U.S. patent application number 09/781097 was filed with the patent office on 2001-07-26 for cleaning/sanitizing methods, compositions, and/or articles for produce.
Invention is credited to Baker, Keith Homer, Jones, Kyle David, Murch, Bruce Prentiss, Roselle, Brian Joseph, Trinh, Toan, Ward, Thomas Edward.
Application Number | 20010009891 09/781097 |
Document ID | / |
Family ID | 23968071 |
Filed Date | 2001-07-26 |
United States Patent
Application |
20010009891 |
Kind Code |
A1 |
Murch, Bruce Prentiss ; et
al. |
July 26, 2001 |
Cleaning/sanitizing methods, compositions, and/or articles for
produce
Abstract
Basic cleaning compositions using toxicologically-acceptable
ingredients for cleaning fruits and vegetables are provided. Liquid
formulations comprising detergent surfactant, such as oleate,
alcohol ethoxylates, etc., and neutralized phosphoric acid are
sprayed onto apples, lettuce and the like to remove soil and
unwanted deposits, especially wax. Articles for applying the
compositions to produce by spraying are disclosed. Use of the
compositions for disinfectancy/sanitization of produce and
cleaning/disinfectancy/sanitization of non-food inantimate surfaces
are disclosed.
Inventors: |
Murch, Bruce Prentiss;
(Gosforth, GB) ; Roselle, Brian Joseph;
(Fairfield, OH) ; Jones, Kyle David; (West
Chester, OH) ; Baker, Keith Homer; (Cincinnati,
OH) ; Ward, Thomas Edward; (Oxford, OH) ;
Trinh, Toan; (Maineville, OH) |
Correspondence
Address: |
Ian S. Robinson
The Procter & Gamble Company
Sharon Woods Technical Center
11450 Grooms Road
Cincinnati
OH
45242
US
|
Family ID: |
23968071 |
Appl. No.: |
09/781097 |
Filed: |
February 9, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09781097 |
Feb 9, 2001 |
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09406867 |
Sep 27, 1999 |
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09406867 |
Sep 27, 1999 |
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08495288 |
Jun 27, 1995 |
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5997654 |
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Current U.S.
Class: |
510/111 ;
134/25.3; 510/477; 510/491; 510/505; 510/512 |
Current CPC
Class: |
A23L 5/57 20160801; C11D
3/042 20130101; C11D 3/2075 20130101; C11D 1/04 20130101; C11D
10/04 20130101 |
Class at
Publication: |
510/111 ;
134/25.3; 510/491; 510/512; 510/477; 510/505 |
International
Class: |
B08B 003/04; A01K
043/00; C11D 003/02; C11D 007/02 |
Claims
What is claimed is:
1. A method for cleaning produce comprising the step of contacting
the surfaces of said produce with an aqueous cleaning solution
comprising detergent surfactant; and neutralized ortho-phosphoric
acid in an effective amount to provide removal of waxy materials,
and having a basic pH of greater than about 9.5.
2. The method of claim 1 wherein said aqueous cleaning solution
comprises: (a) from about 0.01% to about 15% of C.sub.8-C.sub.18
fatty acid; (b) optionally, from about 0.1% to about 4% by weight
of nonionic surfactant; (c) optionally, from about 0.1% to about 4%
by weight of organic polycarboxylic acid; (d) optionally, up to
about 0.2% by weight of base-stable anionic surfactant; (e)
optionally, toxicologically-acceptabl- e basic buffer; (f)
optionally, toxicologically-acceptable preservative; (g) from about
0.05% to about 10% of phosphoric acid; and (h) the balance
comprising an aqueous carrier selected from water and, optionally,
low molecular weight, toxicologically-acceptable organic solvent;
wherein said aqueous solution has a pH of more than about 9.5.
3. A composition for cleaning fruits and vegetables according to
claim 1, which comprises: (a) from about 0.01% to about 15% of
C.sub.8-C.sub.18 fatty acid; (b) optionally, from about 0.1% to
about 4% by weight of nonionic surfactant; (c) optionally, from
about 0.1% to about 4% by weight of organic polycarboxylic acid;
(d) optionally, up to about 0.2% by weight of base-stable anionic
surfactant; (e) optionally, toxicologically-acceptable basic
buffer; (f) optionally, toxicologically-acceptable preservative;
(g) from about 0.05% to about 10% of phosphoric acid; and (h) the
balance comprising an aqueous carrier selected from water and,
optionally, low molecular weight, toxicologically-acceptable
organic solvent; wherein said composition has a pH of more than
about 9.5.
4. A composition according to claim 3 which comprises from about
0.1% to about 5% by weight of ortho-phosphoric acid and wherein
said composition has a pH of from about 11.5 to about 12.5.
5. A composition according to claim 3 with an improved tactile
impression for fruits and vegetables, comprising: (a) at least
about 0.75%, by weight, of a C.sub.12-C.sub.18 fatty acid or salt
thereof; (b) at least about 0.05%, by weight, of water-soluble
polyethylene glycol having a molecular weight of about 200, or
higher; (c) a water or water-ethanol fluid carrier, said
composition having a basic pH.
6. A composition according to claim 5 wherein component (a) is salt
of oleic acid.
7. A composition according to claim 5 wherein component (b) has a
molecular weight in the range from about 300 to about 9500.
8. A composition according to claim 5 wherein component (a) is
potassium oleate, and wherein the weight ratio of (a):(b) is in the
range from about 1:2 to about 30:1.
9. A composition according to claim 3 wherein the pH of the
composition is in the range from about 11.5 to about 12.3.
10. A sprayable composition according to claim 3 which has a
viscosity less than about 100 centipoise under shear of greater
than about 1000 sec.sup.-1.
11. A sprayable composition according to claim 10 which has a
viscosity of less than about 50 centipoise.
12. A composition according to claim 3 which additionally comprises
oil derived from grapefruit.
13. The composition of claim 3 wherein said composition contains
from about 0.001% to about 0.05% of an antioxidant.
14. A composition according to claim 3 suitable for cleaning
produce, even when the composition is incompletely removed from
said produce, comprising only GRAS ingredients.
15. The composition of claim 3 wherein said solution contains from
about 0.5% to about 15% by weight of detergent surfactant.
