewashing composition comprising: (a) a cleaning agent
comprising a detersive amount of a surfactant; (b) an alkaline
source in an amount effective to provide a use composition having a
pH of at least about 8 when the use composition is measured at a
solids concentration of about 0.5 wt %; and (c) a corrosion
inhibitor in an amount sufficient for reducing corrosion of a
substrate when the warewashing composition is combined with a
diluent at a dilution ratio of at least about 20:1 of diluent to
warewashing composition to form a use composition, wherein the
corrosion inhibitor comprises a salt of calcium, magnesium, or a
mixture of calcium and magnesium, and wherein the salt has a water
solubility of less than about 0.5 wt % in water at about 20.degree.
C. and atmospheric pressure so that the salt precipitates to form a
protective layer on the substrate in contact with the use
composition.
2. The warewashing composition according to claim 1, wherein the
cleaning agent constitutes from about 0.05 wt % to about 15 wt % of
the warewashing composition.
3. The warewashing composition according to claim 1, wherein the
cleaning agent comprises at least one of an anionic surfactant, a
nonionic surfactant, a cationic surfactant and a zwitterionic
surfactant.
4. The warewashing composition according to claim 1, wherein the
corrosion inhibitor constitutes between about 0.01 wt % and about
15 wt % of the warewashing composition.
5. The warewashing composition according to claim 1, wherein the
warewashing composition comprises less than about 1 wt %
phosphorus-containing compounds.
6. The warewashing composition according to claim 1, further
comprising builder, wherein the builder constitutes about 1 wt % to
about 60 wt % of the warewashing composition and wherein the
builder comprises a non-phosphorous containing builder.
7. The warewashing composition according to claim 1, wherein the
alkaline source constitutes between about 5 wt % and about 40 wt %
of the warewashing composition.
8. The warewashing composition according to claim 1, wherein the
alkaline source comprises at least one of an alkali metal
carbonate, an alkali metal hydroxide and a mixture thereof.
9. The warewashing composition according to claim 8, wherein the
alkaline source comprises at least one of sodium carbonate,
potassium carbonate, sodium bicarbonate, potassium bicarbonate,
sodium sesquicarbonate and potassium sesquicarbonate.
10. The warewashing composition according to claim 8, wherein the
alkaline source comprises at least one of sodium hydroxide and
potassium hydroxide.
11. The warewashing composition according to claim 1, wherein the
salt comprises a water soluble magnesium salt selected from at
least one of magnesium acetate, magnesium benzoate, magnesium
bromide, magnesium bromate, magnesium chlorate, magnesium chloride,
magnesium chromate, magnesium citrate, magnesium formate, magnesium
hexafluorosilicate, magnesium iodate, magnesium iodide, magnesium
lactate, magnesium molybdate, magnesium nitrate, magnesium
perchlorate, magnesium phosphinate, magnesium salicylate, magnesium
sulfate, magnesium sulfite, magnesium tartrate, magnesium
thiosulfate, a hydrate thereof, and a mixture thereof.
12. The warewashing composition according to claim 1, wherein the
salt comprises a water insoluble magnesium salt selected from at
least one of magnesium aluminate, magnesium borate, magnesium
carbonate, magnesium carbonate hydroxide, magnesium ferrate,
magnesium fluoride, magnesium hydroxide, magnesium mandelate,
magnesium oxalate, magnesium oxide, magnesium phosphate, magnesium
silicate, magnesium tungstate, a hydrate thereof, and a mixture
thereof.
13. The warewashing composition according to claim 1, wherein the
salt comprises a water soluble calcium salt selected from at least
one of calcium acetate, calcium benzoate, calcium bromate, calcium
bromide, calcium chlorate, calcium chloride, calcium chromate,
calcium dihydrogen phosphate, calcium dithionate, calcium formate,
calcium gluconate, calcium glycerophosphate, calcium hydrogen
sulfide, calcium iodide, calcium lactate, calcium metasilicate,
calcium nitrate, calcium nitrite, calcium pantothenate, calcium
perchlorate, calcium permanganate, calcium phosphate, calcium
phosphinate, calcium salicylate, calcium succinate, a hydrate
thereof, and a mixture thereof.
14. The warewashing composition according to claim 1, wherein the
salt comprises a water insoluble calcium salt selected from at
least one of calcium aluminate, calcium carbonate, calcium chromium
(III) oxide, calcium citrate, calcium diphosphate, calcium
disilicide, calcium fluoride, calcium hydrogen phosphate, calcium
hydroxide, calcium iron oxide, calcium iodate, calcium laurate,
calcium magnesium carbonate, calcium magnesium silicon oxide,
calcium malonate, calcium metaborate, calcium metaphosphate,
calcium molybdate, calcium oleate, calcium oxalate, calcium oxide,
calcium palmitate, calcium phosphate, calcium silicate, calcium
silicon oxide, calcium silicon titanium oxide, calcium stearate,
calcium sulfate, calcium sulfide, calcium sulfite, calcium
tartrate, calcium titanate, calcium tungstate, a hydrate thereof,
and a mixture thereof.
15. The warewashing composition according to claim 1, wherein the
use composition has a solids content of less than about 1 wt %.
16. A method of cleaning an article and reducing corrosion to a
surface of the article comprising: (a) providing a warewashing
composition, wherein the warewashing composition comprises: (i) a
cleaning agent, wherein the cleaning agent constitutes between
about 0.05 wt % and about 15 wt % of the warewashing composition;
(ii) an alkaline source, wherein the alkaline source constitutes
between about 5 wt % and about 40 wt % of the warewashing
composition; and (iii) a corrosion inhibitor, wherein the corrosion
inhibitor constitutes between about 0.01 wt % and about 15 wt % of
the warewashing composition, wherein the corrosion inhibitor
comprises at least one of a water soluble magnesium salt, a water
insoluble magnesium salt, a water soluble calcium salt and a water
insoluble calcium salt; (b) diluting the warewashing composition
with a diluent to form an aqueous composition; and (c) contacting
the aqueous composition to the article to clean the article and
reduce corrosion to the surface of the article.
17. The method according to claim 16, wherein the cleaning agent
constitutes from about 0.5 wt % to about 10 wt % of the warewashing
composition.
18. The method according to claim 16, wherein the corrosion
inhibitor constitutes between about 0.5 wt % and about 10 wt % of
the warewashing composition.
19. The method according to claim 16, wherein the warewashing
composition comprises less than about 1 wt % phosphorus-containing
compounds.
20. The method according to claim 16, wherein the alkaline source
constitutes between about 10 wt % and about 30 wt % of the
warewashing composition.
21. The method according to claim 16, wherein the alkaline source
comprises at least one of an alkali metal carbonate, an alkali
metal hydroxide and a mixture thereof.
22. The method according to claim 16, wherein the aqueous
composition has a pH of about 8.
23. The method according to claim 16, wherein the aqueous
composition has a solids content of at least about 0.05 wt %.
24. The method according to claim 14, further comprising depositing
a film on a surface of the article.
25-37. (canceled)
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to U.S. Provisional
Application Ser. No. 60/927,575 filed on May 4, 2007 and entitled
"Compositions Containing Magnesium Salts and Methods of Using", the
disclosure of which is incorporated herein by reference.
[0002] This application is also related to: U.S. Patent Application
Ser. No. ______, entitled "Cleaning Compositions with Water
Insoluble Conversion Agents and Methods of Making and Using Them"
(Attorney Docket No. 2454USU1); U.S. patent application Ser. No.
______, entitled, "Composition For In Situ Manufacture Of Insoluble
Hydroxide When Cleaning Hard Surfaces And For Use In Automatic
Warewashing Machines, And Methods For Manufacturing And Using"
(Attorney Docket No. 2437USU1); U.S. patent application Ser. No.
______, entitled "Water Treatment System and Downstream Cleaning
Methods" (Attorney Docket No. 2428USU1); U.S. patent application
Ser. No. ______, entitled "Water Soluble Magnesium Compounds as
Cleaning Agents and Methods of Using Them" (Attorney Docket No.
2372USU1); U.S. patent application Ser. No. ______, entitled
"Cleaning Compositions Containing Water Soluble Magnesium Compounds
and Methods of Using Them" (Attorney Docket No. 2488USU1); U.S.
patent application Ser. No. ______, entitled "MG++ Chemistry and
Method for Fouling Inhibition in Heat Processing of Liquid Foods
and Industrial Processes" (Attorney Docket No. 2400USU1); U.S.
patent application Ser. No. ______, entitled "Compositions
Including Hardness Ion and Gluconate and Methods Employing Them to
Reduce Corrosion and Etch" (Attorney Docket No. 163.2365USU1); U.S.
patent application Ser. No. ______, entitled "Compositions
Including Hardness Ion and Silicate and Methods Employing Them to
Reduce Corrosion and Etch" (Attorney Docket No. 163.2487USU1); and
U.S. patent application Ser. No. ______, entitled "Compositions
Including Hardness Ion and Threshold Agent and Methods Employing
Them to Reduce Corrosion and Etch" (Attorney Docket No.
163.2406USU1), all commonly assigned to Ecolab, Inc., are filed on
the same date as this application being May 2, 2008 and are all
incorporated herein by reference for all purposes.
FIELD OF THE INVENTION
[0003] The present invention relates to warewashing compositions
including a hardness ion (e.g., magnesium and calcium ions) as a
corrosion inhibitor. Such compositions can be used to reduce
corrosion or etching of glass, porcelain and ceramic. The present
invention also relates to methods employing these warewashing
compositions.
BACKGROUND OF THE INVENTION
[0004] The level of hardness in water can have a deleterious effect
in many systems. For example, when hard water is used in
conjunction with cleaning compositions, hard water can cause
precipitation of hard water scale or components of a cleaning
agent. In general, hard water refers to water having a level of
calcium and magnesium ions in excess of about 100 ppm expressed in
units of ppm calcium carbonate. Often, the molar ratio of calcium
to magnesium in hard water is about 2:1 or about 3:1. Although most
locations have hard water, water hardness tends to vary from one
location to another.
[0005] Etching or corrosion of glass, porcelain and ceramic due to
water hardness is a common problem in warewashing and surface
cleaning Water hardness can be addressed in a number of ways. For
example, the water can be softened by replacing the calcium and the
magnesium present in the water with sodium. The warewashing
composition can also include builders or chelating agents at levels
sufficient to handle the water hardness. Water softeners, however,
break down on occasion or run out of material that provides the
softening effect. In addition, certain environments may provide
water having a hardness that exceeds the builder or chelating
capacity of the warewashing detergent composition. As a result,
free calcium ions may be available to attack active components of
the composition, to cause corrosion or precipitation, or other
deletrious affects. Accordingly, conventional cleaning compositions
include additional ingredients to combat corrosion or etch.
[0006] It is entirely unexpected that a hardness ion would have a
beneficial effect on reducing etching and/or corrosion of
glass.
SUMMARY OF THE INVENTION
[0007] The present invention relates to compositions employing
salts of magnesium, calcium and mixtures thereof as a corrosion
inhibitor. The present compositions can reduce corrosion or etch of
glass, porcelain and ceramic surfaces. The present invention also
relates to methods employing these compositions.
[0008] In an embodiment, the present invention relates to a
warewashing composition. This composition includes a cleaning agent
having a detersive amount of a surfactant, an alkaline source in an
amount effective to provide a use composition having a pH of at
least about 8 when the use composition is measured at a solids
concentration of about 0.5 wt %, and a corrosion inhibitor in an
amount sufficient to reduce corrosion of glass when the warewashing
detergent composition is combined with water of dilution at a
dilution ratio of at least about 20:1 water of dilution to
detergent composition to form a use composition. The corrosion
inhibitor includes a salt of calcium, magnesium or a mixture of
calcium and magnesium. The salt has a water solubility of less than
about 0.5 wt. % in water at about 20.degree. C. and atmospheric
pressure so that the salt precipitates to form a protective layer
on a substrate in contact with the use composition.
[0009] In an embodiment, the present invention relates to a method
of cleaning an article and reducing corrosion to a surface of the
article. The method includes providing a warewashing composition,
contacting the warewashing composition with a diluent to form an
aqueous composition and contacting the aqueous composition to the
article to clean the article and reduce corrosion of a surface of
the article. The warewashing composition includes a cleaning agent
constituting between about 0.05 wt % and about 15 wt % of the
warewashing composition, an alkaline source constituting between
about 5 wt % and about 40 wt % of the warewashing composition and a
corrosion inhibitor constituting between about 0.01 wt % and about
15 wt % of the warewashing composition. The corrosion inhibitor
includes at least one of a water soluble magnesium salt, a water
insoluble magnesium salt, a water soluble calcium salt and a water
insoluble calcium salt.
[0010] In an embodiment, the present invention relates to a method
of reducing corrosion of an article during cleaning The method
includes diluting a warewashing detergent composition with water to
form a use composition and contacting the article with the use
composition in an automatic dishwashing machine. The warewashing
detergent composition is diluted at a ratio of at least about 20:1
water to warewashing detergent composition. The warewashing
detergent composition includes a cleaning agent comprising a
detersive amount of a surfactant, an alkaline source in an amount
effective to provide a use composition having a pH of at least
about 8 when measured at a solids concentration of about 0.5 wt %,
and a corrosion inhibitor in an amount sufficient for reducing
corrosion of glass. The corrosion inhibitor includes a salt of
calcium, magnesium, or a mixture of calcium and magnesium and has a
water solubility of less than about 0.5 wt % in water at about
20.degree. C. and atmospheric pressure. The salt precipitates to
form a protective layer on a article in contact with the use
composition.
DETAILED DESCRIPTION OF THE INVENTION
[0011] So that the invention may be more readily understood,
certain terms are first defined.
[0012] As used herein, the term "water soluble" refers to a
compound that can be dissolved in water at a concentration of more
than about 1 wt %.
