U.S. patent number RE36,982 [Application Number 09/248,406] was granted by the patent office on 2000-12-05 for surfactants based aqueous compositions with d-limonene and hydrogen peroxide and methods using the same.
This patent grant is currently assigned to Envirox, L.L.C.. Invention is credited to Arman V. Melikyan, Patrick H. Stewart.
United States Patent |
RE36,982 |
Melikyan , et al. |
December 5, 2000 |
Surfactants based aqueous compositions with D-limonene and hydrogen
peroxide and methods using the same
Abstract
A cleaning composition including a terpene such as D-limonene
and hydrogen peroxide in a surfactants based aqueous solution. The
composition in various specific formulations is a micro-emulsion
useful for a variety of materials and for both industrial and
household applications.
Inventors: |
Melikyan; Arman V. (Danville,
IL), Stewart; Patrick H. (Danville, IL) |
Assignee: |
Envirox, L.L.C. (Georgetown,
IL)
|
Family
ID: |
24315077 |
Appl.
No.: |
09/248,406 |
Filed: |
February 11, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
578971 |
Dec 27, 1995 |
05602090 |
Feb 11, 1997 |
|
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Current U.S.
Class: |
510/372; 134/2;
134/40; 134/42; 510/108; 510/180; 510/191; 510/203; 510/214;
510/238; 510/280; 510/365; 510/383; 510/417; 510/426; 510/428;
8/111; 8/137 |
Current CPC
Class: |
C11D
1/831 (20130101); C11D 3/18 (20130101); C11D
3/2068 (20130101); C11D 3/3409 (20130101); C11D
3/3765 (20130101); C11D 3/3947 (20130101); C11D
17/0021 (20130101); C11D 1/143 (20130101); C11D
1/22 (20130101); C11D 1/72 (20130101) |
Current International
Class: |
C11D
17/00 (20060101); C11D 3/34 (20060101); C11D
3/37 (20060101); C11D 001/831 (); C11D 003/39 ();
C11D 003/44 (); C11D 017/08 () |
Field of
Search: |
;510/372,370,108,180,191,203,214,238,280,365,375,383,417,426,428
;8/111,137 ;134/2,40,42 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Douyon; Lorna M.
Attorney, Agent or Firm: Knechtel, Demeur & Samlan
Claims
What is claimed is:
1. A clear stable liquid micro-emulsion cleanser composition
comprising:
a. from about 0.5% to 10% .Iadd.by weight .Iaddend.of a terpene
.Iadd.solvent .Iaddend.selected from .[.mono- and.]. .Iadd.the
group consisting of .Iaddend.sesquiterpenes and mixtures
thereof;
b. from about 0.5% to about 10% .Iadd.by weight .Iaddend.of a water
soluble glycol ether solvent;
c. from about 0.5% to about 10% .Iadd.by weight .Iaddend.of an
isopropylamine salt of linear alkyl benzene sulfonic acid as a
first anionic surfactant;
d. from about 0.4% to about 10% .Iadd.by weight .Iaddend.of a
sodium 1-octane sulfonate as a second anionic surfactant to provide
coupling and stability effects;
e. from about 0.5% to about 10% .Iadd.by weight .Iaddend.of an
alkyl ethoxylate nonionic surfactant with an HLB of 11 to 15 to
approximate the HLB of the terpene solvent;
f. from about 2.0% to about 22.8% by weight of a 35% by weight
aqueous solution of hydrogen peroxide;
g. from about 0.2% to 4% by weight of a food grade anti-oxidant
based on the terpene weight percentage to stabilize the
terpene;
h. from about 1.0% to 5.0% by weight of a polyacrylate-polyalcohol
polymer used as a thickening agent; and
i. deionized water.
2. A .[.cleaning.]. .Iadd.clear stable liquid micro-emulsion
cleanser .Iaddend.composition according to claim 1 wherein said
terpene solvent is D-limonene.
3. A method of using the micro-emulsion of claim 1 comprising
a. applying said micro-emulsion to a material to be cleaned whereby
said micro-emulsion incorporates soil from said material; and
b. removing said micro-emulsion from said material.
4. A method according to claim 3 including diluting one part of
said micro-emulsion with up to 1000 parts of water prior to
applying said micro-emulsion.
Description
BACKGROUND OF THE INVENTION
This invention relates to improved cleaning compositions and
methods of using the same. More specifically, it relates to aqueous
compositions which are surfactants based and include D-limonene and
hydrogen peroxide.
