Note: Descriptions are shown in the official language in which they were submitted.
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TITLE: SOLID RINSE AID COMPOSITION AND METHOD OF
MAKING SAME
FIELD OF INVENTION
The present invention relates to solid rinse aid compositions, and methods
for manufacturing and using the same. The rinse aid compositions generally
include
a novel solidification system and surfactants designed for use in pressed or
extruded
solid formation. The rinse aids can be used in aqueous use solutions on
articles
including, for example, cookware, dishware, flatware, glasses, cups, hard
surfaces,
healthcare surfaces, glass surfaces, vehicle surfaces, etc. but are
particularly useful
for metal surfaces.
BACKGROUND OF THE INVENTION
Mechanical warewashing machines have been common in the institutional
and household environments for many years. Such automatic warewashing machines
clean dishes using two or more cycles which can include initially a wash cycle
followed by a rinse cycle, but may also utilize soak, pre-wash, scrape,
sanitizing,
drying, and additional wash cycles. Rinse agents are conventionally used in
warewashing applications to promote drying and to prevent the formation of
spots.
Rinse agents may also be used in healthcare environments, typically for
cleaning a medical cart, cage, instrument, or device. Typically, cleaning a
medical
cart, cage, instrument, or device includes contacting the medical cart, cage,
instrument, or device with an aqueous cleaning composition and, rinsing or
contacting the same with a rinse solution comprising a dissolved rinse aid.
The
method can also involve antimicrobial treatment of the medical cart, cage,
instrument, or device by contacting with an aqueous antimicrobial composition
formed by dissolving or suspending a solid antimicrobial composition,
preferably a
solid quaternary ammonium or solid halogen antimicrobial composition.
In either household, institutional, or healthcare environments, rinse agents
to
reduce the formation of spotting have been, commonly been added to water to
form
an aqueous rinse that is sprayed on the hard surfaces after cleaning is
complete. The
precise mechanism through which rinse agents work is not established. One
theory
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holds that the surfactant in the rinse agent is absorbed on the surface at
temperatures
at or above its cloud point, and thereby reduces the solid-liquid interfacial
energy
and contact angle. This leads to the formation of a continuous sheet which
drains
evenly from the surface and minimizes the formation of spots. Generally, high
foaming surfactants have cloud points above the temperature of the rinse
water, and,
according to this theory, would not promote sheet formation, thereby resulting
in
spots. Moreover, high foaming materials are known to interfere with the
operation
of warewashing machines.
A number of rinse aids are currently known, each having certain advantages
and disadvantages. There is an ongoing need for alternative rinse aid
compositions,
especially alternative rinse aid compositions that are environmentally
friendly (e.g.,
biodegradable), non-corrosive to metal, can handle high total dissolved
solids, can
handle high water hardness and are easily manufactured as solids.
SUMMARY OF THE INVENTION
The invention includes a solid rinse aid that is particularly designed for
pressed or extrusion solid formation and which is effective for leaving
spotless
surfaces after rinsing, especially rinsing metals without corrosion. According
to the
invention, a solid acid is combined with a short-chain alkylbenzene and alkyl
naphthalene sulfonate class of hydrotopes, such as sodium xylene sulfonate,
sodium
toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate,
ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene
sulfonate, and/or sodium butylnaphthalene. The short-chain alkylbenzene and
alkyl
naphthalene sulfonate class of hydrotopes act as a solidification agent as
well as a
surfactant and are combined with at least one nonionic low foaming surfactant.
A solid rinse agent composition of the present invention thus includes a solid
acid for hardness control, a short chain alkyl benzene and/or alkyl
naphthalene
sulfonate, preferably sodium xylene sulfonate (SXS), and a surfactant system.
The
surfactant is preferably a non-ionic low foaming surfactant.
The composition of the invention is particularly beneficial for use with hard
water and also high total dissolved solid (TDS) conditions.
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The rinse aid concentrate is typically provided in a solid form. This is
typically prepared by the steps of combining the solid materials then adding
any
liquid components. The material is then pressed or extruded to form a solid.
In
general, it is expected that the solid concentrate will be diluted with water
to provide
the use solution that is then supplied to the surface of a substrate. The use
solution
preferably contains an effective amount of active material to provide spotless
surfaces by rinse water. It should be appreciated that the term "active
materials"
refers to the nonaqueous portion of the use solution that functions to reduce
spotting
and filming.
Some example methods for using the rinse aid generally include the step of
providing the rinse aid, mixing the rinse aid into an aqueous use solution,
and
applying the aqueous use solution to a substrate surface.
In some embodiments, the solid acid is present in an amount of from about 5
wt.% to about 40 wt. %. The short chain alkyl benzene or alkyl naphthalene
sulfonate is present 50wt % to 80 wt % and the nonionic surfactant is present
from
about 5 wt. % to about 20 wt. % for pressed solid and from about 5 wt. % to
about
30 wt. % for an extruded solid. The solid rinse aid can also in some
embodiments
and as enumerated hereinafter, include an additional surfactant, a processing
aids
such as polyethylene glycol or urea, as well as other components such as a
chelant.
preservative, fragrant, or dye.
In some aspects, the present invention is related to methods for rinsing
surfaces in a warewashing application or surfaces involved in healthcare. The
methods comprise providing an aqueous rinse aid composition, diluting the
rinse aid
composition with water to form an aqueous use solution; and applying the
aqueous
use solution to the surfaces.
DESCRIPTION OF THE FIGURES
Figure 1 is s a graph showing hardness performance of compositions of the
invention A and B and different commercial rinse aids A-D.
Figure 2 is a graph showing the total dissolved solids (TDS) performance of
compositions of the invention A and B and different commercial rinse aids A-D.
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Figure 3 is a graph showing the metal compatibility data of compositions of
the invention A and B and different commercial rinse aids A-D.
Figure 4 is a graph showing the foam height of compositions of the invention
A and B and different commercial rinse aid D at dispenser sump concentration
using
Glewvve Foam Apparatus.
Figure 5 is a graph showing foam height of compositions of the invention A
and B and different commercial rinse aids A-D at RTU concentration
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to rinse aid compositions, and methods for
making and using rinse aid compositions. In some aspects, the present
invention
provides rinse aid compositions including a solid acid, a short-chain
alkylbenzene
and alkyl naphthalene sulfonate, such as sodium xylene sulfonate, sodium
toluene
sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium
xylene
sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene sulfonate,
and/or
sodium butylnaphthalene, and at least one additional surfactant preferably a
nonionic
low foaming surfactant.
The compositions of the present invention can be used to reduce spotting and
filming on a variety of surfaces including, but not limited to, plasticware,
cookware,
dishware, flatware, glasses, cups, hard surfaces, glass surfaces, healthcare
surfaces
and vehicle surfaces.
So that the invention may be understood more clearly, certain terms are first
defined.
As used herein, the term "ware" refers to items such as eating, cooking, and
serving utensils. Exemplary items of ware include, but are not limited to:
dishes,
e.g., plates and bowls; silverware, e.g., forks, knives, and spoons; cups and
glasses,
e.g., drinking cups and glasses; serving dishes, e.g., fiberglass trays,
insulated plate
covers. As used herein, the term "warewashing" refers to washing, cleaning, or
rinsing ware. The items of ware that can be contacted, e.g., washed, or
rinsed, with
the compositions of the invention can be made of any material. For example,
ware
includes items made of wood, metal, ceramics, glass, etc. Ware also refers to
items
made of plastic. Types of plastics that can be cleaned or rinsed with the
compositions according to the invention include but are not limited to, those
that
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include polycarbonate polymers (PC), acrilonitrile-butadiene-styrene polymers
(ABS). and polysulfone polymers (PS). Another exemplary plastic that can be
cleaned using the methods and compositions of the invention include
polyethylene
terephthal ate (PET).
As used herein, the term "hard surface" includes showers, sinks, toilets,
bathtubs, countertops, windows, mirrors, transportation vehicles, floors, and
the like.
As used herein, the phrase "healthcare 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.
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.
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,
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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.
By the term "solid" as used with reference to the composition of the
invention, 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 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.
The "cloud point" of a surfactant rinse or sheeting agent is defined as the
temperature at which a 1 wt. % aqueous solution of the surfactant turns cloudy
when
warmed.
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
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.
As used herein, the phrase "medical cart" refers to a cart employed in a
health care environment to transport one or more medical instruments, devices,
or
equipment and that can benefit from cleaning with a use composition of a solid
cleaning composition, rinsing with a use composition of a solid rinse
composition,
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and/or antimicrobial treatment with a use composition of a solid antimicrobial
composition. Medical carts include carts for transporting medical or dental
devices
or instruments or other medical or dental equipment in a health care
environment,
such as a hospital, clinic, dental or medical office, nursing home, extended
care
facility, or the like.
As used herein, the phrase "medical cage" refers to a cage employed in a
health care environment to house and/or transport one or more animals employed
in
experiments, in clinical or toxicological testing, in diagnostics, or the
like. Such
animals include a rodent (e.g. a mouse or a rat), a rabbit, a dog, a cat, or
the like. A
medical cage typically includes an animal cage that actually houses the animal
and
which can be mounted on a wheeled rack. The medical cage can also include one
or
more containers or dispensers for animal food, one or more vessels or
dispensers for
water, and/or one or more systems for identifying the cart or animals. Medical
cages
can benefit from cleaning with a use composition of a solid alkaline cleaning
composition, rinsing with a use composition of a solid rinse composition,
and/or
antimicrobial treatment with a use composition of a solid antimicrobial
composition.
As used herein, the term "instrument" refers to the various medical or dental
instruments or devices that can benefit from cleaning with a use composition
of a
solid alkaline cleaning composition, rinsing with a use composition of a solid
rinse
composition, and/or antimicrobial treatment with a use composition of a solid
antimicrobial composition.
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 in a composition of 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,
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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.
As used herein, the term "alkyl" refers to a straight or branched chain
monovalent hydrocarbon radical optionally containing one or more heteroatomic
substitutions independently selected from S, 0, Si, or N. Alkyl groups
generally
include those with one to twenty atoms. Alkyl groups may be unsubstituted or
substituted with those substituents that do not interfere with the specified
function of
the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl
substituted amino, or halo, for example. Examples of "alkyl" as used herein
include,
but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl,
and
isopropyl, and the like. In addition, "alkyl" may include "alylenes",
"alkenylenes",
or "alkylynes".
As used herein, the term "alkylene" refers to a straight or branched chain
divalent hydrocarbon radical optionally containing one or more heteroatomic
substitutions independently selected from S, 0, Si. or N. Alkylene groups
generally
include those with one to twenty atoms. Alkylene groups may be unsubstituted
or
substituted with those substituents that do not interfere with the specified
function of
the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl
substituted amino, or halo, for example. Examples of "alkylene" as used herein
include, but are not limited to, methylene, ethylene, propane-1,3-diyl,
propane-1,2-
diyl and the like.
As used herein, the term "alkenylene" refers to a straight or branched chain
divalent hydrocarbon radical having one or more carbon--carbon double bonds
and
optionally containing one or more heteroatomic substitutions independently
selected
from S, 0. Si, or N. Alkenylene groups generally include those with one to
twenty
atoms. Alkenylene groups may be unsubstituted or substituted with those
substituents that do not interfere with the specified function of the
composition.
Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted
amino, or
halo, for example. Examples of "alkenylene" as used herein include, but are
not
limited to, ethene-1,2-diyl, propene-1,3-diyl, and the like.
As used herein, the term -alkylyne" refers to a straight or branched chain
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divalent hydrocarbon radical having one or more carbon¨carbon triple bonds and
optionally containing one or more heteroatomic substitutions independently
selected
from S, 0. Si, or N. Alkylyne groups generally include those with one to
twenty
atoms. Alkyl yne groups may be un substituted or substituted with those
substituents
that do not interfere with the specified function of the composition.
Substituents
include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo,
for
example.
As used herein, the term "alkoxy", refers to ¨0¨alkyl groups wherein alkyl is
as defined above.
As used herein, the term "halogen" or "halo" shall include iodine, bromine,
chlorine and fluorine.
As used herein, the terms "mercapto" and "sulfhydryl" refer to the
substituent ¨SH.
As used herein, the term "hydroxy" refers to the substituent ¨OH.
A used herein, the term "amino" refers to the substituent ¨NH2.
