U.S. patent application number 10/154865 was filed with the patent office on 2003-04-24 for siloxane dry cleaning composition and process.
This patent application is currently assigned to GENERAL ELECTRIC COMPANY. Invention is credited to Kilgour, John A., Perry, Robert J., Riccio, Donna Ann, Ryan, Larry D..
Application Number | 20030074742 10/154865 |
Document ID | / |
Family ID | 26882821 |
Filed Date | 2003-04-24 |
United States Patent
Application |
20030074742 |
Kind Code |
A1 |
Perry, Robert J. ; et
al. |
April 24, 2003 |
Siloxane dry cleaning composition and process
Abstract
A dry cleaning composition comprising a volatile siloxane and a
mixture of different classes of organic surfactants and, optionally
water, and a method for dry cleaning comprising contacting an
article with a composition comprising a volatile siloxane and a
mixture of different classes of organic surfactants.
Inventors: |
Perry, Robert J.;
(Niskayuna, NY) ; Riccio, Donna Ann; (Watervliet,
NY) ; Ryan, Larry D.; (Waterford, NY) ;
Kilgour, John A.; (Clifton Part, NY) |
Correspondence
Address: |
Kenneth S. Wheelock
General Electric Company
One Plastics Avenue
Pittsfield
MA
02101
US
|
Assignee: |
GENERAL ELECTRIC COMPANY
|
Family ID: |
26882821 |
Appl. No.: |
10/154865 |
Filed: |
May 24, 2002 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10154865 |
May 24, 2002 |
|
|
|
09742760 |
Dec 20, 2000 |
|
|
|
60187204 |
Mar 3, 2000 |
|
|
|
Current U.S.
Class: |
8/142 ; 510/285;
510/286 |
Current CPC
Class: |
D06L 4/15 20170101; C11D
3/162 20130101 |
Class at
Publication: |
8/142 ; 510/285;
510/286 |
International
Class: |
D06L 001/04; D06F
001/00 |
Claims
Having described the invention that which is claimed is:
1. A dry cleaning composition, comprising a volatile cyclic, linear
or branched siloxane, or mixture thereof, and two or more organic
surfactants.
2. The composition of claim 1, comprising from about 90 to about
99.99 parts by weight of the volatile siloxane and from about 0.001
to less than 10 parts by weight of the surfactants.
3. The composition of claim 2, further comprising from about 0.01
to about 15 parts by weight of water.
4. The composition of claim 1, wherein the surfactants are selected
from the classes of nonionic, cationic, anionic and amphoteric
surfactants.
5. The composition of claim 1, further comprising a silicone
surfactant or mixture of silicone surfactants.
6. The composition of claim 1, comprising two or more nonionic
surfactants.
7. The composition claim 1, comprising two or more cationic
surfactants.
8. The composition of claim 1, comprising two or more anionic
surfactants.
9. The composition of claim 1 comprising two or more amphoteric
surfactants.
10. The composition of claim 6, further comprising a silicone
surfactant or mixture of silicone surfactants.
11. The composition of claim 7, further comprising a silicone
surfactant or mixture of silicone surfactants.
12. The composition of claim 8, further comprising a silicone
surfactant or mixture of silicone surfactants.
13. The composition of claim 9, further comprising a silicone
surfactant or mixture of silicone surfactants.
14. A dry cleaning composition, comprising a volatile cyclic,
linear or branched siloxane, or mixture thereof, and three or more
organic surfactants.
15. The composition of claim 14, comprising from about 90 to about
99.99 parts by weight of the volatile siloxane and from about 0.001
to less than 10 parts by weight of the surfactants.
16. The composition of claim 15, further comprising from about 0.01
to about 15 parts by weight of water.
17. The composition of claim 14, wherein the surfactants are
selected from the classes of nonionic, cationic, anionic and
amphoteric surfactants.
18. The composition of claim 14, further comprising a silicone
surfactant or mixture of silicone surfactants.
19. The composition of claim 14, comprising two or more nonionic
surfactants.
20. The composition claim 14, comprising two or more cationic
surfactants.
21. The composition of claim 14, comprising two or more anionic
surfactants.
22. The composition of claim 14 comprising two or more amphoteric
surfatctants.
23. The composition of claim 19, further comprising a silicone
surfactant or mixture of silicone surfactants.
24. The composition of claim 20, further comprising a silicone
surfactant or mixture of silicone surfactants.
25. The composition of claim 21, further comprising a silicone
surfactant or mixture of silicone surfactants.
26. The composition of claim 22, further comprising a silicone
surfactant or mixture of silicone surfactants.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This Application is a Continuation-in-Part Application of
U.S. Ser. No. 09/ 742,760 filed Dec. 20, 2000 which application
claims rights of priority from U.S. Provisional Patent Application
Serial No. 60/187,204, filed Mar. 3, 2000.
TECHNICAL FIELD
[0002] The present invention is directed to a dry cleaning
composition, more specifically, to a siloxane fluid based
composition, for use in dry cleaning and to a dry cleaning process
using the composition.
BACKGROUND
[0003] Current dry cleaning technology uses perchloroethylene
("PERC") or petroleum-based materials as the cleaning solvent. PERC
suffers from toxicity and odor issues. The petroleum-based products
are not as effective as PERC in cleaning garments.
[0004] Cyclic siloxanes have been reported as spot cleaning
solutions, see U.S. Pat. No. 4,685,930, and as dry cleaning fluids
in dry cleaning machines, see U.S. Pat. No. 5,942,007. Other
patents disclose the use of silicone soaps in petroleum solvents,
see JP 09299687, and the use of silicone surfactants in super
critical carbon dioxide solutions has been reported, see, for
example, U.S. Pat. No. 5,676,705 and Chem. Mark. Rep., Dec. 15,
1997, 252(24), p. 15. Non-volatile silicone oils have also been
used as the cleaning solvent requiring removal by a second washing
with perfluoroalkane to remove the silicone oil, see JP
06327888.
[0005] Numerous other patents have issued in which siloxanes or
organomodified silicones have been present as addenda in PERC or
petroleum based dry cleaning solvents, see, for example, WO
9401510; U.S. Pat. No. 4,911,853; U.S. Pat. No. 4,005,231; U.S.
Pat. No. 4,065,258.
[0006] There is a continued interest in providing an additive or
additives to enhance the cleaning ability of silicone based dry
cleaning solvents.
SUMMARY OF THE INVENTION
[0007] In a first aspect, the present invention is directed to a
dry cleaning composition, comprising a volatile siloxane and two or
more surfactants.
[0008] In a second aspect, the present invention is directed to a
method for dry cleaning an article, comprising contacting the
article with a composition comprising a volatile siloxane and two
or more surfactants.
[0009] In a third aspect, the present invention is directed to a
concentrate composition, comprising two or more surfactants.
[0010] The composition and process of the present invention exhibit
improved performance, such as for example, removal of water soluble
stains from the article, for example a garment, being cleaned,
improved feel and hand, and improved refinishing of the article.
The present invention also provides for the removal of oil soluble
stains such as motor oil and grease.
DETAILED DESCRIPTION OF THE INVENTION
[0011] In a preferred embodiment, the composition comprises, based
on 100 parts by weight ("pbw") of the composition, from greater
than 90 pbw to 99.99 pbw, more preferably from 92 pbw to 99.9 pbw
and even more preferably from 95 pbw to 99.5 pbw of the volatile
siloxane and from 0.001 pbw to less than 10 pbw, more preferably
from 0.01 pbw to 8 pbw and even more preferably from 0.1 pbw to 5
pbw of the surfactants. The composition optionally further
comprises water, preferably from 0.01 pbw to 15 pbw, more
preferably from 0.1 pbw to less than 12 pbw and even more
preferably from 0.2 pbw to 10 pbw of water. The volatile siloxane
utilized in the present invention may be a linear, branched or
cyclic siloxane.
[0012] In a preferred embodiment, the water may be added as "free"
water or may be delivered by an emulsion containing other
components such as siloxanes, hydrocarbons, surfactants, or other
suitable additives. If the water is delivered by an emulsion, the
emulsion may be prepared by such methods as homogenization of the
components or mechanical stirring of the mixture.
[0013] In a preferred embodiment, the surfactant comprises two or
more organic surfactants selected from the classes of nonionic,
cationic, anionic and amphoteric surfactants. In one preferred
embodiment, two organic surfactants are mixed together for use in
the composition. In another preferred embodiment, three organic
surfactants are mixed together for use in the composition. In
another preferred embodiment, four organic surfactants are mixed
together for use in the composition. In another preferred
embodiment, five organic surfactants are mixed together for use in
the composition. In another preferred embodiment, more than five
organic surfactants are mixed together for use in the
composition.
[0014] In another preferred embodiment of the present invention, a
concentrate composition comprises two or more surfactants,
preferably two or more organic surfactants selected from the
classes of nonionic, cationic, anionic and amphoteric surfactants.
The composition comprises, based on 100 pbw of the composition,
from 0.1 to 99.9 pbw of one surfactant and from 0.1 to 99.9 pbw of
a second surfactant. Optionally, the concentrate composition may
further comprise from 0.1 to 99.8 pbw of one or more additional
organic surfactants. The concentrate composition may optionally
further comprise a siloxane fluid. The concentrate composition may
be added to a cleaning fluid, for example a dry cleaning solvent,
for use in cleaning processes.