[0013] As used herein, the terms "slightly soluble" or "slightly
water soluble" refer to a compound that can be dissolved in water
only to a concentration of 0.1 to 1.0 wt-%.
[0014] As used herein, the term "water insoluble" refers to a
compound that can be dissolved in water only to a concentration of
less than about 0.1% by weight.
[0015] As used herein, the terms "chelating agent" and
"sequestrant" refer to a compound that forms a complex (soluble or
not) with water hardness ions (from the wash water, soil and
substrates being washed) in a specific molar ratio. Chelating
agents that can form a water soluble complex include sodium
tripolyphosphate (STPP), ethylenediamine tetracetic acid (EDTA),
diethylenetriamine pentaacetic acid (DTPA), nitrilotriacetic (NTA),
citrate and the like. Sequestrants that can form an insoluble
complex include sodium triphosphate, zeolite A and the like. As
used herein, the terms "chelating agent" and "sequestrant" are
synonymous.
[0016] As used herein, the term "threshold agent" refers to a
compound that inhibits crystallization of water hardness ions from
solution, but that need not form a specific complex with the water
hardness ions. This distinguishes a threshold agent from a
chelating agent or sequestrant. Examples of threshold agents
include, but are not limited to: a polyacrylate, a
polymethacrylate, an olefin/maleic copolymer and the like.
[0017] As used herein, the term "phosphate-free" refers to a
composition, mixture or ingredient that does not contain a
phosphate or phosphate-containing compound or to which a phosphate
or phosphate-containing compound has not been added. Should a
phosphate or phosphate-containing compound be present through
contamination of a phosphate-free composition, mixture or
ingredient, the amount of phosphate shall be less than about 0.5 wt
%. In an embodiment, the amount of phosphate is less than about 0.1
wt %. In an embodiment, the amount of phosphate is less than about
0.01 wt %.
[0018] As used herein, the term "phosphorus-free" refers to a
composition, mixture or ingredient that does not contain phosphorus
or a phosphorus-containing compound or to which phosphorus or a
phosphorus-containing compound has not been added. Should
phosphorus or a phosphorus-containing compound be present through
contamination of a phosphorus-free composition, mixture or
ingredient, the amount of phosphorus shall be less than about 0.5
wt %. In an embodiment, the amount of phosphorus is less than about
0.1 wt %. In an embodiment, the amount of phosphorus is less than
about 0.01 wt %.
[0019] As used herein, the term "cleaning" means to perform or aid
in soil removal, bleaching, microbial population reduction or
combination thereof.
[0020] As used herein, the term "ware" includes items such as
eating and cooking utensils, and other hard surfaces such as
showers, sinks, toilets, bathtubs, countertops, windows, mirrors,
transportation vehicles, and floors.
[0021] As used herein, the term "warewashing" refers to washing,
cleaning or rinsing ware.
[0022] As used herein, the term "hard surface" includes showers,
sinks, toilets, bathtubs, countertops, windows, mirrors,
transportation vehicles, floors, and the like.
[0023] As used herein, the phrase "health care surface" refers to a
surface of an instrument, a device, a cart, a cage, furniture, a
structure, a building, or the like that is employed as part of a
health care activity. Examples of health care surfaces include
surfaces of medical or dental instruments, of medical or dental
devices, of autoclaves and sterilizers, of electronic apparatus
employed for monitoring patient health, and of floors, walls, or
fixtures of structures in which health care occurs. Health care
surfaces are found in hospital, surgical, infirmity, birthing,
mortuary, and clinical diagnosis rooms. These surfaces can be those
typified as "hard surfaces" (such as walls, floors, bed-pans,
etc.,), or fabric surfaces, e.g., knit, woven, and non-woven
surfaces (such as surgical garments, draperies, bed linens,
bandages, etc.,), or patient-care equipment (such as respirators,
diagnostic equipment, shunts, body scopes, wheel chairs, beds,
etc.), or surgical and diagnostic equipment. Health care surfaces
include articles and surfaces employed in animal health care.
[0024] As used herein, the term "instrument" refers to the various
medical or dental instruments or devices that can benefit from
cleaning using water treated according to the methods of the
present invention.
[0025] As used herein, the phrases "medical instrument," "dental
instrument," "medical device," "dental device," "medical
equipment," or "dental equipment" refer to instruments, devices,
tools, appliances, apparatus, and equipment used in medicine or
dentistry. Such instruments, devices, and equipment can be cold
sterilized, soaked or washed and then heat sterilized, or otherwise
benefit from cleaning using water treated according to the present
invention. These various instruments, devices and equipment
include, but are not limited to: diagnostic instruments, trays,
pans, holders, racks, forceps, scissors, shears, saws (e.g. bone
saws and their blades), hemostats, knives, chisels, rongeurs,
files, nippers, drills, drill bits, rasps, burrs, spreaders,
breakers, elevators, clamps, needle holders, carriers, clips,
hooks, gouges, curettes, retractors, straightener, punches,
extractors, scoops, keratomes, spatulas, expressors, trocars,
dilators, cages, glassware, tubing, catheters, cannulas, plugs,
stents, scopes (e.g., endoscopes, stethoscopes, and arthoscopes)
and related equipment, and the like, or combinations thereof.
[0026] As used herein, the phrase "solid cleaning composition"
refers to a cleaning composition in the form of a solid such as a
powder, a flake, a granule, a pellet, a tablet, a lozenge, a puck,
a briquette, a brick, a solid block, a unit dose or another solid
form known to those of skill in the art. The term "solid" refers to
the state of the detergent composition under the expected
conditions of storage and use of the solid detergent composition.
In general, it is expected that the detergent composition will
remain in solid form when exposed to temperatures of up to about
100.degree. F. and greater than about 120.degree. F.
[0027] By the term "solid" as used to describe the processed
composition, it is meant that the hardened composition will not
flow perceptibly and will substantially retain its shape under
moderate stress or pressure or mere gravity, as for example, the
shape of a mold when removed from the mold, the shape of an article
as formed upon extrusion from an extruder and the like. The degree
of hardness of the solid cast composition can range from that of a
fused solid block which is relatively dense and hard, for example,
like concrete, to a consistency characterized as being malleable
and sponge-like, similar to caulking material.
[0028] As used herein, weight percent (wt %), percent by weight, %
by weight, and the like are synonyms that refer to the
concentration of a substance as the weight of that substance
divided by the total weight of the composition and multiplied by
100.
[0029] As used herein, the term "about" modifying the quantity of
an ingredient in the compositions of the invention or employed in
the methods of the invention refers to variation in the numerical
quantity that can occur, for example, through typical measuring and
liquid handling procedures used for making concentrates or use
solutions in the real world; through inadvertent error in these
procedures; through differences in the manufacture, source, or
purity of the ingredients employed to make the compositions or
carry out the methods; and the like. The term "about" also
encompasses amounts that differ due to different equilibrium
conditions for a composition resulting from a particular initial
mixture. Whether or not modified by the term "about", the claims
include equivalents to the quantities.
Corrosion Inhibitor Warewashing Composition
[0030] The present invention relates to warewashing compositions
including hardness ions (e.g., magnesium and calcium ions) as a
corrosion inhibitor. Surprisingly, the inventors have discovered
that warewashing compositions including a mixture of hardness ions
can have a beneficial effect on protecting articles such as glass,
ceramic or porcelain from corrosion in an automatic dishwashing or
warewashing machine. Compositions including hardness ions reduce
the rate of corrosion and etching of various articles. While the
warewashing composition is discussed as being applied in automatic
dishwashing or warewashing machines, the warewashing composition
can be applied in any environment where it is desirable to reduce
corrosion and/or etching of glass, ceramic or porcelain. For
example, the warewashing composition can be used for bottle washing
or as a manual cleaner for cleaning glasses, dishes, etc. in a
sink.
[0031] The source of hardness ions is sufficiently water-soluble so
that when the composition is combined with a diluent, such as
water, the compounds dissolve. In this context, sufficiently
water-soluble means that the source of hardness ions dissolve at a
relatively quick rate in water. In an embodiment, the solubility of
the source of hardness ions is at least about 0.5 wt % in water at
about 20.degree. C. and atmospheric pressure. In an embodiment,
once solubilized, the hardness ions interact to form a salt having
limited water solubility (e.g., even water insoluble). In this
context, the phrase "limited water solubility" means that the salt
has a tendency to precipitate from the solution. In an embodiment,
a salt having limited water solubility has a solubility of less
than about 0.5 wt % in water at about 20.degree. C. and atmospheric
pressure.
[0032] The water-insoluble salt may be formed in-situ when the
diluent is added to the present composition or may be added to a
liquid as a premade complex. Forming the water insoluble salt in
situ can result in its more homogeneous dispersion in solution.
Forming the water insoluble salt as a premade complex can allow use
of lower concentrations while achieving the same level of
effectiveness as forming the corrosion inhibitor in situ.
[0033] In an embodiment, the present compositions can include
sources of water-soluble cations (e.g., two different cations) and
a source of water-soluble anion. The water-soluble cations can be a
mixture of hardness ions. The cations and anion can interact with
each other to mitigate corrosion and etching of surfaces exposed to
an alkalinity source or soft water. The water-soluble cations and
the water-soluble anions can be provided as a mixture of distinct
chemical entities (e.g., powders or granules of salts that have
been mixed) that are combined by the addition of a diluent. Once
combined with the diluent, the source of water-soluble cations and
the source of water-soluble anion form cations and anions,
respectively. The cations and anions interact to form a
water-insoluble salt that precipitates onto the surface and forms a
protective film. In general, the corrosion inhibitor can be used in
any application where it is desirable to reduce surface corrosion,
such as in a detergent composition.
[0034] The warewashing composition includes an effective amount of
a corrosion inhibitor to provide a use composition exhibiting
resistance to glass corrosion after multiple washings. In an
embodiment, the aqueous composition includes water, a cleaning
agent, an alkaline source, hardness ions as a corrosion inhibitor,
and further ingredients that provide a beneficial property for a
particular use. In certain embodiments, the present warewashing
composition includes between about 0.05 wt % and 15 wt % cleaning
agent, about 5 wt % and about 40 wt % alkaline source and about
0.01% and about 15% corrosion inhibitor; about 0.5 wt % and 10 wt %
cleaning agent, about 10 wt % and about 30 wt % alkaline source and
about 0.5% and about 10% corrosion inhibitor; and about 1 wt % and
5 wt % cleaning agent, about 15 wt % and about 20 wt % alkaline
source and about 1% and about 5% corrosion inhibitor.
[0035] Without wishing to be bound by any particular theory, it is
thought that, in certain embodiments, a salt formed from the
hardness ions (e.g., magnesium and calcium) forms a protective film
on the surface of articles exposed to the present composition. The
protective film can be transparent or not visible to the unaided
eye. Such a film can function as a protective layer and slow or
prevent other components that may be present in solution from
attacking and corroding the surface of the article. Thus, the film
functions as a sacrificial layer and allows other components such
as alkalinity sources, builders, or sequestrants, to attack and
remove portions of the film, rather than attack the surface of the
article. In some embodiments, the film is a relatively thin film
that may be easily removed from the surface during subsequent
cleaning so that a new film may be deposited on the surface to
provide a new protective layer. Thus, it does not permanently build
up on the surface and form an iridescent film or surface
cloudiness. As a result, the precipitate film is available to
protect the surface but can be removed and regenerated.
[0036] Although not limiting to the present invention, it is
thought that, in certain embodiments, the corrosion inhibitor
protects the surface by replacing ions extracted from the surface
by an alkalinity source or builder in solution and/or by annealing
the surface to remove surface hydroxyl groups. The protective film
can degrade during subsequent wash cycles and can be continually
regenerated as a result of precipitation of the salt.
[0037] Although not limiting to the present invention, it is
thought that, in certain embodiments, the rate of deposition of
salt is largely dependent on four conditions: (a) the level of
water hardness of the water of dilution; (b) the presence of
phosphorus-containing and non-phosphorus-containing compounds as
builders or chelating agents; (c) the composition of the corrosion
inhibitor; and (d) the ratio of cations to anions provided in the
present composition. It is believed that the ratio of cations to
anions may be manipulated such that the film deposited onto the
surface is thick enough to protect against etching but is thin
enough that it is relatively transparent and/or and substantially
invisible to the naked eye such as by an individual casually
inspecting the glass in normal use situations (e.g., at a dinner
table). In selecting the ratio of cations to anions, numerous
factors can be considered, including, but not limited to: the
hardness level of the water, the cation source, the anion source,
and the material of the surface to be protected.
[0038] Although not limiting to the present invention, it is
thought that, in certain embodiments, it is believed that calcium
and magnesium ions interact with anions at different rates to cause
precipitation. In general, the reaction rates are as follows:
calcium ions>magnesium ions. The reaction rates of the cations
with the anions may be used to determine which cation source may be
most efficient for forming a salt depending on the whether the
diluent is hard water or soft water. By varying the amount of
calcium ions and magnesium ions in solution, it is possible to
provide a corrosion inhibitor that can handle various levels of
water hardness. For example, when the diluent is hard water, it may
be desirable to provide more magnesium ions to decrease the rate of
precipitation. Similarly, when the diluent is soft water, it may be
desirable to provide more calcium ions to increase the rate of
precipitation.
Water Soluble Magnesium Salts
[0039] Suitable water soluble magnesium compounds for use in the
present invention include those selected from: magnesium acetate,
magnesium benzoate, magnesium bromide, magnesium bromate, magnesium
chlorate, magnesium chloride, magnesium chromate, magnesium
citrate, magnesium formate, magnesium hexafluorosilicate, magnesium
iodate, magnesium iodide, magnesium lactate, magnesium molybdate,
magnesium nitrate, magnesium perchlorate, magnesium phosphinate,
magnesium salicylate, magnesium sulfate, magnesium sulfite,
magnesium tartrate, magnesium thiosulfate, a hydrate thereof, and a
mixture thereof. These salts can be provided as hydrated salts or
anhydrous salts.