The methods and compositions of the present invention can comprise,
consist of, or consist essentially of the listed steps or ingredients. As used
herein the
term "consisting essentially of" shall be construed to mean including the
listed
ingredients or steps and such additional ingredients or steps which do not
materially
affect the basic and novel properties of the composition or method. In some
embodiments, a composition in accordance with embodiments of the present
invention that "consists essentially of" the recited ingredients does not
include any
additional ingredients that alter the basic and novel properties of the
composition,
e.g., the drying time, sheeting ability, spotting or filming properties of the
composition.
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.
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
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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.
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.
As used in this specification and the appended claims, the term "or" is
generally
employed in its sense including "and/or" unless the content clearly dictates
otherwise.
Solid Rinse Aid Compositions
A solid rinse agent composition of the present invention includes a solid
acid, a short-chain alkylbenzene or alkyl naphthalene sulfonate, such as
sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate,
potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene
sulfonate,
sodium alkyl naphthalene sulfonate, and/or sodium butylnaphthalene, and a one
or
more surfactants, preferably at least one of which is a nonionic low foaming
surfactant.
The solid rinse aid composition is advantageously formulated to give spotless
surfaces after rinsing, especially in high hardness and high total dissolved
solids
(TDS) situations. The rinse aid is also particularly useful for metal surfaces
and
avoids corrosion of the same.
Solid Acid
The invention includes one or more solid acids. The solid acid of the
composition includes any acid which is naturally or treated to be in solid
form at
room temperature. The term solid here includes forms such as powdered,
particulate, or granular solid forms. Acidic substances (herein referred to as
"acids")
include, but are not limited to, pharmaceutically acceptable organic or
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acids, hydroxyl-acids, amino acids, Lewis acids, mono- or di-alkali or
ammonium
salts of molecules containing two or more acid groups, and monomers or
polymeric
molecules containing at least one acid group. Examples of suitable acid groups
include carboxylic, hydroxamic, amide, phosphates (e.g., mono-hydrogen
phosphates and di-hydrogen phosphates), sulfates, and bi-sulfites.
In particular, the acids are organic acids with 2-18 carbon atoms, including,
but not limited to, short, medium, or long chain fatty acids, hydroxyl acids,
inorganic acids, amino acids, and mixtures thereof. Preferably, the acid is
selected
from the group consisting of lactic acid, gluconic acid, citric acid, tartaric
acid,
hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, maleic acid,
monosodium citrate, disodium citrate, potassium citrate, monosodium tartrate,
disodium tartrate, potassium tartrate, aspartic acid, carboxymethylcellulose,
acrylic
polymers, methacrylic polymers, and mixtures thereof.
For example many organic acids are crystalline solids in pure form (and at
room temperature), e.g. citric acid, oxalic acid, benzoic acid. Sulphamic acid
in an
example of an inorganic acid that is solid a room temperature.
The solid acid or combination of one or more solid acids is present in the
rinse aid compositions of the invention in an amount of from about 5 wt. % to
about
40 wt. %, preferably from about 7.5 wt. % to about 27.5 wt. % and more
preferably from about 10 wt. % to about 25 wt. %.
Short Chain Alkyl Benzene Or Alkyl Naphthalene Sulfonate
The class of short chain alkyl benzene or alkyl naphthalene sulfonates work
as both a hardening agent and as a hydrotrope and TDS control active in the
composition. The group includes alkyl benzene sulfonates based on toluene,
xylene, and cumene , and alkyl naphthalene sulfonates. Sodium toluene
sulfonate
and sodium xylene sulfonate are the best known hydrotopes. These have the
general
formula below:
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41:>'Z'\ = R3
R2 -
P [
/
g
0 0
0
R1= CI, C2 OR C3 R3 C2, C.3. C4 OR Vi
R2 Oi OR H 114, CI, C2, CI, CA OR H
ALKYLBENZENE SIII_FMATE ALreLNNP:HTHALENE SUISONATE
This group includes but is not limited to sodium xylene sulfonate, sodium
toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate,
ammonium xylene sulfonate, calcium xylene sulfonate, sodium alkyl naphthalene
sulfonate, and sodium butylnaphthalene sulfonate. In a preferred embodiment
the
solidification agent is SXS.
The invention provides a solid rinse aid composition including effective
amounts of one or more of a short chain alkyl benzene or alkyl naphthalene
sulfonates. Surprisingly, this class of hydrotopes has been found to add to
performance of the solid rinse aid as well as functioning as solidification
agent. The
short chain alkyl benzene or alkyl naphthalene sulfonate may also function as
a
builder. The solid rinse aid composition typically has a melt point greater
than
110 F and is dimensionally stable. In some embodiments, the hardening agent of
a
short chain alkyl benzene or alkyl naphthalene sulfonate is present in an
amount of
from about 40 wt. % to about 90 wt. %, preferably from about 45 wt. % to about
85
wt. % and more preferably from about 50 wt. % to about 80 wt. %.
The solid rinse aid can also in some embodiments and as enumerated
hereinafter, include an additional processing aids, such as polyethylene
glycol, or
urea. The additional processing aids if used is present in an amount of from
about .1
wt % to about 10 wt %.
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Nonionic Surfactant
Nonionic surfactants useful in the invention are generally characterized by
the presence of an organic hydrophobic group and an organic hydrophilic group
and
are typically produced by the condensation of an organic aliphatic, alkyl
aromatic or
polyoxyalkylene hydrophobic compound with a hydrophilic alkaline oxide moiety
which in common practice is ethylene oxide or a polyhydration product thereof,
polyethylene glycol. Practically any hydrophobic compound having a hydroxyl,
carboxyl, amino, or amido group with a reactive hydrogen atom can be condensed
with ethylene oxide, or its polyhydration adducts, or its mixtures with
alkoxylenes
such as propylene oxide to form a nonionic surface-active agent. The length of
the
hydrophilic polyoxyalkylene moiety which is condensed with any particular
hydrophobic compound can be readily adjusted to yield a water dispersible or
water
soluble compound having the desired degree of balance between hydrophilic and
hydrophobic properties. Useful nonionic surfactants in the present invention
include:
Examples of suitable nonionic surfactants include alkoxylated surfactants,
such as Dehypon LS-54 (R-(E0)5(1)0)4) and Dehypon LS-36 (R-(E0)3(P0)6); and
capped alcohol alkoxylates, such as Plurafac LF221 and Genepol from Clariant,
Tegoten EC11; mixtures thereof, or the like.))
Other nonionic surfactants that can used include:
1. Block polyoxypropylene-polyoxyethylene polymeric compounds
based upon propylene glycol, ethylene glycol, glycerol, trimethylolpropane,
and
ethylenediamine as the initiator reactive hydrogen compound. Examples of
polymeric compounds made from a sequential propoxylation and ethoxylation of
initiator are commercially available under the trade names Pluronic and
Tetronico
manufactured by BASF Corp.
Pluronic compounds are difunctional (two reactive hydrogens) compounds formed
by condensing ethylene oxide with a hydrophobic base formed by the addition of
propylene oxide to the two hydroxyl groups of propylene glycol. This
hydrophobic
portion of the molecule weighs from 1,000 to 4,000. Ethylene oxide is then
added to
sandwich this hydrophobe between hydrophilic groups, controlled by length to
constitute from about 10% by weight to about 80% by weight of the final
molecule.
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Tetronic0 compounds are tetra-functional block copolymers derived from the
sequential addition of propylene oxide and ethylene oxide to ethylenediamine.
The
molecular weight of the propylene oxide hydrotype ranges from 500 to 7,000;
and,
the hydrophile, ethylene oxide, is added to constitute from 10% by weight to
80% by
weight of the molecule.
2. Condensation products of one mole of alkyl phenol wherein the
alkyl
chain, of straight chain or branched chain configuration, or of single or dual
alkyl
constituent, contains from 8 to 18 carbon atoms with from 3 to 50 moles of
ethylene
oxide. The alkyl group can, for example, be represented by diisobutylene, di-
amyl,
polymerized propylene, iso-octyl, nonyl, and di-nonyl. These surfactants can
be
polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols.
Examples of commercial compounds of this chemistry are available on the market
under the trade names Igepal0 manufactured by Rhone-Poulenc and Triton
manufactured by Dow.
3. Condensation products of one mole of a saturated or unsaturated,
straight or branched chain alcohol having from 6 to 24 carbon atoms with from
3 to
50 moles of ethylene oxide. The alcohol moiety can consist of mixtures of
alcohols
in the above delineated carbon range or it can consist of an alcohol having a
specific
number of carbon atoms within this range. Examples of like commercial
surfactant
are available under the trade names Neodol0 manufactured by Shell Chemical Co.
and Alfonic0 manufactured by Vista Chemical Co.
4. Condensation products of one mole of saturated or unsaturated,
straight or branched chain carboxylic acid having from 8 to 18 carbon atoms
with
from 6 to 50 moles of ethylene oxide. The acid moiety can consist of mixtures
of
acids in the above defined carbon atoms range or it can consist of an acid
having a
specific number of carbon atoms within the range. Examples of commercial
compounds of this chemistry are available on the market under the trade names
Nopalcol0 manufactured by Henkel Corporation and Lipopeg manufactured by
Lipo Chemicals, Inc.
In addition to ethoxylated carboxylic acids, commonly called polyethylene
glycol esters, other alkanoic acid esters formed by reaction with glycerides,
glycerin,
and polyhydric (saccharide or sorbitan/sorbitol) alcohols have application in
this
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invention. All of these ester moieties have one or more reactive hydrogen
sites on
their molecule which can undergo further acylation or ethylene oxide
(alkoxide)
addition to control the hydrophilicity of these substances. Care must be
exercised
when adding these fatty ester or acylated carbohydrates to compositions of the
present invention containing amylase and/or lipase enzymes because of
potential
incompatibility.
In a preferred embodiment the nonionic surfactant is a low-foaming anionic
surfactant. Examples of nonionic low foaming surfactants include:
5. Compounds from (1) which are modified, essentially reversed, by
adding ethylene oxide to ethylene glycol to provide a hydrophile of designated
molecular weight; and, then adding propylene oxide to obtain hydrophobic
blocks
on the outside (ends) of the molecule. The hydrophobic portion of the molecule
weighs from 1,000 to 3,100 with the central hydrophile including 10% by weight
to
80% by weight of the final molecule. These reverse Pluronics are manufactured
by BASF Corporation under the trade name Pluronic R surfactants.
Likewise, the Tetronic R surfactants are produced by BASF Corporation
by the sequential addition of ethylene oxide and propylene oxide to
ethylenediamine. The hydrophobic portion of the molecule weighs from 2.100 to
6,700 with the central hydrophile including 10% by weight to 80% by weight of
the
final molecule.
6. Compounds from groups (1), (2), (3) and (4) which are modified by
"capping" or "end blocking" the terminal hydroxy group or groups (of multi-
functional moieties) to reduce foaming by reaction with a small hydrophobic
molecule such as propylene oxide, butylene oxide, benzyl chloride; and, short
chain
fatty acids, alcohols or alkyl halides containing from 1 to 5 carbon atoms;
and
mixtures thereof. Also included are reactants such as thionyl chloride which
convert
terminal hydroxy groups to a chloride group. Such modifications to the
terminal
hydroxy group may lead to all-block, block-heteric, heteric-block or all-
heteric
nonionics.
Additional examples of effective low foaming nonionics include:
7. The alkylphenoxypolyethoxyalkanols of U.S. Pat. No. 2,903,486
issued Sep. 8, 1959 to Brown et al. and represented by the formula
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($1
nlis);.(0A),-i-oki
in which R is an alkyl group of 8 to 9 carbon atoms, A is an alkylene chain of
3 to 4
carbon atoms, n is an integer of 7 to 16, and m is an integer of 1 to 10.
The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548 issued Aug.
7, 1962 to Martin et al. having alternating hydrophilic oxyethylene chains and
hydrophobic oxypropylene chains where the weight of the terminal hydrophobic
chains, the weight of the middle hydrophobic unit and the weight of the
linking
hydrophilic units each represent about one-third of the condensate.
