Note: Descriptions are shown in the official language in which they were submitted.
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PRO-FRAGRANCE CYCLIC ACETALS
FIF1 D OF THF INVENTION
The present invention relates to pro-fragrance compounds useful in laundry
detergent compositions. The pro-fragrance compounds comprise a fragrance raw
material component and a solubility or substantivity component which can be
independently adjusted to meet the specific requirements of the formulator.
The pro-
fragrance compounds are especially useful for delivering a "through the wash"
fresh-
like or clean-like fragrance to fabric which remains on the fabric and is
continuously
released for extended periods after the conclusion of the laundry cycle.
BA KGROtIND OF THE INVENTION
In addition to the removal of stains, dirt, soil, grime, and grease from
fabric,
laundry detergent formulators have attempted to deliver a "fresh" or "clean"
odor to
washed clothing to provide an olfactory aesthetic benefit and to serve as a
signal that
the product is effective. Laundry detergent compositions, including rinse-
added
fabric softeners and dryer-added substrates, are currently formulated with
perfume
and fragrance ingredients which are aesthetically pleasing to the consumer but
which
fail to deliver a prolonged "fragrance" or "pleasurable smell" to the
finished, cleaned
fabric.
Among the most readily perceived fragrance materials are the perfume "top"
and "middle" notes which are highly volatile compounds and which are usually
detectable at low levels. However, these highly volatile materials are
typically lost
either during the prolonged heating which takes place in an automatic dryer or
they
lack the substantivity necessary to deposit onto the fabric surface and are
therefore
lost during the laundry rinsing process.
Attempts have been made to deliver perfume ingredients onto fabric which
can survive the laundry rinsing and drying cycles and therefore provide a
residual
"fresh" or "clean" odor to the washed material. However, none of these
attempts
have suitably provided fabric with a protracted release of fragrance raw
materials
which provide a "fresh" or "clean" smell for a period up to two weeks after
washing.
There has especially been a long felt need to deliver certain tertiary alcohol
fragrance raw materials inter alia linalool and dihydromyrcenol.
Accordingly, there remains a need in the art for a fragrance delivery system
wherein perfume raw materials are delivered to fabric by way of a laundry
detergent,
rinse-added composition, or dryer-added article of manufacture which provides
the
cleaned clothing or fabric with a "fresh" or "clean" smell for a period up to
two
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2
weeks after washing. Also, there is a need for fragrance releasing compounds
which
deliver a "fresh" or "clean" fragrance in which the solubility and
substantivity
properties of the compound can be varied to match various formulation and
delivery
parameters inter alia compatibility with surface active adjuncts and fabric
type. In
addition, there is a need for a fragrance delivery system suitable for
providing
sustained release or enhanced longevity fragrances to a variety of personal
care and
personal hygiene products inter alia deodorants, body lotions or creams, and
shampoos.
BACKGROUND ART
The following relate to the subject matter of fragrance ingredients. U.S.
5,232,612 Trinh et al., issued August 3, 1996; U.S. 5,506,201 McDermott et
al.,
issued April 9, 1996; U.S. 5,378,468 Suffis et al., issued January 3, 1995; U.
S.
5,266,592 Grub et al., issued November 30, 1993; U. S. 5,081,1 I 1 Akimoto et
al.,
issued January 14, 1992; U. S. 4,994,266 Wells, issued February 19, 1991; U.S.
4,524,018 Yemoto et al., issued June 18, 1985; U. S. 3,849,326 Jaggers et al.,
issued
November 19, 1974; U. S. 3,779,932 Jaggers et al., issued December 18, 1973;
JP
07-179.328 published July 18, 1995; JP OS-230496 published September 7, 1993;
WO 96/14827 published May 23, 1996; WO 95/04,809 published February 16,
1995; and WO 95/16660 published June 22, 1995. In addition, P.M. Muller, D.
Lamparsky Perfumes Arty Science. & Technolo~v Blackie Academic &
Professional, (New York, 1994) is included herein by reference.
SUMMARY OF THE INVENTION
The present invention meets the aforementioned needs in that it has been
surprisingly discovered that certain cyclic acetals can be used to deliver
perfume or
fragrance raw materials onto fabric "through the wash" from a single precursor
pro-
fragrance molecule having variable fabric substantivity, variable solubility
as well as
variable fragrance release rate. These pro-fragrances can be used to deliver
tertiary
alcohol raw materials as well as primary and secondary fragrance raw material
alcohols which impart a "fresh" or "clean" aesthetic odor benefit to fabric or
to
human skin when the skin is contacted with a personal care or personal hygiene
product inter alia deodorants, body lotions or creams, and shampoos, which
comprises the pro-fragrances of the present invention. In addition to the
short-term
pleasurable odor benefits, the pro-fragrances according to the present
invention
continue to release their fragrance raw materials for as long as several weeks
depending upon the structure of the pro-fragrance.
The pro-fragrances described herein comprise fragrance raw materials in a
stable, releasable form. The pro-fragrance containing laundry detergent
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3
compositions of the present invention can comprise any number of pro-
fragrances
and are suitable for delivery of any type of fragrance "characteristic"
desired by the
formulator.
The first aspect of the present invention relates to pro-fragrance compounds
having the formula:
R4 RS R4 RS R6 R7
R3 R6 R3 R8
R2 ~ or R2 ~
Rl O OR 0' _OR
RI
wherein R is a fragrance raw material alcohol, preferably linalool or
dihydromyrcenol; R1, R2, R3, R4, R5, R6, R~, and R8 are each
independently selected from:
a) hydrogen;
b) C 1-C22 linear or branched alkyl;
c) C2-C22 linear or branched alkenyl;
d) C 1-C22 linear or branched alkoxy;
e) C6-C20 substituted or unsubstituted aryl;
f) C2-C20 substituted or unsubstituted alkyleneoxy;
g) C3-C20 substituted or unsubstituted alkyleneoxyalkyl;
h) C6-C20 substituted or unsubstituted alkylenearyl;
i) C6-C20 substituted or unsubstituted aryloxy;
j) C~-C20 substituted or unsubstituted alkyleneoxyaryl;
k) C6-C20 oxyalkylenearyl;
I} C1-C20 alkylenecarboxy having the formula:
-(CH2)xR9
wherein R9 is -CHO, -C02M; -C02R10, -CONH2, -CONHR10,
-CONR10R11, and mixtures thereof; wherein R10 and R11 are each
independently C 1-C 12 linear or branched alkyl, M is hydrogen or a
salt forming cation, x is an integer from 0 to 19;
m) any two R1, R2, R3, R4, R5, R6, R~, or R8 units can be taken
together to form a fused aromatic or non-aromatic ring comprising
from 4 to 7 carbon atoms;
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4
n) two or more Rl, R2, R3, R4, RS, R6, R~, or R$ units can be taken
together to form a bicyclic, tricyclic, or spiroannulated ring
comprising from 5 to $ carbon atoms;
o) an anionic unit having the formula:
-(CH2}yRl 2
wherein R12 is -S03M, -OS03M, -P03M, -OP03M, or mixtures
thereof; wherein M is hydrogen, one or more salt forming cations
sufficient to satisfy charge balance, or mixtures thereof; y is an
interger from 1 to about 22;
p) and mixtures thereof.
The present invention also relates to laundry detergent compositions which
comprise the pro-fragrance cyclic acetals described herein. A further aspect
of the
present invention is the use of the cyclic pro-fragrances of the present
invention as a
post-laundry "freshening agent" for use on fabric which has been laundered but
which has not been worn for an extended period of time. A yet further aspect
of the
present invention is the use of the pro-fragrances of the present invention in
rinse-
added compositions and in dryer-added compositions. The pro-fragrance
compounds of the present invention are also capable of delivering sustained
release
or enhanced longevity fragrances to a variety of personal care and personal
hygiene
products inter alia deodorants, body lotions or creams, and shampoos. These
and
other objects, features and advantages will become apparent to those of
ordinary
skill in the art from a reading of the following detailed description and the
appended
claims.
All percentages, ratios and proportions herein are by weight, unless
otherwise specified. All temperatures are in degrees Celsius (o C) unless
otherwise
specified. All documents cited are in relevant part, incorporated herein by
reference.
DETAILED DESCRIPTION OF THE INVENTION
The pro-fragrances of the present invention comprise a fragrance raw
material component and a substantivity or solubility component. The fragrance
raw
material component can be any perfume or any "fragrance raw material alcohol"
which the formulator wishes to deliver to the fabric surface for subsequent
release
after the laundry cycle. In addition, the pro-fragrances comprise a
substantivity or
solubility component wherein the proper choice of group allows the formulator
to
control the solubility of the pro-fragrance in water, the degree of
substantivity of the
pro-fragrance for fabric, or the bulk properties of the material. The
manipulation of
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the pro-fragrance bulk properties will allow the formulator to produce a pro-
fragrance which is more easily admixed into a particular type of laundry
composition, for example, liquid, granular, high density, encapsulated-
component,
rinse-added, dryer-added, etc.
Once the laundry process is complete and the pro-fragrance has been suitably
delivered to the fabric, the pro-fragrance begins to release the fragrance raw
material
and because this release of material is protracted, the fabric remains "fresh"
and
"clean" smelling longer. However, pro-fragrances according to the present
invention
can also be designed to be activated by a change in pH or to be moisture or
"heat
activated" so as to release a "freshening scent" to the fabric during drying.
Therefore, heat-activated pro-fragrances can be delivered to the fabric
surface. This
results in a fabric having high "initial scent" as well as the lower "clean"
and "fresh"
scent obtained by the protracted release of non-activated pro-fragrances. What
is
meant herein by "heat activated" pro-fragrances are compounds which have a
higher
release rate of their fragrance materials after exposure to elevated
temperatures.
Therefore the formulator may achieve an initial high fragrance delivery
coupled with
the longer term sustained release.
The pro-fragrances of the present invention are therefore a means for
delivering a desired fragrance raw material onto fabric and thereby providing
the
fabric with a longer and more sustained "fresh" or "clean" smell. For the
purposes of
the present invention the term "fragrance raw material alcohol" is defined as
"an
alcohol generally having a molecular weight greater than or equal to 100 g/mol
which provides a fragrance, scent, smell, odor, or character which is
generally
deemed pleasurable to the senses."
Most of the fragrance raw materials which comprise the pro-fragrances of the
present invention are not deliverable as individual compounds to fabric via
the
laundry cycle either due to solubility factors (lost or rinsed away during the
laundry
cycles), substantivity factors (do not sufficiently adhere to fabric surface),
or
volatility factors (evaporation during the drying cycle). Therefore, the pro-
fragrances described herein are a means for delivering certain fragrance raw
materials to fabric which could not have previously been effectively or
efficiently
delivered. In fact, the tertiary alcohol fragrance raw materials are more
suitably
delivered by the pro-fragrances of the present invention than by conventional
pro-
fragrances.
The "fragrance raw materials" which comprise the preferred embodiments
are fragrance raw material alcohols. A listing of common fragrance raw
material
alcohols can be found in various reference sources, for example, "Perfume and
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6
Flavor Chemicals", Vols. I and II; Steffen Arctander Allured Pub. Co. {1994)
and
"Perfumes: Art, Science and Technology"; Muller, P. M. and Lamparsky, D.,
Blackie Academic and Professional ( 1994) all of which are incorporated herein
by
reference.
Those skilled in the art of detergent compositions will recognize that the
terms "substantive" and substantivity" refer to the propensity of a compound
to
adhere to, associate with, or deposit upon a surface, preferably the surface
of fabric.
Therefore, compounds which are more substantive more readily adhere to fabric
surface. However, substantive compounds, in general, do not react with the
surface
onto which they deposit.
