U.S. patent application number 09/208215 was filed with the patent office on 2003-02-20 for uncomplexed cyclodextrin compositions for odor and wrinkle control.
Invention is credited to BOLICH, RAYMOND EDWARD JR., BURNS, ANTHONY JAMES, CAMPBELL, WILLIAM TUCKER, CHUNG, ALEX HAEJOON, COBB, DANIEL SCOTT, MERMELSTEIN, ROBERT, PEFFLY, MARJORIE MOSSMAN, ROSENBALM, ERIN LYNN, SCHNEIDERMAN, EVA, STREUTKER, ALEN DAVID, TORDIL, HELEN BERNARDO, TRINH, TOAN, WARD, THOMAS EDWARD, WOLFF, ANN MARGARET, WOO, RICKY AH-MAN.
Application Number | 20030035748 09/208215 |
Document ID | / |
Family ID | 22075658 |
Filed Date | 2003-02-20 |
United States Patent
Application |
20030035748 |
Kind Code |
A1 |
TRINH, TOAN ; et
al. |
February 20, 2003 |
UNCOMPLEXED CYCLODEXTRIN COMPOSITIONS FOR ODOR AND WRINKLE
CONTROL
Abstract
The present invention relates to a stable, aqueous
odor-absorbing and wrinkle controlling composition, preferably for
use on inanimate surfaces, especially fabrics. The composition
comprises from about 0.1% to about 20%, by weight of the
composition, of solubilized, water-soluble, uncomplexed
cyclodextrin and an effective amount of at least one ingredient to
improve the performance of the composition selected from the group
consisting of: (1) cyclodextrin compatible surfactant; (2)
cyclodextrin compatible antimicrobial active; and (3) mixtures
thereof. The composition also comprises a wrinkle control agent
which is fabric lubricant, shape retention polymer, hydrophilic
plasticizer, lithium salt, or mixtures thereof. Hydrophilic perfume
improves acceptance. Optionally, the composition can contain low
molecular weight polyols; metallic salts to help control odor; a
humectant, etc. The composition is essentially free of any material
that would soil or stain fabric. The composition is preferably
applied as small particle size droplets, especially from spray
containers. The cyclodextrin/surfactant combination, either alone,
or in combination with the other ingredients, provides improved
antimicrobial activity.
Inventors: |
TRINH, TOAN; (MAINEVILLE,
OH) ; BOLICH, RAYMOND EDWARD JR.; (MAINEVILLE,
OH) ; TORDIL, HELEN BERNARDO; (WEST CHESTER, OH)
; MERMELSTEIN, ROBERT; (CINCINNATI, OH) ; PEFFLY,
MARJORIE MOSSMAN; (CINCINNATI, OH) ; WOO, RICKY
AH-MAN; (HAMILTON, OH) ; COBB, DANIEL SCOTT;
(LOVELAND, OH) ; SCHNEIDERMAN, EVA; (FAIRFIELD,
OH) ; WOLFF, ANN MARGARET; (CINCINNATI, OH) ;
ROSENBALM, ERIN LYNN; (FAIRFIELD, OH) ; WARD, THOMAS
EDWARD; (OREGONIA, OH) ; CHUNG, ALEX HAEJOON;
(WEST CHESTER, OH) ; BURNS, ANTHONY JAMES; (WEST
CHESTER, OH) ; CAMPBELL, WILLIAM TUCKER; (WEST
CHESTER, OH) ; STREUTKER, ALEN DAVID; (FLORENCE,
KY) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY
INTELLECTUAL PROPERTY DIVISION
WINTON HILL TECHNICAL CENTER - BOX 161
6110 CENTER HILL AVENUE
CINCINNATI
OH
45224
US
|
Family ID: |
22075658 |
Appl. No.: |
09/208215 |
Filed: |
December 9, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09208215 |
Dec 9, 1998 |
|
|
|
09067385 |
Apr 27, 1998 |
|
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|
Current U.S.
Class: |
422/5 ; 252/8.61;
252/8.81; 252/8.91; 424/76.1 |
Current CPC
Class: |
D06M 16/00 20130101;
C11D 3/3742 20130101; C11D 3/3738 20130101; C11D 3/48 20130101;
C11D 3/502 20130101; A61K 8/738 20130101; C11D 3/33 20130101; D06M
2200/20 20130101; D06M 23/06 20130101; C11D 3/373 20130101; D06F
58/203 20130101; C11D 3/222 20130101; C11D 1/008 20130101; D06M
15/03 20130101; D06M 13/005 20130101; A61Q 15/00 20130101 |
Class at
Publication: |
422/5 ; 252/8.61;
252/8.81; 252/8.91; 424/76.1 |
International
Class: |
A61L 009/01 |
Claims
What is claimed is:
1. A method of treating fabric to reduce wrinkles in said fabric
with an effective amount of stable, aqueous odor-absorbing and
wrinkle reducing composition, said composition comprising: (A). an
effective amount to absorb malodors of solubilized, uncomplexed
cyclodextrin; (B). optionally, an effective amount to improve the
performance of the composition, of cyclodextrin compatible
surfactant; (C). optionally, an effective amount, to kill, or
reduce the growth of microorganisms, of cyclodextrin compatible and
water soluble antimicrobial active; (D). optionally, an effective
amount to improve acceptance of the composition of hydrophilic
perfume containing at least about 50% by weight of the perfume of
ingredients having a ClogP of less than about 3.5 and, optionally,
a minor amount of perfume ingredients selected from the group
consisting of ambrox, bacdanol, benzyl salicylate, butyl
anthranilate, cetalox, damascenone, alpha-damascone,
gamma-dodecalactone, ebanol, herbavert, cis-3-hexenyl salicylate,
alpha-ionone, beta-ionone, alpha-isomethylionone, lilial, methyl
nonyl ketone, gamma-undecalactone, undecylenic aldehyde, and
mixtures thereof; (E). optionally, from about 0.01% to about 3% by
weight of the composition of low molecular weight polyol; (F).
optionally, from about 0.001% to about 0.3% by weight of the
composition of aminocarboxylate chelator; (G). optionally, an
effective amount of metallic salt for improved odor benefit; (H)
optionally, an effective amount of enzyme for improved odor control
benefit; (I). optionally, an effective amount of solubilized,
water-soluble, antimicrobial preservative; (J) an effective amount
of cyclodextrin compatible fabric wrinkle control agent; and (K).
aqueous carrier, said composition being essentially free of any
material that would soil or stain fabric under usage conditions and
having a pH of more than about 3.5, and said composition being
applied as very small droplets having a weight average diameter of
from about 10 .mu.m to about 120 .mu.m.
2. The method of claim 1 wherein said cyclodextrin compatible
fabric wrinkle control agent is selected from the group consisting
of: cyclodextrin compatible fiber lubricants; cyclodextrin
compatible shape retention polymers; cyclodextrin compatible
plasticizers; cyclodextrin compatible lithium salts; and mixtures
thereof.
3. The method of claim 2 wherein said cyclodextrin compatible
fabric wrinkle control agent is cyclodextrin compatible fiber
lubricant.
4. The method of claim 3 wherein said cyclodextrin compatible fiber
lubricant is a silicone.
5. The method of claim 4 wherein said silicone is volatile and is
present at a level of from about 0.1% to about 5%.
6. The method of claim 5 wherein said volatile silicone has the
formula [(CH.sub.3).sub.2SiO)].sub.5.
7. The method of claim 4 wherein said silicone is present at a
level of from about 0.1% to about 5% by weight and is selected from
the group consisting of: a. polyalkyl silicone with the following
structure:
A--Si(R.sub.2)--O--[Si(R.sub.2)--O--].sub.q--Si(R.sub.2)--A wherein
each R is an alkyl, a hydroxy, or a hydroxyalkyl group, and
mixtures thereof, having less than about 8 carbon atoms; q is an
integer from about 7 to about 8,000; each A is a group selected
from hydrogen, methyl, methoxy, ethoxy, hydroxy, and propoxy; b.
silicone having the formula:
HO--[Si(CH.sub.3).sub.2--O].sub.x--{Si(OH)[(CH.sub.2).sub.3--NH--(CH.sub.-
2).sub.2--NH.sub.2]O}.sub.y--H wherein x and y are integers; c.
silicone material having the formula:
(R.sup.1).sub.aG.sub.3-a--Si--(--OSiG.sub.2)-
.sub.n--(OSiG.sub.b(R.sup.1).sub.2-b).sub.m--O--SiG.sub.3-a(R.sup.1).sub.a
wherein G is selected from the group consisting of hydrogen, OH,
and/or C.sub.1-C.sub.5 alkyl; a denotes 0 or an integer from 1 to
3; b denotes 0 or 1; the sum of n+m is a number from 1 to about
2,000; R.sup.1 is a monovalent radical of formula C.sub.pH.sub.2pL
in which p is an integer from 2 to 4 and L is selected from the
group consisting of:
--N(R.sup.2)CH.sub.2--CH.sub.2--N(R.sup.2).sub.2;
--N(R.sup.2).sub.2; --N.sup.+(R.sup.2).sub.3A.sup.-; and
--N.sup.+(R.sup.2)CH.sub.2--CH.sub.2- N.sup.+H.sub.2A.sup.-wherein
each R.sup.2 is chosen from the group consisting of hydrogen, a
C.sub.1-C.sub.5 saturated hydrocarbon radical, and each A.sup.-
denotes compatible anion; d. silicones having the formula:
R.sup.3--N.sup.+(CH.sub.3).sub.2--Z--[Si(CH.sub.3).sub.2O].sub.f-
--Si(CH.sub.3).sub.2--Z--N.sup.+(CH.sub.3).sub.2--R.sup.3.2CH.sub.3COO.sup-
.-wherein Z=--CH.sub.2--CH(OH)--CH.sub.2O--CH.sub.2).sub.3--R.sup.3
denotes a long chain alkyl group; and f denotes an integer of at
least about 2; and e. mixtures thereof.
8. The method of claim 7 wherein said silicone is polyalkyl
silicone
A--Si(R.sub.2)--O--[Si(R.sub.2)--O--].sub.q--Si(R.sub.2)--A with A
and R groups being methyl.
9. The method of claim 7 wherein said silicone is present at a
level of from about 0.2% to about 4% by weight and has a viscosity
of from about 10 cst to about 2,000,000 cst.
10. The method of claim 3 wherein said cyclodextrin compatible
fiber lubricant is finely divided polyethylene.
11. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent is from about 0.05% to about 10% of shape
retention polymer which is a homopolymer and/or a copolymer.
12. The method of claim II wherein the shape retention polymer is
homopolymer and/or copolymer having a glass transition temperature
of from about -20.degree. C. to about 150.degree. C. and comprising
monomers selected from the group consisting low molecular weight
C.sub.1-C.sub.6 unsaturated organic mono- and polycarboxylic acids;
esters said acids with C.sub.1-C.sub.6 alcohols; amides and imides
of said acids; low molecular weight unsaturated alcohols; esters of
said alcohols with low molecular weight carboxylic; ethers of said
alcohols; polar vinyl heterocyclics; unsaturated amines and amides;
vinyl sulfonate; salts of said acids and said amines;;
C.sub.1-C.sub.4 alkyl quaternized derivatives of said amines; low
molecular weight unsaturated hydrocarbons and derivatives; and
mixtures thereof.
13. The method of claim 11 wherein the shape retention polymer
monomers are selected from the group consisting of: acrylic acid,
methacrylic acid, crotonic acid, maleic acid and its half esters,
itaconic acid, and esters of said acids with methanol, ethanol,
1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol,
2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol,
3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol,
3-methyl-1-pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol,
and mixtures thereof; methyl acrylate; ethyl acrylate; t-butyl
acrylate; methyl methacrylate; hydroxyethyl methacrylate; methoxy
ethyl methacrylate; N,N-dimethylacrylamide; N-t-butyl acrylamide;
maleimides; vinyl alcohol; allyl alcohol; vinyl acetate; vinyl
propionate; methyl vinyl ether; vinyl pyrrolidone; vinyl
caprolactam; vinyl pyridine; vinylimidazole; vinyl amine;
diethylene triamine; dimethylaminoethyl methacrylate; ethenyl
formamide; vinyl sulfonate; ethylene; propylene; butadiene;
cyclohexadiene; vinyl chloride; vinylidene chloride; salts thereof
and alkyl quaternized derivatives thereof; and mixtures thereof
14. The method of claim II wherein the shape retention polymer
monomers are selected from the group consisting of: vinyl alcohol;
acrylic acid; methacrylic acid; methyl acrylate; ethyl acrylate;
methyl methacrylate; t-butyl acrylate; t-butyl methacrylate;
n-butyl acrylate; n-butyl methacrylate; dimethylaminoethyl
methacrylate; N,N-dimethyl acrylamide; N,N-dimethyl methacrylamide;
N-t-butyl acrylamide; vinylpyrrolidone; vinyl pyridine; adipic
acid; diethylenetriamine; salts thereof and alkyl quaternized
derivatives thereof; and mixtures thereof.
15. The method of claim 11 wherein said cyclodextrin compatible
wrinkle control agent is copolymer of hydrophilic monomers and
hydrophobic monomers.
16. The method of claim 15 wherein the shape retention copolymer
has a hydrophobic monomer/hydrophilic monomer ratio of from about
95:5 to about 20:80, by weight of the copolymer.
17. The method of claim 16 wherein the shape retention copolymer
has a monomer/hydrophilic monomer ratio of from about 90:10 to
about 40:60, by weight of the copolymer.
18. The method of claim 11 wherein said shape retention polymer is
present at from about 0.1% to about 5% by weight, and has a glass
transition temperature of from about -10.degree. C. to about
100.degree. C.
19. The method of claim 2 wherein said cyclodextrin wrinkle control
agent is shape retention polymer comprising starch, starch
derivatives, and mixtures thereof.
20. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent is from about 0.01% to about 5% of a
hydrophilic plasticizer consisting of a short chain polyhydric
alcohol.
21. The method of claim 20 wherein said short chain polyhydric
alcohol is selected from the group consisting of glycerol, ethylene
glycol, propylene glycol, diethylene glycol, dipropylene glycol,
and mixtures thereof.
22. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent is from about 0.1% to about 10% of lithium
salt and/or lithium salt hydrate selected from the group consisting
of: lithium bromide, lithium lactate, lithium chloride, lithium
acetate, lithium sulfate, lithium tartrate, lithium bitartrate, and
their hydrates, and mixtures thereof.
23. The method of claim 22 wherein said lithium salt and/or lithium
salt hydrate is selected from the group consisting of: lithium
bromide; lithium lactate; their hydrates; and mixtures thereof.
24. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent comprises a mixture of fiber lubricant and
shape retention polymer.
25. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent comprises a mixture of fiber lubricant and
lithium salt.
26. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent comprises a mixture of shape retention
polymer and lithium salt.
27. The method of claim 2 wherein said cyclodextrin compatible
wrinkle control agent comprises a mixture of fiber lubricant, shape
retention polymer, and lithium salt.
28. The method of claim 1 wherein said cyclodextrin is present at a
level of from about 0.01% to about 20% by weight of the
composition, said surfactant is present at a level of from about
0.01% to about 8% by weight of the composition, and said
cyclodextrin is selected from the group consisting of: methyl
substituted cyclodextrins, ethyl substituted cyclodextrins,
hydroxyalkyl substituted cyclodextrins, branched cyclodextrins,
cationic cyclodextrins, quaternary ammonium cyclodextrins, anionic
cyclodextrins, amphoteric cyclodextrins, cyclodextrins wherein at
least one glucopyranose unit has a 3-6-anhydro-cyclomalto
structure, alpha-cyclodextrin, gamma-cyclodextrin, and mixtures
thereof.
29. The method of claim 28 wherein said cyclodextrin is
hydroxypropyl beta-cyclodextrin, methylated beta-cyclodextrin,
alpha-cyclodextrin, hydroxypropyl alpha-cyclodextrin, methylated
alpha-cyclodextrin, and/or mixtures thereof.
30. The method of claim 28 wherein said cyclodextrin is present at
a level of from about 0.01% to about 5% by weight of the
composition and said surfactant is present at a level of from about
0.03% to about 5% by weight of the composition.
31. The method of claim 28 wherein said cyclodextrin is present at
a level of from about 0.5% to about 2%, by weight of the
composition and said surfactant is present at a level of from about
0.05% to about 2% by weight of the composition.
32. The method of claim 1 wherein said surfactant is selected from
the group consisting of: block copolymers of ethylene oxide and
propylene oxide; polyalkyleneoxide polysiloxanes; alkyldiphenyl
oxide disulfonate anionic surfactants, having the general formula:
4wherein R is an alkyl group; and mixtures thereof.
34. The method of claim 32 wherein said surfactant is a block
copolymer of ethylene oxide and propylene oxide.
35. The method of claim 32 wherein said surfactant is
polyalkyleneoxide polysiloxane having the general formula:
R.sup.1--(CH.sub.3).sub.2SiO--[(-
CH.sub.3).sub.2SiO].sub.a]--[(CH.sub.3)(R.sup.1)SiO].sub.b--Si(CH.sub.3).s-
ub.2--R.sup.1 wherein a +b are from about 1 to about 50, 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.4
O).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; total c (for all polyalkyleneoxy side groups)
has a value of from 1 to about 100; d is from 0 to about 14; c+d
has a value of from about 5 to about 150; 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.
36. The method of claim 32 wherein said surfactant is anionic
surfactant having the general formula: 5wherein R is an alkyl
group.
37. The method of claim 31 wherein said surfactant provides a
surface tension of from about 20 dyne/cm to about 45 dyne/cm.
38. The method of claim 1 additionally comprising at least one of
C. -I.
39. An article of manufacture comprising the composition of claim 1
in a spray dispenser.
40. The article of manufacture of claim 39 wherein said spray
dispenser comprises a trigger spray device and is capable of
providing droplets with a weight average diameter of from about 10
to about 120 .mu.m.
41. The method of controlling odor and wrinkles on fabric
comprising spraying an effective amount of the composition of claim
1 onto said fabric using a trigger-spray device.
42. The method of claim 41 wherein the droplets of the spray that
are formed by the trigger spray device have a weight average
diameter of from about 10 to about 120 .mu.m.
43. The method of controlling odor and reducing wrinkles on fabric
comprising spraying an effective amount of the composition of claim
1 onto said fabric using a non-manually operated sprayer.
44. The method of claim 43 wherein said non-manually operated
sprayer is selected from the group consisting of: powered sprayers;
air aspirated sprayers; liquid aspirated sprayers; electrostatic
sprayers; and nebulizer sprayers.
45. The method of claim 43 wherein the droplets of the spray that
are formed by the non-manually operated sprayer have a weight
average diameter of from about 10 to about 120 .mu.m.
46. An article of manufacture comprising container which contains
composition comprising: (A). an effective amount to absorb malodors
of solubilized, uncomplexed cyclodextrin; (B). optionally, an
effective amount to improve the performance of the composition, of
cyclodextrin compatible surfactant; (C). optionally, an effective
amount, to kill, or reduce the growth of microorganisms, of
cyclodextrin compatible and water soluble antimicrobial active;
(D). optionally, an effective amount to improve acceptance of the
composition of hydrophilic perfume containing at least about 50% by
weight of the perfume of ingredients having a ClogP of less than
about 3.5 and, optionally, aminor amount of perfume ingredients
selected from the group consisting of ambrox, bacdanol, benzyl
salicylate, butyl anthranilate, cetalox, damascenone,
alpha-damascone, gamma-dodecalactone, ebanol, herbavert,
cis-3-hexenyl salicylate, alpha-ionone, beta-ionone,
alpha-isomethylionone, lilial, methyl nonyl ketone,
gamma-undecalactone, undecylenic aldehyde, and mixtures thereof;
(E). optionally, from about 0.01% to about 3% by weight of the
composition of low molecular weight polyol; (F). optionally, from
about 0.001% to about 0.3% by weight of the composition of
aminocarboxylate chelator; (G). optionally, an effective amount of
metallic salt for improved odor benefit; (H) optionally, an
effective amount of enzyme for improved odor control benefit; (I).
optionally, an effective amount of solubilized, water-soluble,
antimicrobial preservative; (J) an effective amount of cyclodextrin
compatible fabric wrinkle control agent; and (K). aqueous carrier,
said composition being essentially free of any material that would
soil or stain fabric under usage conditions and having a pH of more
than about 3.5, and said article being in association with a set of
instructions to use the composition in an amount effective to
provide a solution to problems involving, and/or provision of at
least one benefit related to, those selected from the group
consisting of: killing, or reducing the level of, microorganisms;
reducing and/or providing resistance to the formation of wrinkles
in fabric; and/or reducing static in addition to the optional
instructions relating to the use of the composition for reduction
of odors.
47. An article of manufacture according to claim 46 wherein said
instructions relate to the reduction of wrinkles in fabric.
48. An article of manufacture according to claim 47 wherein said
composition contains cyclodextrin compatible fiber lubricant which
is a volatile silicone at a level of from about 0.1% to about 5% by
weight of the composition.
49. An article of manufacture according to claim 47 wherein said
composition contains wrinkle control agent is from about 0.05% to
about 10% of shape retention polymer which is a homopolymer and/or
a copolymer having a glass transition temperature of from about
-20.degree. C. to about 150.degree. C. and comprising monomers
selected from the group consisting low molecular weight
C.sub.1-C.sub.6 unsaturated organic mono- and polycarboxylic acids;
esters said acids with C.sub.1-C.sub.6 alcohols; amides and imides
of said acids; low molecular weight unsaturated alcohols; esters of
said alcohols with low molecular weight carboxylic; ethers of said
alcohols; polar vinyl heterocyclics; unsaturated amines and amides;
vinyl sulfonate; salts of said acids and said amines;;
C.sub.1-C.sub.4 alkyl quatemized derivatives of said amines; low
molecular weight unsaturated hydrocarbons and derivatives; and
mixtures thereof.
50. An article of manufacture according to claim 46 wherein said
instructions relate to the reduction of the level of microorganisms
on the surface being treated and said composition comprises from
about 0.001% to about 0.8%, by weight of the usage composition, of
said antimicrobial active which is selected from the group
consisting of: halogenated compounds, cyclic nitrogen compounds,
quaternary compounds, and phenolic compounds
51. An article of manufacture according to claim 50 wherein said
surfactant is present and is polyalkyleneoxide polysiloxane having
the general formula:
R.sup.1--(CH.sub.3).sub.2SiO--[(CH.sub.3).sub.2SiO].sub.-
a--(CH.sub.3)(R.sup.1)SiO].sub.b--Si(CH.sub.3).sub.2--R.sup.1
wherein a +b are from about 1 to about 50, 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.4
O).sub.c(C.sub.3H.sub.6O).sub- .dR.sup.2 with at least one R.sup.1
being a poly(ethyleneoxide/propyleneox- ide) copolymer group, and
wherein n is 3 or 4; total c (for all polyalkyleneoxy side groups)
has a value of from 1 to about 100; d is from 0 to about 14; c+d
has a value of from about 5 to about 150; 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
52. An article of manufacture according to claim 46 wherein said
instructions relate to the reduction of static on the treated
surface.
Description
[0001] This application is a continuation-in-part of the copending
application of T. Trinh et al., Ser. No. 09/067,385, filed Apr. 27,
1998.
TECHNICAL FIELD
[0002] The present invention relates to stable, preferably
translucent, more preferably clear, aqueous odor-absorbing and
wrinkle controlling compositions, articles of manufacture, and/or
method of use, comprising solubilized, uncomplexed cyclodextrin;
and cyclodextrin-compatible fabric wrinkle control agent; and,
preferably, cyclodextrin compatible antimicrobial active and/or
cyclodextrin compatible surfactant;, hydrophilic perfume providing
improved acceptance; or mixtures thereof. As used herein,
"cyclodextrin compatible" means that the cyclodextrin and the other
material, or active, do not substantially interact so as to
eliminate the odor controlling ability of the cyclodextrin or the
desired effect of the material or active. The odor-absorbing
composition is designed to control odors caused by a broad spectrum
of organic odoriferous materials, which may, or may not, contain
reactive functional groups, and to preferably remain shelf stable
for a substantial period of time. Preferably, the aqueous
odor-absorbing compositions are for use on inanimate surfaces,
especially fabrics, and more specifically, clothes, in order to
restore and/or maintain freshness by reducing malodor without the
need for washing or dry cleaning.