The defoaming nonionic surfactants disclosed in U.S. Pat. No. 3,382,178
issued May 7. 1968 to Li ssant et al. having the general formula Z[(OR),,OH],
wherein Z is alkoxylatable material, R is a radical derived from an alkaline
oxide
which can be ethylene and propylene and n is an integer from, for example, 10
to
2,000 or more and z is an integer determined by the number of reactive
oxyalkylatable groups.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No.
2,677,700, issued May 4, 1954 to Jackson et al. corresponding to the formula
Y(C3H60).(C2H40) H wherein Y is the residue of organic compound having from
1 to 6 carbon atoms and one reactive hydrogen atom, n has an average value of
at
least 6.4, as determined by hydroxyl number and m has a value such that the
oxyethylene portion constitutes 10% to 90% by weight of the molecule.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No.
2,674,619, issued Apr. 6, 1954 to Lundsted et al. having the formula
YRC31-16.0n(C4-140)mHk wherein Y is the residue of an organic compound having
from 2 to 6 carbon atoms and containing x reactive hydrogen atoms in which x
has a
value of at least 2, n has a value such that the molecular weight of the
polyoxypropylene hydrophobic base is at least 900 and m has value such that
the
oxyethylene content of the molecule is from 10% to 90% by weight. Compounds
falling within the scope of the definition for Y include, for example,
propylene
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glycol, glycerine, pentaerythritol, trimethylolpropane, ethylenediamine and
the like.
The oxypropylene chains optionally, but advantageously, contain small amounts
of
ethylene oxide and the oxyethylene chains also optionally, but advantageously,
contain small amounts of propylene oxide.
Additional conjugated polyoxyalkylene surface-active agents which are
advantageously used in the compositions of this invention correspond to the
formula: PRC3H60)n(C2H40)mHli wherein P is the residue of an organic compound
having from 8 to 18 carbon atoms and containing x reactive hydrogen atoms in
which x has a value of 1 or 2, n has a value such that the molecular weight of
the
polyoxyethylene portion is at least 44 and m has a value such that the
oxypropylene
content of the molecule is from 10% to 90% by weight. In either case the
oxypropylene chains may contain optionally, but advantageously, small amounts
of
ethylene oxide and the oxyethylene chains may contain also optionally, but
advantageously, small amounts of propylene oxide.
8. Polyhydroxy fatty acid amide surfactants suitable for use in the
present compositions include those having the structural formula R2CONR1Z in
which: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, ethoxy,
propoxy group, or a mixture thereof; R is a C5-C31 hydrocarbyl, which can be
straight-chain; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain
with at least 3 hydroxyls directly connected to the chain, or an alkoxylated
derivative (preferably ethoxylated or propoxylated) thereof. Z can be derived
from a
reducing sugar in a reductive amination reaction; such as a glycityl moiety.
9. The alkyl ethoxylate condensation products of aliphatic alcohols with
from 0 to 25 moles of ethylene oxide are suitable for use in the present
compositions. The alkyl chain of the aliphatic alcohol can either be straight
or
branched, primary or secondary, and generally contains from 6 to 22 carbon
atoms.
10. The ethoxylated C6-C18 fatty alcohols and C6-C18 mixed ethoxylated
and propoxylated fatty alcohols are suitable surfactants for use in the
present
compositions, particularly those that are water soluble. Suitable ethoxylated
fatty
alcohols include the C10-C18 ethoxylated fatty alcohols with a degree of
ethoxylation
of from 3 to 50.
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11. Suitable nonionic alkylpolysaccharide surfactants, particularly for use
in the present compositions include those disclosed in U.S. Pat. No.
4.565,647,
Llenado, issued Jan. 21, 1986. These surfactants include a hydrophobic group
containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a
polyglycoside,
hydrophilic group containing from 1.3 to 10 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose and
galactosyl moieties can be substituted for the glucosyl moieties. (Optionally
the
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or
galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds
can
be, e.g., between the one position of the additional saccharide units and the
2-, 3-, 4-,
and/or 6-positions on the preceding saccharide units.
12. Fatty acid amide surfactants suitable for use in the present
compositions include those having the formula: R6CON(R7)2 in which R6 is an
alkyl
group containing from 7 to 21 carbon atoms and each R7 is independently
hydrogen,
Cl-C4 alkyl, C1-C4 hydroxyalkyl, or --(C4140)1H, where x is in the range of
from 1
to 3.
13. A useful class of non-ionic surfactants includes the class defined as
alkoxylated amines or, most particularly, alcohol
alkoxylated/aminated/alkoxylated
surfactants. These non-ionic surfactants may be at least in part represented
by the
general formulae:
R20--(P0)5N-(E0)t H,
R20--(P0) N-(E0) t H(E0) t H, and
R2 --N(E0) t H;
in which R2 is an alkyl, alkenyl or other aliphatic group, or an alkyl-aryl
group of
from 8 to 20, preferably 12 to 14 carbon atoms, E0 is oxyethylene, PO is
oxypropylene, s is 1 to 20, preferably 2-5, t is 1-10. preferably 2-5, and u
is 1-10,
preferably 2-5. Other variations on the scope of these compounds may be
represented by the alternative formula:
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R20--(P0) H]RE0),1-1]
in which R2 is as defined above, v is 1 to 20 (e.g., 1, 2, 3, or 4
(preferably 2)), and
w and z are independently 1-10, preferably 2-5.
These compounds are represented commercially by a line of products sold by
Huntsman Chemicals as nonionic surfactants. A preferred chemical of this class
includes Surfonic PEA 25 Amine Alkoxylate.
The treatise Nonionic Surfactants, edited by Schick, M. J., Vol. 1 of the
Surfactant Science Series, Marcel Dekker, Inc., New York, 1983 is an excellent
reference on the wide variety of nonionic compounds generally employed in the
practice of the present invention. A typical listing of nonionic classes, and
species
of these surfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin
and
Heuring on Dec. 30, 1975. Further examples are given in "Surface Active Agents
and Detergents" (Vol. I and 11 by Schwartz, Perry and Berch).
Water
The solid rinse aid composition can in some embodiments includes water.
Water many be independently added to the solid rinse aid composition or may be
provided in the solid rinse aid composition as a result of its presence in a
material
that is added to the solid rinse aid composition. For example, materials added
to the
solid rinse aid composition include water or may be prepared in an aqueous
premix
available for reaction with the solidification agent component(s). Typically,
water is
introduced into the solid rinse aid composition to provide the composition
with a
desired viscosity prior to solidification, and to provide a desired rate of
solidification.
In general, it is expected that water may be present as a processing aid and
may be removed or become water of hydration. It is expected that water may be
present in the solid composition. In the solid composition, it is expected
that the
water will be present in the solid rinse aid composition in the range of
between 0
wt.% and 5wt.%. For example, water is present in embodiments of the solid
rinse
aid composition in the range of between .1 wt.% to about 5 wt.%, or further
embodiments in the range of between .5 wt.% and about 4 wt.%, or yet further
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embodiments in the range of between 1 wt.% and 3 wt.%. It should be
additionally
appreciated that the water may be provided as deionized water or as softened
water.
The components used to form the solid composition can include water as
hydrates or hydrated forms of the binding agent, hydrates or hydrated forms of
any
of the other ingredients, and/or added aqueous medium as an aid in processing.
It is
expected that the aqueous medium will help provide the components with a
desired
viscosity for processing. In addition, it is expected that the aqueous medium
may
help in the solidification process when is desired to form the concentrate as
a solid.
Additional Functional Materials
As indicated above, the solid rinse aid may contain other functional materials
that provide the desired properties and functionality to the solid
composition.
Functional materials include a material that when dispersed or dissolved in a
use
solution, provides a beneficial property in a particular use. Examples of such
a
functional material include preservatives, chelating/sequestering agents;
bleaching
agents or activators; sanitizers/anti-microbial agents; activators; builder or
fillers;
anti-redeposition agents; optical brighteners; dyes: odorants or perfumes;
stabilizers;
processing aids; corrosion inhibitors; fillers; solidifiers; additional
hardening agent;
additional surfactants, solubility modifiers; pH adjusting agents; humectants;
hydrotropes; or a broad variety of other functional materials, depending upon
the
desired characteristics and/or functionality of the composition. In the
context of
some embodiments disclosed herein, the functional materials, or ingredients,
are
optionally included within the solidification matrix for their functional
properties.
Some more particular examples of functional materials are discussed in more
detail
below, but it should be understood by those of skill in the art and others
that the
particular materials discussed are given by way of example only, and that a
broad
variety of other functional materials may be used.
Preservatives
The solid rinse aid composition may also include effective amounts of
preservatives. Often, overall acidity and/or acids in the solid rinse aid
composition
and the use solution serves a preservative and stabilizing function.
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Some embodiments of the inventive solid rinse aid composition also include
a preservative system for acidification of the solid rinse aid including
sodium
bisulfate and organic acids. In at least some embodiments, the solid rinse aid
has pH
of 2.0 or less and the use solution of the solid rinse aid has a pH of at
least pH 4Ø
Typically, sodium bisulfate is included in the solid rinse aid composition as
an acid
source. In certain embodiments, an effective amount of sodium bisulfate and
one or
more other acids are included in the solid rinse aid composition as a
preservative
system. Suitable acids include for example, inorganic acids, such as HC1 and
organic acids. In certain further embodiments, an effective amount of sodium
bisulfate and one or more organic acids are included in the solid rinse aid
composition as a preservative system. Suitable organic acids include sorbic
acid,
benzoic acid, ascorbic acid, erythorbic acid, citric acid, etc... Preferred
organic
acids include benzoic and ascorbic acid. Generally, effective amounts of
sodium
bisulfate with or without additional acids are included such that a use
solution of the
solid rinse aid composition has a pH that shall be less than pH 4.0, often
less pH 3.0,
and may be even less than pH 2Ø
In other embodiments, the solid rinse aid composition includes
sanitizers/anti-microbial agents, in addition to or in alternative the
preservative
system described above. Suitable sanitizers/anti-microbial agents are
described
below.
The preservative component, if present is typically an amount of the solid
rinse aid component in an amount of from about 0.05 to 20 wt % preferably 0.1
to
15 wt % and most preferably 1 wt % to about 10 wt %.
Chelating/Sequestering Agents
The solid rinse aid composition may also include effective amounts of
chelating/sequestering agents, also referred to as builders. In addition, the
rinse aid
may optionally include one or more additional builders as a functional
ingredient.
In general, a chelating agent is a molecule capable of coordinating (i.e.,
binding) the
metal ions commonly found in water sources to prevent the metal ions from
interfering with the action of the other ingredients of a rinse aid or other
cleaning
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composition. The chelating/sequestering agent may also function as a threshold
agent when included in an effective amount.
Often, the solid rinse aid composition is also phosphate-free and/or amino-
carboxylate-free. In embodiments of the solid rinse aid composition that are
phosphate-free, the additional functional materials, including builders
exclude
phosphorous-containing compounds such as condensed phosphates and
phosphonates.
Suitable additional builders include polycarboxylates. Some examples of
polymeric polycarboxylates suitable for use as sequestering agents include
those
having a pendant carboxylate (--0O2) groups and include, for example,
polyacrylic
acid, maleic/olefin copolymer, acrylic/maleic copolymer, polymethacrylic acid,
acrylic acid-methacrylic acid copolymers, hydrolyzed polyacrylamide,
hydrolyzed
polymethacrylamide, hydrolyzed polyamide-methacrylamide copolymers,
hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed
acrylonitrile-methacrylonitrile copolymers, and the like.
In embodiments of the solid rinse aid composition which are not
aminocarboxylate-free may include added chelating/sequestering agents which
are
aminocarboxylates. Some examples of aminocarboxylic acids include. N-
hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA),
ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-
ethylenediaminetiiacetic
acid (HEDTA) (in addition to the HEDTA used in the binder),
diethylenetriaminepentaacetic acid (DTPA), and the like.
In embodiments of the solid rinse aid composition which are not phosphate-
free, added chelating/sequestering agents may include, for example a condensed
phosphate, a phosphonate, and the like. Some examples of condensed phosphates
include sodium and potassium orthophosphate, sodium and potassium
pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate, and the
like.
A condensed phosphate may also assist, to a limited extent, in solidification
of the
composition by fixing the free water present in the composition as water of
hydration.