16. The composition of claim 15 wherein said solution contains from
about 0.75% to about 8% by weight of said detergent surfactant.
17. The composition of claim 3 wherein said solution contains from
about 1% to about 5% by weight of said detergent surfactant.
18. An anhydrous concentrate for preparing the composition of claim
3.
19. An article comprising a spray container, suitable for use by an
individual to clean produce, containing a cleaning solution which
is the composition of claim 10.
20. The article of claim 18 wherein said cleaning solution has a pH
of from about 11.5 to about 12.5.
21. A method for cleaning and/or sanitizing fruits and vegetables
at a basic pH, using a solution comprising: (a) optionally, from
about 0.1% to about 4%, by weight of nonionic surfactant; (b) from
about 0.1% to about 5%, by weight of potassium oleate; (c)
optionally, from about 0.2% to about 4% by weight of organic
polycarboxylate detergency builder; (d) at least about 0.05%, by
weight, of water-soluble polyethylene glycol having a molecular
weight of about 200, or higher; (e) optionally, a
toxicologically-acceptable basic buffer; (f) from about 0.05% to
about 10% of phosphoric acid; and (g) the balance comprising an
aqueous carrier selected from water and water-ethanol; wherein said
composition has a pH of 9.5 or greater, wherein all of the
ingredients of said solution are GRAS, wherein there is at least
0.5% detergent; and wherein said solution is contained in, and
dispensed from, a spray container suitable for use by an
individual.
Description
TECHNICAL FIELD
[0001] The present invention relates to methods for removing dirt
and other unwanted residues from produce, e.g., fruits and
vegetables, which is intended for ingestion by humans or lower
animals and to detersive compositions, especially in liquid form,
which are especially suitable for practicing said methods.
BACKGROUND OF THE INVENTION
[0002] It is well-known and appreciated by consumers that fruits
and vegetables should be thoroughly washed prior to ingestion in
order to remove soils and other unwanted residues which may be
undesirably clinging to the surfaces thereof. In addition, some
consumers wish to remove the artificial "waxy" coatings which may
be applied to some fruits to retard moisture loss for increased
storage life and to enhance their appearance. It has been estimated
that 95% of consumers recognize the need for thorough washing but,
ordinarily, only use tap water for this purpose. On the order of 5%
of those consumers who do wash their vegetables use a household
cleaner, typically a liquid dishwashing product, to help ensure
cleanliness. However, dishwashing products are not specifically
intended for such use, inasmuch as they are usually designed to
provide high, persistent suds which makes them inconvenient to
remove from the fruits or vegetables which have been washed
therewith. It will also be appreciated that the formulation of
truly effective compositions, especially those which can be used
safely by individual consumers, for washing fruits and vegetables
presents a unique problem to the formulator, inasmuch as many
art-disclosed cleaning ingredients would, presumably, not be
desirable for use in direct contact with foods where they might not
be fully removed.
[0003] Moreover, it would be especially desirable to provide
effective, toxicologically-acceptable cleaning compositions for
fruits and vegetables in the form of substantially low-sudsing
liquid solutions which are clear or which have only minimal
haziness. Liquid solutions are convenient for the user, since they
can be applied directly to soiled fruits and vegetables, followed
by rinsing in tap water. The clarity of the liquids connotes
cleanliness to the user and is thus highly desirable. Low sudsing
is an important attribute so that removal of the solution by
rinsing is achieved quickly and easily. It would also be of
advantage if such compositions could be provided in the form of
concentrates, which could be diluted by the consumer before use
and/or applied to the fruits and vegetables as a direct
spray-on.
[0004] Unfortunately, many toxicologically-acceptable cleaning
ingredients do not meet the aforesaid requirements for clear,
low-sudsing, dilutable liquid products. Many detersive surfactants
form cloudy or even opaque suspensions, even in soft water. Of
course, many surfactants are specifically designed to be high
sudsing. Still others form relatively intractable phases in their
concentrated form.
[0005] It has been disclosed that soap and/or certain nonionic
surfactants, properly formulated, e.g., with water-soluble oleate
or laurate salts and other ingredients can provide liquid
compositions having the desired properties described above. It has
also been disclosed that preferred compositions can be formulated
in the basic pH range. Even when such basic compositions do have a
soapy feel, they are preferred over the acidic compositions herein
for removing artificial waxy coatings, especially from fruit such
as apples. However, the invention also comprises basic compositions
having less soapy feel. It has now been discovered that the
addition of neutralized phosphoric acid provides even better
cleaning, especially of waxy material, even at the same pH.
BACKGROUND ART
[0006] The use and selection of cleaning ingredients for the
purpose of washing fruits and vegetables is described by the United
States Code of Federal Regulations, Title 21, Section 173.315:
"Ingredients for use in washing or lye peeling of fruits and
vegetables". These regulations restrict the ingredients that may be
used for direct contact with food to those described as "generally
regarded as safe" (GRAS), and a few other selected ingredients.
These sections also provide certain limitations on the amount of
material that can be used in a given context.
[0007] Among these ingredients, the experienced formulator will
find only a few ingredients which can provide effective cleaning of
hydrophobic residues, such as waxes, oils, or man-made chemical
residues such as pesticides. It is recognized these types of
residues are removed most readily by surface active ingredients in
water, or by organic solvents largely in the absence of water.
Other types of soils, especially particulate insoluble soils that
do not readily disperse in water, are effectively removed by
surface active materials in water, especially when aided by complex
anionic salts, such as citrates (polycarboxylates), or
polyphosphate salts.
[0008] Within this limited group of ingredients the range of
effective cleaning compositions well suited to the task of cleaning
fruits and vegetables, especially as practiced by individual
consumers, have not been previously described. It is desirable to
formulate liquid compositions which are amenable to either direct
application to produce, preferably by spray application, or could
be provided in suitable concentrated form to allow convenient
dilution in a bowl or sink of water for washing of produce by
immersion. Further, it is desirable if the compositions are low
sudsing, and easily rinsed, without leaving residue. Preferred
compositions should be mild to the hands, especially for direct
application.
