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Claims  |
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We claim:
1. A detersive system, that can remove divalent or trivalent ions from
service water and can clean soiled surfaces or articles, comprising:
(a) an effective detersive amount of a soil removing detergent;
(b) an effective amount of a softening agent, dispersed in the detergent,
which softening agent comprises:
(1) about 25 to 95 vol.-% of an exterior organic phase having:
(i) an organic medium; and
(ii) about 0.1 to 99 wt-% based on the organic phase of an organic soluble
hardness ion complexing agent;
(2) about 5 to 75 vol.-% of an inner acidic aqueous phase dispersed within
the exterior organic solvent phase which comprises:
(i) water; and
(ii) about 0.5 to 99 wt-% based on the aqueous phase of an acid; and
(3) about 0.1 to 50 wt-% based on the organic phase of a surfactant that
can stabilize the dispersed aqueous phase within the exterior organic
phase.
2. The detersive system of claim 1 wherein the softening agent comprises
droplets having a droplet size of about 0.05 to 2,000 microns.
3. The detersive system of claim 1 wherein the softening agent comprises
droplets having a droplet size of about 1 to 1,000 microns.
4. The detersive system of claim 1 wherein the detersive system is a solid.
5. The detersive system of claim 1 wherein the detersive system is a
liquid.
6. The detersive system of claim 1 wherein the soil removing detergent
comprises a surfactant selected from the group consisting of nonionic
surfactant, cationic surfactant, and anionic surfactant and mixtures
thereof.
7. The detersive system of claim 1 wherein the soil removing detergent
comprises an inorganic detergent selected from the group consisting of an
alkaline metal silicate, an alkaline metal hydroxide, an alkaline metal
carbonate, an alkaline metal bicarbonate, and mixtures thereof.
8. The detersive system of claim 2 wherein the organic medium is selected
from the group consisting of a liquid paraffinic hydrocarbin, a napthenic
hydrocarbon, petroleum white oil, a wax, a silicone oil, a halogenated
paraffin, a fatty acid, and mixtures thereof.
9. The detersive system of claim 8 wherein the complexing agent is selected
from the group consisting of an alkyl substituted phosphorus acid
compound, an alkyl substituted sulfonic acid compound, a carboxylic acid
compound, or salts thereof and mixtures thereof.
10. The detersive system of claim 9 wherein the alkyl substituted
phosphorus acid is an alkyl substituted phosphoric acid, alkyl substituted
phosphonic acid, alkyl substituted phosphinic acid, salts thereof or
mixtures thereof.
11. The detersive system of claim 10 wherein the alkyl substituted
phosphoric acid is di-2-ethyl-hexylphosphoric acid.
12. The detersive system of claim 5, wherein the acid, of inner acidic
aqueous phase, is selected from the group consisting of hydrochloric acid,
sulfuric acid, phosphoric acid, a carboxylic acid compound, and mixtures
thereof.
13. The detersive system of claim 5 wherein the surfactant that can
stabilize the dispersed inner aqueous phase comprises alkyl substituted
polyethyleneimine or alkyl substituted amine.
14. A warewashing detersive system, capable of removing soil from flatware
or dishware and removing divalent or trivalent ions from service water,
comprising:
(a) about 0.1 to 95 wt-% of a source of an inorganic alkaline detergent;
(b) about 2 to 60 wt-% of a softening agent dispersed in the detersive
system, which softening agent comprises:
(1) about 25 to 95 vol.-% of an exterior organic phase comprising a major
proportion of an organic medium and about 0.5 to 45 wt-% of an organic
soluble hardness ion complexing agent;
(2) about 5 to 75 vol.-% of an inner acidic aqueous phase dispersed within
the exterior organic solvent phase which comprises water and about 0.5 to
99 wt-% of an acid; and
(3) about 0.1 to 50 wt-%, based on the organic phase, of a surfactant to
stabilize the dispersed inner aqueous phase within the exterior organic
phase; and
(c) about 0.1 to 25 wt-% of a source of active halogen.
15. The detersive system of claim 14 wherein the alkaline detergent
comprises an alkali metal carbonate, an alkali metal bicarbonate, an
alkali metal silicate, an alkali metal hydroxide, or mixtures thereof.
16. The detersive system of claim 14 wherein the source of active halogen
comprises an alkali metal hypohalide, an alkali metal dihaloisocyanurate,
a halogenated alkali metal tripolyphosphate or mixtures thereof.
17. The detersive system of claim 14 wherein the dispersed softening agent
comprises droplets having a droplet size of about 0.05 to 2,000 microns.
18. The detersive system of claim 14 wherein the dispersed liquid softening
agent comprises droplets having a droplet size of about 1 to 1,000
microns.
19. The detersive system of claim 14 wherein the detersive system is a
solid.