In embodiments of the solid rinse aid composition which are not phosphate-
free, the composition may include a phosphonate such as 1-hydroxyethane-1,1-
22
a
diphosphonic acid CH3C(OH)[PO(OH)212; aminotri(methylenephosphonic acid) N[CH2
PO(OH)2 13 ; aminotri(methylenephosphonate), sodium salt
01\1aPOCH2N[CH2P0(0Na)2]2
OH
2-hydroxyethyliminobis(methylenephosphonic acid) HOCH2 CH2 N[CH2 PO(OH)2]2;
diethylenetriaminepenta(methylenephosphonic acid) (110)2 POCH2N[CH2 CH2 N[CH2
PO(OH)2]212; diethylenetriaminepenta(methylenephosphonate), sodium salt C9
H(28.)) N3
Nax0i5P5 (x=7); hexamethylenediamine(tetramethylenephosphonate), potassium
salt CIO H(28-
x)N21(x012P4 (x=6); bis(hexamethylene)triamine(pentamethylenephosphonic acid)
(H02)POCH2NRCH2)6N[CH2 PO(OH)2]212 ; and phosphorus acid H3P03. In some
embodiments, a phosphonate combination such as ATMP and DTPMP may be used. A
neutralized or alkaline phosphonate, or a combination of the phosphonate with
an alkali
source prior to being added into the mixture such that there is little or no
heat or gas generated
by a neutralization reaction when the phosphonate is added can be used.
For a further discussion of chelating agents/sequestrants, see Kirk-Othmer,
Encyclopedia of Chemical Technology, Third Edition, volume 5, pages 339-366
and volume
23, pages 319-320.
The chelant/sequestering agent, if present may be in an amount of from about
0.1 wt.
% to about 30 wt. %, preferably from about 1 wt. % to about 25 wt. % and more
preferably
from about 5 wt. % to about 20 wt. %. In some embodiments, the solid acid may
also perform
as a chelant.
Processing Aids
In some embodiments the solid rinse aid composition can include additional
processing aids. Examples of processing aids include an amide such as stearic
monoethanolamide or lauric diethanolamide, or an alkylamide, and the like; a
solid
polyethylene glycol, or a solid EO/PO block copolymer, urea and the like;
starches
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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 rinse aid 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 in the range of up to about 10 wt%. In some embodiments, secondary
hardening agents are may be present in an amount in the range of 0-10 wt%,
often in
the range of 0 to 5 wt% and sometimes in the range of about 0 to about .5 wt-
%.
Additional surfactant
In addition to the nonionic surfactants specified above, the composition may
also include other surfactants as enumerated hereinafter.
Anionic Surfactants
Certain embodiments of the invention contemplate the use of one or more
anionic surfactants which electrostatically interact or ionically interact
with the
positively charged polymer to enhance foam stability. Anionic surfactants are
surface active substances which are categorized as anionics because the charge
on
the hydrophobe is negative; or surfactants in which the hydrophobic section of
the
molecule carries no charge unless the pH is elevated to neutrality or above
(e.g.
carboxylic acids). Carboxylate, sulfonate, sulfate and phosphate are the polar
(hydrophilic) solubilizing groups found in anionic surfactants. Of the cations
(counter ions) associated with these polar groups, sodium, lithium and
potassium
impart water solubility; ammonium and substituted ammonium ions provide both
water and oil solubility; and, calcium, barium, and magnesium promote oil
solubility.
As those skilled in the art understand, anionics are excellent detersive
surfactants and are therefore traditionally favored additions to heavy duty
detergent
compositions as well as rinse aids. Generally, anionics have high foam
profiles
which are useful for the present foaming cleaning compositions. Anionic
surface
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active compounds are useful to impart special chemical or physical properties
other
than detergency within the composition.
The majority of large volume commercial anionic surfactants can be
subdivided into five major chemical classes and additional sub-groups known to
those of skill in the art and described in "Surfactant Encyclopedia,"
Cosmetics &
Toiletries, Vol. 104 (2) 71-86 (1989).
The first class includes acylamino acids (and salts), such as acylgluamates,
acyl peptides, sarcosinates (e.g. N-acyl sarcosinates). taurates (e.g. N-acyl
taurates
and fatty acid amides of methyl tauride), and the like. The second class
includes
carboxylic acids (and salts), such as alkanoic acids (and alkanoates), ester
carboxylic
acids (e.g. alkyl succinates), ether carboxylic acids, and the like. The third
class
includes sulfonic acids (and salts), such as isethionates (e.g. acyl
isethionates),
alkylaryl sulfonates, alkyl sulfonates, sulfosuccinates (e.g. monoesters and
diesters
of sulfosuccinate), and the like. A particularly preferred anionic surfactant
is alpha
olefin sulfonate. The fourth class includes sulfonic acids (and salts), such
as
isethionates (e.g. acyl isethionates), alkylaryl sulfonates, alkyl sulfonates,
sulfosuccinates (e.g. monoesters and diesters of sulfosuccinate), and the
like. The
fifth class includes sulfuric acid esters (and salts), such as alkyl ether
sulfates, alkyl
sulfates, and the like. The fifth class includes sulfuric acid esters (and
salts), such as
alkyl ether sulfates, alkyl sulfates, and the like. A particularly preferred
anionic
surfactant is sodium laurel ether sulfate.
Anionic sulfate surfactants suitable for use in the present compositions
include the linear and branched primary and secondary alkyl sulfates, alkyl
ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide
ether
sulfates, the C5 -C17 acyl-N--(Ci-C4 alkyl) and --N--(C1-C2 hydroxyalkyl)
glucamine
sulfates, and sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
herein).
Ammonium and substituted ammonium (such as mono-, di- and triethanolamine)
and alkali metal (such as sodium, lithium and potassium) salts of the alkyl
mononuclear aromatic sulfonates such as the alkyl benzene sulfonates
containing
from 5 to 18 carbon atoms in the alkyl group in a straight or branched chain,
e.g., the
salts of alkyl benzene sulfonates or of alkyl toluene, xylene, cumene and
phenol
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sulfonates; alkyl naphthalene sulfonate, diamyl naphthalene sulfonate, and
dinonyl
naphthalene sulfonate and alkoxylated derivatives.
Examples of suitable synthetic, water soluble anionic surfactant compounds
include the ammonium and substituted ammonium (such as mono-, di- and
triethanolamine) and alkali metal (such as sodium, lithium and potassium)
salts of
the alkyl mononuclear aromatic sulfonates such as the alkyl benzene sulfonates
containing from 5 to 18 carbon atoms in the alkyl group in a straight or
branched
chain, e.g., the salts of alkyl benzene sulfonates or of alkyl toluene,
xylene, cumene
and phenol sulfonates; alkyl naphthalene sulfonate, diamyl naphthalene
sulfonate,
and dinonyl naphthalene sulfonate and alkoxylated derivatives.
Anionic carboxylate surfactants suitable for use in the present compositions
include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate
surfactants and the soaps (e.g. alkyl carboxyls). Secondary soap surfactants
(e.g.
alkyl carboxyl surfactants) useful in the present compositions include those
which
contain a carboxyl unit connected to a secondary carbon. The secondary carbon
can
be in a ring structure, e.g. as in p-octyl benzoic acid, or as in alkyl-
substituted
cyclohexyl carboxylates. The secondary soap surfactants typically contain no
ether
linkages, no ester linkages and no hydroxyl groups. Further, they typically
lack
nitrogen atoms in the head-group (amphiphilic portion). Suitable secondary
soap
surfactants typically contain 11-13 total carbon atoms, although more carbons
atoms
(e.g., up to 16) can be present.
Other anionic surfactants suitable for use in the present compositions
include olefin sulfonates, such as long chain alkene sulfonates, long chain
hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkane-
sulfonates. Also included are the alkyl sulfates, alkyl poly(ethyleneoxy)ether
sulfates and aromatic poly(ethyleneoxy)sulfates such as the sulfates or
condensation
products of ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylene
groups per molecule). Resin acids and hydrogenated resin acids are also
suitable,
such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin
acids
present in or derived from tallow oil.
The particular salts will be suitably selected depending upon the particular
formulation and the needs therein.
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Further examples of suitable anionic surfactants are given in "Surface Active
Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety
of
such surfactants are also generally disclosed in U.S. Pat. No. 3,929,678.
issued Dec.
30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
Zwitterionic Surfactants
Zwitterionic surfactants can be thought of as a subset of the amphoteric
surfactants. Zwitterionic surfactants can be broadly described as derivatives
of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary
amines, or derivatives of quaternary ammonium, quaternary phosphonium or
tertiary
sulfonium compounds. Typically, a zwitterionic surfactant includes a positive
charged quaternary ammonium or, in some cases, a sulfonium or phosphonium ion,
a negative charged carboxyl group, and an alkyl group. Zwitterionics generally
contain cationic and anionic groups which ionize to a nearly equal degree in
the
isoelectric region of the molecule and which can develop strong "inner-salt"
attraction between positive-negative charge centers. Examples of such
zwitterionic
synthetic surfactants include derivatives of aliphatic quaternary ammonium,
phosphonium, and sulfonium compounds, in which the aliphatic radicals can be
straight chain or branched, and wherein one of the aliphatic substituents
contains
from 8 to 18 carbon atoms and one contains an anionic water solubilizing
group,
e.g., carboxy, sulfonate, sulfate, phosphate, or phosphonate. Betaine and
sultaine
surfactants are exemplary zwitterionic surfactants for use herein.
A general formula for these compounds is:
wherein R1 contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8 to 18
carbon atoms having from 0 to 10 ethylene oxide moieties and from 0 to 1
glyceryl
moiety; Y is selected from the group consisting of nitrogen, phosphorus, and
sulfur
atoms; R2 is an alkyl or monohydroxy alkyl group containing 1 to 3 carbon
atoms; x
is 1 when Y is a sulfur atom and 2 when Y is a nitrogen or phosphorus atom, R3
is
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an alkylene or hydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon
atoms
and Z is a radical selected from the group consisting of carboxylate,
sulfonate,
sulfate, phosphonate, and phosphate groups.
Examples of zwitterionic surfactants having the structures listed above
include: 4-[N,N-di(2-hydroxyethy1)-N-octadecylammonio]-butane-1-car- boxylate;
5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-3-hydroxypentane-1-sul- fate; 3-[P,P-
diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane- -1-phosphate; 3-
[N,N-dipropyl-N-3-dodecoxy-2-hydroxypropyl-ammonio]-propan- e-l-
phosphonate; 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3-(N,N-
dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate; 4-[N,N-di(2(2-
hydroxyethyl)-N(2-hydroxydodecypammonio]-butane-1-carboxyl- ate; 3-ES-ethyl-
S-(3-dodecoxy-2-hydroxypropyl)sulfoniol-propane-1-phosphat- e; 3-[P,P-dimethyl-
P-dodecylphosphonio]-propane-1-phosphonate; and S [N,N-di(3-hydroxypropy1)-N-
hexadecylammonio]-2-hydroxy-pentane-1-sulfate. The alkyl groups contained in
said detergent surfactants can be straight or branched and saturated or
unsaturated.
The zwitterionic surfactant suitable for use in the present compositions
includes a betaine of the general structure:
¨ W¨C142.¨C.Q? .....................
r ¨ctk¨co.t.
These surfactant betaines typically do not exhibit strong cationic or anionic
characters at pH extremes nor do they show reduced water solubility in their
isoelectric range. Unlike "external" quaternary ammonium salts, betaines are
compatible with anionics. Examples of suitable betaines include coconut
acylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C 12-14
acylamidopropylbetaine; C8-14 acylamidohexyldiethyl betaine; 4-C 14-16
acylmethylamidodiethylammonio-l-carboxybutane; C 16-18
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acylamidodimethylbetaine; C 12_16 acylamidopentanediethylbetaine; and C 12_16
acylmethylamidodimethylbetaine.
Sultaines useful in the present invention include those compounds having the
formula (R(R1)2N+R2S03-, in which R is a C6-C18 hydrocarbyl group, each
R1
is typically independently C1-C3 alkyl, e.g. methyl, and R2 is a Ci-C6
hydrocarbyl
group, e.g. a C1-C3 alkylene or hydroxyalkylene group.
A typical listing of zwitterionic classes, and species of these surfactants,
is
given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30,
1975.
Further examples are given in "Surface Active Agents and Detergents" (Vol. I
and II
by Schwartz, Perry and Berch).
