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| United States Patent Application |
20110160114
|
| Kind Code
|
A1
|
|
Smith; Kim R.
;   et al.
|
June 30, 2011
|
CLEANING COMPOSITIONS CONTAINING WATER SOLUBLE MAGNESIUM COMPOUNDS AND
METHODS OF USING THEM
Abstract
The present invention relates to cleaning compositions and methods
employing a water soluble magnesium compound. Such compositions can be
used for reducing scale, rinsing, hard surface cleaning, ware washing,
and corrosion inhibition.
| Inventors: |
Smith; Kim R.; (Woodbury, MN)
; Besse; Michael E.; (Golden Valley, MN)
; Tjelta; Brenda L.; (St. Paul, MN)
; Sanders; Lisa M.; (Eagan, MN)
; Olson; Keith E.; (Apple Valley, MN)
|
| Assignee: |
ECOLAB USA INC.
ST. PAUL
MN
|
| Serial No.:
|
039968 |
| Series Code:
|
13
|
| Filed:
|
March 3, 2011 |
| Current U.S. Class: |
510/180; 510/219 |
| Class at Publication: |
510/180; 510/219 |
| International Class: |
C11D 3/60 20060101 C11D003/60 |
Claims
1.-8. (canceled)
9. A cleaning composition comprising: about 1 to about 60 wt-% water
soluble magnesium salt; about 0 to about 60 wt-% source of alkalinity;
about 0 to about 90 wt-% water; and about 0 to about 20 wt-% surfactant;
10. The composition of claim 9, wherein the composition is substantially
free of chelating agent.
11. The composition of claim 9, wherein the composition further comprises
about 1 to about 7% of a chelating agent.
12. The composition of claim 9, wherein the aqueous composition is
substantially free of threshold agent.
13. The composition of claim 9, wherein the water soluble magnesium salt
comprises an anion that forms a soluble calcium salt.
14. The composition of claim 9, wherein the water soluble magnesium salt
is selected from the group consisting 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 thiosulfate, and hydrates
and mixtures thereof.
15. The composition of claim 9, wherein the source of alkalinity is
selected from the group consisting of an alkali metal carbonate, an
alkali metal hydroxide, and combinations thereof.
16. The composition of claim 15, wherein the alkali metal carbonate is
selected from the group consisting of sodium carbonate, potassium
carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate,
lithium bicarbonate, sodium sesquicarbonate, potassium sesquicarbonate,
lithium sesquicarbonate, and combinations thereof.
17. The composition of claim 15, wherein the alkali metal hydroxide is
selected from the group consisting of sodium hydroxide, lithium
hydroxide, potassium hydroxide, and combinations thereof.
18. The composition of claim 9, wherein the surfactant is selected from
the group consisting of nonionic surfactants, cationic surfactants,
anionic surfactants, amphoteric surfactants, and combinations thereof.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional application of U.S. patent
application Ser. No. 12/785,867, filed on May 24, 2010, published as US
2010-0234262, now allowed, which is a continuation application of U.S.
patent application Ser. No. 12/114,513, filed on May 2, 2008, published
as US 2008-0276967, now allowed, which claims priority to U.S.
Provisional Application Ser. No. 60/927,575, filed on May 4, 2007,
entitled "Compositions Containing Magnesium Salt and Methods of Using",
the disclosures of which are incorporated herein by reference.
[0002] U.S. patent application Ser. No. 12/114,513 is also related to:
U.S. patent application Ser. No. 12/114,329, entitled "Compositions
Including CA and MG Ions and Gluconate and Methods Employing Them to
Reduce Corrosion and Etch", now issued as U.S. Pat. No. 7,709,434; U.S.
patent application Ser. No. 12/114,486, entitled "Cleaning Compositions
with Water Insoluble Conversion Agents and Methods of Making and Using
Them";U.S. patent application Ser. No. 12/114,355, 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"; U.S. patent application Ser. No. 12/114,448,
entitled "Water Treatment System and Downstream Cleaning Methods"; U.S.
patent application Ser. No. 12/114,327, entitled "Water Soluble Magnesium
Compounds as Cleaning Agents and Methods of Using Them"; U.S. patent
application Ser. No. 12/114,428, entitled "MG++ Chemistry and Method for
Fouling Inhibition in Heat Processing of Liquid Foods and Industrial
Processes"; U.S. patent application Ser. No. 12/114,342, entitled
"Compositions Including Hardness Ion and Silicate and Methods Employing
Them to Reduce Corrosion and Etch"; U.S. patent application Ser. No.
12/114,364, entitled "Compositions Including Hardness Ion and Threshold
Agent and Methods Employing Them to Reduce Corrosion and Etch"; U.S.
patent application Ser. No. 12/114,385, entitled "Warewashing
Compositions for Use in Automatic Dishwashing Machines and Method for
Using", filed on May 2, 2008; and U.S. patent application Ser. No.
12/262,627, entitled "MG++ Chemistry and Method for Fouling Inhibition In
Heat Processing of Liquid Foods and Industrial Processes"; U.S. patent
application Ser. No. 12/263,156, entitled "Cleaning Compositions with
Water Insoluble Conversion Agents and Methods of Making and Using Them";
U.S. patent application Ser. No. 12/263,090, entitled "Cleaning
Compositions Containing Water Soluble Magnesium Compounds and Methods of
Using Them"; and U.S. patent application Ser. No. 12/263,021, entitled
"Compositions Including Hardness Ions and Gluconate and Methods Employing
Them to Reduce Corrosion and Etch", filed on Oct. 31, 2008; and U.S.
patent application Ser. No. 12/726,179, entitled "Compositions Including
Hardness Ions and Gluconate and Methods Employing Them to Reduce
Corrosion and Etch", filed on Mar. 17, 2010, all commonly assigned to
Ecolab Inc., and are all incorporated herein by reference for all
purposes.
FIELD OF THE INVENTION
[0003] The present invention relates to compositions and methods employing
a water soluble magnesium compound. The present composition can be
substantially free of chelating agent, threshold agent or sequestrant.
The methods and compositions can provide magnesium ion at predefined
ratios to calcium ion in water, such as magnesium ion in a molar amount
equal to or in excess over a molar amount of calcium ion. These
compositions can be used for reducing scale, rinsing, hard surface
cleaning, and ware washing. These compositions can also be used to reduce
ash build up in laundry cleaning processes.
BACKGROUND OF THE INVENTION
[0004] The level of hardness in water can have a deleterious effect in
many systems. For example, when hard water alone, or in conjunction with
cleaning compositions, contacts a surface, it can cause precipitation of
hard water scale on the contacted surface. In general, hard water refers
to water having a total 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] Water hardness has been addressed in a number of ways. One method
currently used to soften water is via ion exchange, e.g., by adding
sodium to the water to exchange the calcium and magnesium ions in the
water with sodium associated with a resin bed in a water softening unit.
The calcium and magnesium adhere to a resin in the softener. When the
resin becomes saturated it is necessary to regenerate it using large
amounts of sodium chloride dissolved in water. The sodium displaces the
calcium and magnesium, which is flushed out in a briny solution along
with the chloride from the added sodium chloride. When water softeners
regenerate they produce a waste stream that contains significant amounts
of chloride, creating a burden on the system, e.g., sewer system, in
which they are disposed of, including a multitude of downstream water
re-use applications like portable water usages and agriculture.
[0006] Hard water is also known to reduce the efficacy of detergents. One
method for counteracting this includes adding chelating agents or
sequestrants into detersive compositions that are intended to be mixed
with hard water in an amount sufficient to handle the hardness. However,
in many instances the water hardness exceeds the chelating capacity of
the composition. As a result, free calcium ions may be available to
attack active components of the composition, to cause corrosion or
precipitation, or to cause other deleterious effects, such as poor
cleaning effectiveness or lime scale build up.
SUMMARY OF THE INVENTION
[0007] In some aspects, the present invention relates to methods and
compositions that employ a water soluble magnesium salt to counter the
undesirable effects of calcium ion in hard water. In some embodiments of
the present invention, water soluble magnesium salt is used in cleaning
compositions as a replacement for substantial levels of a conventional
builder, chelating agent, sequestrant, and threshold agent.
[0008] In some embodiments, the compositions of the present invention
include water soluble magnesium compound as a substitute for significant
amount of or all of the conventional builder, chelating agent,
sequestrant, or threshold agent. The present composition can be
substantially free of chelating agent threshold agent or sequestrant. The
methods and compositions can provide magnesium ion at predefined ratios
to calcium ion in water, such as magnesium ion in a molar amount equal to
or in excess over a molar amount of calcium ion. It is preferred that the
water soluble magnesium salt include an anion that, together with calcium
ion, forms a water soluble calcium salt. Such compositions can be used
for reducing scale, rinsing, hard surface cleaning, laundry and ware
washing.
[0009] The present invention relates to a method of cleaning an object.
The method can reduce hard water spotting, scaling, ash buildup in
laundry or deposits. The method can include contacting the object with an
aqueous composition comprising water, a water soluble magnesium salt,
and, optionally, an ingredient selected from the group consisting of
source of alkalinity, surfactants, and a mixture thereof. In an
embodiment, the method employs water soluble magnesium compound as a
substitute or partial substitute for conventional builder, chelating
agent, sequestrant, or threshold agent. The method can employ an aqueous
composition that is substantially free of chelating agent threshold agent
or sequestrant. The methods can employ magnesium ion at predefined ratios
to calcium ion in water, such as magnesium ion in a molar amount equal to
or in excess over a molar amount of calcium ion. It is preferred that the
water soluble magnesium salt can include an anion that, together with
calcium ion, forms a water soluble calcium salt.
[0010] The invention also includes cleaning compositions. The cleaning
composition includes water soluble magnesium salt and any of a variety of
other components useful for cleaning an object. For example, the
composition can include water soluble magnesium salt, source of
alkalinity, water, surfactant, or the like. In an embodiment, the
composition can include about 1 to about 60 wt-% water soluble magnesium
salt; about 0 to about 60 wt-% source of alkalinity; about 0 to about 90
wt-% water; about 0 to about 20 wt-% surfactant; and about 0 to about 7
wt-% builder.
[0011] In an embodiment, the composition includes water soluble magnesium
compound as a substitute or partially substituted for conventional
builder, chelating agent, sequestrant, or threshold agent. The
composition can include magnesium ion at predefined ratios to calcium ion
in water, such as magnesium ion in a molar amount equal to or in excess
over a molar amount of calcium ion. It is preferred the water soluble
magnesium salt can include an anion that, together with calcium ion,
forms a water soluble calcium salt.
