FIELD OF THE INVENTION
[0001] This invention relates to cleaning compositions particularly useful in removing stains
from rugs, carpets, and textiles.
BACKGROUND OF THE INVENTION
[0002] A wide variety of carpet cleaning and anti-soiling compositions are available for
do-it-yourself carpet cleaning. Fluorochemical compounds have been described in the
prior art as useful in treating textiles, such as carpets, to impart oil and water
repellency and soil resistance. Although these compositions have found commercial
success, there is a continuing need for alternative formulations offering an increased
cleaning potential for a variety of stains, particularly oily stains. In formulating
a new carpet cleaning composition, it is particularly challenging to impart a new
property into an existing composition without destroying other worthwhile properties
of the composition.
[0003] One problem encountered when carpet has been treated with a cleaning composition
is that frequently the treated portion of the carpet becomes more sensitive to resoiling
than the untreated position of the carpet. Consequently, the resoiling of the treated
portion of the carpet occurs more quickly for "cleaned" carpet as opposed to untreated
carpet. Another problem commonly associated with carpet cleaning compositions is that
the carpet is left with a "sticky" residue such that the "softness" of the carpet
deteriorates after cleaning. Additionally, other undesirable properties include damage
to the carpet by spotting, color loss, or leaving an undesirable residue.
[0004] There remains a need for alternative cleaning compositions useful in removing a variety
of spots, particularly oily type stains from carpet, and other textiles, without imparting
undesirable properties.
SUMMARY OF THE INVENTION
[0005] The need discussed above has been satisfied with the discovery of an aqueous cleaning
composition having a pH level falling within a range of from 4 to 9.5 comprising:
(a) from 0.75% to about 1.15% by weight of sodium lauryl sulfate;
(b) from 0.65% to about 0.85% by weight ethylene glycol monohexyl ether;
(c) from 0.025% to 0.17% by weight of a fluorinated surfactant selected from a mixture
of (i) a perfluoropropionate of formula I and (ii) a perfluoroalkyl phosphate of formula
II, the weight ratio of (i) to (ii) being from 1:1 to 1:2;
(d) from 0.025% to 0.05% by weight of a styrene maleic anhydride polymer; and
(e) from 0.3% to 0.45% by weight of a chelating agent selected from the group consisting
of diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic
acid, sodium or potassium salts thereof, and mixtures thereof, wherein the weight
percentages are based on the total active ingredient weight of the aqueous composition.
[0006] The inventive composition is stable and is particularly effective in removing a variety
of stains from carpeting without contributing to undesirable properties commonly associated
with carpet cleaning compositions. One particular group of stains that may be substantially
removed from textiles using the inventive composition are oily stains. The inventive
composition is useful in cleaning textiles as well as rugs and carpets. Additionally,
prevention of resoiling and stain and dirt repellency are observed as attributes of
the composition.
DETAILED DESCRIPTION OF THIS INVENTION
[0007] The sodium lauryl sulfate component is widely available commercially. Preferably
it is employed in a range of 0.75% to 1.15% by weight, more preferably 0.8% to 1%
by weight, and most preferably from 0.85% to 0.9% by weight % (active ingredient),
with all weight percentages herein based on the total weight of the composition. The
ethylene glycol monohexyl ether is also widely available and is preferably employed
within a range of from 0.65% to 0.85% by weight, more preferably from 0.7% to 0.8%
by weight, and most preferably about 0.75% by weight (active ingredient).
[0008] The fluorinated surfactant acts primarily as an anti-soiling and anti-staining agent
and is a mixture of Formula I and II, where Formula I is:
F(CF₂)
n-CH₂CH₂-S-CH₂CH₂-COOLi
I
wherein n is an integer having a value of 6 to 12 and may be identified as an α -{2-[(2-carboxyethyl)thio]ethyl}-
ω-fluoro-poly(difluoromethylene) lithium salt, and where Formula II is a diethanolamine
salt of a perfluoroalkyl phosphate as represented by the general formula:

wherein n is an integer having a value of 6 to 12. The weight-ratio of the perfluoropropionate
of Formula I to the perfluoroalkyl phosphate of Formula II in the mixture is in the
range of from 1:1 to 1:2, and the amount of the mixture employed in the composition
is from 0.025% to 0.17% by weight, more preferably from 0.1% to 0.15% by weight, most
preferably about 0.1% by weight (active ingredient). Such a mixture may be purchased
from E.I. DuPont de Nemours & Co., Inc. under the chemical name ZONYL™ 7950. The composition
also contains a carboxylated polymer salt, preferably a styrene maleic anhydride polymer,
available commercially such as, for example, ZELAN™338, from E. I. DuPont de Nemours
& Co., Inc. This ingredient is preferably employed in an amount from 0.025% to 0.05%
by weight, and most preferably from 0.03% to 0.04% by weight (active ingredient).