[0015] Compounds suitable as the linear or branched, volatile
siloxane solvent of the present invention are those containing a
polysiloxane structure that includes from 2 to 20 silicon atoms.
Preferably, the linear or branched, volatile siloxanes are
relatively volatile materials, having, for example, a boiling of
below about 300.degree. C. point at a pressure of 760 millimeters
of mercury ("mm Hg").
[0016] In a preferred embodiment, the linear or branched, volatile
siloxane comprises one or more compounds of the structural formula
(I):
M.sub.2+y+2zD.sub.xT.sub.yQ.sub.z (I)
[0017] wherein:
[0018] M is R.sup.1.sub.3SiO.sub.1/2;
[0019] D is R.sup.2R.sup.3SiO.sub.{fraction (2/2)};
[0020] T is R.sup.4SiO.sub.{fraction (3/2)};
[0021] and Q is SiO.sub.{fraction (4/2)}
[0022] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently
a monovalent hydrocarbon radical; and
[0023] x and y are each integers, wherein 0.ltoreq.x.ltoreq.10 and
0.ltoreq.y.ltoreq.10 and 0.ltoreq.z.ltoreq.10.
[0024] Suitable monovalent hydrocarbon groups include acyclic
hydrocarbon radicals, monovalent alicyclic hydrocarbon radicals,
monovalent and aromatic or fluoro containing hydrocarbon radicals.
Preferred monovalent hydrocarbon radicals are monovalent alkyl
radicals, monovalent aryl radicals and monovalent aralkyl radicals.
In a highly preferred embodiment, the monovalent hydrocarbon
radical is a monovalent (C.sub.1-C.sub.6)alkyl radical, most
preferably, methyl.
[0025] As used herein, the term "(C.sub.1-C.sub.6)alkyl" means a
linear or branched alkyl group containing from 1 to 6 carbons per
group, such as, for example, methyl, ethyl, propyl, iso-propyl,
n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, hexyl,
preferably methyl.
[0026] As used herein, the term "aryl" means a monovalent
unsaturated hydrocarbon ring system containing one or more aromatic
or fluoro containing rings per group, which may optionally be
substituted on the one or more aromatic or fluoro containing rings,
preferably with one or more (C.sub.1-C.sub.6)alkyl groups and
which, in the case of two or more rings, may be fused rings,
including, for example, phenyl, 2,4,6-trimethylphenyl,
2-isopropylmethylphenyl, 1-pentalenyl, naphthyl, anthryl,
preferably phenyl.
[0027] As used herein, the term "aralkyl" means an aryl derivative
of an alkyl group, preferably a (C.sub.2-C.sub.6)alkyl group,
wherein the alkyl portion of the aryl derivative may, optionally,
be interrupted by an oxygen atom, such as, for example,
phenylethyl, phenylpropyl, 2-(1-naphthyl)ethyl, preferably
phenylpropyl, phenyoxypropyl, biphenyloxypropyl.
[0028] In a preferred embodiment, the linear or branched, volatile
siloxane comprises one or more of, hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane,
dodecamethylpentasiloxane- , tetradecamethylhexasiloxane or
hexadecamethylheptasiloxane or methyltris(trimethylsiloxy)silane.
In a more highly preferred embodiment, the linear or branched,
volatile siloxane of the present invention comprises
octamethyltrisiloxane, decamethyltetrasiloxane, or
dodecamethylpentasiloxane or methyltris(trimethylsiloxy)silane. In
a highly preferred embodiment, the siloxane component of the
composition of the present invention consists essentially of
decamethyltetrasiloxane.
[0029] Suitable linear or branched volatile siloxanes are made by
known methods, such as, for example, hydrolysis and condensation of
one or more of tetrachlorosilane, methyltrichlorosilane,
dimethyldichlorosilane, trimethyichlorosilane, or by isolation of
the desired fraction of an equilibrate mixture of
hexamethyldisiloxane and octamethylcyclotetrasilox- ane or the like
and are commercially available.
[0030] Compounds suitable as the cyclic siloxane component of the
present invention are those containing a polysiloxane ring
structure that includes from 2 to 20 silicon atoms in the ring.
Preferably, the linear, volatile siloxanes and cyclic siloxanes are
relatively volatile materials, having, for example, a boiling point
of below about 300.degree. C. at a pressure of 760 millimeters of
mercury ("mm Hg").
[0031] In a preferred embodiment, the cyclic siloxane component
comprises one or more compounds of the structural formula (II):
1
[0032] wherein:
[0033] R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are each independently
a monovalent hydrocarbon group, preferably a
(C.sub.1-C.sub.6)alkyl, more preferably, methyl; and a and b are
each integers wherein 0.ltoreq.a.ltoreq.10 and
0.ltoreq.b.ltoreq.10, provided that 3.ltoreq.(a+b).ltoreq.10.
[0034] In a preferred embodiment, the cyclic siloxane comprises one
or more of, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
tetradecamethylcycloheptasiloxane. In a more highly preferred
embodiment, the cyclic siloxane of the present invention comprises
octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane. In a
highly preferred embodiment, the cyclic siloxane component of the
composition of the present invention consists essentially of
decamethylcyclopentasiloxane.
[0035] Suitable cyclic siloxanes are made by known methods, such
as, for example, hydrolysis and condensation of
dimethyldichlorosilane and are commercially available.
[0036] The organic surfactants of the present invention comprise
two or more surfactants selected from nonionic, cationic, anionic
and amphoteric surfactants. The surfactants may comprise two or
more surfactants selected from the same or different classes.
[0037] Compounds suitable for use as the nonionic surfactant of the
present invention are those that carry no discrete charge when
dissolved in aqueous media. Nonionic surfactants are generally
known in the art and include, for example, alkanol amides (such as,
for example, coco, lauric, oleic and stearic monoethanolamides,
diethanolamides and monoisopropanolamides), amine oxides (such as,
for example, polyoxyethylene ethanolamides and polyoxyethylene
propanolamides), polyalkylene oxide block copolymers (such as, for
example, poly(oxyethylene-co-oxypropylene)), ethoxylated alcohols,
(such as, for example, isostearyl polyoxyethylene alcohol, lauryl,
cetyl, stearyl, oleyl, tridecyl, trimethylnonyl, isodecyl,
tridecyl), ethoxylated alkylphenols (such as, for example,
nonylphenol), ethoxylated amines and ethoxylated amides,
ethoxylated fatty acids, ethoxylated fatty esters and ethoxylated
fatty oils (such as, for example, mono- and diesters of acids such
as lauric, isostearic, pelargonic, oleic, coco, stearic, and
ricinoleic, and oils such as castor oil and tall oil), fatty
esters, fluorocarbon containing materials, glycerol esters (such
as, for example, glycerol monostearate, glycerol monolaurate,
glycerol dilaurate, glycerol monoricinoleate, and glycerol oleate),
glycol esters (such as, for example, propylene glycol monostearate,
ethylene glycol monostearate, ethylene glycol distearate,
diethylene glycol monolaurate, diethylene glycol monolaurate,
diethylene glycol monooleate, and diethylene glycol stearate),
lanolin-based surfactants, monoglycerides, phosphate esters,
polysaccharide ethers, propoxylated fatty acids, propoxylated
alcohols, and propoxylated alkylphenols, protein-based organic
surfactants, sorbitan-based surfactants (such as, for example,
sorbitan oleate, sorbitan monolaurate, and sorbitan palmitate),
sucrose esters and glucose esters, and thio- and mercapto-based
surfactants.
[0038] In a preferred embodiment, one component of the present
invention comprises one or more nonionic surfactants according to
one or more of the structural formulas III and IV:
R.sup.9--O--(CH.sub.2--CH.sub.2--O).sub.n--R.sup.10 (III)
R.sup.9--O--(CH.sub.2--C(CH.sub.3)H--O).sub.n--R.sup.10 (IV)
[0039] wherein:
[0040] R.sup.9 is a monovalent hydrocarbon group of from 1 to 30
carbons that may be linear, cyclic, branched, unsaturated, aromatic
or fluoro containing; R.sup.10 is hydrogen or a monovalent
hydrocarbon group of 1 to 30 carbons that may be linear, cyclic,
branched, unsaturated, aromatic or fluoro containing; and n is from
about 1 to about 100, more preferably from about 1 to about 40. In
a highly preferred embodiment, R.sup.9 contains from 2 to about 24
carbons, even more preferably from 8 to 24 carbons, R.sup.10 is H
and n is from about 2 to about 20.
[0041] In another preferred embodiment, one component of the
present invention comprises one or more nonionic surfactants that
may be a sugar-based surfactant according to one or more of the
structural formulas V and VI: 2
[0042] wherein:
[0043] each R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.21,
R.sup.22, R.sup.23, R.sup.24 and R.sup.25 is independently H or a
monovalent hydrocarbon group of 1 to 30 carbons that may be linear,
cyclic, branched, an oxygenated alkane or other chalcogen
containing group. These surfactants may also be the open-chain
analogs. In a preferred embodiment each R.sup.17, R.sup.18,
R.sup.19, R.sup.20, R.sup.21, R.sup.22, R.sup.23, R.sup.24 and
R.sup.25 is independently H or a hydroxy-terminated polyoxyethylene
of 1 to 10 repeat units, a monovalent hydrocarbon group of 1 to 4
carbons or a carboxyalkyl group of from 2 to 9 carbons. In another
preferred embodiment, R.sup.17, R.sup.20 and R.sup.21 are
monovalent hydrocarbon radicals of 8 of 20 carbons and R.sup.25 is
--CH.sub.2--OR' with R' a hydrocarbon group of from 1 to 4
carbons.