BRIEF DESCRIPTION OF THE FIGURES
[0012] FIGS. 1-6 each have an x, y, and z axis. The x-axis is a measure of
the molar ratio of calcium to builder, e.g., STPP, or water soluble
magnesium compound. The y-axis is a measure of the level of light
transmittance thru the samples with 0% being no light transmitted and
100% being the entire beam of light transmitted. Full or partial loss of
transmittance occurs as a consequence of the presence of particulate
formation in the initially clear samples. An effective builder prevents
or reduces precipitation resulting in a clear sample. The z-axis is a
measure of the test temperature, ranging from 20-60.degree. C.
[0013] FIG. 1 is a plot of the performance of STPP as a builder in the
presence of various levels of calcium, at various temperatures, and at a
constant pH of 8.
[0014] FIG. 2 is a plot of the performance of magnesium chloride in
preventing precipitation in the presence of various levels of calcium, at
various temperatures, and at a constant pH of 8.
[0015] FIG. 3 is a plot of the performance of STPP as a builder in the
presence of various levels of calcium, at various temperatures, and at a
constant pH of 10.
[0016] FIG. 4 is a plot of the performance of magnesium chloride in
preventing precipitation in the presence of various levels of calcium, at
various temperatures, and at a constant pH of 10.
[0017] FIG. 5 is a plot of the performance of STPP as a builder in the
presence of various levels of calcium, at various temperatures, and at a
constant pH of 12.
[0018] FIG. 6 is a plot of the performance of magnesium chloride in
preventing precipitation in the presence of various levels of calcium, at
various temperatures, and at a constant pH of 12.
[0019] FIG. 7 is a plot of the performance of sodium citrate as a builder
in the presence of various levels of calcium, at various temperatures,
and at a constant pH of 8.
[0020] FIG. 8 is a plot of the performance of sodium citrate as a builder
in the presence of various levels of calcium, at various temperatures,
and at a constant pH of 10.
[0021] FIG. 9 is a plot of the performance of sodium citrate as a builder
in the presence of various levels of calcium, at various temperatures,
and at a constant pH of 12.
[0022] FIG. 10 illustrates the results of experiments conducted to
determine the impact of a water soluble alkali metal hydroxide such as
sodium hydroxide on the precipitation of water hardness ions (e.g.,
Ca.sup.2 and Mg.sup.2+).
[0023] FIG. 11 illustrates the results of experiments conducted to
determine the impact of a water soluble alkali metal carbonate such as
sodium carbonate on the precipitation of water hardness ions (e.g.,
Ca.sup.2 and Mg.sup.2+).
[0024] FIG. 12 illustrates the results of experiments conducted to
determine the impact of a water soluble alkali metal hydroxide such as
sodium hydroxide and a water soluble alkali metal carbonate such as
sodium carbonate on the precipitation of water hardness ions (e.g.,
Ca.sup.2+ and Mg.sup.2+).
[0025] FIG. 13 is a p
hotograph of two glasses, one subjected to 100 cycles
in a dishwashing machine with magnesium chloride and the other with
magnesium sulfate. The molar ratio of magnesium to calcium was 1:1.
[0026] FIG. 14 shows a photograph of two glasses. The glass on the left
was washed using a conventional, magnesium free warewash detergent. The
glass on the right was washed using magnesium salt containing Formula A.
There is a darker vertical stripe of dye visible on the glass on the
left.
[0027] FIG. 15 shows a p
hotograph of a cup. The left side of the cup was
washed using the conventional, magnesium free warewash detergent. The
right side of the cup washed using magnesium salt containing Formula A.
The two sides of the cup appear equally clean.
[0028] FIG. 16 is a photograph showing two glasses washed with a warewash
detergent and then rinsed as described in Example 4 and illustrating that
adding a hardness ion (Mg.sup.2+) to rinse water reduced formation of
scale from hard water on glasses after warewashing.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0029] So that the invention may be more readily understood certain terms
are first defined.
[0030] 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, EDTA, DTPA, 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.
[0031] As used herein, the term "free of chelating agent" or
"substantially free of chelating agent" refers to a composition, mixture,
or ingredients that does not contain a chelating agent or sequestrant or
to which only a limited amount of a chelating agent or sequestrant has
been added. Should a chelating agent or sequestrant be present, the
amount of a chelating agent or sequestrant shall be less than about 7 wt
%. In some embodiments, such an amount of a chelating agent or
sequestrant is less than about 2 wt-%. In other embodiments, such an
amount of a chelating agent or sequestrant is less then about 0.5 wt-%.
In still yet other embodiments, such an amount of a chelating agent or
sequestrant is less than about 0.1 wt-%.
[0032] As used herein, the term "lacking an effective amount of chelating
agent" refers to a composition, mixture, or ingredients that contains too
little chelating agent or sequestrant to measurably affect the hardness
of water.
[0033] As used herein, the term "water soluble" refers to a compound that
can be dissolved in water at a concentration of more than 1 wt-%.
[0034] 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-%.
[0035] As used herein, the term "water insoluble" refers to a compound
that can be dissolved in water only to a concentration of less than 0.1
wt-%. For example, magnesium oxide is considered to be insoluble as it
has a water solubility (wt %) of about 0.00062 in cold water, and about
0.00860 in hot water. Other insoluble compounds for use with the methods
of the present invention include, for example: magnesium hydroxide with a
water solubility of 0.00090 in cold water and 0.00400 in hot water;
aragonite with a water solubility of 0.00153 in cold water and 0.00190 in
hot water; and calcite with a water solubility of 0.00140 in cold water
and 0.00180 in
hot water.
[0036] 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 ion. This
distinguishes a threshold agent from a chelating agent or sequestrant.
Threshold agents include a polyacrylate, a polymethacrylate, an
olefin/maleic copolymer, and the like.
[0037] As used herein, the term "free of threshold agent" or
"substantially free of threshold agent" refers to a composition, mixture,
or ingredient that does not contain a threshold agent or to which only a
limited amount of a threshold agent has been added. Should a threshold
agent be present, the amount of a threshold agent shall be less than
about 7 wt %. In some embodiments, such an amount of a threshold agent is
less than about 2 wt-%. In other embodiments, such an amount of a
threshold agent is less then about 0.5 wt-%. In still yet other
embodiments, such an amount of a threshold agent is less than about 0.1
wt-%.
[0038] As used herein, the term "antiredeposition agent" refers to a
compound that helps keep a soil composition suspended in water instead of
redepositing onto the object being cleaned.
[0039] As used herein, the term "phosphate-free" or "substantially
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 ingredients,
the amount of phosphate shall be less than about 1.0 wt %. In some
embodiments, the amount of phosphate is less than about 0.5 wt %. In
other embodiments, the amount of phosphate is less then about 0.1 wt %.
In still yet other embodiments, the amount of phosphate is less than
about 0.01 wt %.
[0040] As used herein, the term "phosphorus-free" or "substantially
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 ingredients,
the amount of phosphorus shall be less than about 1.0 wt %. In some
embodiments, the amount of phosphorous is less than about 0.5 wt %. In
other embodiments, the amount of phosphorus is less than about 0.1 wt %.
In still yet other embodiments, the amount of phosphorus is less than
about 0.01 wt %.
[0041] "Cleaning" means to perform or aid in soil removal, bleaching,
microbial population reduction, or combination thereof.
[0042] As used herein, the term "ware" refers to items such as eating and
cooking utensils and other hard surfaces such as showers, sinks, toilets,
bathtubs, countertops, windows, mirrors, transportation vehicles, and
floors. As used herein, the term "warewashing" refers to washing,
cleaning, or rinsing ware.
[0043] As used herein, the term "hard surface" includes showers, sinks,
toilets, bathtubs, countertops, windows, mirrors, transportation
vehicles, floors, and the like.
[0044] 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.
[0045] 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.
[0046] 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.
[0047] As used herein, a 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.
[0048] 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.
[0049] 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.
[0050] 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.
Compositions and Methods of Use
[0051] The present invention relates to cleaning compositions comprising a
water soluble magnesium compound, and methods of use thereof. In some
embodiments, cleaning compositions comprising the hardness ion Mg.sup.2+
can have beneficial effects in reducing certain deleterious effects of
hard water. Unexpectedly, in an embodiment, a composition of water and
the hardness ion Mg.sup.2+ worked as well as a conventional chelating
agent or sequestrant (sodium tripolyphosphate (STPP)) at preventing
precipitation of calcium salts. The present compositions and methods can
include water soluble magnesium salt as a substitute or partial
substitution for a builder, chelating agent, sequestrant, or threshold
agent.
[0052] In some embodiments, the present cleaning composition is free, or
substantially free of added sequestrant, chelating agent, or threshold
agent. In an embodiment, the aqueous composition includes less than 1
wt-% phosphorus and/or less than 1 wt-% phosphate. Conventional cleaning
compositions include chelating agents to reduce problems caused by water
hardness ions. The present compositions, unexpectedly, include a water
soluble salt of the hardness ion magnesium to reduce problems caused by
hard water.
[0053] Cleaning compositions of the present invention comprising water
soluble magnesium salts provide magnesium ion at predefined ratios to
calcium ion in water. The compositions of the present invention can
advantageously be used for reducing lime scale, rinsing, hard surface
cleaning, ware washing, or the like. For example, in some embodiments,
the compositions of the present invention provide magnesium ion in a
molar amount equal to or in excess over a molar amount of calcium ion. In
some embodiments, magnesium ion and calcium ion can be in a molar ratio
of 1:1 or the composition can include a greater amount of magnesium ion.
In other embodiments, magnesium ion and calcium ion can be in a molar
ratio of about 1.5:1 up to about 6:1.
[0054] In other embodiments, cleaning compositions of the present
invention comprise water soluble magnesium salt including an anion of a
water soluble calcium salt. It has been found that such compositions are
more effective than a magnesium salt with an anion of a water insoluble
calcium salt, when used for reducing lime scale, rinsing, hard surface
cleaning, ware washing, or the like. Sulfate forms a water soluble salt
with magnesium, but its calcium salt is sparingly soluble in water. In
some embodiments, the anions that form water soluble salts with both
magnesium ion and calcium ion include chloride and acetate. In some
embodiments, the water soluble magnesium salt includes an anion that
forms an insoluble calcium salt; and the aqueous composition, upon
dilution for use, includes magnesium ion in a molar amount equal to or
greater than two-times the molar amount of calcium ion.
[0055] In some embodiments, the compositions of the present invention lack
an effective amount or are substantially free of, for example, chelating
agent, sequestrant, builder, and threshold agent. In other embodiments,
the compositions of the present invention can contain surfactants and
sheeting agents and mixture thereof.