Many different cleaning compositions have been developed for a
variety of purposes. The art is replete with patents on such
compositions. Depending on the specific materials to be cleaned and
the uses of those materials, different results may be more or less
important. An important goal for almost all such compositions is
chemical stability for long periods of time over a broad
temperature range.
Other goals which may be of greater or lesser importance depending
on the application include action to remove grease and/or
particulate soil, to deodorize, to disinfect, to remove stains, to
remove mildew, to bleach, and to preserve color of the material
being cleaned.
Another desirable characteristic is the capability of use for
industrial or commercial purposes or in the home. In industry, such
compositions are commonly purchased in concentrated form and
diluted by the user, thus saving on shipping, packaging and storage
expenses. In the home or small establishments, the convenience of a
ready to use product is desirable.
Applicants' invention contains no materials which were not
heretofore known in the art of cleaning compositions. However,
their invention relates to new and unobvious combinations of such
materials, which in use provide superior results to those provided
by the prior art.
Of the many patents in the art, Applicants believe the following
are the ones of most interest:
U.S. Pat. No. 4,430,236 discloses an aqueous product containing
hydrogen peroxide, a nonionic surfactant or a mixture of a nonionic
surfactant and an anionic surfactant. Many other patents show the
use of hydrogen peroxide.
U.S. Pat. No. 5,281,280 discloses a mildew remover containing
hypochlorite, bicarbonate and D-limonene. Many other patents exist
showing the use of D-limonene, which provides a pleasant
citrus-like aroma, as well as cleaning properties.
It appears to be significant that Applicants have found no
disclosures of the use of both hydrogen peroxide and a terpene such
as D-limonene together. It is believed that this is because
conventional wisdom would suggest that such a mixture would be
unstable as would most mixtures including hydrogen peroxide because
of its reactivity.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the invention to provide cleaning
compositions which include both hydrogen peroxide and a terpene
such as D-limonene and methods of using the same.
Another object of the invention is to provide cleaning compositions
with high stability for long periods of time under a broad range of
temperatures.
Still another object of the invention is to provide cleaning
compositions which may be prepared in diluted ready to use form or
in concentrated form for industrial use.
Yet another object of the invention is to provide improved cleaning
compositions with selectable multiple purposes, including
degreasing, particulate soil removal, deodorizing, disinfecting,
stain removal, mildew removal, bleaching and color preservation for
hard, resilient and porous surfaces and fiber products.
These and other objects of the invention are provided by the
invention, as described in the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
Most generally the improved compositions all include a terpene, an
anti-oxidant to stabilize the terpene, two anionic surfactants, a
nonionic surfactant, and hydrogen peroxide, all in a deionized
water solution.
The terpene is a terpene hydrocarbon and may be a monoterpene or a
sesquiterpene, or a mixture of both. The terpene may be acyclic,
monocyclic or bicyclic, with monocyclic or bicyclic terpenes being
preferred. The preferred specific terpene is D-limonene, a
biodegradable product derived from orange rind oil.
The terpene is stabilized with a food grade anti-oxidant, e.g., a
butylated hydroxy anisole blend with other materials.
One of the anionic surfactants is preferably the isopropylamine
salt of linear alkylbenzene sulfonic acid. It is an excellent
cleaning surfactant and an effective emulsifier for D-limonene and
other terpenes to form an oil-in-water solution. It is very
biodegradable because of its linear alkyl group. It greatly
facilitates the formulation of a dilutable micro-emulsion
concentrate. One commercial name for this is Biosoft N-411.
An anionic surfactant which is preferred for the second surfactant
is sodium 1-octane sulfonate. It has excellent coupling properties,
is an effective wetting agent, surface tension reducer and
hydrotrope. It is stable over a wide pH range, has good
compatibility with various conventional detergent builders or
additives and stability with respect to hydrogen peroxide. A
commercial name for this surfactant is Bioterge PAS-8S.
The nonionic surfactant is preferably an alkyl ethoxylate having 12
to 15 carbon atoms. It is the condensation product of an aliphatic
alcohol with about 65.6% weight basis etylene oxide. It is highly
water soluble and has a hydrophile-lipophile (HLB) of 13.1:1. It is
available under the commercial name of Neodol 25-9.
