[0001] This invention relates to laundry prespotting compositions. More particularly, this
invention relates to aqueous laundry prespotting compositions having excellent stain
removal properties.
[0002] Current commercially available prespotting compositions fall into two categories,
those based primarily upon water and those based primarily upon solvents. The aqueous
based prespotting compositions are primarily non-aerosol formulations intended for
use in trigger spray bottles or squeeze bottles. These aqueous based prespotting compositions
have good stain removal characteristics against the so-called water-borne stains.
These stains include grape juice, mustard, grass, chocolate, clay and similar stains.
[0003] The solvent based composition formulations typically have been packaged in aerosol
form. These solvent-based compositions typically are more effective in removing oil-borne
stains, such as cooking oil, fat, spaghetti sauce, sebum, grease, motor oil and the
like. It is possible to formulate solvent-based prespotting compositions with reasonable
water-borne stain remover. However, it is desirable to use a composition which has
good removal for both water-borne and oil-borne stains.
[0004] There have been attemps to replace the solvent with water in prespotter compositions
for both aerosol and non-aerosol formulation types. One approach is described in U.
S. Patent 4,438,009, issued March 20, 1984. The compositions described in this patent
are emulsions containing a salt, a nonionic surfactant, from 5 to 60% by weight of
a solvent, and water. These compositions are described as having good stain removal
properties but these compositions require that some solvent be present for the enhanced
stain removal.
[0005] Another approach is set forth in U. S. Patent 4,079,078, issued March 14, 1978. A
typical formulation having certain ingredients corresponding to the teachings of that
patent is tested in Example I herein as a comparative formulation. Such compositions
require a nonionic surfactant, an anionic surfactant, an alkanolamine, a base, water,
a fatty acid corrosion inhibitor, as oleic acid, and optionally, an electrolyte salt
to reduce gel formation, such as sodium citrate, and a color stabilizing agent, as
citric acid in amounts of up to 1%.
[0006] Most commerically available liquid prespotting formulations are totally aqueous.
These aqueous formulations exhibit good stain removal for the water-borne stains but
are inferior to solvent based prespotters for oil removal.
[0007] Most aerosol prespotting formulations and a few liquid formulations are totally non-aqueous.
These formulations have excellent oil-borne stain removal but are less effective against
water-borne stains. Further these solvent products often contribute to soil redeposition.
[0008] The object to the present invention to provide an aqueous liquid prespotting composition
having superior cleaning properties for both oil and water-borne stains.
[0009] Accordingly, the present invention provides a laundry prespotting composition comprising:
(a) from about 0.1 to 6% by weight of a chelating agent; (b) from about 5 to about
40% by weight of at least one nonionic surfactant wherein the surfactant has an HLB
such that the combined HLB for all surfactants present is within the range of from
9 to 13; and (c) water; wherein the composition is substantially solvent free and
wherein the composition has a pH within the range of from about 4.5 to 12.2.
[0010] It has been surprisingly found that the aqueous prespotting composition of the present
invention exhibits good cleaning including oil removal and resoil inhibition under
most conditions encountered in the home laundry. The prespotting composition of the
present invention has cleaning properties equal to or better than solvent containing
compositions.
[0011] The compositions of the present invention are generally liquids of varying viscosities
from rather thin compositions suitable primarily for use as pump spray or squeeze
bottle spray compositions to rather thick formulations which would have to be spread
on the cloth by some alternate method.
[0012] Still further features and advantages of the composition of the present invention
will become more apparent from the following more detailed description thereof.