[0056] The aqueous composition can include any of a variety of additional
components useful in cleaning compositions. Certain of these components
are described in this application. In an embodiment, the aqueous
composition also includes aesthetic adjuvants such as dyes and
fragrances, antimicrobials, bleach, reducing agent, surfactant.
[0057] In some embodiments, the cleaning compositions of the present
invention comprise water soluble magnesium salt, source of alkalinity,
water, surfactant; and optionally are substantially free of chelating and
threshold agents. In an embodiment, this cleaning composition includes
about 1 to about 60 wt-% water soluble magnesium salt; about 0 to about
60 wt-% source of alkalinity; about 0 to about 90 wt-% water; about 0 to
about 20 wt-% surfactant; optionally about 0 to about 7 wt-% of chelating
or threshold agent.
[0058] Such a composition can include, for example, water soluble
magnesium salt, water insoluble magnesium compound, source of alkalinity,
and water. In an embodiment, this cleaning composition includes about 1
to about 60 wt-% water soluble magnesium salt; about 0 to about 30 wt-%
water insoluble magnesium compound; about 0 to about 60 wt-% source of
alkalinity; about 0 to about 90 wt-% water. The composition can be
substantially free of or free of chelating agent.
[0059] The composition can include magnesium compound at a predetermined
ratio to the calcium in water. The magnesium compound can be a water
soluble magnesium salt including an anion that preferably forms a water
soluble salt with calcium. Anions that form water soluble salts with both
magnesium ion and calcium ion include chloride and acetate. Sulfate forms
a water soluble salt with magnesium, but its calcium salt is water
insoluble. The composition can lack an effective amount or be
substantially free of, for example, chelating agent, sequestrant,
builder, threshold agent, surfactant, and sheeting agent.
[0060] Warewashing Composition
[0061] In some embodiments, a cleaning composition of the present
invention comprising water soluble magnesium salt can be a warewashing
composition Table 1 describes ingredients for suitable warewashing
compositions of the present invention including water soluble magnesium
salt.
TABLE-US-00001
TABLE 1
Warewashing Compositions
Warewashing Warewashing
Composition 1 Composition 2
Ingredient (wt-%) (wt-%)
Water soluble magnesium salt 1-60 5-50
alkaline source 0-60 10-50
surfactant 0-20 0.5-15
bleaching agent 0-40 1-20
filler 0-20 3-15
defoaming agent 0-3 0.1-2
anti-deposition agent 0-10 1-5
stabilizing agent 0-15 2-10
dispersant 0-15 2-9
enzyme 0-10 1-5
water 0-90
[0062] In some embodiments, the warewashing detergent composition includes
a cleaning agent, an alkaline source, and water soluble magnesium salt.
The cleaning agent can comprise a detersive amount of a surfactant. The
alkaline source is provided in an amount effect to provide a use
composition having a pH of at least about 8 when measured at a
concentration of about 0.5 wt. %. The warewashing detergent composition
can be formulated to be combined with water of dilution at a dilution
ratio of dilution water to detergent composition of at least about 20:1.
The warewashing composition prior to dilution to provide the use
composition can be referred to as the warewashing composition concentrate
or more simply as the concentrate. The concentrate can be provided in
various forms including as a liquid or as a solid. Pastes and gels can be
considered types of liquid. Powders, agglomerates, pellets, tablets, and
blocks can be considered types of solid.
[0063] The warewashing composition, can be available for cleaning in
environments other than inside an automatic dishwashing or warewashing
machine. For example, the composition can be used as a pot and pan
cleaner for cleaning glass, dishes, etc. in a sink.
[0064] Hard Surface Cleaner
[0065] In some embodiments, the cleaning composition of the present
invention including water soluble magnesium salt can be a hard surface
cleaning composition. Table 2 describes ingredients for suitable hard
surface cleaners including water soluble magnesium salt.
TABLE-US-00002
TABLE 2
Hard Surface Cleaning Compositions
Hard Surface Hard Surface Hard Surface
Cleaner 1 Cleaner 2 Cleaner 3
Ingredient (wt-%) (wt-%) (wt-%)
Water soluble magnesium salt 1-60 5-50 10-40
nonionic surfactant 0-20 0.1-15 0.5-8
anionic surfactant 0-20 0.1-15 0.5-8
amphoteric surfactant 0-10 0.1-8 0.5-5
anti-redeposition agent 0-10 0.1-8 0.3-5
alkalinity source 0-60 0.5-25 1-20
thickener 0-5 0.1-4 0.5-3
organic solvent 0-20 0.1-15 0.5-10
antimicrobial agent 0-20 0.01-15 0.03-10
solidification agent 5-90 10-80 20-60
water balance balance balance
Hard Surface Hard Surface Hard Surface
Cleaner 4 Cleaner 5 Cleaner 6
Ingredient (wt-%) (wt-%) (wt-%)
Water soluble magnesium salt 1-60 5-50 10-40
nonionic surfactant 0-20 0.1-15 0.5-8
anionic surfactant 0-20 0.1-15 0.5-8
amphoteric surfactant 0-10 0.1-8 0.5-5
anti-redeposition agent 0-10 0.1-8 0.3-5
alkalinity source 0-60 0.5-25 1-20
thickener 0-5 0.1-4 0.5-3
organic solvent 0-20 0.1-15 0.5-10
antimicrobial agent 0-20 0.01-15 0.03-10
water balance balance balance
[0066] A hard surface cleaner can be configured to be diluted with water
to provide a use composition that can be used to clean hard surfaces.
Examples of hard surfaces include, but are not limited to: architectural
surfaces such as walls, showers, floors, sinks, mirrors, windows, and
countertops; transportation vehicles such as cars, trucks, buses, trains,
and planes; surgical or dental instruments; food processing equipment;
and washing equipment such as dishwashers or laundry machines.
[0067] Solid Cleaning Compositions
[0068] In some embodiments, the cleaning composition of the present
invention including water soluble magnesium salt can be a solid cleaning
composition. Table 3 describes ingredients for solid cleaning
compositions including water soluble magnesium salt.
TABLE-US-00003
TABLE 3
Solid Cleaning Compositions
Solid Cleaning Solid Cleaning
Composition 1 Composition 2
Ingredient (wt-%) (wt-%)
Water soluble magnesium 0-60 5-50
salt
Surfactant 0-40 1-20
solidifying agent 0-80 0-60
sodium hydroxide 0-60 30-40
alkali metal carbonate 0-60 30-55
water 0-50 0.1-30
binding agent 10-80 1-40
[0069] Shower Cleaner Composition
[0070] In some embodiments, the cleaning compositions of the present
invention including water soluble magnesium salt can be a shower cleaning
composition. Shower cleaning compositions can be employed for cleaning
shower surfaces such as plumbing fixtures, walls, glass shower doors, and
the like. Table 4 describes ingredients for shower cleaning compositions
including water soluble magnesium salt.
TABLE-US-00004
TABLE 4
Shower Cleaning Compositions
Shower Shower Shower
Cleaning Cleaning Cleaning
Composition 1 Composition 2 Composition 3
Ingredient (wt-%) (wt-%) (wt-%)
Water soluble 1-60 5-50 10-40
magnesium salt
sheeting agent/ 0-20 0.1-15 0.5-8
humectant
thickener 0-5 0.1-4 0.5-3
organic solvent 0-20 0.1-15 0.5-10
antimicrobial agent 0-20 0.01-15 0.03-10
solidification agent 5-90 10-80 20-60
water balance balance balance
Shower Shower Shower
Cleaning Cleaning Cleaning
Composition 4 Composition 5 Composition 6
Ingredient (wt-%) (wt-%) (wt-%)
Water soluble 1-60 5-50 10-40
magnesium salt
sheeting agent/ 0-20 0.1-15 0.5-8
humectant
thickener 0-5 0.1-4 0.5-3
organic solvent 0-20 0.1-15 0.5-10
antimicrobial agent 0-20 0.01-15 0.03-10
solidification agent 0-20 0.01-15 0.03-10
water balance balance balance
[0071] A shower cleaner composition can be formulated at a pH of about 6
to about 10 or about 7 to about 8. The formulations can be diluted with
water prior to use. Typically, the concentrates are diluted at a ratio of
at least 1 ounce per gallon of cleaning solution suitable for the end use
of cleaning a shower, but in some applications the concentrates are
suitable for end use without dilution, e.g. where heavy soil levels are
encountered.
[0072] Rinse Agent Composition
[0073] In some embodiments, the cleaning composition of the present
invention including water soluble magnesium salt can be a rinse agent
composition. Table 5 describes ingredients for rinse agent compositions
including water soluble magnesium salt.
TABLE-US-00005
TABLE 5
Rinse Agent Compositions
Rinse Agent Rinse Agent
Composition 1 Composition 2
Ingredient (wt-%) (wt-%)
water soluble magnesium salt 0-60 5-50
sheeting agent 1-90 3-50
humectant 0-90 3-50
water 0-90 3-50
solidification agent 0-90 20-50
defoamer 0-10 0.1-5
pH buffers To desired pH To desired pH
[0074] In some aspects, the compositions of the present invention comprise
a water soluble magnesium salt. In some embodiments, the compositions of
the present invention are free of, or substantially free of, chelating
agents, threshold agents, and/or sequestering agents. In some
embodiments, the compositions of the present invention comprise an
ingredient selected from the group consisting of a source of alkalinity,
a surfactant, and combinations thereof.
[0075] Water Soluble Magnesium Salts
[0076] Suitable water soluble magnesium compounds include those selected
from the group consisting 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 thiosulfate, a hydrate thereof, and
a mixture thereof. These salts can be provided as hydrated salts or
anhydrous salts.
[0077] 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 the group consisting of 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.
[0078] Water soluble magnesium compounds approved as GRAS for direct food
contact include magnesium chloride and magnesium sulfate.
[0079] Alkalinity Source
[0080] In some embodiments, the compositions of the present invention
further comprise one or more alkaline sources. The alkaline source can be
selected such that it enhances the cleaning of an article, and improves
the 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 the caustic based use
compositions.
[0081] The cleaning composition can include an alkali metal carbonate
and/or an alkali metal hydroxide as a suitable alkaline source. Suitable
metal carbonates that can be used include, for example, sodium carbonate,
potassium carbonate, lithium carbonate, sodium bicarbonate, potassium
bicarbonate, lithium bicarbonate, sodium sesquicarbonate, potassium
sesquicarbonate, lithium sesquicarbonate, and combinations thereof.
Suitable alkali metal hydroxides that can be used include, for example,
sodium hydroxide, lithium hydroxide, potassium hydroxide, and
combinations thereof. An alkali metal hydroxide can 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 12-100 U.S. mesh, or as an aqueous
solution, as for example, as a 50 wt-% and a 73 wt-% solution.