[0044] In another preferred embodiment, one component of the
present invention comprises one or more nonionic surfactants that
may be an amine-based or phosphate ester-based surfactant according
to one or more of the structural formulas VII and VIII: 3
[0045] wherein:
[0046] each R.sup.11, R.sup.12, R.sup.13, R.sup.14, R.sup.15, and
R.sup.16 is independently H or a monovalent hydrocarbon group of 1
to 30 carbons that may be linear, cyclic, branched, unsaturated,
aromatic, fluoro containing, an oxygenated alkane or other
chalcogen containing group. In a preferred embodiment, R.sup.11,
R.sup.12, R.sup.14 and R.sup.15 are H or monovalent hydrocarbon
radicals of 1 to 4 carbons and R.sup.13 and R.sup.16 are monovalent
hydrocarbon radicals of 6 to 24 carbons. In another preferred
embodiment, R.sup.11, R.sup.12, R.sup.14 and R.sup.15 are
monovalent hydrocarbon radicals of 6 to 24 carbons and R.sup.13 and
R.sup.16 are H or monovalent hydrocarbon radicals of 1 to 4
carbons.
[0047] Compounds suitable for use as the anionic surfactant of the
present invention are those having polar, solubilizing groups such
as carboxylate, sulfonate, sulfate and phosphate. Anionic
surfactants are generally known in the art and include, for
example, alkyl aryl sulfonates (such as, for example,
alkylbenzenesulfonates), alkyl aryl sulfonic acids (such as, for
example, sodium and ammonium salts of toluene-, xylene- and
isopropylbenzenesulfonic acids), sulfonated amines and sulfonated
amides (such as, for example, amidosulfonates), carboxylated
alcohols and carboxylated alkylphenol ethoxylates, diphenyl
sulfonates, fatty esters, isethionates, lignin-based surfactants,
olefin sulfonates (such as, for example, RCH.dbd.CHSO.sub.3Na,
where R is C.sub.10-C.sub.16), phosphorous-based surfactants,
protein based surfactants, sarcosine-based surfactants (such as,
for example, N-acylsarcosinates such as sodium
N-lauroylsarcosinate), sulfates and sulfonates of oils and/or fatty
acids, sulfates and sulfonates of ethoxylated alkylphenols,
sulfates of alcohols, sulfates of ethoxylated alcohols, sulfates of
fatty esters, sulfates of aromatic or fluoro containing compounds,
sulfosuccinnamates, sulfosuccinates (such as, for example, diamyl-,
dioctyl- and diisobutylsulfosuccinates), taurates, and sulfonic
acids.
[0048] In a preferred embodiment, one component of the present
invention comprises one or more anionic surfactants that may be a
sulfosuccinate, sulfate, sulfonate, carboxylate, or phosphorous
containing surfactant according to one or more of the structural
formulas IX to XIII: 4
(R.sup.28--OSO.sub.3.sup.-).sub.qX.sup.+ (X)
(R.sup.28--SO.sub.3.sup.-).sub.qX.sup.+ (XI)
(R.sup.29--CO.sub.2.sup.-).sub.qX.sup.+ (XII)
(R.sup.30--OPO.sub.3.sup.-).sub.qX.sup.+ (XIII)
[0049] wherein:
[0050] each R.sup.26, R.sup.27, R.sup.28, R.sup.29 and R.sup.30 is
independently a monovalent hydrocarbon group of 1 to 30 carbons
that may be linear, cyclic, branched, unsaturated, aromatic, fluoro
containing, an oxygenated alkane or other chalcogen containing
radical, and X is H or an alkali metal, alkaline earth element or a
chalcogen containing counterion or other suitable cation that does
not unduly interfere with the functioning of the molecule as a
surfactant where the subscript q is the valence or oxidation state
of the cation X. In a preferred embodiment, R.sup.26 and R.sup.27
are each independently a linear, cyclic, or branched monovalent
hydrocarbon group of 4 to 20 carbons, more preferably a linear,
cyclic, or branched monovalent hydrocarbon group of 6 to 13
carbons; R.sup.28 is a monovalent hydrocarbon group of 4 to 20
carbons, more preferably from 8 to 16 carbons; R.sup.29 is
monovalent hydrocarbon group of 8 to 26 carbons, more preferably
from 10 to 20 carbons; and R.sup.30 is monovalent hydrocarbon group
of 8 to 30 carbons.
[0051] Compounds suitable for use as the cationic surfactant of the
present invention are those having a positive charge when dissolved
in aqueous media, which resides on an amino or quaternary nitrogen.
Cationic surfactants are generally known in the art and include,
for example, amine acetates, amines (such as, for example,
oxygen-free amines such as monoalkylamines, dialkylamines and
N-alkyltrimethylene diamines, and oxygen-containing amines such as
amine oxides, ethoxylated alkylamines,
1-(2-hydroxyethyl)-2-imidazolines, and alkoxylates of
ethylenediamine), and quaternary ammonium salts (such as, for
example, dialkyldimethylammonium salts, alkylbenzyldimethylammonium
chlorides, alkyltrimethylammonium salts and alkylpyridium halides),
and quaternary ammonium esters (such as, for example, diethyl ester
dimethyl ammonium chloride).
[0052] In a preferred embodiment, one component of the present
invention comprises one or more cationic surfactants that may be a
quaternary amine-based surfactant according to the structural
formula XIV
(R.sup.31R.sup.32R.sup.33R.sup.34N.sup.+).sub.pJ.sup.- (XIV)
[0053] wherein:
[0054] each R.sup.31, R.sup.32, R.sup.33, and R.sup.34 is
independently H or a monovalent hydrocarbon group of 1 to 30
carbons that may be linear, cyclic, branched, unsaturated,
aromatic, fluoro containing, an oxygenated alkane or other
chalcogen containing group, and J is a suitable anion having an
oxidation state or valence p that does not unduly interfere with
the functioning of the molecule as a surfactant. In a preferred
embodiment, R.sup.31 and R.sup.32 are each independently a
monovalent hydrocarbon radical of 1 to 4 carbons and R.sup.33 and
R.sup.34 are each independently a monovalent hydrocarbon radical of
8 to 24 carbons.
[0055] Compounds suitable for use as the amphoteric surfactant of
the present invention are those containing both an acidic and basic
hydrophilic group. Amphoteric surfactants are compatible with
anionic and cationic surfactants. Amphoteric surfactants are
generally known in the art and include, for example, betaine
derivatives such as alkylbetaines and amidopropylbetaines, block
copolymers, imidazolines and lecithins.
[0056] In a preferred embodiment, one component of the present
invention comprises one or more amphoteric surfactants according to
the structural formula XV: 5
[0057] wherein:
[0058] each R.sup.35, R.sup.36 and R.sup.37 is independently H or a
monovalent hydrocarbon group of 1 to 30 carbons that may be linear,
cyclic, branched, unsaturated, aromatic, fluoro containing, an
oxygenated alkane or other chalcogen containing group, G is a
divalent spacer group, Y is a carboxylate, sulfonate, sulfate,
phosphonate or other similar group. In a preferred embodiment,
R.sup.35 is a monovalent hydrocarbon group of 1 to 4 carbons, more
preferably methyl, and R.sup.36 and R.sup.37 are each independently
monovalent hydrocarbon group of 6 to 24 carbons.
[0059] Surfactants are known in the art and are commercially
available under many trade names from many sources, such as for
example, Akzo Chemical Co., Calgene Chemical Inc., Emkay Chemical
Co., Hercules, Inc., ICI Americas Inc., Lonza, Inc., Rhone Poulenc,
Inc., Union Carbide Corp. and Witco Corp.
[0060] In a preferred embodiment, one component of the present
invention comprises a silicone surfactant or mixture of silicone
surfactants wherein the silicone surfactant comprises one or more
polyether siloxane compounds those according to the structural
formula (formula XVI):
M.sub.eD.sub.fD*.sub.gM*.sub.2-e (XVI)
[0061] wherein:
[0062] M is R.sup.38.sub.3SiO.sub.1/2;
[0063] D is R.sup.39.sub.2SiO.sub.{fraction (2/2)};
[0064] M* is R.sup.40.sub.3SiO.sub.1/2;
[0065] D* is R.sup.41.sub.2SiO.sub.{fraction (2/2)};
[0066] each R.sup.38, R.sup.39 is independently H, a monovalent
hydrocarbon group.