BACKGROUND OF THE INVENTION
[0003] The present invention relates to stable, preferably
translucent, more preferably clear, aqueous odor absorbing and
wrinkle controlling compositions, articles of manufacture and/or
method for use, e.g., on inanimate surfaces, primarily fabrics, and
especially cotton fabrics. Such compositions can optionally provide
a "scent signal" in the form of a pleasant odor which signals the
removal of the malodor. Preferably, the compositions are sprayed
onto fabrics, particularly clothes, to restore their freshness by
reducing malodor and/or removing wrinkles without washing or dry
cleaning. The aqueous odor-absorbing compositions are also
preferably for use on other inanimate surfaces, such as household
upholsteries, drapes, carpets, car interiors, and the like. They
also can be used on, e.g., human and animal surfaces, e.g., skin,
hair, etc.
[0004] Uncomplexed cyclodextrin molecules, which are made up of
varying numbers of glucose units provide the absorbing advantages
of known absorbent deodorizing compositions without harmful effects
to fabrics. While cyclodextrin is an effective odor absorbing
active, some small molecules are not sufficiently absorbed by the
cyclodextrin molecules because the cavity of the cyclodextrin
molecule may be too large to adequately hold the smaller organic
molecule. If a small sized organic odor molecule is not
sufficiently absorbed into the cyclodextrin cavity, a substantial
amount of malodor can remain. In order to alleviate this problem,
low molecular weight polyols can be added to the composition to
enhance the formation of cyclodextrin inclusion complexes.
Furthermore, optional water soluble metal salts can be added to
complex with some nitrogen-containing and sulfur-containing malodor
molecules.
[0005] Since cyclodextrin is a prime breeding ground for certain
microorganisms, especially when in aqueous compositions, it is
preferable to include a water-soluble antimicrobial preservative,
which is effective for inhibiting and/or regulating microbial
growth, to increase storage stability of clear, aqueous
odor-absorbing solutions containing water-soluble cyclodextrin,
when the composition does not contain an antimicrobial material as
described hereinafter.
[0006] It is desirable to provide further improvements such as a
cyclodextrin compatible antimicrobial active that provides
substantial kill of organisms that cause, e.g., odor, infections,
etc. It is also desirable that the compositions contain a
cyclodextrin compatible surfactant to promote spreading of the odor
absorbing composition on hydrophobic surfaces such as polyester,
nylon, etc. as well as to penetrate any oily, hydrophobic soil for
improved malodor control. Furthermore, it is desirable that the
cyclodextrin-compatible surfactant provide in-wear electrostatic
control. It is more preferable that the odor absorbing composition
of the present invention contain both a cyclodextrin-compatible
antibacterial active and a cyclodextrin-compatible surfactant. A
cyclodextrin-compatible active is one which does not substantially
form a complex with cyclodextrin in the composition, at the usage
concentration, so that an effective amount of both the free,
uncomplexed active and free, uncomplexed cyclodextrin are available
for their intended use. Furthermore, it is desirable to include a
humectant to maintain a desirable moisture level in cotton fabrics
while they dry to maximize dewrinkling.
SUMMARY OF THE INVENTION
[0007] The present invention relates to a stable, preferably
translucent, more preferably clear, aqueous odor-absorbing and
wrinkle controlling composition, odor control and wrinkle control
methods and articles of manufacture that use such odor-absorbing
and wrinkle controlling composition, preferably for use on
inanimate surfaces, especially fabrics comprising:
[0008] (A). an effective amount to absorb malodors, typically from
about 0.01% to about 20% by weight of the composition, with
concentrated compositions which are meant to be diluted containing
from about 3% to about 20%, preferably from about 5% to about 10%
by weight of the composition, and, for more dilute "usage
conditions" compositions, a range of from about 0.01% to about 5%,
preferably from about 0.1% to about 3%, more preferably from about
0.5% to about 2%, by weight of the usage composition, of
solubilized, uncomplexed cyclodextrin;
[0009] (B). optionally, an effective amount to improve the
performance of the composition, preferably from about 0.05% to
about 5%, more preferably from about 0.1% to about 3%, and even
more preferably from about 0.2% to about 1.5%, by weight of the
usage composition, of cyclodextrin compatible surfactant that
preferably provides a surface tension of from about 20 dyne/cm to
about 60 dyne/cm, preferably from about 20 dyne/cm to about 45
dyne/cm (with concentrated compositions having a level of from
about 0.1% to about 15%, preferably from about 0.2% to about 8%,
more preferably from about 0.3% to about 5%, by weight of the
concentrated solution, of cyclodextrin-compatible surfactant);
[0010] (C). optionally, an effective amount, to kill, or reduce the
growth of microbes, of cyclodextrin compatible and water soluble
antimicrobial active, preferably from about 0.001% to about 0.8%,
more preferably from about 0.002% to about 0.3%, even more
preferably from about 0.003% to about 0.2%, by weight of the usage
composition, and preferably selected from the group consisting of
halogenated compounds, cyclic nitrogen compounds, quaternary
compounds, and phenolic compounds (with concentrated compositions
having a level of from about 0.003% to about 2%, preferably from
about 0.01% to about 1.2%, more preferably from about 0.1% to about
0.8%, by weight of the concentrated solution, of
cyclodextrin-compatible and water soluble antimicrobial
active);
[0011] (D). optionally, but preferably, an effective amount to
provide olfactory effects of perfume, typically from about 0.003%
to about 0.5%, preferably from about 0.01% to about 0.3%, more
preferably from about 0.05% to about 0.2%, by weight of the usage
composition of hydrophilic perfume, containing at least about 50%,
preferably at least about 60%, more preferably at least about 60%,
even more preferably at least about 70%, and yet more preferably at
least about 80%, by weight of the perfume of perfume ingredients
that have a ClogP of less than about 3.5 and optionally, a minor
amount of perfume ingredients selected from the group consisting of
ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox,
damascenone, alpha-damascone, gamma-dodecalactone, ebanol,
herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone,
alpha-isomethylionone, lilial, methyl nonyl ketone,
gamma-undecalactone, undecylenic aldehyde, and mixtures
thereof;
[0012] (E). optionally, but preferably, from about 0.01% to about
3%, more preferably from about 0.05% to about 1%, and even more
preferably from about 0.1% to about 0.5%, by weight of the usage
composition of low molecular weight polyol;
[0013] (F). optionally, an effective amount to assist in
antimicrobial action of aminocarboxylate chelator; preferably from
about 0.001% to about 0.3%, preferably from about 0.01% to about
0.1%, more preferably from about 0.02% to about 0.05%, by weight of
the usage composition;
[0014] (G). optionally, but preferably, an effective amount of
metallic salt, preferably from about 0.1% to about 10%, more
preferably from about 0.2% to about 8%, even more preferably from
about 0.3% to about 5% by weight of the usage composition,
especially water soluble copper and/or zinc salts, for improved
odor benefit;
[0015] (H) optionally, an effective amount of enzyme, from about
0.0001% to about 0.5%, preferably from about 0.001% to about 0.3%,
more preferably from about 0.005% to about 0.2% by weight of the
usage composition, for improved odor control benefit;
[0016] (I). optionally, an effective amount of solubilized,
water-soluble, antimicrobial preservative, preferably from about
0.0001% to about 0.5%, more preferably from about 0.0002% to about
0.2%, most preferably from about 0.0003% to about 0.1%, by weight
of the composition;
[0017] (J) an effective amount of cyclodextrin compatible fabric
wrinkle control agent, preferably from about 0.05% to about 5%,
more preferably from about 0.2% to about 3%, even more preferably
from about 0.3% to about 2%, by weight of the usage composition;
and
[0018] (K). aqueous carrier,
[0019] said composition preferably containing at least one of (B)
and (C) and preferably being essentially free of any material that
would soil or stain fabric under usage conditions, and/or
preferably having a pH of more than about 3, more preferably more
than about 3.5.
[0020] The present invention also relates to concentrated
compositions, wherein the level of cyclodextrin is from about 3% to
about 20%, more preferably from about 5% to about 10%, by weight of
the composition which are diluted to form compositions with the
usage concentrations of cyclodextrin of, e.g., from about 0.1% to
about 5%, by weight of the diluted composition, as given
hereinabove, which are the "usage conditions".
[0021] The present invention also relates to the compositions
incorporated into a spray dispenser to create an article of
manufacture that can facilitate treatment of articles and/or
surfaces with said compositions containing uncomplexed cyclodextrin
and other optional ingredients at a level that is effective, yet is
not discernible when dried on the surfaces. The spray dispenser
comprises manually activated and non-manual operated spray means
and a container containing the odor-absorbing composition.
[0022] The present invention also comprises the use of small
particle diameter droplets of the compositions herein, even those
which do not contain (B) or (C), to treat surfaces, especially
fabrics, to provide superior performance, e.g., the method of
applying the compositions to fabrics, etc. as very small particles
(droplets) preferably having average particle sizes (diameters) of
from about 10 .mu.m to about 120 .mu.m, more preferably from about
20 .mu.m to about 100 .mu.m.
[0023] In another aspect of the invention herein, compositions that
contain combinations of water soluble antimicrobial actives,
especially those described hereinafter, and especially the
bis-biguamide alkane compounds described hereinafter, and the
surfactants described hereinafter, especially the polyalkylene
oxide polysiloxanes described hereinafter provide superior
antimicrobial action in aqueous solutions, either by themselves, or
in combination with the other ingredients, including the
cyclodextrin.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The present invention relates to a stable, preferably
translucent, more preferably clear, aqueous odor-absorbing and
wrinkle controlling composition, odor control and wrinkle control
methods and articles of manufacture that use such odor-absorbing
and wrinkle controlling composition, preferably for use on fabrics,
comprising:
[0025] (A). an effective amount to absorb malodors, typically from
about 0.01% to about 20% by weight of the composition, with
concentrated compositions which are meant to be diluted containing
from about 3% to about 20%, preferably from about 5% to about 10%
by weight of the composition, and, for more dilute "usage
conditions" compositions, a range of from about 0.01% to about 5%,
preferably from about 0.1% to about 3%, more preferably from about
0.5% to about 2%, by weight of the usage composition, of
solubilized, uncomplexed cyclodextrin;
[0026] (B). optionally, an effective amount to improve the
performance of the composition, preferably from about 0.05% to
about 5%, more preferably from about 0.1% to about 3%, and even
more preferably from about 0.2% to about 1.5%, by weight of the
usage composition, of cyclodextrin compatible surfactant that
preferably provides a surface tension of from about 20 dyne/cm to
about 60 dyne/cm, preferably from about 20 dyne/cm to about 45
dyne/cm (with concentrated compositions having a level of from
about 0.1% to about 8%, preferably from about 0.2% to about 4%,
more preferably from about 0.3% to about 3%, by weight of the
concentrated solution, of cyclodextrin-compatible surfactant);
[0027] (C). optionally, an effective amount, to kill, or reduce the
growth of microbes, of cyclodextrin compatible and water soluble
antimicrobial active, preferably from about 0.001% to about 0.8%,
more preferably from about 0.002% to about 0.3%, even more
preferably from about 0.003% to about 0.2%, by weight of the usage
composition, and preferably selected from the group consisting of
halogenated compounds, cyclic nitrogen compounds, quaternary
compounds, and phenolic compounds (with concentrated compositions
having a level of from about 0.003% to about 2%, preferably from
about 0.01% to about 1.2%, more preferably from about 0.1% to about
0.8%, by weight of the concentrated solution, of
cyclodextrin-compatible and water soluble antimicrobial
active);
[0028] (D). optionally, but preferably, an effective amount to
improve acceptance of the composition, typically from about 0.003%
to about 0.5%, preferably from about 0.01% to about 0.3%, more
preferably from about 0.05% to about 0.2%, by weight of the usage
composition of hydrophilic perfume, containing at least about 50%,
preferably at least about 60%, more preferably at least about 60%,
even more preferably at least about 70%, and yet more preferably at
least about 80%, by weight of the perfume of perfume ingredients
that have a ClogP of less than about 3.5 and optionally, a minor
amount of perfume ingredients selected from the group consisting of
ambrox, bacdanol, benzyl salicylate, butyl anthranilate, cetalox,
damascenone, alpha-damascone, gamma-dodecalactone, ebanol,
herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone,
alpha-isomethylionone, lilial, methyl nonyl ketone,
gamma-undecalactone, undecylenic aldehyde, and mixtures
thereof;
[0029] (E). optionally, but preferably, from about 0.01% to about
3%, more preferably from about 0.05% to about 1%, and even more
preferably from about 0.1% to about 0.5%, by weight of the usage
composition of low molecular weight polyol;
[0030] (F). optionally, an effective amount to assist in
antimicrobial action of aminocarboxylate chelator, preferably from
about 0.001% to about 0.3%, preferably from about 0.01% to about
0.1%, more preferably from about 0.02% to about 0.05%, by weight of
the usage composition;
[0031] (G). optionally, but preferably, an effective amount of
metallic salt, preferably from about 0.1% to about 10%, more
preferably from about 0.2% to about 8%, even more preferably from
about 0.3% to about 5% by weight of the usage composition,
especially water soluble copper and/or zinc salts, for improved
odor benefit;
[0032] (H). optionally, an effective amount of enzyme, from about
0.0001% to about 0.5%, preferably from about 0.001% to about 0.3%,
more preferably from about 0.005% to about 0.2% by weight of the
usage composition, for improved odor control benefit;
[0033] (I). optionally, an effective amount of solubilized,
water-soluble, antimicrobial preservative, preferably from about
0.0001% to about 0.5%, more preferably from about 0.0002% to about
0.2%, most preferably from about 0.0003% to about 0.1%, by weight
of the composition;
[0034] (J). an effective amount of cyclodextrin compatible fabric
wrinkle control agent, preferably selected from the group
consisting of fabric lubricant, shape retention polymer,
hydrophilic plasticizer, lithium salts, and mixtures thereof,
preferably from about 0.05% to about 5%, more preferably from about
0.2% to about 3%, even more preferably from about 0.3% to about 2%
by weight of the usage composition; and
[0035] (K). aqueous carrier,
[0036] said composition preferably containing at least one of (B),
and (C), and preferably being essentially free of any material that
would soil or stain fabric under usage conditions, and/or
preferably having a pH of more than about 3, more preferably more
than about 3.5. In the presence of some preferred shape retention
polymer, the composition preferably has a pH of from about 6.5 to
about 11, more preferably from about 7 to about 10, and even more
preferably from about 7 to about 8.
[0037] The present invention also relates to the compositions
incorporated into a spray dispenser (sprayer) to create an article
of manufacture that can facilitate treatment of articles and/or
surfaces with said compositions containing uncomplexed cyclodextrin
and other optional ingredients at a level that is effective, yet is
not discernible when dried on the surfaces. The spray dispenser
comprises both manually activated and non-manual operated spray
means and a container containing the odor-absorbing
composition.
[0038] The present invention also relates to concentrated
compositions, wherein the level of cyclodextrin is from about 3% to
about 20%, preferably from about 4% to about 15%, more preferably
from about 5% to about 10%, by weight of the concentrated
composition. The concentrated composition is typically diluted to
form usage compositions, with the usage concentration of, e.g.,
from about 0.1% to about 5%, by weight of the usage composition, as
given hereinabove. Specific levels of other optional ingredients in
the concentrated composition can readily be determined from the
desired usage composition and the desired degree of concentration.
These concentrated compositions can be used in a process for
preparing large volumes of treatment composition in which water is
added, either in a separate container, or in the container of the
article of manufacture comprising the spray means.
[0039] The above compositions for odor control are of the type
disclosed in U.S. Pat. Nos. 5,534,165; 5,578,563; 5,663,134;
5,668,097; 5,670,475; and 5,714,137, Trinh et al. issued Jul. 9,
1996; Nov. 26, 1996; Sep. 2, 1997; Sep. 16, 1997; Sep. 23, 1997;
and Feb. 3, 1998 respectively, all of said patents being
incorporated herein by reference. All of the patents, patent
applications, and references referred to herein are incorporated,
either wholly, or in relevant part, by reference. All parts,
ratios, and percentages herein are by weight and all numerical
limits are used with the normal degree of accuracy afforded by the
art unless otherwise specified.
I. Composition
[0040] (A). Cyclodextrin
[0041] As used herein, the term "cyclodextrin" includes any of the
known cyclodextrins such as unsubstituted cyclodextrins containing
from six to twelve glucose units, especially, alpha-cyclodextrin,
beta-cyclodextrin, gamma-cyclodextrin and/or their derivatives
and/or mixtures thereof. The alpha-cyclodextrin consists of six
glucose units, the beta-cyclodextrin consists of seven glucose
units, and the gamma-cyclodextrin consists of eight glucose units
arranged in donut-shaped rings. The specific coupling and
conformation of the glucose units give the cyclodextrins rigid,
conical molecular structures with hollow interiors of specific
volumes. The "lining" of each internal cavity is formed by hydrogen
atoms and glycosidic bridging oxygen atoms; therefore, this surface
is fairly hydrophobic. The unique shape and physical-chemical
properties of the cavity enable the cyclodextrin molecules to
absorb (form inclusion complexes with) organic molecules or parts
of organic molecules which can fit into the cavity. Many odorous
molecules can fit into the cavity including many malodorous
molecules and perfume molecules. Therefore, cyclodextrins, and
especially mixtures of cyclodextrins with different size cavities,
can be used to control odors caused by a broad spectrum of organic
odoriferous materials, which may, or may not, contain reactive
functional groups. The complexation between cyclodextrin and
odorous molecules occurs rapidly in the presence of water. However,
the extent of the complex formation also depends on the polarity of
the absorbed molecules. In an aqueous solution, strongly
hydrophilic molecules (those which are highly water-soluble) are
only partially absorbed, if at all. Therefore, cyclodextrin does
not complex effectively with some very low molecular weight organic
amines and acids when they are present at low levels on wet
fabrics. As the water is being removed however, e.g., the fabric is
being dried off, some low molecular weight organic amines and acids
have more affinity and will complex with the cyclodextrins more
readily.
[0042] The cavities within the cyclodextrin in the solution of the
present invention should remain essentially unfilled (the
cyclodextrin remains uncomplexed) while in solution, in order to
allow the cyclodextrin to absorb various odor molecules when the
solution is applied to a surface. Non-derivatised (normal)
beta-cyclodextrin can be present at a level up to its solubility
limit of about 1.85% (about 1.85 g in 100 grams of water) at room
temperature. Beta-cyclodextrin is not preferred in compositions
which call for a level of cyclodextrin higher than its water
solubility limit. Non-derivatised beta-cyclodextrin is generally
not preferred when the composition contains surfactant since it
affects the surface activity of most of the preferred surfactants
that are compatible with the derivatised cyclodextrins.
[0043] Preferably, the odor absorbing solution of the present
invention is clear. The term "clear" as defined herein means
transparent or translucent, preferably transparent, as in "water
clear," when observed through a layer having a thickness of less
than about 10 cm.
[0044] Preferably, the cyclodextrins used in the present invention
are highly water-soluble such as, alpha-cyclodextrin and/or
derivatives thereof, gamma-cyclodextrin and/or derivatives thereof,
derivatised beta-cyclodextrins, and/or mixtures thereof. The
derivatives of cyclodextrin consist mainly of molecules wherein
some of the OH groups are converted to OR groups. Cyclodextrin
derivatives include, e.g., those with short chain alkyl groups such
as methylated cyclodextrins, and ethylated cyclodextrins, wherein R
is a methyl or an ethyl group; those with hydroxyalkyl substituted
groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl
cyclodextrins, wherein R is a --CH.sub.2--CH(OH)--CH.- sub.3 or a
--CH.sub.2CH.sub.2--OH group; branched cyclodextrins such as
maltose-bonded cyclodextrins; cationic cyclodextrins such as those
containing 2-hydroxy-3-(dimethylamino)propyl ether, wherein R is
CH.sub.2--CH(OH)--CH.sub.2--N(CH.sub.3).sub.2 which is cationic at
low pH; quaternary ammonium, e.g.,
2-hydroxy-3-(trimethylammonio)propyl ether chloride groups, wherein
R is CH.sub.2--CH(OH)--CH.sub.2--N.sup.+(CH.sub.- 3).sub.3Cl.sup.-;
anionic cyclodextrins such as carboxymethyl cyclodextrins,
cyclodextrin sulfates, and cyclodextrin succinylates; amphoteric
cyclodextrins such as carboxymethyl/quaternary ammonium
cyclodextrins; cyclodextrins wherein at least one glucopyranose
unit has a 3-6-anhydro-cyclomalto structure, e.g., the
mono-3-6-anhydrocyclodextri- ns, as disclosed in "Optimal
Performances with Minimal Chemical Modification of Cyclodextrins",
F. Diedaini-Pilard and B. Perly, The 7th International Cyclodextrin
Symposium Abstracts, April 1994, p. 49, said references being
incorporated herein by reference; and mixtures thereof. Other
cyclodextrin derivatives are disclosed in U.S. Pat. No. 3,426,011,
Parmerter et al., issued Feb. 4, 1969; U.S. Pat. Nos. 3,453,257;
3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter
et al., and all issued Jul. 1, 1969; U.S. Pat. No. 3,459,731,
Gramera et al., issued Aug. 5, 1969; U.S. Pat. No. 3,553,191,
Parmerter et al., issued Jan. 5, 1971; U.S. Pat. No. 3,565,887,
Parmerter et al., issued Feb. 23, 1971; U.S. Pat. No. 4,535,152,
Szejtli et al., issued Aug. 13, 1985; U.S. Pat. No. 4,616,008,
Hirai et al., issued Oct. 7, 1986; U.S. Pat. No. 4,678,598, Ogino
et al., issued Jul. 7, 1987; U.S. Pat. No. 4,638,058, Brandt et
al., issued Jan. 20, 1987; and U.S. Pat. No. 4,746,734, Tsuchiyama
et al., issued May 24, 1988; all of said patents being incorporated
herein by reference.
[0045] Highly water-soluble cyclodextrins are those having water
solubility of at least about 10 g in 100 ml of water at room
temperature, preferably at least about 20 g in 100 ml of water,
more preferably at least about 25 g in 100 ml of water at room
temperature. The availability of solubilized, uncomplexed
cyclodextrins is essential for effective and efficient odor control
performance. Solubilized, water-soluble cyclodextrin can exhibit
more efficient odor control performance than non-water-soluble
cyclodextrin when deposited onto surfaces, especially fabric.
[0046] Examples of preferred water-soluble cyclodextrin derivatives
suitable for use herein are hydroxypropyl alpha-cyclodextrin,
methylated alpha-cyclodextrin, methylated beta-cyclodextrin,
hydroxyethyl beta-cyclodextrin, and hydroxypropyl
beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably
have a degree of substitution of from about 1 to about 14, more
preferably from about 1.5 to about 7, wherein the total number of
OR groups per cyclodextrin is defined as the degree of
substitution. Methylated cyclodextrin derivatives typically have a
degree of substitution of from about 1 to about 18, preferably from
about 3 to about 16. A known methylated beta-cyclodextrin is
heptakis-2,6-di-O-methyl-.beta.-cyclodextrin, commonly known as
DIMEB, in which each glucose unit has about 2 methyl groups with a
degree of substitution of about 14. A preferred, more commercially
available, methylated beta-cyclodextrin is a randomly methylated
beta-cyclodextrin, commonly known as RAMEB, having different
degrees of substitution, normally of about 12.6. RAMEB is more
preferred than DIMEB, since DIMEB affects the surface activity of
the preferred surfactants more than RAMEB. The preferred
cyclodextrins are available, e.g., from Cerestar USA, Inc. and
Wacker Chemicals (USA), Inc.
[0047] It is also preferable to use a mixture of cyclodextrins.