[0082] In some embodiments, the compositions of the present invention
comprise an alkaline source in an amount of at least about 5 wt-%, at
least about 10 wt-%, or at least about 15 wt-%. The cleaning compositions
can include about 10 to about 95 wt-%, about 20 to about 75 wt-%, or
about 25 to about 65 wt-% of a source of alkalinity. It is to be
understood that all ranges and values between these ranges and values are
encompassed by the present invention
[0083] In some embodiments, the alkaline source can be provided 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-%. In certain embodiments, it is expected
that the solid cleaning composition can provide a use composition that is
useful at pH levels below about 8. In such compositions, an alkaline
source can be omitted, and additional pH adjusting agents can be used to
provide the use composition with the desired pH. Accordingly, it should
be understood that the source of alkalinity can be characterized as an
optional component.
[0084] Secondary Alkalinity Sources
[0085] Compositions of the present invention can also include a secondary
alkaline source separate from the source of alkalinity discussed above.
The secondary source of alkaline can comprise about 0 to about 75 wt-%,
about 0.1 to about 70 wt-%, about 1 to about 25 wt-%, about 20 to about
60 wt-%, or about 30 to about 70 wt-% of the total composition.
[0086] Secondary alkalinity sources can include, for example, inorganic
alkalinity sources, such as an alkali metal hydroxide or silicate, or the
like. Suitable alkali metal hydroxides include, for example, sodium,
potassium, or lithium hydroxide. An alkali metal hydroxide may be added
to the composition in a variety of forms, including for example in the
form of solid beads, dissolved in an aqueous solution, or a combination
thereof. Examples of useful alkaline metal silicates include sodium,
potassium, or lithium silicate (with a M.sub.2O:SiO.sub.2 ratio of 1:1.8
to 5:1, M representing an alkali metal) or metasilicate.
[0087] Other sources of alkalinity include: a metal borate such as sodium
or potassium borate; ethanolamines and amines; and other like alkaline
sources.
[0088] Builder
[0089] In some embodiments, the compositions of the present invention
comprise about 0 to about 5 wt %, about 0 to about 4 wt %, or about 0 to
about 2 wt % of a builder. In other embodiments, the compositions of the
present invention are substantially free of a builder. If a builder is
included in the present cleaning composition, it is a builder that has a
higher chelation constant for calcium versus that of 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.
[0090] Threshold Agent
[0091] In some embodiments, the compositions of the present invention
comprise about 0 to about 5 wt %, about 0 to about 4 wt %, or about 0 to
about 2 wt % of a threshold agent. In other embodiments, the compositions
of the present invention are substantially free of a threshold agent. If
a threshold agent is included in the present cleaning composition, it is
preferred that it is a threshold agent, which inhibits or inhibits to a
greater extent the crystal growth of the calcite form of calcium
carbonate and not the aragonite form of calcium carbonate.
[0092] Chelating Agent or Sequestrant
[0093] The present composition can be substantially free of added
sequestrant or chelating agent or, even, free of added sequestrant or
chelating agent. Chelating agents or sequestrants include phosphonates,
phosphates, aminocarboxylates, polycarboxylates, and the like.
[0094] An ineffective amount of chelating agent or sequestrant will vary
with the hardness of the water and the dilution rate of a concentrate. In
an embodiment, for 17 grain hard water, an ineffective amount of a
chelating agent or sequestrant in a use composition can be less than
about 15 wt-%. This is based on a detergent used at a 1000 ppm
concentration and STPP as chelating agent/sequestrant. This 15 wt-% STPP
would chelate about 25% of the hardness ions present. One skilled in the
art will realize that the effective level of a chelating agent or
sequestrant will be dependent upon the chemical structure of the compound
and the dilution rate of the formulation containing it.
[0095] A typical warewash concentrate is diluted by about 500-fold to
about 2000-fold, which yields an ineffective amount of a chelating agent
or sequestrant in a it's concentrate of less than 15 wt-%. In an
embodiment, the ineffective amount is less than 5 wt-%. In an embodiment,
the ineffective amount is less than 1 wt-%.
[0096] Water
[0097] As used herein with respect to ingredients of the present
compositions, water refers to portable water as obtained from a municipal
or private water system, e.g., a public water supply or a well. The water
can be 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. 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. In general, hard water refers to water having a
level of calcium and magnesium ions in excess of about 100 ppm. 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.
[0098] Organic Surfactants or Cleaning Agents
[0099] In some embodiments, 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.
[0100] 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.
[0101] Additional suitable nonionic surfactants having a polyalkylene
oxide polymer portion include nonionic surfactants of C6-C24 alcohol
ethoxylates (e.g., C6-C14 alcohol ethoxylates) having 1 to about 20
ethylene oxide groups (e.g., about 9 to about 20 ethylene oxide groups);
C6-C24 alkylphenol ethoxylates (e.g., C8-C10 alkylphenol ethoxylates)
having 1 to about 100 ethylene oxide groups (e.g., about 12 to about 20
ethylene oxide groups); C6-C24 alkylpolyglycosides (e.g., C6-C20
alkylpolyglycosides) having 1 to about 20 glycoside groups (e.g., about 9
to about 20 glycoside groups); C6-C24 fatty acid ester ethoxylates,
propoxylates or glycerides; and C4-C24 mono or dialkanolamides.
[0102] 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.
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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).
[0107] 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 sodium
dodecylbenzene sulfonic acid, potassium laureth-7 sulfate, and sodium
tetradecenyl sulfonate.
[0108] The surfactant can be present at amounts of about 0 to about 20
wt-% about 0.1 to about 10 wt-%, about 0.2 to about 5 wt-%.
Additional Ingredients
[0109] In some embodiments, the compositions of the present invention
further comprise an additional ingredient. Additional ingredients
suitable for use with the compositions of the present invention include,
but are not limited to, detersive polymers, rinse aid compositions,
softeners, source of acidity, anti-corrosion agent, detergent filler,
defoamer, anti-redeposition agent, antimicrobial, aesthetic enhancing
agent, e.g., dye, odorant, perfume, optical brightener, lubricant
composition, bleaching agent, enzyme, effervescent agent, activator for
the source of alkalinity, calcium salt, and/or other such additives or
functional ingredients.
[0110] The additional ingredient or ingredients will vary according to the
type of composition being manufacture, and the intended end use of the
composition. In some embodiments, the composition includes as an additive
one or more of cleaning enzyme, detersive polymer, antimicrobial,
activators for the source of alkalinity, or mixtures thereof.
[0111] pH Modifier
[0112] The pH modifier can be an organic or inorganic source of alkalinity
or a pH buffering agent. Nonlimiting examples include the alkali metal
hydroxides, alkali metal carbonates, alkanolamines, salts of weak organic
acids, etc. Suitable pH modifiers include sodium hydroxide, lithium
hydroxide, potassium hydroxide, calcium hydroxide, 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.
[0113] The pH modifier can be present at amounts of about 0 to about 60
wt-% about 0.5 to about 25 wt-%, about 1 to about 20 wt-%,
[0114] Processing Aid
[0115] Processing aids are materials which enhance the production process
for the detergent composition. 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 would of course vary with the manufacturing procedure
and specific detergent composition.
[0116] The processing aid can be present at amounts of about 1 to about 70
wt-% about 2 to about 50 wt-%, about 3 to about 30 wt.
[0117] Active Oxygen Compounds
[0118] 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.
[0119] 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.
[0120] The active oxygen compound can be in the present solid composition
at amounts of about 0 to about 25 wt-% peroxygen compounds, and peroxygen
compound adducts, about 2 to about 15 wt-% peroxygen compounds, and
peroxygen compound adducts, or about 5 wt-% to about 12 wt-% peroxygen
compounds, and peroxygen compound adducts.
[0121] Inorganic Active Oxygen Compound
[0122] 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:
hydrogen peroxide; group 1 (IA) active oxygen compounds, for example
lithium peroxide, sodium peroxide, and the like; group 2 (IIA) active
oxygen compounds, for example magnesium peroxide, calcium peroxide,
strontium peroxide, barium peroxide, and the like; group 12 (IIB) active
oxygen compounds, for example zinc peroxide, and the like; 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; 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; 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; 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; group VIIa
active oxygen compounds such as sodium periodate, potassium perchlorate
and the like.
[0123] Other active inorganic oxygen compounds can include transition
metal peroxides; and other such peroxygen compounds, and mixtures
thereof.
[0124] 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 to about 40 wt-% hydrogen
peroxide or 5 to 50 wt-% hydrogen peroxide.
[0125] 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.
[0126] Organic Active Oxygen Compound
[0127] 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.
[0128] 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.
[0129] 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.
[0130] Active Oxygen Compound Adducts
[0131] 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.
[0132] Antimicrobials
[0133] 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.
[0134] 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.
[0135] 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.
[0136] Common antimicrobial agents include phenolic antimicrobials such as
pentachlorophenol, orthophenylphenol, a chloro-p-benzylphenol,
p-chloro-m-xylenol. Halogen containing antibacterial agents include
sodium trichloroisocyanurate, sodium dichloro isocyanate (anhydrous or
dihydrate), iodine-poly(vinylpyrrolidinone) 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, 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 0.001 to 75 wt-% of the composition, about 0.01 to 20 wt-%,
or about 0.05 to about 10 wt-%.
[0137] If present in compositions, the additional antimicrobial agent can
be about 0.01 to about 15 wt-% of the composition, 0.05 to about 10 wt-%,
or about 0.1 to about 5 wt-%. In a use solution the additional
antimicrobial agent can be about 0.001 to about 5 wt-% of the
composition, about 0.01 to about 2 wt-%, or about 0.05 to about 0.5 wt-%.
[0138] Activators
[0139] 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.
[0140] 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 to
about 10 wt-% of the composition.
[0141] In an embodiment, the activator for the source of alkalinity
combines with the active oxygen to form an antimicrobial agent.
[0142] 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.
[0143] 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.
[0144] Rinse Aid Functional Materials
[0145] 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 a 1 wt-% aqueous
solution of the surfactant turns cloudy when warmed.
[0146] 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 60.degree. C. or
higher, 70.degree. C. or higher, 80.degree. C. or higher, etc., depending
on the use locus hot water temperature and the temperature and type of
rinse cycle.
[0147] 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 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.
[0148] 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 10 to 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 15 to 175 and each end are independently
integers of about 10 to 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.
[0149] 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.
[0150] The rinse aid functional material can be in the present solid
composition at amounts of about 0 to about 75 wt-%, about 2 to about 50
wt-%, or about 5 wt-% to about 40 wt-%.