Betaines and sultaines and other such zwitterionic surfactants are present in
an amount of from Anionic surfactants are present in the composition in any
detersive amount which can range typically from about 0.01 wt. % to about 75
wt. %
of the rinse aid composition. In a preferred embodiment, about 10 wt. % to
about 30
wt. % and more preferably from about 15 wt. % to about 25 wt. %.
Semi-Polar Nonionic Surfactants
The semi-polar type of nonionic surface active agents is another class of
nonionic surfactant useful in compositions of the present invention.
Generally,
semi-polar nonionics are high foamers and foam stabilizers, which can limit
their
application in CIP systems. However, within compositional embodiments of this
invention designed for high foam cleaning methodology, semi-polar nonionics
would have immediate utility. The semi-polar nonionic surfactants include the
amine oxides, phosphine oxides, sulfoxides and their alkoxylated derivatives.
Amine oxides are tertiary amine oxides corresponding to the general
formula:
Ito
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wherein the arrow is a conventional representation of a semi-polar bond; and
R1, R2,
and R3 may be aliphatic, aromatic, heterocyclic, alicyclic, or combinations
thereof.
Generally, for amine oxides of detergent interest, 121 is an alkyl radical of
from 8 to
24 carbon atoms; R2 and R3 are alkyl or hydroxyalkyl of 1-3 carbon atoms or a
mixture thereof; R2 and R3 can be attached to each other, e.g. through an
oxygen or
nitrogen atom, to form a ring structure; R4 is an alkaline or a
hydroxyalkylene group
containing 2 to 3 carbon atoms; and n ranges from 0 to 20.
Useful water soluble amine oxide surfactants are selected from the coconut
or tallow alkyl di-(lower alkyl) amine oxides, specific examples of which are
dodecyldimethylamine oxide, tridecyldimethylamine oxide,
tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,
hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,
octadecyldimethylamine oxide, dodecyldipropylamine oxide,
tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,
tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis(2-
hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-1-h-
ydroxypropylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-
trioctadecyldimethylamine oxide and 3-dodecoxy-2-hydroxypropyldi-(2- -
hydroxyethyl)amine oxide.
Useful semi-polar nonionic surfactants also include the water soluble
phosphine oxides having the following structure:
1;0
wherein the arrow is a conventional representation of a semi-polar bond; and
R1 is
an alkyl, alkenyl or hydroxyalkyl moiety ranging from 10 to 24 carbon atoms in
chain length; and R2 and R3 are each alkyl moieties separately selected from
alkyl or
hydroxyalkyl groups containing 1 to 3 carbon atoms.
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Examples of useful phosphine oxides include dimethyldecylphosphine oxide,
dimethyltetradecylphosphine oxide, methylethyltetradecylphosphine oxide,
dimethylhexadecylphosphine oxide, diethyl-2-hydroxyoctyldecylphosp- hine
oxide,
bis(2-hydroxyethyl)dodecylphosphine oxide, and
bis(hydroxymethyl)tetradecylphosphine oxide.
Semi-polar nonionic surfactants useful herein also include the water soluble
sulfoxide compounds which have the structure:
wherein the arrow is a conventional representation of a semi-polar bond; and,
RI is
an alkyl or hydroxyalkyl moiety of 8 to 28 carbon atoms, from 0 to 5 ether
linkages
and from 0 to 2 hydroxyl substituents; and R2 is an alkyl moiety consisting of
alkyl
and hydroxyalkyl groups having 1 to 3 carbon atoms.
Useful examples of these sulfoxides include dodecyl methyl sulfoxide; 3-
hydroxy tridecyl methyl sulfoxide; 3-methoxy tridecyl methyl sulfoxide: and 3-
hydroxy-4-dodecoxybutyl methyl sulfoxide.
Further examples of suitable anionic surfactants are given in "Surface Active
Agents
and Detergents" (Vol. I and 11 by Schwartz, Perry and Berch). A variety of
such
surfactants are also generally disclosed in U.S. Pat. No. 3,929,678, issued
Dec. 30,
1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23.
Cationic Surfactants
Surface active substances are classified as cationic if the charge on the
hydrotrope portion of the molecule is positive. Surfactants in which the
hydrotrope
carries no charge unless the pH is lowered close to neutrality or lower, but
which are
then cationic (e.g. alkyl amines), are also included in this group. In theory,
cationic
surfactants may be synthesized from any combination of elements containing an
"onium" structure RnX+Y-- and could include compounds other than nitrogen
(ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium). In
practice, the cationic surfactant field is dominated by nitrogen containing
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compounds, probably because synthetic routes to nitrogenous cationics are
simple
and straightforward and give high yields of product, which can make them less
expensive.
Cationic surfactants preferably include, more preferably refer to, compounds
containing at least one long carbon chain hydrophobic group and at least one
positively charged nitrogen. The long carbon chain group may be attached
directly
to the nitrogen atom by simple substitution; or more preferably indirectly by
a
bridging functional group or groups in so-called interrupted alkylamines and
amido
amines. Such functional groups can make the molecule more hydrophilic and/or
more water dispersible, more easily water solubilized by co-surfactant
mixtures,
and/or water soluble. For increased water solubility, additional primary,
secondary
or tertiary amino groups can be introduced or the amino nitrogen can be
quaternized
with low molecular weight alkyl groups. Further, the nitrogen can be a part of
branched or straight chain moiety of varying degrees of unsaturation or of a
saturated or unsaturated heterocyclic ring. In addition, cationic surfactants
may
contain complex linkages having more than one cationic nitrogen atom.
The surfactant compounds classified as amine oxides, amphoterics and
zwitterions are themselves typically cationic in near neutral to acidic pH
solutions
and can overlap surfactant classifications. Polyoxyethylated cationic
surfactants
generally behave like nonionic surfactants in alkaline solution and like
cationic
surfactants in acidic solution.
The simplest cationic amines, amine salts and quaternary ammonium
compounds can be schematically drawn thus:
-IT R R X'
in which, R represents a long alkyl chain, R', R", and RI" may be either long
alkyl
chains or smaller alkyl or aryl groups or hydrogen and X represents an anion.
The
amine salts and quaternary ammonium compounds are preferred for practical use
in
this invention due to their high degree of water solubility.
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The majority of large volume commercial cationic surfactants can be
subdivided into four major classes and additional sub-groups known to those of
skill
in the art and described in "Surfactant Encyclopedia," Cosmetics & Toiletries,
Vol.
104 (2) 86-96 (1989). The first class includes alkylamines and their salts.
The
second class includes alkyl imidazolines. The third class includes ethoxylated
amines. The fourth class includes quaternaries, such as
alkylbenzyldimethylammonium salts, alkyl benzene salts, heterocyclic ammonium
salts, tetra alkylammonium salts, and the like. Cationic surfactants are known
to
have a variety of properties that can be beneficial in the present
compositions.
These desirable properties can include detergency in compositions of or below
neutral pH, antimicrobial efficacy, thickening or gelling in cooperation with
other
agents, and the like.
Cationic surfactants useful in the compositions of the present invention
include those having the formula R 1 mR2,YLZ wherein each Rl is an organic
group
containing a straight or branched alkyl or alkenyl group optionally
substituted with
up to three phenyl or hydroxy groups and optionally interrupted by up to four
of the
following structures:
(1:) 0
11
*C===...,,,a,=============..
II
........................................ "C"""
11
peaxecoN C axe
or an isomer or mixture of these structures, and which contains from 8 to 22
carbon
atoms. The R1 groups can additionally contain up to 12 ethoxy groups. m is a
number from 1 to 3. Preferably, no more than one R1 group in a molecule has 16
or
more carbon atoms when m is 2, or more than 12 carbon atoms when m is 3. Each
R2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a
benzyl group with no more than one R2 in a molecule being benzyl, and x is a
number from 0 to 11, preferably from 0 to 6. The remainder of any carbon atom
positions on the Y group is filled by hydrogens.
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Y can be a group including, but not limited to:
1
ptonc1
(C21:140,¨ ¨c10), tii ta 12 P
c
I H
or a mixture thereof.
Preferably, L is l or 2, with the Y groups being separated by a moiety
selected from Rl and R2 analogs (preferably alkylene or alkenylene) having
from 1
to 22 carbon atoms and two free carbon single bonds when L is 2. Z is a water
soluble anion, such as sulfate, methylsulfate, hydroxide, or nitrate anion,
particularly
preferred being sulfate or methyl sulfate anions, in a number to give
electrical
neutrality of the cationic component.
Amphoteric Surfactants
Amphoteric, or ampholytic, surfactants contain both a basic and an acidic
hydrophilic group and an organic hydrophobic group. These ionic entities may
be
any of the anionic or cationic groups described herein for other types of
surfactants.
A basic nitrogen and an acidic carboxylate group are the typical functional
groups
employed as the basic and acidic hydrophilic groups. In a few surfactants,
sulfonate,
sulfate, phosphonate or phosphate provide the negative charge.
Amphoteric surfactants can be broadly described as derivatives of aliphatic
secondary and tertiary amines, in which the aliphatic radical may be straight
chain or
branched and wherein one of the aliphatic substituents contains from 8 to 18
carbon
atoms and one contains an anionic water solubilizing group, e.g., carboxy,
sulfo,
sulfato, phosphato, or phosphono. Amphoteric surfactants are subdivided into
two
major classes known to those of skill in the art and described in "Surfactant
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Encyclopedia," Cosmetics & Toiletries, Vol. 104 (2) 69-71 (1989). The first
class
includes acyl/dialkyl ethylenediamine derivatives (e.g. 2-alkyl hydroxyethyl
imidazoline derivatives) and their salts. The second class includes N-
alkylamino
acids and their salts. Some amphoteric surfactants can be envisioned as
fitting into
both classes.
Atnphoteric surfactants can be synthesized by methods known to those of
skill in the art. For example, 2-alkyl hydroxyethyl imidazoline is synthesized
by
condensation and ring closure of a long chain carboxylic acid (or a
derivative) with
dialkyl ethylenediamine. Commercial amphoteric surfactants are derivatized by
subsequent hydrolysis and ring-opening of the imidazoline ring by alkylation--
for
example with ethyl acetate. During alkylation, one or two carboxy-alkyl groups
react to form a tertiary amine and an ether linkage with differing alkylating
agents
yielding different tertiary amines.
Long chain imidazole derivatives having application in the present invention
generally have the general formula:
NONO)ACTTATE (DonoMONATE
OT):C.O00:
Iõ
RaYMIC:112ClizNwil RCONTICTIzal2,W ClizalaMOFT
pH-.ZIPeuvrion
AMPEWERIC
SU:Ã170NATE
- - = -
11CONIKT14:1E:LN
wherein R is an acyclic hydrophobic group containing from 8 to 18 carbon atoms
and M is a cation to neutralize the charge of the anion, generally sodium.
Commercially prominent imidazoline-derived amphoterics that can be employed in
the present compositions include for example: Cocoamphopropionate,
Cocoamphocarboxy-propionate, Cocoamphoglycinate, Cocoamphocarboxy-
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glycinate, Cocoamphopropyl-sulfonate, and Cocoamphocarboxy-propionic acid.
Preferred amphocarboxylic acids are produced from fatty imidazolines in which
the
dicarboxylic acid functionality of the amphodicarboxylic acid is diacetic acid
and/or
dipropionic acid.
The carboxymethylated compounds (glycinates) described herein above
frequently are called betaines. Betaines are a special class of amphoteric
discussed
herein below in the section entitled, Zwitterion Surfactants.
Long chain N-alkylamino acids are readily prepared by reacting RNH2, in
which R=C8-C18 straight or branched chain alkyl, fatty amines with
halogenated
carboxylic acids. Alkylation of the primary amino groups of an amino acid
leads to
secondary and tertiary amines. Alkyl substituents may have additional amino
groups that provide more than one reactive nitrogen center. Most commercial N-
alkylamine acids are alkyl derivatives of beta-alanine or beta-N(2-
carboxyethyl)
alanine. Examples of commercial N-alkylamino acid ampholytes having
application
in this invention include alkyl beta-amino dipropionates, RN(C2H4COOM)2 and
RNHC2H4COOM. In these, R is preferably an acyclic hydrophobic group
containing from 8 to 18 carbon atoms, and M is a cation to neutralize the
charge of
the anion.