Pro-fra rake, noes
The pro-fragrances of the present invention are derivatives of substituted and
unsubstituted 2-hydroxytetrahydrofuran having the formula:
R4 RS
R3 R6
RRl O~OR
and derivatives of substituted and unsubstituted 2-hydroxytetrahydropyran
having
the formula:
RS R6
R4 R~
R3 ~R8
R2
R~ O OR
wherein R is 2,4-dimethyl-3-cyclo-hexene-1-methyl (Floralol), 2,4-dimethyl
cyclohexane methyl (Dihydro floralol), 5,6-dimethyl-1-methylethenyl-
bicyclo[2.2.1]hept-5-ene-2-methyl (Arbozol), 2,4,6-trimethyl-3-cyclohexene-1-
methyl (Isocyclo geranyl), 4-(1-methylethyl)cyclohexylmethyl (Mayol), a-3,3-
trimethyl-2-norboranylmethyl, 1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methyl,
2-
phenylethyl, 2-cyclohexylethyl, 2-(o-methylphenyl)ethyl, 2-(m-
methylphenyl)ethyl,
2-(p-methylphenyl)ethyl, 6,6-dimethylbicyclo[3.1.1 ]kept-2-ene-2-ethyl
(nopyl), 2-
(4-methylphenoxy)ethyl, 3,3-dimethyl-D2-b-norbornanylethyl, 2-methyl-2-
cyclohexylethyl, 1-(4-isopropylcyclohexyl)ethyl, 1-phenyl-1-hydroxyethyl, 1,1-
dimethyl-2-phenylethyl, 1,1-dimethyl-2-(4-methylphenyl)ethyl, 1-phenylpropyl,
3-
phenylpropyl, 2-phenylpropyl (Hydrotropic Alcohol), 2-(cyclododecyl)-propan-1-
yl
(Hydroxyambran}, 2,2-dimethyl-3-(3-methylphenyl)propan-1-yl (Majantol), 2-
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methyl-3-phenylpropyl, 3-phenyl-2-propen-1-yl (cinnamyl alcohol), 2-methyl-3-
phenyl-2-propen-1-yl (methyicinnamyl alcohol), a-n-pentyl-3-phenyl-2-propen-1-
yl
(a-amylcinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4-
methylphenyl)-2-propyl, 3-(4-methylcyclohex-3-ene)butyl, 2-methyl-4-(2,2,3-
trimethyl-3-cyclopenten-1-yl)butyl, 2-ethyl-4-(2,2,3-trimethylcyclopent-3-
enyl)-2-
buten-1-yI, 3-methyl-2-buten-1-yl, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-
yl)-
2-buten-1-yl, 3-hydroxy-2-butanone, ethyl 3-hydroxybutyrate, 4-phenyl-3-buten-
2-
yl, 2-methyl-4-phenylbutan-2-yl, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-hydroxy-
3-
methoxyphenyl)butan-2-one, cis-3-pentenyl, 3-methylpentyl, 3-methyl-3-penten-1-
yI, 2-methyl-4-phenylpentyl (Pamplefleur), 3-methyl-5-phenylpentyl
(Phenoxanyl),
2-methyl-5-phenylpentyl, 2-methyl-5-(2,3-dimethyltricyclo-[2.2.1.0(2,6)]hept-3-
yl)-
2-penten-1-yl (santalyl), 4-methyl-1-phenyl-2-pentyl, (I-methyl-
bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-yl, 3-methyl-1-phenylpent-3-yl,
1,2-
dimethyl-3-(1-methylethenyl)cyclopent-1-yl, 2-isopropyl-4-methyl-2-hexenyl,
cis-3-
hexen-1-yl, trans-2-hexen-1-yl, 2-isopropenyl-5-methyl-4-hexen-1-yl
(Lavandulyl),
2-ethyl-2-prenyl-3-hexenyl (silwanol), 2-ethylhexyl, 1-hydroxymethyl-4-
isopropenyl-1-cyclohexenyl (Dihydrocuminyl), 1-methyl-4-isopropenylcyclohex-6-
en-2-yl (carvenyl), 6-methyl-3-isopropenylcyclohex-1-yl, 1-methyl-4-
isopropenylcyclohex-3-yl, 4-iso-propyl-1-methylcyclohex-3-yl, 4-tert-
butylcyclohexyl, 2-tert-butylcyclohexyl, 2-tert-butyl-4-methylcyclohexyl, 4-
isopropylcyclohexyl, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-yl, 2-(5,6,6-
trimethyl-2-norbornyl)cyclohexyl, isobornylcyclohexyl, 3,3,5-
trimethylcyclohexyl,
1-methyl-4-isopropylcyclohex-3-yl (menthol), 1,2-dimethyl-3-(1-methylethyl)-
cyclohexan-1-yl, heptyl, 2,4-dimethylhept-1-yl, 2,4-dimethyl-2,6-heptandienyl,
6,6-
dimethyl-2-oxymethylbicyclo[3.1.1]hept-2-en-1-yl (myrtenyl), 4-methyl-2,4-
heptadien-1-yl, 3,4,5,6,6-pentamethyl-2-heptyl, 3,6-dimethyl-3-vinyl-5-hepten-
2-yl,
6,6-dimethyl-3-hydroxy-2-methylenebicyclo[3.1.1]-heptyl, 1,7,7-
trirnethylbicyclo-
[2.2.1]hept-2-yl, 2,6-dimethylhept-2-yl, 2,6,6-trimethylbicyclo[1.3.3]kept-2-
yl,
octyl, 2-octenyl, 2-methyloctan-2-yl, 2-methyl-6-methylene-7-octen-2-yl
(myrcenyl), 7-methyloctan-I-yl, 3,7-dimethyl-6-octenyl, 3,7-dimethyl-7-
octenyl,
3,7-dimethyl-6-octen-1-yl (citronellyl), 3,7-dimethyl-2,6-octadien-1-yl
(geranyl),
3,7-dimethyl-2,6-octadien-1-yl (neryl), 3,7-dimethyl-1,6-octadien-3-yl
(linalyl), 3,7-
dimethyloctan-1-yl (pelagryl), 3,7-dimethyloctan-3-yl (tetrahydrolinalyl), 2,4-
octadien-1-yl, 3,7-dimethyl-6-octen-3-yl, 2,6-dimethyl-7-octen-2-yl, 2,6-
dimethyl-
5,7-octadien-2-yl, 4,7-dimethyl-4-vinyl-6-octen-3-yl, 3-methyloctan-3-yl, 2,6-
dimethyloctan-2-yl, 2,6-dimethyloctan-3-yl, 3,6-dimethyloctan-3-yl, 2,6-
dimethyl-7-
octen-2-yl, 2,6-dimethyl-3,5-octadien-2-yl (mugyl), 3-methyl-1-octen-3-yl, 7-
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8
hydroxy-3,7-dimethyloctanalyl, 3-nonyl, 6,8-dimethylnonan-2-yl, 3-
(hydroxymethyl)-2-nonanone, 2-nonen-1-yl, 2,4-nonadien-1-yl, 2,6-nonadien-1-
yl,
cis-6-nonen-1-yl, 3,7-dimethyl-1,6-nonadien-3-yl, decyl, 9-decenyl, 2-benzyl-M-
dioxa-5-yl, 2-decen-1-yl, 2,4-decadien-1-yl, 4-methyl-3-decen-5-yl, 3,7,9-
trimethyl-
1,6-decadien-3-yl (isobutyl linallyl), undecyl, 2-undecen-1-yl, 10-undecen-1-
yl, 2-
dodecen-1-yl, 2,4-dodecadien-1-yl, 2,7,11-trimethyl-2,6,10-dodecatrien-1-yl
(farnesyl), 3,7,11-trimethyl-1,6,10,-dodecatrien-3-yl, 3,7,11,15-
tetramethylhexadec-
2-en-1-yl (phytyl), 3,7,11,15-tetramethylhexadec-1-en-3-yl (iso phytol), p-
methoxybenzyl (anisyl), para-cymen-7-yl (cuminyl), 4-methylbenzyl, 3,4-
methylenedioxybenzyl, 2-(methyl)carboxy-1-hydroxyphenyl, 2-(benzyl)carboxy-1-
hydroxyphenyl, 2-(cis-3-hexenyl)-carboxy-1-hydroxyphenyl, 2-(n-pentyl)carboxy-
1-
hydroxyphenyl, 2-(2-phenylethyl)carboxy-1-hydroxyphenyl, 2-(n-hexyl)carboxy-1-
hydroxyphenyl, 2-methyl-5-isopropyl-1-hydroxyphenyl, 4-ethyl-2-methoxyphenyl,
4-allyl-2-methoxy-1-hydroxyphenyl (eugenyl), 2-methoxy-4-(1-propenyl}-1-
hydroxyphenyl (isoeugenyl), 4-allyl-2,6-dimethoxy-1-hydroxyphenyl, 4-tert-
butyl-1-
hydroxyphenyl, 2-ethoxy-4-methyl-1-hydroxyphenyl, 2-methyl-4-vinyl-1-
hydroxyphenyl, 2-isopropyl-5-methyl-1-hydroxyphenyl (thymyl), 2-(isopentyl)-
carboxy-1-hydroxyphenyl, 2-(ethyl)carboxy-1-hydroxyphenyl, 6-(methyl)carboxy-
2,5-dimethyl-1,3-dihydroxyphenyl, 5-methoxy-3-methyl-1-hydroxyphenyl, 2-tert-
butyl-4-methyl-1-hydroxyphenyl, 1-ethoxy-2-hydroxy-4-propenylphenyl, 4-methyl-
1-hydroxyphenyl, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-
hydroxybenzaldehyde, decahydro-2-naphthyl, 2,5,5-trimethyl-octahydro-2-
naphthyl,
1,3,3-trimethyl-2-norbornyl (fenchyl), 3a,4,5,6,7,7a-hexahydro-2,4-dimethyl-
4,7-
methano-1H-inden-5-yl, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-1H-
inden-5-yl, 2-methyl-2-vinyl-5-(1-hydroxy-1-methylethyl)tetrahydrofuranyl, b-
caryophyllenyl, and mixtures thereof.
Preferred R is 3,7-dimethyl-1,6-octadien-3-of (linalool, as a racemic mixture
or as each optical isomer alone), 2,6-dimethyl-7-octen-2-of (dihydromyrcenol,
as a
racemic mixture or as each optical isomer alone), and mixtures thereof.
Rl, R2, R3, R4, R5, R6, R7, and Rg units are each independently:
a) hydrogen;
b) C 1-C2~, preferably C 1-C 12, more preferably C 1-C6 linear or
branched alkyl;
c) C2-C22, preferably C2-C12, more preferably C2-C6 linear or
branched alkenyl;
d) C 1-C22, preferably C 1-C 12, more preferably C 1-C6 linear or
branched alkoxy;
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e) C6-C2p, preferably C6-C 1 p, more preferably C6 substituted or
unsubstituted aryl;
f) C2-C2p, preferably C2-C 12, more preferably C2-C6 substituted or
unsubstituted alkyleneoxy;
g) C3-C2p, preferably C3-C 12, more preferably C3-C6 substituted or
unsubstituted alkyleneoxyalkyl;
h) C~-C2p, preferably C~-C 12, more preferably C~ substituted or
unsubstituted alkylenearyl;
i) C6-C2p, preferably C6-C 1 p, more preferably C6 substituted or
unsubstituted aryloxy;
j) C~-C2p, preferably Cg-C12, more preferably Cg substituted or
unsubstituted alkyleneoxyaryl;
k) C~-C2p, preferably C~-C11, more preferably C~ oxyalkylenearyl;
1) C2-C2p, preferably C2-C 12, more preferably C2-C6 alkylenecarboxy
having the formula:
-(C H2)xR9
wherein R9 is -CHO, -C02M; -C02Rlp, -CONH2, -CONHR10,
-CONR1pR11, and mixtures thereof; wherein Rlp and R11 are each
independently C 1-C 12 linear or branched alkyl, preferably methyl or
ethyl; M is hydrogen or a salt forming cation, preferably sodium or
potassium; x is an integer from 0 to 19;
m) any two R 1, R2, R3, R4, R5, R6, R~, or R8 units can be taken
together to form a fused aromatic or non-aromatic ring comprising
from 4 to 7 carbon atoms;
n) two or more R1, R2, R3, R4, R5, R6, R~, or R8 units can be taken
together to form a bicyclic, tricyclic, or spiroannulated ring
comprising from 5 to 8 carbon atoms;
o) an anionic unit having the formula:
-(CH2~R12
wherein R12 is -S03M, -OS03M, -P03M, -OP03M, or mixtures
thereof; wherein M is hydrogen, one or more salt forming cations
sufficient to satisfy charge balance, preferably sodium or potassium;
or mixtures thereof; y is an integer from 1 to about 22;
p) and mixtures thereof.
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lU
For the purposes of the present invention substituted or unsubstituted
alkyleneoxy units are defined as moieties having the formula:
R14
-(CH2CHO~R13
wherein R13 is hydrogen; R14 is hydrogen, methyl, ethyl, and mixtures thereof;
the
index x is from 1 to about 10.
For the purposes of the present invention substituted or unsubstituted
alkyleneoxyalkyl are defined as moieties having the formula:
R14
I
-(CHZCHO)x(CH2)yRl 3
wherein R 13 is hydrogen, C 1-C 1 g alkyl, C 1-C4 alkoxy, and mixtures
thereof; R 14 is
hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about
9 and
the index y is from 1 to about 18.
For the purposes of the present invention substituted or unsubstituted
alkylenearyl units are defined as moieties having the formula:
Rt3
-(C H2)p
~Rt4
wherein R13 and R14 are each independently hydrogen, hydroxy, C 1-C4 alkoxy,
nitrilo, halogen, nitro, carboxyl (-CHO; -C02H; -C02R'; -CONH2; -CONHR'; -
CONK'2; wherein R' is C 1-C 12 linear or branched alkyl), amino, alkylamino,
and
mixtures thereof, p is from 1 to about 14.
For the purposes of the present invention substituted or unsubstituted aryloxy
units are defined as moieties having the formula:
Rt3
-O
~Rt4
wherein R13 and R14 are each independently hydrogen, hydroxy, C1-C4 alkyl, C1-
C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -C02H; -C02R'; -CONH2; -
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11
CONHR'; -CONR'2; wherein R' is C 1-C 15 linear or branched alkyl), amino,
alkylamino, and mixtures thereof.
For the purposes of the present invention substituted or unsubstituted
alkyleneoxyaryl units are defined as moieties having the formula:
Rt3
-(CH2)qp
~R~4
wherein R13 and R14 are each independently hydrogen, hydroxy, C1-C4 alkyl, C1-
C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -C02H; -C02R'; -CONH2; -
CONHR'; -CONR'2; wherein R' is C1-C12 linear or branched alkyl), amino,
alkylamino, and mixtures thereof, q is from 1 to about 14.
For the purposes of the present invention substituted or unsubstituted
oxyalkylenearyl units are defined as moieties having the formula:
R~3
-O(CH2)w
~R~4
wherein R 13 and R 14 are each independently hydrogen, hydroxy, C 1-C4 alkyl,
C 1-
C4 alkoxy, nitrilo, halogen, nitro, carboxyl (-CHO; -C02H; -C02R'; -CONH2; -
CONHR'; -CONR'2; wherein R' is C1-C12 linear or branched alkyl), amino,
alkylarnino, and mixtures thereof, w is from I to about 14.
As described herein above, any two R1, R2, R3, R4, R5, R6, R~, or Rg units
can be taken together to form a fused aromatic or non-aromatic ring comprising
from
4 to 7 carbon atoms. Those skilled in the art will recognize that in the case
of fused
aromatic rings only one R1, R2, R3, R4, R5, R6, R~, or Rg unit will be present
on a
carbon atom which is part of an aromatic ring. The other R1, R2, R3, R4, RS,
R6,
R~, or Rg unit will be absent. For example, when R1 and R3 units of a
tetrahydropyranyl pro-fragrance are taken together to form a six membered
fused
aromatic ring (a ring comprising 6 carbon atoms) the compound which results
has
the general formula:
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12
RS R6
R~
~ R8
O OR
wherein the units R2 and R4 are absent by virtue of chemical bonding
requirements.
The same applies if a fused aromatic ring is formed which includes two other
carbons of the tetrahydropyranyl ring, i.e. R4 and R6 will not be present if
R3 and
RS are taken together to form a fused aromatic ring. The same substitution and
bonding requirements apply to tetrahydrofuranyl based pro-fragrances.