[0151] Additional Bleaching Agents
[0152] 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.
[0153] 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 0-10 wt-% or about 1-6 wt-%.
The present solid compositions can include bleaching agent in an amount
of about 0 to about 60 wt-% about 1 to about 20 wt-%, about 3 to about 8
wt-% or about 3 to about 6 wt-%.
[0154] Hardening Agents
[0155] The detergent 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 detergent composition
during use.
[0156] The amount of hardening agent included in the detergent composition
will vary according to factors including, but not limited to: the type of
detergent composition being prepared, the ingredients of the detergent
composition, the intended use of the detergent 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 detergent 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 solid detergent 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.
[0157] 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.
[0158] 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 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% to
about 75% by weight and particularly about 3% to about 15% by weight.
Suitable polyethylene glycol compounds include, but are not limited to:
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.
[0159] Particular inorganic hardening agents are hydratable inorganic
salts, including, but not limited to: sulfates, acetates, and
bicarbonates. In an exemplary embodiment, the inorganic hardening agents
are present at concentrations of up to about 50% by weight, particularly
about 5% to about 25% by weight, and more particularly about 5% to about
15% by weight.
[0160] 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% to about 90% by weight urea, particularly
between about 8% and about 40% by weight urea, and more particularly
between about 10% and about 30% by weight urea.
[0161] 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.
[0162] Secondary Hardening Agents/Solubility Modifiers.
[0163] 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 about 0 to about 20 wt-% or about 10 to about 15 wt-%.
[0164] Detergent Fillers
[0165] 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 50 wt-%, of
about 1 to about 20 wt-% about 3 to about 15 wt-%, about 1 to about 30
wt-%, or about 1.5 to about 25 wt-%.
[0166] Defoaming Agents
[0167] An effective amount of a defoaming agent for reducing the stability
of foam may also be included in the present cleaning compositions. The
cleaning composition can include about 0-10 wt-% of a defoaming agent,
e.g., about 0.01-3 wt-%. The defoaming agent can be provided in an amount
of about 0.0001% to about 10 wt-% about 0.001% to about 5 wt-%, or about
0.01% to about 1.0 wt-%
[0168] 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.
[0169] Anti-Redeposition Agents
[0170] A cleaning 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 to about 10 wt-%, e.g., about 1
to about 5 wt-% of an anti-redeposition agent.
[0171] Optical Brighteners
[0172] 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.
[0173] 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.
[0174] 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.
[0175] 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.
[0176] For laundry cleaning or sanitizing compositions, suitable optical
brighteners include stilbene derivatives, which can be employed at
concentrations of up to 1 wt-%.
[0177] Stabilizing Agents
[0178] The solid detergent 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. Suitable ranges of the stabilizing agent include up to about
20 wt-%, about 0.5 to about 15 wt-%, or about 2 to about 10 wt-%.
[0179] Dispersants
[0180] The solid detergent 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-%, about 0.5 to about 15 wt-%, or about 2 to about 9 wt-%.
[0181] Enzymes
[0182] Enzymes that can be included in the solid detergent composition
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-%, about 0.5 to about 10 wt-%, or about 1 to about 5 wt-%.
[0183] Thickeners
[0184] The solid detergent 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.
[0185] 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.
[0186] 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.
[0187] 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.
[0188] 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).
[0189] 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.
[0190] 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.
[0191] The thickener can be in the present solid composition at amounts of
about 0 to about 10 wt-%, about 0.5 to about 5 wt-%, or about 1 wt-% to
about 3 wt-%.
[0192] Dyes/Odorants
[0193] 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.
[0194] 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.
[0195] The dye or odorant can be in the present solid composition at
amounts of about 0 to about 4 wt-%, about 0.1 to about 1 wt-%,
[0196] 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 cleaning enzyme, detersive polymer,
antimicrobial, activators for the source of alkalinity, or mixtures
thereof.
Use Compositions
[0197] The compositions of the present invention comprising water soluble
magnesium salt can be provided in the form of a concentrate or a use
solution. 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, rising, or the like. In an
embodiment, when the composition is provided as a concentrate, the
concentrate includes between about 100 parts per million (ppm) to about
5000 ppm cleaning composition including water soluble magnesium salt. 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 at about 0 to about
0.75 wt-%.
[0198] 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. 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. In an embodiment, when
the detergent composition is provided as a use solution, the use solution
includes about 0.1 to about 200 ppm cleaning composition including water
soluble magnesium salt or about 1 to about 100 ppm cleaning composition
including water soluble magnesium salt. In an embodiment, the use
solution includes about 3 to about 75 ppm cleaning composition including
water soluble magnesium salt.
[0199] The concentrate may be diluted with water at the location of use to
provide the use solution. When the detergent 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 detergent 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
detergent may be provided in a unit dose form or in a multi-use form. In
larger warewashing machines, a large quantity of detergent composition
may be provided in a compartment that allows for the release of a single
dose amount of the detergent 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 detergent 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.
[0200] The detergent 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 detergent composition to dissolve a
portion of the detergent 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 detergent composition.
[0201] Solid Cleaning Compositions
[0202] In some embodiments, the present invention also relates to solid
cleaning compositions comprising water soluble magnesium salt. For
example, the present invention includes a cast solid block of the
cleaning composition including water soluble magnesium salt. By way of
further example, the present invention includes compositions comprising a
pressed solid block or puck of the cleaning composition comprising water
soluble magnesium salt.
[0203] According to the present invention, a solid cleaning composition
comprising water soluble magnesium salt can be prepared by a method
including: providing a powder or crystalline form of cleaning composition
including water soluble magnesium salt; melting the powder or crystalline
form of the cleaning composition including water soluble magnesium salt;
transferring the molten cleaning composition including water soluble
magnesium salt into a mold; and cooling the molten composition to
solidify it.
[0204] According to the present invention, a solid cleaning composition
comprising water soluble magnesium salt can be prepared by a method
including: providing a powder or crystalline form of a cleaning
composition including water soluble magnesium salt; gently pressing the
calcium magnesium gluconate to form a solid (e.g., block or puck).
[0205] 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. 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 120.degree. F.
[0206] 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.
[0207] 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 10 kg. In certain embodiments, a multiple-use form of the solid
cleaning composition has a mass of about 1 to 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 500 g.
[0208] Packaging System
[0209] 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.
[0210] 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.
[0211] Suitable packaging used to contain the compositions is manufactured
from a flexible, easy opening film material.
[0212] Dispensing of the Processed Compositions
[0213] The solid cleaning composition according to the present invention
can be dispensed in any suitable method generally known. The cleaning or
rinsing 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.
[0214] 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
[0215] 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
[0216] It is contemplated that the cleaning compositions of the invention
can be used in a broad variety of industrial, household, health care,
vehicle care, and other such applications. Some examples include surface
disinfectant, ware cleaning, laundry cleaning, laundry sanitizing,
vehicle cleaning, floor cleaning, surface cleaning, pre-soaks, clean in
place, and a broad variety of other such applications.
[0217] In some embodiments, 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.
[0218] In some aspects, the present invention relates to a method of
cleaning an object, comprising contacting the object with an aqueous
composition comprising water, a water soluble magnesium salt, and an
ingredient selected from the group consisting of source of alkalinity,
and surfactant, and a mixture thereof. This composition can be
substantially free of chelating agents and/or threshold agents.
[0219] During contacting, the aqueous composition can include magnesium
ion in a molar amount equal to or in excess over a molar amount of
calcium ion. The method can also include recovering the object with an
acceptable amount of hard water spotting, scaling, or deposits. As used
herein, an acceptable amount of hard water spotting in a warewash test,
refers to a test method were the results are good for a rating of 1-2
marginal at a rating of 3 and fail for 4-5. The table below summarizes
the rating system used.
TABLE-US-00006
Rating Spots Film
1 No spots No film
2 1/4 glass spotted Trace/barely perceptible
3 1/2 glass spotted Slight film
4 3/4 glass spotted Moderate film
5 Whole glass spotted Heavy film
[0220] The method can reduce any of a variety of detrimental effects of
hard water. In an embodiment, the method can reduce precipitation of
calcium salt. In an embodiment, the method can reduce scaling.
[0221] In an embodiment, the aqueous composition containing excess calcium
ion contains at least about 50 ppm calcium ion, e.g. at least about 5
grain per gallon of hardness due to calcium ion. In an embodiment of this
method, adding includes adding the water soluble magnesium compound to
achieve a total wt-% of magnesium ion of about half the wt-% of calcium
ion. For example, at least about 2 grains of total magnesium ion for
water containing 5 grains of calcium ion as water hardness. In an
embodiment of this method, adding includes adding water soluble magnesium
compound including an anion that forms a soluble salt with calcium (e.g.,
MgCl.sub.2) to achieve a total wt-% of magnesium ion of greater than
about half the wt-% of calcium ion (which is about a 1:1 molar ratio). In
an embodiment of this method, adding includes adding water soluble
magnesium compound including an anion that forms an insoluble salt with
calcium (e.g., MgSO.sub.4) to achieve a total wt-% of magnesium ion of
about the wt-% of calcium ion (which is about a 2:1 molar ratio).
[0222] 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. The compositions can be
applied in a variety of areas including kitchens, bathrooms, factories,
hospitals, dental offices and food plants, and can be applied to a
variety of hard surfaces having smooth, irregular or porous topography. A
use concentration of a composition of the present invention can be
applied to or brought into contact with an object 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.
[0223] Exemplary articles that can be treated, i.e., cleaned, with the use
solution comprising a detersive composition and treated water include,
but are not limited to motor vehicle exteriors, textiles, food contacting
articles, clean-in-place (CIP) equipment, health care surfaces and hard
surfaces. Exemplary motor vehicle exteriors include cars, trucks,
trailers, buses, etc. that are commonly washed in commercial vehicle
washing facilities. Exemplary textiles include, but are not limited to,
those textiles that generally are considered within the term "laundry"
and include clothes, towels, sheets, etc. In addition, textiles include
curtains. Exemplary food contacting articles include, but are not limited
to, dishes, glasses, eating utensils, bowls, cooking articles, food
storage articles, etc. Exemplary CIP equipment includes, but is not
limited to, pipes, tanks, heat exchangers, valves, distribution circuits,
pumps, etc. Exemplary health care surfaces include, but are not limited
to, surfaces of medical or dental devices or instruments. Exemplary hard
surfaces include, but are not limited to, floors, counters, glass, walls,
etc. Hard surfaces can also include the inside of dish machines, and
laundry machines. In general, hard surfaces can include those surfaces
commonly referred to in the cleaning industry as environmental surfaces.