Preferred amphoteric surfactants include those derived from coconut
products such as coconut oil or coconut fatty acid. The more preferred of
these
coconut derived surfactants include as part of their structure an
ethylenediamine
moiety, an alkanolamide moiety, an amino acid moiety, preferably glycine, or a
combination thereof; and an aliphatic substituent of from 8 to 18 (preferably
12)
carbon atoms. Such a surfactant can also be considered an alkyl
amphodicarboxylic
acid. Disodium cocoampho dipropionate is one most preferred amphoteric
surfactant and is commercially available under the tradename MiranolTm FBS
from
Rhodia Inc., Cranbury, N.J. Another most preferred coconut derived amphoteric
surfactant with the chemical name disodium cocoampho diacetate is sold under
the
tradename Miranol C2M-SF Conc., also from Rhodia Inc., Cranbury, N.J.
A typical listing of amphoteric classes, and species of these surfactants, is
given in U.S. Pat. No. 3,929,678 issued to Laughlin and Heuring on Dec. 30,
1975.
36
Further examples are given in ''Surface Active Agents and Detergents" (Vol. I
and II by
Schwartz, Perry and Berch).
Additional surfactant may be present in the compositions in any detersive
amount so
long as they do not interfere with the electrostatic, ionic interactions that
provide for foam
stabilization.
Bleaching Agents
The rinse aid can optionally include bleaching agent. Bleaching agent can be
used for
lightening or whitening a substrate, and can include bleaching compounds
capable of
liberating an active halogen species, such as C12, Br2, -0C1" and/or -0Br-, or
the like, under
conditions typically encountered during the cleansing process. Suitable
bleaching agents for
use can include, for example, chlorine-containing compounds such as a
chlorine, a
hypochlorite, chloramines, of the like. Some examples of halogen-releasing
compounds
include the alkali metal dichloroisocyanurates, chlorinated trisodium
phosphate, the alkali
metal hypochlorites, monochloramine and dichloroamine, and the like.
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). A bleaching agent
may also
include an agent containing or acting as a source of active oxygen. The active
oxygen
compound acts to provide a source of active oxygen, for example, may release
active oxygen
in aqueous solutions. An active oxygen compound can be inorganic or organic,
or can be a
mixture thereof. Some examples of active oxygen compound include peroxygen
compounds,
or peroxygen compound adducts. Some examples of active oxygen compounds or
sources
include hydrogen peroxide, perborates, sodium carbonate peroxyhydrate,
phosphate
peroxyhydrates, potassium permonosulfate, and sodium perborate mono and
tetrahydrate,
with and without activators such as tetraacetylethylene diamine, and the like.
A rinse aid
composition may include a minor but effective amount of a bleaching agent, for
example, in
some embodiments, in the range of up to about 10 wt. %, and in some
embodiments, in the
range of about 0.1 to about 6 wt. %.
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Activators
In some embodiments, the antimicrobial activity or bleaching activity of the
rinse aid 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.
In some embodiments, an activator component can include in the range of up
to about 75 % by wt. of the composition, in some embodiments, in the range of
about 0.01 to about 20% by wt, or in some embodiments, in the range of about
0.05
to 10% by weight of the composition. In some embodiments, an activator for an
active oxygen compound combines with the active oxygen to form an
antimicrobial
agent.
In some embodiments, the rinse aid composition includes a solid, such as a
solid flake, pellet, or block, and an activator material for the active oxygen
is
coupled to the solid. The activator can be coupled to the solid by any of a
variety of
methods for coupling one solid 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 of the rinse aid composition. Alternatively, the solid activator can be
formed
around and encasing the solid rinse aid composition. By way of further
example, the
solid activator can be coupled to the solid rinse aid composition by the
container or
package for the composition, such as by a plastic or shrink wrap or film.
Fillers
The rinse aid can optionally include a minor but effective amount of one or
more of a filler which does not necessarily perform as a rinse and/or cleaning
agent
per se, but may cooperate with a rinse agent to enhance the overall capacity
of the
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composition. Some examples of suitable fillers may include sodium chloride,
starch, sugars, C1 -C10 alkylene glycols such as propylene glycol, and the
like. In
some embodiments, a filler can be included in an amount in the range of up to
about
20 wt. %, and in some embodiments, in the range of about 1-15 wt. %. Sodium
sulfate is conventionally used as inert filler.
Anti-Redeposition Agents
The rinse aid composition can optionally include an anti-redeposition agent
capable of facilitating sustained suspension of soils in a rinse solution and
preventing removed soils from being redeposited onto the substrate being
rinsed.
Some examples of suitable anti-redeposition agents can 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 rinse aid composition may include up
to
about 10 wt. %, and in some embodiments, in the range of about lto about 5 wt.
%,
of an anti-redeposition agent.
Dyes/Odorants
Various dyes, odorants including perfumes, and other aesthetic enhancing
agents may also be included in the rinse aid. Dyes may be included to alter
the
appearance of the composition, as for example, FD&C Blue 1 (Sigma Chemical),
FD&C Yellow 5 (Sigma Chemical), 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.
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 Cl S-jasmine or jasmal, vanillin, and the like.
39
Functional Polydimethylsiloxones
The composition can also optionally include one or more functional
polydimethylsiloxones. For example, in some embodiments, a polyalkylene oxide-
modified
polydimethylsiloxane, nonionic surfactant or a polybetaine-modified
polysiloxane amphoteric
surfactant can be employed as an additive. Both, in some embodiments, are
linear
polysiloxane copolymers to which polyethers or polybetaines have been grafted
through a
hydrosilation reaction. Some examples of specific siloxane surfactants are
known as
SILWET surfactants available from Union Carbide or ABIL polyether or
polybetaine
polysiloxane copolymers available from Goldschmidt Chemical Corp., and
described in U.S.
Pat. No. 4,654,161. In some embodiments, the particular siloxanes used can be
described as
having, e.g., low surface tension, high wetting ability and excellent
lubricity. For example,
these surfactants are said to be among the few capable of wetting
polytetrafluoroethylene
surfaces. The siloxane surfactant employed as an additive can be used alone or
in combination
with a fluorochemical surfactant. In some embodiments, the fluorochemical
surfactant
employed as an additive optionally in combination with a silane, can be, for
example, a
nonionic fluorohydrocarbon, for example, fluorinated alkyl polyoxyethylene
ethanols,
fluorinated alkyl alkoxylate and fluorinated alkyl esters.
Further description of such functional polydimethylsiloxones and/or
fluorochemical
surfactants are described in U.S. Pat. Nos. 5,880,088; 5,880,089; and
5,603,776. We have
found, for example, that the use of certain polysiloxane copolymers in a
mixture with
hydrocarbon surfactants provide excellent rinse aids on plasticware. We have
also found that
the combination of certain silicone polysiloxane copolymers and fluorocarbon
surfactants
with conventional hydrocarbon surfactants also provide excellent rinse aids on
plasticware.
This combination has been found to be better than the individual components
except with
certain polyalkylene oxide-modified polydimethylsiloxanes and polybetaine
polysiloxane
copolymers, where the effectiveness is about equivalent. Therefore, some
embodiments
encompass the polysiloxane copolymers alone and the combination with the
fluorocarbon
surfactant can involve polyether polysiloxanes, the nonionic siloxane
surfactants. The
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amphoteric siloxane surfactants, the polybetaine polysiloxane copolymers may
be
employed alone as the additive in the rinse aids to provide the same results.
In some embodiments, the composition may include functional
polydimethylsiloxones in an amount in the range of up to about 10 wt-%. For
example, some embodiments may include in the range of about 0.1 to 10 wt-% of
a
polyalkylene oxide-modified polydimethylsiloxane or a polybetaine-modified
polysiloxane, optionally in combination with about 0.1 to 10 wt-% of a
fluorinated
hydrocarbon nonionic surfactant.
Humectant
The composition can also optionally include one or more humectants. A
humectant is a substance having an affinity for water. The humectant can be
provided in an amount sufficient to aid in reducing the visibility of a film
on the
substrate surface. The visibility of a film on substrate surface is a
particular concern
when the rinse water contains in excess of 200 ppm total dissolved solids.
Accordingly, in some embodiments, the humectant is provided in an amount
sufficient to reduce the visibility of a film on a substrate surface when the
rinse
water contains in excess of 200 ppm total dissolved solids compared to a rinse
agent
composition not containing the humectant. The terms "water solids filming" or
"filming" refer to the presence of a visible, continuous layer of matter on a
substrate
surface that gives the appearance that the substrate surface is not clean.
Some example humectants that can be used include those materials that
contain greater than 5 wt. % water (based on dry humectant) equilibrated at
50%
relative humidity and room temperature. Exemplary humectants that can be used
include glycerin, propylene glycol, sorbitol, alkyl polyglycosides,
polybetaine
polysiloxanes, and mixtures thereof. In some embodiments, the rinse agent
composition can include humectant in an amount in the range of up to about 75%
based on the total composition, and in some embodiments, in the range of about
5
wt. % to about 75 wt. % based on the weight of the composition.
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Other Ingredients
A wide variety of other ingredients useful in providing the particular
composition being formulated to include desired properties or functionality
may also
be included. For example, the rinse aid may include other active ingredients,
such as
pH modifiers, buffering agents, cleaning enzyme, carriers, processing aids, or
others,
and the like.
Additionally, the rinse aid can be formulated such that during use in aqueous
operations, for example in aqueous cleaning operations, the rinse water will
have a
desired pH. For example, compositions designed for use in rinsing may be
formulated such that during use in aqueous rinsing operation the rinse water
will
have a pH in the range of about 3 to about 5. or in the range of about 5 to
about 9.
Liquid product formulations in some embodiments have a (10% dilution) pH in
the
range of about 2 to about 4. Techniques for controlling pH at recommended
usage
levels include the use of buffers, alkali, acids, etc., and are well known to
those
skilled in the art.
Processing and/or Manufacturing of the Composition
The present solid composition can be made by an advantageous method of
pressing the solid composition. Specifically, in a forming process, the liquid
and
solid components are introduced into the final mixing system and are
continuously
mixed until the components form a substantially homogeneous semi-solid mixture
in
which the components are distributed throughout its mass. In an exemplary
embodiment, the components are mixed in the mixing system for at least
approximately 5 seconds. The mixture is then discharged from the mixing system
into, or through, a die, press or other shaping means. The product is then
packaged.
In an exemplary embodiment, the solid formed composition begins to harden
between approximately 1 minute and approximately 3 hours. Particularly, the
formed composition begins to harden in between approximately 1 minute and
approximately 2 hours. More particularly, the formed composition begins to
harden
in between approximately 1 minute and approximately 20 minutes.
The method of the present invention can produce a stable solid without
employing a melt and solidification of the melt as in conventional casting.
Forming
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a melt requires heating a composition to melt it. The heat can be applied
externally
or can be produced by a chemical exotherm (e.g., from mixing caustic (sodium
hydroxide) and water). Heating a composition consumes energy. Handling a hot
melt requires safety precautions and equipment. Further, solidification of a
melt
requires cooling the melt in a container to solidify the melt and form the
cast solid.
Cooling requires time and/or energy. In contrast, the present method can
employ
ambient temperature and humidity during solidification or curing of the
present
compositions. The solids of the present invention are held together not by
solidification from a melt but by a binding agent produced in the admixed
particles
and that is effective for producing a stable solid.
While the invention advantageously may be formed to solid by pressing,
other methods of solid formation may also be used such as extrusion, cast
molding
and the like.
In an exemplary embodiment, a single- or twin-screw extruder may be used
to combine and mix one or more components agents at high shear to form a
homogeneous mixture. In some embodiments, the processing temperature is at or
below the melting temperature of the components. The processed mixture may be
dispensed from the mixer by pressing, forming, extruding or other suitable
means,
whereupon the composition hardens to a solid form. The structure of the matrix
may
be characterized according to its hardness, melting point, material
distribution,
crystal structure, and other like properties according to known methods in the
art.
Generally, a solid composition processed according to the method of the
invention is
substantially homogeneous with regard to the distribution of ingredients
throughout
its mass and is dimensionally stable.
The resulting solid composition may take forms including, but not limited to:
an extruded, molded or formed solid pellet, block, tablet, powder, granule,
flake; or
the formed solid can thereafter be ground or formed into a powder, granule, or
flake.