Hydrogen peroxide (H.sub.2 O.sub.2) is an important part of the
compositions because it greatly improves the cleaning, deodorizing
and disinfecting performance by its addition. It is conveniently
supplied in a concentration of 35% by weight in an aqueous
solution. Applicants' experiments have shown that this solution
remains stable when combined with the other ingredients in a
micro-emulsion when the solution is over half of the
micro-emulsion.
The present maximum allowable actual concentration of hydrogen
peroxide in a product to avoid health and environmental hazards is
7.9%. Using a 35% aqueous solution, this translates to a maximum
percentage of 22.8% of the peroxide solution in the composition in
its concentrated forms. In view of the reactivity of hydrogen
peroxide and expected greater reactivity when combined with
terpenes, it would have been expected that even such a lower
concentration would be unstable, but such is not the case. In fact,
all formulations are stable for long periods of time and over a
broad temperature range, including both those compositions
containing a higher hydrogen peroxide percentage than 7.9%.
Applicants' invention is not limited by any theory expressed
herein. However, it is presently believed that these results may
come from both the second anionic surfactant and the use of the
final ingredient, deionized water. If the water were not deionized,
divalent metals could be present and react with the hydrogen
peroxide.
Stability may be further improved by the addition of other
ingredients, such as chelating agents. One of the these could be
sodium ethylene diaminetetraacetate.
An advantage of all the compositions is that they are clear
micro-emulsions. Thus during application to surfaces or materials,
the surfaces can be seen by the users and the progress can be
observed.
Generally, the actual concentration of hydrogen peroxide is varied
downward from the 7.9% level discussed above depending on the risk
of contact with human skin in actual use. The highest
concentrations may be used in commercial or industrial use where
the compositions are sold in bulk quantities and are to be diluted
just before use. In compositions sold for use in the household,
dilution is not expected, so the hydrogen peroxide level is the
lowest. Other variations will be based on the materials to be
cleaned and the specific purposes. None of the compositions are
intended for use as body cleaners.
Table 1 sets forth formulations for five compositions within the
scope of the invention, with Product Numbers 110, 120, 140, 141 and
142. All of the ingredients of Products 110 and 120 have been
disclosed above. Product 110 is a multi-purpose product with high
percentages of active ingredients. It is intended for dilution just
before use and is sold to commercial and industrial users. Product
120 is much less concentrated and is sold in ready to use form as a
household all purpose cleaner.
Product 140 is another formulation for industrial or commercial use
with appropriate high concentration. This product (as well as
Products 141 and 142) includes an additional water soluble
co-solvent, namely a glycol ether. A preferred co-solvent is
ethylene glycol monobutyl ether because it is effective in removing
organic or petroleum soils due to its ether linkage. This is
commercially available under the name Glycol EB. Hence, these three
products all are superior when such soils are part of the
problem.
Product 141 and Product 142 both additionally include a thickening
agent, a modified polyacrylate-polyalcohol polymer commercially
available under the name Thix. The increased viscosity and the
other variations in percentages make Product 141 more useful as a
carpet spotter because it safeguards the color of the carpet and
eliminates odors. Product 142 has an increase in hydrogen peroxide
and a decrease in deionized water relative to Product 141. It is
preferred for more stringent fiber cleaning and greater
deodorization, for example when pet soil is a problem. Both
Products 141 and 142 are intended for undiluted household use.
TABLE 1 ______________________________________ Ingredient 110 120
140 141 142 ______________________________________ D-limomene 7.08%
1.32% 6.58% 0.55% 0.55% Anti- 0.02% 0.02% 0.02% 0.02% 0.02% oxidant
Glycol EB 0.00% 0.00% 7.00% 0.58% 0.58% Biosoft 8.55% 1.60% 7.95%
0.66% 0.66% N-411 Neodol 6.41% 1.20% 5.96% 0.50% 0.50% 25-9
Bioterge 5.74% 1.07% 5.34% 0.44% 0.44% PAS-8S Di Water 49.61%
92.01% 44.51% 93.41% 92.21% H.sub.2 O.sub.2 22.60% 2.80% 22.60%
2.80% 4.00% (35%) Thix 0.00% 0.00% 0.00% 1.00% 1.00% Total 100.00%
100.00% 100.00% 100.00% 100.00%
______________________________________ Description of Ingredients
for the Above Formulation Table
______________________________________ D-limosene A terpene derived
from distilled orange rind oil. Anti-oxidant A butylated hydroxy
anisole blend. Glycol EB Ethylene glycol monobutyl ether. Biosoft
N-411 Isopropylamine salt of linear alkylbenzene sulfonic acid
(Amionic surfactant) Neodol 25-9 An alkyl ethoxylate having 12 to
15 carbon atoms. (Nonionic surfactant) Bioterge PAS-8S Sodium
1-octane sulfonate. (Amionic surfacant) Di Water Deionized water.