Such hard surfaces can be made from a variety of materials including, for
example, ceramic, metal, glass, wood or hard plastic.
[0224] The present invention may be better understood with reference to
the following examples. These examples are intended to be representative
of specific embodiments of the invention, and are not intended as
limiting the scope of the invention.
EXAMPLES
Example 1
Water Soluble Magnesium Compounds Reduce Precipitation of Calcium Salts
from Hard Water
[0225] This Example demonstrates that adding a hardness ion (Mg.sup.2+) to
water worked as well as a conventional chelating agent or sequestrant
(sodium tripolyphosphate (STPP)) at preventing precipitation of calcium
salts.
[0226] Formation of a precipitate in water reduces the transmission of
visible light through the water. A transmittance of 100% indicates that
no precipitate formed, while a transmittance of 0% indicates that so much
precipitate formed that light no longer passed through the sample.
Transmittance was measured for water containing either MgCl.sub.2
(present invention) or STPP (comparative example) at pH values of about
8, about 10, and about 12, and at temperatures of about 20.degree. C.,
about 45.degree. C., and about 70.degree. C. Temperatures were chosen in
an attempt to reflect room temperature (20.degree. C.), general laundry
temperature (45.degree. C.) and general automatic warewashing temperature
(70.degree. C.). The results are reported in FIGS. 1-6 and the Tables
below.
[0227] The graphs in FIGS. 1-6, which each have an x, y, and z axis. The
x-axis is a measure of the molar ratio of calcium to builder, e.g., STPP
or water soluble magnesium compound. The y-axis is a measure of the level
of light transmittance thru the samples with 0% being no light
transmitted and 100% being the entire beam of light transmitted. Full or
partial loss of transmittance occurs as a consequence of the presence of
particulate formation in the initially clear samples. An effective
builder prevents or reduces precipitation resulting in a clear sample.
The z-axis is a measure of the test temperature, ranging from
20-60.degree. C.
[0228] FIG. 1 is illustrative of a comparative example. FIG. 1 is a plot
of the performance of STPP as a builder in the presence of various levels
of calcium, at various temperatures, and at a constant pH of 8 and
illustrating the impact of Ca/builder ratio and temperature on the
building performance of STPP. Data for FIG. 1 is provided in the table
below (Table 6). Generally, the plot of FIG. 1 shows that STPP is a good
chelating agent and as expected as the concentration of calcium ions
increases and as the temperature increases, STPP has decreasing
effectiveness in chelating calcium ions as reflected in the reduction in
the transmittance of the samples.
TABLE-US-00007
TABLE 6
% Ca/STPP Ca/STPP
pH T (C.) ppm CaCO3 Transmittance (wt) (molar)
8 20 50 100 0.07 0.61
8 20 300 81.1 0.40 3.68
8 20 600 67.4 0.80 7.36
8 45 50 99.2 0.07 0.61
8 45 300 72.6 0.40 3.68
8 45 600 64.1 0.80 7.36
8 70 50 99.1 0.07 0.61
8 70 300 41.3 0.40 3.68
8 70 600 41.5 0.80 7.36
[0229] FIG. 2 is illustrative of the invention. FIG. 2 is a plot of the
performance of magnesium chloride in preventing precipitation in the
presence of various levels of calcium, at various temperatures, and at a
constant pH of 8. Data for FIG. 2 is provided in the table below (Table
7). This graph shows that a water soluble salt of magnesium (e.g.,
magnesium chloride) was unexpectedly capable of controlling the
precipitation of water hardness even at a neutral pH. Generally, the plot
of FIG. 2 shows that magnesium chloride is a good chelating agent and as
the concentration of calcium ions increases and as the temperature
increases, magnesium chloride has decreasing effectiveness in chelating
calcium ions as reflected in the reduction in the transmittance of the
samples. The results shown in FIG. 2 are surprisingly consistent with
that shown in the comparative FIG. 1.
TABLE-US-00008
TABLE 7
% Ca/MgCl.sub.2
pH T (C.) ppm CaCO3 Transmittance Ca/MgCl.sub.2 (wt) (molar)
8 20 50 98.1 0.07 0.32
8 20 300 91.1 0.40 1.90
8 20 600 48 0.80 3.81
8 45 50 96.2 0.07 0.32
8 45 300 92.3 0.40 1.90
8 45 600 55.8 0.80 3.81
8 70 50 96.3 0.07 0.32
8 70 300 92.3 0.40 1.90
8 70 600 50.9 0.80 3.81
[0230] FIG. 3 is a plot illustrative of a comparative example. FIG. 3
shows the performance of STPP as a builder in the presence of various
levels of calcium, at various temperatures, and at a constant pH of 10.
Data for FIG. 3 is provided in the table below (Table 8). A comparison of
this graph with the results obtained at pH 8 (FIG. 1) shows that the
increased alkalinity gives reduced building performance at elevated
temperatures, particularly around 60.degree. C.
TABLE-US-00009
TABLE 8
Ppm % Ca/STPP
pH Temp (.degree. C.) CaCO.sub.3 Transmittance Ca/STTP (wt) (molar)
10 20 50 99.7 0.07 0.61
10 20 300 70.6 0.40 3.68
10 20 600 51.2 0.80 7.36
10 45 50 98.5 0.07 0.61
10 45 300 49.9 0.40 3.68
10 45 600 36.8 0.80 7.36
10 70 50 98.2 0.07 0.61
10 70 300 22.4 0.40 3.68
10 70 600 26 0.80 7.36
[0231] FIG. 4 is a plot illustrative of the invention. FIG. 4 shows the
performance of magnesium chloride in preventing precipitation in the
presence of various levels of calcium, at various temperatures, and at a
constant pH of 10. Data for FIG. 4 is provided in the table below (Table
9). This graph shows that a water soluble salt of magnesium (e.g.,
magnesium chloride) was unexpectedly capable of controlling the
precipitation of water hardness even at a basic pH. The increased
alkalinity did not significantly affect the degree of calcium
precipitation compared to pH 8 (FIG. 2). This is unexpected.
TABLE-US-00010
TABLE 9
% Ca/MgCl.sub.2
pH T (.degree. C.) ppm CaCO3 Transmittance Ca/MgCl.sub.2 (wt) (molar)
10 20 50 97.4 0.07 0.32
10 20 300 87.8 0.40 1.90
10 20 600 37.6 0.80 3.81
10 45 50 96.5 0.07 0.32
10 45 300 81.1 0.40 1.90
10 45 600 35.4 0.80 3.81
10 70 50 86.1 0.07 0.32
10 70 300 72.4 0.40 1.90
10 70 600 38.1 0.80 3.81
10 45 300 79.9 0.40 1.90
10 45 300 82 0.40 1.90
10 45 300 81.4 0.40 1.90
[0232] FIG. 5 is a plot illustrative of a comparative example. FIG. 5
shows the performance of STPP as a builder in the presence of various
levels of calcium, at various temperatures, and at a constant pH of 12.
Data for FIG. 5 is provided in the table below (Table 10). This graph
shows that STPP has quit working to control calcium precipitation at
molar ratios of 4 Ca/STPP and higher with light transmittance dropping
down to about 20%. Once again, elevated temperatures make the STPP system
more sensitive to water hardness.
TABLE-US-00011
TABLE 10
Ppm % Ca/STPP
pH Temp(.degree. C.) CaCO.sub.3 Transmittance Ca/STTP (wt) (molar)
12 20 50 98.8 0.07 0.61
12 20 300 35.4 0.40 3.68
12 20 600 25.5 0.80 7.36
12 45 50 99.2 0.07 0.61
12 45 300 26.4 0.40 3.68
12 45 600 19.7 0.80 7.36
12 70 50 100 0.07 0.61
12 70 300 20.3 0.40 3.68
12 70 600 13.4 0.80 7.36
[0233] FIG. 6 is illustrative of the invention. The data for FIG. 6 is
shown in the table below (Table 11). FIG. 6 shows a plot of the
performance of magnesium chloride in preventing precipitation in the
presence of various levels of calcium, at various temperatures, and at a
constant pH of 12. A comparison of this graph with FIG. 5 shows that
under very alkaline conditions a water soluble magnesium compound such as
magnesium chloride is comparable to STPP in controlling water hardness
TABLE-US-00012
TABLE 11
% Ca/MgCl.sub.2
pH T (.degree. C.) ppm CaCO3 Transmittance Ca/MgCl.sub.2 (wt) (molar)
12 20 50 78.9 0.07 0.32
12 20 300 65.9 0.40 1.90
12 20 600 30.9 0.80 3.81
12 45 50 69 0.07 0.32
12 45 300 57.6 0.40 1.90
12 45 600 27.6 0.80 3.81
12 70 50 62.9 0.07 0.32
12 70 300 51.1 0.40 1.90
12 70 600 24.7 0.80 3.81
[0234] As can be seen in FIGS. 1-6, magnesium chloride matched or exceeded
the ability of STPP to soften water under most conditions. By matched or
exceeded the ability we mean that the magnesium chloride reduced lime
scale (as reflected by percent transmittance) to a level comparable to or
lower than that achieved with STPP, e.g., for most molar ratios of
calcium and builder. In particular, the performance of magnesium chloride
at pH values of 8 and 10 exceeded the performance of STPP at all
temperature values.
[0235] At a pH value of 12, magnesium chloride started at about 80%
transmittance, but had a lower slope compared to STPP. The lower slope
indicates better control of water hardness precipitation as the ratio of
calcium/builder increased.
[0236] The data obtained for sodium citrate with water soluble magnesium
salt is shown in the Table below and in FIGS. 7-9.
TABLE-US-00013
TABLE 12
%
Water Hardness Transmittance Builder pH
Temperature: 20.degree. C.
50 100.0 3 citrate/1 Mg* 8
300 100 3 citrate/1 Mg* 8
600 99.5 3 citrate/1 Mg* 8
50 99.0 citrate 8
300 72.6 citrate 8
600 90.8 citrate 8
600 48 Mg 8
300 91.1 Mg 8
50 98.1 Mg 8
50 100.0 3 citrate/1 Mg 10
300 100 3 citrate/1 Mg 10
600 82.1 3 citrate/1 Mg 10
50 99.2 citrate 10
300 53.4 citrate 10
600 91.1 citrate 10
50 97.4 Mg 10
300 87.8 Mg 10
600 37.6 Mg 10
50 99.8 3 citrate/1 Mg 12
300 60.7 3 citrate/1 Mg 12
600 27.6 3 citrate/1 Mg 12
50 99.5 citrate 12
300 42.7 citrate 12
600 20 citrate 12
50 78.9 Mg 12
300 65.9 Mg 12
600 30.9 Mg 12
Temperature: 50.degree. C.