Such mixtures absorb odors more broadly by complexing with a wider
range of odoriferous molecules having a wider range of molecular
sizes. Preferably at least a portion of the cyclodextrins is
alpha-cyclodextrin and its derivatives thereof, gamma-cyclodextrin
and its derivatives thereof, and/or derivatised beta-cyclodextrin,
more preferably a mixture of alpha-cyclodextrin, or an
alpha-cyclodextrin derivative, and derivatised beta-cyclodextrin,
even more preferably a mixture of derivatised alpha-cyclodextrin
and derivatised beta-cyclodextrin, most preferably a mixture of
hydroxypropyl alpha-cyclodextrin and hydroxypropyl
beta-cyclodextrin, and/or a mixture of methylated
alpha-cyclodextrin and methylated beta-cyclodextrin.
[0048] For controlling odor on fabrics, the composition is
preferably used as a spray. It is preferable that the usage
compositions of the present invention contain low levels of
cyclodextrin so that a visible stain does not appear on the fabric
at normal usage levels. Preferably, the solution used to treat the
surface under usage conditions is virtually not discernible when
dry. Typical levels of cyclodextrin in usage compositions for usage
conditions are from about 0.01% to about 5%, preferably from about
0.1% to about 4%, more preferably from about 0.5% to about 2% by
weight of the composition. Compositions with higher concentrations
can leave unacceptable visible stains on fabrics as the solution
evaporates off of the fabric. This is especially a problem on thin,
colored, synthetic fabrics. In order to avoid or minimize the
occurrence of fabric staining, it is preferable that the fabric be
treated at a level of less than about 5 mg of cyclodextrin per gram
of fabric, more preferably less than about 2 mg of cyclodextrin per
gram of fabric. The presence of the surfactant can improve
appearance by minimizing localized spotting.
[0049] Concentrated compositions can also be used in order to
deliver a less expensive product. When a concentrated product is
used, i.e., when the level of cyclodextrin used is from about 3% to
about 20%, more preferably from about 5% to about 10%, by weight of
the concentrated composition, it is preferable to dilute the
concentrated composition before treating fabrics in order to avoid
staining. Preferably the concentrated cyclodextrin composition is
diluted with about 50% to about 6000%, more preferably with about
75% to about 2000%, most preferably with about 100% to about 1000%
by weight of the concentrated composition of water. The resulting
diluted compositions have usage concentrations of cyclodextrin as
discussed hereinbefore, e.g., of from about 0.1% to about 5%, by
weight of the diluted composition.
[0050] (B). Cyclodextrin-Compatible Surfactant
[0051] The cyclodextrin-compatible surfactant B., provides a low
surface tension that permits the composition to spread readily and
more uniformly on hydrophobic surfaces like polyester and nylon. It
has been found that the aqueous solution, without such a surfactant
will not spread satisfactorily. The spreading of the composition
also allows it to dry faster, so that the treated material is ready
to use sooner. Furthermore, the composition containing a
cyclodextrin-compatible surfactant can penetrate hydrophobic, oily
soil better for improved malodor control. The composition
containing a cyclodextrin-compatible surfactant also provides
improved "in-wear" electrostatic control. For concentrated
compositions, the surfactant facilitates the dispersion of many
actives such as antimicrobial actives and perfumes in the
concentrated aqueous compositions.
[0052] The surfactant is also needed in the composition of the
present invention that contains a wrinkle control agent such as
silicone and/or shape retention polymer. For such agents, the
surfactant is also needed, e.g., as a dispersing agent, an
emulsifying agent and/or a solubilizing agent.
[0053] The surfactant for use in providing the required low surface
tension in the composition of the present invention should be
cyclodextrin-compatible, that is it should not substantially form a
complex with the cyclodextrin so as to diminish performance of the
cyclodextrin and/or the surfactant. Complex formation diminishes
both the ability of the cyclodextrin to absorb odors and the
ability of the surfactant to lower the surface tension of the
aqueous composition.
[0054] Suitable cyclodextrin-compatible surfactants can be readily
identified by the absence of effect of cyclodextrin on the surface
tension provided by the surfactant. This is achieved by determining
the surface tension (in dyne/cm.sup.2) of aqueous solutions of the
surfactant in the presence and in the absence of about 1% of a
specific cyclodextrin in the solutions. The aqueous solutions
contain surfactant at concentrations of approximately 0.5%, 0.1%,
0.01%, and 0.005%. The cyclodextrin can affect the surface activity
of a surfactant by elevating the surface tension of the surfactant
solution. If the surface tension at a given concentration in water
differs by more than about 10% from the surface tension of the same
surfactant in the 1% solution of the cyclodextrin, that is an
indication of a strong interaction between the surfactant and the
cyclodextrin. The preferred surfactants herein should have a
surface tension in an aqueous solution that is different (lower) by
less than about 10%, preferably less than about 5%, and more
preferably less than about 1% from that of the same concentration
solution containing 1% cyclodextrin.
[0055] Nonlimiting examples of cyclodextrin-compatible nonionic
surfactants include block copolymers of ethylene oxide and
propylene oxide. Suitable block polyoxyethylene-polyoxypropylene
polymeric surfactants, that are compatible with most cyclodextrins,
include those based on ethylene glycol, propylene glycol, glycerol,
trimethylolpropane and ethylenediamine as the initial reactive
hydrogen compound. Polymeric compounds made from a sequential
ethoxylation and propoxylation of initial compounds with a single
reactive hydrogen atom, such as C.sub.12-18 aliphatic alcohols, are
not generally compatible with the cyclodextrin. Certain of the
block polymer surfactant compounds designated Pluronic.RTM. and
Tetronic.RTM. by the BASF-Wyandotte Corp., Wyandotte, Mich., are
readily available.
[0056] Nonlimiting examples of cyclodextrin-compatible surfactants
of this type include:
[0057] Pluronic Surfactants with the general formula
H(EO).sub.n(PO).sub.m(EO).sub.nH, wherein EO is an ethylene oxide
group, PO is a propylene oxide group, and n and m are numbers that
indicate the average number of the groups in the surfactants.
Typical examples of cyclodextrin-compatible Pluronic surfactants
are:
1 Name Average MW Average n Average m L-101 3,800 4 59 L-81 2,750 3
42 L-44 2,200 10 23 L-43 1,850 6 22 F-38 4,700 43 16 P-84 4,200 19
43, and mixtures thereof.
[0058] Tetronic Surfactants with the general formula: 1
[0059] wherein EO, PO, n, and m have the same meanings as above.
Typical examples of cyclodextrin-compatible Tetronic surfactants
are:
2 Name Average MW Average n Average m 901 4,700 3 18 908 25,000 114
22,
[0060] and mixtures thereof.
[0061] "Reverse" Pluronic and Tetronic surfactants have the
following general formulas:
Reverse Pluronic Surfactants H(PO).sub.m(EO).sub.n(PO).sub.mH
Reverse Tetronic Surfactants
[0062] 2
[0063] wherein EO, PO, n, and m have the same meanings as above.
Typical examples of cyclodextrin-compatible Reverse Pluronic and
Reverse Tetronic surfactants are:
3 Name Average MW Average n Average m Reverse Pluronic surfactants:
10 R5 1,950 8 22 25 R1 2,700 21 6 Reverse Tetronic surfactants 130
R2 7,740 9 26 70 R2 3,870 4 13 and mixtures thereof.
[0064] A preferred class of cyclodextrin-compatible nonionic
surfactants are the polyalkylene oxide polysiloxanes having a
dimethyl polysiloxane hydrophobic moiety and one or more
hydrophilic polyalkylene side chains, and having 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)--R.sup.1
[0065] 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
[0066] 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. Each
polyalkylene oxide polysiloxane has at least one R.sup.1 group
being a poly(ethyleneoxide/propyleneoxide) copolymer group.
[0067] Nonlimiting examples of this type of surfactants are the
Silwet.RTM. surfactants which are available OSi Specialties, Inc.,
Danbury, Conn. Representative Silwet surfactants are as
follows.
4 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
[0068] 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 polyalkylene oxide
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 surfactants are L-7600, L-7602, L-7604, L-7605, L-7622,
L-7657, and mixtures thereof. Besides surface activity,
polyalkylene oxide polysiloxane surfactants can also provide other
benefits, such as antistatic benefits, lubricity and softness to
fabrics.
[0069] The preparation of polyalkylene oxide polysiloxanes is well
known in the art. Polyalkylene oxide polysiloxanes of the present
invention can be prepared according to the procedure set forth in
U.S. Pat. No. 3,299,112, incorporated herein by reference.
Typically, polyalkylene oxide polysiloxanes of the surfactant blend
of the present invention are readily prepared by an addition
reaction between a hydrosiloxane (i.e., a siloxane containing
silicon-bonded hydrogen) and an alkenyl ether (e.g., a vinyl,
allyl, or methallyl ether) of an alkoxy or hydroxy end-blocked
polyalkylene oxide). The reaction conditions employed in addition
reactions of this type are well known in the art and in general
involve heating the reactants (e.g., at a temperature of from about
85.degree. C. to 110.degree. C.) in the presence of a platinum
catalyst (e.g., chloroplatinic acid) and a solvent (e.g.,
toluene).
[0070] Nonlimiting examples of cyclodextrin-compatible anionic
surfactants are the alkyldiphenyl oxide disulfonate, having the
general formula: 3
[0071] wherein R is an alkyl group. Examples of this type of
surfactants are available from the Dow Chemical Company under the
trade name Dowfax.RTM. wherein R is a linear or branched
C.sub.6-C.sub.16 alkyl group. An example of these
cyclodextrin-compatible anionic surfactant is Dowfax 3B2 with R
being approximately a linear C.sub.10 group. These anionic
surfactants are preferably not used when the antimicrobial active
or preservative, etc., is cationic to minimize the interaction with
the cationic actives, since the effect of both surfactant and
active are diminished.
[0072] The surfactants above are either weakly interactive with
cyclodextrin (less than 5% elevation in surface tension, or
non-interactive (less than 1% elevation in surface tension). Normal
surfactants like sodium dodecyl sulfate and
dodecanolpoly(6)ethoxylate are strongly interactive, with more than
a 10% elevation in surface tension in the presence of a typical
cyclodextrin like hydroxypropyl-beta-cyclodextrin and methylated
beta-cyclodextrin.
[0073] Typical levels of cyclodextrin-compatible surfactants in
usage compositions are from about 0.01% to about 2%, preferably
from about 0.03% to about 0.6%, more preferably from about 0.05% to
about 0.3%, by weight of the composition. Typical levels of
cyclodextrin-compatible surfactants in concentrated compositions
are from about 0.1% to about 8%, preferably from about 0.2% to
about 4%, more preferably from about 0.3% to about 3%, by weight of
the concentrated composition. For composition containing wrinkle
control agent, typical levels of cyclodextrin-compatible
surfactants in the usage compositions are from about 0.05% to about
5%, preferably from about 0.1% to about 3%, more preferably from
about 0.2% to about 1.5%, by weight of the composition.
[0074] (C). Cyclodextrin-Compatible Antimicrobial Active
[0075] The solubilized, water-soluble antimicrobial active, C., is
useful in providing protection against organisms that become
attached to the treated material. The antimicrobial should be
cyclodextrin-compatible, e.g., not substantially forming complexes
with the cyclodextrin in the odor absorbing composition. The free,
uncomplexed antimicrobial, e.g., antibacterial, active provides an
optimum antibacterial performance.
[0076] Sanitization of fabrics can be achieved by the compositions
of the present invention containing, antimicrobial materials, e.g.,
antibacterial halogenated compounds, quaternary compounds, and
phenolic compounds.
[0077] Biguamides.
[0078] Some of the more robust cyclodextrin-compatible
antimicrobial halogenated compounds which can function as
disinfectants/sanitizers as well as finish product preservatives
(vide infra), and are useful in the compositions of the present
invention include 1,1'-hexamethylene
bis(5-(p-chlorophenyl)biguamide), commonly known as chlorhexidine,
and its salts, e.g., with hydrochloric, acetic and gluconic acids.
The digluconate salt is highly water-soluble, about 70% in water,
and the diacetate salt has a solubility of about 1.8% in water.
When chlorhexidine is used as a sanitizer in the present invention
it is typically present at a level of from about 0.001% to about
0.4%, preferably from about 0.002% to about 0.3%, and more
preferably from about 0.05% to about 0.2%, by weight of the usage
composition. In some cases, a level of from about 1% to about 2%
may be needed for virucidal activity.
[0079] Other useful biguamide compounds include Cosmoci.RTM.
CQ.RTM., Vantocil.RTM. IB, including poly (hexamethylene biguamide)
hydrochloride. Other useful cationic antimicrobial agents include
the bis-biguamide alkanes. Usable water soluble salts of the above
are chlorides, bromides, sulfates, alkyl sulfonates such as methyl
sulfonate and ethyl sulfonate, phenylsulfonates such as
p-methylphenyl sulfonates, nitrates, acetates, gluconates, and the
like.
[0080] Examples of suitable bis biguamide compounds are
chlorhexidine;
1,6-bis-(2-ethylhexylbiguanidohexane)dihydrochloride;
1,6-di-(N.sub.1,N.sub.1'-phenyldiguanido-N.sub.5,N.sub.5')-hexane
tetrahydrochloride;
1,6-di-(N.sub.1,N.sub.1'-phenyl-N.sub.1,N.sub.1'-meth-
yldiguanido-N.sub.5,N.sub.5')-hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-o-chlorophenyldiguanido-N.sub.5,N.sub.5')-hexane
dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,6-dichlorophenyldiguanido-N.su-
b.5,N.sub.5')hexane dihydrochloride;
1,6-di[N.sub.1,N.sub.1'-.beta.-(p-met- hoxyphenyl)
diguanido-N.sub.5,N.sub.5']-hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-.alpha.-methyl-.beta.-phenyldiguanido-N.sub.5,N.s-
ub.5')-hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-p-nitrophenyldiguan-
ido-N.sub.5,N.sub.5')hexane
dihydrochloride;.omega.:.omega.'-di-(N.sub.1,N-
.sub.1'-phenyldiguanido-N.sub.5,N.sub.5')-di-n-propylether
dihydrochloride;.omega:omega'-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-
-N.sub.5,N.sub.5')-di-n-propylether tetrahydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,4-dichlorophenyldiguanido-N.sub.5,N.sub.5')hexa-
ne tetrahydrochloride;
1,6-di(N.sub.1,N.sub.1'-p-methylphenyldiguanido-N.s-
ub.5,N.sub.5')hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,4,5-trichl-
orophenyldiguanido-N.sub.5,N.sub.5')hexane tetrahydrochloride;
1,6-di[N.sub.1,N.sub.1'-.alpha.-(p-chlorophenyl)
ethyldiguanido-N.sub.5,N- .sub.5'] hexane dihydrochloride;.omega.:
.omega.'di(N.sub.1,
N.sub.1'-p-chlorophenyldiguanido-N.sub.5,N.sub.5').sub.m-xylene
dihydrochloride;
1,12-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-N.sub.5-
,N.sub.5') dodecane dihydrochloride;
1,10-di(N.sub.1,N.sub.1'-phenyldiguan- ido-N.sub.5,N.sub.5')-decane
tetrahydrochloride; 1,12-di(N.sub.1,N.sub.1'--
phenyldiguanido-N.sub.5,N.sub.5') dodecane tetrahydrochloride;
1,6-di(N.sub.1,N.sub.1'-o-chlorophenyldiguanido-N.sub.5,N.sub.5')
hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-N.sub.5,-
N.sub.5')-hexane tetrahydrochloride; ethylene bis (1-tolyl
biguamide); ethylene bis (p-tolyl biguamide); ethylene
bis(3,5-dimethylphenyl biguamide); ethylene bis(p-tert-amylphenyl
biguamide); ethylene bis(nonylphenyl biguamide); ethylene bis
(phenyl biguamide); ethylene bis (N-butylphenyl biguamide);
ethylene bis (2,5-diethoxyphenyl biguamide); ethylene
bis(2,4-dimethylphenyl biguamide); ethylene
bis(o-diphenylbiguamide); ethylene bis(mixed amyl naphthyl
biguamide); N-butyl ethylene bis(phenylbiguamide); trimethylene
bis(o-tolyl biguamide); N-butyl trimethylene bis(phenyl biguamide);
and the corresponding pharmaceutically acceptable salts of all of
the above such as the acetates; gluconates; hydrochlorides;
hydrobromides; citrates; bisulfites; fluorides; polymaleates;
N-coconutalkylsarcosinates; phosphites; hypophosphites;
perfluorooctanoates; silicates; sorbates; salicylates; maleates;
tartrates; fumarates; ethylenediaminetetraacetates- ;
iminodiacetates; cinnamates; thiocyanates; arginates;
pyromellitates; tetracarboxybutyrates; benzoates; glutarates;
monofluorophosphates; and perfluoropropionates, and mixtures
thereof. Preferred antimicrobials from this group are
1,6-di-(N.sub.1,N.sub.1'-phenyldiguanido-N.sub.5,N.sub.5')- -hexane
tetrahydrochloride; 1,6-di(N.sub.1,N.sub.1'-o-chlorophenyldiguanid-
o-N.sub.5,N.sub.5')-hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,6-di-
chlorophenyldiguanido-N.sub.5,N.sub.5')hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,4-dichlorophenyldiguanido-N.sub.5,N.sub.5')hexa-
ne tetrahydrochloride; 1,6-di
[N.sub.1,N.sub.1'-.alpha.-(p-chlorophenyl)
ethyldiguanido-N.sub.5,N.sub.5'] hexane
dihydrochloride;.omega.:.omega.'d- i(N.sub.1,
N.sub.1'-p-chlorophenyldiguanido-N.sub.5,N.sub.5').sub.m-xylene
dihydrochloride;
1,12-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-N.sub.5-
,N.sub.5') dodecane dihydrochloride;
1,6-di(.sub.1,N.sub.1'-o-chlorophenyl- diguanido-N.sub.5,N.sub.5')
hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-N.sub.5,N.sub.5')-hexane
tetrahydrochloride; and mixtures thereof; more preferably,
1,6-di(N.sub.1,N.sub.1'-o-chlorophenyldiguanido-N.sub.5,N.sub.5')-hexane
dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,6-dichlorophenyldiguanido-N.su-
b.5,N.sub.5')hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-2,4-dichlorop-
henyldiguanido-N.sub.5,N.sub.5')hexane tetrahydrochloride;
1,6-di[N.sub.1,N.sub.1'-.alpha.-(p-chlorophenyl)
ethyldiguanido-N.sub.5,N- .sub.5'] hexane dihydrochloride; .omega.:
.omega.'di(N.sub.1,
N.sub.1'-p-chlorophenyldiguanido-N.sub.5,N.sub.5').sub.m-xylene
dihydrochloride;
1,12-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-N.sub.5-
,N.sub.5') dodecane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-o-chloropheny- ldiguanido-N.sub.5,N.sub.5')
hexane dihydrochloride;
1,6-di(N.sub.1,N.sub.1'-p-chlorophenyldiguanido-N.sub.5,N.sub.5')-hexane
tetrahydrochloride; and mixtures thereof. As stated hereinbefore,
the bis biguamide of choice is chlorhexidine its salts, e.g.,
digluconate, dihydrochloride, diacetate, and mixtures thereof.
[0081] Quaternary Compounds.
[0082] A wide range of quaternary compounds can also be used as
antimicrobial actives, in conjunction with the preferred
surfactants, for compositions of the present invention that do not
contain cyclodextrin. Non-limiting examples of useful quaternary
compounds include: (1) benzalkonium chlorides and/or substituted
benzalkonium chlorides such as commercially available Barquat.RTM.
(available from Lonza), Maquat.RTM. (available from Mason),
Variquat.RTM. (available from Witco/Sherex), and Hyamine.RTM.)
(available from Lonza); (2) di(C.sub.6-C.sub.14)alkyl di short
chain (C.sub.1-4 alkyl and/or hydroxyalkyl) quaternary such as
Bardac.RTM. products of Lonza, (3) N-(3-chloroallyl) hexaminium
chlorides such as Dowicide.RTM. and Dowicil.RTM. available from
Dow; (4) benzethonium chloride such as Hyamine.RTM. 1622 from Rohm
& Haas; (5) methylbenzethonium chloride represented by
Hyamine.RTM. 10.times.supplied by Rohm & Haas, (6)
cetylpyridinium chloride such as Cepacol chloride available from of
Merrell Labs. Examples of the preferred dialkyl quaternary
compounds are di(C.sub.8-C.sub.12)dialkyl dimethyl ammonium
chloride, such as didecyldimethylammonium chloride (Bardac 22), and
dioctyldimethylammonium chloride (Bardac 2050). Typical
concentrations for biocidal effectiveness of these quaternary
compounds range from about 0.001% to about 0.8%, preferably from
about 0.005% to about 0.3%, more preferably from about 0.01% to
about 0.2%, and even more preferably from about 0.03% to about
0.1%, by weight of the usage composition. The corresponding
concentrations for the concentrated compositions are from about
0.003% to about 2%, preferably from about 0.006% to about 1.2%, and
more preferably from about 0.1% to about 0.8% by weight of the
concentrated compositions.
[0083] The surfactants, when added to the antimicrobials tend to
provide improved antimicrobial action. This is especially true for
the siloxane surfactants, and especially when the siloxane
surfactants are combined with the chlorhexidine antimicrobial
actives.
[0084] (D). Perfume
[0085] The odor absorbing composition of the present invention can
also optionally provide a "scent signal" in the form of a pleasant
odor which signals the removal of malodor from fabrics. The scent
signal is designed to provide a fleeting perfume scent, and is not
designed to be overwhelming or to be used as an odor masking
ingredient. When perfume is added as a scent signal, it is added
only at very low levels, e.g., from about 0% to about 0.5%,
preferably from about 0.003% to about 0.3%, more preferably from
about 0.005% to about 0.2%, by weight of the usage composition.
[0086] Perfume can also be added as a more intense odor in product
and on surfaces. When stronger levels of perfume are preferred,
relatively higher levels of perfume can be added. Any type of
perfume can be incorporated into the composition of the present
invention. It is essential, however, that the perfume be added at a
level wherein even if all of the perfume in the composition were to
complex with the cyclodextrin molecules, there will still be an
effective level of uncomplexed cyclodextrin molecules present in
the solution to provide adequate odor control. In order to reserve
an effective amount of cyclodextrin molecules for odor control,
perfume is typically present at a level wherein less than about 90%
of the cyclodextrin complexes with the perfume, preferably less
than about 50% of the cyclodextrin complexes with the perfume, more
preferably, less than about 30% of the cyclodextrin complexes with
the perfume, and most preferably, less than about 10% of the
cyclodextrin complexes with the perfume. The cyclodextrin to
perfume weight ratio should be greater than about 8:1, preferably
greater than about 10:1, more preferably greater than about 20:1,
even more preferably greater than 40:1 and most preferably greater
than about 70:1.
[0087] Preferably the perfume is hydrophilic and is composed
predominantly of ingredients selected from two groups of
ingredients, namely, (a) hydrophilic ingredients having a ClogP of
less than about 3.5, more preferably less than about 3.0, and (b)
ingredients having significant low detection threshold, and
mixtures thereof. Typically, at least about 50%, preferably at
least about 60%, more preferably at least about 70%, and most
preferably at least about 80% by weight of the perfume is composed
of perfume ingredients of the above groups (a) and (b). For these
preferred perfumes, the cyclodextrin to perfume weight ratio is
typically of from about 2:1 to about 200:1; preferably from about
4:1 to about 100:1, more preferably from about 6:1 to about 50:1,
and even more preferably from about 8:1 to about 30:1.
[0088] (a). Hydrophilic Perfume Ingredients
[0089] The hydrophilic perfume ingredients are more soluble in
water, have less of a tendency to complex with the cyclodextrins,
and are more available in the odor absorbing composition than the
ingredients of conventional perfumes. The degree of hydrophobicity
of a perfume ingredient can be correlated with its octanol/water
partition coefficient P. The octanol/water partition coefficient of
a perfume ingredient is the ratio between its equilibrium
concentration in octanol and in water. A perfume ingredient with a
greater partition coefficient P is considered to be more
hydrophobic. Conversely, a perfume ingredient with a smaller
partition coefficient P is considered to be more hydrophilic. Since
the partition coefficients of the perfume ingredients normally have
high values, they are more conveniently given in the form of their
logarithm to the base 10, logP. Thus the preferred perfume
hydrophilic perfume ingredients of this invention have logP of
about 3.5 or smaller, preferably of about 3.0 or smaller.