H.sub.2 O.sub.2 (35%) Hydrogen peroxide bleach 35% weight solution
in water. Thix A modified polyacrylate-polyalcohol polymer.
(Thickening agent) ______________________________________
Table 2 discloses seven broad uses of Applicants' compositions with
numerous specific uses comprised therein. The first column states
the uses. The second column references the five formulations
disclosed in Table 1. The third column states the desired dilution,
if any, before use. The fourth column states the remaining steps of
the method of use.
TABLE 2
__________________________________________________________________________
WATER TO APPLICABLE FORMULA FORMULA METHOD
__________________________________________________________________________
FOR USE AS A MULTI-PURPOSE CLEANER. 110 (commercial) 20:1 to 1000:1
Commercial products 110 and 140 are diluted Formulations may be
balanced to provide a broad 0:1 to 100:1old) in the filed by means
of ventrri eductor range of cleaning effectiveness without
possbility 20:1 to 1000:1) driven with water pressure to provide of
damage to any water-safe surface or fiber. Each multiple levels of
water dilution, specific application's cleaning needs are
effectively automatically to satisfy a broad range satisfied by
varying the water to cleaner ratio at the of cleaning needs. work
site. Applications effectively satisfied by one 1. 20:1 Degreasing
solution for kitchens formula are: and mechanical Working areas. 1.
Cleaning Hard & resilient surfaces 2. 54:1 A Pre-spray and soak
method is used 2. Cleaning Glass & mirrors for heavily Soiled
floors or walls, carpets, 3. Cleaning & disinfecting Bathroom
urinals bathroom urinals, commodes, sinks, fixtures commodes, sinks
& fixtures and walls, stalls and floors adjacent to 4. Cleaning
& removing spots from Fibers ... ie. those areas. Carpet,
upholstery, Fabrics 3. 256:1 No rinse wipe down cleaner and
bathroom floor moping solution. 4. 512:1 General mop bucket and
mechanical scrubbing equipment solution. Glass and mirror cleaner.
5. 1000:1 Mechanical scrubbing machine solution for high gloss
floors. FOR USE IN ELIMINATION OF ODORS. 10:1 to 54:1 110 The
affected area is sprayed wtth the These formulation are
particularly effective for 0:1 to 10:1old) appropriate dilution and
allowed to soak for soluablizing soils and oxidizing odors
associated with 140 (commercial) 10:1 to 54:1 three to fifteen
minutes depending on the urine, feces, decomposing food, smoke and
mildew. 0:1(household) severity, type of soil and surface. The
affected 0:1household) surface is then scrubbed and rinsed with
water to remove soils and residual cleaner. FOR USE AS A
DISINFECTANT. 110 (commercial) 10:1 to 54:1 The affected area is
sprayed with the These formulations demonstrate effective bacteria
0:1(household) appropriate dilution (lower water dilutions
destruction properties for Gram Positive an Gram 10:1 to 54:1cial)
result in stronger disinfectant properties). The Negative Bacteria
as well as Yeast and Mold. 0:1 141 (household) affected area is
allowed to soak for two to ten 0:1household) minutes depending on
the dilution ratio (lower water dilutions work faster). The
affected area is then scrubbed or wiped and or rinsed with water
(higher water dilutions do not require rinsing). FOR USE ON HARD
& RESILIENT 110 (commercial) 20:1 to 1000:1 The surface is
cleaned by mop or mechanical SURFACES. These formulations are
effective 0:1 to 100:1ousehold) scrubbing machines at approriate
dilution cleaning agents for hard or resilient surfaces at high 140
(commercial) 0:1 to 1000:1 levels. For heavy soils the lower
dilutions water dilution ratios. Products using this technology 141
(household) 0:q are pre-sprayed on the surface and allowed to
provide penetrating solvency for porous surfaces. 0:1(household)
soak for three to fifteen minutes and then Bleaching action is
surface-safe and particularly scubbed and rinsed with water.
effective on grouted ceramic tile.
__________________________________________________________________________
Various changes and modifications will be apparent to those skilled
in the art. All of these are to be included within the scope of the
appended claims.
* * * * *