In addition, a moiety substituted at a ring carbon may necessitate the use of
both substituent groups on a carbon atom to form the moiety. For example, both
R3
and R4 are needed to form an exocyclic double bond as in the general formula:
RS R6
R~
R2 ~ R8
Rl O OR
As described herein above, any two or more R1, R2, R3, R4, RS, R6, R~, or
R8 units can be taken together to form a bicyclic, tricyclic, or
spiroannulated ring
comprising from 5 to 8 carbon atoms. An example in which an R1 and R~ unit are
taken together to form a bicyclo[2.2.2J ring can be depicted by the general
formula:
R6 R8
OR
RS
R4 O
R2
R3
In addition, two R1, R2, R3, R4, R5, R6, R~, or R8 units which are on the same
ring
carbon atom may be taken together to form a spiroannulated ring, an example of
which is the tetrahydropyranyl pro-fragrance in which RS and R6 units are
taken
together to form a cyclohexane ring, having the general formula:
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13
R4 R~
R3 Rg
Rl~ ~O~ ~OR
The pro-fragrances of the present invention release "fragrance raw material
alcohols" which provide a pleasurable "fresh" and/or "clean" smell or scent to
fabric
to which the pro-fragrances are applied. Non-limiting examples of alcohols
suitably
released by the hydrolysis of the orthoester pro-accords include methanol, 2,4-
dimethyl-3-cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane
methanol
(Dihydro floralol), 5,6-dimethyl-1-methylethenylbicyclo[2.2.1]hept-5-ene-2-
methanol (Arbozol), 2,4,6-trimethyl-3-cyclohexene-1-methanol (Isocyclo
geraniol),
4-(I-methylethyl)cyclohexanemethanol (Mayol), a-3,3-trimethyl-2-norborane
methanol, 1,1-dimethyl-1-(4-methylcyclohex-3-enyl)methanol, ethanol, 2-
phenylethanol, 2-cyclohexyl ethanol, 2-(o-methylphenyl)-ethanol, 2-(m-
methylphenyl)ethanol, 2-(p-methylphenyl)ethanol, 6,6-dimethylbicyclo-[3.1.1
]hept-
2-ene-2-ethanol (nopol), 2-(4-methylphenoxy)ethanol, 3,3-dimethyl-D2-b-
norbornane ethanol, 2-methyl-2-cyclohexylethanol, I-{4-isopropylcyclohexyl)-
ethanol, I-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-
methyl-
phenyl)ethanol, n-propanol, 2-propanol, I-phenylpropanol, 3-phenylpropanol, 2-
phenylpropanol (Hydrotropic Alcohol), 2-{cyclododecyl)propan-1-of (Hydroxy-
ambran), 2,2-dimethyl-3-(3-methylphenyl)propan-1-of (Majantol), 2-methyl-3-
phenylpropanol, 3-phenyl-2-propen-I-of (cinnamyl alcohol), 2-methyl-3-phenyl-2-
propen-1-of (methylcinnamyl alcohol), a-n-pentyl-3-phenyl-2-propen-1-of (a-
amyl-
cinnamyl alcohol), ethyl-3-hydroxy-3-phenyl propionate, 2-(4-methyiphenyl)-2-
propanol, n-butanol, 2-butanol, 3-methylbutanol, 3-(4-methylcyclohex-3-
ene)butanol, 2-methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)butanol, 2-ethyl-4-
(2,2,3-trimethyl-cyclopent-3-enyl)-2-buten-1-ol, 3-methyl-2-buten-I-ol, 2-
methyl-4-
(2,2,3-trimethyl-3-cyclopenten-1-yI)-2-buten-1-ol, 3-hydroxy-2-butanone, ethyl
3-
hydroxybutyrate, 4-phenyl-3-buten-2-ol, 2-methyl-4-phenylbutan-2-ol, 4-(4-
hydroxyphenyl)butan-2-one, 4-(4-hydroxy-3-methoxyphenyl)butan-2-one, pentanol,
cis-3-pentenol, 3-methyl-pentanol, 3-methyl-3-penten-1-ol, 2-methyl-4-
phenylpentanol (Pamplefleur), 3-methyl-5-phenylpentanol (Phenoxanol), 2-methyl-
5-phenylpentanol, 2-methyl-5-(2,3-dimethyltricyclo[2.2.1.0(2,6)]hept-3-yl)-2-
penten-1-of (santalol), 4-methyl-1-phenyl-2-pentanol, (1-methyl-
bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol, 3-methyl-1-phenylpentan-3-
ol,
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1,2-dimethyl-3-(1-methylethenyl)cyclopentan-1-ol, 2-isopropyl-5-methyl-2-
hexenol,
cis-3-hexen-1-ol, trans-2-hexen-1-ol, 2-isoproenyl-4-methyl-4-hexen-1-of
(Lavandulol), 2-ethyl-2-prenyl-3-hexenol, 1-hydroxymethyl-4-iso-propenyl-1-
cyclohexene (Dihydrocuminyl alcohol), 1-methyl-4-isopropenylcyclohex-6-en-2-of
(carvenol), 6-methyl-3-isopropenylcyclohexan-1-ol, 1-methyl-4-iso-
propenylcyclohexan-3-ol, 4-isopropyl-1-methylcyclohexan-3-ol, 4-tert-
butylcyclo-
hexanol, 2-tert-butylcyclohexanol, 2-tert-butyl-4-methylcyclohexanol, 4-
isopropyl-
cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-ol, 2-(5,6,6-trimethyl-
2-
norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-trimethylcyclohexanol, 1-
methyl-4-isopropylcyclohexan-3-ol, 1,2-dimethyl-3-(1-methylethyl)cyclohexan-1-
ol,
heptanol, 2,4-dimethylheptan-1-ol, 2,4-dimethyl-2,6-heptandienol, 6,6-dimethyl-
2-
oxymethylbicyclo[3.1.1]kept-2-ene (myrtenol}, 4-methyl-2,4-heptadien-1-ol,
3,4,5,6,6-pentamethyl-2-heptanol, 3,6-dimethyl-3-vinyl-5-hepten-2-ol, 6,6-
dimethyl-
3-hydroxy-2-methylenebicyclo[3.1.1 ]heptane, 1,7,7-trimethylbicyclo[2.2.1
]heptan-
2-0l, 2,6-dimethylheptan-2-ol, 2,6,6-trimethylbicyclo[1.3.3]heptan-2-ol,
octanol, 2-
octenol, 2-methyloctan-2-ol, 2-methyl-6-methylene-7-octen-2-of (myrcenol), 7-
methyloctan-1-ol, 3,7-dimethyl-6-octenol, 3,7-dimethyl-7-octenol, 3,7-dimethyl-
6-
octen-1-of (citronellol), 3,7-dimethyl-2,6-octadien-1-of (geraniol), 3,7-
dimethyl-2,6-
octadien-1-of (nerol), 3,7-dimethyl-1,6-octadien-3-of (linalool), 3,7-
dimethyloctan-
1-0l (pelagrol), 3,7-dimethyloctan-3-of (tetrahydrolinalool), 2,4-octadien-1-
ol, 3,7-
dimethyl-6-octen-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-5,7-octadien-2-
ol,
4,7-dimethyl-4-vinyl-6-octen-3-ol, 3-methyloctan-3-ol, 2,6-dimethyloctan-2-ol,
2,6-
dimethyloctan-3-oI, 3,6-dimethyloctan-3-ol, 2,6-dimethyl-7-octen-2-ol, 2,6-
dimethyI-3,5-octadien-2-of (muguol), 3-methyl-1-octen-3-ol, 7-hydroxy-3,7-
dimethyloctanal, 3-nonanol, 2,6-nonadien-1-ol, cis-6-nonen-1-ol, 6,8-
dimethylnonan-2-ol, 3-(hydroxymethyl)-2-nonanone, 2-nonen-1-ol, 2,4-nonadien-1-
ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanol, 9-decenol, 2-benzyl-M-dioxa-5-ol,
2-
decen-1-ol, 2,4-decadien-1-ol, 4-methyl-3-decen-5-ol, 3,7,9-trimethyl-1,6-
decadien-
3-0l (isobutyl linalool), undecanol, 2-undecen-1-ol, 10-undecen-1-ol, 2-
dodecen-1-
ol, 2,4-dodecadien-l-o1, 2,7,11-trimethyl-2,6,10-dodecatrien-1-of (farnesol),
3,7,11-
trimethyl-1,6,10,-dodecatrien-3-ol, 3,7,11,15-tetramethylhexadec-2-en-1-of
(phytol),
3,7,11,15-tetramethylhexadec-1-en-3-of (iso phytol), benzyl alcohol, p-methoxy
benzyl alcohol {anisyl alcohol), para-cymen-7-of (cuminyl alcohol), 4-methyl
benzyl alcohol, 3,4-methylenedioxy benzyl alcohol, methyl salicylate, benzyl
salicylate, cis-3-hexenyl salicylate, n-pentyl salicylate, 2-phenylethyl
salicylate, n-
hexyl salicylate, 2-methyl-5-isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-
2-
methoxyphenol (eugenol), 2-methoxy-4-(1-propenyl)phenol (isoeugenol), 4-allyl-
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1$
2,6-dimethoxy-phenol, 4-tert-butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-
vinylphenol, 2-isopropyl-5-methylphenol (thymol), pentyl-ortho-hydroxy
benzoate,
ethyl 2-hydroxy-benzoate, methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-
5-methoxy-I-methylbenzene, 2-tert-butyl-4-methyl-I-hydroxybenzene, I-ethoxy-2-
hydroxy-4-propenylbenzene, 4-hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde,
2-ethoxy-4-hydroxybenzaldehyde, decahydro-2-naphthol, 2,5,5-trimethyl-
octahydro-
2-naphthol, 1,3,3-trimethyl-2-norbornanol (fenchol), 3a,4,5,6,7,7a-hexahydro-
2,4-
dimethyl-4,7-methano-1 H-inden-5-ol, 3a,4,5,6,7,7a-hexahydro-3,4-dimethyl-4,7-
methano-1H-inden-5-ol, 2-methyl-2-vinyl-5-(1-hydroxy-1-
methylethyl)tetrahydrofuran, b-caryophyllene alcohol, and mixtures thereof.
Preferred alcohols released by the compounds of the present invention are 4-
(1-methylethyl)cyclohexanemethanol {mayol}, 2,4-dimethyl-3-cyclohexen-1-
ylmethanol (floralol), 2,4-dimethylcyclohex-I-ylmethanol (dihydrofloralol),
2,4,6-
trimethyl-3-cyclohexen-1-ylmethanol (isocyclogeraniol), 2-phenylethanol, I-(4-
isopropylcyclohexyl)ethanol (mugetanol), 2-(o-methylphenyl)ethanol (ortho-
hawthanol), 2-(m-methylphenyl)ethanol (meta-hawthanol), 2-(p-methylphenyl)-
ethanol (para-hawthanol), 2,2-dimethyl-3-(3-methylphenyl)propan-I-of
(majantol),
3-phenyl-2-propen-I-of (cinnamic alcohol), 2-methyl-4-(2,2,3-trimethyl-3-
cyclopenten-1-yl)-2-buten-I-of (santalaire), 3-methyl-S-phenylpentan-1-of
(phenoxanol), 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten-2-of
(ebanol), 2-methyl-4-phenylpentan-1-of (pamplefleur), cis-3-hexen-I-ol, 3,7-
dimethyl-6-octen-1-oI (citronellol), 3,7-dimethyl-2,6-octadien-1-of (geraniol,
nerol
or mixtures thereof), 7-methoxy-3,7-dimethyloctan-2-of (osyrol), 3,7-dimethyl-
1,6-
octadien-3-of (linalool), 2,6-dimethyl-7-octen-2-of (dihydromyrcenol) 6,8-
dimethylnonan-2-ol, cis-6-nonen-1-ol, 2,6-nonadien-I-ol, 4-methyl-3-decen-5-of
(undecavertol), benzyl alcohol, 2-methoxy-4-(I-propenyl)phenol (isoeugenol), 2-
methoxy-4-(2-propenyl)phenol (eugenol), 4-hydroxy-3-methoxybenzaldehyde
(vanillin), and mixtures thereof; more preferably 3,7-dimethyl-1,6-octadien-3-
of
(linalool), 2,6-dimethyl-7-octen-2-of (dihydromyrcenol), and mixtures thereof.
According to the present invention all isomers of a fragrance raw material
whether in the form of the pro-fragrance or the released fragrance raw
material, are
suitable for use in the present invention. When optical isomers are possible,
fragrance raw materials may be included as either the separate chemical isomer
or as
the combined racemic mixture. For example, 3,7-dimethyl-6-octen-1-ol, commonly
known by those of ordinary skill in the art as b-citronellol or cephrol,
comprises a
pair of optical isomers, R-(+)-b-citronellol and S-(-)-b-citronellol. Each of
these
materials separately or as a racemic pair are suitable for use as fragrance
raw
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materials in the present invention. However, those skilled in the art of
fragrances, by
utilization of the present invention, should not disregard any olfactory
differences
that individual optical isomers impart. By way of example, carvone, 2-methyl-5-
(1-
methylethenyl)-2-cyclohexene-1-one exists as two isomers; d carvone and 1-
carvone.
d Carvone is found in oil of caraway and renders a completely different
fragrance
from 1-carvone which is found in spearmint oil. According to the present
invention a
pro-fragrance which releases d carvone will result in a different fragrance
than one
which releases I-carvone. The same applies to 1-carvone.
Similarly, the tetrahydrofuranyl and tetrahydropyranyl pro-fragrances each
will have at least one chiral center which is the C-1 carbon contained within
the
furanyl or pyranyl ring and when taken together with fragrance alcohols having
a
chiral center, the pro-fragrances of the present invention have the capacity
to form
diasteriomeric pairs. According to the present invention, no single isomer or
isomer
pair is favored over another single isomer or isomer pair, however, if the
formulator
chooses one isomer or pair of isomers over the other because of their
fragrance
"character" or other bulk property characteristic, the choice does not
diminish the
value of the other remaining isomer or isomer pair for the purposes of the
present
invention.
In addition, the present invention relates to fragrance delivery systems
useful
in laundry detergent compositions, and rinse-added and dryer-added fabric
conditioning compositions. The fragrance delivery systems of the present
invention
provide slow, sustained release of fragrance raw materials which provide the
clothing or fabric article with a pleasant "fresh" or "clean" scent. In
addition, as
described herein above, the formulator may modify the pyranyl or furanyl
portion of
the pro-fragrance materials in order to provide increased fabric substantivity
or
laundry liquor solubility to the compounds which comprise the fragrance
delivery
system.
In general, the laundry detergent compositions of the present invention which
have increased fragrance retention and fragrance longevity, comprise:
A) at least about 0.01 %, preferably from about 0.01 % to about 10%,
more preferably from about 0.1 % to about 1 % by weight, of a
fragrance delivery system comprising:
ii) one or more pro-fragrance compounds of the present
invention;
iii) optionally fragrance carriers and other fragrance delivery
adjuncts;
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iv) optionally one or more non-pyranyl or non-furanyl pro-
fragrance materials;
B) at least about 0.01% by weight, preferably from about 0.1% to about
60%, more preferably from about 0.1 % to about 30% by weight, of a
detersive surfactant selected from the group consisting of anionic,
cationic, nonionic, zwitterionic, ampholytic surfactants, and mixtures
thereof, preferably said surfactant is an anionic surfactant; and
C) the balance carriers and adjunct ingredients said adjunct ingredients
are selected from the group consisting of builders, optical brighteners,
bleaches, bleach boosters, bleach catalysts, bleach activators, soil
release polymers, dye transfer agents, dispersents, enzymes, suds
suppressers, dyes, perfumes, colorants, filler salts, hydrotropes,
enzymes, photoactivators, fluorescers, fabric conditioners,
hydrolyzable surfactants, preservatives, anti-oxidants, chelants,
stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides,
fungicides, anti corrosion agents, and mixtures thereof..