[0067] each R.sup.40 is independently H, a monovalent hydrocarbon
group, or
[0068]
--(CH.sub.2).sub.h--O--(C.sub.2H.sub.4O).sub.i--(C.sub.3H.sub.6O).s-
ub.j--(C.sub.nO.sub.2nO).sub.k--R.sup.42, provided that at least
one R.sup.40
is--(CH.sub.2).sub.h--O--(C.sub.2H.sub.4O).sub.i--(C.sub.3H.sub.-
6O).sub.j--(C.sub.nO.sub.2nO).sub.k--R.sup.42;
[0069] each R.sup.41 is independently H, a monovalent hydrocarbon
group, or
[0070]
--(CH.sub.2).sub.h--O--(C.sub.2H.sub.4O).sub.i--(C.sub.3H.sub.6O).s-
ub.j--(C.sub.nO.sub.2nO).sub.k--R.sup.42, provided that at least
one R.sup.41 is
--(CH.sub.2).sub.h--O--(C.sub.2H.sub.4O).sub.i--(C.sub.3H.sub-
.6O).sub.j--(C.sub.nO.sub.2nO).sub.k--R.sup.42;
[0071] R.sup.42 is H, a monovalent hydrocarbon group or
alkyloxy;
[0072] 0.ltoreq.e.ltoreq.2;
[0073] 0.ltoreq.f.ltoreq.1000;
[0074] 0.ltoreq.g.ltoreq.50, provided that g.gtoreq.1 if e is
2;
[0075] 1.ltoreq.h.ltoreq.16;
[0076] 0.ltoreq.i.ltoreq.30;
[0077] 0.ltoreq.j.ltoreq.30;
[0078] 0.ltoreq.k.ltoreq.30; and
[0079] 4.ltoreq.n.ltoreq.8, provided that i+j+k>0.
[0080] In a preferred embodiment, 2.ltoreq.i.ltoreq.25,
0.ltoreq.j.ltoreq.25 and 0.ltoreq.k.ltoreq.25, more preferably k is
0.
[0081] The composition of the present invention may, optionally,
contain other components, such as, for example, fabric
conditioners, brighteners, bleaching agents, enzymes,
water-repellent treatments, anti-static agents, fragrances and
detergents.
[0082] Generally the compositions of the present invention comprise
two or more surfactants selected from the group consisting of
anionic, nonionic, cationic and amphoteric surfactants. In one
preferred embodiment, the composition of the present invention
comprises two or more anionic surfactants, or two or more cationic
surfactants, or two or more nonionic surfactants or two or more
amphoteric surfactants, preferably two or more anionic surfactants
or two or more nonionic surfactants. In another preferred
embodiment, the composition of the present invention comprises a
sulfosuccinate surfactant and a sulfonic acid surfactant, more
preferably sulfosuccinate and dodecylbenzenesulfonic acid, or a
sulfated anionic surfactant and a sulfosuccinate, or a sulfated
anionic surfactant and a sulfonic acid surfactant, more preferably
sulfosuccinate and dodecylbenzenesulfonic acid, or a nonionic
polymeric surfactant and an ethoxylated alcohol.
[0083] In another preferred embodiment, the composition of the
present invention comprises at least two surfactants selected from
anionic, nonionic, cationic and amphoteric surfactants, provided
that at least two of the surfactants are selected from two
different members of the group of surfactants, such that there is
at least one anionic surfactant and at least one cationic
surfactant, or at least one anionic surfactant and at least one
nonionic surfactant, or at least one nonionic surfactant and at
least one cationic surfactant, or at least one anionic surfactant
and at least one amphoteric surfactant, or at least one amphoteric
surfactant and at least one cationic surfactant or at least one
nonionic surfactant and at least one amphoteric surfactant. In a
highly preferred embodiment, the composition of the present
invention comprises a sulfoccinate and a quaternary ammonium salt,
or a sulfated anionic surfactant and an ethoxylated alcohol, or a
sulfonic acid, more preferably dodecylbenzenesulfonic acid, and a
nonionic polymeric surfactant, or a sulfosuccinate and a nonionic
polymeric surfactant, or a sulfonic acid, more preferably
dodecylbenzenesulfonic acid, and an ethoxylated alcohol, or a
sulfonic acid, more preferably dodecylbenzenesulfonic acid, and a
quaternary ammonium salt, or a sulfated anionic surfactant and a
quaternary ammonium salt, or a sulfated anionic surfactant and a
nonionic polymeric surfactant, or a sulfated anionic surfactant and
an ethoxylated alcohol, or a sulfated anionic surfactant and a
quaternary ammonium salt, or an ethoxylated alcohol and a
quaternary ammonium salt, or a sulfosuccinate, a sulfated anionic
surfactant and two different ethoxylated alcohols, or a
sulfosuccinate, a sulfated anionic surfactant and a quaternary
ammonium salt.
[0084] In another preferred embodiment, the composition of the
present invention comprises at least three surfactants selected
from the group consisting of anionic, nonionic, cationic and
amphoteric surfactants. Preferably these surfactants may be chosen
wherein each of the three surfactants are selected from different
surfactants in terms of anionic, nonionic, cationic or amphoteric,
for example is at least one anionic surfactant, at least one
cationic surfactant and at least one nonionic surfactant, or at
least one anionic surfactant, at least one cationic surfactant and
at least one amphoteric surfactant, or at least one cationic
surfactant, at least one nonionic surfactant and at least one
amphoteric surfactant. In a highly preferred embodiment, the
composition of the present invention comprises a sulfosuccinate, a
sulfated anionic surfactant, two different ethoxylated alcohols,
and a quaternary ammonium salt, or a sulfated anionic surfactant,
an ethoxylated alcohol and a quaternary ammonium salt.
[0085] In another preferred embodiment, the composition of the
present invention comprises at least four surfactants selected from
the group of anionic, nonionic, cationic and amphoteric
surfactants, provided that at least one surfactant is selected from
each member of the group of surfactants, such that there is at
least one anionic surfactant, at least one cationic surfactant, at
least one nonionic surfactant and at least one amphoteric
surfactant.
[0086] The dry cleaning composition of the present invention is
made by adding to the siloxane fluid two or more surfactants and
mixing to form a homogeneous solution. The surfactants may be mixed
together before addition to the siloxane, or they may added to the
siloxane individually.
[0087] In a preferred embodiment, the dry cleaning composition of
the present invention further comprises a minor amount, preferably,
less than 50 pbw per 100 pbw of the composition, more preferably,
less than 10 pbw per 100 pbw of the composition, of one or more
non-siloxane fluids. Suitable non-siloxane fluids include aqueous
fluids, such as, for example, water, and organic fluids, for
example, hydrocarbon fluids and halogenated hydrocarbon fluids.
[0088] According to the process of the present invention, an
article, such as for example, a textile or leather article,
typically, a garment, is dry cleaned by contacting the article with
the composition of the present invention. In a preferred
embodiment, the articles to be cleaned include textiles made from
natural fibers, such as for example, cotton, wool, linen and hemp,
from synthetic fibers, such as, for example, polyester fibers,
polyamide fibers, polypropylene fibers and elastomeric fibers, from
blends of natural and synthetic fibers, from natural or synthetic
leather or natural or synthetic fur.
[0089] The article and dry cleaning composition are then separated,
by, for example, one or more of draining and centrifugation. In a
preferred embodiment, separation of the article and dry cleaning
composition is followed by the application of heat, preferably,
heating to a temperature of from 15.degree. C. to 120.degree. C.,
preferably from 20.degree. C. to 100.degree. C., or reduced
pressure, preferably, a pressure of from 1 mm Hg to 750 mm Hg, or
by application of both heat and reduced pressure, to the
article.
[0090] The surfactant components of the dry cleaning composition
are typically depleted through use in the cleaning cycle. Some of
the surfactants remain on the articles being cleaned. To promote
efficient cleaning of articles, the dry cleaning solvent is
periodically cleaned or refreshed, preferably distilled, to remove
the dirt that has been removed from the articles being cleaned.
Once the solvent has been cleaned, additional surfactants are
typically added to the cleaned solvent to replenish the amount of
surfactants in the solvent. This process is repeated periodically,
depending on the number of uses and the amount of soil on articles
being cleaned, so that the solvent will effectively clean and
remove soil from articles, and each time, additional surfactants
are added to the solvent.
[0091] In another preferred embodiment, the concentrate composition
of the present invention is added to the dry cleaning composition
to replenish the surfactants that have been depleted.
[0092] The concentrate composition of the present invention can be
made in any of the combinations of organic disclosed above, such
as, for example, a concentrate composition comprising at least one
anionic surfactant and at least one cationic surfactant, or at
least two anionic surfactants. The concentrate composition may
optionally further comprise a siloxane fluid. In a highly preferred
embodiment, the concentrate composition of the present invention
comprises at least one anionic surfactant and at least one nonionic
surfactant, and optionally, a siloxane fluid. The concentrate
composition may optionally further comprise additional components
known in the art, such as, for example, brighteners, softeners,
water, fragrances and the like.
[0093] The concentrate composition of the present invention is made
by adding together two or more surfactants in desired amounts, and
optionally, a siloxane fluid, and stirring to form a homogeneous
solution. The concentrate may then be added to a siloxane fluid to
form a dry cleaning fluid at any time, such as before the initial
cleaning, or after the fluid has been used to replenish the amount
of surfactant in the cleaning fluid. The surfactant level in the
cleaning fluid is depleted through routine use and cleaning.