[0009] Food Chemical News, Inc., 1991, p. 334.1, reports that PEG
200-9500 has been cleared under .sctn.178.3750 as a component in
articles for use in contact with food (Fed. Register, Oct. 15,
1968). Nonetheless, for washing produce, polyethylene glycol should
be affirmed as GRAS.
SUMMARY OF THE INVENTION
[0010] The present invention encompasses methods for cleaning
produce, especially fruits and vegetables, (and compositions, as
disclosed hereinafter, for practicing said methods) at a basic pH.
The present invention comprises several aspects including: I. A
method for cleaning produce comprising contacting the surfaces of
said produce by direct application of an aqueous cleaning solution
typically comprising:
[0011] (a) from about 0.01% to about 15% of C.sub.8-C.sub.18 fatty
acid;
[0012] (b) optionally, from about 0.1% to about 4% by weight of
nonionic surfactant, especially ethoxylated and/or propoxylated
adducts of aliphatic C.sub.12-18 alcohols, but preferably less than
about one eighth of the amount of said fatty acid;
[0013] (c) optionally, from about 0.1% to about 4% by weight of
organic polycarboxylic acid, preferably citric acid;
[0014] (d) optionally, up to about 0.2% by weight of base-stable
anionic surfactant such as the alkali or alkaline earth salts of
dodecylbenzene sulfonate;
[0015] (e) optionally, toxicologically-acceptable basic buffer such
as potassium and/or sodium basic materials, e.g., the hydroxides
and/or salts of carbonate and/or bicarbonate;
[0016] (f) optionally, toxicologically-acceptable preservative;
[0017] (g) optionally, but preferably, from about 0.05% to about
10%, preferably from about 0.1% to about 5%, more preferably from
about 0.3% to about 2% of phosphoric acid;
[0018] (h) optionally, at least about 0.05%, preferably from about
0.1% to about 10%, most preferably from about 0.25% to about 3.0%,
by weight, of water-soluble polyethylene glycol having a molecular
weight of about 200, or higher; and
[0019] (i) the balance comprising an aqueous carrier selected from
water and, optionally, low molecular weight,
toxicologically-acceptable organic solvent such as ethanol,
glycerol, etc.;
[0020] all of the acidic materials above being, of course,
neutralized under the alkaline conditions of the product,
preferably neutralized with sodium and/or potassium, preferably
potassium, compatible basic material, wherein said aqueous solution
has a pH in the range of 9.5 or greater, preferably more than about
11, and even more preferably from about 11.5 to about 12.5, and
said composition preferably being essentially free of any material
that is not toxicologically acceptable.
[0021] The inventions disclosed herein preferably encompass
compositions for use in a method for cleaning fruits and vegetables
at a basic pH above about 9.5, comprising:
[0022] (a) from about 0.01% to about 15% of C.sub.8-C.sub.18 fatty
acid which is neutralized, preferably a member selected from the
group consisting of sodium or potassium oleate (preferred), or from
about 0.5% to 10% by weight of sodium or potassium laurate;
[0023] (b) optionally, from about 0.1% to about 4% by weight of
nonionic surfactant, especially ethoxylated/propoxylated adducts of
aliphatic C.sub.12-18 alcohols, but preferably less than about one
eighth of the amount of said fatty acid;
[0024] (c) optionally, but preferably, from about 0.2% to about 4%
by weight of potassium and/or sodium polycarboxylate, having
detergent building capability and preferably being derived from
natural sources, such as potassium and/or sodium citrate, as a
dispersant for particulate soils;
[0025] (d) optionally, up to about 0.2% by weight of base-stable
anionic surfactant such as the alkali or alkaline earth salts of
dodecylbenzene sulfonate;
[0026] (e) optionally, toxicologically-acceptable basic buffer such
as potassium and/or sodium basic materials, e.g., the hydroxides
and/or salts of carbonate and/or bicarbonate;
[0027] (f) optionally, toxicologically-acceptable preservative;
[0028] (g) optionally, but preferably, from about 0.05% to about
10%, preferably from about 0.1% to about 5%, more preferably from
about 0.3% to about 2% of phosphoric acid; and
[0029] (h) optionally, at least about 0.05%, preferably from about
0.1% to about 10%, most preferably from about 0.25% to about 3.0%,
by weight, of water-soluble polyethylene glycol having a molecular
weight of about 200, or higher;
[0030] (i) the balance preferably comprising aqueous carrier
selected from water and, optionally, low molecular weight,
toxicologically-acceptable organic solvent such as ethanol,
glycerol, etc., preferably selected from water and
water-ethanol;
[0031] wherein said aqueous cleaning solution has a pH of 9.5 or
greater, and preferably employs carbonate salt, or salts, as buffer
(e), preferably with hydroxide base, to provide a pH of from about
11 to about 12.5, more preferably from about 11.5 to about 12.5.
The compostions can also be formulated as concentrates, in which at
least part of (i) is removed and the levels of the remaining
ingredients are adjusted to complete the formula. In all of the
above lists of components, if an ingredient can be classified in
more than one place, it will be classified in the first place it
can appear.
[0032] A more specific method for cleaning fruits and vegetables at
a basic pH, preferably more than about 9.5, comprises contacting
the surfaces of said fruits and vegetables with an aqueous cleaning
solution comprising potassium oleate, preferably at a level of more
than about 0.5%. Potassium oleate is mild, rinses well, has minimal
odor, is effective in removing unwanted materials, especially wax,
from apples, does not oversuds, and is very safe, even when the
composition is misused and the vegetable, or fruit, etc., is not
completely rinsed. Therefore, it is a uniquely preferred surfactant
for use in cleaning food materials like vegetables and fruits. The
potassium cation is more useful than the sodium cation, especially
in the absence of polyethylene glycol, since the potassium oleate
is quite soluble whereas the sodium oleate tends to form a less
soluble soap, especially at low temperatures.
[0033] A concentrated, alkaline method for cleaning produce
comprises contacting the surfaces of produce with a cleaning
solution containing from about 0.5% to about 15%, preferably from
about 0.75% to about 8%, more preferably from about 1% to about 5%,
detergent surfactant, preferably one that is GRAS, and more
preferably said oleate surfactant, said cleaning solution having a
pH of from about 9.5 to about 12.5, preferably from about 11 to
about 12.5, especially when the detergent surfactant is a soap such
as the said oleate, more preferably from about 11.5 to about 12.3.