[0040] Suitable water soluble magnesium compounds include magnesium
salts with an anion that also forms a soluble salt with calcium.
Such salts include those selected from: magnesium acetate,
magnesium benzoate, magnesium bromide, magnesium bromate, magnesium
chlorate, magnesium chloride, magnesium chromate, magnesium
formate, magnesium iodide, magnesium lactate, magnesium nitrate,
magnesium perchlorate, magnesium phosphinate, magnesium salicylate,
a hydrate thereof, and a mixture thereof. These salts can be
provided as hydrated salts or anhydrous salts.
[0041] Water soluble magnesium compounds approved as GRAS for
direct food contact include magnesium chloride and magnesium
sulfate.
[0042] A cast or pressed solid block or puck of water soluble
magnesium compound can also contain water insoluble magnesium
compound. The water insoluble compound can slow the speed at which
the water soluble magnesium compound dissolves to provide a useful
solid cleaning composition. In certain embodiments, the ratio of
water soluble to water insoluble magnesium compound can be about
1:10 to about 10:1, about 1:5 to about 5:1, or about 1:3 to about
3:1.
Water Insoluble Magnesium Salts
[0043] Suitable water insoluble magnesium compounds include those
selected from: magnesium aluminate, magnesium borate, magnesium
carbonate, magnesium carbonate hydroxide, magnesium ferrate,
magnesium fluoride, magnesium hydroxide, magnesium mandelate,
magnesium oxalate, magnesium oxide, magnesium phosphate, magnesium
silicate, magnesium tungstate, a hydrate thereof, and a mixture
thereof. These salts can be provided as hydrated compounds or
anhydrous compounds.
[0044] In certain embodiments, suitable water insoluble magnesium
compounds include calcium magnesium silicon oxide in a form
selected from: akermanite, diopside, merwinite, and
monticellite.
Water Soluble Calcium Salts
[0045] Suitable water soluble calcium salts include those selected
from: calcium acetate, calcium benzoate, calcium bromate, calcium
bromide, calcium chlorate, calcium chloride, calcium chromate,
calcium dihydrogen phosphate, calcium dithionate, calcium formate,
calcium gluconate, calcium glycerophosphate, calcium hydrogen
sulfide, calcium iodide, calcium lactate, calcium metasilicate,
calcium nitrate, calcium nitrite, calcium pantothenate, calcium
perchlorate, calcium permanganate, calcium phosphate, calcium
phosphinate, calcium salicylate, calcium succinate, a hydrate
thereof, and a mixture thereof. These salts can be provided as
hydrated compounds or anhydrous compounds.
Water Insoluble Calcium Salts
[0046] Water insoluble calcium salts include those selected from:
calcium aluminate, calcium carbonate, calcium chromium (III) oxide,
calcium citrate, calcium diphosphate, calcium disilicide, calcium
fluoride, calcium hydrogen phosphate, calcium hydroxide, calcium
iron oxide, calcium iodate, calcium laurate, calcium magnesium
carbonate, calcium magnesium silicon oxide, calcium malonate,
calcium metaborate, calcium metaphosphate, calcium molybdate,
calcium oleate, calcium oxalate, calcium oxide, calcium palmitate,
calcium phosphate, calcium silicate, calcium silicon oxide, calcium
silicon titanium oxide, calcium stearate, calcium sulfate, calcium
sulfide, calcium sulfite, calcium tartrate, calcium titanate,
calcium tungstate, a hydrate thereof, and a mixture thereof These
salts can be provided as hydrated compounds or anhydrous
compounds.
Diluent
[0047] Typically, the diluent used to dilute the present
composition is water. It is expected that water available at one
location may have a relatively low level of water hardness while
water at another location may have a relatively high level of water
hardness. It is expected that larger amounts of the present
compositions may be employed without deleterious effects. Thus, the
present composition can be provided such that the anti-corrosion
and anti-etch properties of the corrosion inhibitor are present
regardless of whether the diluent is soft water or hard water.
[0048] As used herein with respect to ingredients of the present
compositions, water refers to water as obtained from a municipal or
private water system, e.g., a public water supply or a well. The
water can be softened water, hard water, city water, well water,
water supplied by a municipal water system, water supplied by a
private water system, treated water, or water directly from the
system or well.
Additional Ingredients
[0049] Warewashing compositions made according to the invention may
further include additional functional materials or additives that
provide a beneficial property for a particular use. Examples of
conventional additives include one or more of each of a detersive
polymer, cleaning agent, rinse aid composition, softener, source of
acidity, anti-corrosion agent, secondary hardening agent,
solubility modifier, detergent filler, defoamer, anti-redeposition
agent, antimicrobial, rinse aid composition, gluconate or system,
aesthetic enhancing agent (i.e., dye, odorant, perfume), optical
brightener, lubricant composition, bleaching agent or additional
bleaching agent, enzyme, effervescent agent, activator for the
source of alkalinity, other such additives or functional
ingredients, and the like, and mixtures thereof.
[0050] Adjuvants and other additive ingredients will vary according
to the type of composition being manufactured, and the intended end
use of the composition. In certain embodiments, the composition
includes as an additive one or more of a cleaning enzyme, detersive
polymer, antimicrobial, activators for the source of alkalinity, or
mixtures thereof.
pH Modifier
[0051] The pH modifier can be an organic or inorganic source of
alkalinity or a pH buffering agent. The warewashing composition may
include an effective amount of one or more alkaline sources to
enhance cleaning of a substrate and improve soil removal
performance of the composition. In general, an effective amount of
one or more alkaline sources should be considered as an amount that
provides a use composition having a pH of at least about 8. When
the use composition has a pH of between about 8 and about 10, it
can be considered mildly alkaline, and when the pH is greater than
about 12, the use composition can be considered caustic. In
general, it is desirable to provide the use composition as a mildly
alkaline cleaning composition because it is considered to be more
safe than caustic-based use compositions.
[0052] Nonlimiting examples of suitable pH modifiers include alkali
metal hydroxides, alkali metal carbonates, alkanolamines, salts of
weak organic acids, etc. Exemplary alkali metal hydroxides include,
for example sodium hydroxide, lithium hydroxide, potassium
hydroxide and calcium hydroxide. Exemplary metal carbonates
include, but are not limited to: sodium carbonate, lithium
carbonate, potassium carbonate, calcium carbonate (in aragonite
form) and mixtures thereof. Suitable pH modifiers include acetate,
formate, gluconate, and the like. Suitable pH modifiers have no or
only weak calcium sequestration capability at the pH of the use
solution. Alkali metal hydroxides may be added to the composition
in the form of solid beads, dissolved in an aqueous solution, or a
combination thereof. Alkali metal hydroxides are commercially
available as a solid in the form of prilled solids or beads having
a mix of particle sizes ranging from about about 12-100 U.S. mesh,
or as an aqueous solution, as for example, as about a 50 wt % and
about a 73 wt % solution.
[0053] In general, it is expected that the concentrate will include
the pH modifier in an amount of at least about 5 wt %, at least
about 10 wt %, or at least about 15 wt %. In order to provide
sufficient room for other components in the concentrate, the pH
modifier can be provided in the concentrate in an amount of less
than about 60 wt %. In addition, the alkaline source can be
provided at a level of less than about 40 wt %, less than about 30
wt % or less than about 20 wt %. It is expected that the
warewashing composition may provide a use composition that is
useful at pH levels below about 8.
Organic Surfactants or Cleaning Agents
[0054] The composition can include at least one cleaning agent
which can be a surfactant or surfactant system. A variety of
surfactants can be used in a cleaning composition, including
anionic, nonionic, cationic, and zwitterionic surfactants, which
are commercially available from a number of sources. Suitable
surfactants include nonionic surfactants. Suitable nonionic
surfactants include low foaming non-ionic surfactants. For a
discussion of surfactants, see Kirk-Othmer, Encyclopedia of
Chemical Technology, Third Edition, volume 8, pages 900-912.
[0055] Nonionic surfactants are useful in the present solid
compositions, include those having a polyalkylene oxide polymer as
a portion of the surfactant molecule. Such nonionic surfactants
include, for example, chlorine-, benzyl-, methyl-, ethyl-, propyl-,
butyl- and other like alkyl-capped polyethylene and/or
polypropylene glycol ethers of fatty alcohols; polyalkylene oxide
free nonionics such as alkyl polyglycosides; sorbitan and sucrose
esters and their ethoxylates; alkoxylated ethylene diamine;
carboxylic acid esters such as glycerol esters, polyoxyethylene
esters, ethoxylated and glycol esters of fatty acids, and the like;
carboxylic amides such as diethanolamine condensates,
monoalkanolamine condensates, polyoxyethylene fatty acid amides,
and the like; and ethoxylated amines and ether amines commercially
available from Tomah Corporation and other like nonionic compounds.
Silicone surfactants such as the ABIL B8852 (Goldschmidt) can also
be used.
[0056] Additional suitable nonionic surfactants having a
polyalkylene oxide polymer portion include nonionic surfactants of
C.sub.6-C.sub.24 alcohol ethoxylates (e.g., C.sub.6-C.sub.14
alcohol ethoxylates) having 1 to about 20 ethylene oxide groups
(e.g., about 9 to about 20 ethylene oxide groups); C.sub.6-C.sub.24
alkylphenol ethoxylates (e.g., C.sub.8-C.sub.10 alkylphenol
ethoxylates) having 1 to about 100 ethylene oxide groups (e.g.,
about 12 to about 20 ethylene oxide groups); C.sub.6-C.sub.24
alkylpolyglycosides (e.g., C.sub.6-C.sub.20 alkylpolyglycosides)
having 1 to about 20 glycoside groups (e.g., about 9 to about 20
glycoside groups); C.sub.6-C.sub.24 fatty acid ester ethoxylates,
propoxylates or glycerides; and C.sub.4-C.sub.24 mono or
dialkanolamides.
[0057] Specific alcohol alkoxylates include alcohol ethoxylate
propoxylates, alcohol propoxylates, alcohol propoxylate ethoxylate
propoxylates, alcohol ethoxylate butoxylates, and the like;
nonylphenol ethoxylate, polyoxyethylene glycol ethers and the like;
and polyalkylene oxide block copolymers including an ethylene
oxide/propylene oxide block copolymer such as those commercially
available under the trademark PLURONIC (BASF-Wyandotte), and the
like.
[0058] Suitable nonionic surfactants include low foaming nonionic
surfactants. Examples of suitable low foaming nonionic surfactants
include secondary ethoxylates, such as those sold under the trade
name TERGITOL.TM., such as TERGITOL.TM. 15-S-7 (Union Carbide),
Tergitol 15-S-3, Tergitol 15-S-9 and the like. Other suitable
classes of low foaming nonionic surfactant include alkyl or
benzyl-capped polyoxyalkylene derivatives and
polyoxyethylene/polyoxypropylene copolymers.
[0059] A useful nonionic surfactant for use as a defoamer is
nonylphenol having an average of 12 moles of ethylene oxide
condensed thereon, it being end capped with a hydrophobic portion
comprising an average of 30 moles of propylene oxide.
Silicon-containing defoamers are also well-known and can be
employed in the compositions and methods of the present
invention.
[0060] Suitable amphoteric surfactants include amine oxide
compounds having the formula:
##STR00001##
where R, R', R'', and R''' are each a C.sub.1-C.sub.24 alkyl, aryl
or aralkyl group that can optionally contain one or more P, O, S or
N heteroatoms.
[0061] Another class of suitable amphoteric surfactants includes
betaine compounds having the formula:
##STR00002##
where R, R', R'' and R''' are each a C.sub.1-C.sub.24 alkyl, aryl
or aralkyl group that can optionally contain one or more P, O, S or
N heteroatoms, and n is about 1 to about 10. Suitable surfactants
include food grade surfactants, linear alkylbenzene sulfonic acids
and their salts, and ethylene oxide/propylene oxide derivatives
sold under the Pluronic.TM. trade name. Suitable surfactants
include those that are compatible as an indirect or direct food
additive or substance; especially those described in the Code of
Federal Regulations (CFR), Title 21--Food and Drugs, parts 170 to
186 (which is incorporated herein by reference).
[0062] Anionic surfactants suitable for the present cleaning
compositions, include, for example, carboxylates such as
alkylcarboxylates (carboxylic acid salts) and
polyalkoxycarboxylates, alcohol ethoxylate carboxylates,
nonylphenol ethoxylate carboxylates, and the like; sulfonates such
as alkylsulfonates, alkylbenzenesulfonates, alkylarylsulfonates,
sulfonated fatty acid esters, and the like; sulfates such as
sulfated alcohols, sulfated alcohol ethoxylates, sulfated
alkylphenols, alkylsulfates, sulfosuccinates, alkylether sulfates,
and the like; and phosphate esters such as alkylphosphate esters,
and the like. Suitable anionics include sodium alkylarylsulfonate,
alpha-olefin sulfonate, and fatty alcohol sulfates. Examples of
suitable anionic surfactants include, for example, sodium
dodecylbenzene sulfonic acid, potassium laureth-7 sulfate, and
sodium tetradecenyl sulfonate.
[0063] The warewashing composition, when provided as a concentrate,
can include the cleaning agent in a range of about 0.01 wt % to
about 20 wt %, about 0.1 wt % to about 15 wt %, about 1 wt % to
about 15 wt %, about 1.5 wt % to about 10 wt % and about 2 wt % to
about 5 wt %. Additional exemplary ranges of surfactant in a
concentrate include about 0.5 wt % to about 5 wt % and about 1 wt %
to about 3 wt %.
Builder
[0064] If a builder is included in the present solid composition,
it is a builder incapable of chelating a significant amount of or
any of the magnesium. Zeolite 3A is an example of this type of
builder. A purpose of such builder can be to increase the molar
ratio of Mg/Ca in the use solution. This can reduce the amount of
magnesium compound used as an ingredient in the solid
composition.
