U.S. patent application number 11/438879 was filed with the patent office on 2006-09-28 for method for treating hydrophilic stains in a lipophilic fluid system.
Invention is credited to Robb Richard Gardner, William Michael Scheper.
Application Number | 20060213015 11/438879 |
Document ID | / |
Family ID | 33563923 |
Filed Date | 2006-09-28 |
United States Patent
Application |
20060213015 |
Kind Code |
A1 |
Gardner; Robb Richard ; et
al. |
September 28, 2006 |
Method for treating hydrophilic stains in a lipophilic fluid
system
Abstract
A fabric article treatment composition comprising a polar
solvent and a hydrophobic surfactant, wherein the composition is
miscible in a lipophilic fluid is provided.
Inventors: |
Gardner; Robb Richard;
(Cincinnati, OH) ; Scheper; William Michael;
(Guilford, IN) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY;INTELLECTUAL PROPERTY DIVISION
WINTON HILL BUSINESS CENTER - BOX 161
6110 CENTER HILL AVENUE
CINCINNATI
OH
45224
US
|
Family ID: |
33563923 |
Appl. No.: |
11/438879 |
Filed: |
May 23, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10876181 |
Jun 24, 2004 |
|
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11438879 |
May 23, 2006 |
|
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60483346 |
Jun 27, 2003 |
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Current U.S.
Class: |
8/142 |
Current CPC
Class: |
C11D 3/43 20130101; C11D
17/041 20130101; C11D 11/0017 20130101; D06L 1/02 20130101; D06L
1/00 20130101 |
Class at
Publication: |
008/142 |
International
Class: |
D06L 1/04 20060101
D06L001/04 |
Claims
1. A method for removing and/or reducing a hydrophilic stain from a
fabric article in need of treatment, the method comprising the
steps of: (i) contacting the hydrophilic stain on a fabric article
with a fabric article treatment composition thereby forming a
pretreated fabric article; and (ii) contacting the pretreated
fabric article with a lipophilic fluid such that the hydrophilic
stain is removed and/or reduced; wherein the fabric article
treatment composition is miscible with the lipophilic fluid and
comprises: a) a polar solvent exhibiting at least one of the
following Hansen solubility parameters: i) a fractional polar value
(f.sub.P) of greater than 0.02; ii) a fractional hydrogen bonding
value (f.sub.H) of greater than 0.10; and b) a hydrophobic
surfactant.
2. The method according to claim 1 wherein the pretreated fabric
article is formed inside a fabric article treating apparatus.
3. The method according to claim 1 wherein the pretreated fabric
article is formed prior to placing the fabric article inside a
fabric article treating apparatus.
4. The method according to claim 1 wherein the polar solvent
exhibits a fractional polar value (f.sub.P) of greater than
0.05.
5. The method according to claim 1 wherein the polar solvent
exhibits a fractional hydrogen bonding value (f.sub.H) of greater
than 0.20.
6. The method according to claim 1 wherein the polar solvent is
selected from the group consisting of: water, alcohols, glycols,
polyglycols, ethers, carbonates, esters, ketones, amines, amides,
ureas, alkanolamines, alkanolamides, phosphate esters, alkyl
nitrites and mixtures thereof.
7. The method according to claim 6 wherein the polar solvent
comprises from about 0% to about 50% by weight of the composition
of water.
8. The method according to claim 7 wherein the polar solvent
comprises from about 0.01% to about 20% by weight of the
composition of water.
9. The method according to claim 6 wherein the polar solvent
comprises a glycol and/or polyglycol and/or derivatives
thereof.
10. The method according to claim 6 wherein the polar solvent
comprises an alkoxy alcohol.
11. The method according to claim 1 wherein the composition
comprises from about 2% to about 50% by weight of the composition
of the hydrophobic surfactant.
12. The fabric article treatment composition according to claim 11
wherein the composition comprises from about 10% to about 30% by
weight of the composition of the hydrophobic surfactant.
13. The method according to claim 11 wherein the hydrophobic
surfactant exhibits an HLB value of from about 3 to about 9.
14. The method according to claim 1 wherein the hydrophobic
surfactant is selected from the group consisting of: silicone-based
surfactants, organosulfosuccinate surfactants, alkanolamines,
alkanolamides, alcohol alkoxylates, gemini surfactants, polyhydroxy
fatty acid amides, alkylhydrogen phosphates and salts thereof,
saccharide derivatives and mixtures thereof.
15. The method according to claim 1 wherein the composition further
comprises a cleaning adjunct and/or a lipophilic fluid.
16. The method according to claim 1 wherein the composition
exhibits a flash point of greater than 37.degree. C.
17. The method according to claim 1 further comprises a carrier
solvent selected from the group consisting of: silicone solvents,
hydrofluoroether solvents, perfluorinated solvents, hydrocarbon
solvents, halogenated hydrocarbons, and mixtures thereof.
18. A method for removing and/or reducing a hydrophilic stain from
a fabric article in need of treatment, the method comprising the
steps of: (i) contacting the hydrophilic stain on a fabric article
with a fabric article treatment composition thereby forming a
pretreated fabric article; and (ii) contacting the pretreated
fabric article with a lipophilic fluid such that the hydrophilic
stain is removed and/or reduced; wherein the fabric article
treatment composition is miscible with the lipophilic fluid and
comprises: a) from about 50% to about 70% by weight of the fabric
article treatment composition of a first polar solvent; b. from
about 10% to about 30% by weight of the fabric article treatment
composition of a second polar solvent different from the first; c.
from about 10% to about 30% by weight of the fabric article
treatment composition of a hydrophobic surfactant; and wherein the
fabric article treatment composition is miscible in a lipophilic
fluid.
19. The method according to claim 18 wherein the first polar
solvent comprises 3-methoxy-3-methyl-1-butanol.
20. The method according to claim 18 wherein the second polar
solvent comprises water.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Divisional Application of copending
U.S. patent application Ser. No. 10/876,181, filed on Jun. 24,
2004, which claims the benefit of U.S. Provisional Application Ser.
No. 60/483,346, filed on Jun. 27, 2003.
FIELD OF THE INVENTION
[0002] The present invention relates to a fabric article treatment
composition, more particularly a fabric article treatment
composition suitable for use in a lipophilic fluid-based fabric
article treating system and methods for using the fabric article
treatment composition.
BACKGROUND OF THE INVENTION
[0003] Conventional water-based fabric article treating systems
have utilized hydrophilic pretreating compositions that are
effective at removing and/or reducing hydrophilic stains.
[0004] Conventional dry cleaning systems have utilized hydrophobic
pretreating compositions that are effective at removing and/or
reducing hydrophobic stains.
[0005] Recently, formulators have been exploring lipophilic
fluid-based fabric article treating systems. Removal of hydrophilic
stains in such lipophilic fluid-based systems has been a challenge.
Accordingly, there is a need for a fabric article treatment
composition that is effective at removing hydrophilic stains from
fabric articles wherein the fabric articles are then subjected to a
lipophilic fluid-based fabric article treating system.
SUMMARY OF THE INVENTION
[0006] The present invention fulfills the need described above by
providing a fabric article treatment composition that is miscible
in a lipophilic fluid.
[0007] In one aspect of the present invention, a fabric article
treatment composition comprising: [0008] a) a polar solvent
exhibiting at least one of the following Hansen solubility
parameters: [0009] i) a fractional polar value (f.sub.P) of greater
than 0.02; and/or [0010] ii) a fractional hydrogen bonding value
(f.sub.H) of greater than 0.10; and [0011] b) a hydrophobic
surfactant;
[0012] wherein the fabric article treatment composition is miscible
in a lipophilic fluid, is provided.
[0013] In another aspect of the present invention, an article of
manufacture comprising: [0014] a) a container; and [0015] b) a
fabric article treatment composition according to the present
invention contained within the container, is provided.
[0016] In still another aspect of the present invention, a method
for removing a hydrophilic stain from a fabric article in need of
treatment, the method comprising contacting the hydrophilic stain
with a fabric article treatment composition that is miscible in a
lipophilic fluid to form a pretreated fabric article, is
provided.
[0017] In yet another aspect of the present invention, a fabric
article treated by a method in according to the present invention,
is provided.
[0018] Accordingly, the present invention provides a fabric article
treatment composition, an article of manufacture comprising the
fabric article treatment composition, a method for treating a
fabric article with the fabric article treatment composition and a
fabric article treated by such a method.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
[0019] "Fabric article" as used herein is intended to mean any
article that is customarily cleaned in a conventional laundry
process or in a dry cleaning process. As such the term encompasses
articles of clothing, linen, drapery, and clothing accessories. The
term also encompasses other items made in whole or in part of
fabric, such as tote bags, furniture covers, tarpaulins and the
like.