[0009] The chelating agent(s) used are preferably aminopolycarboxylic acid compounds in
which the amino nitrogen has attached thereto two or more substituent groups. Preferred
are the acids and potassium or sodium salts of ethylenediaminetetraacetic acid (EDTA),
diethylenetriaminepentaacetic acid (DTPA), and N-hydroxyethylethylenediaminetriacetic
acid (HEDTA) and mixtures thereof. Most preferred is tetrasodium ethylenediaminetetraacetate
(Na₄EDTA). Preferably the chelating agent is used in an amount ranging from 0.3% to
0.45% by weight, more preferably from 0.35% to 0.4% by weight, and most preferably
from 0.37% to 0.39% by weight (active ingredient).
[0010] The compositions of the invention may include optional ingredients for performing
specifically desired functions such as sequestrates, e.g., citric acid, sodium hexametaphosphate,
and the like; organic liquid solvents for water-soluble stains, e.g., monohydric aliphatic
alcohols having 1 to 6 carbon atoms; corrosion inhibitors, such as, citric acid, formaldehyde
(formalin), sodium citrate, sodium nitrate, ammonia, and so on; preservatives, such
as methyl- and ethylparaben, 1,2-benzoisothiazole-3(2H)-ones (including the preservative
KATHON™CG-ICP, available from Rohm and Haas).
[0011] The compositions of the invention are preferably formulated as aqueous solutions
or emulsions and can be dispensed for use as liquids using conventional dispensing
devices such as squeeze bottles fitted with a suitable dispensing nozzle or containers
fitted with trigger spray pumps which are well known in the art.
[0012] The pH of the aqueous compositions of the invention preferably falls within a range
of from 4 to 9.5, more preferably from 5 to 8, and most preferably between 6 and 7.
If the composition requires an pH adjustment to fall within this range, known pH adjusting
agents may be employed.
[0013] The composition may be prepared using conventional techniques known to those skilled
in the art. The composition is a substantially clear liquid having the viscosity similar
to that of water and may be stored as a stable liquid for extended periods.
[0014] Preferably, carpets are cleaned by applying the composition directly on the carpet,
by spraying for example, followed by rubbing the sprayed area with a suitable device,
such as, for example, a clean damp cloth or sponge mop, with rinsing of the device
until the stain or soil is removed. Textiles may also be cleaned by the composition
in a similar manner.
[0015] The composition of the invention is illustrated by the following examples of specific
formulations without, however, being limited thereto.
EXAMPLES
[0016] Formulas A-C were prepared by techniques familiar to those skilled in the art using
ingredients as shown in the Tables. Formulas A-C were each tested for stability for
6 weeks at room temperature, 105°F., 120°F. and 40°F. Additionally, the formulas were
subjected to a freeze-thaw test for 3 cycles (thaw for 24 hours after freezing). All
tests results for Formulas A-C showed the formulas as stable.