Such compositions when used in an effective amount to clean apples
coated with wax, will provide more effective removal of the wax
when combined with the neutralized phosphoric acid. Removal of wax
from apples is one of the most difficult cleaning tasks and
therefore is indicative of overall superior performance. It is
important to remove as much wax as possible to minimize the amount
of any undesirable materials that may be trapped by the wax.
[0034] Another preferred variation in the above methods for
cleaning produce involves placing said cleaning solutions in a
spray container to provide a spray of said solution to distribute
the said solution, or solutions, over the surfaces of the produce
while utilizing only a minimum amount of the cleaning solution and
minimizing the exposure of the remaining solution to the
atmosphere, where the solution is more likely to be contaminated
and/or exposed to oxygen, both of which tend to cause undesirable
changes in the solutions from aesthetic and/or performance
considerations. In such spray processes, there is only need for a
relatively small amount of material in the package, and for
individual consumer use, this is desirable, since some consumers
will not be able to manipulate large weights. For individual
consumer usage, typically, the container will contain no more than
about two gallons (about eight liters), preferably no more than
about one gallon (about four liters), especially when the container
is a spray container, even one that has a tube that permits the
spray device to be manipulated while the bulk container remains in
place. More preferably such spray containers contain about one
liter, or less, of cleaning solution.
[0035] The invention encompasses basic cleaning compositions in
both concentrated and dilute forms, especially adapted for
practicing said methods. (In the following disclosure, the lower
amounts of the specified ingredients denote the dilute forms of the
compositions herein and the higher amounts denote the concentrated
forms which are typically diluted by a factor of from about 2 to
about 3.) The compositions can be concentrated even more to
non-aqueous liquids or solids according to the teaching in U.S.
Pat. No. 5,280,042, Lopes, said patent being incorporated by
reference. Such compositions include the following.
[0036] A composition for cleaning fruits and vegetables at a basic
pH, comprising:
[0037] (a) from about 0.1% to about 15%, preferably from about 1%
to about 5%, by weight of a member selected from the group
consisting of sodium or potassium oleate (preferred), sodium or
potassium laurate, or mixtures thereof;
[0038] (b) optionally, from about 0.1% to about 4%, preferably
about 0.3% to about 1.0%, by weight of nonionic surfactant as
described above;
[0039] (c) from about 0.2% to about 4% by weight of polycarboxylic
acid salt, especially potassium hydrogen citrate;
[0040] (d) from about 0.3% to about 5% of ortho-phosphoric acid;
and
[0041] (e) the balance comprising aqueous carrier selected from
water and water-ethanol;
[0042] wherein said composition has a pH of 9.5 or greater.
[0043] Preferably, the basic compositions herein contain from about
0.5% to about 1.5% by weight of potassium, and/or sodium, carbonate
and/or bicarbonate buffer and have a pH of from about 11.5 to about
12.5.
[0044] Preferred compositions for use herein in a concentrated
alkaline method contain from about 0.1% to about 15%, preferably
from about 0.5% to about 8%, more preferably from about 1% to about
5%, detergent surfactant, preferably one that is GRAS; from about
0.3% to about 5% of ortho-phosphoric acid and have a pH of from
about 9.5 to about 12.5, preferably from about 11.5 to about 12.3.
Such compositions, when used in an effective amount to clean apples
coated with wax, will provide more effective removal of the wax.
Removal of wax from apples is one of the most difficult cleaning
tasks and therefore is indicative of overall superior
performance.
[0045] The present invention also encompasses detersive
compositions with an improved tactile impression which are
especially adapted for cleaning fruits and vegetables,
comprising:
[0046] (a) at least about 0.1%, preferably from about 0.5% to about
8%, most preferably from about 1% to about 5%, by weight, of a
C.sub.12-C.sub.18 fatty acid or salt thereof,
[0047] (b) at least about 0.05%, preferably from about 0.1% to
about 10%, most preferably from about 0.25% to about 3.0%, by
weight, of water-soluble polyethylene glycol having a molecular
weight of about 200, or higher;
[0048] (c) from about 0.1% to about 5% of neutralized
ortho-phosphoric acid; and
[0049] (d) water or water-ethanol fluid carrier, said composition
having a basic pH.
[0050] The balance of the composition can comprise various optional
adjunct materials, pH-adjusting agents, perfumes or essences,
preservatives and the like.
[0051] In a preferred mode, component (b) has a molecular weight in
the range from about 300 to about 9500.
[0052] Typical compositions herein are wherein component (a) is
potassium oleate, and wherein the weight ratio of (a):(b) is in the
range from about 1:2 to about 30:1, preferably from about 1:1 to
about 15:1.
[0053] The compositions having improved tactile impression are
typically formulated in the basic pH range, preferably from about
pH 9.5 to about pH 12.5. Preferred compositions have a viscosity at
room temperature of less than about 100 centipoise, preferably less
than about 50 centipoise for sprayable compositions.
[0054] Preferred compositions for use herein contain only materials
that are GRAS, including, of course, direct food additives affirmed
as GRAS, to protect against possible misuse by the consumer.
Traditionally, most suggestions for cleaning of fruits and/or
vegetables have contemplated a commercial scale where there is
typically more control over the conditions, especially the amount
and thoroughness of rinsing. The present invention, especially the
methods involving use of hand held trigger activated spray means
are primarily/solely suitable for use by individual consumers so
that it is essential that extra safety be built into the product.
Failure to rinse thoroughly after cleaning is less of a concern if
all of the ingredients are GRAS. This is especially important when
concentrated basic compositions suitable for removal of wax from
apples are used. The larger amounts of materials needed for removal
of wax create an heretofore unknown level of risk for the
individual consumers, many of whom are not likely to read, or
follow, instructions which would permit safe use of non-GRAS
materials.
[0055] The ingredients in the above compositions are preferably
selected and used in proportions which provide substantially clear
compositions. "Substantially clear" includes only minimal haziness,
and preferably the compositions are completely clear. The
ingredients are also selected to have minimal odor, both initially
and after storage. The lack of odor is especially important in
compositions for use on food. The compositions preferably have a
viscosity that is more than about 2 centipoise, preferably more
than about 10 centipoise when at rest, but thin under shear to
permit easy dispensing, especially from spray containers.