50 99.0 3 citrate/1 Mg 8
300 100 3 citrate/1 Mg 8
600 95.7 3 citrate/1 Mg 8
50 99.1 citrate 8
300 64.2 citrate 8
600 91.1 citrate 8
50 96.2 Mg 8
300 92.3 Mg 8
600 55.8 Mg 8
50 100.0 3 citrate/1 Mg 10
300 87 3 citrate/1 Mg 10
600 69.1 3 citrate/1 Mg 10
50 95.8 citrate 10
300 50.9 citrate 10
600 68.5 citrate 10
50 96.5 Mg 10
300 81.1 Mg 10
600 35.4 Mg 10
50 98.3 3 citrate/1 Mg 12
300 31.9 3 citrate/1 Mg 12
600 24.2 3 citrate/1 Mg 12
50 97.4 citrate 12
300 37.3 citrate 12
600 17.5 citrate 12
50 69.0 Mg 12
300 57.6 Mg 12
600 27.6 Mg 12
Temperature: 70.degree. C.
50 98.1 3 citrate/1 Mg 8
300 99.8 3 citrate/1 Mg 8
600 96.4 3 citrate/1 Mg 8
50 99.0 citrate 8
300 50.6 citrate 8
600 91.1 citrate 8
50 96.3 Mg 8
300 92.3 Mg 8
600 50.9 Mg 8
50 99.1 3 citrate/1 Mg 10
300 60.8 3 citrate/1 Mg 10
600 68.5 3 citrate/1 Mg 10
50 95.5 citrate 10
300 35.2 citrate 10
600 68 citrate 10
50 86.1 Mg 10
300 72.4 Mg 10
600 38.1 Mg 10
50 96.3 3 citrate/1 Mg 12
300 27.3 3 citrate/1 Mg 12
600 22.7 3 citrate/1 Mg 12
50 98.7 citrate 12
300 28.1 citrate 12
600 14.2 citrate 12
50 62.9 Mg 12
300 51.1 Mg 12
600 24.7 Mg 12
[0237] FIG. 7 is a plot of the performance of sodium citrate as a builder
in the presence of various levels of calcium, at various temperatures,
and at a constant pH of 8 and illustrating the impact of Ca/builder ratio
and temperature on the building performance of STPP.
[0238] FIG. 8 is a plot of the performance of sodium citrate as a builder
in the presence of various levels of calcium, at various temperatures,
and at a constant pH of 10. A comparison of this graph with the results
obtained at pH 8 (FIG. 7) shows that the increased alkalinity gives
reduced building performance at elevated temperatures, particularly
around 60.degree. C.
[0239] FIG. 9 is a plot of the performance of sodium citrate as a builder
in the presence of various levels of calcium, at various temperatures,
and at a constant pH of 12. This graph shows that sodium citrate is an
effective builder under most conditions but is adversely affected by high
pH and temperature. Once again elevated temperatures make the sodium
citrate system more sensitive to water hardness.
[0240] FIGS. 10-12 illustrate the results of experiments conducted to
determine the level of calcium precipitation in the presence of
MgCl.sub.2 when the composition also included calcium chloride, sodium
hydroxide, or sodium carbonate.
[0241] FIG. 10 illustrates the results of experiments conducted to
determine the impact of a water soluble alkali metal hydroxide such as
sodium hydroxide on the precipitation of water hardness ions (e.g.,
Ca.sup.2 and Mg.sup.2+). Table 13 shows the component compositions and
clarity grade for each composition.
TABLE-US-00014
TABLE 13
MgCl.sub.2 (ppm) CaCl.sub.2 (ppm) NaOH (ppm) clarity
600.00 0.00 0.00 0.0
450.00 150.00 0.00 0.0
300.00 300.00 0.00 0.0
150.00 450.00 0.00 0.0
0.00 600.00 0.00 0.0
0.00 0.00 600.00 0.0
150.00 0.00 450.00 2.0
300.00 0.00 300.00 0.0
450.00 0.00 150.00 0.0
0.00 150.00 450.00 0.0
0.00 300.00 300.00 0.0
0.00 450.00 150.00 0.0
300.00 150.00 150.00 0.0
150.00 300.00 150.00 0.0
150.00 150.00 300.00 0.0
450.00 75.00 75.00 0.0
75.00 450.00 75.00 0.0
75.00 75.00 450.00 0.0
200.00 200.00 200.00 0.0
FIG. 10 shows a ternary graph illustrating clarity as a function of the
concentrations of water soluble magnesium salt (e.g., MgCl2), water
soluble calcium salt (e.g., CaCl2), and source of alkalinity (e.g.,
sodium hydroxide). The ternary graph was produced by entering the data
from Table 1.10 into a statistical program, Design Expert, version
6.0.11, available from Stat Ease, Minneapolis, Minn. The graph shows that
the presence of sodium hydroxide did not cause significant precipitation
of water hardness ions under the test conditions.
[0242] FIG. 11 illustrates the results of experiments conducted to
determine the impact of a water soluble alkali metal carbonate such as
sodium carbonate on the precipitation of water hardness ions (e.g.,
Ca.sup.2 and Mg.sup.2+). Table 14 shows the component compositions and
clarity grade for each composition.
TABLE-US-00015
TABLE 14
MgCl.sub.2 (ppm) CaCl.sub.2 (ppm) NaOH (ppm) clarity
600.00 0.00 0.00 0.0
450.00 150.00 0.00 0.0
300.00 300.00 0.00 0.0
150.00 450.00 0.00 0.0
0.00 600.00 0.00 0.0
0.00 0.00 600.00 0.0
150.00 0.00 450.00 0.0
300.00 0.00 300.00 0.0
450.00 0.00 150.00 0.0
0.00 150.00 450.00 2.0
0.00 300.00 300.00 2.0
0.00 450.00 150.00 2.0
300.00 150.00 150.00 0.0
150.00 300.00 150.00 0.0
150.00 150.00 300.00 2.0
450.00 75.00 75.00 0.0
75.00 450.00 75.00 0.0
75.00 75.00 450.00 0.0
200.00 200.00 200.00 2.0
[0243] FIG. 11 shows a ternary graph illustrating clarity as a function of
the concentrations of water soluble magnesium salt (e.g., MgCl2), water
soluble calcium salt (e.g., CaCl2), and source of alkalinity (e.g. sodium
carbonate). The ternary graph was produced by entering the data from
Table 14 into a statistical program, Design Expert, version 6.0.11,
available from Stat Ease, Minneapolis, Minn. The graph shows that the
presence of sodium carbonate caused significant precipitation under the
conditions of the test.
[0244] FIG. 12 illustrates the results of experiments conducted to
determine the impact of a water soluble alkali metal hydroxide such as
sodium hydroxide and a water soluble alkali metal carbonate such as
sodium carbonate on the precipitation of water hardness ions (e.g.,
Ca.sup.2+ and Mg.sup.2+). Table 15 shows the component compositions and
clarity grade for each composition.
TABLE-US-00016
TABLE 15
Na.sub.2CO.sub.3/1
MgCl.sub.2 (ppm) CaCl.sub.2 (ppm) NaOH (ppm) clarity
600.00 0.00 0.00 0.0
450.00 150.00 0.00 0.0
300.00 300.00 0.00 0.0
150.00 450.00 0.00 0.0
0.00 600.00 0.00 0.0
0.00 0.00 600.00 0.0
150.00 0.00 450.00 2.0
300.00 0.00 300.00 2.0
450.00 0.00 150.00 0.0
0.00 150.00 450.00 2.0
0.00 300.00 300.00 2.0
0.00 450.00 150.00 0.0
300.00 150.00 150.00 1.0
150.00 300.00 150.00 1.0
150.00 150.00 300.00 3.0
450.00 75.00 75.00 0.0
75.00 450.00 75.00 0.0
75.00 75.00 450.00 3.0
200.00 200.00 200.00 0.0
[0245] FIG. 12 shows a ternary graph illustrating clarity as a function of
the concentrations of water soluble magnesium salt (e.g., MgCl.sub.2),
water soluble calcium salt (e.g., CaCl.sub.2), and source of alkalinity
(e.g. sodium carbonate and sodium hydroxide). The ternary graph was
produced by entering the data from Table 15 into a statistical program,
Design Expert, version 6.0.11, available from Stat Ease, Minneapolis,
Minn. The graph shows that the presence of sodium carbonate caused
significant precipitation under the conditions of the test.
[0246] Comparing FIG. 12 to FIGS. 10 and 11 indicates that the presence of
a combination of water soluble alkali metal hydroxide plus water soluble
alkali metal carbonate was unexpectedly worse than either alkalinity
source alone in causing water hardness ions to precipitate.
[0247] As can be seen in FIGS. 1-9, magnesium chloride matched or exceeded
the ability of STPP to soften water under most conditions. By matched or
exceeded the ability we mean that the magnesium chloride reduced scale
(as reflected by percent transmittance) to a level comparable to or lower
than that achieved with STPP, e.g., for most molar ratios of calcium and
builder. In particular, the performance of magnesium chloride at pH
values of 8 and 10 exceeded the performance of STPP at all temperature
values.
[0248] At a pH value of 12, magnesium chloride started at about 80%
transmittance, but had a lower slope compared to STPP. The lower slope
indicates better control of water hardness precipitation as the ratio of
calcium/builder increased.
[0249] The results of experiments conducted to determine the level of
calcium precipitation in the presence of MgCl.sub.2 when the composition
also included calcium chloride, sodium hydroxide, or sodium carbonate are
illustrated in FIGS. 10-12. These Figures show that magnesium compounds
(e.g., MgCl.sub.2) acted in a synergistic manner with chelating
hydroxyacids and their salts. In particular, these ternary graphs that
MgCl.sub.2 prevented calcium from precipitating out and provided a
synergistic effect in reducing hard water precipitation when combined
with another builder. Synergy in these graphs appears as points having a
greater transmittance than that expected from the weighted arithmatic
average of the individual components.
[0250] Comparing FIG. 12 to FIGS. 10 and 11 shows that the ratio where the
moles Mg.gtoreq.moles Ca, which corresponds roughly to about 0.5 Mg
compound.gtoreq.Ca compound by weight, and with at least 70% alkalinity
(as sodium carbonate) was the area of worst precipitation of hard water
where the alkalinity is a mixture of sodium carbonate and sodium
hydroxide. In the mixed alkalinity system, the ratio of Mg to Ca did not
markedly affect the results as long as both were present. The greater
effect on preventing or reducing precipitation in the presence of water
hardness was that the ratio of the sum of (Mg+Ca) by weight was about
1/3.sup.rd or less than the total amount of combined alkalinity.