FORMULA A |
COMPONENT |
WT% |
Water |
q.s. |
Sodium lauryl sulfate a.(29%) |
3 |
Ethylene glycol monohexyl ether b. |
0.75 |
Isopropyl Alcohol |
2 |
Fluorinated Surfactant (25%) c. |
0.4 |
Carboxylated Polymer Salt (25%) d. |
0.15 |
Tetrasodium ethylenediamine tetraacetate e. (38%) |
1 |
Fragrances |
0.2 |
Preservativef. |
0.05 |
Citric Acid |
0.11 |
pH = >6.5 |
a. RHODAPON™ LCP-manufactured by Rhome-Poulenc, Inc., active ingredient 0.87 wt.%. |
b. HEXYL CELLOSOLVE™ - manufactured by Union Carbide Company. |
c. ZONYL™ 7950, a 10-15% mixture of a perfluoropropionate of Formula I herein; 15-20%
of a mixture of perfluoroalkyl phosphates of Formula II herein (the perfluoroalkyl
phosphate salts are obtained by neutralization of the corresponding acid with diethanolamine);
5-10% trichlorotrifluoroethane; 25-30% isopropyl alcohol; 35-40% water - manufactured
by E. I. DuPont de Nemours Co., Inc., active ingredient 0.1 wt.%. |
d. ZELAN™ 338, a styrene maleic anhydride polymer - manufactured by E. I. DuPont de
Nemours Co., Inc., active ingredient 0.0375 wt.%. |
e. Active Ingredient 0.38 wt.%. |
f. KATHAN™CG-ICP, active ingredient 0.00075 wt.%. |
[0017]
FORMULA B |
COMPONENT |
WT% |
Water D.I. |
q.s. |
Sodium lauryl sulfate (29%)a. |
3 |
Ethylene glycol monohexyl etherb. |
0.75 |
Isopropyl Alcohol |
2 |
Fluorinated Surfactant (25%)c. |
0.5 |
Carboxylated Polymer Salt (25%)d. |
0.3 |
Tetrasodium ethylenediamine tetraacetate e.(38%) |
1 |
Fragrance |
0.2 |
Preservativef. |
0.08 |
Citric Acid |
0.12 |
pH= >6.5 |
a. RHODAPON™ LCP-manufactured by Rhome-Poulenc, Inc., active ingredient 0.87 wt.%. |
b. HEXYL CELLOSOLVE™ - manufactured by Union Carbide Company. |
c. ZONYL™ 7950, a 10-15% mixture of a perfluoropropionate of Formula I herein; 15-20%
of a mixture of perfluoroalkyl phosphates of Formula II herein (the perfluoroalkyl
phosphate salts are obtained by neutralization of the corresponding acid with diethanolamine);
5-10% trichlorotrifluoroethane; 25-30% isopropyl alcohol; 35-40% water - manufactured
by E. I. DuPont de Nemours Co., Inc., active ingredient 0.125 wt.%. |
d. ZELAN™ 338, a styrene maleic anhydride polymer - manufactured by E. I. DuPont de
Nemours Co., Inc., active ingredient 0.075 wt.%. |
e. Active Ingredient 0.38 wt.%. |
f. KATHON™CG-ICP, active ingredient 0.0012 wt.%. |
[0018]
FORMULA C |
COMPONENT |
WT% |
Water D.I. |
q.s. |
Sodium lauryl sulfate (29%) a. |
3 |
Ethylene glycol monohexyl ether b. |
0.75 |
Isopropyl Alcohol |
2 |
Fluorinated Surfactant c.(25%) |
0.5 |
Carboxylated Polymer Salt d.(25%) |
0.15 |
Tetra sodium ethylenediamine tetraacetate e.(38%) |
1 |
Fragrance |
0.2 |
Preservativef. |
0.08 |
Citric Acid |
0.11 |
pH= ≈6.5 |
a. RHODAPON™ LCP-manufactured by Rhome-Poulenc, Inc., active ingredient 0.87 wt.%. |
b. HEXYL CELLOSOLVE™ - manufactured by Union Carbide Company. |
c. ZONYL™ 7950, a 10-15% mixture of a perfluoropropionate of Formula I herein; 15-20%
of a mixture of perfluoroalkyl phosphates of Formula II herein (the perfluoroalkyl
phosphate salts are obtained by neutralization of the corresponding acid with diethanolamine);
5-10% trichlorotrifluoroethane; 25-30% isopropyl alcohol; 35-40% water - manufactured
by E. I. DuPont de Nemours Co., Inc., active ingredient 0.125 wt.%. |
d. ZELAN™ 338, a styrene maleic anhydride polymer - manufactured by E. I. DuPont de
Nemours Co., Inc., active ingredient 0.0375 wt.%. |
e. Active Ingredient 0.38 wt.%. |
f. KATHON™CG-ICP, active ingredient 0.0012 wt.%. |

Example 1
[0019] The effect of Formula A on the color and overall appearance of each of the carpets
listed in Table A was conducted.
