Note: Descriptions are shown in the official language in which they were submitted.
CA 02307892 2000-04-28
WO 99!21954 PCTIIB98/OI632
LAUNDRY COMPOSITIONS HAVING
REDUCED MALODOR AND
METHODS FOR PROVIDING THE SAME
FIELD OF THE INVENTION
The present invention relates to laundry detergent, fabric softener and fabric
appearance compositions having reduced malodor and to methods for providing
said
compositions. The reduced malodor compositions of the present invention
comprise an
effective amount of a pro-accord material which effectively masks the
degradation
products typical of fabric softener actives.
BACKGROUND OF THE INVENTION
Laundry detergent and fabric softener compositions comprise active ingredients
inter alia surfactants, diester and diamide quaternary ammonium compounds all
of which
are derived from fatty acids. Fatty acids and materials made from fatty acid
sources,
especially those having one or more sites of unsaturation, degrade over time
due to the
effects of oxygen as well as other factors. In fact, the breakdown of fatty
acids is
attributed to the "spoiled" or "rancid" odor associated with lard, vegetable
oils, etc. no
longer deemed fit form human consumption.
Laundry detergent and fabric softener compositions, whether liquid rinse-added
or substrate-added (i.e. dryer sheets), also develop malodors due to the
breakdown of
materials which are comprised of fatty acid moieties. One proposed remedy has
been the
inclusion of perfumes and other fragrance raw materials into the compositions
to mask
the objectionable odor. In order for a material to be effective as a perfume
or fragrance it
must be volatile enough to be "smelled". However, it is because of the high
volatility of
perfume ingredients that laundry detergent compositions and fabric softener
compositions become depleted of masking scents long before the formation of
malodors
occurs later in the shelf life of the product.
In addition, fabric softener compositions are typically acidic (pH from 2.5 to
5.5)
while laundry detergent compositions are alkaline (pH from 8 to about 11 ).
Therefore, a
perfume ingredient or masking agent which is effective in one pH range may be
ineffectual in another. In addition, the formulator must consider the synergy
that
perfume raw materials and masking agents might have with other adjunct
ingredients
which make up the laundry or fabric conditioning compositions. Therefore, the
fact that a
material may serve as effective malodor control masking agent in a fabric
softener
composition does not mean the same material will be effective in a laundry
detergent
composition.
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WO 99/21954 PCT/1B98I01632
2
Accordingly, there remains a need in the art for compounds which mask malodors
and methods for masking these malodors with form in all types of laundry
detergent and
fabric softener compositions. Indeed, there is a long felt need to have a
method for
controllably releasing a fragrance raw material or odor masking agent which
provides the
consumer with confidence that a laundry detergent or fabric softening
composition is still
effective.
BACKGROUND ART
The following relate to the subject matter of fragrance ingredients. U.S.
5,626,852 Suds et al., issued May 6, 1997; 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.
5,081,111 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
Daggers et al., issued November 19, 19?4; U. S. 3,779,932 Daggers et al.,
issued
December I 8, 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 I6, 1995; and WO 95/16660 published June 22, 1995. In addition, P.M.
Muller, D. Lamparsky Perfumes Art. Science, & Technoloey 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 fragrance raw materials can serve to mask the
formation of
malodors in laundry detergent compositions, fabric softener compositions, and
the like
and that these materials are deliverable in a releasable and sustainable
manner by the
inclusion of certain pro-accords into the laundry formulation. The pro-accords
act to
slowly release fragrance raw materials which are volatile enough to be
aesthetically
appreciated while being strong enough to mask the malodors which can form
during
certain storage and usage conditions. However, because there is a continuous
release of
fragrance raw materials over time by the pro-accords, the pleasurable scent
does not
dissipate or evaporate in a manner similar to free perfumes and fragrance
materials. In
fact, the formulator by applying the conditions set forth in the present
specification can
design pro-accord molecules which will continue to release fragrance raw
materials for
varying lengths of time. Also, the fragrance raw materials releasable by the
pro-accords
of the present invention, may be any fragrance raw material convertible to a
releasable
pro-accord inter alia aldehydes, ketones, akohols, terpenes, and esters.
CA 02307892 2000-04-28
WO 99/21954 PC'T/1B98IO1632
A first aspect of the present invention relates to a method for providing a
laundry
detergent compositions having reduced development of malodor, comprising the
step of
adding an effective amount of a pro-accord to a laundry detergent composition
comprising:
a) 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;
b) 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.