20. The detersive system of claim 14 wherein the detersive system is a
liquid.
21. The detersive system of claim 14 wherein the organic medium is selected
from the group consisting of a liquid paraffinic hydrocarbon, petroleum
white oil, a wax, a silicone oil, a halogenated paraffin, a fatty acid and
mixtures thereof.
22. The detersive system of claim 14 wherein the complexing agent is
selected from the group consisting of an alkyl substituted phosphorous
acid compound, an alkyl substituted sulfonic acid compound, a carboxylic
acid compound, or salts thereof and mixtures thereof.
23. The detersive system of claim 22 wherein the alkyl substituted
phosphorus acid is an alkyl substituted phosphoric acid, alkyl substituted
phosphonic acid, alkyl substituted phosphinic acid, salts thereof or
mixtures thereof.
24. The detersive system of claim 23 wherein the alkyl substituted
phosphoric acid is di-2-ethyl-hexylphosphoric acid.
25. The detersive system of claim 14, wherein the acid, of the inner acidic
aqueous phase, is selected from the group consisting of hydrochloric acid,
sulfuric acid, phosphoric acid, a carboxylic acid compound and mixtures
thereof.
26. A detersive laundry system, that can remove soil from fabric and remove
divalent ions or trivalent ions from service water, comprising:
(a) about 0.1 to 50 wt-% of a soil removing detergent;
(b) about 0.1 to 95 wt-% of a source of alkalinity; and
(c) about 2 to 60 wt-% of a softening agent dispersed within a detersive
system comprising:
(1) about 25 to 95 vol.-% of an exterior organic phase which comprises a
major proportion of an organic medium, and about 0.5 to 45 wt-% of an
organic soluble hardness ion complexing agent;
(2) about 5 to 75 vol.-% of an inner acidic aqueous phase dispersed within
the exterior organic solvent phase which comprises water, and about 0.5 to
99 wt-% of an acid; and
(3) about 0.1 to 50 wt-%, based on the organic phase, of a surfactant to
stabilize the dispersed inner aqueous phase within the exterior phase.
27. The detersive system of claim 26 wherein the soil removing detergent
comprises an anionic surfactant, a nonionic surfactant, a cationic
surfactant, or mixtures thereof.
28. The detersive system of claim 27 wherein the anionic surfactant
comprises an alkyl sulfonate composition, an alkyl benzene sulfonate
composition, an alkyl sulphate composition, or mixtures thereof.
29. The detersive system of claim 26 wherein the source of alkalinity
comprises an alkali metal carbonate, an alkali metal bicarbonate, an
alkali metal silicate, an alkali metal hydroxide and mixtures thereof.
30. The detersive system of claim 26 wherein the dispersed softening agent
comprises droplets having a droplet size of about 0.05 to 2,000 microns.
31. The detersive system of claim 26 wherein the dispersed softening agent
comprises droplets having a droplet size of about 1 to 1,000 microns.
32. The detersive system of claim 26 wherein the detersive system is a
solid.
33. The detersive system of claim 26 wherein the detersive system is a
liquid.
34. The detersive system of claim 26 wherein the soil removing detergent
comprises an inorganic detergent selected from the group consisting of an
alkaline metal silicate, an alkaline metal hydroxide, an alkaline metal
carbonate, an alkaline metal bicarbonate, and mixtures thereof.
35. The detersive system of claim 26 wherein the organic medium is selected
from the group consisting of a liquid paraffinic hydrocarbon, a napthenic
hydrocarbon, petroleum white oil, a wax, a silicone oil, a halogenated
paraffin, a fatty acid and mixtures thereof.
36. The detersive system of claim 26 wherein the complexing agent is
selected from the group consisting of an alkyl substituted phosphorus acid
compound, an alkyl substituted sulfonic acid compound, a carboxylic acid
compound, and mixtures thereof.
37. The detersive system of claim 26, wherein the inner acidic aqueous
phase acid is selected from the group consisting of hydrochloric acid,
sulfuric acid, phosphoric acid, a carboxylic acid compound, a polyacrylic
acid compound, and mixtures thereof.
38. The detersive system of claim 26 wherein the surfactant that can
stabilize the dispersed inner aqueous phase comprises alkyl substituted
polyethylenimine or an alkyl substituted amine.
39. A method of preparing a detersive system, that can remove divalent or
trivalent ions from service water and can clean soiled surfaces or
articles, comprising dispersing in a soil removing detergent an effective
amount of a softening agent product made by combining an exterior organic
phase and an interior aqueous phase wherein the exterior organic phase is
present at a concentration of about 25 to 95 vol-% and comprises a
proportion of an organic medium and about 0.1 to 99 wt-% based on the
organic phase of an organic soluble hardness ion complexing agent; wherein
the inner aqueous phase comprises 5 to 75 vol-% of the softening agent and
comprises a proportion of water and about 0.5 to 99 wt-% based on the
aqueous phase of an acid and about 0.1 to 50 wt-% based on the organic
phase of a surfactant that can stabilize the dispersed aqueous phase
within the exterior organic phase.