[0020] "Stain" means any undesirable substance on a fabric article
that is desired to be removed. Generally, stains are found only on
a portion of the article and are generated by accidental contact
between the soil and the fabric article. By the term "hydrophilic
stains" it is meant that the stain is comprised of water at the
time it first came in contact with the fabric article, or the stain
retains a significant portion of water on the fabric article.
Examples of hydrophilic stains include, but are not limited to,
beverages, many food soils, water soluble dyes, bodily fluids such
as sweat, urine or blood, outdoor soils such as grass stains and
mud.
[0021] "Miscible" as used herein means that greater than 5% and/or
greater than 20% and/or greater than 50% by weight of a material is
soluble in and/or dispersible in another material. For example that
greater than 5% by weight of the fabric article treatment
composition of the present invention is soluble in and/or
dispersible in a lipophilic fluid.
[0022] "Pretreated fabric article" as used herein means a fabric
article that has been contacted with a fabric article treatment
composition of the present invention prior to subsequent contact
with a discrete lipophilic fluid.
[0023] "Discrete lipophilic fluid" as used herein means a
lipophilic fluid that is not part of the neat fabric article
treatment composition. Typically, the discrete lipophilic fluid
when combined with the fabric article treatment composition makes
up greater than 30% and/or greater than 50% and/or greater than 70%
by weight of the fabric article treatment composition.
Notwithstanding the above, a lipophilic fluid can be present in a
neat fabric article treatment composition (such as in a product
that a consumer purchases and uses to contact a stain on a fabric
article in a pretreating step prior to subjecting the pretreated
fabric article to a fabric article treating process, such as a
lipophilic fluid-based system).
[0024] "Weight average molecular weight" as used herein means the
weight average molecular weight as determined using gel permeation
chromatography according to the protocol found in Colloids and
Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162,
2000, pg. 107-121.
Fabric Article Treatment Composition
[0025] The fabric article treatment composition comprises a polar
solvent and a hydrophobic surfactant, wherein the fabric article
treatment composition is miscible in a lipophilic fluid.
[0026] In one embodiment, the fabric article treatment composition
comprises from about 10% to about 99.9% and/or from about 20% to
about 95% and/or from about 30% to about 90% by weight of the
fabric article treatment of the polar solvent.
[0027] In another embodiment, the fabric article treatment
composition comprises from about 0.1% to about 90% and/or from
about 5% to about 80% and/or from about 10% to about 80% and/or
from about 10% to about 30% by weight of the fabric article
treatment composition of the hydrophobic surfactant.
[0028] In still another embodiment, the fabric article treatment
composition comprises the polar solvent and the hydrophobic
surfactant at a weight ratio of polar solvent to hydrophobic
surfactant of from about 10:1 to about 1:10 and/or from about 10:1
to about 1:5 and/or from about 5:1 to about 1:1.
[0029] In yet another embodiment, the fabric article treatment
composition has a flash point of greater than 37.degree. C. and/or
greater than 50.degree. C.
[0030] In one embodiment, a neat fabric article treatment
composition, such as that contained in a container or some other
delivery device prior to contacting the fabric comprises: [0031] a.
from about 5% to about 99.9% and/or from about 10% to about 40% by
weight of the fabric article treatment composition of a polar
solvent; and [0032] b. from about 0.1% to about 90% and/or from
about 10% to about 40% by weight of the fabric article treatment
composition of a hydrophobic surfactant.
[0033] In another embodiment, a fabric article treatment
composition, in use, such as
[0034] when the
pretreated fabric article is contacted with a discrete lipophilic
fluid, comprises:
[0035] a. from about 1% to about 99% and/or from about 5% to about
40% by weight of the fabric article treatment composition of a
polar solvent; [0036] b. from about 0.1% to about 90% and/or from
about 5% to about 40% by weight of the fabric article treatment
composition of a hydrophobic surfactant; and [0037] c. from about
0.1% to about 95% and/or from about 5% to about 50% by weight of
the fabric article treatment composition of a lipophilic fluid.
[0038] In other embodiments, the fabric article treatment
composition comprises a polar solvent and a hydrophobic surfactant
at a ratio of polar solvent to hydrophobic surfactant of from about
20:1 to about 1:20 and/or from about 10:1 to about 1:10.
[0039] Preferred fabric article treatment composition suitable for
use herein can further be qualified for use on the basis of having
an excellent garment care profile. Garment care profile testing is
well known in the art and involves testing a composition to be
qualified using a wide range of garment or fabric article
components, including fabrics, threads and elastics used in seams,
etc., and a range of buttons. Preferred fabric article treatment
compositions for use herein have an excellent garment care profile,
for example they have a good shrinkage or fabric puckering
profile.
A. Polar Solvent
[0040] The polar solvents according to the present invention
exhibit at least one of the following Hansen solubility parameters:
[0041] a fractional polar value (f.sub.P) of greater than 0.02
and/or greater than 0.05; and/or [0042] a fractional hydrogen
bonding value (f.sub.H) of greater than 0.10 and/or greater than
0.2.
[0043] Nonlimiting examples of polar solvents suitable for use in
the fabric article treatment composition of the present invention
include: water, alcohols, glycols, polyglycols, ethers, carbonates,
dibasic esters, ketones, other oxygenated solvents, and mixtures
thereof. Further examples of alcohols include: C1-C126 alcohols,
such as propanol, ethanol, isopropyl alcohol, etc. . . . , benzyl
alcohol, and diols such as 1,2-hexanediol. The Dowanol.RTM. series
by Dow Chemical are examples of glycols and polyglycols useful in
the present invention, such as Dowanol.RTM. TPM, TPnP, DPnB, DPnP,
TPnB, PPh, DPM, DPMA, DB, and others. Further examples include
propylene glycol, butylene glycol, polybutylene glycol and more
hydrophobic glycols. Examples of carbonate solvents are ethylene,
propylene and butylene carbonates such as those available under the
Jeffsol.RTM. tradename. Polar solvents for the present invention
can be further identified through their dispersive (.delta..sub.D),
polar (.delta..sub.P) and hydrogen bonding (.delta..sub.H) Hansen
solubility parameters. Preferred polar solvents or polar solvent
mixtures have fractional polar (f.sub.P) and fractional hydrogen
bonding (f.sub.H) values of f.sub.P>0.02 and f.sub.H>0.10,
where
f.sub.P=.delta..sub.P/(.delta..sub.D+.delta..sub.P+.delta..sub.H)
and
f.sub.H=.delta..sub.H/(.delta..sub.D+.delta..sub.P+.delta..sub.H),
more preferably f.sub.P>0.05 and f.sub.H>0.20, and most
preferably f.sub.P>0.07 and f.sub.H>0.30.
[0044] In one embodiment, the polar solvent is selected from the
group consisting of: water, alcohols, glycols, polyglycols, ethers,
carbonates, esters, ketones, other oxygenated solvents, amines,
amides, ureas, alkanolamines, alkanolamides phosphate esters, alkyl
nitriles and mixtures thereof.
[0045] In one embodiment, the polar solvent comprises from about 0%
to about 50% and/or from about 0.01 to about 20% by weight of
water
B. Hydrophobic Surfactant
[0046] "Hydrophobic surfactant" conventionally refers to materials
that are surface-active either in the water, the lipophilic fluid,
or a mixture of the two. Some illustrative surfactants include
nonionic, cationic and silicone surfactants as used in conventional
aqueous detergent systems.
[0047] Suitable nonionic surfactants include, but are not limited
to: [0048] a) Polyethylene oxide condensates of nonyl phenol and
myristyl alcohol, such as in U.S. Pat. No. 4,685,930 Kasprzak; and
[0049] b) fatty alcohol ethoxylates, R--(OCH.sub.2CH.sub.2).sub.aOH
a=1 to 100, typically 12-40, R=hydrocarbon residue 8 to 20 C atoms,
typically linear alkyl. Examples polyoxyethylene lauryl ether, with
4 or 23 oxyethylene groups; polyoxyethylene cetyl ether with 2, 10
or 20 oxyethylene groups; polyoxyethylene stearyl ether, with 2,
10, 20, 21 or 100 oxyethylene groups; polyoxyethylene (2), (10)
oleyl ether, with 2 or 10 oxyethylene groups. Commercially
available examples include, but are not limited to: ALFONIC, BRIJ,
GENAPOL, NEODOL, SURFONIC, TRYCOL. See also U.S. Pat. No. 6,013,683
Hill et al.
[0050] Suitable cationic surfactants include, but are not limited
to dialkyldimethylammonium salts having the formula:
R'R''N.sup.+(CH.sub.3).sub.2X.sup.- where each R'R'' is
independently selected from the group consisting of 12-30 C atoms
or derived from tallow, coconut oil or soy, X.dbd.Cl or Br,
Examples include: didodecyldimethylammonium bromide (DDAB),
dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium
bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl
ammonium chloride, didocosyldimethyl ammonium chloride,
dicoconutdimethyl ammonium chloride, ditallowdimethyl ammonium
bromide (DTAB). Commercially available examples include, but are
not limited to: ADOGEN, ARQUAD, TOMAH, VARIQUAT. See also U.S. Pat.