[0020] Samples of the carpets were cut in 12" x 12" pieces. For the control, each sample
of carpet was sprayed with 25 g of distilled water and then wiped 25 cycles with a
white washcloth. For the testing of Formula A, 25 g of Formula A was sprayed on each
sample of carpet, and then the carpet was wiped with a white washcloth for 25 cycles.
All carpet samples were then allowed to dry followed by vacuuming. This procedure
was repeated four times.
[0021] Twenty-one panelists were selected and the control carpet samples and the carpet
samples cleaned with Formula A were shown to them. The panelists were instructed that
all samples (both the controls and the carpet cleaned with Formula A) had been treated
with a carpet cleaner. They were then asked if treatment with the "cleaners" (i.e.
water or Formula A) had damaged the carpets.
[0022] Table I illustrates the panel results. Out of 21 people paneled, the number of people
who gave a response 'yes' to the question on whether the carpet appeared damaged.
As employed throughout the examples, when the data is analyzed using the "Chi Square
method" (as described in
Statistical Analysis (2nd Edition) by Samuel B. Richmond, The Ronald Press Co., New York, 1964, p. 290-303)
at a 95% confidence level, 15 panelists for each product tested per carpet would have
had to give a 'yes' response for there to be any significance between the products
tested. As shown by the data, at most only one panelist saw a difference with the
carpet cleaned by Formula A.
[0023] The carpet samples cleaned with Formula A were also compared to virgin pieces of
the same carpet using a Minolta CHROMOMETER™ Model C-R 110 reflectometer. Table II
illustrates the reflectometer readings taken. Δ E represents the difference in reflected
light between the carpets cleaned with product, and a virgin piece of the same carpet.
This value has been corrected for any carpet fiber change by rubbing. A Δ E value
less than 2.0 is usually undetected by the human eye.
Table II
Reflectometer Results |
Carpet |
Δ E Formula A |
DuPont: |
|
STAINMASTER CHAMPLIN Almond |
-1.57 |
STAINMASTER CHAMPLIN Ocean Blue |
0.69 |
STAINMASTER CHAMPLIN Embers |
-2.30 |
STAINMASTER CHAMPLIN Golf Green |
-0.17 |
Philadelphia: |
|
MAINSTREET Cotton Seed |
-0.24 |
MAINSTREET Imperial Red |
-1.47 |
MAINSTREET Smoked Blue |
0.02 |
MAINSTREET Laguna Green |
-2.58 |
Etoil: |
|
Wool Geranium |
0.97 |
Wool Elegan |
2.14 |
Lees: |
|
Polyester Parchment |
0.29 |
Polyester Bordeaux |
0.69 |
Polyester Sapphire* |
-- |
*Reflectometer readings could not be done on this color because it is out of range
(too dark). |
EXAMPLE 2
[0024] The removal of feline malodor with Formula A was tested as follows. Two Philadelphia:
MAINSTREET Cotton Seed carpet samples were stained with 2 g of cat urine obtained
by Buckshire Labs, Perkosie, Pennsylvania. One carpet sample was left as the control.
One of the carpet samples was then cleaned with 25 g of Formula A by spraying the
composition on the carpet and then allowing it to set for 10 minutes. The carpet cleaned
was then blotted with white paper towel until the visual stain was gone. The carpet
was then dried overnight and subjected to fifteen (15) panelists thereafter. The panel
was asked the question: "Is the pet stain removed?" The fifteen (15) panelists responded
'yes' the stain was removed, providing a 95% confidence level (using the Chi-Square
method).
Example 4
[0025] A twelve (12) key stain test was conducted using the test carpets Philadelphia MAINSTREET:
Cotton Seed and STAINMASTER CHAMPLAIN: Almond. Formulas A, B and C were tested. For
each Formula, twenty-four (24) strips of each type of carpet were treated. Two carpet
strips were prepared for each stain. Lipstick, crayon and ink were drawn on individual
strips of carpeting in the shape of an "X". Grape juice, wine and coffee (5 g each)
were tipped via beaker on individual strips of carpeting. Tomato sauce, chocolate
and salad dressing (1 gram); motor oil and mustard (0.40 grams); and liquid make-up
(0.30 grams) were applied using a spatula and 2" x 2" square template on individual
strips. One set of stains were left for 30 minutes and the other set for 7 days. Stains
were cleaned with 6 grams of the appropriate formula using white washcloths and 50
strokes. This procedure was repeated for each of the Formulas A, B and C.