[0090] The logP of many perfume ingredients have been reported; for
example, the Pomona92 database, available from Daylight Chemical
Information Systems, Inc. (Daylight CIS), Irvine, Calif., contains
many, along with citations to the original literature. However, the
logP values are most conveniently calculated by the "CLOGP"
program, also available from Daylight CIS. This program also lists
experimental logP values when they are available in the Pomona92
database. The "calculated logP" (ClogP) is determined by the
fragment approach of Hansch and Leo (cf., A. Leo, in Comprehensive
Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor
and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated
herein by reference). The fragment approach is based on the
chemical structure of each perfume ingredient, and takes into
account the numbers and types of atoms, the atom connectivity, and
chemical bonding. The ClogP values, which are the most reliable and
widely used estimates for this physicochemical property, are used
instead of the experimental logP values in the selection of perfume
ingredients which are useful in the present invention.
[0091] Non-limiting examples of the more preferred hydrophilic
perfume ingredients are allyl amyl glycolate, allyl caproate, amyl
acetate, amyl propionate, anisic aldehyde, anisyl acetate, anisole,
benzaldehyde, benzyl acetate, benzyl acetone, benzyl alcohol,
benzyl formate, benzyl iso valerate, benzyl propionate, beta gamma
hexenol, calone, camphor gum, laevo-carveol, d-carvone,
laevo-carvone, cinnamic alcohol, cinnamyl acetate, cinnamic
alcohol, cinnamyl formate, cinnamyl propionate, cis-jasmone,
cis-3-hexenyl acetate, coumarin, cuminic alcohol, cuminic aldehyde,
Cyclal C, cyclogalbanate, dihydroeuginol, dihydro isojasmonate,
dimethyl benzyl carbinol, dimethyl benzyl carbinyl acetate, ethyl
acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl
anthranilate, ethyl benzoate, ethyl butyrate, ethyl cinnamate,
ethyl hexyl ketone, ethyl maltol, ethyl-2-methyl butyrate, ethyl
methylphenyl glycidate, ethyl phenyl acetate, ethyl salicylate,
ethyl vanillin, eucalyptol, eugenol, eugenyl acetate, eugenyl
formate, eugenyl methyl ether, fenchyl alcohol, flor acetate
(tricyclo decenyl acetate), fructone, frutene (tricyclo decenyl
propionate), geraniol, geranyl oxyacetaldehyde, heliotropin,
hexenol, hexenyl acetate, hexyl acetate, hexyl formate, hinokitiol,
hydratropic alcohol, hydroxycitronellal, hydroxycitronellal diethyl
acetal, hydroxycitronellol, indole, isoamyl alcohol, iso cyclo
citral, isoeugenol, isoeugenyl acetate, isomenthone, isopulegyl
acetate, isoquinoline, keone, ligustral, linalool, linalool oxide,
linalyl formate, lyral, menthone, methyl acetophenone, methyl amyl
ketone, methyl anthranilate, methyl benzoate, methyl benzyl
acetate, methyl cinnamate, methyl dihydrojasmonate, methyl eugenol,
methyl heptenone, methyl heptine carbonate, methyl heptyl ketone,
methyl hexyl ketone, methyl isobutenyl tetrahydropyran,
methyl-N-methyl anthranilate, methyl beta naphthyl ketone, methyl
phenyl carbinyl acetate, methyl salicylate, nerol, nonalactone,
octalactone, octyl alcohol (octanol-2), para-anisic aldehyde,
para-cresol, para-cresyl methyl ether, para hydroxy phenyl
butanone, para-methoxy acetophenone, para-methyl acetophenone,
phenoxy ethanol, phenoxyethyl propionate, phenyl acetaldehyde,
phenylacetaldehyde diethyl ether, phenylethyl oxyacetaldehyde,
phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl dimethyl
carbinol, prenyl acetate, propyl butyrate, pulegone, rose oxide,
safrole, terpineol, vanillin, viridine, and mixtures thereof.
[0092] Nonlimiting examples of other preferred hydrophilic perfume
ingredients which can be used in perfume compositions of this
invention are allyl heptoate, amyl benzoate, anethole,
benzophenone, carvacrol, citral, citronellol, citronellyl nitrile,
cyclohexyl ethyl acetate, cymal, 4-decenal, dihydro isojasmonate,
dihydro myrcenol, ethyl methyl phenyl glycidate, fenchyl acetate,
florhydral, gamma-nonalactone, geranyl formate, geranyl nitrile,
hexenyl isobutyrate, alpha-ionone, isobomyl acetate, isobutyl
benzoate, isononyl alcohol, isomenthol, para-isopropyl
phenylacetaldehyde, isopulegol, linalyl acetate, 2-methoxy
naphthalene, menthyl acetate, methyl chavicol, musk ketone, beta
naphthol methyl ether, neral, nonyl aldehyde, phenyl heptanol,
phenyl hexanol, terpinyl acetate, Veratrol, yara-yara, and mixtures
thereof.
[0093] The preferred perfume compositions used in the present
invention contain at least 4 different hydrophilic perfume
ingredients, preferably at least 5 different hydrophilic perfume
ingredients, more preferably at least 6 different hydrophilic
perfume ingredients, and even more preferably at least 7 different
hydrophilic perfume ingredients. Most common perfume ingredients
which are derived from natural sources are composed of a multitude
of components. When each such material is used in the formulation
of the preferred perfume compositions of the present invention, it
is counted as one single ingredient, for the purpose of defining
the invention.
[0094] (b). Low Odor Detection Threshold Perfume Ingredient
[0095] The odor detection threshold of an odorous material is the
lowest vapor concentration of that material which can be
olfactorily detected. The odor detection threshold and some odor
detection threshold values are discussed in, e.g., "Standardized
Human Olfactory Thresholds", M. Devos et al, IRL Press at Oxford
University Press, 1990, and "Compilation of Odor and Taste
Threshold Values Data", F. A. Fazzalari, editor, ASTM Data Series
DS 48A, American Society for Testing and Materials, 1978, both of
said publications being incorporated by reference. The use of small
amounts of perfume ingredients that have low odor detection
threshold values can improve perfume odor character, even though
they are not as hydrophilic as perfume ingredients of group (a)
which are given hereinabove. Perfume ingredients that do not belong
to group (a) above, but have a significantly low detection
threshold, useful in the composition of the present invention, are
selected from the group consisting of ambrox, bacdanol, benzyl
salicylate, butyl anthranilate, cetalox, damascenone,
alpha-damascone, gamma-dodecalactone, ebanol, herbavert,
cis-3-hexenyl salicylate, alpha-ionone, beta-ionone,
alpha-isomethylionone, lilial, methyl nonyl ketone,
gamma-undecalactone, undecylenic aldehyde, and mixtures thereof.
These materials are preferably present at low levels in addition to
the hydrophilic ingredients of group (a), typically less than about
20%, preferably less than about 15%, more preferably less than
about 10%, by weight of the total perfume compositions of the
present invention. However, only low levels are required to provide
an effect.
[0096] There are also hydrophilic ingredients of group (a) that
have a significantly low detection threshold, and are especially
useful in the composition of the present invention. Examples of
these ingredients are allyl amyl glycolate, anethole, benzyl
acetone, calone, cinnamic alcohol, coumarin, cyclogalbanate, Cyclal
C, cymal, 4-decenal, dihydro isojasmonate, ethyl anthranilate,
ethyl-2-methyl butyrate, ethyl methylphenyl glycidate, ethyl
vanillin, eugenol, flor acetate, florhydral, fructone, frutene,
heliotropin, keone, indole, iso cyclo citral, isoeugenol, lyral,
methyl heptine carbonate, linalool, methyl anthranilate, methyl
dihydrojasmonate, methyl isobutenyl tetrahydropyran, methyl beta
naphthyl ketone, beta naphthol methyl ether, nerol, para-anisic
aldehyde, para hydroxy phenyl butanone, phenyl acetaldehyde,
vanillin, and mixtures thereof Use of low odor detection threshold
perfume ingredients minimizes the level of organic material that is
released into the atmosphere.
[0097] (E). Low Molecular Weight Polyols
[0098] Low molecular weight polyols with relatively high boiling
points, as compared to water, such as ethylene glycol, diethylene
glycol, propylene glycol and/or glycerol are preferred optional
ingredients for improving odor control performance of the
composition of the present invention. Not to be bound by theory, it
is believed that the incorporation of a small amount of low
molecular weight glycols into the composition of the present
invention enhances the formation of the cyclodextrin inclusion
complexes as the fabric dries.
[0099] It is believed that the polyols' ability to remain on the
fabric for a longer period of time than water, as the fabric dries
allows it to form ternary complexes with the cyclodextrin and some
malodorous molecules. The addition of the glycols is believed to
fill up void space in the cyclodextrin cavity that is unable to be
totally filled by some malodor molecules of relatively smaller
sizes. Preferably the glycol used is glycerin, ethylene glycol,
propylene glycol, dipropylene glycol or mixtures thereof, more
preferably ethylene glycol and propylene glycol. Cyclodextrins
prepared by processes that result in a level of such polyols are
highly desirable, since they can be used without removal of the
polyols.
[0100] Some polyols, e.g., dipropylene glycol, are also useful to
facilitate the solubilization of some perfume ingredients in the
composition of the present invention.
[0101] Typically, glycol is added to the composition of the present
invention at a level of from about 0.01% to about 3%, by weight of
the composition, preferably from about 0.05% to about 1%, more
preferably from about 0.1% to about 0.5%, by weight of the
composition. The preferred weight ratio of low molecular weight
polyol to cyclodextrin is from about 2:1,000 to about 20:100, more
preferably from about 3:1,000 to about 15:100, even more preferably
from about 5:1,000 to about 10:100, and most preferably from about
1:100 to about 7:100.
[0102] (F). Optional Aminocarboxylate Chelators
[0103] Chelators, e.g., ethylenediaminetetraacetic acid (EDTA),
hydroxyethylene-diaminetriacetic acid,
diethylenetriaminepentaacetic acid, and other aminocarboxylate
chelators, and mixtures thereof, and their salts, and mixtures
thereof, can optionally be used to increase antimicrobial and
preservative effectiveness against Gram-negative bacteria,
especially Pseudomonas species. Although sensitivity to EDTA and
other aminocarboxylate chelators is mainly a characteristic of
Pseudomonas species, other bacterial species highly susceptible to
chelators include Achromobacter, Alcaligenes, Azotobacter,
Escherichia, Salmonella, Spirillum, and Vibrio. Other groups of
organisms also show increased sensitivities to these chelators,
including fungi and yeasts. Furthermore, aminocarboxylate chelators
can help, e.g., maintaining product clarity, protecting fragrance
and perfume components, and preventing rancidity and off odors.
[0104] Although these aminocarboxylate chelators may not be potent
biocides in their own right, they function as potentiators for
improving the performance of other antimicrobials/preservatives in
the compositions of the present invention. Aminocarboxylate
chelators can potentiate the performance of many of the cationic,
anionic, and nonionic antimicrobials/preservatives, phenolic
compounds, and isothiazolinones, that are used as
antimicrobials/preservatives in the composition of the present
invention. Nonlimiting examples of cationic
antimicrobials/preservatives potentiated by aminocarboxylate
chelators in solutions are chlorhexidine salts (including
digluconate, diacetate, and dihydrochloride salts), and
Quatemium-15, also known as Dowicil 200, Dowicide Q, Preventol D1,
benzalkonium chloride, cetrimonium, myristalkonium chloride,
cetylpyridinium chloride, lauryl pyridinium chloride, and the like.
Nonlimiting examples of useful anionic antimicrobials/preservatives
which are enhanced by aminocarboxylate chelators are sorbic acid
and potassium sorbate. Nonlimiting examples of useful nonionic
antimicrobials/preservatives which are potentiated by
aminocarboxylate chelators are DMDM hydantoin, phenethyl alcohol,
monolaurin, imidazolidinyl urea, and Bronopol
(2-bromo-2-nitropropane-1,3- -diol).
[0105] Examples of useful phenolic antimicrobials/preservatives
potentiated by these chelators are chloroxylenol, phenol,
tert-butyl hydroxyanisole, salicylic acid, resorcinol, and sodium
o-phenyl phenate. Nonlimiting examples of isothiazolinone
antimicrobials/preservatives which are enhanced by aminocarboxylate
chelators are Kathon, Proxel and Promexal.
[0106] The optional chelators are present in the compositions of
this invention at levels of, typically, from about 0.01% to about
0.3%, more preferably from about 0.02% to about 0.1%, most
preferably from about 0.02% to about 0.05% by weight of the usage
compositions to provide antimicrobial efficacy in this
invention.
[0107] Free, uncomplexed aminocarboxylate chelators are required to
potentiate the efficacy of the antimicrobials. Thus, when excess
alkaline earth (especially calcium and magnesium) and transitional
metals (iron, manganese, copper, and others) are present, free
chelators are not available and antimicrobial potentiation is not
observed. In the case where significant water hardness or
transitional metals are available or where product esthetics
require a specified chelator level, higher levels may be required
to allow for the availability of free, uncomplexed aminocarboxylate
chelators to function as antimicrobial/preservative
potentiators.
[0108] (G). Metal Salts
[0109] Optionally, but highly preferred, the present invention can
include metallic salts for added odor absorption and/or
antimicrobial benefit for the cyclodextrin solution. The metallic
salts are selected from the group consisting of copper salts, zinc
salts, and mixtures thereof.
[0110] Copper salts have some antimicrobial benefits. Specifically,
cupric abietate acts as a fungicide, copper acetate acts as a
mildew inhibitor, cupric chloride acts as a fungicide, copper
lactate acts as a fungicide, and copper sulfate acts as a
germicide. Copper salts also possess some malodor control
abilities. See U.S. Pat. No. 3,172,817, Leupold, et al., which
discloses deodorizing compositions for treating disposable
articles, comprising at least slightly water-soluble salts of
acylacetone, including copper salts and zinc salts, all of said
patents are incorporated herein by reference.
[0111] The preferred zinc salts possess malodor control abilities.
Zinc has been used most often for its ability to ameliorate
malodor, e.g., in mouth wash products, as disclosed in U.S. Pat.
Nos. 4,325,939, issued Apr. 20, 1982 and 4,469,674, issued Sept. 4,
1983, to N. B. Shah, et al., all of which are incorporated herein
by reference. Highly-ionized and soluble zinc salts such as zinc
chloride, provide the best source of zinc ions. Zinc borate
functions as a fungistat and a mildew inhibitor, zinc caprylate
functions as a fungicide, zinc chloride provides antiseptic and
deodorant benefits, zinc ricinoleate functions as a fungicide, zinc
sulfate heptahydrate functions as a fungicide and zinc undecylenate
functions as a fungistat.
[0112] Preferably the metallic salts are water-soluble zinc salts,
copper salts or mixtures thereof, and more preferably zinc salts,
especially ZnCl.sub.2. These salts are preferably present in the
present invention primarily to absorb amine and sulfur-containing
compounds that have molecular sizes too small to be effectively
complexed with the cyclodextrin molecules. Low molecular weight
sulfur-containing materials, e.g., sulfide and mercaptans, are
components of many types of malodors, e.g., food odors (garlic,
onion), body/perspiration odor, breath odor, etc. Low molecular
weight amines are also components of many malodors, e.g., food
odors, body odors, urine, etc.
[0113] When metallic salts are added to the composition of the
present invention they are typically present at a level of from
about 0.1% to about 10%, preferably from about 0.2% to about 8%,
more preferably from about 0.3% to about 5% by weight of the usage
composition. When zinc salts are used as the metallic salt, and a
clear solution is desired, it is preferable that the pH of the
solution is adjusted to less than about 7, more preferably less
than about 6, most preferably, less than about 5, in order to keep
the solution clear.
[0114] (H). Enzymes
[0115] Enzymes can be used to control certain types of malodor,
especially malodor from urine and other types of excretions,
including regurgitated materials. Proteases are especially
desirable. The activity of commercial enzymes depends very much on
the type and purity of the enzyme being considered Enzymes are
normally incorporated at levels sufficient to provide up to about 5
mg by weight, preferably from about 0.001 mg to about 3 mg, more
preferably from about 0.002 mg to about 1 mg, of active enzyme per
gram of the aqueous compositions. Stated otherwise, the aqueous
compositions herein can comprise from about 0.0001% to about 0.5%,
preferably from about 0.001% to about 0.3%, more preferably from
about 0.005% to about 0.2% by weight of a commercial enzyme
preparation. Protease enzymes are usually present in such
commercial preparations at levels sufficient to provide from 0.0005
to 0.1 Anson units (AU) of activity per gram of aqueous
composition.
[0116] Nonlimiting examples of suitable, commercially available,
water soluble proteases are pepsin, tripsin, ficin, bromelin,
papain, rennin, and mixtures thereof. Papain can be isolated, e.g.,
from papaya latex, and is available commercially in the purified
form of up to, e.g., about 80% protein, or cruder, technical grade
of much lower activity. Other suitable examples of proteases are
the subtilisins which are obtained from particular strains of B.
subtilis and B. licheniforms. Another suitable protease is obtained
from a strain of Bacillus, having maximum activity throughout the
pH range of 8-12, developed and sold by Novo Industries A/S under
the registered trade name ESPERASE.RTM.. The preparation of this
enzyme and analogous enzymes is described in British Patent
Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable
for removing protein-based stains that are commercially available
include those sold under the trade names ALCALASE.RTM. and
SAVINASE.RTM. by Novo Industries A/S (Denmark) and MAXATASE.RTM. by
International Bio-Synthetics, Inc. (The Netherlands). Other
proteases include Protease A (see European Patent Application
130,756, published Jan. 9, 1985); Protease B (see European Patent
Application Serial No. 87303761.8, filed Apr. 28, 1987, and
European Patent Application 130,756, Bott et al, published Jan. 9,
1985); and proteases made by Genencor International, Inc.,
according to one or more of the following patents: Caldwell et al,
U.S. Pat. Nos. 5,185,258, 5,204,015 and 5,244,791.
[0117] A wide range of enzyme materials and means for their
incorporation into liquid compositions are also disclosed in U.S.
Pat. No. 3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes
are further disclosed in U.S. Pat. No. 4,101,457, Place et al,
issued Jul. 18, 1978, and in U.S. Pat. No. 4,507,219, Hughes,
issued Mar. 26, 1985. Other enzyme materials useful for liquid
formulations, and their incorporation into such formulations, are
disclosed in U.S. Pat. No. 4,261,868, Hora et al, issued Apr. 14,
1981. Enzymes can be stabilized by various techniques, e.g., those
disclosed and exemplified in U.S. Pat. No. 3,600,319, issued Aug.
17, 1971 to Gedge, et al., European Patent Application Publication
No. 0 199 405, Application No. 86200586.5, published Oct. 29, 1986,
Venegas, and in U.S. Pat. No. 3,519,570. All of the above patents
and applications are incorporated herein, at least in pertinent
part.
[0118] Enzyme-polyethylene glycol conjugates are also preferred.
Such polyethylene glycol (PEG) derivatives of enzymes, wherein the
PEG or alkoxy-PEG moieties are coupled to the protein molecule
through, e.g., secondary amine linkages. Suitable derivatization
decreases immunogenicity, thus minimizes allergic reactions, while
still maintaining some enzymatic activity. An example of
protease-PEG's is PEG-subtilisin Carlsberg from B. lichenniformis
coupled to methoxy-PEGs through secondary amine linkage, and is
available from Sigma-Aldrich Corp., St. Louis, Mo.
[0119] (I). Preservative
[0120] Optionally, but preferably, solubilized, water-soluble,
antimicrobial preservative can be added to the composition of the
present invention if the antimicrobial material C. is not
sufficient, or is not present, because cyclodextrin molecules are
made up of varying numbers of glucose units which can make them a
prime breeding ground for certain microorganisms, especially when
in aqueous compositions. This drawback can lead to the problem of
storage stability of cyclodextrin solutions for any significant
length of time. Contamination by certain microorganisms with
subsequent microbial growth can result in an unsightly and/or
malodorous solution. Because microbial growth in cyclodextrin
solutions is highly objectionable when it occurs, it is highly
preferable to include a solubilized, water-soluble, antimicrobial
preservative, which is effective for inhibiting and/or regulating
microbial growth in order to increase storage stability of the
preferably clear, aqueous odor-absorbing solution containing
water-soluble cyclodextrin.
[0121] Typical microorganisms that can be found in cyclodextrin
supplies and whose growth can be found in the presence of
cyclodextrin in aqueous cyclodextrin solutions include bacteria,
e.g., Bacillus thuringiensis (cereus group) and Bacillus
sphaericus; and fungi, e.g., Aspergillus ustus. Bacillus sphaericus
is one of the most numerous members of Bacillus species in soils.
Aspergillus ustus is common in grains and flours which are raw
materials to produce cyclodextrins. Microorganisms such as
Escherichia coli and Pseudomonas aeruginosa are found in some water
sources, and can be introduced during the preparation of
cyclodextrin solutions. Other Pseudomonas species, such as P.
cepacia, are typical microbial contaminants in surfactant
manufacturing facilities and may readily contaminate packed
finished products. Typical other bacterial contaminants may include
Burkholderia, Enterobacter and Gluconobacter species.
Representative fungal species which may be associated with
agricultural soils, crops and in the case of this invention, corn
products such as cyclodextrins include Aspergillus Absidia,
Penicillium Paecilomyces, and other species.
[0122] It is preferable to use a broad spectrum preservative, e.g.,
one that is effective on both bacteria (both gram positive and gram
negative) and fungi. A limited spectrum preservative, e.g., one
that is only effective on a single group of microorganisms, e.g.,
fungi, can be used in combination with a broad spectrum
preservative or other limited spectrum preservatives with
complimentary and/or supplementary activity. A mixture of broad
spectrum preservatives can also be used. In some cases where a
specific group of microbial contaminants is problematic (such as
Gram negatives), aminocarboxylate chelators, such as those
described hereinbefore, can be used alone or as potentiators in
conjunction with other preservatives. These chelators which
include, e.g., ethylenediaminetetraacetic acid (EDTA),
hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic
acid, and other aminocarboxylate chelators, and mixtures thereof,
and their salts, and mixtures thereof, can increase preservative
effectiveness against Gram-negative bacteria, especially
Pseudomonas species.
[0123] Antimicrobial preservatives useful in the present invention
include biocidal compounds, i.e., substances that kill
microorganisms, or biostatic compounds, i.e., substances that
inhibit and/or regulate the growth of microorganisms. Preferred
antimicrobial preservatives are those that are water-soluble and
are effective at low levels because the organic preservatives can
form inclusion complexes with the cyclodextrin molecules and
compete with the malodorous molecules for the cyclodextrin
cavities, thus rendering the cyclodextrins ineffective as odor
controlling actives. Water-soluble preservatives useful in the
present invention are those that have a solubility in water of at
least about 0.3 g per 100 ml of water, i.e., greater than about
0.3% at room temperature, preferably greater than about 0.5% at
room temperature. These types of preservatives have a lower
affinity to the cyclodextrin cavity, at least in the aqueous phase,
and are therefore more available to provide antimicrobial activity.
Preservatives with a water-solubility of less than about 0.3% and a
molecular structure that readily fits into the cyclodextrin cavity,
have a greater tendency to form inclusion complexes with the
cyclodextrin molecules, thus rendering the preservative less
effective to control microbes in the cyclodextrin solution.
Therefore, many well known preservatives such as short chain alkyl
esters of p-hydroxybenzoic acid, commonly known as parabens;
N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl) urea, also known as
3,4,4'-trichlorocarbanilide or triclocarban;
2,4,4'-trichloro-2'-hydroxy diphenyl ether, commonly known as
triclosan are not preferred in the present invention since they are
relatively ineffective when used in conjunction with
cyclodextrin.