No. 6,013,683 Hill et al.
[0051] Nonlimiting examples of hydrophobic surfactants suitable for
use in the present invention include structure having the following
general formulas: Y.sub.u-(L.sub.t-X.sub.v).sub.x-Y'.sub.w (I)
L.sub.y-(X.sub.vY.sub.u).sub.x-L'.sub.z (II)
[0052] and mixtures thereof;
wherein L and L' are solvent compatibilizing (or lipophilic)
moieties, which are independently selected from:
[0053] (a) C1-C22 alkyl or C4-C12 alkoxy, linear or branched,
cyclic or acyclic, saturated or unsaturated, substituted or
unsubstituted; [0054] (b) siloxanes having the formula:
M.sub.aD.sub.bD'.sub.cD''.sub.d wherein a is 0-2; b is 0-1000; c is
0-50; d is 0-50, provided that a+c+d is at least 1;
[0055] M is R.sup.1.sub.3-eX.sub.eSiO.sub.1/2 wherein R.sup.1 is
independently H, or an alkyl group, X is hydroxyl group, and e is 0
or 1;
[0056] D is R.sup.4.sub.2SiO.sub.2/2 wherein R.sup.4 is
independently H or an alkyl group;
[0057] D' is R.sup.5.sub.2SiO.sub.2/2 wherein R.sup.5 is
independently H, an alkyl group or
(CH.sub.2).sub.f(C.sub.6Q.sub.4).sub.gO--(C.sub.2H.sub.4O).sub.h-(C.sub.3-
H.sub.6O).sub.i(C.sub.kH.sub.2k).sub.j-R.sup.3, provided that at
least one R.sup.5 is
(CH.sub.2).sub.f(C.sub.6Q.sub.4).sub.gO--(C.sub.2H.sub.4O).sub.h-(C.sub.3-
H.sub.6O).sub.i(C.sub.kH.sub.2k).sub.j-R.sup.3, wherein R.sup.3 is
independently H, an alkyl group or an alkoxy group, f is 1-10, g is
0 or 1, h is 1-50, i is 0-50, j is 0-50, k is 4-8; C.sub.6Q.sub.4
is unsubstituted or substituted; Q is independently selected from
H, C.sub.1-10 alkyl, C.sub.2-10 alkenyl, and mixtures thereof;
and
[0058] D'' is R.sup.6.sub.2SiO.sub.2/2 wherein R.sup.6 is
independently H, an alkyl group or
(CH.sub.2).sub.l(C.sub.6Q.sub.4).sub.m(A).sub.n-[(T).sub.o-(A').sub.p-].s-
ub.q-(T').sub.rZ(G).sub.s, wherein l is 1-10; m is 0 or 1; n is
0-5; o is 0-3; p is 0 or 1; q is 0-10; r is 0-3; s is 0-3;
C.sub.6Q.sub.4 is unsubstituted or substituted; Q is independently
selected from H, C.sub.1-10 alkyl, C.sub.2-10 alkenyl, and mixtures
thereof; A and A' are each independently a linking moiety
representing an ester, a keto, an ether, a thio, an amido, an
amino, a C.sub.1-4 fluoroalkyl, a C.sub.1-4 fluoroalkenyl, a
branched or straight chained polyalkylene oxide, a phosphate, a
sulfonyl, a sulfate, an ammonium, and mixtures thereof; T and T'
are each independently a C.sub.1-30 straight chained or branched
alkyl or alkenyl or an aryl which is unsubstituted or substituted;
Z is a hydrogen, carboxylic acid, a hydroxy, a phosphato, a
phosphate ester, a sulfonyl, a sulfonate, a sulfate, a branched or
straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl
unsubstituted or substituted with a C.sub.1-30 alkyl or alkenyl, a
carbohydrate unsubstituted or substituted with a C.sub.1-10 alkyl
or alkenyl or an ammonium; G is an anion or cation such as H.sup.+,
Na.sup.+, Li.sup.+, K.sup.+, NH.sub.4.sup.+, Ca.sup.+2, Mg.sup.+2,
Cl.sup.-, Br.sup.-, I.sup.-, mesylate or tosylate; and D'' can be
capped with C1-C4 alkyl or hydroxy groups;
[0059] Y and Y' are hydrophilic moieties, which are independently
selected from hydroxy; polyhydroxy; C1-C3 alkoxy; mono- or
di-alkanolamine; C1-C4 alkyl substituted alkanolamine; substituted
heterocyclic containing O, S, N; sulfates; carboxylate; carbonate;
and when Y and/or Y' is ethoxy (EO) or propoxy (PO), it must be
capped with R, which is selected from the group consisting of:
[0060] (i) a 4 to 8 membered, substituted or unsubstituted,
heterocyclic ring containing from 1 to 3 hetero atoms; and [0061]
(ii) linear or branched, saturated or unsaturated, substituted or
unsubstituted, cyclic or acyclic, aliphatic or aromatic hydrocarbon
radicals having from about 1 to about 30 carbon atoms;
[0062] X is a bridging linkage selected from O; S; N; P; C1 to C22
alkyl, linear or branched, saturated or unsaturated, substituted or
unsubstituted, cyclic or acyclic, aliphatic or aromatic,
interrupted by O, S, N, P; glycidyl, ester, amido, amino,
PO.sub.4.sup.2-, HPO.sub.4.sup.-, PO.sub.3.sup.2-, HPO.sub.3.sup.-,
which are protonated or unprotonated; [0063] u and w are integers
independently selected from 0 to 20, provided that u+w.gtoreq.1;
[0064] t is an integer from 1 to 10; [0065] v is an integer from 0
to 10; [0066] x is an integer from 1 to 20; and [0067] y and z are
integers independently selected from 1 to 10.
[0068] Nonlimiting examples of surfactants having the above formula
include: [0069] (1) alkanolamines/alkanolamides; [0070] (2)
phophate/phosphonate esters; [0071] (3) gemini surfactants
including, but are not limited to, gemini diols, gemini amide
alkoxylates, gemini amino alkoxylates; [0072] (4) capped nonionic
surfactants; [0073] (5) capped silicone surfactants such as
nonionic silicone ethoxylates, silicone amine [0074] derivatives;
[0075] (6) alkyl alkoxylates; [0076] (7) polyol surfactants; and
[0077] (8) mixtures thereof.
[0078] Another class of surfactants can include siloxane-based
surfactants. The siloxane-based surfactants in this application may
be siloxane polymers for other applications. The siloxane-based
surfactants typically have a weight average molecular weight from
500 to 20,000 daltons. Such materials, derived from
poly(dimethylsiloxane), are well known in the art. In the present
invention, not all such siloxane-based surfactants are suitable,
because they do not provide improved cleaning of soils compared to
the level of cleaning provided by the lipophilic fluid itself.