[0026] After drying, thirty (30) panelists were asked to rate the carpets using the following
scale:
Scale
[0027]
1 - No removal
2 - Slight removal
3 - Moderate removal
4 - Almost complete removal
5 - Complete removal
Results:
[0028]
30 Minute Stains |
|
Philadelphia Untreated |
|
Formula A |
Formula B |
Formula C |
Lipstick |
2.92 |
2.95 |
2.63 |
Crayon |
4.86 |
4.83 |
4.83 |
Ink |
3.59 |
3.92 |
3.98 |
Make-Up |
3.48 |
3.62 |
3.78 |
Tomato Sauce |
4.90 |
4.85 |
4.88 |
Salad Dressing |
4.15 |
4.08 |
4.05 |
Motor Oil |
3.77 |
3.33 |
3.75 |
Mustard |
2.98 |
2.73 |
2.70 |
Chocolate |
4.18 |
3.38 |
4.05 |
Grape Juice |
4.22 |
4.07 |
4.10 |
Red Wine |
3.78 |
3.65 |
3.66 |
Coffee |
4.08 |
4.27 |
4.43 |
Results:
[0029]
30 Minute Stains |
|
STAINMASTER |
|
Formula A |
Formula B |
Formula C |
Lipstick |
3.80 |
3.62 |
3.42 |
Crayon |
4.98 |
4.88 |
4.98 |
Ink |
2.83 |
3.03 |
2.90 |
Make-Up |
3.53 |
3.45 |
3.37 |
Tomato Sauce |
4.96 |
4.98 |
4.96 |
Salad Dressing |
4.95 |
4.85 |
4.80 |
Motor Oil |
4.98 |
4.33 |
4.54 |
Mustard |
2.95 |
3.25 |
3.13 |
Chocolate |
3.52 |
3.35 |
3.50 |
Grape Juice |
3.65 |
3.48 |
3.27 |
Red Wine |
3.20 |
2.85 |
3.07 |
Coffee |
3.07 |
2.87 |
3.37 |
Results:
[0030]
7 Day Stains |
|
Philadelphia Untreated |
|
Formula A |
Formula B |
Formula C |
Lipstick |
3.80 |
3.62 |
3.42 |
Crayon |
4.98 |
4.88 |
4.98 |
Ink |
2.83 |
3.03 |
2.90 |
Make-Up |
3.53 |
3.45 |
3.37 |
Tomato Sauce |
4.96 |
4.98 |
4.96 |
Salad Dressing |
4.95 |
4.85 |
4.80 |
Motor Oil |
4.98 |
4.33 |
4.54 |
Mustard |
2.95 |
3.25 |
3.13 |
Chocolate |
3.52 |
3.35 |
3.50 |
Grape Juice |
3.65 |
3.48 |
3.27 |
Red Wine |
3.20 |
2.85 |
3.07 |
Coffee |
3.07 |
2.87 |
3.37 |
Results:
[0031]
7 Day Stains |
|
STAINMASTER |
|
Formula A |
Formula B |
Formula C |
Lipstick |
3.05 |
3.38 |
3.45 |
Crayon |
4.90 |
4.83 |
4.87 |
Ink |
3.72 |
3.58 |
3.23 |
Make-Up |
3.83 |
3.63 |
3.88 |
Tomato Sauce |
4.66 |
4.59 |
4.71 |
Salad Dressing |
4.73 |
4.77 |
4.62 |
Motor Oil |
4.59 |
4.27 |
4.03 |
Mustard |
3.83 |
4.07 |
3.89 |
Chocolate |
3.33 |
2.90 |
2.73 |
Grape Juice |
3.64 |
3.23 |
3.45 |
Red Wine |
3.25 |
3.13 |
3.12 |
Coffee |
3.15 |
3.15 |
3.07 |
Example 5
[0032] DuPont STAINMASTER Nylon (Color: Ocean Blue), Etoil Wool (Color: Elegan), Lees Polyester
(Color: Sapphire) were tested to determine whether treatment of the carpets with Formula
A left the carpet soft (desirable) or sticky (undesirable).