[0056] Below pH about 9.7, the compositions can exhibit some
objectionable fatty acid odor. Even at the optimal pH's above 11,
some odor can persist. In order to mask this odor, the compositions
can contain a GRAS perfume, or essence, ingredient. Especially
preferred for this use are oils derived from citrus fruit, e.g.,
oranges, lemons, limes, grapefruits, tangerines, tangelos, etc.
which contain relatively large amounts of terpenes.
[0057] All documents cited herein are incorporated herein by
reference.
DETAILED DESCRIPTION OF THE INVENTION
[0058] The following toxicologically-acceptable ingredients are
used in the preparation of the preferred compositions herein. By
"toxicologically-acceptable" is meant that any residues from the
ingredients of the compositions which may remain on the fruits or
vegetables cleansed therewith are safe for ingestion by humans
and/or lower animals.
[0059] Nonionic Surfactant--The nonionic surfactant is preferably
selected from materials known in the art, such as alkylene oxide
(ethylene oxide and/or propylene oxide) adducts of C.sub.10-18
aliphatic alcohols or acids, C.sub.10-18 aliphatic alcohol adducts
of glucose (alkyl polyglucosides). The specific nonionic surfactant
selected ideally has a hydrophilic-lipophilic balance (HLB) greater
than about 10, and a cloud point above about 35.degree. C. in the
composition. The United States Code of Federal Regulations (CFR)
specifically describes an ethylene oxide/propylene oxide adduct of
C12-18 aliphatic alcohol of molecular weight of about 800. Such a
material is available as PLURAFAC RA-20 (BASF).
[0060] In the basic compositions containing soap, the alkoxylated
alcohol functions mainly as a dispersant for any soap curd which
may form during the cleansing operation. Further, it is recognized
that the selection of non-nitrogen containing nonionics can
minimize the possibility of microbial growth in the dilute
surfactant compositions.
[0061] Fatty Acid and/or Salts Thereof--The acidic compositions
herein are preferably formulated using an unsaturated fatty acid;
oleic acid is preferred and convenient for this use. However, the
particular oleic acid that is selected should preferably be low in
polyunsaturates, e.g., contain less than about 10%, preferably less
than about 7%, more preferably less than about 5%, polyunsaturated
acid minor components, and will typically have an Iodine Value (IV)
of from about 70 to about 100, preferably from about 83 to about
95, more preferably from about 85 to about 90. Polyunsaturated
fatty acids are not preferred herein, due to odor problems.
However, this is primarily from aesthetic considerations since such
acids are effective in cleaning. The amount of polyunsaturated
fatty acids should be less than about 8%, preferably 0%. The amount
of polyunsaturated fatty acids with more than about two double
bonds should be less than about 1%, preferably 0%. Saturated fatty
acids are unacceptable as they have limited solubility for longer
chainlength materials (.gtoreq.C.sub.12), or have unacceptable odor
(.ltoreq.C.sub.10). For example, stearic and/or tallow fatty acids
soaps, even potassium soaps, do not have enough solubility at room
temperature, where most produce cleaning is done by individual
consumers, to formulate even compositions containing the minimum of
about 0.1% soap required for acceptable cleaning. Other specific
solubilizing surfactants in higher proportions would be required to
solubilize these saturated fatty acids. Pamolyn 100 FGK oleic acid
is a good example of a suitable commercial fatty acid.
[0062] Phosphoric Acid
[0063] Phosphoric acid is an extremely desirable component for
improving the removal of, e.g., wax from apples. The advantage is
not due solely to pH since the improvement is observed at any pH.
E.g., as disclosed hereinafter, when the pH is varied from about 11
to about 12, the results are superior when the neutralized
ortho-phosphoric acid is present. The result is also not due to any
ability of the neutralized phosphoric acid to act as a builder to
inhibit the problems associated with water hardness, since the
results are improved when the compositions are used full strength
by application directly on the waxed surface.
[0064] It is surprising that the neutralized orthophosphoric acid
provides such a large benefit. The advantage is especially noticed
when the compositions are used full strength, e.g., by spraying the
composition directly onto the surface of the produce.
[0065] Polyethylene Glycol--The water-soluble polyethylene glycol
polymer (PEG) employed herein is the known article of commerce and
is available under a variety of trade names, of which CARBOWAX
(Union Carbide Corporation) is exemplary. PEG's in the average
molecular weight range of from about 200 to about 20,000 can be
used herein, and PEG as CARBOWAX in the average molecular weight
range of at least about 200, typically 300 to about 9500, is
convenient and preferred. As disclosed above, the compositions
herein will comprise at least about 0.05%, by weight, of the PEG
and will typically comprise from about 0.1% to about 10%, by
weight, of PEG. The amounts used can vary with the molecular weight
of the PEG, the amount of oleate or other fatty acid used in the
composition, the desired viscosity of the composition, and like
factors within the discretion of the formulator. The following
Table 1 illustrates the variation in viscosity which can be
effected using various levels of PEG and varying PEG molecular
weights in a liquid composition (Control) comprising 3% potassium
oleate. Table 1 also illustrates the effect of sodium benzoate (Bz)
on viscosity.
1 TABLE 1 Viscosity (cP* as made) Viscosity (cP* as made)
Composition 72.degree. F. (22.degree. C.) 43.degree. F. (6.degree.
C.) Control (no PEG) 7 110 Control + 0.674% Bz 23 1000 Control +
0.118% Bz 7 159 Control + 0.1% PEG 400 5 36 Control + 0.5% PEG 400
2 17 Control + 0.1% PEG 8000 5 23 Control + 0.5% PEG 8000 8 4
*Viscosity in centipoise as measured using Brookfield LVTD #2
spindle, 60 rpm at the designated temperature.
[0066] In a typical mode, the preferred compositions herein that
have an improved tactile impression will comprise oleate:PEG weight
ratios in the range from about 1:2 to about 30:1, preferably from
about 1:1 to about 15:1.