[0094] Testing for water soluble stain removal was accomplished
using fabric swatches supplied by the International Fabricare
Institute ("IFI") (Silver Spring, Md.) that contained a water
soluble dye. The color change of a swatch of this material was
measured by a Minolta CR-300.RTM. Colorimeter using the Hunter
Color Number difference calculations. The larger the change in
Hunter Color Number (.DELTA.E), the greater the dye removal and the
more efficient the cleaning.
[0095] The following examples are to illustrate the invention and
are not to be construed as limiting the claims.
EXAMPLES (Group A)
[0096] Testing procedure: Circular swatches (from IFI) containing a
water soluble dye were measured by the calorimeter, and the initial
color values for L, a and b (as defined by the Hunter Color
Numbers) were recorded. The fabric swatches were then placed in
vials containing the cleaning composition of the present invention,
and the vial was shaken for 10 minutes at ambient temperature. The
fabric swatch was removed and allowed to drip dry for 2 to 5
seconds, then placed on absorbent toweling and allowed to air dry
for 16 to 24 hours. A second reading of each fabric swatch was
taken and the color difference (.DELTA.E) was determined using the
following formula:
.DELTA.E=[(L.sub.1-L.sub.2).sup.2+(a.sub.1-a.sub.2).sup.2=(b.sub.1-b.sub.2-
).sup.2].sup.1/2
[0097] This color difference represents the relative amount of
cleaning, with the higher .DELTA.E indicative of better cleaning
performance.
Surfactants used in the Examples
[0098]
1 Surfactant Type of Surfactant A Aerosol OT* (anionic
sulfosuccinate surfactant) B Aerosol GPG* (anionic sulfosuccinate
surfactant) C Aerosol TR* (anionic sulfosuccinate surfactant) D
DDBSA (dodecylbenzenesulfonic acid - anionic surfactant) E Glucopon
.TM. 425** (nonionic polymeric surfactant) F Anionic surfactant -
R--SO.sub.4--Na.sup.+ where R is C.sub.14-C.sub.16 alkene G Anionic
surfactant - R--PhO--(EO).sub.3--OSO.sub.3--Na.sup.+ where R is
C.sub.12 H Ethoxylated Alcohol (R--O--(CH.sub.2CH.sub.2O).sub.9H
where R is C.sub.12-C.sub.13) I Ethoxylated Alcohol
(R--O--(CH.sub.2CH.sub.2O).sub.7H where R is C.sub.14-C.sub.15) J
Quaternary Ammonium Salt (R.sub.2R'MeN.sup.+Cl.sup.- where R' is
alkyl, R is polyether) K Ethoxylated Alcohol
(R--O--(CH.sub.2CH.sub.2O)H where R is C.sub.4) L Ethoxylated
Alcohol (R--O--(CH.sub.2CH.sub.2O).sub.2H where R is C.sub.4) M
Ethoxylated Alcohol (R--O--(CH.sub.2CH.sub.2O).sub.3H where R is
C.sub.12-C.sub.15) N AtPhos 3250 O AtPhos 3226 P Yelkin TS
(Lecithin) Q Ultralec F (Lecithin) R 1,2-hexanediol S Ethoxylated
Alcohol (R--O--(CH.sub.2CH.sub.2O).su- b.2H where R is ethylhexyl)
T 1,2-butanediol U 1,2-decandiol V Didecyldimethylammonium bromide
W Cetyltrimethyl ammonium bromide X 1,6-hexanediol Y
1,10-decanediol Z Dihexadecyldimethyl ammonium bromide AA BET-C30
(amphoteric) BB JC HA (amphoteric) CC Ethoxylated Alcohol
(R--O--(CH.sub.2CH.sub.2O).sub.2H where R is C.sub.6) DD Fluorad
FC135 EE Fluorad FC430 *Commercially available from Cytek
Industries **Commercially available from Henkel Canada Ltd.
[0099] A cleaning composition according to the present invention
containing a cyclic siloxane (D.sub.5) and a mixture of two
surfactants from different surfactant classes was made. Fabric
swatches were cleaned using the above procedure, and the color
difference was measured to determine the effectiveness of the
cleaning composition. A solution of cyclic siloxane (D.sub.5)
without a surfactant was used as a control. Results are shown in
Table 1 below.
2TABLE 1 Binary Mixtures of Surfactants in D5 En- Good hanced Surf.
Amt Surf. Amt Delta Clean- Clean- Exp. D.sub.5 1 (g) 2 (g) E ing
ing Control Control -- -- -- -- 1.9 -- 1 14.7 A 0.15 D 0.15 43.7 X
2 14.25 A 0.15 D 0.6 46.7 X 3 14.25 A 0.6 D 0.15 18.3 X 4 14.7 A
0.15 F 0.15 2.9 X 5 14.25 A 0.15 F 0.6 11.7 X 6 14.25 A 0.6 F 0.15
6.4 X 7 14.7 A 0.15 G 0.15 5.5 X 8 14.25 A 0.15 G 0.6 18.7 X X 9
14.25 A 0.6 G 0.15 10.8 X X 10 14.7 A 0.15 H 0.15 15.4 X 11 14.25 A
0.15 H 0.6 22.6 X 12 14.25 A 0.6 H 0.15 10.0 X 13 14.7 A 0.15 I
0.15 22.6 X 14 14.25 A 0.15 I 0.6 7.8 X 15 14.25 A 0.6 I 0.15 22.2
X 16 14.7 A 0.15 J 0.15 14.0 X 17 14.25 A 0.15 J 0.6 11.8 X 18
14.25 A 0.6 J 0.15 23.1 X X 19 14.7 A 0.15 E 0.15 17.5 X X 20 14.25
A 0.15 E 0.6 3.8 X 21 14.25 A 0.6 E 0.15 30.2 X X 22 14.7 A 0.15 N
0.15 14.3 X 23 14.7 A 0.15 O 0.15 12.2 X 24 14.7 A 0.15 P 0.15 6.7
X 25 14.7 A 0.15 Q 0.15 3.0 X 26 14.25 A 0.60 R 0.15 2.5 X 27 14.25
A 0.15 R 0.60 4.1 X 28 14.7 A 0.15 R 0.15 10.5 X 29 14.7 A 0.15 S
0.15 3.8 X 30 14.7 A 0.15 T 0.15 20.8 X 31 14.7 A 0.15 U 0.15 9.0 X
32 14.25 B 0.6 R 0.15 3.2 X 33 14.25 B 0.15 R 0.60 14.3 X 34 14.7 B
0.15 R 0.15 22.6 X X 35 14.7 B 0.15 S 0.15 0.7 36 14.7 B 0.15 T
0.15 6.5 X 37 14.7 B 0.15 U 0.15 2.8 X 38 14.25 C 0.6 R 0.15 1.8 39
14.25 C 0.15 R 0.60 3.9 X 40 14.7 C 0.15 R 0.15 24.5 X X 41 14.7 C
0.15 S 0.15 1.2 42 14.7 C 0.15 T 0.15 24.1 X 43 14.7 C 0.15 U 0.15
4.0 X 44 14.7 D 0.15 F 0.15 26.7 X 45 14.25 D 0.15 F 0.6 46.4 X X
46 14.25 D 0.6 F 0.15 44.4 X 47 14.7 D 0.15 G 0.15 38.7 X 48 14.25
D 0.15 G 0.6 48.5 X X 49 14.25 D 0.6 G 0.15 41.2 X 50 14.7 D 0.15 H
0.15 38.9 X 51 14.25 D 0.15 H 0.6 46.7 X 52 14.25 D 0.6 H 0.15 45.6
X 53 14.7 D 0.15 I 0.15 35.3 X 54 14.25 D 0.15 I 0.6 45.5 X 55
14.25 D 0.6 I 0.15 33.6 X 56 14.7 D 0.15 J 0.15 13.7 X 57 14.25 D
0.15 J 0.6 35.8 X 58 14.25 D 0.6 J 0.15 42.1 X 59 14.7 D 0.15 E
0.15 38.7 X 60 14.25 D 0.15 E 0.6 43.0 X X 61 14.25 D 0.6 E 0.15
2.7 X 62 14.85 D 0.015 I 0.135 27.8 X 63 14.85 D 0.015 V 0.135 10.3
X 64 14.25 E 0.60 R 0.15 12.0 X 65 14.25 E 0.15 R 0.60 25.6 X 66
14.7 E 0.15 R 0.15 28.6 X X 67 14.7 F 0.15 H 0.15 11.6 X 68 14.25 F
0.15 H 0.6 4.8 X 69 14.25 F 0.6 H 0.15 19.0 X X 70 14.7 F 0.15 I
0.15 29.7 X X 71 14.25 F 0.15 I 0.6 3.0 X 72 14.25 F 0.6 I 0.15
19.9 X 73 14.7 F 0.15 J 0.15 25.3 X 74 14.25 F 0.15 J 0.6 11.2 X 75
14.25 F 0.6 J 0.15 8.6 X 76 14.7 F 0.15 E 0.15 8.1 X 78 14.25 F