[0033] Each of the carpets were cut into 12" x 12" pieces. Each carpet piece was treated
with 16.6 grams of Formula A and rubbed into the carpet with white paper towel for
approximately 50 strokes. The carpets were then allowed to dry overnight. Twenty (20)
people were paneled, asking them the following question: "Is the carpet soft, not
sticky?"
[0034] Table III illustrates the panel results. The table shows out of twenty (20) people
paneled, how many gave a response of 'yes' to the question asked.
Averaged Panel Results
[0035]

Example 6
[0036] Resoiling was tested on carpeting that was cleaned with Formula A. Carpets tested
were DuPont STAINMASTER CHAMPLIN: Almond and Philadelphia MAINSTREET: Cotton Seed.
The test procedure involved a 1' x 3' section of carpet (for each carpet tested).
One portion of the section was used as a control. For the test, 50 grams of Formula
A was sprayed on the other portion of the carpet. The product was then wiped into
the carpet using clean, white absorbent cloth in the designated section, then allowed
to dry. The carpet piece was then placed in hallway, rotating 180° every week, until
the carpet was visually dirty. The carpet piece was then removed from hallway and
vacuumed. Reflectometer readings were taken of the sections, comparing the portion
cleaned with Formula A to the virgin carpet to see if Formula A resoiled more quickly
than the untreated Control portion. Both types of carpets were then visually paneled
by thirty (30) people using the following scale:
Scale
[0037]
- 1 =
- very soiled
- 5 =
- slightly soiled
[0038] Visual Panel Results are shown in Table IV below.

The results indicate that Formula A did not contribute to resoiling but rather provided
a soil repellant effect to the carpet.
[0039] Reflectometer readings were also taken of the carpet sections, with results summarized
in Table V below.

1. An aqueous cleaning composition having a pH level falling within a range of from 4
to 9.5 comprising:
(a) from 0.75% to 1.15% by weight of sodium lauryl sulfate;
(b) from 0.65% to 0.85% by weight ethylene glycol monohexyl ether;
(c) from 0.025% to 0.17% by weight of a fluorinated surfactant selected from a mixture
of (i) a perfluoropropionate of the Formula I
F(CF₂)n-CH₂CH₂-S-CH₂CH₂-COOLi I
wherein n is an integer having a value of 6 to 12; and (ii) a perfluoroalkyl phosphate
of formula II

wherein n is an integer having a value of 6 to 12; and the weight ratio of (i) to
(ii) being from 1:1 to 1:2;
(d) from 0.025% to 0.05% by weight of a styrene maleic anhydride polymer; and
(e) from 0.3% to 0.45% by weight of a chelating agent selected from the group consisting
of diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic
acid, sodium or potassium salts thereof, and mixtures thereof, wherein said weight
percentages are based on the total active ingredient weight of the aqueous composition.
2. A composition according to claim 1 wherein said chelating agent is sodium ethylenediaminetetraacetate.
3. A composition according to claim 2 wherein (a) is present in a range from 0.8% to
1% by weight.
4. A composition according to any one of the preceding claims wherein (b) is present
in a range from 0.65% to 0.85% by weight.
5. A composition according to any one of the preceding claims wherein (c) is present
in a range from 0.1% to 0.15% by weight.
6. A composition according to any one of the preceding claims wherein (d) is present
in a range from 0.03% to 0.04% by weight.
7. A composition according to any one of the preceding claims wherein (e) is present
in a range from 0.35% to 0.45% by weight.
8. A composition according to any one of the preceding claims wherein (a) is present
in an amount from 0.85% to 0.9% by weight.
9. A composition according to any one of the preceding claims wherein (b) is present
in an amount of about 0.75% by weight.
10. A composition according to any one of the preceding claims wherein (c) is present
in an amount of about 0.1% by weight.
11. A composition according to any one of the preceding claims wherein (d) is present
in an amount of 0.03% to 0.04% by weight and (e) is present in an amount of 0.37%
to 0.39% by weight.
12. A composition according to any one of the preceding claims wherein said pH is between
6 and 7.
13. A method of cleaning a rug, carpet or textile by using as a cleaning agent an aqueous
cleaning composition according to any one of the preceding claims.