[0065] Suitable inorganic builders include silicates, carbonates,
sulfates, salts or acid forms thereof, mixtures thereof, and the
like. Suitable silicates include zeolites and aluminosilicates,
such as sodium aluminosilicate (SAS). Suitable carbonates include
alkali metal salts, such as alkali metal carbonates, bicarbonates,
and/or sesquicarbonates. In an embodiment, the compositions and
methods of the present invention include a builder including an
alkali metal carbonate.
[0066] The concentrate can include about 1 wt % to about 60 wt %,
about 3 wt % to about 50 wt % and about 6 wt % to about 45 wt % of
the builders. Additional ranges of the builders include about 3 wt
% to about 20 wt %, about 6 wt % to about 15 wt %, about 25 wt % to
about 50 wt % and about 35 wt % to about 45 wt %, depending upon
whether the warewashing composition is provided as a liquid or as a
solid.
[0067] Water conditioning polymers can be used as a form of
builder. Exemplary water conditioning polymers include, but are not
limited to, polycarboxylates. Exemplary polycarboxylates that can
be used as builders and/or water conditioning polymers include, but
are not limited to, those having pendant carboxylate
(--CO.sub.2.sup.-) groups and include, for example, polyacrylic
acid, maleic/olefin copolymer, acrylic/maleic copolymer,
polymethacrylic acid, acrylic acid-methacrylic acid copolymers,
hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide,
hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed
polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed
acrylonitrile-methacrylonitrile copolymers and the like. For a
further discussion of chelating agents/sequestrants, see
Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition,
volume 5, pages 339-366 and volume 23, pages 319-320, the
disclosure of which is incorporated by reference herein. The
concentrate can include the water conditioning polymer in an amount
of between about 0.1 wt % and about 5 wt %, and between about 0.2
wt % and about 2 wt %.
Chelating Agent or Sequestrant
[0068] The composition can include a sequestrant or chelating
agent. In general, a chelating agent is a molecule capable of
coordinating (i.e., binding) the metal ions commonly found in
natural water to prevent the metal ions from interfering with the
action of the other detersive ingredients of a cleaning
composition. In general, chelating/sequestering agents can
generally be referred to as a type of builder. The
chelating/sequestering agent may also function as a threshold agent
when included in an effective amount. Chelating agents or
sequestrants include phosphonates, phosphates, aminocarboxylates
and polycarboxylates.
[0069] Exemplary phosphonates include phosphonic acids and
phosphonate salts, such as 1-hydroxy ethylidene-1,1-diphosphonic
acid (CH.sub.3C(PO.sub.3H.sub.2).sub.2OH) (HEDP),
amino[tri(methylene phosphonic acid)] (ATMP), ethylene
diamine[tetra methylene-phosphonic acid)], 2-phosphene
butane-1,2,4-tricarboxylic acid (PBTC), as well as their alkyl
metal salts, ammonium salts, or alkyloyl amine salts, such as mono,
di, or tetra-ethanolamine salts. Phosphonates include phosphorus
acid, H.sub.3PO.sub.3, and its salts.
[0070] Phosphonates include organic phosphonates. Organic
phosphonates include low molecular weight phosphonopolycarboxylic
acids, such as one having about 2-4 carboxylic acid moieties and
about 1-3 phosphonic acid groups. Some examples of organic
phosphonates include 1-hydroxyethane-1,1-diphosphonic acid:
CH.sub.3C(OH)[PO(OH).sub.2].sub.2; 1-phosphono-1-methylsuccinic
acid, phosphonosuccinic acid; 2-phosphonobutane-1,2,4-tricarboxylic
acid; other similar organic phosphonates; and salts thereof.
[0071] Phosphonates include amino phosphonates, phosphonates with
an amino or imino (e.g. nitrogen) moiety. Such amino phosphonates
include: ethylene diamine (tetramethylene phosphonates);
nitrilotrismethylene phosphates; diethylenetriamine (pentamethylene
phosphonates); aminotri(methylenephosphonic acid):
N[CH.sub.2PO(OH).sub.2].sub.3;
[0072] aminotri(methylenephosphonate), sodium salt:
##STR00003##
2-hydroxyethyliminobis(methylenephosphonic acid)
HOCH.sub.2CH.sub.2N[CH.sub.2PO(OH).sub.2].sub.2;
diethylenetriaminepenta(methylenephosphonic acid)
(HO).sub.2POCH.sub.2N[CH.sub.2CH.sub.2N[CH.sub.2PO
(OH).sub.2].sub.2].sub.2;
diethylenetriaminepenta(methylenephosphonate), sodium salt
C.sub.9H.sub.(28-x)N.sub.3Na.sub.xO.sub.15P.sub.5 (x=7);
hexamethylenediamine(tetramethylenephosphonate), potassium salt
C.sub.10H.sub.(28-x)N.sub.2K.sub.xO.sub.12P.sub.4 (x=6);
bis(hexamethylene)triamine(pentamethylenephosphonic acid)
(HO.sub.2)POCH.sub.2N[(CH.sub.2).sub.6N[CH.sub.2PO(OH).sub.2].sub.2].sub.-
2. These amino phosphonates commonly contain alkyl or alkaline
groups with less than 8 carbon atoms.
[0073] Commercially available phosphonates include those sold under
the trade name DEQUEST.RTM. including, for example,
1-hydroxyethylidene-1,1-diphosphonic acid, available from Monsanto
Industrial Chemicals Co., St. Louis, Mo., as DEQUEST.RTM. 2010;
amino(tri(methylenephosphonic acid)),
(N[CH.sub.2PO.sub.3H.sub.2].sub.3), available from Monsanto as
DEQUEST.RTM. 2000; ethylenediamine[tetra(methylenephosphonic acid)]
available from Monsanto as DEQUEST.RTM. 2041; and
2-phosphonobutane-1,2,4-tricarboxylic acid available from Mobay
Chemical Corporation, Inorganic Chemicals Division, Pittsburgh,
Pa., as Bayhibit AM; and amino[tri(methylene phosphonic acid)]
(ATMP) available as Briquest 301-50A: Amino Tri (Methylene
Phosphonic Acid) (ATMP), 50%, low ammonia from Albright &
Wilson.
[0074] Phosphate-containing chelating agents or sequestrants
include phosphates such as phosphoric acid and its salts, condensed
or polyphosphates and their salts, and aminophosphates and their
salts. Condensed or polyphosphates include tripolyphosphates,
pyrophosphates, and glassy polymeric meta-phosphates; and their
salts, such as alkali metal, ammonium, alkanolammonium, and mixed
salts. Examples of such phosphates include sodium or potassium
orthophosphate, sodium or potassium pyrophosphate, sodium or
potassium tripolyphosphate, sodium hexametaphosphate, and the like.
Aminophosphates include nitrilotrismethylene phosphates and other
aminophosphates with alkyl or alkaline groups with less than 8
carbon atoms.
[0075] Aminocarboxylate chelating agents or sequestrants include
acid and/or salt forms (e.g., alkali metal salts) of these
compounds. Examples of aminocarboxylates include amino acetates and
salts thereof. Amino acetates include: N-hydroxyethylaminodiacetic
acid; hydroxyethylenediaminetetraacetic acid; nitrilotriacetic acid
(NTA); ethylenediaminetetraacetic acid (EDTA);
N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA);
diethylenetriaminepentaacetic acid (DTPA); and alanine-N,N-diacetic
acid; n-hydroxyethyliminodiacetic acid; and the like; their alkali
metal salts; and mixtures thereof.
[0076] Polycarboxylates include iminodisuccinic acids (IDS), sodium
polyacrylates, citric acid, gluconic acid, oxalic acid, salts
thereof, mixtures thereof, and the like. Additional
polycarboxylates include citric or citrate-type chelating agent,
polymeric polycarboxylate, acrylic or polyacrylic acid-type
stabilizing agents. As used herein, polycarboxylate refers either
or both of the acid and salt forms.
[0077] Examples of low molecular weight polycarboxylates chelating
agents or sequestrants include: C.sub.4-C.sub.20-di-, -tri- and
-tetracarboxylic acids, such as succinic acid, propanetricarboxylic
acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid
and alkyl- and alkenylsuccinic acids with C.sub.2-C.sub.16-alkyl-
or -alkenyl radicals; C.sub.4-C.sub.20-hydroxy carboxylic acids,
such as malic acid, tartaric acid, gluconic acid, glutaric acid,
citric acid, lactobionic acid and sucrosemono-, -di- and
-tricarboxylic acids; aminopolycarboxylates, such as
nitrilotriacetic acid, methylglycinediacetic acid, alaninediacetic
acid, ethylenediaminetetraacetic acid and serinediacetic acid.
[0078] Examples of oligomeric or polymeric polycarboxylates
suitable as builders include: oligomaleic acids as described, for
example, in EP-A-451 508 and EP-A-396 303; co- and terpolymers of
unsaturated C.sub.4-C.sub.8-dicarboxylic acids, possible
co-monomers which may be present being monoethylenically
unsaturated monomers from group (i) in amounts of up to 95% by
weight, from group (ii) in amounts of up to 60% by weight, from
group (iii) in amounts of up to 20% by weight. Examples of suitable
unsaturated C.sub.4-C.sub.8-dicarboxylic acids include maleic acid,
fumaric acid, itaconic acid and citraconic acid.
[0079] The group (i) includes monoethylenically unsaturated
C.sub.3-C.sub.8-monocarboxylic acids, such as acrylic acid,
methacrylic acid, crotonic acid and vinylacetic acid, for example
acrylic acid and methacrylic acid. Group (ii) includes
monoethylenically unsaturated C.sub.2-C.sub.22-olefins, vinyl alkyl
ethers with C.sub.1-C.sub.8-alkyl groups, styrene, vinyl esters of
C.sub.1-C.sub.8-carboxylic acids, (meth)acrylamide and
vinylpyrrolidone, for example C.sub.2-C.sub.6-olefins, vinyl alkyl
ethers with C.sub.1-C.sub.4-alkyl groups, vinyl acetate and vinyl
propionate. Group (iii) includes (meth)acrylic esters of
C.sub.1-C.sub.8-alcohols, (meth)acrylnitrile, (meth)acrylamides of
C.sub.1-C.sub.8-amines, N-vinylformamide and vinylimidazole.
[0080] If the polymers contain vinyl esters as monomers of group
(ii) these can also be partially or completely hydrolyzed to vinyl
alcohol structural units. Co- and terpolymers are disclosed, for
example, in U.S. Pat. No. 3,887,806 and DE-A 43 13 909.
[0081] Copolymers of dicarboxylic acids include copolymers of
maleic acid and acrylic acid in the ratio of 10:90 to 95:5 by
weight. These can have a ratio of from 30:70 to 90:10 by weight,
with molecular weights of from 10,000 to 150,000. Terpolymers of
maleic acid, acrylic acid and a vinyl ester of a
C.sub.1-C.sub.3-carboxylic acid can be employed with the ratio of
from 10 (maleic acid):90 (acrylic acid+vinyl ester) to 95 (maleic
acid):5 (acrylic acid+vinyl ester) by weight, for example, with the
ratio of acrylic acid to vinyl ester in the range from 20:80 to
80:20 by weight. By way of further example, terpolymers of maleic
acid, acrylic acid and vinyl acetate or vinyl propionate can have
the ratio of from 20 (maleic acid):80 (acrylic acid+vinyl ester) to
90 (maleic acid):10 (acrylic acid+vinyl ester) by weight, for
example, with the ratio of acrylic acid to the vinyl ester in the
range from 30:70 to 70:30 by weight. Additional copolymers of
maleic acid with C.sub.2-C.sub.8-olefins have the molar ratio from
40:60 to 80:20 for, for example, copolymers of maleic acid with
ethylene, propylene or isobutene in the molar ratio 50:50.
[0082] Graft polymers of unsaturated carboxylic acids on low
molecular weight carbohydrates or hydrogenated carbohydrates can be
employed as polycarboxylate builders. Such graft polymers are
described in, for example, U.S. Pat. No. 5,227,446, DE-A-44 15 623,
DE-A-43 13 909. Suitable unsaturated carboxylic acids for graft
polymers include, for example, maleic acid, fumaric acid, itaconic
acid, citraconic acid, acrylic acid, methacrylic acid, crotonic
acid and vinylacetic acid, and mixtures of acrylic acid and maleic
acid, which are grafted on in amounts of from 40 to 95% of the
weight of the component to be grafted. It is additionally possible
for up to 30% by weight, based on the component to be grafted, of
other monoethylenically unsaturated monomers to be present for
modification. Suitable modifying monomers include the
abovementioned monomers of groups (ii) and (iii).
[0083] Suitable grafting bases include degraded polysaccharides,
such as acidically or enzymatically degraded starches, inulins or
cellulose, reduced (hydrogenated or reductively aminated) degraded
polysaccharides, such as mannitol, sorbitol, aminosorbitol and
glucamine, and polyalkylene glycols with molecular weights of up to
5,000 such as polyethylene glycols, ethylene oxide/propylene oxide
or ethylene oxide/butylene oxide block copolymers, random ethylene
oxide/propylene oxide or ethylene oxide/butylene oxide copolymers,
alkoxylated mono- or polyhydric C.sub.1-C.sub.22-alcohols, see U.S.
Pat. No. 4,746,456.
[0084] Graft polymers include grafted degraded or degraded reduced
starches and grafted polyethylene oxides, employing from 20 to 80%
by weight of monomers, based on the grafting component, in the
graft polymerization. These can include a mixture of maleic acid
and acrylic acid in the ratio of from 90:10 to 10:90 by weight for
grafting.
[0085] Polyglyoxylic acids suitable as builders are described, for
example, in EP-B-001 004, U.S. Pat. No. 5,399,286, DE-A-41 06 355
and EP-A-656 914. The end groups of the polyglyoxylic acids may
have various structures.