In an exemplary embodiment, extruded pellet materials formed have a weight of
between approximately 50 grams and approximately 250 grams, extruded solids
have a weight of approximately 100 grams or greater, and solid blocks formed
have
a mass of between approximately 1 and approximately 10 kilograms. The solid
compositions provide for a stabilized source of functional materials. In a
preferred
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embodiment, the solid composition may be dissolved, for example, in an aqueous
or
other medium, to create a concentrated and/or use solution. The solution may
be
directed to a storage reservoir for later use and/or dilution, or may be
applied
directly to a point of use.
In certain embodiments, the solid rinse aid composition is provided in the
form of a unit dose. A unit dose refers to a solid rinse aid 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.
In other embodiments, the solid rinse aid 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 rinse compositions for multiple washing
cycles.
In certain embodiments, the solid rinse aid 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 rinse aid composition has a mass of about 1 to 10 kg. In further
embodiments,
a multiple-use form of the solid rinse aid composition has a mass of about 5
kg to
about 8 kg. In other embodiments, a multiple-use form of the solid rinse aid
composition has a mass of about 5 g to about 1 kg, or about 5 g and to 500 g.
Packaging System
The solid rinse aid composition can be, but is not necessarily, incorporated
into a packaging system or receptacle. The packaging receptacle or container
may
be rigid or flexible, and include any material suitable for containing the
compositions produced, as for example elass, metal, plastic film or sheet,
cardboard,
cardboard composites, paper, or the like. Rinse aid compositions may be
allowed to
solidify in the packaging or may be packaged after formation of the solids in
commonly available packaging and sent to distribution center before shipment
to the
consumer.
For solids, advantageously, in at least some embodiments, since the rinse is
processed at or near ambient temperatures, the temperature of the processed
mixture
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is low enough so that the mixture may be cast or extruded directly into 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. In some
embodiments, the packaging used to contain the rinse aid is manufactured from
a
flexible, easy opening film material.
Dispensing/Use of the Rinse Aid
The rinse aid can be dispensed as a concentrate or as a use solution. In
addition, the rinse aid concentrate can be provided in a solid form or in a
liquid
form. In general, it is expected that the concentrate will be diluted with
water to
provide the use solution that is then supplied to the surface of a substrate.
In some
embodiments, the aqueous use solution may contain about 2,000 parts per
million
(ppm) or less active materials, or about 1,000 ppm or less active material, or
in the
range of about 10 ppm to about 500 ppm of active materials, or in the range of
about
10 to about 300 ppm, or in the range of about 10 to 200 ppm.
The use solution can be applied to the substrate during a rinse application,
for example, during a rinse cycle, for example, in a warewashing machine, a
car
wash application, institutional healthcare surface cleaning or the like. In
some
embodiments, formation of a use solution can occur from a rinse agent
installed in a
cleaning machine, for example onto a dish rack. The rinse agent can be diluted
and
dispensed from a dispenser mounted on or in the machine or from a separate
dispenser that is mounted separately but cooperatively with the dish machine.
For example, in some embodiments, liquid rinse agents can be dispensed by
incorporating compatible packaging containing the liquid material into a
dispenser
adapted to diluting the liquid with water to a final use concentration. Some
examples of dispensers for the liquid rinse agent of the invention are
DRYMASTER-P sold by Ecolab Inc., St. Paul, Minn.
In other example embodiments, solid products may be conveniently
dispensed by inserting a solid material in a container or with no enclosure
into a
spray-type dispenser such as the volume SOL-ET controlled ECOTEMP Rinse
Injection Cylinder system manufactured by Ecolab Inc., St. Paul, Minn. Such a
dispenser cooperates with a washing machine in the rinse cycle. When demanded
by the
machine, the dispenser directs water onto the solid block of rinse agent which
effectively
dissolves a portion of the block creating a concentrated aqueous rinse
solution which is then
fed directly into the rinse water forming the aqueous rinse. The aqueous rinse
is then
contacted with the surfaces to affect a complete rinse. This dispenser and
other similar
dispensers are capable of controlling the effective concentration of the
active portion in the
aqueous rinse by measuring the volume of material dispensed, the actual
concentration of the
material in the rinse water (an electrolyte measured with an electrode) or by
measuring the
time of the spray on the cast block. In general, the concentration of active
portion in the
aqueous rinse is preferably the same as identified above for liquid rinse
agents. Some other
embodiments of spray-type dispenser are 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. An example of
a particular
product shape is shown in FIG. 9 of U.S. Patent No. 6,258,765.
The composition of the invention is particularly beneficial for use with hard
water.
The composition can provide good rinsing and levels up to 20gpg water
hardness.
In some embodiments, it is believed that the rinse aid composition of the
invention can
be used in a high solids containing water environment in order to reduce the
appearance of a
visible film caused by the level of dissolved solids provided in the water. In
general, high
solids containing water is considered to be water having a total dissolved
solids (TDS) content
in excess of 200 ppm. In certain localities, the service water contains total
dissolved solids
content in excess of 400 ppm, and even in excess of 800 ppm. The applications
where the
presence of a visible film after washing a substrate is a particular problem
includes the
restaurant or warewashing industry, the car wash industry, the healthcare
instrument
reprocessing and cart washing sections, and the general cleaning of hard
surfaces.
When used in these automated washing applications such as ware washers and
healthcare instrument and cart washers, the rinse aid should provide effective
sheeting action
and low foaming properties. It is believed that the rinse aid
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composition of this invention is adventurously formulated to control the
issues
mentioned above
Methods and Compositions for Cleaning, Rinsing, and Antimicrobial
Treatment of Medical Carts, Cages, Instruments, or Devices
The present methods and solid rinse aid compositions may be used for
cleaning a medical cart, cage, instrument, or device in a medical or health
care
environment. Typically, cleaning a medical cart, cage, instrument, or device
includes
contacting the medical cart, cage, instrument, or device with an aqueous
cleaning
composition and then according to the invention, rinsing or contacting the
same with
a rinse solution comprising a dissolved rinse aid of the invention. The method
can
also involve antimicrobial treatment of the medical cart, cage, instrument, or
device
by contacting with an aqueous antimicrobial composition formed by dissolving
or
suspending a solid antimicrobial composition, preferably a solid quaternary
ammonium or solid halogen antimicrobial composition.
Contacting with a cleaning composition can take place through manual
application in a wash area or bay or through application by cart, cage,
instrument, or
device washing apparatus. In a manual method rinsing and/or antimicrobial
treatment can also take place in the wash area or bay, or in a separate area
or bay. A
typical cart, cage, instrument, or device washing apparatus includes a wash
station
which applies the cleaning composition. Typically such a washing apparatus
also
includes a rinse station that can rinse the cart, cage, instrument, or device
with water
or another suitable rinse composition, such as a solid neutral or neutralizing
rinse
composition. Such a washing apparatus can also, optionally, include an
antimicrobial treatment station that can contact the cart, cage, instrument,
or device
with a dissolved solid antimicrobial composition, such as a solid quaternary
ammonium or solid halogen antimicrobial composition. A washing apparatus can
conduct one or more of washing, rinsing, and/or antimicrobial treatment of
steps at
one, two, three, or more stations.
The present methods and compositions for rinsing a medical cart, cage,
instrument, or device can be employed for rinsing a medical cart, cage,
instrument,
or device made of a variety of materials in a medical or health care
environment.
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Typically, rinsing a medical cart, cage, instrument, or device includes
rinsing the
medical cart, cage, instrument, or device using an aqueous rinse composition
formed
by dissolving or suspending the solid rinse composition of the invention.
Contacting with a rinsing composition can take place through manual
application in a rinse area or bay or through application by cart, cage,
instrument, or
device washing and/or rinsing apparatus. In a manual method cleaning and/or
antimicrobial treatment can also take place in the rinse area or bay, or in a
separate
area or bay. A typical cart, cage, instrument, or device washing apparatus
includes a
rinse station that can rinse the cart, cage, instrument, or device with a
liquid rinse
composition formed from a solid neutral or neutralizing rinse composition.
Such a
washing apparatus can also, optionally, include a washing and/or antimicrobial
treatment station.
The antimicrobial composition employed either for manual or machine
medical cart, cage, instrument, or device antimicrobial treatment can be a
solid
antimicrobial composition, preferably a solid quaternary ammonium or solid
halogen antimicrobial composition, which is described in greater detail herein
below.
[0042] Methods for Medical Cart Cleaning
[0043] Medical cart cleaning can be accomplished either manually or with a
machine. Manual medical cart cleaning can include preparing a use composition
of a
solid cleaning composition and applying it to the medical cart. Applying
typically
includes wiping or scrubbing the medical cart with a brush, a towel, or a
sponge
soaked with the cleaning composition. Applying can also include spraying the
cart
with the use composition. Manual medical cart cleaning can also include
preparing a
use composition of a rinse composition, preferably a neutral rinse
composition, and
applying it to the medical cart. Applying a rinse composition can include
spraying,
pouring, or wiping the use composition onto the cart. Manual medical cart
cleaning
can also include preparing a use composition of a solid antimicrobial
composition,
preferably a solid quaternary ammonium or solid halogen antimicrobial
composition, and applying it to the medical cart. Applying an antimicrobial
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composition can include spraying, pouring, or wiping the use composition onto
the
cart. Drying the medical cart, either manually or air drying, typically
follows rinsing.
Machine cleaning of a medical cart can employ any of a variety of
configurations of medical cart cleaning apparatus. Such apparatus can be
adapted to
dispense the solid detergent, rinse aid composition of the invention and/or
antimicrobial composition. A medical cart cleaning apparatus typically
includes at
least one chamber that houses the medical cart during washing, rinsing, and/or
antimicrobial treatment.
Smaller medical cart cleaning apparatus typically include a single chamber
sized to house, for example, 1-3 medical carts. Medical carts can be
introduced into
the smaller apparatus by an operator through a door or other coverable opening
in
the chamber. The apparatus then subjects the carts in the chamber to one or
more of
washing, rinsing, antimicrobial treatment, and/or drying cycles. Washing
typically
occurs by spraying the medical cart with a use wash composition. Rinsing
typically
occurs by spraying the medical cart with a use rinse composition. Optionally,
antimicrobial treatment can occur by spraying the medical cart with a use
antimicrobial composition. Drying can occur by blowing ambient or heated air,
or
by treating with steam. Medical carts can be removed from the chamber by an
operator through the same door or other coverable opening or through an exit
door
or other coverable opening on an opposite side of the apparatus.
Larger medical cart cleaning apparatus typically includes a transport
apparatus that transports one or several carts through one or more chambers
including washing, rinsing, optionally antimicrobial treatment, and/or drying
stations. Such a medical cart cleaning apparatus can resemble a touchless car
wash
sized and configured for cleaning medical carts instead of cars. Typically the
cart is
transported through the washing, rinsing, optional antimicrobial treatment,
and/or
drying stations by a track or rail apparatus while tipped at an acute angle
from the
horizontal, with its doors (if any) open. This tipping can keep the doors open
and
allow liquid to drain off any normally horizontal surfaces of the medical
cart. The
entry to a larger medical cart cleaning apparatus can be covered, for example,
by a
door or with hanging plastic strips that allow entry of carts but that retain
use
compositions in the apparatus. The wash station typically sprays the medical
cart
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with use wash composition. A rinse station typically sprays the medical cart
with use
rinse composition. An optional antimicrobial treatment station typically
sprays the
medical cart with use antimicrobial composition. At the drying station,
blowers blow
ambient or heated air on the cart, or the cart is steam treated.
Alternatively, the cart
can be removed from the apparatus and towel dried. One or more stations can be
at
different, overlapping, or the same locations. The exit from the apparatus can
be
covered in the same manner as the entrance.
Mechanical cart washers can employ up to about 30 to about 40 gallons of
use composition of cleaning composition per wash cycle, up to about 30 to
about 40
gallons of use composition rinse composition per rinse cycle, and, optionally,
up to
about 30 to about 40 gallons of use antimicrobial composition per
antimicrobial
treatment cycle. The actual amount of cleaning, rinsing, or antimicrobial
composition used will be based on the judgment of the user, and will depend
upon
factors such as the particular product formulation of the composition. the
concentration of the composition, the number of soiled carts to be cleaned and
the
degree of soiling of the carts.