[0079] Suitable siloxane-based surfactants comprise a polyether
siloxane having the formula:
M.sub.aD.sub.bD'.sub.cD''.sub.dM'.sub.2-a wherein a is 0-2; b is
0-1000; c is 0-50; d is 0-50, provided that a+c+d is at least
1;
[0080] M is R.sup.1.sub.3-eX.sub.eSiO.sub.1/2 wherein R.sup.1 is
independently H or an alkyl group, X is hydroxyl group, and e is 0
or 1;
[0081] M' is R.sup.2.sub.3SiO.sub.1/2 wherein R.sup.2 is
independently H, an alkyl group, or
(CH.sub.2).sub.f(C.sub.6Q.sub.4).sub.gO--(C.sub.2H.sub.4O).sub.h-(C.sub.3-
H.sub.6O).sub.i(C.sub.kH.sub.2k).sub.j-R.sup.3, provided that at
least one R.sup.2 is
(CH.sub.2).sub.f(C.sub.6Q.sub.4).sub.gO--(C.sub.2H.sub.4O).sub.h-(C.sub.3-
H.sub.6O).sub.i(C.sub.kH.sub.2k).sub.j-R.sup.3, wherein R.sup.3 is
independently H, an alkyl group or an alkoxy group, f is 1-10, g is
0 or 1, h is 1-50, i is 0-50, j is 0-50, k is 4-8; C.sub.6Q.sub.4
is unsubstituted or substituted; Q is independently selected from
H, C.sub.1-10 alkyl, C.sub.1-10 alkenyl, and mixtures thereof;
[0082] D is R.sup.4.sub.2SiO.sub.2/2 wherein R.sup.4 is
independently H or an alkyl group;
[0083] D' is R.sup.5.sub.2SiO.sub.2/2 wherein R.sup.5 is
independently H, an alkyl group, or
(CH.sub.2).sub.f(C.sub.6Q.sub.4).sub.gO--(C.sub.2H.sub.4O).sub.h-(C.sub.3-
H.sub.6O).sub.i(C.sub.kH.sub.2k).sub.j-R.sup.3, provided that at
least one R.sup.5 is
(CH.sub.2).sub.f(C.sub.6Q.sub.4).sub.gO--(C.sub.2H.sub.4O).sub.h-(C.sub.3-
H.sub.6O).sub.i(C.sub.kH.sub.2k).sub.j-R.sup.3, wherein R.sup.3 is
independently H, an alkyl group or an alkoxy group, f is 1-10, g is
0 or 1, h is 1-50, i is 0-50, j is 0-50, k is 4-8; C.sub.6Q.sub.4
is unsubstituted or substituted; Q is independently selected from
H, C.sub.1-10 alkyl, C.sub.1-10 alkenyl, and mixtures thereof;
and
[0084] D'' is R.sup.6.sub.2SiO.sub.2/2 wherein R.sup.6 is
independently H, an alkyl group or
(CH.sub.2).sub.l(C.sub.6Q.sub.4).sub.m(A).sub.n-[(T).sub.o-(A').sub.p-].s-
ub.q-(T').sub.rZ(G).sub.s, wherein l is 1-10; m is 0 or 1; n is
0-5; o is 0-3; p is 0 or 1; q is 0-10; r is 0-3; s is 0-3;
C.sub.6Q.sub.4 is unsubstituted or substituted; Q is independently
selected from H, C.sub.1-10 alkyl, C.sub.1-10 alkenyl, and mixtures
thereof; A and A' are each independently a linking moiety
representing an ester, a keto, an ether, a thio, an amido, an
amino, a C.sub.1-4 fluoroalkyl, a C.sub.1-4 fluoroalkenyl, a
branched or straight chained polyalkylene oxide, a phosphate, a
sulfonyl, a sulfate, an ammonium, and mixtures thereof; T and T'
are each independently a C.sub.1-30 straight chained or branched
alkyl or alkenyl or an aryl which is unsubstituted or substituted;
Z is a hydrogen, carboxylic acid, a hydroxy, a phosphato, a
phosphate ester, a sulfonyl, a sulfonate, a sulfate, a branched or
straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl
unsubstituted or substituted with a C.sub.1-30 alkyl or alkenyl, a
carbohydrate unsubstituted or substituted with a C.sub.1-10 alkyl
or alkenyl or an ammonium; G is an anion or cation such as H.sup.+,
Na.sup.+, Li.sup.+, K.sup.+, NH.sub.4.sup.+, Ca.sup.+2, Mg.sup.+2,
Cl.sup.-, Br.sup.-, I.sup.-, mesylate or tosylate.
[0085] Examples of the types of siloxane-based surfactants
described herein above may be found in EP-1,043,443A1, EP-1,041,189
and WO-01/34,706 (all to GE Silicones) and U.S. Pat. No. 5,676,705,
U.S. Pat. No. 5,683,977, U.S. Pat. No. 5,683,473, and
EP-1,092,803A1 (all assigned to Lever Brothers).
[0086] Nonlimiting commercially available examples of suitable
siloxane-based surfactants are TSF 4446 (ex. General Electric
Silicones), XS69-B5476 (ex. General Electric Silicones); Jenamine
HSX (ex. DelCon) and Y12147 (ex. OSi Specialties).
[0087] Yet another class of materials suitable for the surfactant
component is organic in nature. Preferred materials are
organosulfosuccinate surfactants, with carbon chains of from about
6 to about 20 carbon atoms. Most preferred are
organosulfosuccinates containing dialkly chains, each with carbon
chains of from about 6 to about 20 carbon atoms. Also preferred are
chains containing aryl or alkyl aryl, substituted or unsubstituted,
branched or linear, saturated or unsaturated groups. Nonlimiting
commercially available examples of suitable organosulfosuccinate
surfactants are available under the trade names of Aerosol OT and
Aerosol TR-70 (ex. Cytec).
[0088] Suitable silicone surfactants include, but are not limited
to the polyalkyleneoxide polysiloxanes having a dimethyl
polysiloxane hydrophobic moiety and one or more hydrophilic
polyalkylene side chains and have the general formula:
R.sup.1--(CH.sub.3).sub.2SiO--[(CH.sub.3).sub.2SiO].sub.a-[(CH.sub.3)(R.s-
up.1)SiO].sub.b-Si(CH.sub.3).sub.2--R.sup.1 wherein a+b are from
about 1 to about 50, preferably from about 3 to about 30 , more
preferably from about 10 to about 25, and each R.sup.1 is the same
or different and is selected from the group consisting of methyl
and a poly(ethyleneoxide/propyleneoxide) copolymer group having the
general formula:
--(CH.sub.2).sub.nO(C.sub.2H.sub.4O).sub.c(C.sub.3H.sub.6O).sub.-
dR.sup.2 with at least one R.sup.1 being a
poly(ethyleneoxide/propyleneoxide) copolymer group, and wherein n
is 3 or 4, preferably 3; total c (for all polyalkyleneoxy side
groups) has a value of from 1 to about 100, preferably from about 6
to about 100; total d is from 0 to about 14, preferably from 0 to
about 3; and more preferably d is 0; total c+d has a value of from
about 5 to about 150, preferably from about 9 to about 100 and each
R.sup.2 is the same or different and is selected from the group
consisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and an
acetyl group, preferably hydrogen and methyl group. Examples of
these surfactants may be found in U.S. Pat. No. 5,705,562 Hill and
U.S. Pat. No. 5,707,613 Hill, both of which are incorporated herein
by reference.
[0089] Examples of this type of surfactants are the Silwet.RTM.
surfactants which are available CK Witco, OSi Division, Danbury,
Conn. Representative Silwet.RTM. surfactants are as follows.
TABLE-US-00001 Name Average MW Average a + b Average total c L-7608
600 1 9 L-7607 1,000 2 17 L-77 600 1 9 L-7605 6,000 20 99 L-7604
4,000 21 53 L-7600 4,000 11 68 L-7657 5,000 20 76 L-7602 3,000 20
29
[0090] The molecular weight of the polyalkyleneoxy group (R.sup.1)
is less than or equal to about 10,000. Preferably, the molecular
weight of the polyalkyleneoxy group is less than or equal to about
8,000, and most preferably ranges from about 300 to about 5,000.
Thus, the values of c and d can be those numbers which provide
molecular weights within these ranges. However, the number of
ethyleneoxy units (C.sub.2H.sub.4O) in the polyether chain
(R.sup.1) must be sufficient to render the polyalkyleneoxide
polysiloxane water dispersible or water soluble. If propyleneoxy
groups are present in the polyalkylenoxy chain, they can be
distributed randomly in the chain or exist as blocks. Preferred
Silwet.RTM. surfactants are L-7600, L-7602, L-7604, L-7605, L-7657,
and mixtures thereof. Besides surface activity, polyalkyleneoxide
polysiloxane surfactants can also provide other benefits, such as
antistatic benefits, and softness to fabric articles.
[0091] The preparation of polyalkyleneoxide polysiloxanes is well
known in the art. Polyalkyleneoxide polysiloxanes of the present
invention can be prepared according to the procedure set forth in
U.S. Pat. No. 3,299,112.
[0092] Another suitable silicone surfactant is SF-1488, which is
available from GE silicone fluids.
[0093] These and other surfactants suitable for use in combination
with the lipophilic fluid as adjuncts are well known in the art,
being described in more detail in Kirk Othmer's Encyclopedia of
Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants
and Detersive Systems". Further suitable nonionic detergent
surfactants are generally disclosed in U.S. Pat. No. 3,929,678,
Laughlin et al., issued Dec. 30, 1975, at column 13, line 14
through column 16, line 6.
[0094] In one embodiment, the hydrophobic surfactant exhibits an
HLB value of from about 0.1 to about 12 and/or from about 3 to
about 9.
[0095] In another embodiment, the hydrophobic surfactant is
selected from the group consisting of: silicone-based surfactants,
organosulfosuccinate surfactants, alkanolamines, alkanolamides,
alcohol alkoxylates, gemini surfactants, polyhydroxy fatty acid
amides, alkylhydrogen phosphates and salts thereof, saccharide
derivatives and Alkanolamine based surfactants have the ability to
aid in cleaning for water soluble and water based soils. However,
these functionalities typically do not have good compatibility in
dry cleaning solvent such as decamethylcyclopentasiloxane.
[0096] Suitable alkanolamine surfactant would have the general
formula (I) wherein the H moiety is an alkanolamine moiety having
the following formula: ##STR1## wherein R.sup.1, R.sup.2, R.sup.3
are same or different and are independently selected from H,
hydrocarbons, polyoxyalkylenes, siloxanes or flurorinated groups;
and at least one hydroxyl group is present in the alkanolamine
moiety, either to terminate one or more R groups or be present
within one or more of the R groups as a secondary hydroxyl group.