[0086] Polyamidocarboxylic acids and modified polyamidocarboxylic
acids suitable as builders are disclosed, for example, in EP-A-454
126, EP-B-511 037, WO 94/01486 and EP-A-581 452.
[0087] Additional chelating agents or sequestrants include
polyaspartic acid or cocondensates of aspartic acid with other
amino acids, C.sub.4-C.sub.2-mono- or -dicarboxylic acids and/or
C.sub.4-C.sub.25-mono- or -diamines. Polyaspartic acids include
those prepared in phosphorus-containing acids and modified with
C.sub.6-C.sub.22-mono- or -dicarboxylic acids or with
C.sub.6-C.sub.22-mono- or -diamines.
[0088] Condensation products of citric acid with hydroxy carboxylic
acids or polyhydroxy compounds which are suitable as organic
cobuilders are disclosed, for example, in WO 93/22362 and WO
92/16493. Carboxyl-containing condensates of this type normally
have molecular weights of up to 10,000, for example, up to
5,000.
[0089] Polymeric polycarboxylates include, for example, polyacrylic
acid, maleic/olefin copolymer, acrylic/maleic copolymer,
polymethacrylic acid, acrylic acid-methacrylic acid copolymers,
hydrolyzed polyacrylamide, hydrolyzed polymethacrylamide,
hydrolyzed polyamide-methacrylamide copolymers, hydrolyzed
polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed
acrylonitrile-methacrylonitrile copolymers, and the like.
Activators
[0090] In some embodiments, the antimicrobial activity or bleaching
activity of the composition can be enhanced by the addition of a
material which, when the composition is placed in use, reacts with
the active oxygen to form an activated component. For example, in
some embodiments, a peracid or a peracid salt is formed. For
example, in some embodiments, tetraacetylethylene diamine can be
included within the composition to react with the active oxygen and
form a peracid or a peracid salt that acts as an antimicrobial
agent. Other examples of active oxygen activators include
transition metals and their compounds, compounds that contain a
carboxylic, nitrile, or ester moiety, or other such compounds known
in the art. In an embodiment, the activator includes
tetraacetylethylene diamine; transition metal; compound that
includes carboxylic, nitrile, amine, or ester moiety; or mixtures
thereof.
[0091] In some embodiments, an activator component can include in
the range of 0.001 to 75 wt %, about 0.01 to about 20 wt %, or
about 0.05 wt % to about 10 wt % of the composition.
[0092] In an embodiment, the activator for the source of alkalinity
combines with the active oxygen to form an antimicrobial agent.
[0093] The solid composition typically remains stable even in the
presence of activator of the source of alkalinity. In many
compositions it would be expected to react with and destabilize or
change the form of the source of alkalinity. In contrast, in an
embodiment of the present invention, the composition remains solid;
it does not swell, crack, or enlarge as it would if the source of
alkalinity were reacting with the activator.
[0094] In an embodiment, the composition includes a solid block,
and an activator material for the active oxygen is coupled to the
solid block. The activator can be coupled to the solid block by any
of a variety of methods for coupling one solid cleaning composition
to another. For example, the activator can be in the form of a
solid that is bound, affixed, glued or otherwise adhered to the
solid block. Alternatively, the solid activator can be formed
around and encasing the block. By way of further example, the solid
activator can be coupled to the solid block by the container or
package for the cleaning composition, such as by a plastic or
shrink wrap or film.
Additional Bleaching Agents
[0095] Additional bleaching agents for use in inventive
formulations for lightening or whitening a substrate, include
bleaching compounds capable of liberating an active halogen
species, such as Cl.sub.2, Br.sub.2, I.sub.2, ClO.sub.2, BrO.sub.2,
IO.sub.2, --OCl.sup.-, OBr.sup.- and/or, --OI.sup.-, under
conditions typically encountered during the cleansing process.
Suitable bleaching agents for use in the present cleaning
compositions include, for example, chlorine-containing compounds
such as a chlorite, a hypochlorite, chloramine. Suitable
halogen-releasing compounds include the alkali metal
dichloroisocyanurates, chlorinated trisodium phosphate, the alkali
metal hypochlorites, alkali metal chlorites, monochloramine and
dichloramine, and the like, and mixtures thereof. Encapsulated
chlorine sources may also be used to enhance the stability of the
chlorine source in the composition (see, for example, U.S. Pat.
Nos. 4,618,914 and 4,830,773, the disclosure of which is
incorporated by reference herein). A bleaching agent may also be an
additional peroxygen or active oxygen source such as hydrogen
peroxide, perborates, for example sodium perborate mono and
tetrahydrate, sodium carbonate peroxyhydrate, phosphate
peroxyhydrates, and potassium permonosulfate, with and without
activators such as tetraacetylethylene diamine, and the like, as
discussed above.
[0096] A cleaning composition may include a minor but effective
additional amount of a bleaching agent above that already available
from the stabilized source of alkalinity, e.g., about 0.1 wt % to
about 60 wt %, about 1 wt % to about 20 wt %, about 3 wt % to about
8 wt %, and about 3 wt % to about 6 wt %.
Detergent Fillers
[0097] A cleaning composition may include an effective amount of
one or more of a detergent filler which does not perform as a
cleaning agent per se, but cooperates with the cleaning agent to
enhance the overall processability of the composition. Examples of
fillers suitable for use in the present cleaning compositions
include sodium sulfate, sodium chloride, starch, sugars,
C.sub.1-C.sub.10 alkylene glycols such as propylene glycol, and the
like. A filler such as a sugar (e.g. sucrose) can aid dissolution
of a solid composition by acting as a disintegrant. A detergent
filler can be included in an amount up to about 1 wt % to about 20
wt % and between about 3 wt % and about 15 wt %.
Defoaming Agents
[0098] An effective amount of a defoaming agent for reducing the
stability of foam may also be included in the present compositions.
The composition can include about 0.01 wt % and about 3 wt %
[0099] Examples of defoaming agents suitable for use in the present
compositions include silicone compounds such as silica dispersed in
polydimethylsiloxane, EO/PO block copolymers, alcohol alkoxylates,
fatty amides, hydrocarbon waxes, fatty acids, fatty esters, fatty
alcohols, fatty acid soaps, ethoxylates, mineral oils, polyethylene
glycol esters, alkyl phosphate esters such as monostearyl
phosphate, and the like. A discussion of defoaming agents may be
found, for example, in U.S. Pat. No. 3,048,548 to Martin et al.,
U.S. Pat. No. 3,334,147 to Brunelle et al., and U.S. Pat. No.
3,442,242 to Rue et al., the disclosures of which are incorporated
by reference herein.
Anti-Redeposition Agents
[0100] The composition may also include an anti-redeposition agent
capable of facilitating sustained suspension of soils in a cleaning
solution and preventing the removed soils from being redeposited
onto the substrate being cleaned. Examples of suitable
anti-redeposition agents include fatty acid amides, fluorocarbon
surfactants, complex phosphate esters, styrene maleic anhydride
copolymers, and cellulosic derivatives such as hydroxyethyl
cellulose, hydroxypropyl cellulose, and the like. A cleaning
composition may include about 0.5 wt % to about 10 wt % and between
about 1 wt % and about 5 wt % anti-redeposition agent.
Stabilizing Agents
[0101] The composition may also include a stabilizing agent.
Examples of suitable stabilizing agents include, but are not
limited to: borate, calcium/magnesium ions, propylene glycol, and
mixtures thereof. The composition need not include a stabilizing
agent, but when the composition includes a stabilizing agent, it
can be included in an amount that provides the desired level of
stability of the composition. Exemplary ranges of the stabilizing
agent include up to about 20 wt %, between about 0.5 wt % and about
15 wt % and between about 2 wt % and about 10 wt %
Dispersants
[0102] The composition may also include a dispersant. Examples of
suitable dispersants that can be used in the solid detergent
composition include, but are not limited to: maleic acid/olefin
copolymers, polyacrylic acid, and mixtures thereof. The composition
need not include a dispersant, but when a dispersant is included it
can be included in an amount that provides the desired dispersant
properties. Suitable ranges of the dispersant in the composition
can be up to about 20 wt %, between about 0.5 wt % and about 15 wt
% or between about 2 wt % and about 9 wt %.
Enzymes
[0103] Enzymes that can be included in the compositions include
those enzymes that aid in the removal of starch and/or protein
stains. Suitable types of enzymes include, but are not limited to:
proteases, alpha-amylases, and mixtures thereof. Suitable proteases
that can be used include, but are not limited to: those derived
from Bacillus licheniformix, Bacillus lenus, Bacillus alcalophilus,
and Bacillus amyloliquefacins. Suitable alpha-amylases include
Bacillus subtilis, Bacillus amyloliquefaciens, and Bacillus
licheniformis. The composition need not include an enzyme, but when
the composition includes an enzyme, it can be included in an amount
that provides the desired enzymatic activity when the solid
detergent composition is provided as a use composition. Suitable
ranges of the enzyme in the composition include up to about 15 wt
%, from about 0.5 wt % to about 10 wt %, and from about 1 wt % to
about 5 wt %.
Silicates
[0104] Silicates can be included in the warewashing composition to
provide for metal protection. Silicates are additionally known to
provide alkalinity and additionally function as anti-redeposition
agents. Exemplary silicates include, but are not limited to, sodium
silicate and potassium silicate. The warewashing composition can be
provided without silicates, but when silicates are included, they
can be included in amounts that provide for desired metal
protection. The concentrate can include silicates in amounts of at
least about 1 wt %, at least about 5 wt %, at least about 10 wt %
and at least about 15 wt %. In addition, in order to provide
sufficient room for other components in the concentrate, the
silicate component can be provided at a level of less than about 35
wt %, less than about 25 wt %, less than about 20 wt %, and less
than about 15 wt %.
Water
[0105] The concentrate can include water. In general, it is
expected that water may be present as a processing aid and may be
removed or become water of hydration. It is expected that water may
be present in both the liquid concentrate and in the solid
concentrate. It is expected that the aqueous medium will help
provide the components with a desired viscosity for processing. In
addition, it is expected that the aqueous medium may help in the
solidification process when it is desired to form the concentrate
as a solid. In the case of the liquid concentrate, it is expected
that water will be present in a range of between about 5 wt % and
about 60 wt %, between about 10 wt % and about 35 wt % and between
about 15 wt % and about 25 wt %.
[0106] When the concentrate is provided as a solid, it can be
provided in the form of a block or pellet. It is expected that
blocks will have a size of at least about 5 grams and can include a
size of greater than about 50 grams. In the case of a solid
concentrate, it is expected that the water will be present up to
about 10 wt %, between about 0.1 wt % and about 10 wt %, between
about 1 wt % and about 5 wt % and between about 2 wt % and about 3
wt %. It should be additionally appreciated that the water may be
provided as deionized water or as softened water.
[0107] When the components that are processed to form the
concentrate are processed into a block, it is expected that the
components can be processed by extrusion techniques or casting
techniques. In general, when the components are processed by
extrusion techniques, it is believed that the composition can
include a relatively smaller amount of water as an aid for
processing compared with the casting techniques. In general, when
preparing the solid by extrusion, it is expected that the
composition can contain between about 2 wt % and about 10 wt %
water. When preparing the solid by casting, it is expected that the
amount of water can be provided in an amount of between about 20 wt
% and about 40 wt %.
Processing Aid
[0108] Processing aids are materials which enhance the production
process for the compositions. They can serve as drying agents,
modify the rate of solidification, alter the transfer of water of
hydration in the formula, or even act as the solidifying matrix
itself. Processing aids can have some overlap with other
functionalities in the formula. Nonlimiting examples include
silica, alkali metal silicates, urea, polyethylene glycols, solid
surfactants, sodium carbonate, potassium chloride, sodium sulfate,
sodium hydroxide, water, etc. Which processing aid(s) is suitable
varies with the manufacturing procedure and specific
composition.
[0109] The processing aid can be present at amounts of from about 1
wt % to about 70 wt %, from about 2 wt % to about 50 wt % and from
about 3 wt % to about 30 wt %.
Active Oxygen Compounds
[0110] The active oxygen compound acts to provide a source of
active oxygen, but can also act to form at least a portion of the
solidification agent. The active oxygen compound can be inorganic
or organic, and can be a mixture thereof. Some examples of active
oxygen compound include peroxygen compounds, and peroxygen compound
adducts that are suitable for use in forming the binding agent.
[0111] Many active oxygen compounds are peroxygen compounds. Any
peroxygen compound generally known and that can function, for
example, as part of the binding agent can be used. Examples of
suitable peroxygen compounds include inorganic and organic
peroxygen compounds, or mixtures thereof.
[0112] Examples of inorganic active oxygen compounds include the
following types of compounds or sources of these compounds, or
alkali metal salts including these types of compounds, or forming
an adduct therewith:
[0113] hydrogen peroxide;
[0114] group 1 (IA) active oxygen compounds, for example lithium
peroxide, sodium peroxide, and the like;
[0115] group 2 (IIA) active oxygen compounds, for example magnesium
peroxide, calcium peroxide, strontium peroxide, barium peroxide,
and the like;
[0116] group 12 (IIB) active oxygen compounds, for example zinc
peroxide, and the like;
[0117] group 13 (IIIA) active oxygen compounds, for example boron
compounds, such as perborates, for example sodium perborate
hexahydrate of the formula
Na.sub.2[Br.sub.2(O.sub.2).sub.2(OH).sub.4].6H.sub.2O (also called
sodium perborate tetrahydrate and formerly written as
NaBO.sub.3.4H.sub.2O); sodium peroxyborate tetrahydrate of the
formula Na.sub.2Br.sub.2(O.sub.2).sub.2[(OH).sub.4].4H.sub.2O (also
called sodium perborate trihydrate, and formerly written as
NaBO.sub.3.3H.sub.2O); sodium peroxyborate of the formula
Na.sub.2[B.sub.2(O.sub.2).sub.2(OH).sub.4] (also called sodium
perborate monohydrate and formerly written as NaBO.sub.3.H.sub.2O);
and the like; e.g., perborate;
[0118] group 14 (IVA) active oxygen compounds, for example
persilicates and peroxycarbonates, which are also called
percarbonates, such as persilicates or peroxycarbonates of alkali
metals; and the like; e.g., percarbonate, e.g., persilicate;
[0119] group 15 (VA) active oxygen compounds, for example
peroxynitrous acid and its salts; peroxyphosphoric acids and their
salts, for example, perphosphates; and the like; e.g.,
perphosphate;
[0120] group 16 (VIA) active oxygen compounds, for example
peroxysulfuric acids and their salts, such as peroxymonosulfuric
and peroxydisulfuric acids, and their salts, such as persulfates,
for example, sodium persulfate; and the like; e.g., persulfate;
[0121] group VIIa active oxygen compounds such as sodium periodate,
potassium perchlorate and the like.