A machine that washes medical carts can also be employed to wash other
wheeled medical equipment or supplies such as wheel chairs, wheeled stands,
such
as those that hold intravenous bags, tubes and pumps, wheeled (metro) shelves,
and
the like.
The above description provides a basis for understanding the broad meets
and bounds of the invention. The following examples and test data provide an
understanding of certain specific embodiments of the invention. These examples
are
not meant to limit the scope of the invention. Unless otherwise noted, all
parts,
percentages, and ratios reported in the following examples are on a weight
basis, and
all reagents used in the examples were obtained, or are available, from the
chemical
suppliers described below, or may be synthesized by conventional techniques.
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EXAMPLES
The following materials are used in the examples that follow:
Plurafac SLF-180: Fatty alcohol alkoxyl ate
Dehypon GRA: Fatty alcohol alkoxylate
Kathon ¨preservative available from Dow Chemical with active ingredient 5-
chloro-2-methy1-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one
Sodium Xylene Sulfonate
Citric acid
Control is Water (0 or 17gpg depending on experimental purpose).
Commercial Rinse aid A is a commercially available rinse aid from Steris.
Commercial Rinse aid B is a commercially available rinse aid from Getinge
that includes phosphoric acid.
Commercial Rinse aid C is a commercially available liquid rinse aid from
Ecolab.
Commercial rinse aid D is a commercially available solid rinse aid from Ecolab
that does not include any hardness or TDS components.
Compositions of the invention were formulated per below and tested.
Composition of Composition of
the Invention A the Invention B
Name Wt % Wt %
Water Deionized 0.5 0.5
dye 0.15 0.15
Kathon GC-ICP
Preservative 1.4 1.4
Plurafac SLF-180 13.1 7.1
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Sodium Xylene
Sulfonate 96% 69.85 69.85
Citric Acid, USP,
Anhydrous Grade 15 15
Dehypon GRA 6
Example 1
A hardness test was performed with Commercially available rinse aids and
compositions of the invention per the methodology below.
Hardness Test (17 grain Water)
Stainless Steel 304
Glass microscope slide
1. Obtain 15 of each coupon: stainless steel 304 #4 finish and glass
(microscope
slides).
2. Wash each coupon thoroughly with a soft sponge and Pantastic . Rinse with
5 grain water and DI water. Lay flat and let dry over night.
3. Obtain 30 8oz glass French square vials.
4. Rinse each vial with 5 grain water and DI water, lay flat and let dry over
night.
5. Prepare the following Chemistries:
Sample Description Water
condition
1 control 17gp2
2 Commercial rinse aid A 2000ppm 17gpg
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3 Commercial rinse aid B 2000ppm 17gpg
4 Commercial Rinse aid C 500ppm 17gpg
Commercial Rinse aid C 1000ppm 17gpg
6 Commercial Rinse aid C 2000ppm l7gp2
7 Commercial Rinse aid D 50ppm l7gp2
8 Commercial Rinse aid D 125ppm 17gpg
9 Commercial Rinse aid D 200ppm 17gpg
Composition of the 50ppm 17gpg
Invention A
11 Composition of the 125ppm 17gpg
Invention A
12 Composition of the 200ppm 17gp2
Invention A
13 Composition of the 50ppm 17gPg
Invention B
14 Composition of the 125ppm 17gpg
Invention B
Composition of the 200ppm 17gpg
Invention B
6. To 2 separate glass French square vials 200mL of control (17 grain water)
was added along with surfaces; stainless steel 304 #4 finish and glass
microscope slide in each separate vial. The vials were labeled.
5 7. Step 6 was repeated for all chemistries with 17 grain water.
8. All of the vials were put in a 70 C temperature controlled oven and allowed
to incubate for 8 hours.
Results are shown in Figure 1. As can be seen, From the Image analysis
10 means, one can see that the Compositions of the invention outperform the
other rinse
aid products.
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Example 2
Next the performance of the different rinse aids was tested in different
levels
of total dissolved solids per the methodology below.
Total Dissolve Solids (1000ppm NaCl in 0 grain Water)
Stainless Steel 304 #4 finish
1. Before beginning the dip tester was pre-heated to 150 F.
2. Obtain 15 of each coupon: stainless steel 304 #4 finish (3x5in).
3. Wash each coupon thoroughly with a soft sponge and Pantastic . Rinse with
5 grain water and DI water. Lay flat and let dry over night.
4. Prepare the following Chemistries in a 1L beaker:
Sample Description NaCl
1 control 1000ppm
2 Commercial Rinse aid A 2000ppm 1000ppm
3 Commercial Rinse aid B 2000ppm 1000ppm
4 Commercial Rinse aid C 500ppm 1000ppm
5 Commercial Rinse aid C 1000ppm 1000ppm
6 Commercial Rinse aid C 2000ppm 1000ppm
7 Commercial Rinse aid D 50ppm 1000ppm
8 Commercial Rinse aid D 125ppm 1000ppm
9 Commercial Rinse aid D 200ppm 1000ppm
10 Composition of the 50ppm 1000ppm
Invention A
11 Composition of the 125ppm 1000ppm
Invention A
12 Composition of the 200ppm 1000ppm
Invention A
13 Composition of the 50ppm 1000ppm
Invention B
14 Composition of the 125ppm 1000ppm
Invention B
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15 Composition of the 200ppm 1000ppm
Invention B
5. To the 1L beaker 1000mL of control (0 grain water + 1000ppm NaC1) was
added; the beaker was placed in a microwave and heated to 150 F. The
beaker was then placed in a dip tester water bath (water temperature set at
150F).
6. Set the dip tester to have the coupon in solution for 1 minute static soak.
7. After one minute when the coupon comes out of solution and the plank has
risen all the way, the coupons are suspended in air for 2 minutes.
8. After 2 minutes, the coupon is removed from the dip tester and set on a
rack
in the vertical position to cool down to room temperature.
9. Steps 4-7 were repeated for all chemistries with 0 grain water.
The results are shown in Figure 2. One can see that the compositions of the
invention outperform all other rinse at with increased levels of total
dissolved
solids in the rinse water.
Example 3
Material Corrosion/Compatibility Test (0 grain Water)
1. Obtain coupons of desired substrate material (Aluminum).
2. Wash each coupon thoroughly with a soft sponge and Commercially
available detergent. Rinse with 0 grain water and DI water. Lay flat and let
dry over night.
3. Obtain 8oz glass French square vials.
4. Rinse each vial with 0 grain water and DI water, lay flat and let dry over
night.
5. Prepare the following Chemistries:
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corrosion
Study
Description Ogpg
Control: Ogpg Water
Commercial Rinse aid A 2000ppm
Commercial Rinse aid B 2000ppm
Commercial Rinse aid C 500ppm
Commercial Rinse aid C 1000ppm
Commercial Rinse aid C 2000ppm
Commercial Rinse aid D 50ppm
Commercial Rinse aid D 125ppm
Commercial Rinse aid D 200ppm
Composition of the Invention A 50ppm
Composition of the Invention A 125ppm
Composition of the Invention A 200ppm
Composition of the Invention B 50ppm
Composition of the Invention B 125ppm
Composition of the Invention B 200ppm
6. To 2 separate glass French square vials 200mL of control (0 grain water)
was
added along with coupons with material to be studied: example: aluminum
6061 and aluminum 1100. The vials were labeled.
7. Step 6 was repeated for every chemistry with 0 grain water.
8. All of the vials were put in the 160 F oven and allowed to incubate for 8
hours.
9. Coupons were removed from each test solution with a clean tweezers.
10. Inductively coupled plasma (ICP) spectroscopy was used to analyze Al
concentration in each test solution respectively.
Figure 3 shows the results for the Al coupon and one can see that the
compositions of the invention demonstrated very little corrosion. Other metal
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coupons tested showed that the formulations of the invention are compatible
with all
metals.
Example 4
The foaming tendency at use was tested on Sump solutions per below.
The Inversion foam test is used to simulate Sump solution agitation. Rinse
additive
is added to the graduated cylinder, and the foam generated is measured after
10 180
inversions.
APPARATUS AND MATERIALS:
1. 250mL Graduated Cylinder with stopper.
2. Room temperature 5 grain water.
Description 0 gpg Shake Test
Commercial Rinse aid A Liquid product; N/A
Commercial Rinse aid B Liquid product; N/A
Commercial Rinse aid C Liquid product; N/A
Commercial Rinse aid D 5% 10%
Composition of the 5% 10%
Invention A
Composition of the 5% 10%
Invention B
PROCEDURE:
1. Rinse the graduated cylinder thoroughly with soft water, followed by DI
water and air
dry.
2. Prepare desired 5% and/or 10% simulated sump solution of solid rinse aids,
stir
until dissolved.
3. Pour 150mL of the 5% or 10% solution or the as is liquid commercial rinse
aids
into the graduated cylinder and cap with a stopper.
57
A .=
4. From a vertical position, rotate the cylinder about 1800 and back to the
vertical
position.
5. Repeat this action 10 times at a frequency of about 1 cycle/second.
6. The foam height was immediately recorded when the cylinder was placed on
the flat surface.
Read the foam height as the difference between the top of the liquid level to
the top of the
foam level. The top of the foam level is the level at which the foam is opaque
and the operator
cannot see through the cylinder.
7. Repeat for each chemistry.
The results are shown in Figure 4 and here again the formulations of the
invention
demonstrated better foam control.
Other Embodiments
It is to be understood that while the invention has been described in
conjunction with
the detailed description thereof, the foregoing description is intended to
illustrate, and not
limit the scope of the invention, which is defined by the scope of the
appended claims. Other
aspects, advantages, and modifications are within the scope of the following
claims.
It is to be understood that wherever values and ranges are provided herein,
all values
and ranges encompassed by these values and ranges, are meant to be encompassed
within the
scope of the present invention. Moreover, all values that fall within these
ranges, as well as
the upper or lower limits of a range of values, are also contemplated by the
present
application.
Example 5
Finally, the following procedure was used to evaluate the foaming tendency of
the different
rinse additives at use concentrations.
58
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FOAM RINSE ADDITIVE EVALUATION
APPARATUS AND MATERIALS:
= Glewvve Foam apparatus.
= Hot soft water.
= Small and large weigh boats
PROCEDURE:
= Rinse the Glewwe apparatus thoroughly by filling it with soft water and
running the
pump. Drain the apparatus by opening the gate valve. If foam is generated
during
this cleaning, repeat the procedure until it is not.
= Close the gate valve and remove the top lid.
= Fill the chimney with hot soft water to the base of the ruler, 0", 3L of
water.
= Turn on the pump switch and adjust the temperature to 100, 120, 140 or
160 F by
adding either cold or hot soft water. Tests were run at 160F.
= Adjust the pressure to 6 psi by using the knob located below the pressure
gauge.
Stop the pump.
= Re-adjust the water level to 0" as required.
= Turn on the pump, allow the pressure to reach 6 psi, and add desired
concentration
of the rinse additive or surfactant combination to be evaluated. Note the
time.
= After 1 minute, stop the pump and record the foam height and
characteristics at time
zero, 15 seconds and 1 minute.
= Open the gate valve to drain the machine and repeat the cleaning
procedure.
UNSTABLE - foam breaks rapidly (less than 15 seconds)
PARTIALLY STABLE - foam breaks slowly (within a minute)
STABLE - foam remains for several minutes
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PCT/US2013/059013
Glewwe Foam test
at 160F (in)
Sample Description Ogpg
initial 15s lmin
1 control
2 Commercial Rinse aid A 2000ppm
3 Commercial Rinse aid B 2000ppm
4 Commercial Rinse aid C 500ppm
Commercial Rinse aid C 1000ppm
6 Commercial Rinse aid C 2000ppm
7 Commercial Rinse aid D 50ppm
8 Commercial Rinse aid D 125ppm
9 Commercial Rinse aid D 200ppm
Composition of the Invention 50ppm
A
11 Composition of the Invention 125ppm
A
12 Composition of the Invention 200ppm
A
13 Composition of the Invention 50ppm
14 Composition of the Invention 125ppm
Composition of the Invention 200ppm
The results are shown in Figure 5. The figures shows that the foam profile at
dispenser pump concentration are better than the controls. Foam control is a
very
important aspect of rinse aids.
5