0.15 E 0.6 20.3 X X 79 14.25 F 0.6 E 0.15 32.5 X X 80 14.85 F 0.075
R 0.075 17.8 X X 81 14.85 F 0.075 U 0.075 7.0 X 82 14.7 G 0.15 H
0.15 31.4 X 83 14.25 G 0.15 H 0.6 10.3 X 84 14.25 G 0.6 H 0.15 6.6
X 85 14.7 G 0.15 I 0.15 28.2 X X 86 14.25 G 0.15 I 0.6 2.4 X 87
14.25 G 0.6 I 0.15 24.1 X X 88 14.7 G 0.15 J 0.15 25.4 X 89 14.25 G
0.15 J 0.6 25.3 X 90 14.25 G 0.6 J 0.15 10.8 X 91 14.7 G 0.15 E
0.15 14.7 X X 92 14.25 G 0.15 E 0.6 5.3 X 93 14.25 G 0.6 E 0.15
26.7 X X 94 14.85 G 0.075 R 0.075 7.8 X 95 14.85 G 0.075 U 0.075
17.4 X X 96 14.7 H 0.15 J 0.15 35.7 X 97 14.25 H 0.15 J 0.6 35.1 X
98 14.25 H 0.6 J 0.15 10.7 X 99 14.7 H 0.15 E 0.15 18.5 X 100 14.25
H 0.15 E 0.6 33.2 X 101 14.25 H 0.6 E 0.15 26.1 X 102 14.7 I 0.15 J
0.15 35.0 X 103 14.25 I 0.15 J 0.6 34.8 X 104 14.25 I 0.6 J 0.15
7.2 X 105 14.7 I 0.15 E 0.15 5.7 X 106 14.25 I 0.15 E 0.6 2.9 X 107
14.25 I 0.6 E 0.15 22.7 X 108 14.7 W 0.15 M 0.15 27.4 X 109 14.7 W
0.15 R 0.15 24.8 X X 110 14.7 W 0.15 X 0.15 7.7 X 111 14.7 W 0.15 T
0.15 17.3 X 112 14.7 W 0.15 U 0.15 3.9 X 113 14.7 W 0.15 Y 0.15 4.2
X 114 14.85 W 0.075 E 0.075 1.8 115 14.85 W 0.015 E 0.135 6.1 X 116
14.85 W 0.075 I 0.075 32.1 X X 117 14.85 W 0.015 I 0.135 4.8 X 118
14.85 W 0.015 F 0.135 1.8 119 14.85 W 0.135 F 0.015 2.2 X 120 14.85
W 0.015 G 0.135 13.1 X X 121 14.85 W 0.135 G 0.015 1.2 122 14.7 V
0.15 M 0.15 19.7 X 123 14.7 V 0.15 R 0.15 10.1 X 124 14.7 V 0.15 X
0.15 7.3 X 125 14.7 V 0.15 T 0.15 11.3 X 126 14.7 V 0.15 U 0.15
23.0 X X 127 14.7 V 0.15 Y 0.15 19.8 X X 128 14.85 V 0.075 E 0.075
18.2 X X 129 14.85 V 0.015 E 0.135 7.2 X X 130 14.85 V 0.075 I
0.075 23.2 X X 131 14.85 V 0.015 I 0.135 25.5 X X 132 14.85 V 0.015
F 0.135 8.9 X 133 14.85 V 0.135 F 0.015 29.3 X X 134 14.85 V 0.015
G 0.135 17.1 X X 135 14.85 V 0.135 G 0.015 37.8 X X 136 14.7 Z 0.15
M 0.15 25.3 X X 137 14.7 Z 0.15 R 0.15 26.2 X X 138 14.7 Z 0.15 X
0.15 20.1 X 139 14.7 Z 0.15 T 0.15 3.8 X 140 14.7 Z 0.15 U 0.15 2.2
X 141 14.7 Z 0.15 Y 0.15 1.5 142 14.25 AA 0.6 R 0.15 6.4 X 143
14.25 AA 0.15 R 0.6 25.7 X 144 14.7 AA 0.15 R 0.15 15.5 X 145 14.25
AA 0.6 E 0.15 17.8 X X 146 14.25 AA 0.15 E 0.6 36.7 X X 147 14.7 AA
0.15 E 0.15 9.7 X 148 14.25 BB 0.6 R 0.15 31.6 X X 149 14.25 BB
0.15 R 0.6 30.3 X X 150 14.7 BB 0.15 R 0.15 34.9 X X 151 14.25 BB
0.6 E 0.15 34.1 X 152 14.25 BB 0.15 E 0.6 32.7 X X 153 14.7 BB 0.15
E 0.15 29.3 X X 154 14.25 R 0.6 I 0.15 2.0 155 14.25 R 0.15 I 0.6
28.0 X 156 14.7 R 0.15 I 0.15 8.1 X 157 14.7 S 0.15 I 0.15 8.2 X
158 14.7 S 0.15 M 0.15 17.7 X 159 14.7 CC 0.15 I 0.15 7.0 X 160
14.7 CC 0.15 M 0.15 2.3 X 161 14.85 DD 0.015 A 0.135 1.5 162 14.85
EE 0.015 A 0.135 9.7 X X
[0100] As shown in Table 1, almost all the binary mixtures
exhibited good cleaning when compared to the control. The
synergistic relationship exhibited by some of the mixtures of
different surfactant classes was highly unexpected and is denoted
in the column labeled enhanced cleaning. Results were considered
unexpected when a .DELTA.E value greater the average of the two
single surfactant .DELTA.E values resulted from an experiment. Such
unexpected results are noted with a mark in all the columns, infra,
entitled "enhanced cleaning."
[0101] Table 2 shows the results of using a mixture of two
different surfactants from different surfactant classes in a linear
volatile siloxane. A solution of MD.sub.2M was used as a
control.
3TABLE 2 Binary Mixtures of Surfactants in MD2M Surf delta Good
Enhanced Run MD2M Surfactant amt 2 amt E Cleaning Cleaning 163
14.85 A 0.075 E 0.075 18.6 X X 164 14.85 C 0.075 R 0.075 30.5 X X
165 14.85 F 0.075 I 0.075 12.6 X 166 14.85 G 0.075 I 0.075 17.0 X X
167 14.85 G 0.075 E 0.075 5.7 X 168 14.85 Z 0.075 R 0.075 24.0 X X
169 14.85 E 0.075 R 0.075 12.7 X 170 14.85 BB 0.075 E 0.075 43.8 X
171 14.85 BB 0.075 R 0.075 54.8 X 172 14.25 A 0.6 G 0.15 12.5 X X
173 14.7 A 0.15 E 0.15 19.3 X 174 14.25 A 0.6 J 0.15 25.5 X X 175
14.7 C 0.15 R 0.15 10.0 X 176 14.25 D 0.15 F 0.6 54.5 X 177 14.25 D
0.15 G 0.6 34.3 X 178 14.25 D 0.15 E 0.6 40.6 X 179 14.7 F 0.15 I
0.15 14.5 X 180 14.25 F 0.6 E 0.15 9.4 X 181 14.7 G 0.15 I 0.15
37.4 X 182 14.7 G 0.15 E 0.15 16.5 X 183 14.7 Z 0.15 R 0.15 35.4 X
184 14.85 V 0.075 E 0.075 27.2 X X 185 14.85 V 0.075 I 0.075 26.5 X
X 186 14.85 F 0.075 R 0.075 13.5 X 187 14.7 E 0.15 R 0.15 25.3 X
188 14.7 BB 0.15 E 0.15 49.2 X 189 14.7 BB 0.15 R 0.15 46.1 X
control 15 -- -- -- -- 1.9 X
[0102] Table 2 shows good cleaning behavior in linear siloxane
solvent. Several binary compositions exhibited enhanced (unexpected
results) cleaning characteristics.
[0103] A cleaning composition according to the present invention
containing a cyclic siloxane (D.sub.5) and a mixture of three or
more surfactants from different surfactant classes was made. Fabric
swatches were cleaned using the above procedure, and the color
difference was measured to determine the effectiveness of the
cleaning composition. A solution of cyclic siloxane (D.sub.5)
without a surfactant was used as a control.
4TABLE 3 Mixtures of Three or More Surfactants Exp D5 Surf Amt Surf
Amt Surf Amt # pbw 1 pbw 2 pbw 3 pbw Water .DELTA.E 190 99 A 0.45 R
0.45 V 0.1 -- 22.6 191 95 A 2.25 R 2.25 V 0.5 -- 11.9 192 98 A 0.45
R 0.45 V 0.1 1 13.7 193 99 A 0.45 R 0.45 I 0.1 -- 14.1 194 95 A
2.25 R 2.25 I 0.5 -- 10.5 195 98 A 0.45 R 0.45 I 0.1 1 3.1 196 99 A
0.45 R 0.45 E 0.1 -- 28.3 197 95 A 2.25 R 2.25 E 0.5 -- 5.6 198 98
A 0.45 R 0.45 E 0.1 1 16.4 199 99 F 0.1 R 0.45 I 0.1 -- 20.4 200 95
F 0.5 R 2.25 I 2.25 -- 14.1 201 98 F 0.1 R 0.45 I 0.1 1 15.7 202 99
E 0.45 I 0.45 R 0.1 -- 9.4 203 95 E 2.45 I 2.45 R 0.1 -- 4.3 204 98
E 0.45 I 0.45 R 0.1 1 12.9 205 99 E 0.45 I 0.45 V 0.1 -- 7.9 206 95
E 2.45 I 2.45 V 0.1 -- 13.1 207 98 E 0.45 I 0.45 V 0.1 1 5.4 208 99
E 0.45 I 0.45 F 0.1 -- 17.5 209 95 E 2.45 I 2.45 F 0.1 -- 2.5 210
98 E 0.45 I 0.45 F 0.1 1 2.6
[0104] Table 3 shows that good cleaning can be obtained from
mixtures of three organic surfactants with water optionally
present.