[0122] Other active inorganic oxygen compounds can include
transition metal peroxides; and other such peroxygen compounds, and
mixtures thereof.
[0123] In certain embodiments, the compositions and methods of the
present invention employ certain of the inorganic active oxygen
compounds listed above. Suitable inorganic active oxygen compounds
include hydrogen peroxide, hydrogen peroxide adduct, group IIIA
active oxygen compounds, group VIA active oxygen compound, group VA
active oxygen compound, group VIIA active oxygen compound, or
mixtures thereof. Examples of such inorganic active oxygen
compounds include percarbonate, perborate, persulfate,
perphosphate, persilicate, or mixtures thereof. Hydrogen peroxide
presents an example of an inorganic active oxygen compound.
Hydrogen peroxide can be formulated as a mixture of hydrogen
peroxide and water, e.g., as liquid hydrogen peroxide in an aqueous
solution. The mixture of solution can include about 5 wt % to about
40 wt % hydrogen peroxide or about 5 wt % to about 50 wt % hydrogen
peroxide.
[0124] In an embodiment, the inorganic active oxygen compounds
include hydrogen peroxide adduct. For example, the inorganic active
oxygen compounds can include hydrogen peroxide, hydrogen peroxide
adduct, or mixtures thereof. Any of a variety of hydrogen peroxide
adducts are suitable for use in the present compositions and
methods. For example, suitable hydrogen peroxide adducts include
percarbonate salt, urea peroxide, peracetyl borate, an adduct of
H.sub.2O.sub.2 and polyvinyl pyrrolidone, sodium percarbonate,
potassium percarbonate, mixtures thereof, or the like. Suitable
hydrogen peroxide adducts include percarbonate salt, urea peroxide,
peracetyl borate, an adduct of H.sub.2O.sub.2 and polyvinyl
pyrrolidone, or mixtures thereof. Suitable hydrogen peroxide
adducts include sodium percarbonate, potassium percarbonate, or
mixtures thereof, e.g., sodium percarbonate.
[0125] Any of a variety of organic active oxygen compounds can be
employed in the compositions and methods of the present invention.
For example, the organic s active oxygen compound can be a
peroxycarboxylic acid, such as a mono- or di-peroxycarboxylic acid,
an alkali metal salt including these types of compounds, or an
adduct of such a compound. Suitable peroxycarboxylic acids include
C.sub.1-C.sub.24 peroxycarboxylic acid, salt of C.sub.1-C.sub.24
peroxycarboxylic acid, ester of C.sub.1-C.sub.24 peroxycarboxylic
acid, diperoxycarboxylic acid, salt of diperoxycarboxylic acid,
ester of diperoxycarboxylic acid, or mixtures thereof.
[0126] Suitable peroxycarboxylic acids include C.sub.1-C.sub.10
aliphatic peroxycarboxylic acid, salt of C.sub.1-C.sub.10 aliphatic
peroxycarboxylic acid, ester of C.sub.1-C.sub.10 aliphatic
peroxycarboxylic acid, or mixtures thereof; e.g., salt of or adduct
of peroxyacetic acid; e.g., peroxyacetyl borate. Suitable
diperoxycarboxylic acids include C.sub.4-C.sub.10 aliphatic
diperoxycarboxylic acid, salt of C.sub.4-C.sub.10 aliphatic
diperoxycarboxylic acid, or ester of C.sub.4-C.sub.10 aliphatic
diperoxycarboxylic acid, or mixtures thereof; e.g., a sodium salt
of perglutaric acid, of persuccinic acid, of peradipic acid, or
mixtures thereof.
[0127] Organic active oxygen compounds include other acids
including an organic moiety. Suitable organic active oxygen
compounds include perphosphonic acids, perphosphonic acid salts,
perphosphonic acid esters, or mixtures or combinations thereof.
[0128] Active oxygen compound adducts include any generally known
and that can function, for example, as a source of active oxygen
and as part of the solidified composition. Hydrogen peroxide
adducts, or peroxyhydrates, are suitable. Some examples of source
of alkalinity adducts include the following: alkali metal
percarbonates, for example sodium percarbonate (sodium carbonate
peroxyhydrate), potassium percarbonate, rubidium percarbonate,
cesium percarbonate, and the like; ammonium carbonate
peroxyhydrate, and the like; urea peroxyhydrate, peroxyacetyl
borate; an adduct of H.sub.2O.sub.2 polyvinyl pyrrolidone, and the
like, and mixtures of any of the above.
Antimicrobials
[0129] Antimicrobial agents are chemical compositions that can be
used in a solid functional material that alone, or in combination
with other components, act to reduce or prevent microbial
contamination and deterioration of commercial products material
systems, surfaces, etc. In some aspects, these materials fall in
specific classes including phenolics, halogen compounds, quaternary
ammonium compounds, metal derivatives, amines, alkanol amines,
nitro derivatives, analides, organosulfur and sulfur-nitrogen
compounds and miscellaneous compounds.
[0130] It should also be understood that the source of alkalinity
used in the formation of compositions embodying the invention also
act as antimicrobial agents, and can even provide sanitizing
activity. In fact, in some embodiments, the ability of the source
of alkalinity to act as an antimicrobial agent reduces the need for
secondary antimicrobial agents within the composition. For example,
percarbonate compositions have been demonstrated to provide
excellent antimicrobial action. Nonetheless, some embodiments
incorporate additional antimicrobial agents.
[0131] The given antimicrobial agent, depending on chemical
composition and concentration, may simply limit further
proliferation of numbers of the microbe or may destroy all or a
portion of the microbial population. The terms "microbes" and
"microorganisms" typically refer primarily to bacteria, virus,
yeast, spores, and fungus microorganisms. In use, the antimicrobial
agents are typically formed into a solid functional material that
when diluted and dispensed, optionally, for example, using an
aqueous stream forms an aqueous disinfectant or sanitizer
composition that can be contacted with a variety of surfaces
resulting in prevention of growth or the killing of a portion of
the microbial population. A three log reduction of the microbial
population results in a sanitizer composition. The antimicrobial
agent can be encapsulated, for example, to improve its
stability.
[0132] Common antimicrobial agents include, for example, phenolic
antimicrobials such as pentachlorophenol, orthophenylphenol, a
chloro-p-benzylphenol and p-chloro-m-xylenol. Halogen containing
antibacterial agents include, for example, sodium
trichloroisocyanurate, sodium dichloro isocyanate (anhydrous or
dihydrate), iodine-poly(vinylpyrolidinone) complexes, bromine
compounds such as 2-bromo-2-nitropropane-1,3-diol, and quaternary
antimicrobial agents such as benzalkonium chloride, didecyldimethyl
ammonium chloride, choline diiodochloride and tetramethyl
phosphonium tribromide. Other antimicrobial compositions such as
hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine, dithiocarbamates
such as sodium dimethyldithiocarbamate, and a variety of other
materials are known in the art for their anti-microbial properties.
In some embodiments, an antimicrobial component, such as TAED can
be included in the range of from 0.001 wt % to about 75 wt % of the
composition, from about 0.01 wt % to about 20 wt %, or from about
0.05 wt % to about 10 wt %.
[0133] If present in compositions, the additional antimicrobial
agent can constitute between about 0.01 wt % and about 30 wt % of
the composition, between about 0.05 wt % and about 10 wt %, or
between about 0.1 wt % and about 5 wt %. In a use solution the
additional antimicrobial agent can be between about 0.001 wt % and
about 5 wt % of the composition, between about 0.01 wt % and about
2 wt %, or between about 0.05 wt % and about 0.5 wt %.
Rinse Aid Functional Materials
[0134] Functional materials of the invention can include a
formulated rinse aid composition containing a wetting or sheeting
agent combined with other optional ingredients in a solid made
using the complex of the invention. The rinse aid component of the
present invention can include a water soluble or dispersible low
foaming organic material capable of reducing the surface tension of
the rinse water to promote sheeting action and to prevent spotting
or streaking caused by beaded water after rinsing is completed.
This is often used in warewashing processes. Such sheeting agents
are typically organic surfactant-like materials having a
characteristic cloud point. The cloud point of the surfactant rinse
or sheeting agent is defined as the temperature at which about a 1
wt % aqueous solution of the surfactant turns cloudy when
warmed.
[0135] There are two general types of rinse cycles in commercial
warewashing machines, a first type generally considered a
sanitizing rinse cycle uses rinse water at a temperature of about
180.degree. F., about 80.degree. C. or higher. A second type of
non-sanitizing machines uses a lower temperature non-sanitizing
rinse, typically at a temperature of about 125.degree. F., about
50.degree. C. or higher. Surfactants useful in these applications
are aqueous rinses having a cloud point greater than the available
hot service water. Accordingly, the lowest useful cloud point
measured for the surfactants of the invention is approximately
40.degree. C. The cloud point can also be about 60.degree. C. or
higher, about 70.degree. C. or higher, about 80.degree. C. or
higher, etc., depending on the use locus hot water temperature and
the temperature and type of rinse cycle.
[0136] Suitable sheeting agents, typically include a polyether
compound prepared from ethylene oxide, propylene oxide, or a
mixture in a homopolymer or block or heteric copolymer structure.
Such polyether compounds are known as polyalkylene oxide polymers,
polyoxyalkylene polymers or polyalkylene glycol polymers. Such
sheeting agents require a region of relative hydrophobicity and a
region of relative hydrophilicity to provide surfactant properties
to the molecule. Such sheeting agents have a molecular weight in
the range of about 500 to about 15,000. Certain types of (PO)(EO)
polymeric rinse aids have been found to be useful containing at
least one block of poly(PO) and at least one block of poly(EO) in
the polymer molecule. Additional blocks of poly(EO), poly PO or
random polymerized regions can be formed in the molecule.
[0137] Particularly useful polyoxypropylene polyoxyethylene block
copolymers are those including a center block of polyoxypropylene
units and blocks of polyoxyethylene units to each side of the
center block. Such polymers have the formula shown below:
(EO).sub.n--(PO).sub.m-(EO).sub.n
wherein n is an integer of 20 to 60, each end is independently an
integer of about 10 to about 130. Another useful block copolymer
are block copolymers having a center block of polyoxyethylene units
and blocks of polyoxypropylene to each side of the center block.
Such copolymers have the formula:
(PO).sub.n-(EO).sub.m--(PO).sub.n
wherein m is an integer of about 15 to about 175 and each end are
independently integers of about 10 to about 30. The solid
functional materials of the invention can often use a hydrotrope to
aid in maintaining the solubility of sheeting or wetting agents.
Hydrotropes can be used to modify the aqueous solution creating
increased solubility for the organic material. Suitable hydrotropes
are low molecular weight aromatic sulfonate materials such as
xylene sulfonates and dialkyldiphenyl oxide sulfonate
materials.
[0138] In an embodiment, compositions according to the present
invention provide desirable rinsing properties in ware washing
without employing a separate rinse agent in the rinse cycle. For
example, good rinsing occurs using such compositions in the wash
cycle when rinsing employs just soft water.
Hardening Agents
[0139] The compositions may also include a hardening agent in
addition to, or in the form of, the builder. A hardening agent is a
compound or system of compounds, organic or inorganic, which
significantly contributes to the uniform solidification of the
composition. The hardening agents should be compatible with the
cleaning agent and other active ingredients of the composition and
should be capable of providing an effective amount of hardness
and/or aqueous solubility to the processed detergent composition.
The hardening agents should also be capable of forming a
homogeneous matrix with the cleaning agent and other ingredients
when mixed and solidified to provide a uniform dissolution of the
cleaning agent from the composition during use.
[0140] The amount of hardening agent included in the composition
will vary according to factors including, but not limited to: the
type of composition being prepared, the ingredients of the
composition, the intended use of the composition, the quantity of
dispensing solution applied to the detergent composition over time
during use, the temperature of the dispensing solution, the
hardness of the dispensing solution, the physical size of the
composition, the concentration of the other ingredients, and the
concentration of the cleaning agent in the composition. The amount
of the hardening agent included in the composition should be
effective to combine with the cleaning agent and other ingredients
of the composition to form a homogeneous mixture under continuous
mixing conditions and a temperature at or below the melting
temperature of the hardening agent.
[0141] The hardening agent may also form a matrix with the cleaning
agent and other ingredients which will harden to a solid form under
ambient temperatures of about 30.degree. C. to about 50.degree. C.,
particularly about 35.degree. C. to about 45.degree. C., after
mixing ceases and the mixture is dispensed from the mixing system,
within about 1 minute to about 3 hours, particularly about 2
minutes to about 2 hours, and particularly about 5 minutes to about
1 hour. A minimal amount of heat from an external source may be
applied to the mixture to facilitate processing of the mixture. The
amount of the hardening agent included in the detergent composition
should be effective to provide a desired hardness and desired rate
of controlled solubility of the processed composition when placed
in an aqueous medium to achieve a desired rate of dispensing the
cleaning agent from the solidified composition during use.