[0124] The water-soluble antimicrobial preservative in the present
invention is included at an effective amount. The term "effective
amount" as herein defined means a level sufficient to prevent
spoilage, or prevent growth of inadvertently added microorganisms,
for a specific period of time. In other words, the preservative is
not being used to kill microorganisms on the surface onto which the
composition is deposited in order to eliminate odors produced by
microorganisms.
[0125] Instead, it is preferably being used to prevent spoilage of
the cyclodextrin solution in order to increase the shelf-life of
the composition. Preferred levels of preservative are from about
0.0001% to about 0.5%, more preferably from about 0.0002% to about
0.2%, most preferably from about 0.0003% to about 0.1%, by weight
of the usage composition.
[0126] In order to reserve most of the cyclodextrins for odor
control, the cyclodextrin to preservative molar ratio should be
greater than about 5:1, preferably greater than about 10:1, more
preferably greater than about 50:1, even more preferably greater
than about 100:1.
[0127] The preservative can be any organic preservative material
which will not cause damage to fabric appearance, e.g.,
discoloration, coloration, bleaching. Preferred water-soluble
preservatives include organic sulfur compounds, halogenated
compounds, cyclic organic nitrogen compounds, low molecular weight
aldehydes, quaternary ammonium compounds, dehydroacetic acid,
phenyl and phenolic compounds, and mixtures thereof.
[0128] The following are non-limiting examples of preferred
water-soluble preservatives for use in the present invention. A
more complete list is found in U.S. Pat. No. 5,714,137,
incorporated hereinbefore by reference.
[0129] 1). Organic Sulfur Compounds
[0130] Preferred water-soluble preservatives for use in the present
invention are organic sulfur compounds. Some non-limiting examples
of organic sulfur compounds suitable for use in the present
invention are:
[0131] (a) 3-Isothiazolone Compounds
[0132] A preferred preservative is an antimicrobial, organic
preservative containing 3-isothiazolone groups.
[0133] This class of compounds is disclosed in U.S. Pat. No.
4,265,899, Lewis et al., issued May 5, 1981, and incorporated
herein by reference. A preferred preservative is a water-soluble
mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and
2-methyl-4-isothiazolin-3-one, more preferably a mixture of about
77% 5-chloro-2-methyl-4-isothiazolin-3- -one and about 23%
2-methyl-4-isothiazolin-3-one, a broad spectrum preservative
available as a 1.5% aqueous solution under the trade name
Kathon.RTM. CG by Rohm and Haas Company.
[0134] When Kathon.RTM. is used as the preservative in the present
invention it is present at a level of from about 0.0001% to about
0.01%, preferably from about 0.0002% to about 0.005%, more
preferably from about 0.0003% to about 0.003%, most preferably from
about 0.0004% to about 0.002%, by weight of the composition.
[0135] Other isothiazolins include 1,2-benzisothiazolin-3-one,
available under the trade name Proxel.RTM. products; and
2-methyl-4,5-trimethylene-- 4-isothiazolin-3-one, available under
the trade name Promexal.RTM.. Both Proxel and Promexal are
available from Zeneca. They have stability over a wide pH range
(i.e., 4-12). Neither contain active halogen and are not
formaldehyde releasing preservatives. Both Proxel and Promexal are
effective against typical Gram negative and positive bacteria,
fungi and yeasts when used at a level from about 0.001% to about
0.5%, preferably from about 0.005% to about 0.05%, and most
preferably from about 0.01% to about 0.02% by weight of the usage
composition.
[0136] (b) Sodium Pyrithione
[0137] Another preferred organic sulfur preservative is sodium
pyrithione, with water solubility of about 50%. When sodium
pyrithione is used as the preservative in the present invention it
is typically present at a level of from about 0.0001% to about
0.01%, preferably from about 0.0002% to about 0.005%, more
preferably from about 0.0003% to about 0.003%, by weight of the
usage composition.
[0138] Mixtures of the preferred organic sulfur compounds can also
be used as the preservative in the present invention.
[0139] 2). Halogenated Compounds
[0140] Preferred preservatives for use in the present invention are
halogenated compounds. Some non-limiting examples of halogenated
compounds suitable for use in the present invention are:
[0141] 5-bromo-5-nitro-1,3-dioxane, available under the trade name
Bronidox L.RTM. from Henkel. Bronidox L.RTM. has a solubility of
about 0.46% in water. When Bronidox is used as the preservative in
the present invention it is typically present at a level of from
about 0.0005% to about 0.02%, preferably from about 0.001% to about
0.01%, by weight of the usage composition;
[0142] 2-bromo-2-nitropropane-1,3-diol, available under the trade
name Bronopol.RTM. from Inolex can be used as the preservative in
the present invention. Bronopol has a solubility of about 25% in
water. When Bronopol is used as the preservative in the present
invention it is typically present at a level of from about 0.002%
to about 0.1%, preferably from about 0.005% to about 0.05%, by
weight of the usage composition;
[0143] 1,1'-hexamethylene bis(5-(p-chlorophenyl)biguamide),
commonly known as chlorhexidine, and its salts, e.g., with acetic
and gluconic acids can be used as a preservative in the present
invention. The digluconate salt is highly water-soluble, about 70%
in water, and the diacetate salt has a solubility of about 1.8% in
water. When chlorhexidine is used as the preservative in the
present invention it is typically present at a level of from about
0.0001% to about 0.04%, preferably from about 0.0005% to about
0.01%, by weight of the usage composition.
[0144] 1,1,1-Trichloro-2-methylpropan-2-ol, commonly known as
chlorobutanol, with water solubility of about 0.8%; a typical
effective level of chlorobutanol is from about 0.1% to about 0.5%,
by weight of the usage composition.
4,4'-(Trimethylenedioxy)bis-(3-bromobenzamidine) diisethionate, or
dibromopropamidine, with water solubility of about 50%; when
dibromopropamidine is used as the preservative in the present
invention it is typically present at a level of from about 0.0001%
to about 0.05%, preferably from about 0.0005% to about 0.01% by
weight of the usage composition.
[0145] Mixtures of the preferred halogenated compounds can also be
used as the preservative in the present invention.
[0146] 3). Cyclic Organic Nitrogen Compounds
[0147] Preferred water-soluble preservatives for use in the present
invention are cyclic organic nitrogen compounds. Some non-limiting
examples of cyclic organic nitrogen compounds suitable for use in
the present invention are:
[0148] (a) Imidazolidinedione Compounds
[0149] Preferred preservatives for use in the present invention are
imidazolidione compounds. Some non-limiting examples of
imidazolidinedione compounds suitable for use in the present
invention are:
[0150] 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione,
commonly known as dimethyloldimethylhydantoin, or DMDM hydantoin,
available as, e.g., Glydan.RTM. from Lonza. DMDM hydantoin has a
water solubility of more than 50% in water, and is mainly effective
on bacteria. When DMDM hydantoin is used, it is preferable that it
be used in combination with a broad spectrum preservative such as
Kathon CG.RTM., or formaldehyde. A preferred mixture is about a
95:5 DMDM hydantoin to 3-butyl-2-iodopropynylcarbamate mixture,
available under the trade name Glydant Plus.RTM. from Lonza. When
Glydant Plus.RTM. is used as the preservative in the present
invention, it is typically present at a level of from about 0.005%
to about 0.2% by weight of the usage composition;
[0151]
N-[1,3-bis(hydroxymethyl)2,5-dioxo-4-imidazolidinyl]-N,N'-bis(hydro-
xymethyl) urea, commonly known as diazolidinyl urea, available
under the trade name Germall II.RTM. from Sutton Laboratories, Inc.
(Sutton) can be used as the preservative in the present invention.
When Germall II is used as the preservative in the present
invention, it is typically present at a level of from about 0.01%
to about 0.1% by weight of the usage composition;
[0152]
N,N"-methylenebis{N'-[1-(hydroxymethyl)-2,5-dioxo-4-imidazolidinyl]-
urea}, commonly known as imidazolidinyl urea, available, e.g.,
under the trade name Abiol.RTM. from 3V-Sigma, Unicide U-13.RTM.
from Induchem, Germall 115.RTM. from (Sutton) can be used as the
preservative in the present invention. When imidazolidinyl urea is
used as the preservative, it is typically present at a level of
from about 0.05% to about 0.2%, by weight of the usage
composition.
[0153] Mixtures of the preferred imidazolidinedione compounds can
also be used as the preservative in the present invention.
[0154] (b) Polymethoxy Bicyclic Oxazolidine
[0155] Another preferred water-soluble cyclic organic nitrogen
preservative is polymethoxy bicyclic oxazolidine, available under
the trade name Nuosept.RTM. C from Huls America. When Nuosept.RTM.
C is used as the preservative, it is typically present at a level
of from about 0.005% to about 0.1%, by weight of the usage
composition.
[0156] Mixtures of the preferred cyclic organic nitrogen compounds
can also be used as the preservative in the present invention.
[0157] 4). Low Molecular Weight Aldehydes
[0158] (a). Formaldehyde
[0159] A preferred preservative for use in the present invention is
formaldehyde. Formaldehyde is a broad spectrum preservative which
is normally available as formalin which is a 37% aqueous solution
of formaldehyde. When formaldehyde is used as the preservative in
the present invention, typical levels are from about 0.003% to
about 0.2%, preferably from about 0.008% to about 0.1%. more
preferably from about 0.01% to about 0.05%, by weight of the usage
composition.
[0160] (b) Glutaraldehyde
[0161] A preferred preservative for use in the present invention is
glutaraldehyde. Glutaraldehyde is a water-soluble, broad spectrum
preservative commonly available as a 25% or a 50% solution in
water. When glutaraldehyde is used as the preservative in the
present invention it is typically present at a level of from about
0.005% to about 0.1%, preferably from about 0.01% to about 0.05%,
by weight of the usage composition.
[0162] 5). Quaternary Compounds
[0163] Preferred preservatives for use in the present invention are
cationic and/or quaternary compounds. Such compounds include
polyaminopropyl biguamide, also known as polyhexamethylene
biguamide having the general formula:
HCl.NH.sub.2--(CH.sub.2).sub.3--[--(CH.sub.2).sub.3--NH--C(.dbd.NH)--NH--C-
(.dbd.NH.HCl)--NH--(CH.sub.2).sub.3--].sub.x--(CH.sub.2).sub.3--NH--C(.dbd-
.NH--NH.CN
[0164] Polyaminopropyl biguamide is a water-soluble, broad spectrum
preservative which is available as a 20% aqueous solution available
under the trade name Cosmocil CQ.RTM. from ICI Americas, Inc., or
under the trade name Mikrokill.RTM. from Brooks, Inc.
[0165] 1-(3-Chlorallyl) -3,5,7-triaza-1-azoniaadamantane chloride,
available, e.g., under the trade name Dowicil 200 from Dow
Chemical, is an effective quaternary ammonium preservative; it is
freely soluble in water; however, it has the tendency to discolor
(yellow), therefore it is not highly preferred.
[0166] Mixtures of the preferred quaternary ammonium compounds can
also be used as the preservative in the present invention.
[0167] When quaternary ammonium compounds are used as the
preservative in the present invention, they are typically present
at a level of from about 0.005% to about 0.2%, preferably from
about 0.01% to about 0.1%, by weight of the usage composition.
[0168] 6). Dehydroacetic Acid
[0169] A preferred preservative for use in the present invention is
dehydroacetic acid. Dehydroacetic acid is a broad spectrum
preservative preferably in the form of a sodium or a potassium salt
so that it is water-soluble. This preservative acts more as a
biostatic preservative than a biocidal preservative. When
dehydroacetic acid is used as the preservative it is typically used
at a level of from about 0.005% to about 0.2%, preferably from
about 0.008% to about 0.1%, more preferably from about 0.01% to
about 0.05%, by weight of the usage composition.
[0170] 7). Phenyl and Phenolic Compounds
[0171] Some non-limiting examples of phenyl and phenolic compounds
suitable for use in the present invention are:
[0172] 4,4'-diamidino-.alpha.,.omega.-diphenoxypropane
diisethionate, commonly known as propamidine isethionate, with
water solubility of about 16%; and
4,4'-diamidino-.alpha.,.omega.-diphenoxyhexane diisethionate,
commonly known as hexamidine isethionate. Typical effective level
of these salts is about 0.0002% to about 0.05% by weight of the
usage composition.
[0173] Other examples are benzyl alcohol, with a water solubility
of about 4%; 2-phenylethanol, with a water solubility of about 2%;
and 2-phenoxyethanol, with a water solubility of about 2.67%;
typical effective level of these phenyl and phenoxy alcohol is from
about 0.1% to about 0.5%, by weight of the usage composition.
[0174] 8). Mixtures Thereof
[0175] The preservatives of the present invention can be used in
mixtures in order to control a broad range of microorganisms.
[0176] Bacteriostatic effects can sometimes be obtained for aqueous
compositions by adjusting the composition pH to an acid pH, e.g.,
less than about pH 4, preferably less than about pH 3, or a basic
pH, e.g., greater than about 10, preferably greater than about 11.
Low pH for microbial control is not a preferred approach in the
present invention because the low pH can cause chemical degradation
of the cyclodextrins. High pH for microbial control is also not
preferred because at high pH's, e.g., greater than about 10,
preferably greater than about 11, the cyclodextrins can be ionized
and their ability to complex with organic materials is reduced.
Therefore, aqueous compositions of the present invention should
have a pH of from about 3 to about 10, preferably from about 4 to
about 8, more preferably from about 4.5 to about 6. The pH is
typically adjusted with inorganic molecules to minimize
complexation with cyclodextrin.
[0177] (J). Cyclodextrin Compatible Wrinkle Control Agent
[0178] The composition can also optionally contain an effective
amount of a cyclodextrin-compatible fabric wrinkle control agent,
preferably selected from the group consisting of: fiber lubricant,
shape retention polymer, hydrophilic plasticizer, lithium salt, and
mixtures thereof.
[0179] 1) Cyclodextrin Compatible Fiber Lubricants
[0180] The present invention can use a cyclodextrin compatible
fiber lubricant to impart a lubricating property or increased
gliding ability to fibers in fabric, particularly clothing. Not to
be bound by theory, it is believed that water and other alcoholic
solvents break or weaken the hydrogen bonds that hold the wrinkles,
the cyclodextrin compatible fabric lubricant facilitates the fibers
to glide on one another to further release the fibers from the
wrinkle condition in wet or damp fabric. After the fabric is dried,
the residual silicone can provide lubricity to reduce the tendency
of fabric rewrinkling.
[0181] a) Cyclodextrin Compatible Silicone
[0182] The present invention can use silicone to impart a
lubricating property or increased gliding ability to fibers in
fabric, particularly clothing. The silicone useful in providing
fiber lubricity in the composition of the present invention should
be cyclodextrin-compatible, that is it should not substantially
form complex with cyclodextrin so as to diminish performance of the
cyclodextrin and/or the silicone. Complex formation diminishes both
the ability of the cyclodextrin to absorb odors and the ability of
the silicone to provide fiber lubricity. The preferred cyclodextrin
compatible silicones have pendant alkyl groups having less than
about 8, preferably less than about 6, carbon atoms, and do not
have pendant aryl groups. Nonlimiting examples of useful silicones
include noncurable silicones such as polydimethylsilicone and
volatile silicones, and curable silicones such as aminosilicones
and hydroxysilicones. When the composition of this invention is to
be dispensed from a spray dispenser in a consumer household
setting, the noncurable silicones such as polydimethylsilicone,
especially the volatile silicones, are preferred. Curable and/or
reactive silicones such as amino-functional silicones silicones and
silicones with reactive groups such as Si--OH, Si--H, silanes, and
the like, are not preferred in this situation, because the portion
of the composition that is sprayed but misses the garment, and
falls instead on flooring surfaces, such as rugs, carpets, concrete
floors, tiled floors, linoleum floors, bathtub floors, can leave a
silicone layer that is accumulated and/or cured and/or bonded to
the flooring surfaces. Such silicones that are accumulated on such
surfaces, and especially those that are bonded to such surfaces are
difficult to remove. Flooring surfaces thus become slippery and can
present a safety hazard to the household members. The curable and
reactive silicones can be used in compositions specifically
designed for use in enclosed areas such as in a dewrinkling
cabinet. Many types of aminofunctional silicones also cause fabric
yellowing. Thus, the silicones that cause fabric discoloration are
also not preferred.
[0183] The word "silicone" as used herein preferably refers to
emulsified and/or microemulsified silicones, including those that
are commercially available and those that are emulsified and/or
microemulsified in the composition, unless otherwise described.
Some non-limiting examples of silicones which are useful in the
present invention are: non-volatile silicone fluids such as
polydimethyl siloxane gums and fluids; volatile silicone fluid
which can be a cyclic silicone fluid of the formula
[(CH.sub.3).sub.2SiO].sub.n where n ranges between about 3 to about
7, preferably about 5, or a linear silicone polymer fluid having
the formula
(CH.sub.3).sub.3SiO[(CH.sub.3).sub.2SiO].sub.mSi(CH.sub.3).sub.3
where m can be 0 or greater and has an average value such that the
viscosity at 25.degree. C. of the silicone fluid is preferably
about 5 centistokes or less.
[0184] Thus one type of silicone that is useful in the composition
of the present invention is polyalkyl silicone with the following
structure:
A--Si(R.sub.2)--O--[Si(R.sub.2)--O--].sub.q--Si(R.sub.2)--A
[0185] The alkyl groups substituted on the siloxane chain (R) or at
the ends of the siloxane chains (A) can have any structure as long
as the resulting silicones remain fluid at room temperature and do
not substantially form a complex with cyclodextrin.
[0186] Each R group preferably is alkyl, hydroxy, or hydroxyalkyl
group, and mixtures thereof, having less than about 8, preferably
less than about 6 carbon atoms, more preferably, each R group is
methyl, ethyl, propyl, hydroxy group, and mixtures thereof, most
preferably each R group is methyl. Aryl, alkylaryl and/or arylalkyl
groups are not preferred. Each A group which blocks the ends of the
silicone chain is hydrogen, methyl, methoxy, ethoxy, hydroxy,
propoxy, and mixtures thereof, preferably methyl. q is preferably
an integer from about 7 to about 8,000. The preferred silicones are
polydimethyl siloxanes; more preferred silicones are polydimethyl
siloxanes having a viscosity of from about 10 to about 1000,000
centistokes at 25.degree. C. Mixtures of volatile silicones and
non-volatile polydimethyl siloxanes are also preferred. Suitable
examples include silicones offered by Dow Corning Corporation and
General Electric Company. Preferably, the silicones are
hydrophobic; are neither irritating, toxic, nor otherwise harmful
when applied to fabric or when they come in contact with human
skin; are compatible with other components of the composition
beside cyclodextrin; are chemically stable under normal use and
storage conditions; and are capable of being deposited on
fabric.
[0187] Suitable methods for preparing these silicone materials are
disclosed in U.S. Pat. Nos. 2,826,551 and 3,964,500, incorporated
herein by reference. Silicones useful in the present invention are
also commercially available. Suitable examples include silicones
offered by Dow Corning Corporation and General Electric
Company.
[0188] Other useful silicone materials, but less preferred than
polydimethyl polysiloxane, include materials of the formula:
HO--[Si(CH.sub.3).sub.2--O].sub.x--{Si(OH)[(CH.sub.2).sub.3--NH--(CH.sub.2-
).sub.2--NH.sub.2]O}.sub.y--H
[0189] wherein x and y are integers which depend on the molecular
weight of the silicone, preferably having a viscosity of from about
10,000 cst to about 500,000 cst at 25.degree. C. This material is
also known as "amodimethicone". Although silicones with a high
number, e.g., greater than about 0.5 millimolar equivalent of amine
groups can be used, they are not preferred because they can cause
fabric yellowing.
[0190] Similarly, silicone materials which can be used correspond
to the formulas:
(R.sup.1).sub.aG.sub.3-a--Si--(--OSiG.sub.2).sub.n--(OSiG.sub.b(R.sup.1).s-
ub.2-b).sub.m--O--SiG.sub.3-a(R.sup.1).sub.a
[0191] wherein G is selected from the group consisting of hydrogen,
OH, and/or C.sub.1-C.sub.5 alkyl; a denotes 0 or an integer from 1
to 3; b denotes 0 or 1; the sum of n+m is a number from 1 to about
2,000; R.sup.1 is a monovalent radical of formula C.sub.pH.sub.2pL
in which p is an integer from 2 to 4 and L is selected from the
group consisting of:
[0192] --N(R.sup.2)CH.sub.2--CH.sub.2--N(R.sup.2).sub.2;
[0193] --N(R.sup.2).sub.2;
[0194] --N.sup.+(R.sup.2).sub.3 A.sup.-; and
[0195] --N.sup.+(R.sup.2)CH.sub.2--CH.sub.2N.sup.+H.sub.2
A.sup.-
[0196] wherein each R.sup.2 is chosen from the group consisting of
hydrogen, a C.sub.1-C.sub.5 saturated hydrocarbon radical, and each
A.sup.- denotes compatible anion, e.g., a halide ion; and
R.sup.3--N.sup.+(CH.sub.3).sub.2--Z--[Si(CH.sub.3).sub.2O].sub.f--Si(CH.su-
b.3).sub.2--Z--N.sup.+(CH.sub.3).sub.2--R.sup.3.2CH.sub.3COO.sup.-
[0197] wherein
[0198] Z=--CH.sub.2--CH(OH)--CH.sub.2O--CH.sub.2).sub.3--
[0199] R.sup.3 denotes a long chain alkyl group; and
[0200] f denotes an integer of at least about 2.
[0201] In the formulas herein, each definition is applied
individually and averages are included.
[0202] Another silicone material which can be used, but is less
preferred than polydimethyl siloxanes, has the formula:
(CH.sub.3).sub.3--Si--[OSi(CH.sub.3).sub.2].sub.n--{--O--Si(CH.sub.3)[(CH.-
sub.2).sub.3--NH--(CH.sub.2).sub.2--NH.sub.2]}.sub.mOSi(CH.sub.3).sub.3
[0203] wherein n and m are the same as before. The preferred
silicones of this type are those which do not cause fabric
discoloration.
[0204] Alternatively, the silicone material can be provided as a
moiety or a part of a non-silicone molecule. Examples of such
materials are copolymers containing silicone moieties, typically
present as block and/or graft copolymers.
[0205] When silicone is present, it is present at least an
effective amount to provide lubrication of the fibers, typically
from about 0.1% to about 5%, preferably from about 0.2% to about
3%, more preferably from about 0.3% to about 2%, by weight of the
usage composition.
[0206] b) Synthetic Solid Particles
[0207] Solid polymeric particles of average particle size smaller
than about 10 microns, preferably smaller than 5 microns, more
preferably smaller than about 1 micron, e.g., Velustrol P-40
oxidized polyethylene emulsion available from Clariant, can be used
as a lubricant, since they can provide a "roller-bearing" action.
When solid polymeric particles are present, they are present at an
effective amount to provide lubrication of the fibers, typically
from about 0.01% to about 3%, preferably from about 0.05% to about
1%, more preferably from about 0.1% to about 0.5%, by weight of the
usage composition.
[0208] 2) Cyclodextrin Compatible Shape Retention Polymer
[0209] These polymers can be natural, or synthetic, and can act by
forming a film, and/or by providing adhesive properties. E.g., the
present invention can optionally use film-forming and/or adhesive
polymer to impart shape retention to fabric, particularly clothing.
By "adhesive" it is meant that when applied as a solution or a
dispersion to a fiber surface and dried, the polymer can attach to
the surface. The polymer can form a film on the surface, or when
residing between two fibers and in contact with the two fibers, it
can bond the two fibers together. Other polymers such as starches
can form a film and/or bond the fibers together when the treated
fabric is pressed by a hot iron. Such a film will have adhesive
strength, cohesive breaking strength, and cohesive breaking
strain.