[0013] The first component of the compositions to the present invention is a chelating agent.
It is thought that the chelating agent functions in the composition to the present
invention to assist in removal of certain heavy ions which inhibit the surfactancy
of the nonionic surfactants. Also these chelating agents act in concert with the nonionic
surfactant so that the surfactant is in the right configuration to attack oily stains
from an aqueous system. Suitable chelating agents include the salts of ethylenediamine
tetraacetic acid (EDTA) such as ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic
acid diammonium salt, ethylenediaminetetraacetic acid trisodium salt, ethylenediaminetetraacetic
acid tetrasodium salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic
acid tetrammonium salt, etc., the salts of diethylenetriaminepentaacetic acid (DTPA)
such as diethylenetriaminepentaacetic acid pentasodium salt, diethylenetriaminepentaacetic
acid pentapotassium salt, etc., the salts of (N-hydroxyethyl) ethylenediaminetriacetic
acid (HEDTA) such as (N-hydroxyethyl) ethylenedianinetriacetic acid trisodium salt,
(N-hydroxyethyl) ethylenediaminetriacetic acid tripotassium salt, etc., the salts
of nitrilotriacetic acid (NTA) such as nitrilotriacetic acid trisodium salt, nitrilotriacetic
acid tripotassium salt, etc., other chelating agents such as triethanolamine, diethanolamine,
monoethanolamine, etc. and mixtures thereof. Preferred chelating agents are the EDTA
and the NTA type chelating agents especially the salts of ethylenediaminetretraacetic
acid and particularly the tetrasodium, trisodium and disodium salts of ethylenediaminetetraacetic
acid.
[0014] Typically the chelating agents are present in the composition of the present invention
in an amount of from about 0.1 to 6% by weight. It is within this weight range that
the optimum cleaning and prespotting efficiency is obtained. It is perferred that
the chelating agents be present in the amount of from about 1.0 to 4% by weight and
preferable from 1.5 to 3.0% by weight.
[0015] The chelating agents, especially the EDTA, DTPA, and HEDTA types, can be added to
the composition of the present invention in the salt form, which is prefered since
the salts are water soluble, or in the water insoluble free acid form. If the chelating
agents are added in the free acid form, the free acids must be at least partially
neutralized to make them water soluble and form the chelating agent salts in situ.
Suitable bases to neutralize the free acids are sodium hydroxide, potassium hydroxide
and ammonium hydroxide. Sufficient base is added to solublize the free acid chelating
agent and to bring the pH of the composition within the range of about 4.5 to 12.2.
[0016] If the chelating agents are added as salts, these salts are often quite basic, having
a pH often above 10. It may be necessary to add some acid or other pH buffering material
to the composition of the present invention to adjust the pH to within a range of
from 4.5 to 12.2 and preferably 6.5 to 8.5 and optimum 7 to 8. Suitable acids include
citric acid, oxalic acid, acetic acid, hydrochloric acid, phosphoric., and the like.
The primary function of the acid is to control the pH so that the chelating agent
and the surfactants can remove the stains from the fabrics. Certain organic acids
also have some chelating properties and therefore may contribute to the overall cleaning
efficiency of the prespotting composition. Generally the acids, if used, are present_in
the compositions in the amount of from 0.2 to 2% by weight, however the amount of
acid used is not critical. The preferred acid is citric acid.
[0017] Citric acid may also be employed as a chelating agent, since it possesses chelating
properties. For this purpose it is employed in cnelating amounts from about 1.0 to
4.0% by weight and, preferably, from 1.5 to 3.0% by weight. A suitable base can be
employed to adjust the pH of the composition to within the preferred range from 6.5
to 8.5 and, optimally, between 7 and 8.
[0018] Accordingly, citric acid may be employed herein as a first component of the inventive
composition to assist in removing heavy ions and/or to act in concert with the nonionic
surfactant to aid in attacking oily stains. If desired, it is also employed in combination