[0142] The hardening agent may be an organic or an inorganic
hardening agent. A particular organic hardening agent is a
polyethylene glycol (PEG) compound. The solidification rate of
detergent compositions comprising a polyethylene glycol hardening
agent will vary, at least in part, according to the amount and the
molecular weight of the polyethylene glycol added to the
composition. Examples of suitable polyethylene glycols include, but
are not limited to: solid polyethylene glycols of the general
formula H(OCH.sub.2CH.sub.2).sub.nOH, where n is greater than about
15, more particularly about 30 to about 1700. Typically, the
polyethylene glycol is a solid in the form of a free-flowing powder
or flakes, having a molecular weight of about 1,000 to about
100,000, particularly having a molecular weight of at least about
1,450 to about 20,000, more particularly between about 1,450 to
about 8,000. The polyethylene glycol is present at a concentration
of from about 1 wt % to about 75 wt % and particularly about 3 wt %
to about 15 wt %. Suitable polyethylene glycol compounds include,
for example, PEG 4000, PEG 1450, and PEG 8000 among others, with
PEG 4000 and PEG 8000 being most preferred. An example of a
commercially available solid polyethylene glycol includes, but is
not limited to: CARBOWAX, available from Union Carbide Corporation,
Houston, Tex.
[0143] Particular inorganic hardening agents are hydratable
inorganic salts, including, for example, sulfates, acetates, and
bicarbonates. In an exemplary embodiment, the inorganic hardening
agents are present at concentrations of up to about 50 wt %,
particularly from about 5 wt % to about 25 wt %, and more
particularly from about 5 wt % to about 15 wt %.
[0144] Urea particles may also be employed as hardeners in the
detergent compositions. The solidification rate of the compositions
will vary, at least in part, to factors including, but not limited
to: the amount, the particle size, and the shape of the urea added
to the detergent composition. For example, a particulate form of
urea may be combined with a cleaning agent and other ingredients,
as well as a minor but effective amount of water. The amount and
particle size of the urea is effective to combine with the cleaning
agent and other ingredients to form a homogeneous mixture without
the application of heat from an external source to melt the urea
and other ingredients to a molten stage. The amount of urea
included in the solid detergent composition should be effective to
provide a desired hardness and desired rate of solubility of the
composition when placed in an aqueous medium to achieve a desired
rate of dispensing the cleaning agent from the solidified
composition during use. In an exemplary embodiment, the detergent
composition includes between about 5 wt % and about 90 wt % urea,
particularly between about 8 wt % and about 40 wt % urea, and more
particularly between about 10 wt % and about 30 wt % urea.
[0145] The urea may be in the form of prilled beads or powder.
Prilled urea is generally available from commercial sources as a
mixture of particle sizes ranging from about 8-15 U.S. mesh, as for
example, from Arcadian Sohio Company, Nitrogen Chemicals Division.
A prilled form of urea is milled to reduce the particle size to
about 50 U.S. mesh to about 125 U.S. mesh, particularly about
75-100 U.S. mesh, particularly using a wet mill such as a single or
twin-screw extruder, a Teledyne mixer, a Ross emulsifier, and the
like.
Secondary Hardening Agents/Solubility Modifiers
[0146] The present compositions may include a minor but effective
amount of a secondary hardening agent, as for example, an amide
such stearic monoethanolamide or lauric diethanolamide, or an
alkylamide, and the like; a solid polyethylene glycol, or a solid
EO/PO block copolymer, and the like; starches that have been made
water-soluble through an acid or alkaline treatment process;
various inorganics that impart solidifying properties to a heated
composition upon cooling, and the like. Such compounds may also
vary the solubility of the composition in an aqueous medium during
use such that the cleaning agent and/or other active ingredients
may be dispensed from the solid composition over an extended period
of time. The composition may include a secondary hardening agent in
an amount of from about 5 wt % to about 20 wt % or from about 10 wt
% to about 15 wt %.
Thickeners
[0147] The compositions can include a rheology modifier or a
thickener. The rheology modifier may provide the following
functions: increasing the viscosity of the compositions; increasing
the particle size of liquid use solutions when dispensed through a
spray nozzle; providing the use solutions with vertical cling to
surfaces; providing particle suspension within the use solutions;
or reducing the evaporation rate of the use solutions.
[0148] The rheology modifier may provide a use composition that is
pseudo plastic, in other words the use composition or material when
left undisturbed (in a shear mode), retains a high viscosity.
However, when sheared, the viscosity of the material is
substantially but reversibly reduced. After the shear action is
removed, the viscosity returns. These properties permit the
application of the material through a spray head. When sprayed
through a nozzle, the material undergoes shear as it is drawn up a
feed tube into a spray head under the influence of pressure and is
sheared by the action of a pump in a pump action sprayer. In either
case, the viscosity can drop to a point such that substantial
quantities of the material can be applied using the spray devices
used to apply the material to a soiled surface. However, once the
material comes to rest on a soiled surface, the materials can
regain high viscosity to ensure that the material remains in place
on the soil. In an embodiment, the material can be applied to a
surface resulting in a substantial coating of the material that
provides the cleaning components in sufficient concentration to
result in lifting and removal of the hardened or baked-on soil.
While in contact with the soil on vertical or inclined surfaces,
the thickeners in conjunction with the other components of the
cleaner minimize dripping, sagging, slumping or other movement of
the material under the effects of gravity. The material should be
formulated such that the viscosity of the material is adequate to
maintain contact substantial quantities of the film of the material
with the soil for at least a minute, five minutes or more.
[0149] Examples of suitable thickeners or rheology modifiers are
polymeric thickeners including, but not limited to: polymers or
natural polymers or gums derived from plant or animal sources. Such
materials may be polysaccharides such as large polysaccharide
molecules having substantial thickening capacity. Thickeners or
rheology modifiers also include clays.
[0150] A substantially soluble polymeric thickener can be used to
provide increased viscosity or increased conductivity to the use
compositions. Examples of polymeric thickeners for the aqueous
compositions of the invention include, but are not limited to:
carboxylated vinyl polymers such as polyacrylic acids and sodium
salts thereof, ethoxylated cellulose, polyacrylamide thickeners,
cross-linked, xanthan compositions, sodium alginate and algin
products, hydroxypropyl cellulose, hydroxyethyl cellulose, and
other similar aqueous thickeners that have some substantial
proportion of water solubility. Examples of suitable commercially
available thickeners include, but are not limited to: Acusol,
available from Rohm & Haas Company, Philadelphia, Pa.; and
Carbopol, available from B.F. Goodrich, Charlotte, N.C.
[0151] Examples of suitable polymeric thickeners include, but not
limited to: polysaccharides. An example of a suitable commercially
available polysaccharide includes, but is not limited to, Diutan,
available from Kelco Division of Merck, San Diego, Calif.
Thickeners for use in the solid detergent compositions further
include polyvinyl alcohol thickeners, such as, fully hydrolyzed
(greater than 98.5 mol acetate replaced with the --OH
function).
[0152] An example of a suitable polysaccharide includes, but is not
limited to, xanthans. Such xanthan polymers are suitable due to
their high water solubility, and great thickening power. Xanthan is
an extracellular polysaccharide of Xanthomonas campestras. Xanthan
may be made by fermentation based on corn sugar or other corn
sweetener by-products. Xanthan includes a poly
beta-(1-4)-D-Glucopyranosyl backbone chain, similar to that found
in cellulose. Aqueous dispersions of xanthan gum and its
derivatives exhibit novel and remarkable rheological properties.
Low concentrations of the gum have relatively high viscosities
which permit it to be used economically. Xanthan gum solutions
exhibit high pseudo plasticity, i.e. over a wide range of
concentrations, rapid shear thinning occurs that is generally
understood to be instantaneously reversible. Non-sheared materials
have viscosities that appear to be independent of the pH and
independent of temperature over wide ranges. Suitable xanthan
materials include crosslinked xanthan materials. Xanthan polymers
can be crosslinked with a variety of known covalent reacting
crosslinking agents reactive with the hydroxyl functionality of
large polysaccharide molecules and can also be crosslinked using
divalent, trivalent or polyvalent metal ions. Such crosslinked
xanthan gels are disclosed in U.S. Pat. No. 4,782,901, which is
herein incorporated by reference. Suitable crosslinking agents for
xanthan materials include, but are not limited to: metal cations
such as Al+3, Fe+3, Sb+3, Zr+4 and other transition metals.
Examples of suitable commercially available xanthans include, but
are not limited to: KELTROL.RTM., KELZAN.RTM. AR, KELZAN.RTM. D35,
KELZAN.RTM. S, KELZAN.RTM. XZ, available from Kelco Division of
Merck, San Diego, Calif. Known organic crosslinking agents can also
be used. A suitable crosslinked xanthan is KELZAN.RTM. AR, which
provides a pseudo plastic use solution that can produce large
particle size mist or aerosol when sprayed.
Optical Brighteners
[0153] Optical brightener is also referred to as fluorescent
whitening agents or fluorescent brightening agents provide optical
compensation for the yellow cast in fabric substrates. With optical
brighteners yellowing is replaced by light emitted from optical
brighteners present in the area commensurate in scope with yellow
color. The violet to blue light supplied by the optical brighteners
combines with other light reflected from the location to provide a
substantially complete or enhanced bright white appearance. This
additional light is produced by the brightener through
fluorescence. Optical brighteners absorb light in the ultraviolet
range 275 through 400 nm. and emit light in the ultraviolet blue
spectrum 400-500 nm.
[0154] Fluorescent compounds belonging to the optical brightener
family are typically aromatic or aromatic heterocyclic materials
often containing condensed ring system. An important feature of
these compounds is the presence of an uninterrupted chain of
conjugated double bonds associated with an aromatic ring. The
number of such conjugated double bonds is dependent on substituents
as well as the planarity of the fluorescent part of the molecule.
Most brightener compounds are derivatives of stilbene or
4,4'-diamino stilbene, biphenyl, five membered heterocycles
(triazoles, oxazoles, imidazoles, etc.) or six membered
heterocycles (cumarins, naphthalamides, triazines, etc.). The
choice of optical brighteners for use in detergent compositions
will depend upon a number of factors, such as the type of
detergent, the nature of other components present in the detergent
composition, the temperature of the wash water, the degree of
agitation, and the ratio of the material washed to the tub size.
The brightener selection is also dependent upon the type of
material to be cleaned, e.g., cottons, synthetics, etc. Since most
laundry detergent products are used to clean a variety of fabrics,
the detergent compositions should contain a mixture of brighteners
which are effective for a variety of fabrics. It is of course
necessary that the individual components of such a brightener
mixture be compatible.
[0155] Optical brighteners useful in the present invention are
commercially available and will be appreciated by those skilled in
the art. Commercial optical brighteners which may be useful in the
present invention can be classified into subgroups, which include,
but are not necessarily limited to, derivatives of stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles and other miscellaneous agents. Examples of these
types of brighteners are disclosed in "The Production and
Application of Fluorescent Brightening Agents", M. Zahradnik,
Published by John Wiley & Sons, New York (1982), the disclosure
of which is incorporated herein by reference.
[0156] Stilbene derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
of bis(triazinyl)amino-stilbene; bisacylamino derivatives of
stilbene; triazole derivatives of stilbene; oxadiazole derivatives
of stilbene; oxazole derivatives of stilbene; and styryl
derivatives of stilbene.
[0157] For laundry cleaning or sanitizing compositions, suitable
optical brighteners include stilbene derivatives, which can be
employed at concentrations of up to 1 wt %.
Dyes/Odorants
[0158] Various dyes, odorants including perfumes, and other
aesthetic enhancing agents may also be included in the composition.
Dyes may be included to alter the appearance of the composition, as
for example, Direct Blue 86 (Miles), Fastusol Blue (Mobay Chemical
Corp.), Acid Orange 7 (American Cyanamid), Basic Violet 10
(Sandoz), Acid Yellow 23 (GAF), Acid Yellow 17 (Sigma Chemical),
Sap Green (Keyston Analine and Chemical), Metanil Yellow (Keystone
Analine and Chemical), Acid Blue 9 (Hilton Davis), Sandolan
Blue/Acid Blue 182 (Sandoz), Hisol Fast Red (Capitol Color and
Chemical), Fluorescein (Capitol Color and Chemical), Acid Green 25
(Ciba-Geigy), and the like.
[0159] Fragrances or perfumes that may be included in the
compositions include, for example, terpenoids such as citronellol,
aldehydes such as amyl cinnamaldehyde, a jasmine such as
C1S-jasmine or jasmal, vanillin, and the like.
Use Compositions
[0160] The present warewashing compositions include concentrate
compositions and use compositions. In general, a concentrate refers
to a composition that is intended to be diluted with water to
provide a use solution that contacts an object to provide the
desired cleaning, rinsing, or the like. The warewashing composition
that contacts the articles to be washed in an automatic dishwashing
process can be referred to as the use composition. The use solution
can include additional functional ingredients at a level suitable
for cleaning, rinsing, or the like. In an embodiment, the use
solution includes additional functional ingredients of from about
0.05 wt % to about 75 wt %.
[0161] A use solution may be prepared from the concentrate by
diluting the concentrate with water at a dilution ratio that
provides a use solution having desired detersive properties. The
water that is used to dilute the concentrate to form the use
composition can be referred to as water of dilution or a diluent,
and can vary from one location to another. The resistance to
corrosion can be provided when the diluent added to the concentrate
to form the use solution is hard water or soft water, and can be
added to a warewashing composition. In an exemplary embodiment, the
concentrate may be diluted at a weight ratio of diluent to
concentrate of at least about 20:1 or about 20:1 to about 2000:1.
The use composition can have a solids content that is sufficient to
provide the desired level of detersive properties while avoiding
wasting the warewashing composition. The solids concentration
refers to the concentration of the non-water components in the use
composition. In an embodiment when the composition is provided as a
use solution, the use composition can have a solids content of at
least about 0.05 wt % to provide a desired level of cleaning In
addition, the use composition can have a solids content of less
than about 1.0 wt % to avoid using too much of the composition. The
use composition can have a solids content of about 0.05 wt % to
about 0.75 wt %.