[0210] The polymer useful in providing shape retention in the
composition of the present invention should be
cyclodextrin-compatible, that is it should not substantially form
complex with cyclodextrin so as to diminish performance of the
cyclodextrin and/or the polmer. Complex formation affects both the
ability of the cyclodextrin to absorb odors and the ability of the
polymer to impart shape retention to fabric.
[0211] Nonlimiting examples for natural polymers are starches and
their derivatives, and chitins and their derivatives.
[0212] The synthetic polymers useful in the present invention are
comprised of monomers. Some nonlimiting examples of monomers which
can be used to form the synthetic polymers of the present invention
include: low molecular weight C.sub.1-C.sub.6 unsaturated organic
mono- and polycarboxylic acids, such as acrylic acid, methacrylic
acid, crotonic acid, maleic acid and its half esters, itaconic
acid, and mixtures thereof; esters of said acids with
C.sub.1-C.sub.6 alcohols, such as methanol, ethanol,
[0213] 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,
1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,
1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol,
2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol, cyclohexanol,
2-ethyl-1-butanol, and the like, and mixtures thereof. Nonlimiting
examples of said esters are methyl acrylate, ethyl acrylate,
t-butyl acrylate, methyl methacrylate, hydroxyethyl methacrylate,
methoxy ethyl methacrylate, and mixtures thereof; amides and imides
of said acids, such as N,N-dimethylacrylamide, N-t-butyl
acrylamide, maleimides; low molecular weight unsaturated alcohols
such as vinyl alcohol (produced by the hydrolysis of vinyl acetate
after polymerization), allyl alcohol; esters of said alcohols with
low molecular weight carboxylic acids, such as, vinyl acetate,
vinyl propionate; ethers of said alcohols such as methyl vinyl
ether; polar vinyl heterocyclics, such as vinyl pyrrolidone, vinyl
caprolactam, vinyl pyridine, vinylimidazole, and mixtures thereof;
other unsaturated amines and amides, such as vinyl amine,
diethylene triamine, dimethylaminoethyl methacrylate, ethenyl
formamide; vinyl sulfonate; salts of acids and amines listed above;
low molecular weight unsaturated hydrocarbons and derivatives such
as ethylene, propylene, butadiene, cyclohexadiene, vinyl chloride;
vinylidene chloride; and mixtures thereof and alkyl quatemized
derivatives thereof, and mixtures thereof. Preferably, said
monomers are selected from the group consisting of vinyl alcohol;
acrylic acid; methacrylic acid; methyl acrylate; ethyl acrylate;
methyl methacrylate; t-butyl acrylate; t-butyl methacrylate;
n-butyl acrylate; n-butyl methacrylate; dimethylaminoethyl
methacrylate; N,N-dimethyl acrylamide; N,N-dimethyl methacrylamide;
N-t-butyl acrylamide; vinylpyrrolidone; vinyl pyridine; adipic
acid; diethylenetriamine; salts thereof and alkyl quatemized
derivatives thereof, and mixtures thereof. Monomers which provide
pendant groups that can complex with cyclodextrin are not preferred
because they can form complex with cyclodextrin. Examples of such
monomers are acrylic or methacrylic acid esters of C.sub.7-C.sub.18
alcohols, such as neodecanol, 3-heptanol, benzyl alcohol,
2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,
3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, and 1-decanol;
styrene; t-butylstyrene; vinyl toluene; and the like.
[0214] Preferably, said monomers form homopolymers and/or
copolymers (i.e., the film-forming and/or adhesive polymer) having
a glass transition temperature (Tg) of from about -20.degree. C. to
about 150.degree. C., preferably from about -10C to about
150.degree. C., more preferably from about 0.degree. C. to about
100.degree. C., most preferably, the adhesive polymer hereof, when
dried to form a film will have a Tg of at least about 25.degree.
C., so that they are not unduly sticky, or "tacky" to the touch.
Preferably said polymer is soluble and/or dispersible in water
and/or alcohol. Said polymer typically has a molecular weight of at
least about 500, preferably from about 1,000 to about 2,000,000,
more preferably from about 5,000 to about 1,000,000, and even more
preferably from about 30,000 to about 300,000 for some
polymers.
[0215] Some non-limiting examples of homopolymers and copolymers
which can be used as film-forming and/or adhesive polymers of the
present invention are: adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer; adipic acid/epoxypropyl
diethylenetriamine copolymer;
poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinyl
alcohol; polyvinylpyridine n-oxide; methacryloyl ethyl
betaine/methacrylates copolymer; ethyl acrylate/methyl
methacrylate/methacrylic acid/acrylic acid copolymer; polyamine
resins; and polyquaternary amine resins; poly(ethenylformamide);
poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-6%
vinylamine); poly(vinyl alcohol-co-12% vinylamine); poly(vinyl
alcohol-co-6% vinylamine hydrochloride); and poly(vinyl
alcohol-co-12% vinylamine hydrochloride). Preferably, said
copolymer and/or homopolymers are selected from the group
consisting of adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer;
poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinyl
alcohol; ethyl acrylate/methyl methacrylate/methacrylic
acid/acrylic acid copolymer; methacryloyl ethyl
betaine/methacrylates copolymer; polyquaternary amine resins;
poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl
alcohol-co-6% vinylamine); poly(vinyl alcohol-co-12% vinylamine);
poly(vinyl alcohol-co-6% vinylamine hydrochloride); and poly(vinyl
alcohol-co-12% vinylamine hydrochloride).
[0216] Nonlimiting examples of the preferred polymer that are
commercially available are: polyvinylpyrrolidone/dimethylaminoethyl
methacrylate copolymer, such as Copolymer 958.RTM., molecular
weight of about 100,000 and Copolymer 937, molecular weight of
about 1,000,000, available from GAF Chemicals Corporation; adipic
acid/dimethylaminohydroxypropyl diethylenetriamine copolymer, such
as Cartaretin F-4.RTM. and F-23, available from Sandoz Chemicals
Corporation; methacryloyl ethyl betaine/methacrylates copolymer,
such as Diaformer Z-SM.RTM., available from Mitsubishi Chemicals
Corporation; polyvinyl alcohol copolymer resin, such as Vinex
2019.RTM., available from Air Products and Chemicals or
Moweol.RTM., available from Clariant; adipic acid/epoxypropyl
diethylenetriamine copolymer, such as Delsette 101.RTM., available
from Hercules Incorporated; polyamine resins, such as Cypro
515.RTM., available from Cytec Industries; polyquaternary amine
resins, such as Kymene 557H.RTM., available from Hercules
Incorporated; and polyvinylpyrrolidone/acrylic acid, such as
Sokalan EG 310.RTM., available from BASF.
[0217] Preferred polymers useful in the present invention are
selected from the group consisting of copolymers of hydrophilic
monomers and hydrophobic monomers. The polymer can be linear random
or block copolymers, and mixtures thereof. Such
hydrophobic/hydrophilic copolymers typically have a hydrophobic
monomer/hydrophilic monomer ratio of from about 95:5 to about
20:80, preferably from about 90:10 to about 40:60, more preferably
from about 80:20 to about 50:50 by weight of the copolymer. The
hydrophobic monomer can comprise a single hydrophobic monomer or a
mixture of hydrophobic monomers, and the hydrophilic monomer can
comprise a single hydrophilic monomer or a mixture of hydrophilic
monomers. The term "hydrophobic" is used herein consistent with its
standard meaning of lacking affinity for water, whereas
"hydrophilic" is used herein consistent with its standard meaning
of having affinity for water. As used herein in relation to monomer
units and polymeric materials, including the copolymers,
"hydrophobic" means substantially water insoluble; "hydrophilic"
means substantially water soluble. In this regard, "substantially
water insoluble" shall refer to a material that is not soluble in
distilled (or equivalent) water, at 25.degree. C., at a
concentration of about 0.2% by weight, and preferably not soluble
at about 0.1% by weight (calculated on a water plus monomer or
polymer weight basis). "Substantially water soluble" shall refer to
a material that is soluble in distilled (or equivalent) water, at
25.degree. C., at a concentration of about 0.2% by weight, and are
preferably soluble at about 1% by weight. The terms "soluble",
"solubility" and the like, for purposes hereof, corresponds to the
maximum concentration of monomer or polymer, as applicable, that
can dissolve in water or other solvents to form a homogeneous
solution, as is well understood to those skilled in the art.
[0218] Nonlimiting examples of useful hydrophobic monomers are
acrylic acid C.sub.1-C.sub.6 alkyl esters, such as methyl acrylate,
ethyl acrylate, t-butyl acrylate; methacrylic C.sub.1-C.sub.6 alkyl
esters, such as methyl methacrylate, methoxy ethyl methacrylate;
vinyl alcohol esters of carboxylic acids, such as, vinyl acetate,
vinyl propionate, vinyl ethers, such as methyl vinyl ether; vinyl
chloride; vinylidene chloride; ethylene, propylene and other
unsaturated hydrocarbons; and the like; and mixtures thereof. Some
preferred hydrophobic monomers are methyl acrylate, methyl
methacrylate, t-butyl acrylate, t-butyl methacrylate, n-butyl
acrylate, n-butyl methacrylate, and mixtures thereof.
[0219] Nonlimiting examples of useful hydrophilic monomers are
unsaturated organic mono- and polycarboxylic acids, such as acrylic
acid, methacrylic acid, crotonic acid, maleic acid and its half
esters, itaconic acid; unsaturated alcohols, such as vinyl alcohol,
allyl alcohol; polar vinyl heterocyclics, such as vinyl
pyrrolidone, vinyl caprolactam, vinyl pyridine, vinylimidazole;
vinyl amine; vinyl sulfonate; unsaturated amides, such as
acrylamides, e.g., N,N-dimethylacrylamide, N-t-butyl acrylamide;
hydroxyethyl methacrylate; dimethylaminoethyl methacrylate; salts
of acids and amines listed above; and the like; and mixtures
thereof. Some preferred hydrophilic monomers are acrylic acid,
methacrylic acid, N,N-dimethyl acrylamide, N,N-dimethyl
methacrylamide, N-t-butyl acrylamide, dimethylamino ethyl
methacrylate, vinyl pyrrolidone, salts thereof and alkyl quatemized
derivatives thereof, and mixtures thereof.
[0220] Non limiting examples of polymers for use in the present
invention include the following, where the composition of the
copolymer is given as approximate weight percentage of each monomer
used in the polymerization reaction used to prepare the polymer:
vinyl pyrrolidone/vinyl acetate copolymers (at ratios of up to
about 30% by weight of vinyl pyrrolidone); vinyl pyrrolidone/vinyl
acetate/butyl acrylate copolymer (10/78/12 and 10/70/20); vinyl
pyrrolidone/vinyl propionate copolymer (5/95); vinyl
caprolactam/vinyl acetate copolymer (5/95); and resins sold under
the trade names Ultrahold CA 8.RTM. by Ciba Geigy (ethyl
acrylate/acrylic acid/N-t-butyl acrylamide copolymer); Resyn
28-1310.RTM. by National Starch and Luviset CA 66.RTM. by BASF
(vinyl acetate/crotonic acid copolymer 90/10); Luviset CAP.RTM. by
BASF (vinyl acetate/vinyl propionate/crotonic acid 50/40/10);
Amerhold DR-25.RTM. by Union Carbide (ethyl acrylate/methacrylic
acid/methyl methacrylate/acrylic acid copolymer), and Poligen
A.RTM. by BASF (polyacrylate dispersion). One highly preferred
polymer is composed of acrylic acid and t-butyl acrylate monomeric
units, preferably with acrylic acid/t-butyl acrylate ratio of from
about 90:10 to about 10:90, preferably from about 70:30 to about
15:85, more preferably from about 50:50 to about 20:80, by weight
of the polymer. Nonlimiting examples of acrylic acid/tert-butyl
acrylate copolymers useful in the present invention are those with
an approximate acrylic acid/tert-butyl acrylate weight ratio of
about 25:75 and an average molecular weight of from about 70,000 to
about 100,000, and those with an approximate acrylic
acid/tert-butyl acrylate weight ratio of about 35:65 and an average
molecular weight of from about 60,000 to about 90,000.
[0221] The film-forming and/or adhesive polymer of the present
invention is present at least an effective amount to provide shape
retention, typically from about 0.05% to about 5%, preferably from
about 0.1% to about 3%, more preferably from about 0.2% to about
2%, even more preferably from about 0.3% to about 1%, by weight of
the usage composition.
[0222] The adhesive polymer is present in the composition in a
sufficient amount to result in an amount of from about 0.001% to
about 1%, preferably from about 0.01% to about 0.5%, more
preferably from about 0.02% to about 0.4% by weight of polymer per
weight of dry fabrics.
[0223] It is not intended to exclude the use of higher or lower
levels of the polymers, as long as an effective amount is used to
provide adhesive and film-forming properties to the composition and
the composition can be formulated and effectively applied for its
intended purpose.
[0224] Concentrated compositions can also be used in order to
provide a less expensive product. When a concentrated product is
used, i.e., when the wrinkle reducing active is from about 5% to
about 50%, by weight of the concentrated composition, it is
preferable to dilute the composition before treating fabric.
Preferably, the wrinkle reducing active is diluted with about 50%
to about 10,000%, more preferably from about 50% to about 8,000%,
and even more preferably from about 50% to about 5,000%, by weight
of the composition, of water.
[0225] Silicones and film-forming polymers can be combined to
produce preferred wrinkle reducing actives. Typically the weight
ratio of silicone to film-forming polymer is from about 10:1 to
about 1:10, preferably from about 5:1 to about 1:5, and more
preferably from about 2:1 to about 1:2. Typically, the preferred
wrinkle reducing active of silicone plus polymer is present at a
level of from about 0.1% to about 8%, preferably from about 0.3% to
about 5%, more preferably from about 0.5% to about 3%, by weight of
the composition.
[0226] Other preferred adhesive and/or film forming polymers that
are useful in the composition of the present invention actually
contain silicone moieties in the polymers themselves, typically
present as block and/or graft copolymers.
[0227] The preferred polymers for use herein have the
characteristic of providing a natural appearing "drape" in which
the fabric does not form wrinkles, or resist deformation.
[0228] Starch
[0229] Starch is not normally preferred, since it makes the fabric
resistant to deformation. However, it does provide increased "body"
which is often desired. Starch is particularly preferred in
compositions of this invention to be used with ironing. When used,
starch is solubilized or dispersed in the composition. Any type of
starch, e.g. those derived from corn, wheat, rice, grain sorghum,
waxy grain sorghum, waxy maize or tapioca, or mixtures thereof and
water soluble or dispersible modifications or derivatives thereof,
can be used in the composition of the present invention. Modified
starches that can be used include natural starches that have been
degraded to obtain a lower viscosity by acidic, oxidative or
enzymic depolymerization. Additionally, low viscosity commercially
available propoxylated and/or ethoxylated starches are useable in
the present composition and are preferred since their low viscosity
at relatively high solids concentrations make them very adaptable
to spraying processes. Suitable alkoxylated, low viscosity starches
are submicron sized particles of hydrophobic starch that are
readily dispersed in water and are prepared by alkoxylation of
granular starch with a monofunctional alkoxylating agent which
provides the starch with ether linked hydrophilic groups. A
suitable method for their preparation is taught in U.S. Pat. No.
3,462,283. In accordance with the invention, the propoxylated or
ethoxylated starch derivatives are dispersed in the aqueous medium
in an amount of from about 0.1% to about 10%, preferably from about
0.5% to about 6%, more preferably from about 1% to about 4% by
weight of the usage composition.
[0230] Preferred pH Range
[0231] Compositions according to the present invention, which
contain a shape retention polymer having hydrophilic monomers with
an acid functional pending group, such as acrylic acid, methacrylic
acid, crotonic acid, maleic acid and its half esters, itaconic
acid, and mixtures thereof, preferably are adjusted to have a pH of
greater than about 6.5, preferably from about 7 and about 11, more
preferably from about 8 to about 10.5, most preferably from about 9
to about 10.5 to improve the solubility of the polymer. Above pH
11, the ability of cyclodextrin to form complexes and to control
odor is diminished. This is achieved by the addition of a caustic
alkali. Example of suitable caustic alkalis for use herein include
sodium and potassium hydroxide.
[0232] These polymers, by themselves, also provide odor control to
some amine type malodors. If amine malodor control is desired, the
pH of the solution should be kept as low as possible, preferably
from about 4 to about 8, more preferably from about 6.5 to about
7.5.
[0233] 3) Optional Cyclodextrin-Compatible Hydrophilic
Plasticizer
[0234] Optionally, the composition can contain a
cyclodextrin-compatible hydrophilic plasticizer to soften both the
fabric fibers, especially cotton fibers, and the adhesive and/or
film-forming shape retention polymers. Examples of the preferred
hydrophilic plasticizers are short chain polyhydric alcohols, such
as is glycerol, ethylene glycol, propylene glycol, diethylene
glycol, dipropylene glycol, sorbitol, erythritol or mixtures
thereof, more preferably diethylene glycol, dipropylene glycol,
ethylene glycol, propylene glycol and mixtures thereof.
[0235] The aqueous compositions containing these plasticizers also
tend to provide a slower drying profile for clothing/fabrics, to
allow time for any wrinkles to disappear when the clothing/fabrics
are hung to dry. This is balanced by the desire by most consumer to
have the garments to dry faster. Therefore, when needed, the
plasticizers should be used at an effective, but as low as
possible, level in the composition. When a hydrophilic plasticizer
is used, it is present in the at a level of from 0.01% to 5%,
preferably from 0.05% to 2%, more preferably from 0. 1% to 1% by
weight of the usage composition.
[0236] (4) Lithium Salts.
[0237] Lithium salts are disclosed to be used as solubilizing aids
in the production silk fibroin using lithium bromide, e.g., U.S.
Pat. No. 4,233,212, issued Nov. 11, 1980 to Otoi et al., and
lithium thiocyanate, e.g., U.S. Pat. No. 5,252,285, issued Oct. 12,
1993 to Robert L. Lock. U.S. Pat. No. 5,296,269, issued Mar. 22,
1994 to Yang et al. discloses a process to produce crease-resistant
silk using lithium bromide and lithium chloride. U.S. Pat. No.
5,199,954, issued Apr. 6, 1993 to Schultz et al. discloses a hair
dye composition containing lithium bromide. Lithium salts are
disclosed as static control agents in a liquid softener composition
in U.S. Pat. No. 4,069,159, issued Jan. 17, 1978 to Mason Hayek.
All of these patents are incorporated herein by reference.
[0238] It is now found that aqueous composition comprising lithium
salts and lithium salt hydrates provides improved fabric wrinkle
control. Lithium salts that are useful in the present invention are
cyclodextrin compatible lithium salts. Cyclodextrin compatible
lithium salts are those having counterions that do not have the
tendency to form a complex with cyclodextrin. Nonlimiting examples
of cyclodextrin compatible lithium salts that are useful in the
present invention are lithium bromide, lithium bromide hydrate,
lithium chloride, lithium chloride hydrate, lithium acetate,
lithium acetate dihydrate, lithium lactate, lithium sulfate,
lithium sulfate monohydrate, lithium tartrate, lithium bitartrate,
and mixtures thereof, preferably lithium bromide, lithium lactate,
and mixtures thereof. Some water soluble salts such as lithium
benzoate are not preferred because they can form complex with
cyclodextrin. Useful levels of lithium salts are from about 0.1% to
about 10%, preferably from about 0.5% to about 7%, more preferably
from about 1% to about 5%, by weight of the usage composition.
[0239] (5) Mixtures Thereof.
[0240] As stated hereinbefore, the composition can also contain
mixtures of fiber lubricant, shape retention polymer, plasticizer,
and/or lithium salts.
[0241] (K) Carrier
[0242] Aqueous solutions are preferred for odor control. The dilute
aqueous solution provides the maximum separation of cyclodextrin
molecules on the fabric and thereby maximizes the chance that an
odor molecule will interact with a cyclodextrin molecule.
[0243] The preferred carrier of the present invention is water. The
water which is used can be distilled, deionized, or tap water.
Water is the main liquid carrier due to its low cost, availability,
safety, and environmental compatibility. Water not only serves as
the liquid carrier for the cyclodextrins, but it also facilitates
the complexation reaction between the cyclodextrin molecules and
any malodorous molecules that are on the fabric when it is treated.
It has recently been discovered that water has an unexpected odor
controlling effect of its own. It has been discovered that the
intensity of the odor generated by some polar, low molecular weight
organic amines, acids, and mercaptans is reduced when the
odor-contaminated fabrics are treated with an aqueous solution. Not
to be bound by theory, it is believed that water solubilizes and
depresses the vapor pressure of these polar, low molecular weight
organic molecules, thus reducing their odor intensity.
[0244] Water is also very useful for fabric wrinkle removal or
reduction. Not to be bound by theory, it is believed that water
breaks many intrafiber and interfiber hydrogen bonds that keep the
fabric in a wrinkle state. It also swells, lubricates and relaxes
the fibers to help the wrinkle removal process.
[0245] The level of liquid carrier in the compositions of the
present invention is typically greater than about 80%, preferably
greater than about 90%, more preferably greater than about 95%, by
weight of the composition. When a concentrated composition is used,
the level of liquid carrier is typically from about 50% to about
98%, by weight of the composition, preferably from about 60% to
about 97%, more preferably from about 70% to about 95%, by weight
of the composition.
[0246] Optionally, in addition to water, the carrier can contain a
low molecular weight organic solvent that is highly soluble in
water, e.g., ethanol, propanol, isopropanol, and the like, and
mixtures thereof. Low molecular weight alcohols can help the
treated fabric to dry faster. The optional solvent is also useful
in the solubilization of some shape retention polymers described
hereinbefore. The optional water soluble low molecular weight
solvent can be used at a level of up to about 50%, typically from
about 1% to about 20%, preferably from about 2% to about 15%, more
preferably from about 5% to about 10%, by weight of the total
composition. Factors that need to consider when a high level of
solvent is used in the composition are odor, flammability, and
environment impact.
[0247] (L) Other Optional Ingredients
[0248] The composition of the present invention can optionally
contain adjunct odor-controlling materials, chelating agents,
antistatic agents, insect and moth repelling agents, colorants,
especially bluing agents, antioxidants, and mixtures thereof in
addition to the cyclodextrin molecules. The total level of optional
ingredients is low, preferably less than about 5%, more preferably
less than about 3%, and even more preferably less than about 2%, by
weight of the usage composition. These optional ingredients exclude
the other ingredients specifically mentioned hereinbefore.
Incorporating adjunct odor-controlling materials can enhance the
capacity of the cyclodextrin to control odors as well as broaden
the range of odor types and molecule sizes which can be controlled.
Such materials include, for example, metallic salts, water-soluble
cationic and anionic polymers, zeolites, water-soluble bicarbonate
salts, and mixtures thereof.
[0249] (1) Water-Soluble Polyionic Polymers
[0250] Some water-soluble polyionic polymers, e.g., water-soluble
cationic polymer and water-soluble anionic polymers can be used in
the composition of the present invention to provide additional odor
control benefits.
[0251] a. Cationic Polymers, e.g., Polyamines
[0252] Water-soluble cationic polymers, e.g., those containing
amino functionalities, amido functionalities, and mixtures thereof,
are useful in the present invention to control certain acid-type
odors.
[0253] b. Anionic Polymers, e.g., Polyacrylic Acid
[0254] Water-soluble anionic polymers, e.g., polyacrylic acids and
their water-soluble salts are useful in the present invention to
control certain amine-type odors. Preferred polyacrylic acids and
their alkali metal salts have an average molecular weight of less
than about 20,000, preferably less than 10,000, more preferably
from about 500 to about 5,000. Polymers containing sulfonic acid
groups, phosphoric acid groups, phosphonic acid groups, and their
water-soluble salts, and mixtures thereof, and mixtures with
carboxylic acid and carboxylate groups, are also suitable.
[0255] Water-soluble polymers containing both cationic and anionic
functionalities are also suitable. Examples of these polymers are
given in U.S. Pat. 4,909,986, issued Mar. 20, 1990 to N. Kobayashi
and A. Kawazoe, incorporated herein by reference. Another example
of water-soluble polymers containing both cationic and anionic
functionalities is a copolymer of dimethyldiallyl ammonium chloride
and acrylic acid, commercially available under the trade name
Merquat 280.RTM. from Calgon.