Hydrocarbon groups may be linear or branched, cyclic or acyclic,
saturated or unsaturated, and contain about 1-30 carbons,
preferably about 6 to 30 carbons, more preferably about 8 to 18
carbons. Silicone and fluorinated groups may consist of 1-50 repeat
units.
[0097] The method of functionalizing the alkanolamine moiety may
be, but not limited to alkylation, esterification, etherification,
amidation, amination and other linking chemistries. Thus, the
corresponding bridging group B.sub.j can be alkyl, ester, ether,
amido, and amino linking groups.
[0098] The number and size of the solvotrope groups S.sub.k used
for a given alkanolamine group is important for optimized
performance. When a surfactant contains too numerous and/or too
large solvotrope groups, the surfactants may exhibit too high a
solubility profile in the solvent or too high a molecular weight,
both of which lead to ineffective cleaning and/or soil removal
performance. Moreover, the surfactant may become a solid, which
makes solubiliztion in the solvent and formulation difficulty. On
the other hand, when the surfactant contains too few and/or too
small solvotrope groups, the surfactant may exhibit poor solubility
in the solvent and reduce the effectiveness of the alkanolamine
moiety in cleaning and/or soil removal.
[0099] The present invention alkanolamine based surfactants may
comprise one or more polyalkylene oxide units or solvatrope groups,
S within the surfactant structure. The alkoxy moieties are selected
from ethoxy (EO), propoxy (PO), butoxy (BO), higher alkoxy
moieties, and mixtures thereof, such as mixed EO/PO, EO/B, PO/BO,
EO/PO/BO, and the like, wherein the number of repeat units (m) may
be 1 to 50. The alkoxy moieties may be either a distribution having
an average degree of alkoxylation of m repeat units, or a
monodispersed moiety with m repeat units of alkoxylation
[0100] In one embodiment of the present invention, the
functionalized alkanolamine moiety has an average of at least 1
solvotrope moiety per surfactant molecule. Preferably, the
surfactant molecule contains sufficient number of solvotrope
moieties to provide solvent compatibility. In another embodiment of
the invention, the alkanolamine moiety has an average of at least 2
solvent compatibility groups per alkanolamine moiety (i.e., a
moiety having a "twin tail" structure). The solvotrope moiety can
be selected from OH, alkoxy, and mixtures thereof.
[0101] The following are nonlimiting examples of functionalized
alkanolamine containing surfactants useful in the present
invention: ##STR2##
[0102] The alkanolamine based surfactants of the present invention
have at least 1 free hydroxyl per molecule.
[0103] In some embodiments, the composition comprises from about
0.01 to about 10 wt % of an alkanolamine based surfactant, from
about 0 to about 20 wt % of water, from about 0.1 to about 20 wt %
of other detergent adjuncts, and the balance of lipophilic fluids.
These cleaning compositions have been shown to enhance the overall
cleaning and stain removal performance of the composition. These
compositions are particularly effective in the cleaning and
removing stains of blood, grass and clay.
[0104] Phosphate/phosphonate ether surfactants have the general
formula (I) wherein the B moiety can be a phosphate based moiety
having the following formula: ##STR3## wherein R.sup.1, R.sup.2,
R.sup.3 are independently selected from H, OR.sup.4,
C.sub.1-C.sub.22 alkyl, which are linear or branched, substituted
or unsubstituted, cyclic or acyclic, and optionally interrupted by
O, N, S, or P; R.sup.4 is selected from: ##STR4## H, Na, K, Li,
C.sub.1-C.sub.22 alkyl, which are linear or branched, substituted
or unsubstituted, cyclic or acyclic, and optionally interrupted by
O, N, S, or P; R.sup.5 is selected from H, CH.sub.3,
C.sub.2H.sub.5, C.sub.3H.sub.7, C.sub.4H.sub.9; and n is an integer
from 0 to 10.
[0105] The following are nonlimiting examples of functionalized
phosphate ester containing surfactants useful in the present
invention: ##STR5##
[0106] In some embodiments, the composition comprises from about
0.01 to about 10 wt % of a phosphate based surfactant, from about 0
to about 20 wt % of water, from about 0.1 to about 20 wt % of other
detergent adjuncts, and the balance of lipophilic fluids. These
cleaning compositions have been shown to enhance the overall
cleaning and stain removal performance of the composition. These
compositions are particularly effective in the cleaning and
removing stains of blood, grass and tea.
[0107] Whereas the conventional surfactants generally have one
hydrophilic group and one hydrophobic group, the Gemini surfactants
are compounds having at least two hydrophobic groups and at least
two hydrophilic groups. See J. American Chemical Soc., 115,
10083-10090 (1993); and Chemtech, March 1993, pp 30-33. Gemini
surfactants have been found to be very effective emulsifiers when
used at very low concentrations in comparison to conventional
surfactants. This characteristic further leads to superior
detergency at very low concentrations.
[0108] The following are nonlimiting examples of Gemini surfactants
suitable for use in the present invention: ##STR6##
[0109] In some embodiments, the composition comprises from about
0.01 to about 10 wt % of a gemini surfactant, from about 0 to about
20 wt % of water, from about 0.1 to about 20 wt % of other
detergent adjuncts, and the balance of lipophilic fluids. These
cleaning compositions have been shown to enhance the overall
cleaning and stain removal performance of the composition. These
compositions are particularly effective in the cleaning and
removing clays and make-up stains.
[0110] In one embodiment of the present invention, a capped
nonionic surfactant according to formula (i) can have the general
formula:
R.sup.1O[CH.sub.2CH(R.sup.3)O].sub.x[CH.sub.2].sub.kCH(OH)[CH.sub.2].sub.-
jO.sub.nR.sup.2 wherein R.sup.1 and R.sup.2 are linear or branched,
saturated or unsaturated, aliphatic or aromatic hydrocarbon
radicals having from about 1 to about 30 carbon atoms; R.sup.3 is
H, or a linear aliphatic hydrocarbon radical having from about 1 to
about 4 carbon atoms; x is an integer having an average value from
1 to about 40, wherein when x is 2 or greater, R.sup.3 may be the
same or different and k and j are integers having an average value
of from about 1 to about 12, and more preferably 1 to about 5, n is
an integer from 0 to 1; further wherein when x is 15 or greater and
R.sup.3 is H and methyl, at least four of R.sup.3 are methyl,
further wherein when x is 15 or greater and R.sup.3 includes H and
from 1 to 3 methyl groups, then at least one R.sup.3 is ethyl,
propyl or butyl, further wherein R.sup.2 can optionally be
alkoxylated, wherein said alkoxy is selected from ethoxy, propoxy,
butyloxy and mixtures thereof; wherein R.sup.1 and R.sup.2 are
preferably linear or branched, saturated or unsaturated, aliphatic
or aromatic hydrocarbon radicals having from about 6 to about 22
carbon atoms with about 8 to about 18 carbon atoms being most
preferred. R.sup.2 can optionally be alkoxylated, wherein the
alkoxy is selected from ethoxy, propoxy, butyloxy and mixtures
thereof. H or a linear aliphatic hydrocarbon radical having from
about 1 to about 2 carbon atoms is most preferred for R.sup.3.
Preferably, x is an integer having an average value of from about 1
to about 20, more preferably from about 6 to about 15. Also,
preferred in the present invention are alcohol surfactants.
[0111] In another embodiment of the present invention, the capped
nonionic surfactant according to formula (i) can be an ether-capped
poly(oxyalkylated) alcohol surfactant, specifically, with the
formula: RO(R.sup.1O).sub.xCH(CH.sub.3)OR.sup.2 wherein, R is
selected from the group consisting of linear or branched, saturated
or unsaturated, substituted or unsubstituted, aliphatic or aromatic
hydrocarbon radicals having from about 1 to about 30 carbon atoms;
R.sup.1 may be the same or different, and is independently selected
from the group consisting of branched or linear C.sub.2 to C.sub.7
alkylene in any given molecule; x is a number from 1 to about 30;
and R.sup.2 is selected from the group consisting of: [0112] (iii)
a 4 to 8 membered substituted, or unsubstituted heterocyclic ring
containing from 1 to 3 hetero atoms; and [0113] (iv) linear or
branched, saturated or unsaturated, substituted or unsubstituted,
cyclic or acyclic, aliphatic or aromatic hydrocarbon radicals
having from about 1 to about 30 carbon atoms; provided that when
R.sup.2 is (ii) then either: (A) at least one of R.sup.1 is other
than C.sub.2 to C.sub.3 alkylene; or (B) R.sup.2 has from 6 to 30
carbon atoms, and with the further proviso that when R.sup.2 has
from 8 to 18 carbon atoms, R is other than C.sub.1 to C.sub.5
alkyl.