[0067] Tactile Impression--The compositions herein which contain
the polyethylene glycol are characterized not only by their
excellent cleaning performance and sudsing/rinsability properties,
but also by their improved viscosity properties and improved
"feel". While, as disclosed above, the improved viscosities of the
compositions herein are readily demonstrated quantitatively using
standard measurement techniques, the improved feel of the
compositions which come into contact with the users' hands is a
qualitative tactile impression. However, this improved,
"non-slippery", "non-soapy" improvement in skin feel can be
demonstrated by rubbing Test (PEG-containing) and Control (no PEG)
compositions on the hands or inner forearms of volunteer graders.
Even in such rudimentary tests, the graders can readily distinguish
the improved tactile impression of the compositions made in
accordance with this invention.
[0068] Optional Surfactants--Optionally, base stable anionic
surfactants can be employed, as allowed by the United States Code
of Federal Regulations, Title 21, Section 173.315. Preferred are
salts of dodecylbenzene sulfonate, typically at levels up to 0.2%.
Also described in the CFR are phosphate esters of ethylene and/or
ethylene/propylene oxide adducts of aliphatic alcohols, dioctyl
sulfosuccinate, and 2-ethylhexyl sulfate.
[0069] Sequestrant/builder--The organic polycarboxylic acid, or
salt thereof, e.g., citric acid, or sodium and/or potassium
citrate, and/or ethylenediaminetetraacetic acid, or sodium and/or
potassium ethylenediaminetetraacetate, are standard items of
commerce and are GRAS. Other organic poly carboxylic acids,
especially those that are GRAS, such as tartaric, malic, etc.
acids, can also be used. When formulating the basic formulations
herein, it is preferred to use the potassium salt, as compared with
the sodium salt, to provide ease of formulatability. Complex
phosphates can also be used, but are generally avoided due to
regulatory considerations.
[0070] Buffer--Toxicologically-acceptable basic buffers can be used
in the compositions herein to maintain product pH in the base
range. For ease of formulatability, it is highly preferred that
such basic buffers be in their potassium salt form. Potassium
citrate is a preferred dispersant for particulate soils. Potassium
carbonate is a convenient and preferred basic pH buffer. Sodium
bicarbonate is a highly desirable material to add to the
compositions of this invention as a part of the buffering system
since it is readily available as baking soda in food grade and is
therefore relatively inexpensive, while providing a highly
desirable purity to the composition. Compositions formulated with a
mixture of potassium and sodium cations in molar ratios of from
about 1:1 to about 10:1, preferably from about 2:1 to about 8:1,
more preferably from about 4:1 to about 5:1 potassium to sodium,
e.g., as provided by mixtures of potassium hydroxide (hydrate) and
sodium bicarbonate, have desirable rheological properties. The
compositions are sufficiently viscous, so as to cling to the fruit
or vegetable until spread, but are readily dispensed, e.g, by means
of a spray device, either aerosol or finger-activated pump. The
levels and identities of the ingredients are adjusted to provide
products having the desired viscosities as set forth herein, e.g.,
more than about 2, preferably more than about 5, more preferably
more than about 10 centipoise when at rest, and less than about
150, preferably less than about 100, more preferably less than
about 50 centipoise under shear of.gtoreq..about.1000
sec.sup.-1.
[0071] The ability of the preferred compositions containing
mixtures of both sodium and potassium cations to shear thin is
important to promote easy dispensing, especially when the
compositions are sprayed, while maintaining the ability to be
thick, cling, and delay run off after being applied to the
produce.
[0072] The pH is preferably not greater than about 12.5, and
especially does not contain large amounts of buffer at higher pHs
for consumer safety, especially when the compositions are
sprayed.
[0073] Preservative--Formulating the present compositions at high
pH reduces the tendency for biological growth of contaminants, such
as bacteria, fungi, or molds. At neutral pH, an increased reliance
on preservatives is required to insure the lack of biological
growth through contamination in making or in use. Standard
food-grade preservatives such as ethylenediaminetetraacetic acid
and/or the salts thereof, at a level of from about 0.01% to about
0.2% of ethylenediaminetetraacetic acid, or its sodium and/or
potassium salts, can be used although, in general, the basic pH
compositions herein do not require a preservative.
[0074] Antioxidants--The use of commercial oleic acid, or oleate
salts, can be complicated by development of off-odors and/or
yellowing of the compositions in which they appear. These
undesirable properties are believed to be caused by complex side
reactions initiated by the reaction of oxygen with primarily the
polyunsaturated components of the fatty acid stock. These results
can be avoided, or minimized, by avoiding contact with air, or by
controlling the quality of the fatty acid stock so that the amount
and type of polyunsaturates are minimized as described above,
and/or by the addition of antioxidants.
[0075] It has been found, that the addition of tocopherols (e.g.,
Vitamin E, or tocopherol acetates) in alkaline formulations is
advantageous, as they do not degrade, nor do they impart a strong
color. They inhibit the development of off-odors for extended
periods of time so that the need for masking scents is minimized,
or eliminated, particularly for oleic acid stocks of high quality,
as described above. The use of butylated phenols, such as BHT and
BHA is also useful, but the quantity should be limited to avoid
imparting colors to the compositions. Other food grade antioxidants
such as Vitamin C and sulfites, are desirable to prevent
deterioration of the compositions by the action of oxygen, but care
must be taken since vitamin C can suffer color degradation and
sulfites can cause odor problems. Sulfites also have been the
target of potential health concerns.
[0076] Fluid Carrier--The major proportion, e.g., more than about
two thirds, (typically, 80%-98%, by weight) of the compositions
herein comprises water as the solubilizing carrier for the
ingredients. As noted in the Examples hereinafter, water-ethanol
can also be employed and is especially preferred when formulating
the basic pH compositions herein. The ethanol level preferably
should not exceed 2% in the solution used to clean the produce, to
avoid an alcoholic odor, especially when spraying. Other
compatible, water-soluble, low molecular weight solvents such as
glycerol can also be used.
[0077] The compositions herein are preferably used by placing them
in a package comprising either an aerosol container or a
non-aerosol spray device "spray means." Said spray means is any of
the manually activated, preferably "trigger-type," means for
producing a spray of liquid droplets as is known in the art.