with other chelating agents of the invention, to assist in controlling the final pH
of the composition, when such other chelating agents are added as salts.
[0019] The compositions of the present invention also include at least one nonionic surfactant.
A single nonionic surfactant having an appropriate HLB can be utilized or mixtures
of nonionic surfactants such that the HLB of the resulting mixture of nonionic surfactants
is within the appropriate range. It has generally been found that the nonionic surfactant
or mixture of nonionic surfactants should have an HLB within the range of from 9 to
13 for optium efficiency. It is perferred that the HLB be between 10 and 12. The optimum
HLB range is from 10.5 to 11.5.
[0020] Suitable nonionic surfactants include the ethoxylated nonylphenols such as the Surfonic
N series available from Texaco Chemicals; and the ethoxylated octylphenols including
the Triton X series available from Rohm & Haas; the ethoxylated secondary fatty alcohols
such as the Tergitol series available from Union Carbide; the ethoxylated primary
fatty alcohols such as the Neodols available from Shell Chemicals; the ethoxylated
sorbitan fatty acid esters such as the lweens from ICI America and the sorbitan fatty
acid esters such as the Spans from ICI America.
[0021] The perferred surfactants include the ethoxylated nonylphenols especially those having
a degree of ethyloxylation of from 3 to 10 moles of ethylene oxide, the ethoxylated
octylphenols expecially those having from 3 to 10 moles of ethylene oxide and the
ethoxylated fatty secondary alcohols especially those having from 3 to 10 moles of
ethylene oxide. As noted above mixtures of nonionic surfactants, which individually
have an HLB outside the range, can be utilized so long as the resultant HLB value
of the mixture is within the range as set forth above. It is within this HLB range
that the stain removal properties of the composition of the present invention are
at a maximum. Outside this range there is not sufficient oil and water dispersibility
to provide suitable stain removing properties. Generally it has been found that the
nonionic surfactants which are water dispersible have the best stain removal properties
in the compositions of the present invention. It is thought that water dispersible
surfactants act both against oil and water borne stains.
[0022] Generally the composition should include from 5 to 40% by weight of at least one
nonionic surfactant and preferably from 5 to 20% by weight and optimally 7 to 20%
by weight of at least one nonionic surfactant.
[0023] The compositions of the present invention are characterized as being substantially
solvent free. By the term "substantially solvent free" is meant a composition which
contains less than 1% by weight of an organic water immiscible solvent such as isoparaffinic
hydrocarbons, deodorized kerosene, d-limonene, the chlorinated solvents such as perchloroethylene,
methylene chloride, etc., This term is meant to exclude those non-polar water insoluble
solvents typically used in stain removal compositions.
[0024] The compositions of the present invention can also include small additional amounts
of other conventional materials including perfumes, defoamers, bacteriacides, bacterstats
and the like. Generally these materials are present in amounts of less than 2% by
weight based on the amount of the composition.
[0025] Although the compositions of the present invention are primarily designed for use
as prespotting compositions, these compositions can also be used as laundry detergents
or cleaning agents. These compositions can be used as heavy duty liquid laundry cleaning
compositions.
[0026] The compositions of the present invention can be prepared by any conventional means.
Suitable methods include cold blending or other mixing processes. It is not necessary
to use high shear or other strenuous mixing techniques to prepare the compositions
of the present invention.
[0027] The prespotting compositions of the present invention will now be illustrated by
way of the following examples where all part percentages are by weight and all temperatures
and degrees celeius unless otherwise indicated.
Example A
[0028] An artificial sebum soil was prepared as follows:
Part A