[0114] In yet another embodiment of the present invention, the
capped nonionic surfactant according to formula (i) can be an
ether-capped poly(oxyalkylated) alcohols having the formula:
RO(R.sup.1O).sub.xR.sup.2
[0115] In one aspect of the present invention R is a linear or
branched, saturated or unsaturated, substituted or unsubstituted,
aliphatic hydrocarbon radical having from about 1 to about 20
carbon atoms, even more preferably R is a linear or branched,
saturated, aliphatic hydrocarbon radicals having from about 4 to
about 18 carbon atoms. In one aspect of the present invention R,
R.sup.1 and R.sup.2 are selected such that the ether-capped
poly(oxyalkylated) alcohol surfactant contains one or more chiral
carbon atoms.
[0116] In one aspect of the present invention, R is a hydrocarbon
radical of the formula: ##STR7## wherein R.sup.4, R.sup.5, and
R.sup.6 are each independently selected from hydrogen, and
C.sub.1-C.sub.3 alkyl, more preferably hydrogen, C.sub.1-C.sub.2
alkyl, even more preferably hydrogen, and methyl, provided that
R.sup.4, R.sup.5, and R.sup.6 are not all hydrogen and, when t is
0, at least R.sup.4 or R.sup.5 is not hydrogen; q, r, s, t are each
independently integers from 0 to 13. In one more preferred form of
this aspect R is selected from the formulas: ##STR8## wherein n, m,
j and k are each independently integers from 0 to 13.
[0117] In one aspect of the present invention R.sup.2 is a
hydrocarbon radical of the formula: --C(CH.sub.3).sub.2R.sup.3
R.sup.3 is selected from the group consisting of linear or
branched, saturated or unsaturated, substituted or unsubstituted,
aliphatic or aromatic hydrocarbon radicals having from about 1 to
about 30, more preferably 1 to 20, even more preferably 1 to 15,
carbon atoms, provided that when R.sup.3 is methyl, R is branched.
In one embodiment of this aspect of the present invention, R.sup.3
is ethyl. In one aspect of the present invention R.sup.2 is a 4 to
8 membered substituted, or unsubstituted heterocyclic ring
containing from 1 to 3 hetero atoms. In one embodiment of this
aspect of the invention the hetero atoms are selected from the
group comprising oxygen, nitrogen, sulfur and mixtures thereof. In
one embodiment of this aspect of the invention R.sup.2 is a 5 or 6
member heterocycle. In another embodiment of this aspect of the
present invention R.sup.2 is selected from the group consisting of:
##STR9## wherein each R.sup.7 is independently selected from the
group consisting of hydrogen, linear or branched, saturated or
unsaturated, substituted or unsubstituted, aliphatic hydrocarbon or
alkoxy radical having from about 1 to about 10 carbon atoms, or
R.sup.7 is a saturated or unsaturated, substituted or
unsubstituted, alicyclic or aromatic hydrocarbon radical having,
from about 1 to about 10 carbon atoms, which is fused to the
heterocyclic ring; each A is independently selected from the group
consisting of O, and N(R.sup.8).sub.a, wherein R.sup.8 is
independently selected from the group consisting of hydrogen,
linear or branched, saturated or unsaturated, substituted or
unsubstituted, aliphatic hydrocarbon radical having from about 1 to
about 10 carbon atoms, and a is either 0 or 1; z is an integer from
1 to 3.
[0118] In another embodiment of this aspect of the present
invention R.sup.2 is selected from the group consisting of:
##STR10## wherein R.sup.7 is defined as above.
[0119] The following are nonlimiting examples of capped nonionic
surfactants suitable for use in the present invention:
##STR11##
[0120] In some embodiments, the composition comprises from about
0.01 to about 10 wt % of a capped nonionic surfactant, from about 0
to about 20 wt % of water, from about 0.1 to about 20 wt % of other
detergent adjuncts, and the balance of lipophilic fluids. These
cleaning compositions have been shown to enhance the overall
cleaning and stain removal performance of the composition. These
compositions are particularly effective in the cleaning and
removing stains of grass and clay.
[0121] In one embodiment of the present invention, the amide
containing surfactant has a structure according to formula (i) or
(ii) below: ##STR12## R.dbd.C.sub.1-C.sub.22 linear alkyl, alkyl
substituted aromatic, C.sub.3-C.sub.22 branched alkyl, linear
alkenyl, branched alkenyl, C.sub.5-C.sub.22 cyclic alkyl, cyclic
alkenyl, aryl [0122] L=C.sub.1-C.sub.12 substituted/unsubstituted
alkyl, alkyl substituted aromatic, C.sub.3-C.sub.12 branched alkyl,
linear alkenyl, branched alkenyl, C.sub.5-C.sub.12 cyclic alkyl,
cyclic alkenyl, aryl [0123] or
--[(CR.sub.2R.sub.3).sub.k-X].sub.m-(CR.sub.4R.sub.5).sub.n-; where
R.sub.2,R.sub.3,R.sub.4,R.sub.5.dbd.H, alkyl, X.dbd.O, N, k=2-6,
m=0-5 & n=2-6 [0124] A=H, --(R.sub.6O).sub.xR.sub.7; where
R.sub.6.dbd.C.sub.2-C.sub.4 alkylene and R.sub.7.dbd.H or R
mixtures thereof.
[0125] Another class of materials can include polyol-based
surfactants. "Polyol", as used herein, means any aliphatic or
aromatic compound containing at least two free hydroxyl groups. In
practicing the processes disclosed herein, the selection of a
suitable polyol is simply a matter of choice. For example, suitable
polyols may be selected from the following classes: saturated and
unsaturated straight and branched chain linear aliphatic; saturated
and unsaturated cyclic aliphatic, including heterocyclic aliphatic;
or mononuclear or polynuclear aromatics, including heterocyclic
aromatics. Carbohydrates and glycols are exemplary polyols.
Especially preferred glycols include glycerin. Monosaccharides
suitable for use herein include, for example, mannose, galactose,
arabinose, xylose, ribose, apiose, rhamnose, psicose, fructose,
sorbose, tagitose, ribulose, xylulose, and erythrulose.
Oligosaccharides suitable for use herein include, for example,
maltose, kojibiose, nigerose, cellobiose, lactose, melibiose,
gentiobiose, turanose, rutinose, trehalose, sucrose and raffinose.
Polysaccharides suitable for use herein include, for example,
amylose, glycogen, cellulose, chitin, inulin, agarose, zylans,
mannan and galactans. Although sugar alcohols are not carbohydrates
in a strict sense, the naturally occurring sugar alcohols are so
closely related to the carbohydrates that they are also preferred
for use herein. The sugar alcohols most widely distributed in
nature and suitable for use herein are sorbitol, mannitol and
galactitol. Other polyols include pentaerythritol and derivatives
thereof.
[0126] Particular classes of materials suitable for use herein
include monosaccharides, disaccharides and sugar alcohols. Other
classes of materials include sugar ethers, alkoxylated polyols,
such as polyethoxy glycerol and other polyols containing amines
such as glucosamine.
[0127] Polyol based surfactants have the ability to aid in cleaning
for water soluble and water based soils. However, these
functionalities typically do not have good compatibility in dry
cleaning solvent such as decamethylcyclopentasiloxane. The present
invention utilizes a solvent compatibility group functionalized
onto a polyol for improved cleaning.
[0128] Example of a general sucrose based structure is shown in the
following structure: ##STR13## where R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, R.sup.6, R.sup.7, and R.sup.8 can be any
combination of H, hydrocarbon, polyoxyalkylene, siloxane or
flurorinated groups. Hydrocarbon groups may consist of 1-30 carbons
that may be linear, cyclic, branched, saturated or unsaturated.
Silicone and fluorinated groups may consist of 1-50 repeat units. R
substitution on the polyol may be a distribution with an average
degree of substitution when total substitution is not complete. The
number and size of the solvent compatible groups used for a given
polyol is important for optimized performance. Too large and/or too
many solvent compatibility groups can lead to various unwanted
properties such as too high a solubility profile in the solvent,
too high a molecular weight leading to molecule inefficiency and
potentially the materials becoming a solid making solubiliztion in
the solvent and formulation difficulty. Too few and/or too small
solvent compatible groups can lead to reduced performance of the
polyol due to poor solubility in the solvent.
[0129] The present invention polyol based surfactants may comprise
one or more polyalkylene oxide units within the structure. EO/PO/BO
and higher materials are alkoxy moieties, preferably selected from
ethoxy, propoxy, butoxy and mixed EO/PO, EO/BO. PO/BO, EO/PO/BO
groups wherein the number of repeat units (m) may consist of 1-50
units. The alkoxy moieties may be either a distribution or with an
average degree of alkoxylation being corresponding to m or it may
be a single specific chain with an alkoxylation number exactly
corresponding to m. Placement of the alkoxy moieties in the
structure may be near the polyol moiety or on the ends on the R
units.
[0130] The following general example of ethoxylated sucrose is
shown below: ##STR14## R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5,
R.sup.6, R.sup.7, and R.sup.8 can be any combination of H,
hydrocarbon, polyoxyalkylene, siloxane or flurorinated groups. The
method of functionalizing the polyol may be, but not limited to
esterification, etherification, amidation and other linking
chemistries.