[0256] When a water-soluble polymer is used it is typically present
at a level of from about 0.001% to about 3%, preferably from about
0.005% to about 2%, more preferably from about 0.01% to about 1%,
and even more preferably from about 0.05% to about 0.5%, by weight
of the usage composition.
[0257] (2). Soluble Carbonate and/or Bicarbonate Salts
[0258] Water-soluble alkali metal carbonate and/or bicarbonate
salts, such as sodium bicarbonate, potassium bicarbonate, potassium
carbonate, cesium carbonate, sodium carbonate, and mixtures thereof
can be added to the composition of the present invention in order
to help to control certain acid-type odors. Preferred salts are
sodium carbonate monohydrate, potassium carbonate, sodium
bicarbonate, potassium bicarbonate, and mixtures thereof. When
these salts are added to the composition of the present invention,
they are typically present at a level of from about 0.1% to about
5%, preferably from about 0.2% to about 3%, more preferably from
about 0.3% to about 2%, by weight of the composition. When these
salts are added to the composition of the present invention it is
preferably that incompatible metal salts not be present in the
invention. Preferably, when these salts are used the composition
should be essentially free of zinc and other incompatible metal
ions, e.g., Ca, Fe, Ba, etc. which form water-insoluble salts.
[0259] (3). Additional Odor Absorbers
[0260] When the clarity of the solution is not needed, and the
solution is not sprayed on fabrics, other optional odor absorbing
materials, e.g., zeolites and/or activated carbon, can also be
used.
[0261] (a). Zeolites
[0262] A preferred class of zeolites is characterized as
"intermediate" silicate/aluminate zeolites. The intermediate
zeolites are characterized by SiO.sub.2/AlO.sub.2 molar ratios of
less than about 10. Preferably the molar ratio of
SiO.sub.2/AlO.sub.2 ranges from about 2 to about 10. The
intermediate zeolites have an advantage over the "high" zeolites.
The intermediate zeolites have a higher affinity for amine-type
odors, they are more weight efficient for odor absorption because
they have a larger surface area, and they are more moisture
tolerant and retain more of their odor absorbing capacity in water
than the high zeolites. A wide variety of intermediate zeolites
suitable for use herein are commercially available as Valfor.RTM.
CP301-68, Valfor.RTM. 300-63, Valfor.RTM. CP300-35, and Valfor.RTM.
CP300-56, available from PQ Corporation, and the CBV100.RTM. series
of zeolites from Conteka.
[0263] Zeolite materials marketed under the trade name
Abscents.RTM. and Smellrite.RTM., available from The Union Carbide
Corporation and UOP are also preferred. These materials are
typically available as a white powder in the 3-5 micron particle
size range. Such materials are preferred over the intermediate
zeolites for control of sulfur-containing odors, e.g., thiols,
mercaptans.
[0264] (b). Activated Carbon
[0265] The carbon material suitable for use in the present
invention is the material well known in commercial practice as an
absorbent for organic molecules and/or for air purification
purposes. Often, such carbon material is referred to as "activated"
carbon or "activated" charcoal. Such carbon is available from
commercial sources under such trade names as; Calgon-Type CPG.RTM.;
Type PCB.RTM.; Type SGL.RTM.; Type CAL.RTM.; and Type OL.RTM..
[0266] (4). Antistatic Agents
[0267] The composition of the present invention can optionally
contain an effective amount of antistatic agent to provide the
treated clothes with in-wear static. Preferred antistatic agents
are those that are water soluble in at least an effective amount,
such that the composition remains a clear solution. Examples of
these antistatic agents are monoalkyl cationic quaternary ammonium
compounds, e.g., mono(C.sub.10-C.sub.14 alkyl)trimethyl ammonium
halide, such as monolauryl trimethyl ammonium chloride,
hydroxycetyl hydroxyethyl dimethyl ammonium chloride, available
under the trade name Dehyquart E.RTM. from Henkel, and ethyl
bis(polyethoxy ethanol) alkylammonium ethylsulfate, available under
the trade name Variquat 66.RTM. from Witco Corp., polymeric
quaternary ammonium salts, such as polymers conforming to the
general formula:
--[N(CH.sub.3).sub.2--(CH.sub.2).sub.3--NH--CO--NH--(CH.sub.2).sub.3--N(CH-
.sub.3).sub.2.sup.+--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2].sub.x.sup.2+2x[Cl.-
sup.-]
[0268] available under the trade name Mirapol A-15.RTM. from
Rhne-Poulenc, and
--[N(CH.sub.3).sub.2--(CH.sub.2).sub.3--NH--CO--(CH.sub.2).sub.4--CO--NH---
(CH.sub.2).sub.3--N(CH.sub.3).sub.2--(CH.sub.2CH.sub.2OCH.sub.2CH.sub.2]---
.sub.x.sup.+x[Cl.sup.-],
[0269] available under the trade name Mirapol AD-1.RTM. from
Rhne-Poulenc, quatemized polyethyleneimines,
vinylpyrrolidone/methacrylamidopropyltrime- thylammonium chloride
copolymer, available under the trade name Gafquat HS-100.RTM. from
GAF; triethonium hydrolyzed collagen ethosulfate, available under
the trade name Quat-Pro E.RTM. from Maybrook; neutralized
sulfonated polystyrene, available, e.g., under the trade name Versa
TL-130.RTM. from Alco Chemical, neutralized sulfonated
styrene/maleic anhydride copolymers, available, e.g., under the
trade name Versa TL-4.RTM. from Alco Chemical; polyethylene
glycols; and mixtures thereof.
[0270] It is preferred that a no foaming, or low foaming, agent is
used, to avoid foam formation during fabric treatment. It is also
preferred that polyethoxylated agents such as polyethylene glycol
or Variquat 66.RTM. are not used when alpha-cyclodextrin is used.
The polyethoxylate groups have a strong affinity to, and readily
complex with, alpha-cyclodextrin which in turn depletes the
uncomplexed cyclodextrin available for odor control.
[0271] When an antistatic agent is used it is typically present at
a level of from about 0.05% to about 10%, preferably from about
0.1% to about 5%, more preferably from about 0.3% to about 3%, by
weight of the usage composition.
[0272] (6). Insect and/or Moth Repelling Agent
[0273] The composition of the present invention can optionally
contain an effective amount of insect and/or moth repelling agents.
Typical insect and moth repelling agents are pheromones, such as
anti-aggregation pheromones, and other natural and/or synthetic
ingredients. Preferred insect and moth repellent agents useful in
the composition of the present invention are perfume ingredients,
such as citronellol, citronellal, citral, linalool, cedar extract,
geranium oil, sandalwood oil, 2-(diethylphenoxy)ethanol,
1-dodecene, etc. Other examples of insect and/or moth repellents
useful in the composition of the present invention are disclosed in
U.S. Pat. Nos. 4,449,987, 4,693,890, 4,696,676, 4,933,371,
5,030,660, 5,196,200, and in "Semio Activity of Flavor and
Fragrance Molecules on Various Insect Species", B. D. Mookherjee et
al., published in Bioactive Volatile Compounds from Plants, ASC
Symposium Series 525, R. Teranishi, R. G. Buttery, and H. Sugisawa,
1993, pp. 35-48, all of said patents and publications being
incorporated herein by reference. When an insect and/or moth
repellent is used it is typically present at a level of from about
0.005% to about 3%, by weight of the usage composition.
[0274] (6). Colorant
[0275] Colorants and dyes, especially bluing agents, can be
optionally added to the odor absorbing compositions for visual
appeal and performance impression. When colorants are used, they
are used at extremely low levels to avoid fabric staining.
Preferred colorants for use in the present compositions are highly
water-soluble dyes, e.g., Liquitint.RTM. dyes available from
Milliken Chemical Co. Non-limiting examples of suitable dyes are,
Liquitint Blue HP.RTM., Liquitint Blue 65.RTM., Liquitint Patent
Blue.RTM., Liquitint Royal Blue.RTM., Liquitint Experimental Yellow
8949-43.RTM., Liquitint Green HMC.RTM., Liquitint Yellow II.RTM.,
and mixtures thereof, preferably Liquitint Blue HP.RTM., Liquitint
Blue 65.RTM., Liquitint Patent Blue.RTM., Liquitint Royal
Blue.RTM., Liquitint Experimental Yellow 8949-43.RTM., and mixtures
thereof.
[0276] (8). Optional Anti-Clogging Agent
[0277] Optional anti-clogging agent which enhances the wetting and
anti-clogging properties of the composition, especially when starch
is present, is chosen from the group of polymeric glycols of
alkanes and olefins having from 2 to about 6, preferably 2 carbon
atoms. The anti-clogging agent inhibits the formation of "plugs" in
the spray nozzle. An example of the preferred anti-clogging agent
is polyethylene glycol having an average molecular weight of from
about 800 to about 12,000, more preferably from about 1,400 to
about 8,000. When used, the anti-clogging agent is present at a
level of from about 0.01% to about 1%, preferably from about 0.05%
to about 0.5%, more preferably, from about 0.1% to about 0.3% by
weight of the usage composition.
[0278] (9) Mixtures Thereof
II. Article of Manufacture
[0279] The composition of the present invention can also be used in
an article of manufacture comprising said composition plus a spray
dispenser. When the commercial embodiment of the article of
manufacture is used, it is optional, but preferable, to include the
preservative. Therefore, the most basic article of manufacture
comprises uncomplexed cyclodextrin, a carrier, and a spray
dispenser.
[0280] The article of manufacture can also comprise the composition
of the present invention in a container in association with a set
of instructions to use the composition in an amount effective to
provide a solution to problems involving and/or provision of a
benefit related to those selected from the group consisting of:
killing or reducing the level of, microorganisms; reducing
wrinkles; and/or reducing static in addition to the reduction in
odors. It is important that the consumer be aware of these
additional benefits, since otherwise the consumer would not know
that the composition would solve these problems and/or provide
these benefits.
[0281] As used herein, the phrase "in association with" means the
set of instructions are either directly printed on the container
itself or presented in a separate manner including, but not limited
to, a brochure, print advertisement, electronic advertisement,
and/or verbal communication, so as to communicate the set of
instructions to a consumer of the article of manufacture. The set
of instructions preferably comprises the instruction to apply an
effective amount of the composition, preferably by spraying, to
provide the indicated benefit, e.g., wrinkle reduction,
antimicrobial action, and/or anti-static effect and, optionally the
provision of the main effect of odor control and/or reduction.
[0282] Spray Dispenser
[0283] The article of manufacture herein comprises a spray
dispenser. The cyclodextrin composition is placed into a spray
dispenser in order to be distributed onto the fabric. Said spray
dispenser for producing a spray of liquid droplets can be any of
the manually activated means as is known in the art, e.g.
trigger-type, pump-type, non-aerosol self-pressurized, and
aerosol-type spray means, for treating the odor-absorbing
composition to small fabric surface areas and/or small articles, as
well as non-manually operated, powered sprayers for conveniently
treating the odor-absorbing composition to large fabric surface
areas and/or a large number of garments and/or articles. The spray
dispenser herein does not normally include those that will
substantially foam the clear, aqueous odor absorbing composition.
It has been found that the performance is increased by providing
smaller particle droplets. Desirably, the Sauter mean particle
diameter is from about 10 .mu.m to about 120 .mu.m, more
preferably, from about 20 .mu.m to about 100 .mu.m. Dewrinkling
benefits are improved by providing small particles (droplets), as
discussed hereinbefore, especially when the surfactant is
present.
[0284] The spray dispenser can be an aerosol dispenser. Said
aerosol dispenser comprises a container which can be constructed of
any of the conventional materials employed in fabricating aerosol
containers. The dispenser must be capable of withstanding internal
pressure in the range of from about 20 to about 110 p.s.i.g., more
preferably from about 20 to about 70 p.s.i.g. The one important
requirement concerning the dispenser is that it be provided with a
valve member which will permit the clear, aqueous odor absorbing
composition contained in the dispenser to be dispensed in the form
of a spray of very fine, or finely divided, particles or droplets.
The aerosol dispenser utilizes a pressurized sealed container from
which the clear, aqueous odor-absorbing composition is dispensed
through a special actuator/valve assembly under pressure. The
aerosol dispenser is pressurized by incorporating therein a gaseous
component generally known as a propellant. Common aerosol
propellants, e.g., gaseous hydrocarbons such as isobutane, and
mixed halogenated hydrocarbons, which are not preferred.
Halogenated hydrocarbon propellants such as chlorofluoro
hydrocarbons have been alleged to contribute to environmental
problems. Hydrocarbon propellants can form complexes with the
cyclodextrin molecules thereby reducing the availability of
uncomplexed cyclodextrin molecules for odor absorption. Preferred
propellants are compressed air, nitrogen, inert gases, carbon
dioxide, etc. A more complete description of commercially available
aerosol-spray dispensers appears in U.S. Pat. No. 3,436,772,
Stebbins, issued Apr. 8, 1969; and U.S. Pat. No. 3,600,325, Kaufman
et al., issued Aug. 17, 1971; both of said references are
incorporated herein by reference.
[0285] Preferably the spray dispenser can be a self-pressurized
non-aerosol container having a convoluted liner and an elastomeric
sleeve. Said self-pressurized dispenser comprises a liner/sleeve
assembly containing a thin, flexible radially expandable convoluted
plastic liner of from about 0.010 to about 0.020 inch thick, inside
an essentially cylindrical elastomeric sleeve. The liner/sleeve is
capable of holding a substantial quantity of odor-absorbing fluid
product and of causing said product to be dispensed. A more
complete description of self-pressurized spray dispensers can be
found in U.S. Pat. No. 5,111,971, Winer, issued May 12, 1992, and
U.S. Pat. No. 5,232,126, Winer, issued Aug. 3, 1993; both of said
references are herein incorporated by reference. Another type of
aerosol spray dispenser is one wherein a barrier separates the odor
absorbing composition from the propellant (preferably compressed
air or nitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued
Apr. 7, 1981, and incorporated herein by reference. Such a
dispenser is available from EP Spray Systems, East Hanover,
N.J.
[0286] More preferably, the spray dispenser is a non-aerosol,
manually activated, pump-spray dispenser. Said pump-spray dispenser
comprises a container and a pump mechanism which securely screws or
snaps onto the container. The container comprises a vessel for
containing the aqueous odor-absorbing composition to be
dispensed.
[0287] The pump mechanism comprises a pump chamber of substantially
fixed volume, having an opening at the inner end thereof. Within
the pump chamber is located a pump stem having a piston on the end
thereof disposed for reciprocal motion in the pump chamber. The
pump stem has a passageway there through with a dispensing outlet
at the outer end of the passageway and an axial inlet port located
inwardly thereof.
[0288] The container and the pump mechanism can be constructed of
any conventional material employed in fabricating pump-spray
dispensers, including, but not limited to: polyethylene;
polypropylene; polyethyleneterephthalate; blends of polyethylene,
vinyl acetate, and rubber elastomer. A preferred container is made
of clear, e.g., polyethylene terephthalate. Other materials can
include stainless steel. A more complete disclosure of commercially
available dispensing devices appears in: U.S. Pat. No. 4,895,279,
Schultz, issued Jan. 23, 1990; U.S. Pat. No. 4,735,347, Schultz et
al., issued Apr. 5, 1988; and U.S. Pat. No. 4,274,560, Carter,
issued Jun. 23, 1981; all of said references are herein
incorporated by reference.
[0289] Most preferably, the spray dispenser is a manually activated
trigger-spray dispenser. Said trigger-spray dispenser comprises a
container and a trigger both of which can be constructed of any of
the conventional material employed in fabricating trigger-spray
dispensers, including, but not limited to: polyethylene;
polypropylene; polyacetal; polycarbonate;
polyethyleneterephthalate; polyvinyl chloride; polystyrene; blends
of polyethylene, vinyl acetate, and rubber elastomer. Other
materials can include stainless steel and glass. A preferred
container is made of clear, e.g. polyethylene terephthalate. The
trigger-spray dispenser does not incorporate a propellant gas into
the odor-absorbing composition, and preferably it does not include
those that will foam the odor-absorbing composition. The
trigger-spray dispenser herein is typically one which acts upon a
discrete amount of the odor-absorbing composition itself, typically
by means of a piston or a collapsing bellows that displaces the
composition through a nozzle to create a spray of thin liquid. Said
trigger-spray dispenser typically comprises a pump chamber having
either a piston or bellows which is movable through a limited
stroke response to the trigger for varying the volume of said pump
chamber. This pump chamber or bellows chamber collects and holds
the product for dispensing. The trigger spray dispenser typically
has an outlet check valve for blocking communication and flow of
fluid through the nozzle and is responsive to the pressure inside
the chamber. For the piston type trigger sprayers, as the trigger
is compressed, it acts on the fluid in the chamber and the spring,
increasing the pressure on the fluid. For the bellows spray
dispenser, as the bellows is compressed, the pressure increases on
the fluid. The increase in fluid pressure in either trigger spray
dispenser acts to open the top outlet check valve. The top valve
allows the product to be forced through the swirl chamber and out
the nozzle to form a discharge pattern. An adjustable nozzle cap
can be used to vary the pattern of the fluid dispensed.
[0290] For the piston spray dispenser, as the trigger is released,
the spring acts on the piston to return it to its original
position. For the bellows spray dispenser, the bellows acts as the
spring to return to its original position. This action causes a
vacuum in the chamber. The responding fluid acts to close the
outlet valve while opening the inlet valve drawing product up to
the chamber from the reservoir.
[0291] A more complete disclosure of commercially available
dispensing devices appears in U.S. Pat. No. 4,082,223, Nozawa,
issued Apr. 4, 1978; U.S. Pat. No. 4,161,288, McKinney, issued Jul.
17, 1985; U.S. Pat. No. 4,434,917, Saito et al., issued Mar. 6,
1984; and U.S. Pat. No. 4,819,835, Tasaki, issued Apr. 11, 1989;
U.S. Pat. No. 5,303,867, Peterson, issued Apr. 19, 1994; all of
said references are incorporated herein by reference.
[0292] A broad array of trigger sprayers or finger pump sprayers
are suitable for use with the compositions of this invention. These
are readily available from suppliers such as Calmar, Inc., City of
Industry, California; CSI (Continental Sprayers, Inc.), St. Peters,
Missouri; Berry Plastics Corp., Evansville, Ind., a distributor of
Guala.RTM. sprayers; or Seaquest Dispensing, Cary, Ill.
[0293] The preferred trigger sprayers are the blue inserted
Guala.RTM. sprayer, available from Berry Plastics Corp., or the
Calmar TS800-1A.RTM., TS1300.RTM., and TS-800-2.RTM., available
from Calmar Inc., because of the fine uniform spray
characteristics, spray volume, and pattern size. More preferred are
sprayers with precompression features and finer spray
characteristics and even distribution, such as Yoshino sprayers
from Japan. Any suitable bottle or container can be used with the
trigger sprayer, the preferred bottle is a 17 fl-oz. bottle (about
500 ml) of good ergonomics similar in shape to the Cinch.RTM.
bottle. It can be made of any materials such as high density
polyethylene, polypropylene, polyvinyl chloride, polystyrene,
polyethylene terephthalate, glass, or any other material that forms
bottles. Preferably, it is made of high density polyethylene or
clear polyethylene terephthalate.
[0294] For smaller fluid ounce sizes (such as 1 to 8 ounces), a
finger pump can be used with canister or cylindrical bottle. The
preferred pump for this application is the cylindrical Euromist
II.RTM. from Seaquest Dispensing. More preferred are those with
precompression features.
[0295] The article of manufacture herein can also comprise a
non-manually operated spray dispenser (sprayer). By "non-manually
operated" it is meant that the spray dispenser can be manually
activated, but the force required to dispense the odor absorbing
composition is provided by another, non-manual means. Non-manually
operated sprayers include, but are not limited to, powered
sprayers, air aspirated sprayers, liquid aspirated sprayers,
electrostatic sprayers, and nebulizer sprayers. The odor absorbing
composition is placed into a spray dispenser in order to be
distributed onto the fabric.
[0296] Powered sprayers include self contained powered pumps that
pressurize the aqueous odor absorbing composition and dispense it
through a nozzle to produce a spray of liquid droplets. Powered
sprayers are attached directly or remotely through the use of
piping/tubing to a reservoir (such as a bottle) to hold the aqueous
odor absorbing composition. Powered sprayers may include, but are
not limited to, centrifugal or positive displacement designs. It is
preferred that the powered sprayer be powered by a portable DC
electrical current from either disposable batteries (such as
commercially available alkaline batteries) or rechargeable battery
units (such as commercially available nickel cadmium battery
units). Powered sprayers may also be powered by standard AC power
supply available in most buildings. The discharge nozzle design can
be varied to create specific spray characteristics (such as spray
diameter and particle size). It is also possible to have multiple
spray nozzles for different spray characteristics. The nozzle may
or may not contain an adjustable nozzle shroud that would allow the
spray characteristics to be altered.
[0297] Nonlimiting examples of commercially available powered
sprayers are disclosed in U.S. Pat. No. 4,865,255, Luvisotto,
issued Sep. 12, 1989 which is incorporated herein by reference.
Preferred powered sprayers are readily available from suppliers
such as Solo, Newport News, Virginia (e.g., Solo Spraystar.TM.
rechargeable sprayer, listed as manual part #: U.S. Pat. No.
460,395) and Multi-sprayer Systems, Minneapolis, Minn. (e.g.,
model: Spray 1).
[0298] Air aspirated sprayers include the classification of
sprayers generically known as "air brushes". A stream of
pressurized air draws up the aqueous odor absorbing composition and
dispenses it through a nozzle to create a spray of liquid. The odor
absorbing composition can be supplied via separate piping/tubing or
more commonly is contained in ajar to which the aspirating sprayer
is attached.
[0299] Nonlimiting examples of commercially available air aspirated
sprayers appears in U.S. Pat. No. 1,536,352, Murray, issued Apr.
22, 1924 and U.S. Pat. No. 4,221,339, Yoshikawa, issues Sep. 9,
1980; all of said references are incorporated herein by reference.
Air aspirated sprayers are readily available from suppliers such as
The Badger Air-Brush Co, Franklin Park, Ill. (e.g., model #: 155)
and Wilton Air Brush Equipment, Woodridge, Ill. (e.g., stock #:
415-4000, 415-4001, 415-4100).
[0300] Liquid aspirated sprayers are typical of the variety in
widespread use to spray garden chemicals. The aqueous odor
absorbing composition is drawn into a fluid stream by means of
suction created by a Venturi effect. The high turbulence serves to
mix the aqueous odor absorbing composition with the fluid stream
(typically water) in order to provide a uniform
mixture/concentration. It is possible with this method of delivery
to dispense the aqueous concentrated odor absorbing composition of
the present invention and then dilute it to a selected
concentration with the delivery stream.
[0301] Liquid aspirated sprayers are readily available from
suppliers such as Chapin Manufacturing Works, Batavia, New York
(e.g., model #: 6006).
[0302] Electrostatic sprayers impart energy to the aqueous odor
absorbing composition via a high electrical potential. This energy
serves to atomize and charge the aqueous odor absorbing
composition, creating a spray of fine, charged particles. As the
charged particles are carried away from the sprayer, their common
charge causes them to repel one another. This has two effects
before the spray reaches the target. First, it expands the total
spray mist. This is especially important when spraying to fairly
distant, large areas. The second effect is maintenance of original
particle size. Because the particles repel one another, they resist
collecting together into large, heavier particles like uncharged
particles do. This lessens gravity's influence, and increases the
charged particle reaching the target. As the mass of negatively
charged particles approach the target, they push electrons inside
the target inwardly, leaving all the exposed surfaces of the target
with a temporary positive charge. The resulting attraction between
the particles and the target overrides the influences of gravity
and inertia. As each particle deposits on the target, that spot on
the target becomes neutralized and no longer attractive. Therefore,
the next free particle is attracted to the spot immediately
adjacent and the sequence continues until the entire surface of the
target is covered. Hence, charged particles improve distribution
and reduce drippage.