For the purposes of the present invention the term "one or more non-pyranyl
or non-furanyl pro-fragrance materials" is defined as other compounds which
can
suitably release a fragrance raw material, for example, as disclosed in U.S.
5,378,468 Suffis et al., issued January 3, 1995, incorporated herein by
reference.
In general, the rinse added fabric softening compositions of the present
invention which have increased fragrance retention and fragrance longevity,
comprise:
A) at least about 0.01 %, preferably from about 0.01 % to about 10%,
more preferably from about 0.1% to about 1% by weight, of a
fragrance delivery system comprising:
i) one or more pro-fragrance compounds according to the
present invention;
ii) optionally one or more fragrance raw materials;
iii) optionally fragrance carriers and other fragrance delivery
adjuncts;
B) from about 99.99%, preferably from about 85% to about 99.9% by
weight of the composition, of ingredients useful for formulating
fabric softening compositions, said ingredients selected from the
group consisting of cationic fabric softening agents; nonionic fabric
softening agents; liquid carrier; concentration aid; soil release agent;
perfume; and preservatives/stabilizers, and mixtures thereof;
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C) at least about 50% of a liquid carrier; and
D) optionally from about 0.01 % to about 15% by weight, of
concentration aids;
wherein further said compositions have a pH of less than about 6 at 20 o C.
In general, the dryer-added added fabric softening and fabric appearance
benefit compositions are delivered by a article of manufacture such as a
substrate,
preferably a flexible substrate which is added to the dryer, said articles of
manufacture comprise:
A) at least about 0.01 %, preferably from about 0.01 % to about 10%,
more preferably from about 0.1 % to about 1 % by weight, of a
fragrance delivery system comprising:
i) one or more pro-fragrance compounds according to the
present invention;
ii) optionally one or more fragrance raw materials;
iii) optionally fragrance carriers and other fragrance delivery
adjuncts;
B) a fabric treatment component comprising:
a) from about 1 % to about 60% by weight, of a polyamine
having the formula;
i) a polyamine having a backbone of the formula:
H
~2N-RJn+1-LN-Rjrri ~N-Rjp NfI2
wherein R is C2-Cg alkylene, C3-Cg alkyl substituted
alkylene, and mixtures thereof, preferably ethylene,
1,2-propylene, 1,3-propylene, more preferably
ethylene;
ii) a polyamine having a backbone of the formula:
CHI-CH
I
NH2
wherein y is from 5 to about 10,000; and
iii) optionally from 0% to 100% of the polyamine
backbone NH units are substituted by one or more
units having the formula:
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-(Rl OhcR2
wherein R1 is C2-C6 alkylene, C3-C6 alkyl
substituted alkylene, and mixtures thereof; R2 is
hydrogen, C1-C4 alkyl, and mixtures thereof,
preferably hydrogen and methyl; wherein m is from 2
to about 700; n is from 0 to about 350; x is from 1 to
12, preferably from 1 to about 4; y is from 5 to 5000.
b) from about 40% to about 99% by weight, of a carboxylic acid
carrier;
wherein the fabric treatment composition has a viscosity of less than
about 2000 centipoise at 1000 C and a melting point from about 250
C to about 950 C; and
C) dispensing means which provides for release of an effective amount
of said polyamine (i) and carboxylic acid carrier (ii) to fabrics in an
automatic laundry dryer at operating temperatures.
surfactant systems
The instant cleaning compositions may contain at least about 0.01 % by
weight of a surfactant selected from the group consisting of anionic,
cationic,
nonionic, ampholytic and zwitterionic surface active agents. Preferably the
solid
(i.e. granular) and viscous semi-solid (i.e. gelatinous, pastes, etc.) systems
of the
present invention, surfactant is preferably present to the extent of from
about 0.1%
to 60 %, more preferably 0.1 % to about 30% by weight of the composition.
Nonlimiting examples of surfactants useful herein typically at levels from
about 1% to about 55%, by weight, include the conventional C11-C1 g alkyl
benzene
sulfonates ("LAS") and primary, branched-chain and random C10-C2p alkyl
sulfates
("AS"), the C 10-C 1 g secondary (2,3) alkyl sulfates of the formula
CH3(CH2)x(CHOS03 M+) CH3 and CH3 (CH2)y(CHOS03 M+) CH2CH3 where
x and (y + 1 ) are integers of at least about 7, preferably at least about 9,
and M is a
water-solubilizing cation, especially sodium, unsaturated sulfates such as
oleyl
sulfate, the C 10-C 1 g alkyl alkoxy sulfates ("AEXS"; especial ly EO 1-7
ethoxy
sulfates), C 10-C 1 g alkyl alkoxy carboxylates (especially the EO 1-5
ethoxycarboxylates), the C 10-18 glycerol ethers, the C 10-C 1 g alkyl
polyglycosides
and their corresponding sulfated polyglycosides, and C 12-C 1 g alpha-
sulfonated
fatty acid esters. If desired, the conventional nonionic and amphoteric
surfactants
such as the C 12-C 1 g alkyl ethoxylates ("AE") including the so-called narrow
peaked alkyl ethoxylates and C6-C 12 alkyl phenol alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy), C 12-C 18 betaines and sulfobetaines
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WO 99/00377 PCT/US98/13278
("sultaines"), C I 0-C I g amine oxides, and the like, can also be included in
the
overall compositions. The C 10-C I g N-alkyl polyhydroxy fatty acid amides are
highly preferred, especially the C I 2-C I g N-methylglucamides. See WO
9,206,154.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C I 0-C I g N-(3-methoxypropyl) glucamide. The N-propyl
through
N-hexyl C 12-C I g glucamides can be used for low sudsing. C I 0-C20
conventional
soaps may also be used. If high sudsing is desired, the branched-chain C l 0-C
16
soaps may be used. Mixtures of anionic and nonionic surfactants are especially
useful. Other conventional useful surfactants are described further herein and
are
listed in standard texts.
Anionic surfactants can be broadly described as the water-soluble salts,
particularly the alkali metal salts, of organic sulfuric reaction products
having in
their molecular structure an alkyl radical containing from about 8 to about 22
carbon
atoms and a radical selected from the group consisting of sulfonic acid and
sulfuric
acid ester radicals. ( Included in the term alkyl is the alkyl portion of
higher acyl
radicals.) Important examples of the anionic synthetic detergents which can
form
the surfactant component of the compositions of the present invention are the
sodium or potassium alkyl sulfates, especially those obtained by sulfating the
higher
alcohols (C8-I 8 carbon atoms) produced by reducing the glycerides of tallow
or
coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl
group contains from about 9 to about I S carbon atoms, (the alkyl radical can
be a
straight or branched aliphatic chain); sodium alkyl glyceryl ether sulfonates,
especially those ethers of the higher alcohols derived from tallow and coconut
oil;
sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or
potassium salts of sulfuric acid ester of the reaction product of one mole of
a higher
fatty alcohol (e.g. tallow or coconut alcohols) and about I to about 10 moles
of
ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether
sulfates with about 1 to about 10 units of ethylene oxide per molecule and in
which
the alkyl radicals contain from 8 to 12 carbon atoms; the reaction products of
fatty
acids are derived from coconut oil sodium or potassium salts of fatty acid
amides of
a methyl tauride in which the fatty acids, for example, are derived from
coconut oil
and sodium or potassium beta-acetoxy- or beta-acetamido-alkanesulfonates where
the alkane has from 8 to 22 carbon atoms.
Additionally, secondary alkyl sulfates may be used by the formulator
exclusively or in conjunction with other surfactant materials and the
following
identifies and illustrates the differences between sulfated surfactants and
otherwise
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21
conventional alkyl sulfate surfactants. Non-limiting examples of such
ingredients
are as follows.
Conventional primary alkyl sulfates (AS), such as those illustrated above,
have the general formula ROS03-M+ wherein R is typically a linear C8-22
hydrocarbyl group and M is a water solublizing cation. Branched chain primary
alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20 carbon
atoms are
also know; see, for example, Eur. Pat. Appl. 439,316, Smith et al., filed
January 21,
1991.
Conventional secondary alkyl sulfate surfactants are those materials which
have the sulfate moiety distributed randomly along the hydrocarbyl "backbone"
of
the molecule. Such materials may be depicted by the structure
CH3(CH2)n(CHOS03-M+)(CH2)mCH3
wherein m and n are integers of 2 of greater and the sum of m + n is typically
about
9 to 17, and M is a water-solublizing cation.
The aforementioned secondary alkyl sulfates are those prepared by the
addition of H2S04 to olefins. A typical synthesis using alpha olefins and
sulfuric
acid is disclosed in U.S. Pat. No. 3,234,258, Moms, issued February 8, 1966 or
in
U.S. Pat. No. 5,075,041, Lutz, issued December 24,1991. See also U.S. Patent
5,349,101, Lutz et al., issued September 20, 1994; U.S. Patent 5,389,277,
Prieto,
issued February 14, 1995.
The preferred surfactants of the present invention are anionic surfactants,
however, other surfactants useful herein are described below.
The compositions of the present invention can also comprise at least about
0.01 %, preferably at least 0.1 %, more preferably from about 1 % to about
30%, of an
nonionic detersive surfactant. Preferred nonionic surfactants such as C I2-C 1
g alkyl
ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and
C6-
C 12 alkyl phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy),
block alkylene oxide condensate of C6 to C 12 alkyl phenols, alkylene oxide
condensates of Cg-C22 alkanols and ethylene oxide/propylene oxide block
polymers
(PluronicT""-BASF Corp.), as well as semi polar nonionics (e.g., amine oxides
and
phosphine oxides) can be used in the present compositions. An extensive
disclosure
of these types of surfactants is found in U.S. Pat. 3,929,678, Laughlin et
al., issued
December 30, 1975, incorporated herein by reference.
Alkylpolysaccharides such as disclosed in U.S. Pat. 4,565,647 Llenado
(incorporated herein by reference) are also preferred nonionic surfactants in
the
compositions of the invention.
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22
More preferred nonionic surfactants are the polyhydroxy fatty acid amides
having the formula:
O Rg
R~-C-N-Q
wherein R~ is CS-C3 I alkyl, preferably straight chain C~-C 1 g alkyl or
alkenyl,
more preferably straight chain Cg-CIA alkyl or alkenyl, most preferably
straight
chain C I 1-C 15 alkyl or alkenyl, or mixtures thereof; Rg is selected from
the group
consisting of hydrogen, C I -Cq alkyl, C 1-C4 hydroxyalkyl, preferably methyl
or
ethyl, more preferably methyl. Q is a polyhydroxyalkyl moiety having a Linear
alkyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated
derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures
thereof.
Preferred Q is derived from a reducing sugar in a reductive amination
reaction.
More preferably Q is a glycityl moiety. Suitable reducing sugars include
glucose,
fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials,
high
dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can
be
utilized as well as the individual sugars listed above. These corn syrups may
yield a
mix of sugar components for Q. It should be understood that it is by no means
intended to exclude other suitable raw materials. Q is more preferably
selected from
the group consisting of -CH2(CHOH)nCH20H, -CH(CH20H)(CHOH)n-1CH20H,
-CH2(CHOH)2-(CHOR')(CHOH)CH20H, and alkoxylated derivatives thereof,
wherein n is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic
or
aliphatic monosaccharide. Most preferred substituents for the Q moiety are
glycityls wherein n is 4, particularly -CH2(CHOH)4CH20H.
RICO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, tallowamide, etc.
R8 can be, for example, methyl, ethyl, propyl, isopropyl, butyl, 2-hydroxy
ethyl, or 2-hydroxy propyl.
Q can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, I-deoxylactityl,
1-deoxygalactityl, I-deoxymannityl, I-deoxymaltotriotityl, etc.
A particularly desirable surfactant of this type for use in the compositions
herein is alkyl-N-methyl glucomide, a compound of the above formula wherein R~
is alkyl (preferably C 1 I-C 1 ~), Rg, is methyl and Q is 1-deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C I O-C I g N-(3-methoxypropyl) glucamide. The N-propyl
through
N-hexyl C I2-C I g glucamides can be used for low sudsing. C I O-C20
conventional
soaps may also be used. If high sudsing is desired, the branched-chain CI0-CI6
soaps may be used.
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23
Bui - Detergent builders can optionally be included in the compositions
herein to assist in controlling mineral hardness. Inorganic as well as organic
builders can be used. Builders are typically used in fabric laundering
compositions
to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the
composition and its desired physical form. When present, the compositions will
typically comprise at least about 1 % builder. Formulations typically comprise
from
about 5% to about 50%, more typically about 5% to about 30%, by weight, of
detergent builder. Granular formulations typically comprise from about 10% to
about 80%, more typically from about 15% to about 50% by weight, of the
detergent builder. Lower or higher levels of builder, however, are not meant
to be
excluded.
Inorganic or P-containing detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric
meta-
phosphates), phosphonates, phytic acid, silicates, carbonates (including
bicarbonates
and sesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate
builders are required in some locales. Importantly, the compositions herein
function
surprisingly well even in the presence of the so-called "weak" builders (as
compared
with phosphates) such as citrate, or in the so-called "underbuilt" situation
that may
occur with zeolite or layered silicate builders.
Examples of silicate builders are the alkali metal silicates, particularly
those
having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates,
such as
the layered sodium silicates described in U.S. Patent 4,664,839, issued May
12,
1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered
silicate
marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite
builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has
the delta-Na2Si05 morphology form of layered silicate. It can be prepared by
methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043.
SKS-6 is a highly preferred layered silicate for use herein, but other such
layered
silicates, such as those having the general formula NaMSix02x+1 ~yH20 wherein
M
is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a
number
from 0 to 20, preferably 0 can be used herein. Various other layered silicates
from
Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma
forms. As noted above, the delta-Na2Si05 (NaSKS-6 form) is most preferred for
use herein. Other silicates may also be useful such as for example magnesium
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24
silicate, which can serve as a crispening agent in granular formulations, as a
stabilizing agent for oxygen bleaches, and as a component of suds control
systems.
Examples of carbonate builders are the alkaline earth and alkali metal
carbonates as disclosed in German Patent Application No. 2,321,001 published
on
November 15, 1973.
Aluminosilicate builders are useful in the present invention. Aluminosilicate
builders are of great importance in most currently marketed heavy duty
granular
detergent compositions, and can also be a significant builder ingredient in
liquid
detergent formulations. Aluminosilicate builders include those having the
empirical
formula:
[Mz(zA102)y] ~xH20
wherein z and y are integers of at least 6, the molar ratio of z to y is in
the range
from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available.