Example 2
Soluble Magnesium Salt Including Anion of Soluble Calcium Salt Reduced
Formation of Scale from Hard Water in Warewashing at Lower Ratios
[0251] Surprisingly, a water soluble magnesium salt (MgCl.sub.2) providing
an anion that forms a water soluble calcium salt reduced formation of
lime scale from hard water at lower ratios of Mg.sup.2+ to Ca.sup.2+ than
a magnesium salt (MgSO.sub.4) providing an anion of a water insoluble
calcium salt.
[0252] A first glass and a second glass were run though a dishwashing
machine for 100 cycles using 17 grain hard water in a dishwashing machine
with water soluble magnesium compound, magnesium chloride or magnesium
sulfate, introduced as the sole rinse agent. The water soluble magnesium
compounds were introduced at molar ratios of magnesium ion to calcium ion
of 1:1. No detergent was used in any of the wash cycles.
[0253] The results in FIG. 13 compare glasses rinsed with two sources of
water soluble magnesium compound as the source of the added magnesium
ion. Magnesium chloride and calcium chloride are both soluble. However,
magnesium sulfate is soluble but calcium sulfate is only slightly
soluble. The water solubility's of different magnesium compounds are
shown in Table 16.
TABLE-US-00017
TABLE 16
Compound Water Solubility (20.degree. C.)
magnesium chloride 54.6
magnesium sulfate 33.7
calcium chloride 42.0
calcium sulfate 0.2
[0254] Interestingly, magnesium chloride effectively reduced formation of
lime scale from hard water at a lower concentration than magnesium
sulfate.
[0255] A magnesium compound such as magnesium chloride where the analogous
calcium salt is water soluble was found to be more effective in
preventing hard water scale than one where the analogous calcium salt is
water insoluble. FIG. 13 illustrates this at a 1:1 molar ratio of total
magnesium ion to calcium ion for both salts.
Example 3
Cleaning Composition Containing Water Soluble Magnesium Salt Removed
Protein Soil in Warewashing
[0256] Surprisingly, adding a hardness ion (Mg.sup.2) to a phosphorus-free
ware washing composition resulted in equal or better cleaning performance
compared to a conventional, magnesium salt free, phosphorus containing
warewash detergent.
[0257] A first glass (H) was soiled with milk and washed with 1000 ppm of
Formula A at 160.degree. F. in 17 gpg hard water. A second glass (I) was
soiled with milk and washed with 1000 ppm of a comparable, conventional
warewash detergent at 160.degree. F. in 17 grain hard water. The soiling
and wash sequence was repeated 10 times for each glass.
[0258] The glasses were then treated with Comassie Blue dye, which stains
protein blue. The intensity of blue color on the treated glasses was
directly proportional to the level of protein (i.e., milk) remaining on
the surface. The glasses were filled with a white powder (to provide
greater contrast for the blue color), visually inspected, and
photographed.
TABLE-US-00018
Formula A
Ingredient Wt-%
sodium hydroxide 48
water 14
zinc chloride, 62.5% 0.2
sodium aluminate, 45% 0.2
ethoxy-propoxy copolymer 1
maleic-acrylate copolymer 2
sodium polyacrylate 4
dispersant
sodium sulfate 11
magnesium chloride 10
sodium citrate 10
[0259] In a second experiment, a first side (J) of a coffee cup heavily
soiled with coffee and creamer (which contains protein) was placed in a
1000 ppm solution of a warewash detergent in 17 grain hard water for 30
seconds at ambient temperature. A second side (K) of the coffee cup was
soaked in a 1000 ppm solution of Formula A in 17 grain hard water for 30
seconds at ambient temperature. A portion of the cup between the two
sides, was not treated with detergent. The cup was not stained with
Comassie Blue dye. The cup was visually inspected and photographed.
[0260] FIG. 14 shows the photograph of the two glasses. The glass washed
using the conventional, magnesium free warewash detergent is on the left
and the glass washed using magnesium salt containing Formula A is on the
right. As shown in FIG. 14, there is a darker vertical stripe of dye
visible on the lower portion of the glass on the left. The magnesium salt
containing, phosphorus-free detergent did not have such a stripe. Thus it
was determined that the compositions of the present invention removed
more protein than magnesium salt free, phosphorus containing,
conventional warewash detergent.
[0261] FIG. 15 shows a p
hotograph of the cup. The left side of the cup was
washed using the conventional, magnesium free warewash detergent. The
right side of the cup washed using magnesium salt containing Formula A.
As shown in FIG. 15, the two sides of the cup appear equally clean. The
magnesium salt containing, phosphorus-free detergent cleaned as well as
the magnesium salt free, phosphorus containing, conventional warewash
detergent.
Example 4
Warewashing or Rinsing with Water Containing Water Soluble Magnesium
Compound Reduced Formation of Scale from Hard Water
[0262] Surprisingly, adding a hardness ion (Mg.sup.2) to rinse water
reduced formation of scale from hard water on glasses after warewashing.
[0263] A first glass and a second glass were repeatedly washed (100
cycles) with a warewash detergent (1000 ppm). The first glass was washed
with a warewash detergent (Formula A, Example 3) containing magnesium
chloride in water of 17 grain per gallon (gpg) water hardness and rinsed
with water of 17 grain hardness, which corresponds to about 300 ppm Ca
calculated as CaCO.sub.3 and about 100 ppm Mg calculated as CaCO.sub.3.
The second glass was washed with a warewash detergent (Formula A)
containing magnesium chloride in 5 gpg water hardness and rinsed with
water of 5 grain hardness also containing about 48 ppm magnesium ion. The
rinse water did not contain any additive (e.g., rinse aid) beyond
magnesium compound.
[0264] After washing with warewash detergent, rinsing, and drying, the two
glasses (FIG. 16) exhibited comparable clarity. Washing in 17 grain hard
water followed by rinsing with water would normally be expected to yield
glassware with more spotting than in softer water (left glass in FIG.
16). Washing in 5 grain hard water followed by rinsing with water
typically yields clear glassware, and this is confirmed by FIG. 16 (right
glass). In this experiment, washing with a detergent containing magnesium
chloride and/or rinsing with water containing magnesium ion reduced or
eliminated the cloudiness typically observed when using hard water, e.g.,
17 grain hard water. Low levels of magnesium ions were effective in
reducing scale build-up at various levels of water hardness.
Example 5
Cleaning Composition Containing Water Soluble Magnesium Salt Removed Soil
From Hard Surface Without Spotting
[0265] Surprisingly, adding a hardness ion (Mg.sup.2) to a surfactant
resulted in a hard surface cleaner with reduced spotting from cleaning
with hard water.
[0266] A shower cleaner was prepared containing 0.1% of a reverse EO-PO
copolymer as a sheeting agent and 0.005% magnesium chloride for scale
control. Half of a black ceramic tile was cleaned with the magnesium salt
containing hard surface cleaner. A portion of the remaining half was
cleaned with the same composition lacking magnesium salt, that is, 0.1%
of the reverse EO-PO copolymer. Another portion of that remaining half
was left untreated. The tile was then rinsed with 17 grain hard water and
allowed to air dry. The tile was visually inspected for water spotting.
[0267] No water spotting was observed on the side treated with the hard
surface cleaner containing magnesium salt. Numerous water spots were seen
on the portion cleaned with the conventional cleaner (i.e., surfactant)
and the uncleaned portion of the tile.
Example 6
Water Soluble Magnesium Compound Reduced Streaking by Glass Cleaner
[0268] Surprisingly, glass cleaner containing a hardness ion (Mg.sup.2+)
cleaned glass with reduced streaking
[0269] The commercial glass cleaner of Formula B was diluted 1:16 in 17
grain hard water and used to clean a window. At a 1:16 dilution, the
glass cleaner of Formula B lacks sufficient builder to counter 17 grain
hard water. Another portion of the same window was cleaned with a 1:16
dilution of Formula B in which the use composition also contained 200 ppm
magnesium chloride.
TABLE-US-00019
Formula B
Ingredient wt-%
water 73
polycarboxylate, Sodium Salt 1
n-propoxypropanol 18
monoethanolamine 1.9
propoxy-ethoxy copolymer 0.10
sodium lauryl sulfate 30%, 4.9
citric acid, 50% 0.10
tetrasodium EDTA, 40% 1.0
dye 0.05
fragrance 0.10
[0270] It was observed that streaking on the glass was greatly reduced
with the addition of the water soluble magnesium salt to the formula.
Example 7
Use of a Water Soluble Magnesium Compound in a Builder Free Detergent
Composition
[0271] A ten cycle test was run to determine the effectiveness of a known
conventional cleaning composition comprising a builder, i.e., Solid
Power.RTM., commercially available from Ecolab Inc., when the builder was
replaced with a water soluble magnesium salt, e.g., MgCl.sub.2.
Evaluation included washing glasses soiled with milk/grease with a water
temperature of 160.degree. F.
[0272] All of the washed glasses were visually scored for spotting and
also for residual soil film with "1" being a perfectly clean glass and
"5" totally covered by the spots or residual
soil film. The following
table summarizes the glass grading scale.
TABLE-US-00020
TABLE 17
Rating Spots Film
1 No spots No film
2 1/4 glass spotted Trace/barely perceptible
3 1/2 glass spotted Slight film
4 3/4 glass spotted Moderate film
5 Whole glass spotted Heavy film
[0273] The results are shown in the table below. The conventional cleaning
composition was also used as a control.
TABLE-US-00021
TABLE 8
Soiled Clean
Glasses for Glasses for Use
Water Type of Soil Soil Solution
Hardness Test Removal Redeposit pH at
(grains) Score Measurement Measurement 1200 ppm
Solid 17 Spots 4.8 5.0 12.04
Power (control), Film 2.9 2.0
1200 ppm
1200 ppm Solid 17 Spots 3.8 4.2 11.19
Power w/ 300 ppm Film 3.1 2.8
MgCl.sub.2
1200 ppm Solid 17 Spots 3.3 2.8 11.36
Power w/ 150 ppm Film 2.7 2.0
MgCl.sub.2
[0274] As can be seen in this table, the composition comprising a water
soluble magnesium compound instead of a traditional builder achieved
equal if not greater results in cleaning than the conventional detergent
comprising a builder.
[0275] 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. It should also be noted that, as used
in this specification and the appended claims, the term "configured"
describes a system, apparatus, or other structure that is constructed or
configured to perform a particular task or adopt a particular
configuration. The term "configured" can be used interchangeably with
other similar phrases such as arranged and configured, constructed and
arranged, adapted and configured, adapted, constructed, manufactured and
arranged, and the like.
[0276] 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.
[0277] 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.
* * * * *