[0303] Nonlimiting examples of commercially available electrostatic
sprayers appears in U.S. Pat. No. 5,222,664, Noakes, issued Jun.
29, 1993; U.S. Pat. No. 4,962,885, Coffee, issued Oct. 16, 1990;
U.S. Pat. No. 2,695,002, Miller, issued November 1954; U.S. Pat.
No. 5,405,090, Greene, issued Apr. 11, 1995; U.S. Pat. No.
4,752,034, Kuhn, issued Jun. 21, 1988; U.S. Pat. No. 2,989,241,
Badger, issued June 1961; all of said patents are incorporated
herein by reference. Electrostatic sprayers are readily available
from suppliers such as Tae In Tech Co, South Korea and Spectrum,
Houston, Tex.
[0304] Nebulizer sprayers impart energy to the aqueous odor
absorbing composition via ultrasonic energy supplied via a
transducer. This energy results in the aqueous odor absorbing
composition to be atomized. Various types of nebulizers include,
but are not limited to, heated, ultrasonic, gas, venturi, and
refillable nebulizers.
[0305] Nonlimiting examples of commercially available nebulizer
sprayers appears in U.S. Pat. Nos. 3,901,443, Mitsui, issued Aug.
26, 1975; U.S. Pat. No. 2,847,248, Schmitt, issued August 1958;
U.S. Pat. No. 5,511,726, Greenspan, issued Apr. 30, 1996; all of
said patents are incorporated herein by reference. Nebulizer
sprayers are readily available from suppliers such as A&D
Engineering, Inc., Milpitas, Calif. (e.g., model A&D Un-231
ultrasonic handy nebulizer) and Amici, Inc., Spring City, Pa.
(model: swirler nebulizer).
[0306] The preferred article of manufacture herein comprises a
non-manually operated sprayer, such as a battery-powered sprayer,
containing the aqueous odor absorbing composition. More preferably
the article of manufacture comprises a combination of a
non-manually operated sprayer and a separate container of the
aqueous odor absorbing composition, to be added to the sprayer
before use and/or to be separated for filling/refilling. The
separate container can contain an usage composition, or a
concentrated composition to be diluted before use, and/or to be
used with a diluting sprayer, such as with a liquid aspirated
sprayer, as described herein above. Also, as described
hereinbefore, the separate container should have structure that
mates with the rest of the sprayer to ensure a solid fit without
leakage, even after motion, impact, etc. and when handled by
inexperienced consumers.
III. Method of Use
[0307] The cyclodextrin solution, which contains, e.g., surfactant,
antimicrobial compound, and/or wrinkle control agent, etc., can be
used by distributing, e.g., by placing, an effective amount of the
aqueous solution onto the surface or article to be treated.
Distribution can be achieved by using a spray device, a roller, a
pad, etc., preferably a spray dispenser. For odor control, an
effective amount, as defined herein, means an amount sufficient to
absorb odor to effect a noticeable reduction in the perceived odor,
preferably to the point that it is not discernible, by the human
sense of smell. Preferably, the amount of solution is not so much
as to saturate or create a pool of liquid on said article or
surface and so that when dry there is no visual deposit readily
discernible. For wrinkle control, an effective amount means an
amount sufficient to remove or noticeably reduce the appearance of
wrinkles on fabric.
[0308] Preferably, the present invention does not encompass
distributing the cyclodextrin solution on to shiny surfaces
including, e.g., chrome, glass, smooth vinyl, leather, shiny
plastic, shiny wood, etc. It is preferable not to distribute the
cyclodextrin solution onto shiny surfaces because spotting and
filming can more readily occur on such surfaces. However, when
appearance is not important, the composition of the present
invention can be sprayed onto shiny surfaces to obtain odor control
benefit. Although the cyclodextrin solution can be used on human
skin, care should be taken, especially when an antimicrobial active
is present in the composition.
[0309] The compositions and articles of the present invention which
contain a fabric wrinkle control agent can be used to treat
fabrics, garments, and the like to remove or reduce, undesirable
wrinkles, in addition to the removal or reduction of undesirable
odor on said objects.
[0310] An effective amount of the liquid composition of the present
invention is preferably sprayed onto fabrics, particularly
clothing. When the composition is sprayed onto fabric, an effective
amount should be deposited onto the fabric, with the fabric
becoming damp or totally saturated with the composition, typically
from about 5% to about 150%, preferably from about 10% to about
100%, more preferably from about 20% to about 75%, by weight of the
fabric. The amount of active typically sprayed onto the fabric is
from about 0.002% to about 5%, preferably from about 0.01% to about
1%, more preferably from about 0.03% to about 0.5%, by weight of
the fabric. It is highly preferable to use the preferred particles
sizes described hereinbefore, since the areas that receive too much
liquid will be slow to dry. Once an effective amount of the
composition is sprayed onto the fabric the fabric is optionally,
but preferably stretched. The fabric is typically stretched
perpendicular to the wrinkle. The fabric can also be smoothed by
hand after it has been sprayed. The smoothing movement works
particularly well on areas of clothing that have an interface sewn
into them, or on the hems of clothing. Once the fabric has been
sprayed and optionally, but preferably, stretched, it is hung until
dry.
[0311] The compositions of the present invention can also be used
as ironing aids, especially when the fabric wrinkle control agent
is a fiber lubricant. An effective amount of the composition can be
sprayed onto fabric and the fabric is ironed at the normal
temperature at which it should be ironed. The fabric can either be
sprayed with an effective amount of the composition, allowed to dry
and then ironed, or sprayed and ironed immediately.
[0312] In a still further aspect of the invention, the composition
can be sprayed onto fabrics by in an in-home de-wrinkling chamber
containing the fabric to be deodorized and/or dewrinkled, thereby
providing ease of operation. Conventional personal as well as
industrial deodorizing and/or de-wrinkling apparatuses are suitable
for use herein. Traditionally, these apparatuses act by a steaming
process which effects a relaxation of the fibers. Examples of home
dewrinkling chambers include shower stalls. The spraying of the
composition or compounds onto the fabrics can then occur within the
chamber of the apparatus or before placing the fabrics into the
chamber. Again, the spraying means should preferably be capable of
providing droplets with a weight average diameter of from about 8
to about 100 .mu.m, preferably from about 10 to about 50 .mu.m.
Preferably, the loading of moisture on fabrics made of natural and
synthetic fibers is from about 5 to about 25%, more preferably from
about 5 to about 10% by weight of the dried fabric. Other
conventional steps that can be carried out in the dewrinkling
apparatus can be applied such as heating and drying. Preferably,
for optimum dewrinkling benefit, the temperature profile inside the
chamber ranges from about 40.degree. C. to about 80.degree. C.,
more preferably from about 50.degree. C. to about 70.degree. C. The
preferred length of the drying cycle is from about 15 to about 60
minutes, more preferably from about 20 to about 45 minutes.
[0313] The steaming step in the dewrinkling apparatus may also be
eliminated if the composition is maintained at a temperature range
from about 22.degree. C. (about 72.degree. F.) to about 76.degree.
C. (170.degree. F.) before spraying.
[0314] The present invention also encompasses the method of
spraying an effective amount of cyclodextrin solution onto
household surfaces. Preferably said household surfaces are selected
from the group consisting of countertops, cabinets, walls, floors,
bathroom surfaces and kitchen surfaces so long as the composition
does not cause an unacceptable appearance or a safety hazard.
However, the anti wrinkling benefit is primarily seen on, e.g.,
curtains etc.
[0315] The present invention encompasses the method of spraying a
mist of an effective amount of cyclodextrin solution onto fabric
and/or fabric articles. Preferably, said fabric and/or fabric
articles include, but are not limited to, clothes, curtains,
drapes, upholstered furniture, carpeting, bed linens, bath linens,
tablecloths, sleeping bags, tents, car interiors, etc.
[0316] The compositions herein are especially useful, when used to
treat garments for extending the time before another wash cycle is
needed. Such garments include uniforms and other garments which are
normally treated in an industrial process, which can be refreshed
and the time between treatments extended.
[0317] The present invention also encompasses the methods of
spraying a mist of an effective amount of cyclodextrin solution
onto and into shoes wherein said shoes are not sprayed to
saturation; shower curtains; garbage cans and/or recycling bins.
The present invention also relates to the method of spraying a mist
of an effective amount of cyclodextrin solution into the air to
absorb malodor. The present invention relates to the method of
spraying a mist of an effective amount of cyclodextrin solution
into and/or onto major household appliances including, but not
limited to: refrigerators, freezers, washing machines, automatic
dryers, ovens, microwave ovens, dishwashers, cat litter, pet
bedding and pet houses to absorb malodor. However, it is recognized
that all of these methods make use of the cyclodextrin and not the
anti-wrinkling agent.
[0318] The present invention relates to the method of spraying a
mist of an effective amount of cyclodextrin solution onto household
pets to absorb malodor. Depending on the pet, this may also provide
an anti-wrinkling benefit.
[0319] The presence of the highly preferred surfactant promotes
spreading of the solution and the highly preferred antimicrobial
active provides improved odor control as well as antimicrobial
action, by minimizing the formation of odors. Both the surfactant
and the antimicrobial active provide improved performance and the
mixture is especially good. When the compositions are applied in
the form of the very small particles (droplets), as disclosed
hereinbefore, additional benefits are found, since the distribution
is even further improved and overall performance is improved.
[0320] All percentages, ratios, and parts herein, in the
Specification, Examples, and claims are by weight and are the
normal approximations unless otherwise stated.
[0321] The following are non-limiting examples of the instant
composition. Perfume compositions that are used herein are as
follows:
5 Perfume Perfume Ingredients Wt. % Wt. % Wt. % Perfume A B C
Anisic aldehyde -- -- 2 Benzophenone 3 5 -- Benzyl acetate 10 15 5
Benzyl salicylate 5 20 5 Cedrol 2 -- -- Citronellol 10 -- 5
Coumarin -- -- 5 Cymal -- -- 3 Dihydromyrcenol 10 -- 5 Flor acetate
5 -- 5 Galaxolide 10 -- -- Lilial 10 15 20 Linalyl acetate 4 -- 5
Linalool 6 15 5 Methyl dihydro jasmonate 3 10 5 Phenyl ethyl
acetate 2 5 1 Phenyl ethyl alcohol 15 10 20 alpha-Terpineol 5 -- 8
Vanillin -- -- 1 Total 100 100 100 Perfume D E Amyl salicylate 8 --
Benzyl acetate 8 8 Benzyl Salicylate -- 2 Citronellol 7 27
Dihydromyrcenol 2 -- Eugenol 4 -- Flor acetate 8 -- Galaxolide 1 --
Geraniol 5 -- Hexyl cinnamic aldehyde 2 -- Hydroxycitronellal 3 --
Lilial 2 -- Linalool 12 13 Linalyl acetate 5 -- Lyral 3 -- Methyl
dihydrojasmonate 3 -- Nerol 2 -- Phenoxy ethyl propionate -- 3
Phenylethyl acetate 5 17 Phenylethyl alcohol 8 17 alpha-Terpineol 5
13 alpha-Terpinene 5 -- Tetrahydromyrcenol 2 -- Total 100 100
Perfume F Benzophenone 0.50 Benzyl acetate 3.00 Benzyl propionate
1.00 beta gamma Hexenol 0.20 Cetalox 0.10 cis 3 Hexenyl acetate
0.15 cis Jasmone 0.10 cis-2-Hexenyl salicylate 1.00 Citral 0.50
Citronellal nitrile 0.70 Citronellol 3.65 Coumarin 0.70 Cyclal C
0.30 Cyclo glalbanate 0.40 beta Damascone 0.05 Dihydro myrcenol
1.00 Ebanol 0.50 Flor acetate 5.00 Florhydral 0.70 Fructose 8.50
Frutene 3.00 Geranyl nitrile 0.40 Heliotropin 0.70
Hydroxycitronellal 2.50 Linalool 2.00 Linalyl acetate 1.50 Methyl
dihydro jasmonate 5.00 Methyl heptine carbonate 0.05 Methyl iso
butenyl tetrahy- 0.15 dro pyran Methyl phenyl carbinyl ace- 0.50
tate Nonalactone 1.50 P. T. Bucinal 8.40 para Hydroxy phenyl butan-
1.30 one Phenoxy ethanol 28.55 Phenyl ethyl acetate 0.80 Phenyl
ethyl alcohol 10.00 Prenyl acetate 1.50 Terpineol 1.50 Verdox 2.10
Vanillin 0.50 Total 100.00 Perfume G Anisic aldehyde 2.80 Benzyl
acetone 1.00 cis 3 Hexenyl acetate 0.30 Citronellal nitrile 1.30
Citronellol 6.90 Coumarin 1.30 Cyclal C 0.30 Cyclo galbanate 0.70
Cymal 1.05 delta Damascone 0.05 Dihydro myrcenol 1.30 Dipropylene
glycol 10.20 Dodecalactone 0.50 Ebanol 0.10 Ethyl vanillin 0.10
Flor acetate 8.00 Florhydral 1.30 Fructone 6.00 Galaxolide (50% in
isopro- 4.00 pyl myristate) gamma Methyl ionone 1.00 Geranyl
nitrile 0.30 Helional 1.50 Hydroxycitronellal 2.00 Iso bornyl
acetate 1.80 Ligustral 0.10 Linalool 2.50 Methyl dehydro jasmonate
6.20 Methyl heptine carbonate 0.10 Methyl iso butenyl tetrahy- 0.30
dro pyran Methyl phenyl carbinyl ace- 1.00 tate Orange terpenes
2.00 P. T. Bucinal 10.00 Phenyl ethyl alcohol 20.00 Prenyl acetate
1.50 Verdox 2.50 Total 100.00
[0322]
6 Example Ingredients Wt % Wt % Wt % Wt % Wt % Wt % Examples I Ia
Ib Ic Id Ie If HPBCD.sup.(a) 1.0 -- 1.0 -- 1.0 -- RAMEB.sup.(b) --
1.0 -- 1.0 -- 0.8 D5 volatile sili- 0.5 0.5 0.5 0.35 1.0 -- cone
PDMS 10,000 -- -- -- 0.35 -- 0.5 cst Silwet L-7600 0.5 -- -- -- 0.1
-- Silwet L-7602 -- 0.5 -- 0.7 -- 0.5 Silwet L-7622 -- -- 0.5 --
1.0 -- Propylene gly- 0.06 -- -- -- 0.1 -- col Kathon 3 ppm 3 ppm 3
ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
.sup.(a)Hydroxypropyl-beta-cyclodextrin. .sup.(b)Randomly
methylated-beta-cyclodextrin. Examples II IIa IIb IIc IId IIe IIf
HPBCD 1.0 -- 1.0 -- 1.0 -- RAMEB -- 1.0 -- 1.0 -- 0.8 Lithium brom-
3.0 -- 2.0 3.0 -- 3.0 ide Lithium lactate -- 3.0 -- -- 2.5 -- D5
volatile sili- 0.5 -- -- 0.35 1.0 -- cone PDMS 10,000 -- -- -- 0.35
-- 0.5 cst Silwet L-7600 0.5 -- -- -- 0.1 -- Silwet L-7604 -- 0.1
-- 0.7 -- 0.5 Silwet L-7622 -- -- -- -- 1.0 -- Propylene gly- 0.06
-- -- -- 0.1 -- col Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Distilled water Bal. Bal. Bal. Bal. Bal. Bal. Examples III IIIa
IIIb IIIc IIId IIIe IIIf HPBCD 1.0 -- 1.0 -- 1.0 -- RAMEB -- 1.0 --
1.0 -- 0.8 Zn Cl.sub.2 1.0 1.0 0.7 1.0 0.7 0.7 LiBr 3.0 2.0 3.0 3.0
-- 3.0 LiSO.sub.4 -- -- -- -- 2.0 -- D5 volatile sili- 0.5 0.5 --
0.35 1.0 -- cone PDMS 10,000 -- -- -- 0.35 -- 0.5 cst Silwet L-7600
0.5 -- -- -- 0.1 -- Silwet L-7602 -- 0.5 -- 0.7 -- 0.5 Silwet
L-7622 -- -- -- -- 1.0 -- Perfume A 0.1 -- -- -- -- -- Perfume B --
0.2 -- -- -- -- Perfume C -- -- 0.05 -- -- -- Perfume E -- -- --
0.1 -- -- Perfume F -- -- -- -- 0.05 -- Perfume G -- -- -- -- --
0.1 Propylene gly- 0.06 -- -- -- 0.1 -- col HCl to pH 4 to pH 4 to
pH 4 to pH 4 to pH 4 to pH 4 Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3
ppm Distilled water Bal. Bal. Bal. Bal. Bal. Bal. Examples IV IVa
IVb IVc IVd IVe IVf HPBCD 1.0 -- 1.0 -- 1.0 -- RAMEB -- 1.0 -- 1.0
-- 0.8 Chlorhexidine 0.01 0.02 0.01 0.01 0.05 0.05 D5 volatile
sili- 0.5 0.5 0.5 0.35 -- -- cone PDMS 10,000 -- -- -- 0.35 -- 0.5
cst Silwet L-7600 0.5 -- -- -- 0.1 -- Silwet L-7602 -- 0.5 -- 0.7
-- 0.5 Silwet L-7622 -- -- 0.5 -- -- -- Lithium bro- -- -- -- 3.0
-- 2.0 mide Lithium lactate -- -- -- -- 3.0 -- Propylene gly- 0.06
-- -- -- 0.1 -- col Perfume A 0.1 -- -- -- -- -- Perfume B -- 0.2
-- -- -- -- Perfume C -- -- 0.05 -- -- -- Perfuem E -- -- -- 0.1 --
-- Perfume F -- -- -- -- 0.05 -- Perfume G -- -- -- -- -- 0.1
Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal.
Bal. Bal. Bal. Bal. Bal. Examples V Va Vb Vc Vd Ve Vf HPBCD 1.0 --
0.6 -- 1.0 -- RAMEB -- 1.0 -- 1.0 -- 0.6 Luviset CA 0.4 -- -- -- --
-- 66.sup.(a) Luviset CAP.sup.(b) -- 0.5 -- -- -- -- Sokalan EG --
-- 0.4 -- -- -- 310.sup.(c) Ultrahold CA -- -- -- 1.0 -- --
8.sup.(d) Amerhold -- -- -- -- 0.75 -- DR-25.sup.(e) Poligen
A.sup.(f) -- -- -- -- -- 0.25 Silwet L-7600 0.25 -- -- 0.2 -- --
Silwet L-7602 -- 0.25 -- 0.2 0.4 -- Silwet L-7604 -- -- 0.2 -- --
0.15 Diethylene gly- 0.1 -- 0.1 0.2 0.2 0.15 col Propylene gly-
0.06 -- -- -- 0.1 -- col NaOH/HCl to pH 9 to pH 9 to pH 8 to pH 8
to pH 7 to pH 8 Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm
Distilled water Bal. Bal. Bal. Bal. Bal. Bal. .sup.(a)Vinyl
acetate/crotonic acid copolymer. .sup.(b)Vinyl acetate/vinyl
propionate/crotonic acid copolymer.
.sup.(c)Polyvinylpyrrolidone/acrylic acid copolymer. .sup.(d)Ethyl
acrylate/acrylic acid/N-t-butyl acrylamide copolymer. .sup.(e)Ethyl
acrylate/methacrylic acid/methyl methacrylate/acrylic acid
copolymer. .sup.(f)Polyacrylate dispersion. Example VI VIa VIb VIc
VId VIe HPBCD 1.0 -- 0.5 -- 0.7 RAMEB -- 0.5 -- 1.0 -- Cartaretin
1.0 -- -- -- -- F-23.sup.(g) Copolymer -- 0.3 -- -- -- 937.sup.(h)
Copolymer -- -- 0.4 -- -- 958.sup.(i) Diaformer -- -- -- 0.5 --
Z-SM.sup.(j) Vinex 2019.sup.(k) -- -- -- -- 0.5 D5 volatile sili-
0.25 -- 0.5 0.2 -- cone PDMS 10,000 -- 0.25 -- 0.2 -- cst Silwet
L-7600 0.3 -- -- -- 0.1 Silwet L-7602 -- 0.25 -- 0.4 -- Silwet
L-7622 -- -- 0.5 -- -- Diethylene gly- -- -- 0.2 -- -- col
Propylene gly- 0.06 -- -- -- 0.1 col Perfume A 0.1 -- -- -- --
Perfume B -- 0.05 -- -- -- Perfume C -- -- 0.05 -- -- Perfume E --
-- -- 0.1 -- Perfume F -- -- -- -- 0.05 Perfume G -- -- -- -- --
Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal.
Bal. Bal. .sup.(g)Adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer.
.sup.(h)Polyvinylpyrrolidone/dimethylaminoethyl methacrylate
copolymer. .sup.(i)Polyvinylpyrrolidone/dimethylaminoethyl
methacrylate copolymer. .sup.(j)Methacryloyl ethyl
betaine/methacrylates copolymer. .sup.(k)Polyvinyl alcohol
copolymer resin. Examples VII VIIa VIIb VIIc VIId VIIe VIIf HPBCD
1.0 -- 0.6 -- 1.0 -- RAMEB -- 0.8 -- 1.0 -- 0.5 Copolymer A.sup.(l)
0.4 1.0 -- -- -- -- Copolymer -- -- 0.3 0.6 -- -- B.sup.(m)
PVA.sup.(n) -- -- -- -- 1.0 0.5 Velustrol -- -- -- -- 0.3 0.2
P-40.sup.(o) D5 volatile sili- 0.5 -- -- -- -- -- cone PDMS 1,000
-- -- 0.3 -- -- 0.2 cst Silwet L-7600 0.5 -- -- -- 0.25 0.25 Silwet
L-7602 -- -- 0.3 -- -- -- Diethylene gly- -- 1.0 0.3 -- -- 0.3 col
Propylene gly- 0.06 -- -- -- 0.1 0.1 col Glycerin -- -- -- -- 0.2
-- Perfume A 0.1 -- -- -- -- -- Perfume B -- 0.1 -- -- -- --
Perfume C -- -- 0.05 -- -- -- Perfume E -- -- -- 0.1 -- -- Perfume
F -- -- -- -- 0.05 -- Perfume G -- -- -- -- -- 0.05 NaOH/HCl to pH
9 to pH 7 to pH 9 to pH 7 -- -- Kathon 3 ppm 3 ppm 3 ppm 3 ppm 3
ppm 3 ppm Distilled water Bal. Bal. Bal. Bal. Bal. Bal.
.sup.(l)Acrylic acid/tert-butyl acrylate copolymer, with an
approximate acrylic acid/tert-butyl acrylate weight ratio of about
25/75 and an average molecular weight of from about 70,000 to about
100,000. .sup.(m)Acrylic acid/tert-butyl acrylate copolymer, with
an approximate acrylic acid/tert-butyl acetate weight ratio of
about 35/65 and an average molecular weight of from about 60,000 to
about 90,000. .sup.(n)Polyvinyl alcohol, about 25,000 average
molecular weight. .sup.(o)Oxidized polyethylene emulsion.
[0323] The compositions of the above Examples are sprayed onto
clothing using, e.g., the TS-800 sprayer from Calmar, and allowed
to evaporate off of the clothing.
[0324] The compositions of the above Examples are sprayed onto
clothing, a kitchen countertop, using a blue inserted Guala.RTM.
trigger sprayer, available from Berry Plastics Corp. and a
cylindrical Euromist II.RTM. pump sprayer available from Seaquest
Dispensing, respectively, and allowed to evaporate off of the
clothing.
[0325] The compositions of the above Examples contained in
rechargeable battery-operated Solo Spraystar sprayers are sprayed
onto large surfaces of fabric, such as several pieces of clothings,
and allowed to evaporate off of these surfaces. The level of
coverage is uniform and the ease and convenience of application is
superior to conventional manually operated trigger sprayers.
Consumers prefer this method of application.
[0326] The polyalkylene oxide polysiloxane surfactants like the
Silwet surfactants provide substantial improvements in the kill of
the indicated common organisms when there are antibacterial
compounds present. The Pluronic surfactants provide some
improvement, but much less.
* * * * *