40. The detersive system of claim 39 wherein the softening agent comprises
droplets having a droplet size of about 0.05 to 2,000 microns.
41. The detersive system of claim 39 wherein the softening agent comprises
droplets having a droplet size of about 1 to 1,000 microns.
42. The detersive system of claim 39 wherein the detersive system is a
solid.
43. The detersive system of claim 39 wherein the detersive system is a
liquid.
44. The detersive system of claim 39 wherein the soil removing detergent
comprises a surfactant selected from the group consisting of nonionic
surfactant, cationic surfactant, and anionic surfactant and mixtures
thereof.
45. The detersive system of claim 39 wherein the soil removing detergent
comprises an inorganic detergent selected from the group consisting of an
alkaline metal silicate, an alkaline metal hydroxide, an alkaline metal
carbonate, an alkaline metal bicarbonate, and mixtures thereof.
46. The detersive system of claim 40 wherein the organic medium is selected
from the group consisting of a liquid paraffinic hydrocarbon, a naphthenic
hydrocarbon, petroleum white oil, a wax, a silicone oil, a halogenated
paraffin, a fatty acid, and mixtures thereof.
47. The detersive system of claim 46 wherein the complexing agent is
selected from the group consisting of an alkyl substituted phosphorus acid
compound, an alkyl substituted sulfonic acid compound, a carboxylic acid
compound, or salts thereof and mixtures thereof.
48. The detersive system of claim 47 wherein the alkyl substituted
phosphorus acid is an alkyl substituted phosphoric acid, alkyl substituted
phosphonic acid, alkyl substituted phosphinic acid, salts thereof or
mixtures thereof.
49. The detersive system of claim 48 wherein the alkyl subtituted
phosphoric acid is di-2-ethyl-hexylphosphoric acid.
50. The detersive system of claim 43, wherein the acid, of inner acidic
aqueous phase, is selected from the group consisting of hydrochloric acid,
sulfuric acid, phosphoric acid, a carboxylic acid compound, a polyacrylic
acid compound, and mixtures thereof.
51. The detersive system of claim 43 wherein the surfactant that can
stabilize the dispersed inner aqueous phase comprises alkyl substituted
polyethyleneimine or alkyl substituted amine.
52. A method of cleaning soiled articles or surfaces which comprises
dispersing the detersive system of claim 1 in an aqueous medium to form a
use composition and contacting the use composition with the soiled article
or surface. |
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Claims |
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Description |
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FIELD OF THE INVENTION
The invention relates to the use of a detersive system containing a soil
removing detergent and a dispersed aqueous-organic softening agent that
can remove hardness from service water during detergent action. More
specifically, the softening agent of the invention can be used to remove
hardness cations from an aqueous medium or use solution containing a
detersive system either before or during detergent action.
BACKGROUND OF THE INVENTION
Detersive systems have been used for many years in many cleaning
environments including the laundry, warewashing, hard surface cleaning,
and other applications. Typically, detersive systems are concentrates
comprising mixtures of cleaning ingredients that when mixed with water
form a cleaning medium or use composition. Service water, containing some
concentration of hardness ions, supplied by local water utilities is most
commonly used in making the use composition. Hardness ions are typically
undesirable in conjunction with detersive systems since they interfere in
the soil removal mechanism. The quality of service water varies from place
to place throughout the country and can vary in hardness and can vary in
the hardness components. Hardness typically comprises metal ions including
calcium, magnesium, iron, manganese, and other typically divalent or
trivalent metal cations depending on the source of the water. The presence
of hardness cations in service water can substantially reduce the
detersive action or effectiveness of a detersive system, can result in the
incomplete cleaning of laundry, dishware, hard surfaces, and other soiled
items or surfaces and can leave films or scale comprising the hardness
cation and/or components of the detersive system.
A great deal of attention in recent years has been given to the components
of detersive systems that reduce the effects of the hardness components.
Common hardness sequestering agents comprise inorganic chemicals such as a
condensed phosphate compound and a zeolite, and organic sequestrants such
as EDTA, organic phosphonates and organic phosphinates. Such agents are
effective in treating hardness in service water by a chemical reaction
which keeps the ions in the aqueous bulk detersive system but reduces the
hardness effect of the ions on the detersive systems. These agents can be
effective but provide both economic and ecological disadvantages. Other
hardness sequestering agents have been proposed in the prior art but have
encountered economic, environmental, or compatibility problems in
detersive systems.