5TABLE 4 Higher Order Mixtures Surf. Amt Surf. Amt Surf. Amt Surf.
Amt Surf. Amt Delta Run D.sub.5 1 (g) 2 (g) 3 (g) 4 (g) 5 (g) E 1
14.34 B 0.35 F 0.11 K 0.05 J 0.11 M 0.05 25.2 2 14.25 B 0.1 F 0.15
-- -- J 0.5 -- -- 34.1 3 14.25 A 0.1 F 0.15 -- -- J 0.5 -- -- 35.9
4 14.25 C 0.1 F 0.15 -- -- J 0.5 -- -- 34.6 5 14.25 -- -- F 0.15 L
0.1 J 0.5 -- -- 39.1 6 14.34 C 0.35 F 0.11 K 0.05 J 0.11 H 0.05
14.7 7 14.34 B 0.35 F 0.11 L 0.05 J 0.11 H 0.05 12.6 8 14.34 A 0.05
F 0.11 K 0.35 J 0.11 H 0.05 24.6 9 14.25 B 0.1 F 0.15 -- -- J 0.5
-- -- 36.8 10 14.34 C 0.35 F 0.11 L 0.05 J 0.11 M 0.05 20.9 11
14.25 B 0.30 F 0.15 K 0.15 -- -- I 0.15 13.3
[0105] Table 4 shows cleaning benefits derived from a multiple
combination of organic surfactants.
[0106] Concentrates of surfactants were also made as exemplified by
the following 2 examples.
[0107] Concentrate 1:4 parts surfactant B, 2 parts, surfactant E, 2
parts surfactant K and 2 parts surfactant I were added together in
an appropriate container and stirred to form a homogeneous
solution.
[0108] Concentrate 2:2 parts surfactant E, 2 parts, surfactant A;
and 2 parts surfactant R were added together in an appropriate
container and stirred to form a homogeneous solution.
[0109] The present invention exhibits improved performance of dry
cleaning agents for stain removal, particularly water soluble
stains, through the addition of a mixture of different classes of
surfactants, and optionally, water.
Examples (Group B)
[0110] The respective cleaning compositions used in Examples 1-162
were each prepared by combining the components listed below in the
relative amounts set forth below in TABLES I - XIV below:
[0111] methyl terminated tetradimethyl siloxane ("MD.sub.2M");
[0112] decamethylcyclopentasiloxane ("D.sub.5");
[0113] polyether siloxane compounds, each according to structural
formula XVI above, were used:
6 Ratio Number average Polyether C.sub.2H.sub.4O: molecular weight
(MW.sub.n) siloxane e f g C.sub.3H.sub.6O of polyether substituent
R.sup.42 A 2 20 3 50:50 1700 H B 2 15 5 100:0 550 H C 0 3 0 100:0
900 H D 0 3 0 100:0 200 H E 2 500 6.5 50:50 1700 H F 2 400 18 100:0
550 H G 2 2 2.5 100:0 450 H H 2 12 4 100:0 450 H I 2 47 5 100:0 450
H J 2 92 6 100:0 450 H K 2 40 4 50:50 1500 Bu L 2 8 2 0:100 1250 Bu
M 2 0 18 50:50 1500 Bu
[0114] A first set of textile samples (2".times.2" squares of red
satin textile) were soiled with polar stains by pipetting droplets
of an 8 wt % aqueous sodium chloride solution on each of the
textile samples of the set. A second set of textile samples were
soiled with nonpolar stains by pipetting droplets of fresh motor
oil (Quaker State SAE 10W-30) on each of the textile samples of the
set. Each of the dry cleaning compositions was then placed in a 4
ounce bottle. Each of the soiled textile samples was contacted with
a respective one of the cleaning compositions by immersing the
soiled textile sample in 50 g of one of the cleaning compositions.
The textile samples and cleaning compositions were agitated by
gently shaking each of the bottles. Following agitation, each of
the textile samples was removed from the cleaning composition,
allowed to drain, blotted and then heated at .about.50.degree. C.
to dry the samples. The appearance of each of the dried textile
samples was then evaluated by visual inspection and rated on the
following scale (an average of three readings is reported):
[0115] Rating
[0116] 5=complete removal of stain
[0117] 4=slight stain remaining
[0118] 3=moderate stain removal
[0119] 2=slight stain removal
[0120] 1=no stain removal
[0121] The amounts of linear, branched and cyclic siloxanes,
polyether siloxane and water used in each of Examples 1-130, as
well as the type of stain he results obtained in each of those
examples are set forth in TABLES I-IX below.
7 TABLE I Polyether MD.sub.2M, Siloxane, H.sub.2O, EX Amount
Polyether Amount Amount Clean- # (g) Stain Siloxane (g) (g) ing 1
49.5 Salt -- -- -- 2.7 2 49.5 Salt A 0.5 -- 4 3 49 Salt A 0.5 0.5
4.3 4 49.5 Salt F 0.5 -- 3.7 5 49 Salt F 0.5 0.5 3.7 6 49.5 Salt B
0.5 -- 4 7 49 Salt B 0.5 0.5 4 8 49.5 Salt C 0.5 -- 3.3 9 49 Salt C
0.5 0.5 4 10 49.5 Salt D 0.5 -- 5 11 49 Salt D 0.5 0.5 4 12 49.5
Salt E 0.5 -- 3.3 13 49 Salt F 0.5 0.5 4.3 14 49.5 Salt B/E
0.25/0.25 -- 4 15 49 Salt B/E 0.25/0.25 0.5 4.7
[0122]
8 TABLE II Polyether MD.sub.2M, Siloxane, H.sub.2O, EX Amount
Polyether Amount Amount Clean- # (g) Stain Siloxane (g) (g) ing 16
47.5 Salt -- -- -- 2.7 17 47.5 Salt A 2.5 -- 4 18 47 Salt A 2.5 0.5
5 19 47.5 Salt F 2.5 -- 4 20 47 Salt F 2.5 0.5 4.7 21 47.5 Salt B
2.5 -- 4.7 22 47 Salt B 2.5 0.5 4.7 23 47.5 Salt C 2.5 -- 3.7 24 47
Salt C 2.5 0.5 5 25 47.5 Salt D 2.5 -- 4.3 26 47 Salt D 2.5 0.5 5
27 47.5 Salt E 2.5 -- 4 28 47 Salt E 2.5 0.5 4.3 29 47.5 Salt B/E
1.25/1.25 -- 4.7 30 47 Salt B/E 1.25/1.25 0.5 3.7
[0123]
9 TABLE III Polyether MD.sub.2M, Siloxane, H.sub.2O, EX Amount
Polyether Amount Amount Clean- # (g) Stain Siloxane (g) (g) ing 31
49.5 Oil -- -- -- 5 32 49.5 Oil A 0.5 -- 5 33 49 Oil A 0.5 0.5 4.3
34 49.5 Oil F 0.5 -- 4.3 35 49 Oil F 0.5 0.5 4.3 36 49.5 Oil B 0.5
-- 4.3 37 49 Oil B 0.5 0.5 4.3 38 49.5 Oil C 0.5 -- 5 39 49 Oil C
0.5 0.5 5 40 49.5 Oil D 0.5 -- 5 41 49 Oil D 0.5 0.5 5 42 49.5 Oil
E 0.5 -- 5 43 49 Oil E 0.5 0.5 4.7 44 49.5 Oil B/E 0.25/0.25 -- 4.7
45 49 Oil B/E 0.25/0.25 0.5 4.7
[0124]
10 TABLE IV Polyether MD.sub.2M, Siloxane, H.sub.2O, EX Amount
Polyether Amount Amount Clean- # (g) Stain Siloxane (g) (g) ing 46
47.5 Oil -- -- -- 5 47 47.5 Oil A 2.5 -- 4.3 48 47 Oil A 2.5 0.5 5
49 47.5 Oil F 2.5 -- 4.7 50 47 Oil F 2.5 0.5 4.3 51 47.5 Oil B 2.5
-- 5 52 47 Oil B 2.5 0.5 4.3 53 47.5 Oil C 2.5 -- 5 54 47 Oil C 2.5