Part B

[0029] Melt all the components of Part A together at 120-130° F. Add Part B to Part A with
agitation while hot until homogeneous. At this time, 12 grams of air filter dirt (+200
mesh) is added and agitated for 10 minutes. From 50-100 ml of 120° F deionized water
is added with agitation and stirred for 10 minutes. From 900-950 ml (to total 1000
ml) of 120
0 F deionized water is added and agitated until the temperature of the mixture drops
to 110° F. The mixture is agitated in a Gifford Wood Homogenizer for 10 minutes or
until 120° F. Pour the mixture through cheesecloth and store in 100° F oven.
Example B
[0030] Grass stain slurry is prepared by placing 50 grams of fresh grass clippings and 500
grams of water in a blender and gradually increasing the speed to "liquify". Add isopropyl
alcohol as needed (up to 50 grams) to reduce foaming and blend for 20 minutes. Add
remainder of isopropyl alcohol (to 50 grams total) and mix for 5 minutes. Strain through
a 40 mesh screen and keep refrigerated until use.
Example 1
[0031] A liquid prespotting composition having the following composition was prepared:

[0032] This formulation was mixed and then placed into a squeeze bottle having a fountain
type cap for testing. The composition had a pH of 7.9. The formulation was tested
on 4 types of white cloth swatches: 100% cotton, 65/35 polyester/ cotton, 50/50 polyester/cotton,
and 100% polyester. Each swatch was stained with 7 stains, used motor oil, mustard,
grape juice, chocolate, a 20% clay slurry, artificial sebum (Example A), and grass
slurry (Example B). The swatches were saturated with the above formulation and allowed
to sit for 1 minute. The swatches were then washed with Tide detergent available from
Procter & Gamble with a dummy load of cotton towels. The stain removal characteristics
were rated on a 5 point scale with 1 being essentially no removal and 5 being complete
removal. The above formulation is compared to a liquid prespotter formulation (comparative)
containing 2% sodium citrate, 8% of a C12-C15 ethoylated alcohol (7 moles ethylene
oxide), 2.4% sodium xylene sulfonate and 87.6% water. The results are shown in Table
1.

[0033] The formulation of Example 1 had a composite stain removal of approximately 3.75
for all four cloth types while the comparative composition had a composite of 3.46.
The stain removal scores for both formulations are about equal for all stains except
used motor oil. For this stain the comparitive formula did not remove the stain for
any cloth type while the formulation of Example 1 showed improved oil stain removal.
Example 2
[0034] The procedure of Example 1 is repeated except that the formulation is changed as
shown in Table 2. The formulations are tested in accordance with the procedure of
Example 1. As the stain removal scores for stains other than used motor oil are essentially
equivalent only the results showing the increased used motor oil removal are shown
in Table 2.

[0035] As it is apparent from the above, increasing the surfactant level increases the ability
of the formulation to remove used motor oil from a variety of fabrics.
Example 3
[0036] The procedure of Example 1 is followed with the exception that the formulations as
shown in Table 3 were prepared. For comparison, similar formulations were prepared
without the tetrasodium salt of ethylenediamenetetraacedic acids. As the only substantial
differences between the formulations in stain removal is in the used motor oil removal,
this was also shown in Table 3.

Example 4
[0037] Procedure of Example 1 is repeated with the exception that the formulations used
in Table 4 were run.

[0038] As apparent from Table 4, inclusion of small amounts of the surfactants can increase
the oil removal against cotton but can effect its oil removal for other types of cloth.
Example 5
[0039] In order to show the effect of different levels of chelating agent, the formulations
in Table 5 were prepared and tested using the procedure of Example 1.

[0040] As it is apparent from Table 5, at a level of from approximately 0.5 to about 4%
is optimum for best oil removal. Although at very low levels and higher levels of
EDTA some oil removal can be seen. In each of the formulations the citric acid was
adjusted to maintain the pH at approximately 7.9.
Example 6
[0041] In order to show the effect of different chelating agents the formulations shown
in Table 6 were prepared. In some cases the pH was adjusted, while in other cases
the pH of the material by itself was used.

Example 7
[0042] In order to show the effect of varying acids used to adjust the pH, the formulations
shown in Table 7 were prepared, using the procedure of Example l. These formulations
were also tested as in Example 1.

Example 8
[0043] The procedure in formulation of Example 1 was prepared with the exception that the
surfonic N60 was replaced with the following surfactants:

[0044] The oil removal scores are shown in Table 8.