These aluminosilicates can be crystalline or amorphous in structure and can be
naturally-occurring aluminosilicates or synthetically derived. A method for
producing aluminosilicate ion exchange materials is disclosed in U.S. Patent
3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic
crystalline
aluminosilicate ion exchange materials useful herein are available under the
designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an
especially
preferred embodiment, the crystalline aluminosilicate ion exchange material
has the
formula:
Nal2~(A102)12(Si02)12]~xH20
wherein x is from about 20 to about 30, especially about 27. This material is
known
as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein.
Preferably,
the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention
include, but are not restricted to, a wide variety of polycarboxylate
compounds. As
used herein, "polycarboxylate" refers to compounds having a plurality of
carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate
builder can
generally be added to the composition in acid form, but can also be added in
the
form of a neutralized salt. When utilized in salt form, alkali metals, such as
sodium,
potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of
useful materials. One important category of polycarboxylate builders
encompasses
the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg,
U.S.
Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent
3,635,830,
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issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071,
issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also
include
cyclic compounds, particularly alicyclic compounds, such as those described in
U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates,
copolymers of malefic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-
trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid,
the various alkali metal, ammonium and substituted ammonium salts of
polyacetic
acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as
well as
polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid,
polymaleic
acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and
soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly
sodium salt), are polycarboxylate builders of particular importance for heavy
duty
liquid detergent formulations due to their availability from renewable
resources and
their biodegradability. Citrates can also be used in granular compositions,
especially in combination with zeolite and/or layered silicate builders.
Oxydisuccinates are also especially useful in such compositions and
combinations.
Also suitable in the detergent compositions of the present invention are the
3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in
U.S.
Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders
include the CS-C20 alkyl and alkenyl succinic acids and salts thereof. A
particularly preferred compound of this type is dodecenylsuccinic acid.
Specific
examples of succinate builders include: laurylsuccinate, myristylsuccinate,
palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate,
and
the like. Laurylsuccinates are the preferred builders of this group, and are
described
in European Patent Application 86200690.510,200,263, published November 5,
1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226,
Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl,
issued
March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C12-C1 g monocarboxylic acids, can also be incorporated
into the compositions alone, or in combination with the aforesaid builders,
especially citrate and/or the succinate builders, to provide additional
builder activity.
Such use of fatty acids will generally result in a diminution of sudsing,
which
should be taken into account by the formulator.
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26
In situations where phosphorus-based builders can be used, and especially in
the formulation of bars used for hand-laundering operations, the various
alkali metal
phosphates such as the well-known sodium tripolyphosphates, sodium
pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such
as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for
example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and
3,422,137)
can also be used.
('lay Soil Removal/Anti-redenosition Agents
The compositions of the present invention can also optionally contain water-
soluble ethoxylated amines having clay soil removal and antiredeposition
properties.
Granular detergent compositions which contain these compounds typically
contain
from about 0.01 % to about 10.0% by weight of the water-soluble ethoxylates
amines; liquid detergent compositions typically contain about 0.01 % to about
5%.
The most preferred soil release and anti-redeposition agent is ethoxylated
tetraethylenepentamine. Exemplary ethoxylated amines are further described in
U.S.
Patent 4,597,898, VanderMeer, issued July l, 1986. Another group of preferred
clay
soil removal-antiredeposition agents are the cationic compounds disclosed in
European Patent Application 111,965, Oh and Gosselink, published June 27,
1984.
Other clay soil removal/antiredeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application 111,984,
Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in
European Patent Application 112,592, Gosselink, published July 4, 1984; and
the
amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
1985.
Other clay soil removal and/or anti redeposition agents known in the art can
also be
utilized in the compositions herein. Another type of preferred
antiredeposition agent
includes the carboxy methyl cellulose (CMC) materials. These materials are
well
known in the art.
Other Ingredients - A wide variety of other ingredients useful in detergent
compositions can be included in the compositions herein, including other
active
ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solid
fillers for
bar compositions, etc. Other optional ingredients include enzymes, bleaches,
bleach
activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric
conditioners,
hydrolyzable surfactants, optical brighteners, preservatives, anti-oxidants,
chelants,
stabilizers, anti-shrinkage agents, anti-wrinkle agents, soil release agents,
germicides, fungicides, and anti corrosion agents. If high sudsing is desired,
suds
boosters such as the C 10-C 16 alkanolamides can be incorporated into the
compositions, typically at 1 %-10% levels. The C 10-C 14 monoethanol and
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27
diethanol amides illustrate a typical class of such suds boosters. Use of such
suds
boosters with high sudsing adjunct surfactants such as the amine oxides,
betaines
and sultaines noted above is also advantageous. If desired, soluble magnesium
salts
such as MgCl2, MgS04, and the like, can be added at levels of, typically, 0.1
%-2%,
to provide additional suds and to enhance grease removal performance.
Various detersive ingredients employed in the present compositions
optionally can be further stabilized by absorbing said ingredients onto a
porous
hydrophobic substrate, then coating said substrate with a hydrophobic coating.
Preferably, the detersive ingredient is admixed with a surfactant before being
absorbed into the porous substrate. In use, the detersive ingredient is
released from
the substrate into the aqueous washing liquor, where it performs its intended
detersive function.
To illustrate this technique in more detail, a porous hydrophobic silica
(trademark SIPERNAT D 10, DeGussa) is admixed with a proteolytic enzyme
solution containing 3%-5% of C13-15 ethoxylated alcohol (EO 7) nonionic
surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of
silica.
The resulting powder is dispersed with stirring in silicone oil (various
silicone oil
viscosity in the range of 500-12,500 can be used). The resulting silicone oil
dispersion is emulsified or otherwise added to the final detergent matrix. By
this
means, ingredients such as the aforementioned enzymes, bleaches, bleach
activators,
bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and
hydrolyzable surfactants can be "protected" for use in detergent compositions.
The detergent compositions herein will preferably be formulated such that,
during use in aqueous cleaning operations, the wash water will have a pH of
between about 6.5 and about 11, preferably between about 7.5 and 10.5. Laundry
products are typically at pH 9-11. Techniques for controlling pH at
recommended
usage levels include the use of buffers, alkalis, acids, etc., and are well
known to
those skilled in the art.
Granular Compositions
The pro-accords of the present invention can be used in both low density
(below 550 grams/Iiter) and high density granular compositions in which the
density
of the granule is at least 550 grams/liter. Granular compositions are
typically
designed to provide an in the wash pH of from about 7.5 to about 11.5, more
preferably from about 9.5 to about 10.5. Low density compositions can be
prepared
by standard spray-drying processes. Various means and equipment are available
to
prepare high density compositions. Current commercial practice in the field
employs spray-drying towers to manufacture compositions which have a density
less
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28
than about 500 g/l. Accordingly, if spray-drying is used as part of the
overall
process, the resulting spray-dried particles must be further densified using
the means
and equipment described hereinafter. In the alternative, the formulator can
eliminate
spray-drying by using mixing, densifying and granulating equipment that is
commercially available. The following is a nonlimiting description of such
equipment suitable for use herein.
Various means and equipment are available to prepare high density (i.e.,
greater than about 550, preferably greater than about 650, grams/liter or
"g/1"), high
solubility, free-flowing, granular detergent compositions according to the
present
invention. Current commercial practice in the field employs spray-drying
towers to
manufacture granular laundry detergents which often have a density less than
about
500 g/l. In this procedure, an aqueous slurry of various heat-stable
ingredients in the
final detergent composition are formed into homogeneous granules by passage
through a spray-drying tower, using conventional techniques, at temperatures
of
about 175°C to about 225°C. However, if spray drying is used as
part of the overall
process herein, additional process steps as described hereinafter must be used
to
obtain the level of density (i.e., > 650 g/1) required by modern compact, low
dosage
detergent products.
For example, spray-dried granules from a tower can be densified further by
loading a liquid such as water or a nonionic surfactant into the pores of the
granules
and/or subjecting them to one or more high speed mixer/densifiers. A suitable
high
speed mixer/densifier for this process is a device marketed under the
tradename
"Lodige CB 30" or "Lodige CB 30 Recycler" which comprises a static cylindrical
mixing drum having a central rotating shaft with mixing/cutting blades mounted
thereon. In use, the ingredients for the detergent composition are introduced
into the
drum and the shaft/blade assembly is rotated at speeds in the range of 100-
2500 rpm
to provide thorough mixing/densification. See Jacobs et al, U.S. Patent
5,149,455,
issued September 22, 1992. The preferred residence time in the high speed
mixer/densifier is from about 1 to 60 seconds. Other such apparatus includes
the
devices marketed under the tradename "Shugi Granulator" and under the
tradename
"Drais K-TTP 80).
Another process step which can be used to densify further spray-dried
granules involves grinding and agglomerating or deforming the spray-dried
granules
in a moderate speed mixer/densifier so as to obtain particles having lower
intraparticle porosity. Equipment such as that marketed under the tradename
"Lodige KM" (Series 300 or 600) or "Lodige Ploughshare" mixer/densifiers are
suitable for this process step. Such equipment is typically operated at 40-160
rpm.
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29
The residence time of the detergent ingredients in the moderate speed
mixer/densifier is from about 0.1 to 12 minutes. Other useful equipment
includes
the device which is available under the tradename "Drais K-T 160". This
process
step which employs a moderate speed mixer/densifier (e.g. Lodige KM) can be
used
by itself or sequentially with the aforementioned high speed mixer/densifier
(e.g.
Lodige CB) to achieve the desired density. Other types of granules
manufacturing
apparatus useful herein include the apparatus disclosed in U.S. Patent
2,306,898, to
G. L. Heller, December 29, 1942.
While it may be more suitable to use the high speed mixer/densifier followed
by the low speed mixer/densifier, the reverse sequential mixer/densifier
configuration is also contemplated by the invention. One or a combination of
various parameters including residence times in the mixer/densifiers,
operating
temperatures of the equipment, temperature and/or composition of the granules,
the
use of adjunct ingredients such as liquid binders and flow aids, can be used
to
optimize densification of the spray-dried granules in the process of the
invention.
By way of example, see the processes in Appel et al, U.S. Patent 5,133,924,
issued
July 28, 1992 (granules are brought into a deformable state prior to
densification);
Delwel et al, U.S. Patent 4,637,891, issued January 20, 1987 (granulating
spray-
dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S.
Patent
4,726,908, issued February 23, 1988 (granulating spray-dried granules with a
liquid
binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657,
issued
November 3, 1992 (coating densified granules with a liquid binder and
aluminosilicate).
In those situations in which particularly heat sensitive or highly volatile
detergent ingredients or pro-accords are to be incorporated into the final
detergent
composition, processes which do not include spray drying towers are preferred.
The
formulator can eliminate the spray-drying step by feeding, in either a
continuous or
batch mode, starting detergent ingredients directly into mixing/densifying
equipment
that is commercially available. One particularly preferred embodiment involves
charging a surfactant paste and an anhydrous builder material into a high
speed
mixer/densifier (e.g. Lodige CB} followed by a moderate speed mixer/densifler
(e.g.
Lodige KM} to form high density detergent agglomerates. See Capeci et al, U.S.
Patent 5,366,652, issued November 22, 1994 and Capeci et al, U.S. Patent
5,486,303, issued January 23, 1996. Optionally, the liquid/solids ratio of the
starting
detergent ingredients in such a process can be selected to obtain high density
agglomerates that are more free flowing and crisp.
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Optionally, the process may include one or more recycle streams of
undersized particles produced by the process which are fed back to the
mixer/densifiers for further agglomeration or build-up. The oversized
particles
produced by this process can be sent to grinding apparatus and then fed back
to the
mixing/densifying equipment. These additional recycle process steps facilitate
build-up agglomeration of the starting detergent ingredients resulting in a
finished
composition having a uniform distribution of the desired particle size (400-
700
microns) and density (> 550 g/1). See Capeci et al, U.S. Patent 5,516,448,
issued
May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996.
Other suitable processes which do not call for the use of spray-drying towers
are
described by Bonier et al, U.S. Patent 4,828,721, issued May 9, 1989; Beerse
et al,
U.S. Patent 5,108,646, issued April 28, 1992; and, Jolicoeur, U.S. Patent
5,178,798,
issued January 12, 1993.
In yet another embodiment, the high density detergent composition of the
invention can be produced using a fluidized bed mixer. In this process, the
various
ingredients of the finished composition are combined in an aqueous slurry
(typically
80% solids content) and sprayed into a fluidized bed to provide the finished
detergent granules. Prior to the fluidized bed, this process can optionally
include the
step of mixing the slurry using the aforementioned Lodige CB mixer/densifier
or a
"Flexomix 160" mixer/densifier, available from Shugi. Fluidized bed or moving
beds of the type available under the tradename "Escher Wyss" can be used in
such
processes.
Another suitable process which can be used herein involves feeding a liquid
acid precursor of an anionic surfactant, an alkaline inorganic material (e.g.
sodium
carbonate) and optionally other detergent ingredients into a high speed
mixer/densifier (residence time 5-30 seconds) so as to form agglomerates
containing
a partially or totally neutralized anionic surfactant salt and the other
starting
detergent ingredients. Optionally, the contents in the high speed
mixer/densifier can
be sent to a moderate speed mixer/densifier (e.g. Lodige KM) for further
agglomeration resulting in the finished high density detergent composition.
See
Appel et al, U.S. Patent 5,164,108, issued November 17, 1992.
OPTIONAL FABRIC CONDITIONING AGENTS AND ADJUNCTS
Adjunct Cationic Conditioning,- ents
Compositions of the present invention can contain from about 5% to about
95%, preferably from about 15% to about 90%, more preferably from about 25% to
about 85%, and even more preferably from about 25% to about 55%, of
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31
biodegradable cationic softener, preferably an ester quaternary ammonium
compound (EQA).
The optional fabric conditioning component is preferably a fabric softening
compound which is an ester quaternary ammonium (EQA) compound or its
precursor amine having the formula:
CRI)4_ _N~ ((CH2)v Y-R2)p ~ X
P
Formula I
wherein Y is a carboxy moiety having the formula
O O
II II
-O-C.- or -C-O-
the index p is from 1 to 3; the index v is from 1 to 4, and mixtures thereof;
R1 is C1-
C6 alkyl, C1-C4 hydroxy alkyl group, or benzyl, preferably C1-C3 alkyl, for
example, methyl, ethyl, propyl, most preferred is methyl; preferably one R1
moiety
is a short chain alkyl group, preferably methyl; R2 is Cg-C3p saturated alkyl
or Cg-
C3p unsaturated alkyl, Cg-C30 substituted alkyl or Cg-C30 unsubstituted alkyl,
preferably C 1 q-C 1 g saturated alkyl or C 14-C 1 g unsaturated alkyl, C 14-C
1 g
substituted alkyl or C 14-C 1 g unsubstituted alkyl, more preferably linear C
14-(=18
saturated alkyl, wherein each R2 moiety suitable for use has an Iodine Value
of from
about 3 to about 60; the counter ion, X-, can be any softener-compatible
anion,
preferably methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate,
lactate,
nitrate, benzoate, more preferably methylsulfate.
Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl
materials.
It will be understood that substituents R1 and R2 of Formula I can optionally
be substituted with various groups such as alkoxyl or hydroxyl groups. The
preferred compounds can be considered to be diester (DEQA) variations of
ditallow
dimethyl ammonium methyl sulfate (DTDMAMS), which is a widely used fabric
softener. At least 80% of the DEQA is in the diester form, and from 0% to
about
20%, preferably less than about 10%, more preferably less than about 5%, can
be
EQA monoester (e.g., only one -Y-R2 group).
The following are non-limiting examples of EQA Formula I (wherein all long-
chain alkyl substituents are straight-chain):
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ura d
[C2H5]2+N[CH2CH20C(O)CI~H35)2 (CH3S04)-
[CH3][C2H5]+N[CH2CH20C(O)C13H27]2 [HC(O)O]_
[C3H7J[C2H5]+N[CH2CH20C(O)C11H23]2 (CH3S04)-
[CH3]2+N-[CH2CH20C(O)CI~H35]CI-I2CH20C(O)C15H31 (CH3S04)-
[CH3]2+N[CH2CH20C(O)R2]2 (CH3S04)-
where -C(O)R2 is derived from saturated tallow.
Unsaturated
[CH3]2+N[CH2CH20C(O)C1~H33]2 (CH3S04)-
[C2H5]2+N[CH2CH20C(O)C1~H33]2 Cl-
[CH3][C2H5]+N[CH2CH20C(O)C13H25]2 [C6HSC(O)O]
[CH3]2+N-[CH2CH20C(O)C I ~H33 ] CH2CH20C(O)C 1 SH29
(CH3CH2S04)-
[CH3]2+N[CH2CH20C(O)R2]2 (CH3S04)-
where -C(O)R2 is derived from partially hydrogenated tallow or modified tallow
having the characteristics set forth herein.
Other specific examples of biodegradable Formula I compounds suitable for
use in the fabric softening compositions herein are:
N-methyl-N,N-di-(2-C ~ 4-C 1 g-acyloxy ethyl);
N-2-hydroxyethyl ammonium methylsulfate;
[HOCH(CH3)CH2][CH3]+N[CH2CH20C(O)C15H31]2 Br ;
[HOCH(CH3)CH2][CH3]+N[CH2CH20C(O)C15H29]2 [HC(O)O]-; and
[CH2CH20H][CH3]+N[CH2CH20C(O)R2]2 (CH3S04)-. A preferred
compound is N-methyl, N,N-di-(2-oleyloxyethyl) N-2-hydroxyethyl ammonium
methylsulfate.
Further suitable fabric softening compounds are quaternary ammonium
compounds having the formula:
C(R ) -N~ ((CHz)v y~~- R2)p ~ X
a-p
Formula II
wherein Y" is a carboxy moiety having the formula
O O O O
-NR3-C- ~ -C-NR3- ~ -O-C- ~ -C-O-
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and mixtures thereof, wherein at least one Y~~ group is
O O
-NH-C- or -C-NH
the index p is from 1 to 3; the index v is from 1 to 4, and mixtures thereof;
R1 is C1-
C6 alkyl or benzyl, preferably C1-C3 alkyl, for example, methyl, ethyl,
propyl, most
preferred is methyl; preferably one R1 moiety is a short chain alkyl group,
preferably methyl; R2 is Cg-C30 saturated alkyl or Cg-C30 unsaturated alkyl,
Cg-
C30 substituted alkyl or Cg-C3p unsubstituted alkyl, preferably C14-Clg
saturated
alkyl or C 14-C 1 g unsaturated alkyl, C 14-C 1 g substituted alkyl or C 14-C
18
unsubstituted alkyl, more preferably linear C 14-C 1 g saturated alkyl,
wherein each
R2 moiety suitable for use has an Iodine Value of from about 3 to about 60; R3
is R
or H; the counter ion, X-, can be any softener-compatible anion, preferably
methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate,
nitrate,
benzoate, more preferably methylsulfate.
It will be understood that substituents R and R2 of Formula II can optionally
be substituted with various groups such as alkoxyl or hydroxyl groups.
The preferred ester linked compounds (DEQA) can be considered to be
diester variations of ditallow dimethyl ammonium chloride (DTDMAC), which is a
widely used fabric softener. Preferably, at least 80% of the DEQA is in the
diester
form, and from 0% to about 20%, preferably less than about 10%, more
preferably
less than about 5%, can be DEQA monoester (e.g., only one -Y-R2 group). For
optimal antistatic benefit monoester should be low, preferably less than about
2.5%.
The level of monoester can be controlled in the manufacturing of the DEQA.
The quaternary softening compounds with at least partially unsaturated alkyl
or acyl groups have advantages (i.e., antistatic benefits) and are highly
acceptable for
consumer products when certain conditions are met. Antistatic effects are
especially
important where the fabrics are dried in a tumble dryer, and/or where
synthetic
materials which generate static are used. Any reference to IV values
hereinafter
refers to IV of fatty alkyl or acyl groups and not to the resulting
quaternary, e.g.,
DEQA compound. As the IV is raised, there is a potential for odor problems.
For unsaturated softener actives, the optimum storage temperature for
stability
and fluidity depends on the specific IV of, e.g., the fatty acid used to make
DEQA
and/or the level/type of solvent selected. Exposure to oxygen should be
minimized
to keep the unsaturated groups from oxidizing. It can therefore be important
to store
the material under a reduced oxygen atmosphere such as a nitrogen blanket. It
is
important to provide good molten storage stability to provide a commercially
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34
feasible raw material that will not degrade noticeably in the normal
transportation/storage/handling of the material in manufacturing operations.
The following are non-limiting examples of DEQA Formula II (wherein all
long-chain alkyl substituents are straight-chain):
atu
[C2H5]2(+)N[CH2CH20C(O)C1~H35J2 S04CH3(-)
[C3H7J[C2HSJ(+)N[CH2CH20C(O)C11H23J2 S04(-)CH3
[CH3]2(+)N[CH2CH20C(O)R2J2 S04CH3(-)
where -C(O)R2 is derived from saturated tallow.
Unsaturated
[CH3J2(+)N[CH2CH20C(O)C1~H33J2 S04(-)CH3
[C2HSJ2(+)N[CH2CH20C(O)C 1 ~H33J2 Cl(-)
[CH2CH20HJ[CH3](+)N[CH2CH20C(O)R2J2 CH3S04(-)
[CH3J2(+)N[CH2CH20C(O)R2J2 CH3S04(-)
where -C(O)R2 is derived from partially hydrogenated tallow or modified tallow
having the characteristics set forth herein.
Further suitable fabric softening compounds according to the present
invention are ester quaternary ammonium compounds having the formula:
R'
+I
R' N-(CHZ ~ CH-CH2 X-
Ri Q2
R R
Formula III
wherein Q is a carboxy moiety having the formula
O O
II II
-O-C- or -C-O-
the index v is from 1 to 4, and mixtures thereof; R1 is C 1-C4 alkyl, C 1-C4
hydroxy
alkyl group, preferably methyl; preferably one Rl moiety is a short chain
alkyl
group, preferably methyl; R2 is Cg-C3p saturated alkyl or Cg-C3p unsaturated
alkyl,
Cg-C3p substituted alkyl or Cg-C3p unsubstituted alkyl, preferably C14-C18
saturated alkyl or C 14-C 1 g unsaturated alkyl, C 14-C 1 g substituted alkyl
or C 14-C 18
unsubstituted alkyl, more preferably linear C 14-C 1 g saturated alkyl,
wherein each
R2 moiety suitable for use has an Iodine Value of from about 3 to about 60;
the
counter ion X- is methylsulfate.
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An example of the above described ester quaternary ammonium compound
which is suitable for use as a fabric softening compound in the present
invention is
1,2-bis(tallowyloxy)-3-trimethyl ammoniopropane methylsulfate (DTTMAPMS).
Other suitable examples are 1,2-bis(cocoyloxy}-3-trimethyl ammoniopropane
methylsulfate, 1,2-bis(lauryloxy)-3-trimethyl ammoniopropane methylsulfate,
1,2-
bis(oleyloxy)-3-trimethyl ammoniopropane methylsulfate and 1,2-bis(stearyloxy)-
3-
trimethyl ammoniopropane methylsulfate. Replacing one or more or the methyl
moieties in the above examples with ethyl, propyl, isopropyl, butyl, isobutyl,
or
mixtures thereof, result in suitable fabric softening compounds according to
the
present invention. In addition, other anions other than methylsulfate may be
used.
Other examples of suitable Formula III EQA compounds of this invention are
obtained by, e.g., replacing "tallowyl" in the above compounds with, for
example,
cocoyl, lauryl, oleyl, stearyl, palmityl, or the like; replacing "methyl" in
the above
compounds with ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, or the
hydroxy
substituted analogs of these radicals; replacing "methylsulfate" in the above
compounds with chloride, ethylsulfate, bromide, formate, sulfate, lactate,
nitrate, and
the like, but methylsulfate is preferred.
Yet still further suitable fabric softening compounds according to the present
invention are ester quaternary ammonium compounds having the formula:
Rl i +((CH2)v Y-R2}p X_
Ra
Formula IV
wherein Y is a carboxy moiety having the formula
O O
II II
-O-C- or -C-O-
the index p is 2; the index v is from 1 to 4, and mixtures thereof; R1 is Cl-
Cq, alkyl
or hydroxy alkyl, preferably Cl-C3 alkyl, for example, methyl, ethyl, propyl,
most
preferred is methyl; R2 is Cg-C3p saturated or unsaturated, substituted or
unsubstituted alkyl having an Iodine Value of from about 3 to about 60,
preferred R2
is Cg-C 14 linear or branched alkyl; more preferred Cg-C 14 linear alkyl; R4
is a C 1-
C4 alcohol; the counter ion, X-, can be any softener-compatible anion,
preferably
methylsulfate, ethylsulfate, chloride, bromide, formate, sulfate, lactate,
nitrate,
benzoate, more preferably methylsulfate.
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Most preferably, the quaternary ammonium compound is a fully saturated
compound, such as dimethyl bis(tallowyloxyethyl) ammonium methylsulfate,
derived from hardened tallow . Also suitable are dimethyl bis(acyloxyethyl)
ammonium methylsulfate derivatives of Cg-C30 fatty acids, such as dimethyl
bis(tallowyloxyethyl) ammonium methylsulfate; dimethyl bis(oleyloxyethyl)
ammonium methylsulfate or dimethyl bis(cocoyloxyethyl) ammonium
methylsulfate. The composition of the present invention may comprise from
about
15% to about 90% of these quaternary ammonium compounds.
An example of the above described ester quaternary ammonium compounds
suitable for use as a fabric softening compound according to the present
invention is
N-methyl-N,N-bis-(2-C 14-C 1 g-acyloxy)ethyl-N-2-hydroxyethyl ammonium
methylsulfate. A preferred example is N-methyl-N,N-bis(2-oleyloxyethyl)-N-(2-
hydroxyethyl) ammonium methylsulfate.
The fabric conditioning composition can be any of those known in the art
and/or previously disclosed by others in patent applications. Compositions
that are
suitable are disclosed in U.S. Pat. Nos.: 3,944,694, McQueary; 4,073,996,
Bedenk et
al.; 4,237,155, Kardouche; 4,711,730, Gosselink et al.; 4,749,596, Evans et
al.;
4,808,086, Evans et al.; 4,818,569, Trinh et al.; 4,877,896, Maldonado et al.;
4,976,879, Maldonado et al.; 5,041,230, Borcher, Sr. et al.; 5,094,761, Trinh
et al.;
5,102,564, Gardlik et al.; and 5,234,610, Gardlik et al., all of said patents
being
incorporated herein by reference.
The compounds herein can be prepared by standard esterification and
quaternization reactions, using readily available starting materials. General
methods
for preparation are disclosed in U.S. Pat. No. 4,137,180, incorporated herein
by
reference.
As used herein, when the diester quat is specified, it will include the
monoester quat that is normally present. For the optimal antistatic benefit
the
percentage of monoester quat should be as low as possible, preferably less
than
about 20%. The level of monoester quat present can be controlled in the
manufacturing of the EQA.
EQA compounds prepared with fully saturated acyl groups are rapidly
biodegradable and excellent softeners. However, it has been discovered that
compounds prepared with at least partially unsaturated acyl groups have
advantages
(i.e., antistatic benefits) and are highly acceptable for consumer products
when
certain conditions are met.
Variables that must be adjusted to obtain the benefits of using unsaturated
acyl
groups include the Iodine Value (IV) of the fatty acids, the odor of fatty
acid starting
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37
material, and/or the EQA. Any reference to IV values herein refers to IV of
fatty
acyl groups and not to the resulting EQA compound.
Antistatic effects are especially important where the fabrics are dried in a
tumble dryer, and/or where synthetic materials which generate static are used.
As
the IV is raised, there is a potential for odor problems.
Some highly desirable, readily available sources of fatty acids such as
tallow,
possess odors that remain with the compound EQA despite the chemical and
mechanical processing steps which convert the raw tallow to finished EQA. Such
sources must be deodorized, e.g., by absorption, distillation (including
stripping such
as steam stripping), etc., as is well known in the art. In addition, care
should be
taken to minimize the adverse results of contact of the resulting fatty acyl
groups
with oxygen and/or bacteria by adding antioxidants, antibacterial agents, etc.
The
additional expense and effort associated with the unsaturated fatty acyl
groups is
justified by the superior performance.
Generally, hydrogenation of fatty acids to reduce polyunsaturation and to
lower IV to insure good color and odor stability leads to a high degree of
trans
configuration in the molecule. Therefore, diester compounds derived from fatty
acyl
groups having low IV values can be made by mixing fully hydrogenated fatty
acid
with touch hydrogenated fatty acid at a ratio which provides an IV of from
about 3
to about 60. The polyunsaturation content of the touch hardened fatty acid
should be
less than about 5%, preferably less than about 1 %. During touch hardening the
cisltrans isomer weight ratios are controlled by methods known in the art such
as by
optimal mixing, using specific catalysts, providing high H2 availability, etc.