[0162] The concentrate may be diluted with water at the location of
use to provide the use solution. When the composition is used in an
automatic warewashing or dishwashing machine, it is expected that
that the location of use will be inside the automatic warewashing
machine. For example, when the composition is used in a residential
warewashing machine, the composition may be placed in the detergent
compartment of the warewashing machine. Depending on the machine,
the composition may be provided in a unit dose form or in a
multi-use form. When the warewashing composition is used in a
residential or home-style dishwashing machine, the composition can
be placed in the detergent compartment of the dishwashing machine.
Often the detergent compartment is located in the door of the
dishwashing machine. The warewashing composition can be provided in
a form that allows for introduction of a single dose of the
warewashing composition into the compartment. In general, a single
dose refers to the amount of warewashing composition that is
desired for a single warewashing cycle. In larger warewashing
machines, a large quantity of composition may be provided in a
compartment that allows for the release of a single dose amount of
the composition for each wash cycle. Such a compartment may be
provided as part of the warewashing machine or as a separate
structure connected to the warewashing machine. For example, a
block of the composition may be provided in a hopper and introduced
into the warewashing machine when water is sprayed against the
surface of the block to provide a liquid concentrate.
[0163] The warewashing composition may also be dispensed from a
spray-type dispenser. Briefly, a spray-type dispenser functions by
impinging a water spray upon an exposed surface of the composition
to dissolve a portion of the composition, and then immediately
directing the use solution out of the dispenser to a storage
reservoir or directly to a point of use. When used, the product may
be removed from the packaging (e.g. film) and inserted into the
dispenser. The spray of water may be made by a nozzle in a shape
that conforms to the shape of the solid detergent composition. The
dispenser enclosure may also closely fit the shape of the detergent
composition to prevent introducing and dispensing an incorrect
composition.
Embodiments of Liquids and Solids
[0164] The present invention also relates to liquid and solid
cleaning compositions including a hardness ion corrosion inhibitor.
For example, when the composition is provided as a liquid, the
present invention includes a gel or paste including a hardness ion
corrosion inhibitor. For example, when the composition is provided
as a solid, the present invention includes a cast solid including a
hardness ion corrosion inhibitor.
[0165] Exemplary ranges for components of the warewashing
composition when provided as a gel or a paste are shown in Table 1.
Exemplary ranges for components of the warewashing composition when
provided as a solid are shown in Table 2.
TABLE-US-00001 TABLE 1 Gel or Paste Warewashing Composition First
Second Third Exemplary Exemplary Exemplary Component Range (wt %)
Range (wt %) Range (wt %) Water 5-60 10-35 15-25 Alkaline Source
5-40 10-30 15-20 Silicate 0-35 .sup. 5-25 10-20 Builder 1-30 .sup.
3-20 6-15 Stabilizer 0-20 0.5-15 2-10 Dispersant 0-20 0.5-15 2-9
Enzyme 0-15 0.5-10 1-5 Corrosion Inhibitor 0.01-15 0.5-10 1-5
Surfactant 0.05-15 0.5-10 1-5 Fragrance 0-10 0.01-5 0.1-2.sup. Dye
0-1 0.001-0.5.sup. 0.01-0.25
TABLE-US-00002 TABLE 2 Solid Warewashing Composition First Second
Third Exemplary Exemplary Exemplary Component Range (wt %) Range
(wt %) Range (wt %) Water 0-50 1-30 5-20 Alkaline Source 5-40 10-30
15-20 Builder 1-60 25-50 35-45 Bleach 0-55 5-45 10-35 Silicate 0-35
5-25 10-15 Dispersant 0-10 0.001-5 0.01-1 Enzyme 0-15 1-10 2-5
Corrosion Inhibitor 0.01-15 0.05-10 1-5 Surfactant 0.05-15
0.5-10.sup. 1-5 Fragrance 0-10 0.01-5 0.1-2.sup. Dye 0-1 0.001-0.5
0.01-0.25
[0166] The present hardness ion corrosion inhibitor of the
warewashing composition can be provided in any of a variety of
embodiments of compositions. In an embodiment, the present
composition does not include phosphorus or nitrilotriacetic acid
(NTA) containing compounds. Phosphorus-free refers to a
composition, mixture, or ingredients to which phosphorus-containing
compounds are not added. Should phosphorus-containing compounds be
present, the level of phosphorus-containing compounds in the
resulting composition should be less than about 0.5%, less than
about 0.1%, and often less than about 0.01% by weight. NTA-free
refers to a composition, mixture, or ingredients to which
NTA-containing compounds are not added. Should NTA-containing
compounds be present, the level of NTA in the resulting composition
should be less than about 0.5%, less than about 0.1%, and often
less than about 0.01% by weight. When the detergent composition is
NTA-free, the detergent composition is also compatible with
chlorine, which functions as an anti-redeposition and stain-removal
agent.
[0167] In an embodiment, the present composition is substantially
free of zinc. In general, the present composition can be
characterized as substantially free of zinc if the corrosion
inhibitor contains no intentionally added zinc. For example, the
present composition may be characterized as substantially free of
zinc if it contains no zinc, or if zinc is present, the amount of
zinc is less than about 0.01 wt-%. Zinc can unnecessarily consume
certain builders or chelating agents, which is a reason to exclude
it.
[0168] In an embodiment, the present composition includes a source
of hardness ions (e.g., magnesium and calcium ions) that are
characterized by the United States Food and Drug Administration as
direct or indirect food additives.
[0169] According to the present invention, a liquid cleaning
composition including a corrosion inhibitor can be prepared by a
method including: providing a powder or crystalline form of
corrosion inhibitor; melting the powder or crystalline form of the
corrosion inhibitor; providing a sufficient amount of water to
preclude solidification; and transferring the molten corrosion
inhibitor into a mold.
[0170] According to the present invention, a solid cleaning
composition including a corrosion inhibitor can be prepared by a
method including: providing a powder or crystalline form of
corrosion inhibitor; melting the powder or crystalline form of the
corrosion inhibitor; transferring the molten corrosion inhibitor
into a mold; and cooling the molten composition to solidify it.
[0171] According to the present invention, a solid cleaning
composition including a corrosion inhibitor can be prepared by a
method including: providing a powder or crystalline form of a
corrosion inhibitor; gently pressing the corrosion inhibitor to
form a solid (e.g., block or puck).
[0172] A solid cleaning or rinsing composition as used in the
present disclosure encompasses a variety of forms including, for
example, solids, pellets, blocks, and tablets, but not powders. By
way of example, pellets can have diameters of between about 1 mm
and about 10 mm, tablets can have diameters of between about 1 mm
and about 10 mm or between about 1 cm and about 10 cm, and blocks
can have diameters of at least about 10 cm. It should be understood
that the term "solid" refers to the state of the detergent
composition under the expected conditions of storage and use of the
solid cleaning composition. In general, it is expected that the
detergent composition will remain a solid when provided at a
temperature of up to about 100.degree. F. or greater than about
120.degree. F.
[0173] In certain embodiments, the solid cleaning composition is
provided in the form of a unit dose. A unit dose refers to a solid
cleaning composition unit sized so that the entire unit is used
during a single washing cycle. When the solid cleaning composition
is provided as a unit dose, it can have a mass of about 1 g to
about 50 g. In other embodiments, the composition can be a solid, a
pellet, or a tablet having a size of about 50 g to 250 g, of about
100 g or greater, or about 40 g to about 11,000 g.
[0174] In other embodiments, the solid cleaning composition is
provided in the form of a multiple-use solid, such as, a block or a
plurality of pellets, and can be repeatedly used to generate
aqueous detergent compositions for multiple washing cycles. In
certain embodiments, the solid cleaning composition is provided as
a solid having a mass of about 5 g to about 10 kg. In certain
embodiments, a multiple-use form of the solid cleaning composition
has a mass of about 1 to about 10 kg. In further embodiments, a
multiple-use form of the solid cleaning composition has a mass of
about 5 kg to about 8 kg. In other embodiments, a multiple-use form
of the solid cleaning composition has a mass of about 5 g to about
1 kg, or about 5 g and to about 500 g.
Packaging System
[0175] In some embodiments, the solid composition can be packaged.
The packaging receptacle or container may be rigid or flexible, and
composed of any material suitable for containing the compositions
produced according to the invention, as for example glass, metal,
plastic film or sheet, cardboard, cardboard composites, paper, and
the like.
[0176] Advantageously, since the composition is processed at or
near ambient temperatures, the temperature of the processed mixture
is low enough so that the mixture may be formed directly in the
container or other packaging system without structurally damaging
the material. As a result, a wider variety of materials may be used
to manufacture the container than those used for compositions that
processed and dispensed under molten conditions.
[0177] Suitable packaging used to contain the compositions is
manufactured from a flexible, easy opening film material.
Dispensing of the Processed Compositions
[0178] The warewashing composition according to the present
invention can be dispensed in any suitable method generally known.
The warewashing composition can be dispensed from a spray-type
dispenser such as that disclosed in U.S. Pat. Nos. 4,826,661,
4,690,305, 4,687,121, 4,426,362 and in U.S. Pat. Nos. Re 32,763 and
32,818, the disclosures of which are incorporated by reference
herein. Briefly, a spray-type dispenser functions by impinging a
water spray upon an exposed surface of the solid composition to
dissolve a portion of the composition, and then immediately
directing the concentrate solution including the composition out of
the dispenser to a storage reservoir or directly to a point of use.
When used, the product is removed from the package (e.g.) film and
is inserted into the dispenser. The spray of water can be made by a
nozzle in a shape that conforms to the solid shape. The dispenser
enclosure can also closely fit the detergent shape in a dispensing
system that prevents the introduction and dispensing of an
incorrect detergent. The aqueous concentrate is generally directed
to a use locus.
[0179] In an embodiment, the present composition can be dispensed
by immersing either intermittently or continuously in water. The
composition can then dissolve, for example, at a controlled or
predetermined rate. The rate can be effective to maintain a
concentration of dissolved cleaning agent that is effective for
cleaning
[0180] In an embodiment, the present composition can be dispensed
by scraping solid from the solid composition and contacting the
scrapings with water. The scrapings can be added to water to
provide a concentration of dissolved cleaning agent that is
effective for cleaning.
Methods Employing the Present Compositions
[0181] In an embodiment, the present invention includes methods
employing the hardness ion corrosion inhibitor or a composition
including the hardness ion corrosion inhibitor. The method can
result in reducing corrosion or etching of an article. For example,
in an embodiment, the present invention includes a method of
reducing corrosion of a surface of a material exposed to water
hardness. The method includes contacting the surface with a liquid
containing the hardness ion corrosion inhibitor or a composition
including the hardness ion corrosion inhibitor. The liquid can
include dissolved composition. The method can also include
providing the hardness ion corrosion inhibitor or a composition
including the hardness ion corrosion inhibitor; and dissolving the
composition in a liquid diluent (e.g., water). The method can
contact the liquid to any of a variety of surfaces or objects
including surfaces or articles including those made of glass,
ceramic, porcelain, or aluminum.
[0182] In an embodiment, the present invention includes a method of
cleaning an article while also reducing corrosion of the article.
This method can include: providing a liquid or solid composition of
a warewashing composition including a hardness ion corrosion
inhibitor; contacting the solid block with an aqueous composition
to form an aqueous composition including a hardness ion corrosion
inhibitor; and contacting the aqueous composition including a
hardness ion corrosion inhibitor to an article to clean the article
and reduce corrosion of the article.
[0183] In an embodiment, the present methods can include injecting
the present aqueous composition or placing the present composition
into the water flow being used to rinse the surface. In an
embodiment, the present method employs water that wasn't treated
with a polymeric water softener bed such as in use today and which
requires periodic regeneration with sodium chloride to work.
[0184] Contacting can include any of numerous methods for applying
a composition, such as spraying the composition, immersing the
object in the composition, or a combination thereof. A concentrate
or use concentration of a composition of the present invention can
be applied to or brought into contact with an article by any
conventional method or apparatus for applying a cleaning
composition to an object. For example, the object can be wiped
with, sprayed with, and/or immersed in the composition, or a use
solution made from the composition. The composition can be sprayed,
or wiped onto a surface; the composition can be caused to flow over
the surface, or the surface can be dipped into the composition.
Contacting can be manual or by machine.
[0185] The present composition may be applied in any situation
where it is desired to prevent surface corrosion or etching. The
present composition may be employed in a commercial warewashing
composition to protect articles, such as glass, ceramic and
porcelain, from corrosion or etching in automatic dishwashing or
warewashing machines during cleaning or in the cleaning of bottles.
Applications in which the present composition may be used include:
warewashing, rinse aids, cleaning-in-place operations in food and
beverage production facilities, general purpose cleaning and
destaining, bottlewashing, and industrial or household
cleaners.
[0186] It should be understood that certain components that may be
included in a warewashing composition because it is intended to be
used in an automatic dishwashing machine can be excluded from a
cleaning composition that is not intended to be used in an
automatic dishwashing machine, and vice versa. For example,
surfactants that have a tendency to create quite a bit of foaming
may be used in a composition that is not intended to be used in an
automatic dishwashing machine.
[0187] It should 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. Thus, for example, reference to a composition containing
"a compound" includes a mixture of two or more compounds. It should
also be noted that the term "or" is generally employed in its sense
including "and/or" unless the content clearly dictates
otherwise.
[0188] All publications and patent applications in this
specification are indicative of the level of ordinary skill in the
art to which this invention pertains. All publications and patent
applications are herein incorporated by reference to the same
extent as if each individual publication or patent application was
specifically and individually indicated by reference.
[0189] The invention has been described with reference to various
specific and preferred embodiments and techniques. However, it
should be understood that many variations and modifications may be
made while remaining within the spirit and scope of the
invention.
* * * * *