0.5 4 55 47.5 Oil D 2.5 -- 5 56 47 Oil D 2.5 0.5 5 57 47.5 Oil E
2.5 -- 5 58 47 Oil E 2.5 0.5 5 59 47.5 Oil B/E 1.25/1.25 -- 4.7 60
47 Oil B/E 1.25/1.25 0.5 4.3
[0125]
11 TABLE V D.sub.5/ Polyether MD.sub.2M, Siloxane, H.sub.2O, EX
Amount Polyether Amount Amount Clean- # (g) Stain Siloxane (g) (g)
ing 61 24.75/24.75 Salt -- -- -- 3 62 24.75/24.75 Salt A 0.5 -- 4.3
63 24.5/24.5 Salt A 0.5 0.5 4 64 24.75/24.75 Salt F 0.5 -- 4 65
24.5/24.5 Salt F 0.5 0.5 5 66 24.75/24.75 Salt B 0.5 -- 4.3 67
24.5/24.5 Salt B 0.5 0.5 5 68 24.75/24.75 Salt C 0.5 -- 3.3 69
24.5/24.5 Salt C 0.5 0.5 4 70 24.75/24.75 Salt D 0.5 -- 4.3 71
24.5/24.5 Salt D 0.5 0.5 5 72 24.75/24.75 Salt E 0.5 -- 4 73
24.5/24.5 Salt E 0.5 0.5 4.7 74 24.75/24.75 Salt B/E 0.25/0.25 --
3.3 75 24.5/24.5 Salt B/E 0.25/0.25 0.5 4
[0126]
12 TABLE VI Polyether Siloxane, H.sub.2O, EX D.sub.5/MD.sub.2M,
Polyether Amount Amount Clean- # Amount (g) Stain Siloxane (g) (g)
ing 76 24.75/24.75 Salt -- -- -- 2.7 77 23.75/23.75 Salt A 2.5 --
4.3 78 23.5/23.5 Salt A 2.5 0.5 5 79 23.75/23.75 Salt F 2.5 -- 4 80
23.5/23.5 Salt F 2.5 0.5 4.7 81 23.75/23.75 Salt B 2.5 -- 4.7 82
23.5/23.5 Salt B 2.5 0.5 4.7 83 23.75/23.75 Salt C 2.5 -- 3.3 84
23.5/23.5 Salt C 2.5 0.5 5 85 23.75/23.75 Salt D 2.5 -- 4.7 86
23.5/23.5 Salt D 2.5 0.5 5 87 23.75/23.75 Salt E 2.5 -- 4 88
23.5/23.5 Salt E 2.5 0.5 4 89 23.75/23.75 Salt B/E 1.25/1.25 -- 4.7
90 23.5/23.5 Salt B/E 1.25/1.25 0.5 3.7
[0127]
13 TABLE VII Polyether Siloxane, H.sub.2O, EX D.sub.5/MD.sub.2M,
Polyether Amount Amount Clean- # Amount (g) Stain Siloxane (g) (g)
ing 91 24.75/24.75 Oil -- -- -- 3 92 24.75/24.75 Oil A 0.5 -- 4.7
93 24.5/24.5 Oil A 0.5 0.5 4.7 94 24.75/24.75 Oil F 0.5 -- 4.3 95
24.5/24.5 Oil F 0.5 0.5 4.7 96 24.75/24.75 Oil B 0.5 -- 4.3 97
24.5/24.5 Oil B 0.5 0.5 4.7 98 24.75/24.75 Oil C 0.5 -- 4.7 99
24.5/24.5 Oil C 0.5 0.5 4 100 24.75/24.75 Oil D 0.5 -- 5 101
24.5/24.5 Oil D 0.5 0.5 5 102 24.75/24.75 Oil E 0.5 -- 5 103
24.5/24.5 Oil E 0.5 0.5 4.7 104 24.75/24.75 Oil B/E 0.25/0.25 --
4.3 105 24.5/24.5 Oil B/E 0.25/0.25 0.5 4.3
[0128]
14 TABLE VIII Polyether Siloxane, H.sub.2O, EX D.sub.5/MD.sub.2M,
Polyether Amount Amount Clean- # Amount (g) Stain Siloxane (g) (g)
ing 106 24.75/24.75 Oil -- -- -- 5 107 23.75/23.75 Oil A 2.5 -- 4.7
108 23.5/23.5 Oil A 2.5 0.5 5 109 23.75/23.75 Oil F 2.5 -- 4.7 110
23.5/23.5 Oil F 2.5 0.5 4.7 111 23.75/23.75 Oil B 2.5 -- 5 112
23.5/23.5 Oil B 2.5 0.5 4.3 113 23.75/23.75 Oil C 2.5 -- 5 114
23.5/23.5 Oil C 2.5 0.5 5 115 23.75/23.75 Oil D 2.5 -- 5 116
23.5/23.5 Oil D 2.5 0.5 5 117 23.75/23.75 Oil E 2.5 -- 5 118
23.5/23.5 Oil E 2.5 0.5 5 119 23.75/23.75 Oil B/E 1.25/1.25 -- 4.7
120 23.5/23.5 Oil B/E 1.25/1.25 0.5 4.3
[0129]
15 TABLE IX Polyether Siloxane, H.sub.2O, EX D.sub.5/MD.sub.2M,
Polyether Amount Amount Clean- # Amount (g) Stain Siloxane (g) (g)
ing 121 4.95/44.55 Salt E 0.5 -- 2.7 122 4.9/44.1 Salt E 0.5 0.5 5
123 12.37/37.13 Salt E 0.5 -- 3 124 12.25/36.75 Salt E 0.5 0.5 4.7
125 24.75/24.75 Salt E 0.5 -- 3.5 126 24.5/24.5 Salt E 0.5 0.5 4.5
127 37.13/12.37 Salt E 0.5 -- 3 128 36.75/12.25 Salt E 0.5 0.5 5
129 44.55/4.95 Salt E 0.5 -- 2.7 130 44.10/4.9 Salt E 0.5 0.5
4.7
[0130] Examples 131-162 were conducted using 2".times.2" blue 60/40
cotton polyester textile swatches. The salt concentration in the
salt solution used to stain the swatches was either 20%, 8% or 7%
by weight, as noted in the TABLES X-XIV below. The testing was
conducted in the same manner as and the results ranked on the same
scale as in Examples 1-130 above. The amounts of linear or cyclic
siloxane, polyether siloxane and water used in each of Examples
131-162, as well as the type of stain and the results obtained in
each of those examples are set forth in TABLES X-XIV below.
16 TABLE X Polyether Siloxane, H.sub.2O, EX MD.sub.2M, Stain
Polyether Amount Amount Clean- # Amount (g) (20%) Siloxane (g) (g)
ing 131 49.5 Salt -- -- -- 3 132 49.5 Salt E 0.5 -- 2.7 133 49 Salt
E 0.5 0.5 3 134 49.5 Salt C 0.5 -- 4 135 49 Salt C 0.5 0.5 4.3 136
49 Oil -- -- -- 5 137 49.5 Oil E 0.5 -- 5 138 49 Oil E 0.5 0.5 5
139 49.5 Oil C 0.5 -- 5 140 49 Oil C 0.5 0.5 5 141 49 Salt E 0.5
1.5 4.7
[0131]
17 TABLE XI Polyether Siloxane, H.sub.2O, EX MD.sub.2M, Stain
Polyether Amount Amount Clean- # Amount (g) (7%) Siloxane (g) (g)
ing 142 49.5 Salt -- -- -- 3 143 49.5 Salt E 0.5 -- 3 144 49 Salt E
0.5 0.5 5 145 49.5 Salt C 0.5 -- 4.3 146 49 Salt C 0.5 0.5 4
[0132]
18 TABLE XII Polyether Siloxane, H.sub.2O, EX D.sub.5/MD.sub.2M,
Stain Polyether Amount Amount Clean- # Amount (g) (20%) Siloxane
(g) (g) ing 147 24.75/24.75 Salt -- -- -- 3.3 148 24.75/24.75 Salt
E 0.5 -- 3.3 149 24.5/24.5 Salt E 0.5 0.5 3 150 24.75/24.75 Salt C
0.5 -- 4 151 24.5/24.5 Salt C 0.5 0.5 4.7 152 24.75/24.75 Oil -- --
-- 5 153 24.75/24.75 Oil E 0.5 -- 5 154 24.5/24.5 Oil E 0.5 0.5 5
155 24.75/24.75 Oil C 0.5 -- 5 156 24.5/24.5 Oil C 0.5 0.5 5 157
24.75/24.75 Salt E 0.5 1.5 3.3
[0133]
19 TABLE XIII Polyether Siloxane, H.sub.2O, EX MD.sub.2M, Stain
Polyether Amount Amount Clean- # Amount (g) (7%) Siloxane (g) (g)
ing 158 24.75/24.75 Salt -- -- -- 3.3 159 24.75/24.75 Salt E 0.5 --
2 160 24.5/24.5 Salt E 0.5 0.5 4.7 151 24.75/24.75 Salt C 0.5 -- 3
152 24.5/24.5 Salt C 0.5 0.5 2
[0134]
20 TABLE XIV Polyether Siloxane, H.sub.2O, EX D.sub.5/MD.sub.2M,
Stain Polyether Amount Amount Clean- # Amount (g) (8%) Siloxane (g)
(g) ing 153 4.95/44.55 Salt E 0.5 -- 2.7 154 4.9/44.1 Salt E 0.5
0.5 3.7 155 12.37/37.13 Salt E 0.5 -- 3.3 156 12.25/36.75 Salt E
0.5 0.5 4.3 157 24.75/24.75 Salt E 0.5 -- 4 158 24.5/24.5 Salt E
0.5 0.5 4.3 159 37.13/12.37 Salt E 0.5 -- 3.7 160 36.75/12.25 Salt
E 0.5 0.5 3.7 161 44.55/4.95 Salt E 0.5 -- 3.3 162 44.10/4.9 Salt E
0.5 0.5 4
* * * * *