Example 9
[0045] The procedure of Example 1 is repeated with the following formulation:

[0046] The pH of the formulation is between 7 and 8. The formulation is effective in removing
stains as set forth in Example 1.
1. A laundry prespotting composition, characterized by
(a) from about 0.1 to 6% by weight of a chelating agent;
(b) from about 5 to 40% by weight of at least one nonionic surfactant wherein the
surfactant has an HLB such that the combined HLB for all surfactants present is within
the range of from 9 to 13; and
(c) water;
wherein the composition is substantially solvent free and wherein the composition
has a pH within the range of from about 4.5 to 12.2.
2. The composition of claim 1, characterized in that the chelating agent is selected
from the group consisting of salts of ethylenediaminetetraacetic acid, salts of diethylenetriaminepentaacetic
acid, salts of (N-hydroxyethyl) ethylenediaminetriacetic acid, salts of nitrilotriacetic
acid, triethanolamine, diethanolamine, monoethanolamine, and mixtures thereof.
3. The composition of claim 1, characterized in that the chelating agent is selected
from the group consisting of ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic
acid diammonium salt, ethylenediaminetetraacetic acid dipotassium salt, ethylenediaminetetraacetic
acid tripotassium salt, ethylenediaminetetraacetic acid trisodium salt, ethylenediaminetetraacetic
acid tetrasodium salt, ethylenediaminetetraacetic acid tetrapotassium salt, ethylenediaminetetraacetic
acid tetrammonium salt, nitrilotriacetic acid trisodium salt, nitrilotriacetic acid
tripotassium salt, and mixtures thereof.
4. The composition of claim 1, characterized in that the chelating agent is citric
acid.
5. The composition of any of claims 1 to 4, characterized in that the chelating agent
is present in an amount of from l.0 to 4.0% by weight.
6. The composition of any of claims 1 to 5, characterized in that the nonionic surfactant
is selected from the group consisting of ethoxylated nonylphenols, ethoxylated octylphenols,
ethoxylated secondary fatty alcohols, ethoxylated primary fatty alcohols, ethoxylated
sorbitan fatty acid esters, sorbitan fatty acid esters and mixtures thereof.
7. The composition of any of claims 1 to 6, characterized in that the surfactants
are present in the amount from 5.0 to 20.0% by weight.
8. The composition of any of claims 1 to 7, characterized in that the composition
includes an effective amount of an acid sufficient to adjust the pH of the composition
to within the range of 4.5 to 12.2.
9. A laundry prespotting composition characterized by
(a) from about 1.0 to 4.0% by weight of a chelating agent selected from the group
consisting of salts of ethylenediaminetetraacetic acid, salts of diethylenetriaminepentaacetic
acid, salts of (N-hydroxyethyl) ethylenediaminetriacetic acid, salts of nitrilotriacetic
acid and mixtures thereof;
(b) from about 5 to 20% by weight of at least one nonionic surfactant selected from
the group consisting of ethoxylated nonylphenols, ethoxylated octylphenols, ethoxylated
secondary fatty alcohols, ethoxylated primary fatty alcohols, ethoxylated sorbitan
fatty acid esters, sorbitan fatty acid esters and mixtures thereof, wherein surfactant
has an HLB such that the combined HLB for all surfactants present is within the range
of from 10 to 12; and
(c) water wherein the composition is substantially solvent free and wherein the composition
has a pH within the range of 6.5 to 8.5.
10. A laundry prespotting composition, characterized by
(a) from about 1.0 to 4.0% by weight of citric acid;
(b) from about 5 to 20% by weight of a nonionic surfactant having an HLB such that
the combined HLB for all surfactants present is within the range from 10 to 12, said
surfactant selected from the group consisting of ethoxylated nonylphenols, ethoxylated
octylphenols, ethoxylated secondary fatty alcohols, ethoxylated primary fatty alcohols,
ethoxylated sorbitan fatty acid esters, sorbitan fatty acid esters and mixtures thereof;
and
(c) water
the composition being substantially solvent free and having a pH from 6.5 to 8.5.