Typical spray means are disclosed in U.S. Pat. Nos.: 4,082,223,
Nozawa, issued Apr. 4, 1978; 4,161,288, McKinney, issued Jul. 17,
1979; 4,558,821, Tada et al., issued Dec. 17, 1985; 4,434,917,
Saito et al., issued Mar. 6, 1984; and 4,819,835, Tasaki, issued
Apr. 11, 1989, all of said patents being incorporated herein by
reference. The spray bottle, or container can be any of the ones
commonly used for containing hard surface cleaner detergent
compositions. Examples of bottles are those in U.S. Design Pat.
Nos.: 244,991, Weekman et al., issued Jul. 12, 1977; and 275,078,
Wassergord et al., issued Aug. 14, 1984, said patents being
incorporated herein by reference.
[0078] The spray means herein can also include those that
incorporate a compatible propellant gas into the liquid and those
that will foam even detergent compositions having a viscosity of
less than about 15 cps. The device can also be one that can be
adjusted to either give a liquid spray or a foam. The spray means
herein are typically those that act upon a discrete amount of the
composition itself, typically by means of a piston that displaces
the composition and expels the composition through a nozzle to
create a spray of thin liquid.
[0079] Preferred articles include the compositions herein that are
suitable for use in the processes described herein, in a package
that can provide a spray. Such articles are not widely marketed.
This is surprising in view of the clear advantages for such
products for use by individual consumers. The typical use involves
treating individual items of produce, which would make preparation
of a "bath" wasteful.
[0080] In a preferred process for using the products described
herein, and especially those formulated to be used at full
strength, the product is sprayed onto the food product to be
cleaned, rubbed, rinsed and/or wiped off with a suitable clean
material like cloth, sponge, a paper towel, etc.
[0081] Surprisingly, the compositions and processes described
herein can provide effective disinfectancy/sanitization. In order
to provide good kill of microorganisms, especially bacteria, one
should use high concentrations and/or longer exposure times.
Typically, the products should be used full strength and allowed to
remain on the produce for at least about one minute, preferably at
least about five minutes, and, for some microorganisms, even ten
minutes may be required. Longer exposure times (i.e., the time that
the bacteria are in contact with the product) give better
antimicrobial benefits. The importance of time depends both on the
pH of the product and on the formula concentration. At high pH
(.gtoreq. 11.5) and high concentrations, antibacterial efficacy is
achieved quickly. At lower pH values (pH.ltoreq.11) and lower
formula concentrations, a longer period of exposure time is
required to achieve the same efficacy.
[0082] Higher pHs are also better, in general. This factor is
important for the product's performance on the Gram negative
bacteria, e.g., Escherichia coli and Pseudomonas species. Higher
product pH's produce quicker and more complete kill. The opposite
is true for the Gram positive bacteria, e.g., Staphylococcus
aureus. Performance is equal to, or slightly better, as the pH is
lowered from 11.5 to 9.5. However, this is only true when the
formula contains oleic acid.
[0083] As stated above, higher formula concentrations (when done
independently of pH) enhance the antimicrobial efficacy of the
product. The presence of oleic acid is the key factor for the
performance on Gram positive organisms like S. aureus, while the pH
is probably a bigger factor for the Gram negative bacteria, e.g.,
E. coli and Pseudomonas species.
[0084] Packaging the products herein in a container with
instructions for usage in terms of timing and avoidance of dilution
in order to provide disinfectancy/sanitization, will help the
individual consumer by providing information for proper usage in
order to remove/kill microorganisms. It is a special advantage of
the product that it can be used for this purpose at a time in the
food production process where recontamination is minimized.
[0085] The compositions can also be used for cleaning (especially
spot removal), disinfectancy, or sanitization, on non-food (i.e.,
any surface which is not used as food, even those which are not in
contact with food), inanimate, household surfaces, especially those
used in food production and other food-contacting surfaces
(surfaces that come in contact with food). E.g., cutting boards,
counter tops, utensils, dishes, colanders, sinks, sponges, towels,
dish cloths, cloth napkins (serviettes), table cloths, and other
surfaces that come in contact with food. It is desirable to
disinfect/sanitize before the surfaces come in contact with the
food, and is desirable to redisinfect/sanitize whenever the
surfaces become recontaminated. The products herein, containing all
GRAS ingredients, are perfect for this purpose. On hard surfaces,
of course, the compositions can be removed, after sufficient time
has elapsed, by rinsing or by absorption/wiping with an appropriate
object, e.g., paper towel, sponge, squeegee, etc. Rinsing is still
preferred.
[0086] The compositions of this invention can also be used to
treat/clean other non-food inanimate household surfaces, such as
fabrics, e.g., clothing, shoes, and shower curtains, especially
those that are used by infants, especially toys, diapers (napkins),
and bibs. The contaminated fabrics can be disinfected/sanitized,
then rinsed off or washed, while minimizing the risk if the infant
puts the fabric or other article in its mouth. The fabric can be
treated totally, or by spot treatment, then the composition is
removed, e.g., by rinsing/washing, absorbency, and/or mechanical
force.
[0087] For fabrics, the pH of the compositions is preferably below
about 11.5, more preferably below about 11.
[0088] For fabric and hard surfaces, the distribution of the
compositions of this invention can be achieved by using a spray
device, a roller, a pad, etc., or dipping in a "bath" of said
compositions. Spraying is a preferred method.
[0089] All parts, percentages, and ratios herein are "by weight"
unless otherwise stated. All number values are approximate unless
otherwise stated.
[0090] The following Examples illustrate the compositions and
processes of this invention, but are not intended to be limiting
thereof. The exemplified basic liquid compositions can be prepared
at pH 9.5-12.5 by dissolving the ingredients in water or
water-ethanol using conventional mixing apparatus. In a convenient
mode, water is placed in a mixing vessel. Potassium hydroxide, the
ortho-phosphoric acid, any citric acid, any bicarbonate, glycerine
(processing aid), and any ethanol are added in the named sequence,
with stirring. The oleic acid is added with high shear and stirring
is continued. The PEG (which can conveniently be predispersed in
water) is then added. The optional perfume ingredients can be added
any time after the oleic acid has been dissolved in the
mixture.