It has also been found that for good chemical stability of the diester
quaternary compound in molten storage, water levels in the raw material must
be
minimized to preferably less than about 1 % and more preferably less than
about
0.5%. Storage temperatures should be kept as low as possible and still
maintain a
fluid material, ideally in the range of from about 49°C to about
75°C. The optimum
storage temperature for stability and fluidity depends on the specific IV of
the fatty
acid used to make the diester quaternary and the level/type of solvent
selected. Also,
exposure to oxygen should be minimized to keep the unsaturated groups from
oxidizing. It can therefore be important to store the material under a reduced
oxygen
atmosphere such as a nitrogen blanket. It is important to provide good molten
storage stability to provide a commercially feasible raw material that will
not
degrade noticeably in the normal transportation/storage/handling of the
material in
manufacturing operations.
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Adjunct fabric softening compositions employed herein contain as an optional
component, at a level of from about 0% to about 95%, preferably from about 20%
to
about 75%, more preferably from about 20% to about 60%, a carboxylic acid salt
of
a tertiary amine and/or ester amine which has the formula:
R6 -O
RS N O-C- R'
H
R4
wherein RS is a long chain aliphatic group containing from about 8 to about 30
carbon atoms; R4 and R6 are the same or different and are independently
selected
from the group consisting of aliphatic groups containing from about 1 to about
30
carbon atoms, hydroxyalkyl groups of the formula R80H wherein R8 is an
alkylene
group of from about 2 to about 30 carbon atoms, and polyalkyleneoxy moieties
of
the formula R90(R100)m- wherein R9 is hydrogen, C 1-C30 alkyl, C 1-C30
aIkenyl,
and mixtures thereof; R10 is ethylene, 1,2 propylene, 1,3-propylene, and
mixtures
thereof; m is from about 2 to about i 0; wherein further the R4, R5, R6, R8,
and R9
chains can be ester interrupted groups; and wherein R7 is selected from the
group
consisting of C2-C30 linear alkyl, C2-C3p linear alkenyl, Cg-C3p aryl, Cg-C30
alkylaryl, and Cg-C30 arylalkyl; substituted C1-C30 linear alkyl, C1-C30
linear
alkenyl, Cg-C30 aryl, Cg-C30 alkylaryl, and Cg-C30 arylalkyl wherein the
substituents are selected from the group consisting of halogen, carboxyl, and
hydroxyl, said composition having a thermal softening point of from about 35
°C to
about 100 °C.
Preferably, RS is an aliphatic chain containing from about C 1 ~-C3p linear
alkyl, R6 is C12-C30 linear alkyl, and R4 is C1-C30 linear alkyl.
Examples of preferred tertiary amines as starting material for the reaction
between the amine and carboxylic acid to form the tertiary amine salts are:
lauryldimethylamine, myristyldimethylamine, stearyldimethylamine, tallow-
dimethylamine, coconutdimethylamine, dilaurylmethylamine,
distearylmethylamine,
ditallowmethylamine, oleyldimethylamine, dioleylmethylamine, lauryldi(3-
hydroxy-
propyl)amine, stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethyl-
methylamine, and
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39
_(OC2H4)toOH
C~8H3~ //N
'(OC2H4)ioOH
Preferred fatty acids are those wherein R7 is Cg-C30 linear alkyl, more
preferably C 11-C 1 ~ linear alkyl.
Examples of specific carboxylic acids as a starting material are: formic acid,
acetic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic
acid, oxalic
acid, adipic acid, 12-hydroxy stearic acid, benzoic acid, 4-hydroxy benzoic
acid, 3-
chloro benzoic acid, 4-nitro benzoic acid, 4-ethyl benzoic acid, 4-(2-
chloroethyl)-
benzoic acid, phenylacetic acid, (4-chlorophenyl)acetic acid, (4-
hydroxyphenyl)acetic acid, and phthalic acid.
Preferred carboxylic acids are stearic, oleic, lauric, myristic, palmitic, and
mixtures thereof.
The amine salt can be formed by a simple addition reaction, well known in the
art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec. 2, 1980,
which is
incorporated herein by reference. Excessive levels of free amines may result
in odor
problems, and generally free amines provide poorer softening performance than
the
amine salts.
Preferred amine salts for use herein as optional ingredients are those wherein
the amine moiety is a Cg-C30 alkyl or alkenyl dimethyl amine or a di-Cg-C30
alkyl
or alkenyl methyl amine, and the acid moiety is a Cg-C3p alkyl or alkenyl
monocarboxylic acid. The amine and the acid, respectively, used to form the
amine
salt will often be of mixed chain lengths rather than single chain lengths,
since these
materials are normally derived from natural fats and oils, or synthetic
processed
which produce a mixture of chain lengths. Also, it is often desirable to
utilize
mixtures of different chain lengths in order to modify the physical or
performance
characteristics of the softening composition.
Specific preferred amine salts for use in the present invention are
oleyldimethylamine stearate, stearyldimethylamine stearate,
stearyldimethylamine
myristate, stearyldimethylamine oleate, stearyldimethylamine palmitate,
distearyimethylamine palmitate, distearylmethylamine laurate, and mixtures
thereof.
A particularly preferred mixture is oleyldimethylamine stearate and
distearylmethylamine myristate, in a ratio of 1:10 to 10:1, preferably about
1:1.
~iunct Nonionic Conditioning Agents
An optional softening agent of the present invention is a nonionic fabric
softener material. Typically, such nonionic fabric softener materials have an
HLB of
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from about 2 to about 9, more typically from about 3 to about 7. In general,
the
materials selected should be relatively crystalline, higher melting, (e.g.,
>25 °C).
The level of optional nonionic softener in the solid composition is typically
from about 10% to about 50%, preferably from about 15% to about 40%.
Preferred nonionic softeners are fatty acid partial esters of polyhydric
alcohols, or anhydrides thereof, wherein the alcohol, or anhydride, contains
from
about 2 to about 18, preferably from about 2 to about 8, carbon atoms, and
each fatty
acid moiety contains from about 8 to about 30, preferably from about 12 to
about 20,
carbon atoms. Typically, such softeners contain from about one to about 3,
preferably about 2 fatty acid groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene glycol, glycerol,
poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol,
sucrose, erythritol,
pentaerythritol, sorbitol or sorbitan.
The fatty acid portion of the ester is normally derived from fatty acids
having
from about 8 to about 30, preferably from about 12 to about 22, carbon atoms.
Typical examples of said fatty acids being lauric acid, myristic acid,
palmitic acid,
stearic acid, oleic acid, and behenic acid.
Highly preferred optional nonionic softening agents for use in the present
invention are C l 0-C26 acyl sorbitan esters and polyglycerol monostearate.
Sorbitan
esters are esterified dehydration products of sorbitol. The preferred sorbitan
ester
comprises a member selected from the group consisting of C l0-C26 acyl
sorbitan
monoesters and C 10-C26 acyl sorbitan diesters and ethoxylates of said esters
wherein one or more of the unesterified hydroxyl groups in said esters contain
from
1 to about 6 oxyethylene units, and mixtures thereof. For the purpose of the
present
invention, sorbitan esters containing unsaturation (e.g., sorbitan monooleate)
can be
utilized.
Sorbitol, which is typically prepared by the catalytic hydrogenation of
glucose, can be dehydrated in well known fashion to form mixtures of 1,4- and
1,5-
sorbitol anhydrides and small amounts of isosorbides. (See U.S. Pat. No.
2,322,821,
Brown, issued 3une 29, 1943, incorporated herein by reference.)
The foregoing types of complex mixtures of anhydrides of sorbitol are
collectively referred to herein as "sorbitan." It will be recognized that this
"sorbitan"
mixture will also contain some free, uncyclized sorbitol.
The preferred sorbitan softening agents of the type employed herein can be
prepared by esterifying the "sorbitan" mixture with a fatty acyl group in
standard
fashion, e.g., by reaction with a fatty acid halide, fatty acid ester, and/or
fatty acid.
The esterification reaction can occur at any of the available hydroxyl groups,
and
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41
various mono-, di-, etc., esters can be prepared. In fact, mixtures of mono-,
di-, tri-,
etc., esters almost always result from such reactions, and the stoichiometric
ratios of
the reactants can be simply adjusted to favor the desired reaction product.
For commercial production of the sorbitan ester materials, etherification and
esterification are generally accomplished in the same processing step by
reacting
sorbitol directly with fatty acids. Such a method of sorbitan ester
preparation is
described more fully in MacDonald; "Emulsifiers:" Processing and Quality
Control:,
Journal of the American Oil Chemists' ~ocietv, Vol. 45, October 1968.
Details, including formula, of the preferred sorbitan esters can be found in
U.S. Pat. No. 4,128,484, incorporated hereinbefore by reference.
Certain derivatives of the preferred sorbitan esters herein, especially the
"lower" ethoxylates thereof (i.e., mono-, di-, and tri-esters wherein one or
more of
the unesterified -OH groups contain one to about twenty oxyethylene moieties
(Tweens~) are also useful in the composition of the present invention.
Therefore,
for purposes of the present invention, the term "sorbitan ester" includes such
derivatives.
The material which is sold commercially as sorbitan mono-ester (e.g.,
monostearate) does in fact contain significant amounts of di- and tri-esters
and a
typical analysis of sorbitan monostearate indicates that it comprises about
27%
mono-, 32% di- and 30% tri- and tetra-esters. Commercial sorbitan monostearate
therefore is a preferred material. Mixtures of sorbitan stearate and sorbitan
palmitate
having stearate/palmitate weight ratios varying between 10:1 and 1:10, and 1,5-
sorbitan esters are useful. Both the 1,4- and 1,5-sorbitan esters are useful
herein.
Other useful alkyl sorbitan esters for use in the softening compositions
herein
include sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate,
sorbitan monobehenate, sorbitan monooleate, sorbitan dilaurate, sorbitan
dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate,
sorbitan
dioleate, and mixtures thereof, and mixed tallowalkyl sorbitan mono- and di-
esters.
Such mixtures are readily prepared by reacting the foregoing hydroxy-
substituted
sorbitans, particularly the 1,4- and 1,5-sorbitans, with the corresponding
acid, ester,
or acid chloride in a simple esterification reaction. It is to be recognized,
of course,
that commercial materials prepared in this manner will comprise mixtures
usually
containing minor proportions of uncyclized sorbitol, fatty acids, polymers,
isosorbide structures, and the like. In the present invention, it is preferred
that such
impurities are present at as low a level as possible.
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42
The preferred sorbitan esters employed herein can contain up to about 15% by
weight of esters of the C20-C26, and higher, fatty acids, as well as minor
amounts of
Cg, and lower, fatty esters.
Glycerol and polyglycerol esters, especially glycerol, diglycerol,
triglycerol,
and polyglycerol mono- and/or di- esters, preferably mono-, are also prefer ed
herein
(e.g., polyglycerol monostearate with a trade name of Radiasurf 7248).
Glycerol
esters can be prepared from naturally occurring triglycerides by normal
extraction,
purification and/or inter-esterification processes or by esterification
processes of the
type set forth hereinbefore for sorbitan esters. Partial esters of glycerin
can also be
ethoxylated to form usable derivatives that are included within the term
"glycerol
esters."
Useful glycerol and polyglycerol esters include mono-esters with stearic,
oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and the
diesters of
stearic, oleic, palmitic, lauric, isostearic, behenic, and/or myristic acids.
It is under-
stood that the typical mono-ester contains some di- and tri-ester, etc.
The "glycerol esters" also include the polyglycerol, e.g., diglycerol through
octaglycerol esters. The polyglycerol polyols are formed by condensing
glycerin or
epichlorohydrin together to link the glycerol moieties via ether linkages. The
mono-
and/or diesters of the polyglycerol polyols are preferred, the fatty acyl
groups
typically being those described hereinbefore for the sorbitan and glycerol
esters.
The dryer activated fabric softening compositions of the present invention
may further includes a co-softener. The co-softener may comprise a carboxylic
acid
salt of a tertiary amine, tertiary amine ester, or mixtures thereof. The
carboxylic acid
salt forming anion moiety of the co-softener may be selected from the group
consisting of lauric, myristic, palmitic, stearic, oleic and mixtures thereof.
The
amine salt of the co-softener may be selected from the group consisting of
oleyldimethylamine stearate, dioleylmethylamine stearate,
linoleyldimethylamine
stearate, dilinoleylmethylamine stearate, stearyldimethylamine stearate,
distearyl-
methylamine myristate, stearyldimethylamine palmitate, distearylmethylamine
palmitate, distearylmethylamine myristate, distearylmethylamine palmitate,
distearylmethylamine laurate, dioleyldistearylmethylamine oleate,
distearylmethyl-
amine oleate, and mixtures thereof.
Q~tional Cyciodextrin/Perfume Complexes and Free Perfume
The products herein can also contain from about 0.5% to about 60%,
preferably from about 1 % to about 50%, cyclodextrin/perfume inclusion
complexes
and/or free perfume, as disclosed in U.S. Pat. Nos. 5,139,687, Borcher et al.,
issued
Aug. 18, 1992; and 5,234,610, Gardlik et al., to issue Aug. 10, 1993, which
are
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43
incorporated herein by reference. Perfumes are highly desirable, can usually
benefit
from protection, and can be complexed with cyclodextrin. Fabric softening
products
typically contain perfume to provide an olfactory aesthetic benefit and/or to
serve as
a signal that the product is effective.
The optional perfume ingredients and compositions of this invention are the
conventional ones known in the art. Selection of any perfume component, or
amount
of perfume, is based solely on aesthetic considerations. Suitable perfume
compounds
and compositions can be found in the art including U.S. Pat. Nos.: 4,145,184,
Brain
and Cummins, issued Mar. 20, 1979; 4,209,417, Whyte, issued June 24, 1980;
4,515,705, Moeddel, issued May 7, 1985; and 4,152,272, Young, issued May 1,
1979, all of said patents being incorporated herein by reference. Many of the
art
recognized perfume compositions are relatively substantive to maximize their
odor
effect on substrates. However, it is a special advantage of perfume delivery
via the
perfume/cyclodextrin complexes that nonsubstantive perfumes are also
effective.
If a product contains both free and complexed perfume, the escaped perfume
from
the complex contributes to the overall perfume odor intensity, giving rise to
a longer
lasting perfume odor impression.
As disclosed in U.S. Pat. No. 5,234,610, Gardlik/Trinh/Banks/Benvegnu,
issued Aug. 3, 1993, said patent being incorporated herein by reference, by
adjusting
the levels of free perfume and perfume/CD complex it is possible to provide a
wide
range of unique perfume profiles in terms of timing (release) and/or perfume
identity
(character). Solid, dryer-activated fabric conditioning compositions are a
uniquely
desirable way to apply the cyclodextrins, since they are applied at the very
end of a
fabric treatment regimen when the fabric is clean and when there are almost no
additional treatments that can remove the cyclodextrin.