A further aspect of the present invention relates to a method for providing a
fabric
softener compositions having reduced development of malodor, comprising the
step of
adding an effective amount of a pro-accord to a fabric softener composition
comprising:
a) at least about 2%, preferably from about 2%, more preferably from about
3% to about 60%, more preferably to about 40% by weight, of a fabric
softening active having the formula:
(R m N (CH2)ri Q-Rl X
m
wherein each R is independently C 1-C6 alkyl, C 1-C6 hydroxyalkyl,
benzyl, and mixtures thereof; R1 is Cl-C22 alkyl, C3-C2~ alkenyl, and
mixtures thereof; Q is a carbonyl moiety having the formula:
CA 02307892 2000-04-28
WO 99121954 PCT,~IB98/01632
4
-O-O- -O-O- , -N2 O- O R
. , -C-N- ,
O
O R3 O O-C-R1 O
-O-C-O- , -CH-O-C- , -CH-CH~-O-C-
wherein R2 is hydrogen, Cl-C4 alkyl, C1-C4 hydroxyalkyl, and mixtures
thereof; R3 is hydrogen, Cl-C4 alkyl, and mixtures thereof; X is a
softener compatible anion; m is from 1 to 3; n is from 1 to 4; and
b) the balance carriers and adjunct ingredients, said adjunct ingredients
selected from the group consisting of nonionic fabric softening agents,
concentration aid, soil release agent, perfume, preservatives, stabilizers,
colorants, optical brighteners, opacifiers, fabric conditioning agents, anti-
shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting
agents, germicides, fungicides, anti-corrosion agents, antifoam agents,
cationic charge boosters, and mixtures thereof.
The present invention yet further relates to laundry detergent compositions
comprising:
a) an effective amount of a pro-accord;
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;
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.
The present invention also further relates to fabric softener compositions
having
reduced development of product malodor, comprising:
a) an effective amount of a pro-accord;
CA 02307892 2000-04-28
WO 99121954 PCT/IB98/01632
b) at least about 2%, preferably from about 2%, more preferably from about
3% to about 60%, more preferably to about 40% by weight, of a fabric
softening active having the formula:
(R)4-m N (CH,)n-Q-R1 X -
m
wherein each R is independently Cl-C6 alkyl, Cl-C6 hydroxyalkyl,
benzyl, and mixtures thereof; R1 is C1-C~~ alkyl, C3-C22 alkenyl, and
mixtures thereof; Q is a carbonyl moiety having the formula:
O O -1R2 O O R2
-O-C- ~ -C-O- , C- , -C-N- ,
O
O R3 O O-C-R 1 O
-O-C-O- , -CH-O-C- , -CH-CH2-O-C-
wherein R2 is hydrogen, C 1-C4 alkyl, C 1-C4 hydroxyalkyl, and mixtures
thereof; R3 is hydrogen, Cl-C4 alkyl, and mixtures thereof; X is a
softener compatible anion; m is from 1 to 3; n is from 1 to 4; and
c) the balance carriers and adjunct ingredients, said adjunct ingredients
selected from the group consisting of nonionic fabric softening agents,
concentration aid, soil release agent, perfume, preservatives, stabilizers,
colorants, optical brighteners, opacifiers, fabric conditioning agents, anti-
shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting
agents, germicides, fungicides, anti-corrosion agents, antifoam agents,
cationic charge boosters, and mixtures thereof.
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
CA 02307892 2000-04-28
WO 99121954 PCT/IB98101632
b
The present invention relates to a method for providing low or nil malodor
laundry detergent and fabric softener compositions, said method comprising the
step of
adding to a laundry detergent or fabric softener composition one or more pro-
fragrances
or pro-accords which are capable of releasing one or more fragrance raw
materials during
the course of the laundry detergent or fabric softener composition shelf life.
It is not
uncommon that after formulation laundry detergent and fabric softener
compositions
slowly begin forming malodors. While not wishing to be limited by theory, in
many
cases, especially under the circumstances where fatty acids have been used as
starting
materials to prepare detersive surfactants, Diester Quaternary Ammonium
compounds
(DEQA's), and other triglyceride-based compounds, these fatty acyl unit
containing
molecules can begin to oxidize and/or hydrolyze under certain storage and
usage
conditions, especially under the liquid alkaline conditions of certain laun~ry
detergent
compositions and the acidic conditions typical of fabric softener
formulations. This is
especially true when the fatty acyl units contain sites of unsaturation. The
fatty acids
which are released by this degradation process may ultimately include fatty
acids which
have a low odor threshold as well as a foul scent.
This problem is overcome by admixing, in addition to any other desired perfume
or fragrance raw materials, one or more pro-fragrances or pro-accords
according to the
present invention. Each pro-accord, depending upon which fragrance raw
materials
comprise the pro-accord and upon the pro-accord structure, will have a
separate
differential release rate and aroma or smell. The formulator, by judicious
assembly of
the pro-accord molecule itself, can provide a sustained release of fragrance
to a laundry
detergent or fabric softener composition for up to several months past the
normal product
turnover time and thus prolong the storage life time of the product
composition. In
addition, formulation of quicker releasing pro-accords with pro-accords having
a delayed
or more sustained release can provide a product having a mixture of different
scents as
well as providing variable levels of released fragrance. For example, a
product may be
formulated to degrade such that initially low levels of fragrance raw
materials are
present, but at a time when the degradation of fatty acyl groups are more
likely to form
malodors, higher levels of fragrances are released. For some formulations, a
specific
delayed release of a particular fragrance raw material may be used to signal
the end of
suitable shelf life or other product variables.