[0131] In one embodiment of the present invention, the
functionalized polyol has an average of at least 1 solvent
compatibility group per molecule. In another embodiment of the
invention, the polyol has an average of at least 2 solvent
compatibility groups per molecule (twin tail), while in another
embodiment the polyol has an average of from about 3 to about 8
solvent compatibility groups per molecule.
[0132] In one embodiment of the present invention, the
functionalized polyol has an average of at least 2 OH groups per
molecule. In another embodiment of the invention, the polyol has an
average of at least 3 OH groups per molecule, while in another
embodiment the polyol has an average of from about 3 to about 8 OH
groups per molecule.
[0133] In one embodiment of the present invention, the
functionalized polyol may have the 2 or more hydroxyls replaced
with 1 or more of the following groups or combinations of groups:
sulfate, sulfonate, carboxylate, amine, alkanolamine, phosphate and
amide containing moieties. The polyol may be transesterified for
example with methyloleate on several of the hydroxyl groups. The
oleate esters of the polyol then become "capping" groups.
[0134] The following structures exemplify polyol containing
surfactants useful in the present invention: ##STR15##
[0135] Sucrose ester from soybean oil (mainly oleyl). Solvent
compatibility groups a distribution across hydroxyls and above
structure a representation only. ##STR16##
[0136] The polyol based surfactants of the present invention have
at least 2 free hydroxyls per molecule, more preferably higher as
long as solvent compatibility is maintained.
[0137] The polyol based surfactants of the present invention have
at least one compatibility group per molecule, more preferably the
minimum number needed to maintain solvent compatibility.
[0138] The polyol based surfactants of the present invention have R
groups which are unsaturated or branched hydrocarbons ranging from
6 to 30 total carbons, more preferably from 8 to 18 carbons.
[0139] The polyol based surfactants are present in the cleaning
formulations of the present invention at levels from 0.001% to 10%,
more preferably from about 0.01% to 2%.
[0140] In one embodiment, the hydrophobic surfactant comprises one
or more of the following structures: ##STR17##
1-[Bis-(2-hydroxy-ethyl)-amino]-3-(2-ethyl-hexyloxy)-propan-2-ol
##STR18## Dodecanoic acid bis-(2-hydroxy-ethyl)-amide ##STR19##
Phosphoric acid bis-(2-ethyl-hexyl) ester bis(2-ethylhexyl) sodium
sulfosuccinate Optional Ingredients Carrier Solvents
[0141] "Carrier solvents" as used herein means a solvent that is
selected from the group consisting of: silicone solvents,
hydrofluoroether solvents, perfluorinated solvents, hydrocarbon
solvents, halogenated hydrocarbons, and mixtures thereof.
Cleaning Adjuncts
[0142] The compositions of the present invention may optionally
comprise at least one cleaning adjunct. The cleaning adjuncts can
vary widely and can be used at widely ranging levels. For example,
detersive enzymes such as proteases, amylases, cellulases, lipases
and the like as well as bleach catalysts including the macrocyclic
types having manganese or similar transition metals all useful in
laundry and cleaning products can be used herein at very low, or
less commonly, higher levels. Cleaning adjuncts that are catalytic,
for example enzymes, can be used in "forward" or "reverse" modes, a
discovery independently useful from the fabric treating methods of
the present invention. For example, a lipolase or other hydrolase
may be used, optionally in the presence of alcohols as cleaning
adjuncts, to convert fatty acids to esters, thereby increasing
their solubility in the lipophilic fluid. This is a "reverse"
operation, in contrast with the normal use of this hydrolase in
water to convert a less water-soluble fatty ester to a more
water-soluble material. In any event, any cleaning adjunct must be
suitable for use in combination with a lipophilic fluid in
accordance with the present invention.
[0143] Some suitable cleaning adjuncts include, but are not limited
to, builders, surfactants, other than those described above with
respect to the surfactant component, enzymes, bleach activators,
bleach catalysts, bleach boosters, bleaches, alkalinity sources,
antibacterial agents, colorants, perfumes, pro-perfumes, finishing
aids, lime soap dispersants, odor control agents, odor
neutralizers, polymeric dye transfer inhibiting agents, crystal
growth inhibitors, photobleaches, heavy metal ion sequestrants,
anti-tarnishing agents, anti-microbial agents, anti-oxidants,
anti-redeposition agents, polymer dispersants, soil release
polymers, electrolytes, pH modifiers, thickeners, abrasives,
divalent or trivalent ions, metal ion salts, enzyme stabilizers,
corrosion inhibitors, diamines or polyamines and/or their
alkoxylates, suds stabilizing polymers, solvents, process aids,
fabric softening agents, optical brighteners, hydrotropes, suds or
foam suppressors, suds or foam boosters and mixtures thereof.
[0144] Suitable odor control agents, which may optionally be used
as finishing agents, include agents include, cyclodextrins, odor
neutralizers, odor blockers and mixtures thereof. Suitable odor
neutralizers include aldehydes, flavanoids, metallic salts,
water-soluble polymers, zeolites, activated carbon and mixtures
thereof.
[0145] Perfumes and perfumery ingredients useful in the
compositions of the present invention comprise a wide variety of
natural and synthetic chemical ingredients, including, but not
limited to, aldehydes, ketones, esters, and the like. Also included
are various natural extracts and essences which can comprise
complex mixtures of ingredients, such as orange oil, lemon oil,
rose extract, lavender, musk, patchouli, balsamic essence,
sandalwood oil, pine oil, cedar, and the like. Finished perfumes
may comprise extremely complex mixtures of such ingredients.
Pro-perfumes are also useful in the present invention. Such
materials are those precursors or mixtures thereof capable of
chemically reacting, e.g., by hydrolysis, to release a perfume, and
are described in patents and/or published patent applications to
Procter and Gamble, Firmenich, Givaudan and others.
[0146] Bleaches, especially oxygen bleaches, are another type of
cleaning adjunct suitable for use in the compositions of the
present invention. This is especially the case for the activated
and catalyzed forms with such bleach activators as
nonanoyloxybenzenesulfonate and/or any of its linear or branched
higher or lower homologs, and/or tetraacetylethylenediamine and/or
any of its derivatives or derivatives of
phthaloylimidoperoxycaproic acid (PAP) or other imido- or
amido-substituted bleach activators including the lactam types, or
more generally any mixture of hydrophilic and/or hydrophobic bleach
activators (especially acyl derivatives including those of the
C.sub.6-C.sub.16 substituted oxybenzenesulfonates).
[0147] Also suitable are organic or inorganic peracids both
including PAP and other than PAP. Suitable organic or inorganic
peracids for use herein include, but are not limited to:
percarboxylic acids and salts; percarbonic acids and salts;
perimidic acids and salts; peroxymonosulfuric acids and salts;
persulphates such as monopersulfate; peroxyacids such as
diperoxydodecandioic acid (DPDA); magnesium peroxyphthalic acid;
perlauric acid; perbenzoic and alkylperbenzoic acids; and mixtures
thereof.
[0148] One class of suitable organic peroxycarboxylic acids has the
general formula: ##STR20## wherein R is an alkylene or substituted
alkylene group containing from 1 to about 22 carbon atoms or a
phenylene or substituted phenylene group, and Y is hydrogen,
halogen, alkyl, aryl, --C(O)OH or --C(O)OOH. Particularly preferred
peracid compounds are those having the formula: ##STR21## wherein R
is C.sub.1-4 alkyl and n is an integer of from 1 to 5. A
particularly preferred peracid has the formula where R is CH.sub.2
and n is 5 i.e., phthaloylamino peroxy caproic acid (PAP) as
described in U.S. Pat. Nos. 5,487,818, 5,310,934, 5,246,620,
5,279,757 and 5,132,431. PAP is available from Ausimont SpA under
the tradename Euroco. Hydrogen peroxide is a highly preferred
bleaching agent.
[0149] Other cleaning adjuncts suitable for use in the compositions
of the present invention include, but are not limited to, builders
including the insoluble types such as zeolites including zeolites
A, P and the so-called maximum aluminum P as well as the soluble
types such as the phosphates and polyphosphates, any of the
hydrous, water-soluble or water-insoluble silicates,
2,2'-oxydisuccinates, tartrate succinates, glycolates, NTA and many
other ethercarboxylates or citrates; chelants including EDTA,
S,S'-EDDS, DTPA and phosphonates; water-soluble polymers,
copolymers and terpolymers; soil release polymers; optical
brighteners; processing aids such as crisping agents and/fillers;
anti-redeposition agents; hydrotropes, such as sodium, or calcium
cumene sulfonate, potassium napthalenesulfonate, or the like,
humectant; other perfumes or pro-perfumes; dyes; photobleaches;
thickeners; simple salts; alkalis such as those based on sodium or
potassium including the hydroxides, carbonates, bicarbonates and
sulfates and the like; and combinations of one or more of these
cleaning adjuncts.