EXAMPLE 1
[0091]
2 Product Control A B Water Ingredient level % level % level %
level % Water 90.93 90.90 88.20 100.00 KOH 1.33 1.36 3.06 --
Ethanol 2.00 2.00 2.00 -- Glycerin 2.00 2.00 2.00 -- Oleic acid
2.64 2.64 2.64 -- Sodium Bicarbonate 0.55 0.55 0.55 -- Phosphoric
Acid -- -- 1.00 -- Citric acid 0.52 0.52 0.52 -- Essence 0.03 0.03
0.03 -- Neat pH 11.5 12.0 12.2 .about.7.5 Glass flasks are coated
with AP-40 shellac and stress cured for 24 hours @ 140 F. The
flasks at room temperature are then washed with .about. 5 grams (5
squirts of a Calmar #TS-800 sprayer) of the respective products
with a 10 sec. rub, followed immediately with a water rinse, and
allowed to dry. The % Wax removal is determined gravimetrically. %
Wax Removal Control 14%; A 9%; B 38%; and Water 0%. Note: A vs. B
shows a benefit for phosphoric acid addition at similar pH.
[0092]
3 Water Product Control A B C reference Ingredient level % level %
level % level % level % Water 90.93 88.08 88.05 88.05 100.00 KOH
1.33 3.06* 3.06* 3.06 -- Ethanol 2.00 2.00 2.00 2.00 -- Glycerin
2.00 2.00 2.00 2.00 -- Oleic acid 2.64 2.64 2.64 2.64 -- Sodium
Bicarbonate 0.55 0.55 0.55 0.55 -- Phosphoric Acid -- 1.00 1.00
1.00 -- Citric acid 0.52 0.52 0.52 0.52 -- Essence 0.03 0.03 0.03
0.03 -- PEG 3350 -- 0.12 0.15 0.15 0 Neat pH 11.5 12.6 12.0 11.5
.about.7.5 *Target KOH usage. Very small amount of additional KOH,
replacing water, used to adjust to final pH.
[0093] Using varying wax, curing, rub time and flask temperature,
the above compositions were used to clean in a manner similar to
EXAMPLE 1, followed by a determination of the percentage of wax
removed. The test conditions and results are as follows.
4 % Wax Removal Wax/Curing/Rub time/flask Temp. Control A B C Water
Shellac/60 min.@ 75 C/10 51 97 73 82 9 sec./room temp. Carnauba/60
min.@ 43 C/10 64 82 75 73 5 sec./room temp. Shellac/60 min.@ 75
C/20 57 97 96 97 7 sec./40F Shellac/30 min.@ 93 C/20 50 98 61 65 3
sec./room temp.
[0094] The compositions of Examples 1 and 2 are prepared by adding
oleic acid to a mixture of water, KOH, citric acid, phosphoric acid
(if used), sodium bicarbonate, glycerin, and ethanol. The PEG 3350
(if used) and essence are added last.
EXAMPLE 3
[0095]
5 Product A B C D Ingredient level % level % level % level % Water
89.79 90.63 88.068 88.91 KOH 2.12 1.28 2.842 2.00 Ethanol 2.00 2.00
2.00 2.00 Glycerin 2.00 2.00 2.00 2.00 Oleic acid 2.643 2.643 2.643
2.643 Sodium Bicarbonate. 0.547 0.547 0.547 0.547 Phosphoric Acid
0.00 0.00 1.00 1.00 Citric acid 0.52 0.52 0.52 0.52 Essence 0.03
0.03 0.03 0.03 PEG 3350 .350 .350 .350 .350 Neat pH 11.5 10.5 11.5
10.5
[0096] The above formulas are evaluated for ability to kill various
standard microorganisms. Minor adjustments of the pH of the
formulas were done immediately prior to antimicrobial testing to
give the above neat pH values. The formulas kill standard
microorganisms effectively, and the formulas containing phosphoric
acid are better, especially at lower pH. The amount of time
required for control of microorganisms is more than would
ordinarily be provided by a normal cleaning operation. Therefore,
it is important to package the product in a container with
instructions for allowing sufficient time for effective kill to
take place.
EXAMPLE 4
[0097]
6 Product A B Ingredients Level % Level % Oleic Acid 2.64 2.20
Sodium Bicarbonate 0.55 0.55 Phosphoric Acid 1.00 -- Citric Acid
0.52 0.52 EDTA, Sodium Salt 0.05 0.10 GRAS Perfume 0.05 0.08 PEG
3350 2.00 -- KOH * ** Ethanol 2.00 2.00 Water Balance Balance *
Amount sufficient to attain a pH of about 11. ** Amount sufficient
to attain a pH of about 10.5.
[0098] Each of the Compositions of Examples 1 Control, 4A, and 4B
is used to spray on a contaminated Formica.TM. kitchen countertop,
left on the surface for about 10 min., then rinsed off to provide a
sanitizing benefit.
[0099] Each of the Compositions of Examples 2 Control, 4A, or 4B is
used to spray on a contaminated area of a 50/50 poly/cotton shirt,
left on the fabric for about 10 min., then the treated shirt is
added to a laundry load to be washed in a normal fashion in an
automatic washer with a commercial detergent, to provide a
sanitizing benefit.
EXAMPLE 5
[0100]
7 Ingredient Wt % Water 73.26 PEG 3350 0.79 KOH 5.70 Ethanol 6.00
Glycerin 3.00 Oleic acid 7.90 Sodium bicarbonate 1.60 Phosphoric
acid 1.00 Citric acid 1.56 Essence (Grapefruit oil) 0.09
[0101] The concentrated composition in Example 5 can be mixed, for
example, with distilled water at 1 part product to 2 parts water
until uniformly mixed and then used as a lower active liquid.
[0102] EXAMPLE 6
8 Ingredient Wt % Tri-Potassium Phosphate (TKP) 48.8 Potassium
Citrate 10.2 PEG 3350 4.3 Potassium Oleate 36.7
[0103] The anhydrous dry composition in Example 6 can be mixed, for
example, with distilled water at 1 part product to 11 parts water
until uniformly dissolved/mixed and then used in a liquid form.
* * * * *