Accordingly, a substantial need exists for hardness treating or softening
agents that can be used in detersive systems at low concentration which
can effectively soften service water through a mechanism of removing
hardness ions from aqueous media used in detersive systems with no
increase in cost, adverse environmental impact, or compatibility problems
in detersive systems.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a depiction of the mechanism of hardness removal from a bulk
aqueous washing phase.
FIG. 2 is a graphical representation showing the softening properties of
the softener of Example I.
FIG. 3 is a graphical representation showing the softening properties of
the softener of Example V.
BRIEF DISCUSSION OF THE INVENTION
We have found that a dispersion of an aqueous-organic hardness softening,
hardness removing, or water softening, agent can be used in conjunction
with detergent components. In an aqueous detersive system, the softening
agent is a dispersion, in the bulk aqueous phase, of small liquid or solid
organic droplets having an internal aqueous phase. In somewhat greater
detail, the softening agent comprises a dispersion of small droplets
having an exterior organic complexing phase, an inner acidic aqueous phase
and a surfactant stabilizing the phase separation. The exterior organic
phase comprises an organic medium which can be liquid or solid at room
temperature and an organic soluble complexing agent that can bind hardness
components. The inner acidic aqueous phase comprises an acid that acts as
a sink or depository for hardness ions. Our current understanding of the
mechanism of the action of the softening agent is as follows. At the
interface between the organic phase and the bulk aqueous phase, the
complexing agent first reacts with and extracts the hardness cations into
the exterior organic phase, simultaneously releasing protons displaced
from the complexing agent into the bulk phase. The hardness
cation-complexing agent reaction product is then transferred by diffusion
to the interface between the inner acidic aqueous phase and the exterior
organic phase. There the hardness cations on the complexing agent are
exchanged for protons. The cations remain in the aqueous phase. The
protons regenerate the complexing agent for a repeat of the cycle (see
FIG. 1). In this way, calcium, magnesium, iron, manganese, and other
divalent or trivalent hardness cations can be transferred against a
concentration gradient if the complexing agent has an affinity for the
cation and a sufficient pH gradient exists between the inner aqueous phase
of the softening agent through the organic phase to the bulk aqueous
detersive system phase. Protons are thus transferred countercurrently to
the hardness cations and provide a driving force to cause transfer of the
hardness cations.
Briefly, in preparation, the inner acidic aqueous phase is first emulsified
in the exterior organic phase containing an organic soluble complexing
agent with a surfactant to stabilize the emulsion. The softening agent is
then dispensed in the detergent composition. When the detergent
composition is contacted with water to form a detersive system, the
softening agent is then released into the use composition during the
release of the detersive system. Alternatively the softening agent can be
added to the wash medium separately from the detergent composition. The
softening agent thus functions in the use composition as a
water-in-oil-in-water emulsion. The emulsion is designed to be stable or
to stay intact to soften the aqueous medium at least for the duration of a
wash cycle process or step.
One aspect of this invention relates to a detersive system containing the
softening agent. A second aspect of this invention relates to methods of
making detersive systems containing the softening agent. A third aspect of
this invention relates to a method of using a detersive system containing
the softening agent, in an aqueous use medium for cleaning or soil removal
purposes.
DETAILED DISCUSSION OF THE INVENTION
The detersive systems of our invention comprise a soil removing detergent
and a dispersed softening agent having an inner acidic aqueous phase
stabilized by a surfactant within an exterior organic complexing agent
phase. The softening agents can be included in or used in conjunction with
detersive systems formulated to clean dishware and flatware, laundry,
clean-in-place equipment, hard surfaces, and other soiled articles or
surfaces.
SOFTENING AGENT
The softening agent of the invention comprises two phases, an exterior
organic phase and an inner acidic aqueous phase dispersed and contained
within the exterior organic phase. The organic/aqueous phases of the
softening agent are stabilized with a surfactant.
The softening agent contains a surfactant that can stabilize the dispersion
of the inner aqueous phase in the exterior organic phase. Typically, the
surfactant is present in the softening agent and appears at the interface
between the organic phase and the inner aqueous phase. After the softening
agent is prepared, the surfactant can be also present in both the aqueous
and the organic phases. The stabilizing surfactant can be added to the
organic phase during the preparation of the softening agent, and is
typically mixed with the organic phase prior to the preparation of the
softening agent. The inner acidic aqueous phase of the softening agent
serves as a sink or depository to contain the hardness cations which have
been extracted from the bulk aqueous washing phase by the complexing
agent. If substantial amounts of the aqueous phase of the softening agent
are released into the bulk aqueous phase during cleaning, the extent of
softening can be substantially reduced.
The surfactant can be used at a concentration of about 0.01 to about 50
wt-% based on the total weight of the organic phase. Preferably, the
amount of surfactant used ranges from about 1 to 20 wt-% of the organic
phase and most preferably, for rea | | |