[0150] One particularly preferred class of cleaning adjuncts is
additives comprising a strongly polar and/or hydrogen-bonding head
group, further enhances soil removal by the compositions of the
present invention. Examples of the strongly polar and/or
hydrogen-bonding head group are alcohols, carboxylic acids,
sulfates, sulphonates, phosphates, phosphonates, and nitrogen
containing materials. Preferred additives are nitrogen containing
materials selected from the group consisting of primary, secondary
and tertiary amines, diamines, triamines, ethoxylated amines, amine
oxides, amides, betaines, quaternary ammonium salts, and mixtures
thereof. Most highly preferred materials are amino-functional
siloxanes, having one or more of the following properties: i) at
least about 60% by weight silicone content; and ii) alkyleneoxy
groups, most preferably ethyleneoxy groups.
[0151] The compositions of the invention can be formulated as a
liquid, a thickened aqueous liquid, a semi-solid or gel, or a solid
product form. The thickened liquid product form can be manufactured
by incorporation of a thickening agent. Inorganic thickeners
typically comprise clays, silicates and other well known inorganic
thickeners. Organic thickeners include thixotropic and
non-thixotropic thickeners. Preferred thickeners have some
substantial proportion of water solubility to promote easy
removability. Examples of useful soluble organic thickeners for the
compositions of the invention comprise carboxylated vinyl polymers
such as polyacrylic acids and sodium salts thereof, ethoxylated
cellulose, polyacrylamide thickeners, xanthan thickeners, guar gum,
sodium alginate and algin by-products, hydroxy propyl cellulose,
hydroxy ethyl cellulose and other similar aqueous thickeners that
have some substantial proportion of water solubility.
[0152] A hardening agent, as used in the present method and
compositions, is a compound or system of compounds, organic or
inorganic, that significantly contributes to the uniform
solidification of the composition. Preferably, the hardening agent
is compatible with the active ingredients of the composition, and
is capable of providing an effective amount of hardness to the
processed composition. The hardening agent should also be capable
of forming a homogeneous matrix with the ingredients when mixed and
solidified to provide a uniform dissolution of the cleaning agent
from the solid composition during use. The amount of hardening
agent included in the cleaning composition will vary according to
the type of cleaning composition being prepared, the ingredients of
the composition, the intended use of the composition, the quantity
of dispensing solution applied to the solid composition over time
during use, the temperature of the dispensing solution, the
hardness of the dispensing solution, the physical size of the solid
composition, the concentration of the other ingredients, the
concentration of the cleaning agent in the composition, and other
like factors. It is preferred that the amount of the hardening
agent is effective to combine with the cleaning agent and other
ingredients of the composition to form a homogeneous mixture under
continuous mixing conditions and a temperature at or below the
melting temperature of the hardening agent. The hardening agent can
form a matrix with the cleaning agent and other ingredients which
will harden to a solid form under ambient Another preferred
hardening agent is a polyethylene glycol (PEG) or propylene glycol
compound for use in a cleaning composition comprising a nonionic
surfactant cleaning agent, such as a nonyl phenol ethoxylate, a
linear alkyl alcohol ethoxylate, an ethylene oxide/propylene oxide
block copolymers such as the surfactants available commercially
under the trademark PLURONIC from BASF-Wyandotte. The
solidification rate of cleaning compositions comprising a
polyethylene glycol hardening agent made according to the invention
will vary, at least in part, according to the amount and the
molecular weight of the polyethylene glycol added to the
composition.
[0153] The hardening agent may also be a hydratable substance such
as an anhydrous sodium carbonate, anhydrous sodium sulfate, or
combination thereof. A hydratable hardening agent, according to the
invention, is capable of hydrating to bind free water present in a
liquid detergent emulsion to the extent that the liquid emulsion
becomes hardened or solidified to a homogenous solid. The amount of
a hydratable substance included in a detergent composition
processed according to the invention, will vary according to the
percentage of water present in the liquid emulsion as well as the
hydration capacity of the other ingredients.
[0154] Other hardening agents that may be used in a cleaning
composition processed according to the invention include, for
example, urea, also known as carbamide, starches that have been
made water-soluble through an acid or alkaline treatment process,
and various inorganics that impart solidifying properties to a
heated liquid matrix upon cooling.
[0155] The cleaning adjunct(s) preferably comprise(s) from about
0.01% to about 10%, more preferably from about 0.02% to about 7%,
even more preferably from about 0.05% to about 5% by weight of the
composition.
Methods
[0156] The fabric article treatment composition may be applied to a
stain, preferably a hydrophilic stain, on a fabric article in need
of treatment by any suitable means known in the art.
[0157] Nonlimiting examples of such methods of application include
spraying, dipping, brushing, rolling and/or spreading.
[0158] With regard to the manner of using the spot pretreatment
compositions, said compositions are typically used for the direct
treatment of a soil or stained region of a textile or garment. In
accordance with one aspect of the process according to the
invention, a soiled garment is treated by applying an effective
amount of the spot pretreatment composition directly at the
location of a stain and optionally onto the surrounding area of the
stain. This can be done in one or more of the following ways. One
way is simply by means of manually dispensing an effective amount
of the spot pretreatment composition directly from a container or
vessel directly to the location of the stain. To make such a manual
application convenient for the consumer, a number of devices may be
used. For example, the spot pretreatment composition may be
provided in a spray bottle having a manually operated pump, squeeze
bottle, aerosol, or other dispensing container. Such containers are
known to the art. In such a way, localized application of the spot
pretreatment composition is facilitated and simplified by the
requisite operation of the pump of the spray bottle, or by
squeezing the squeeze bottle to dispense an amount of the spot
pretreatment composition, or by spraying the cleaning composition
from the pressurized aerosol container containing the composition
according to the invention. A further particularly useful, known
art dispensing apparatus is that of a container having a liquid
permeable applicator tip or end, such as a porous sponge or porous
fabric applicator tip. In use, a removable cap covering the
applicator tip is withdrawn, the container inverted to allow the
flow of the container's contents to impregnate the permeable
applicator tip and the tip is then manually contacted with the
stain to both transfer an amount of the spot pretreatment
composition, and at the same time to manually agitate or abrade the
textile or garment at the locus of the stain and optionally in the
surrounding region. Such manually applied agitation provides a
mechanical action which acts to physically break up the stain. This
is particularly useful for stains which have been left untreated
for an extended period of time, i.e., days, weeks, and longer
periods, and may have hardened. Such manual agitation, provides in
addition to the mechanical loosening of the stain, further acts to
improve the penetration of the spot pretreatment composition
throughout and among the stained fibers. Such mechanical action
also improves the overall stain removal characteristics of the spot
pretreatment composition. Due to these beneficial characteristics,
containers having a liquid permeable applicator tip or end is
particularly preferred, and such containers are known to the
art.
[0159] Typically, depending on the concentration of the surfactant
blend used, the pre-treatment can be contacted with the stains for
about 10 to about 600 seconds, preferably about 20 to about 300
seconds. Typically, the material is sprayed or physically contacted
with the soiled item. In the case of the use of a liquid material,
common spray, nebulizer, or other equivalent that can apply the
liquid material directly to the stain or spot can be used. In using
the gel or solid formulations of the invention, the solid gel,
block or stick can be directly contacted with the stain or spot
leaving the solid formulation in the form of a thin film or residue
substantially covering the entirety of any spot or stain on the
garment. The pre-treated garment can be left to permit the
surfactant compositions of the formulation to associate with the
stain to pre-treat the stain or spot outside the washing
machine.
[0160] In another embodiment, fabric articles within a fabric
article treating apparatus may initially be contacted by a fabric
article treatment composition according to the present invention
and then subsequently contacted with a discrete lipophilic fluid.
This process may all occur in a hands-free manner within the
apparatus itself.
[0161] In another embodiment, the method comprises the steps of:
[0162] a. contacting a fabric article in need of treatment with a
fabric article treatment composition inside a fabric article
treating apparatus such that a stain on the fabric article is
pretreated; and [0163] b. subsequently contacting the fabric
article with a discrete lipophilic fluid such that the stain on the
fabric article is removed and/or reduced.
[0164] The steps of contacting within the apparatus may be via
automated dosing of the fabric article treatment composition and/or
the discrete lipophilic fluid by the apparatus.
[0165] All documents cited in the Detailed Description of the
Invention are, in relevant part, incorporated herein by reference;
the citation of any document is not to be construed as an admission
that it is prior art with respect to the present invention.
[0166] While particular embodiments of the present invention have
been illustrated and described, it would be obvious to those
skilled in the art that various other changes and modifications can
be made without departing from the spirit and scope of the
invention. It is therefore intended to cover in the appended claims
all such changes and modification that are within the scope of this
invention.
* * * * *