Stabilizers
Stabilizers can be present in the compositions of the present invention. The
term "stabilizer," as used herein, includes antioxidants and reductive agents.
These
agents are present at a level of from 0% to about 2%, preferably from about
0.01
to about 0.2%, more preferably from about 0.05% to about 0.1% for antioxidants
and more preferably from about 0.01 % to about 0.2% for reductive agents.
These
assure good odor stability under long term storage conditions for the
compositions.
Use of antioxidants and reductive agent stabilizers is especially advantageous
for
low scent products (low perfume).
Examples of antioxidants that can be added to the compositions of this
invention include a mixture of ascorbic acid, ascorbic palmitate, propyl
gallate,
available from Eastman Chemical Products, Inc., under the trade names Tenox~
PG
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44
and Tenox S-l; a mixture of BHT, BHA, propyl gallate, and citric acid
available
from Eastman Chemicals Products, Inc., under the trade name Tenox-6; butyiated
hydroxytoluene, available from UOP Process Division under the trade name
Sustane
~ BHT; tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox
TBHQ; natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-
2;
and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA.
Examples of reductive agents include sodium borohydride, hypophosphorous
acid, and mixtures thereof.
Other Adjunct Ingredients
The present invention can include other adjunct components (minor
components) conventionally used in textile treatment compositions, for
example,
colorants, perfumes, perfume systems, preservatives, optical brighteners,
opacifiers,
stabilizers such as guar gum and polyethylene glycol, anti-shrinkage agents,
anti-
wrinkle agents, fabric crisping agents, spotting agents, germicides,
fungicides, anti-
corrosion agents, antifoam agents, and the like.
SUBSTRATE ARTICLES
In preferred embodiments, the present invention encompasses articles of
manufacture. Representative articles are those that are adapted to soften
fabrics in an
automatic laundry dryer, of the types disclosed in U.S. Patent 3,989.631,
Marsan,
issued Nov. 2, 1976; U.S. Patent 4,055,248, Marsan, issued Oct. 25. 1977; U.S.
Patent 4,073,996, Bedenk et al., issued Feb. 14, 1978; U.S. Patent 4.022,938,
Zaki et
al., issued May 10, 1977; U.S. Patent 4,764,289, Trinh, issued Aug. 16, 1988;
U.S.
Patent 4,808,086, Evans et al., issued Feb. 28,1989; U.S. Patent 4,000,340,
Murphy
et al., issued Dec. 28, 1976; U.S. Patent 4,103,047, Zaki et al., issued July
25, 1978;
U. S. Patent 3,736,668, Dillarstone, issued June 5, 1973; U. S. Patent
3,701,202,
Compa et al., issued October 31, 1972; U. S. Patent 3,634,947, Furgal, issued
January 18, 1972; U. S. Patent 3,633,538, Hoeflin, issued January 11, 1972; U.
S.
Patent 3,435,537, Rumsey, issued April I, 1969; all of which are incorporated
herein
by reference.
EXAMPLE 1
Preparation of 3-O-tetrah,~ro~vranvl 3.7-dimethyl-1.6-octadien-3-of
~THP of linaloo~
To a 250 mL round bottomed flask fitted with an argon inlet and condenser is
charged linalool (6.62 g, 41.6 mmol). 2,3-Dihydropyran (5.41 g, 62.4 mmol) is
dissolved in dichloromethane ( 100 mL) and the resulting solution is charged
to the
flask containing the linalool. Pyridinium p-toluenesulphonate (1.07 g, 4.2
mmol) is
added and the fixture stirred at room temperature for approximately 4 hrs. The
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WO 99/00377 PCT/US98/13278
contents of the reaction vessel is transferred to a separatory funnel, diluted
with
diethyl ether (150 mL), extracted with sat. NaCI and the organic phase is
dried over
MgS04. The solvent is removed in vacuo and the resulting oil is purified by
passing the crude material over silica gel and eluting with petroleum ether/2%
ethyl
acetate to yield a colorless oil.
EXAMPLE 2
Preparation of 3-O-tetrahvdronvranyl 2,6-dimethyl-7-octen-2-of
(THP of dihydromyrcenol)
To a 250 mL round bottomed flask fitted with an argon inlet and condenser is
charged linalool ( 10.0 g, 64.0 mmol). 2,3-Dihydropyran (8.07 g, 96.0 mmol) is
dissolved in dichloromethane (75 mL) and the resulting solution is charged to
the
flask containing the linalool. Pyridinium p-toluenesulphonate ( 1.07 g, 4.2
mmol) is
added and the fixture stirred at room temperature for approximately 4 hrs. The
contents of the reaction vessel is transferred to a separatory funnel, diluted
with
diethyl ether (150 mL), extracted with sat. NaCI, then washed with water, and
the
organic phase is dried over MgS04. The solvent is removed in vacuo and the
resulting oil is purified by passing the crude material over silica gel and
eluting with
petroleum ether/2% ethyl acetate to yield a colorless oil.
EXAMPLE 3
Preparation of 3-O-tetrahvdrofuran~ 7-dimethyl-1 6-oct~dien-3-of
(THF of linalool)
To a 250 mL round bottomed flask fitted with an argon inlet and condenser is
charged IinalooI (7.09 g, 44.6 mmol). 2,3-Dihydrofuran (3.16 g, 44.6 mmol) is
dissolved in dichloromethane (100 mL) and the resulting solution is charged to
the
flask containing the linalool. Pyridinium p-toluenesulphonate ( 1.07 g, 4.2
mmol) is
added and the fixture stirred at room temperature for approximately 6 hrs. The
contents of the reaction vessel is transferred to a separatory funnel, diluted
with
diethyl ether ( 150 mL), extracted with sat. NaCI and the organic phase is
dried over
MgS04. The solvent is removed in vacuo and the resulting oil is purified by
passing the crude material over silica gel and eluting with petroleum ether/2%
ethyl
acetate to yield a colorless oil.
EXAMPLE 4
Preparation of 3-O-tetrahvdrofuranvl 2 6-dimethyl-7-octen-2-of
~THF of,~ih dromy~,ce~oll
To a 250 mL round bottomed flask fitted with an argon inlet and condenser is
charged linalool (6.9 g, 44.2 mmol). 2,3-Dihydrofuran (3.13 g, 44.2 mmol) is
dissolved in dichloromethane (75 mL) and the resulting solution is charged to
the
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46
flask containing the linalool. Pyridinium p-toluenesulphonate (trace amount)
is
added and the fixture stirred at room temperature for approximately 6 hrs. The
contents of the reaction vessel is transferred to a separatory funnel, diluted
with
diethyl ether (150 mL), extracted with sat. NaCI, then washed with water, and
the
organic phase is dried over MgS04. The solvent is removed in vacuo and the
resulting oil is purified by passing the crude material over silica gel and
eluting with
petroleum ether/2% ethyl acetate to yield a colorless oil.
EXAMPLES 5 - 13
The following are examples of granular detergent compositions comprising
the pro-fragrances of the present invention.
TABLEI
weight
Ingredient 5 6 7 8
Sodium C11-C13 alkylbenzenesulfonate13.3 13.7 10.4 11.1
Sodium C 14-C 15 alcohol sulfate3.9 4.0 4.5 11.2
Sodium C 14-C 15 alcohol ethoxylate2.0 2.0 0.0 0.0
(0.5) sulfate
Sodium C 14-C 15 alcohol ethoxylate0.5 0.5 0.5 1.0
(6.5)
Tallow fatty acid 0.0 0.0 0.0 1.1
Sodium tripolyphosphate 0.0 41.0 0.0 0.0
Zeolite A, hydrate (0.1-10 micron26.3 0.0 21.3 28.0
size)
Sodium carbonate 23.9 12.4 25.2 16.1
Sodium Polyacrylate (45%) 3.4 0.0 2.7 3.4
Sodium silicate (1:6 ratio Na0/Si02)(46%)2.4 6.4 2.1 2.6
Sodium sulfate 10.~ 10.9 8.2 15.0
Sodium perborate 1.0 1.0 5.0 0.0
Poly(ethyleneglycol), MW 4000 1.7 0.4 1.0 1.1
(50%)
Citric acid 0.0 0.0 3.0 0.0
Nonyl ester of sodium p-hydroxybenzene-0.0 0.0 5.9 0.0
sulfonate
Soil release polymerl 1.5 0.0 0.0 0.0
Soil release polymer2 0.0 1.5 0.0 0.0
Soil release polymer3 0.0 0.5 0.5 0.5
Pro-fragrance4 1.0 1.5 0.0 0.0
Pro-fragrances 0.0 0.0 2.5 1.5
Minors6 7.0 2.1 4.1 6.3
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47
1. Soil release polymer according to U.S. Patent 4,968,451, Scheibel et al.,
issued
November 6, 1990.
2. Soil release polymer according to U.S. Patent 5,415,807, Gosselink, Pan,
Kellett
and Hall, issued May 16, 1995.
3. Soil release polymer according to U.S. Patent 4,702,857, Gosselink, issued
October 27, 1987.
4. Pro-fragrance according to Example 1.
5. Pro-fragrance according to Example 2.
6. Balance to 100% can, for example, include minors like optical brightener,
perfume, suds suppresser, soil dispersant, protease, lipase, cellulase,
chelating
agents, dye transfer inhibiting agents, additional water, and fillers,
including
CaC03, talc, silicates, etc.
The following are examples of liquid laundry detergent compositions
comprising pro-fragrances of the present invention.
TABLE II
Ingredients Weight
9 10 11 12 13
Polyhydroxy coco-fatty 3.50 3.50 3.15 3.50 3.00
acid
amide
NEODOL 23-9 1 2.00 0.60 2.00 0.60 0.60
C~5 Alkyl ethoxylate sulphate19.00 19.40 19.00 17.40 14.00
C25 Alkyl sulfate -- -- -- 2.85 2.30
C 10 -Aminopropylamide -- -- -- 0.75 0.50
Citric acid 3.00 3.00 3.00 3.00 3.00
Tallow fatty acid 2.00 2.00 2.00 2.00 2.00
Ethanol 3.41 3.47 3.34 3.59 2.93
Propanediol 6.22 6.35 6.21 6.56 5.75
Monomethanol amine 1.00 0.50 0.50 0.50 0.50
Sodium hydroxide 3.05 2.40 2.40 2.40 2.40
Sodium p-toluene sulfonate2.50 2.25 2.25 2.25 2.25
Borax 2.50 2.50 2.50 2.50 2.50
Protease 2 0.88 0.88 0.88 0.88 0.88
Lipolase 3 0.04 0.12 0.12 0.12 0.12
Duramyl4 0.10 0.10 0.10 0.10 0.40
CAREZYME 0.053 0.053 0.053 0.053 0.053
Optical Brightener 0.15 0.15 0.15 0.15 0.15
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48
Pro-fragrance 5 1.18 1.18 1.18 1.18 1.75
Soil release agent 6 0.22 0.15 0.15 0.15 0.1
S
Fumed silica 0.119 0.119 0.119 0.119 0.119
Minors, aesthetics, waterbalancbalanc balancbalancbalanc
a a a a a
1. C 12-C 13 alkyl E9 ethoxylate as sold by Shell Oil Co.
2. Bacillus amyloliquefaciens subtilisin as described in WO 95/10615 published
April 20, 1995 by Genencor International.
3. Derived from Humicola lanuginosa and commercially available from Novo.
4. Disclosed in WO 9510603 A and available from Novo.
5. Pro-fragrance according to Example 3.
6. Terephthalate co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et
al.,
issued November 6, 1990.
EXAMPLE 14
The following is an example of a solid bleaching compositon which
comprises a pro-fragrance according to the present invention.
TABLE III
ln~redients weight
Nonanoyloxybenzene sulfonate 7.0
Sodium perborate 20.0
DTPA1 10.0
Citric acid (coated) 20.0
Fragrance2 1.0
Pro-fragrance3 2.0
Sodium sulfate balance
1. Diethylenetriamine pentaacetic acid.
2. Dihydromycenol.
3. Pro-fragrance according to Example 4.
EXAMPLE 15
The following is an example of a liquid bleaching composition comprising a
pro-accord of the present invention.
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49
TABLE IV
Ingredients weight
Sodium hypochlorite 5.25
C 12 Dimethylamine oxide 0.9
Optical brightened 0.3
Fragrance2 1.0
Pro-fragrance3 2.0
Sodium hydroxide 1.0
Water balance
1. 4,4-bis(4-phenyl-2-H-1,2,3-triazolyl)-(2)-stilbene-2,2-disulfonic acid
dipotassium salt.
2. A mixture of linalool (20%), tetrahydrolinalool (30%), Galaxolide (30%),
and
citral dimethylacetal (20%).
3. Pro-fragrance according to Examples 1 and 3 ( 1:1 mixture).
TABLE V
The following are examples of fabric conditioning compositions which
comprise the pro-fragrances of the present invention.
Weight
Ingredients 16 17 18 19 20
DEQA 2.6 2.9 18.0 19.0 19.0
Fatty acid 0.3 - 1.0 - -
Hydrochloride acid 0.02 0.02 0.02 0.02 0.02
PEG - - 0.6 0.6 0.6
Pro-fragrance) 1.0 1.0 1.0 1.0 1.0
Silicone antifoam 0.01 0.01 0.01 0.01 0.01
PEI 1200 E12 2.0 2.0 1.0 1.5 2.5
Dye (ppm) 10 10 50 50 50
Water and minors balancebalance balancebalance balance
1. Pro-fragrance according to Example 1.
2. PE 1200 E1 according to U.S. 5,565,145, Watson et al., issued October 15,
1996.
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TABLE VI
The following are examples of fabric conditioning compositions which
comprise the pro-fragrances of the present invention.
Weight
InarPr~iPntc 21 22 23 24
Polyhydroxy Coco-Fatty Acid3.65 3.50 -- --
Amide
C 12-C 13 Alcohol Ethoxylate3.65 0.80 -- --
E9
Sodium C 12-C 1 S Alcohol 6.03 2.50 -- --
Sulfate
DTDMAMS 1.00 1.00 3.00 3.00
PEI 1200 E1 4.00 4.00 4.00 4.00
Pro-fragrance 1 1 1 I
Perfume/Cyclodextrin Complex-- 20 -- 20
Digeranyl Succinate 1 0.50 1 1
Carriers and minors balancebalance balancebalance
1. PE 1200 E 1 according to U.S. 5,565,145, Watson et al., issued October 15,
1996.
2. Pro-fragrance according to Example 2.