Some pro-fragrances have been formulated for delivery of their fragrance raw
materials after the pro-fragrance or pro-accord has been effectively delivered
to a fabric
surface or, in some cases, to human skin or hair. However, the pro-accords of
the present
invention slowly release their perfume raw materials as the product is stored
in the
CA 02307892 2000-04-28
WO 99121954 PCT/IB98I01632
7
original container in essentially the original compositional form. This slow
release
extends the usable shelf life of laundry and fabric softening compositions.
Typically
these products are stable over an extended period of time, in fact, far beyond
the time in
which the first malodorous materials are formed.
The malodorous compounds have a very low odor threshold, therefore, only a
very small
amount of material need degrade into a malodorous material in order for the
unpleasant
smell to be perceptible to the consumer. Many consumers incorrectly associate
a
malodorous smell as a signal that a material is now no longer "effective". The
ability to
misconstrue that a laundry or fabric softening composition is "beyond shelf
life" due to
malodorous materials is therefore overcome by the present invention.
The pro-fragrances and pro-accords of the present invention begin delivering
the
fragrance raw materials in a slow and controlled manner once admixed within
the final
formulation, or upon activation, for example, placed in to a warehouse having
a
temperature above a critical temperature limit which facilitates degradation
of the
ingredients which lead to malodor formation.
For the purposes of the present invention the term "pro-fragrance" is defined
as
"pro-accord which is designed to release a single fragrance raw material"
whereas a "pro-
accord" is defined as "material which releases two or more fragrance raw
materials".
However, for the purposes of the present invention, because some fragrance
releasing
materials serving as a "pro-fragrance" in one embodiment can equally serve as
a "pro-
accord" in a different embodiment, the term "pro-fragrance" is used
interchangeably with
the term "pro-accord" and either term may be used to stand equally well for
any
fragrance releasing compound described herein singly or collectively.
For the purposes of the present invention "fragrance raw materials" are herein
defined as compounds imparting an odor, fragrance, essence, or scent either
alone or in
combination with other "fragrance raw materials" which is considered
aesthetically
pleasing, preferably said compounds have a molecular weight of at least 100
g/mol.
The pro-accord containing compositions of the present invention can comprise
any number of pro-accords which when taken together are capable of releasing
complex
perfume fragrances. However, in some instances the fragrance releasing pro-
accords of
the present invention are capable of undergoing chemical transformation and
thereby
releasing one or more fragrance raw materials in addition to the fragrance raw
materials
used to prepare the original parent pro-accord. In addition, the pro-
fragrances and pro-
accords of the present invention are suitable for delivery of any type of
fragrance
"characteristic" desired by the formulator.
CA 02307892 2000-04-28
WO 99/21954 PCTIIB98/0163:
The following describe the fragrance releasing pro-accords and pro-fragrances
of
the present invention.
Pro-Accords and Pro-Fra~,rances
For the purposes of the present invention the term "substituted" as it applies
to
linear alkyl, branched alkyl, cyclic alkyl, linear alkenyl, branched alkenyl,
cyclic alkenyl,
branched alkoxy, cyclic alkoxy, alkynyl, and branched alkynyl units are
defined as
"carbon chains which comprise substitutents other than branching of the carbon
atom
chain", for example, other than the branching of alkyl units (e.g. isopropyl,
isobutyl).
Non-limiting examples of "substituents" include hydroxy, C 1-C 12 alkoxy,
preferably
methoxy; C3-C 12 branched alkoxy, preferably isopropoxy; C3-C 12 cyclic
alkoxy;
nitrilo; halogen, preferably chloro and bromo, more preferably chloro; vitro;
morpholino;
cyano; carboxyl, non-limiting examples of which are -CHO; -C02-M+, -CO~R9; -
CONH~; -CONHR9; -CONR9~; wherein R9 is C 1-C 12 linear or branched alkyl); -
S03-
M+; -OS03- M+; -N(R10)2; and -N+(R10)3X- wherein each R10 is independently
hydrogen or C 1-C4 alkyl; and mixtures thereof; wherein M is hydrogen or a
water
soluble cation; and X is chlorine, bromine, iodine, or other water soluble
anion.
For the purposes of the present invention substituted or unsubstituted
alkyleneoxy
units are defined as moieties having the formula:
R8
-(CH~CHO~R~
wherein R~ is hydrogen; R8 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:
R8
-(CH2CH0~(CH2~R~
wherein R~ is hydrogen, C 1-C 1 g alkyl, C 1-C4 alkoxy, and mixtures thereof;
R8 is
hydrogen, methyl, ethyl, and mixtures thereof; the index x is from 1 to about
10 and the
index y is from 2 to about 18.
For the purposes of the present invention substituted or unsubstituted aryl
units
are defined as phenyl moieties having the formula:
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/0163?.
9
R~
Rg
or a. and p-naphthyl moieties having the formula:
R~ R7
or
w
Rg R8
wherein R~ and Rg can be substituted on either ring, alone or in combination,
and R~
and Rg are each independently hydrogen, hydroxy, C 1-C6 alkyl, C2-C6 alkenyl,
C 1-C4
alkoxy, C3-C6 branched alkoxy, nitrilo, halogen, nitro, morpholino, cyano,
carboxyl (-
CHO; -CO~-M+; -CO~R9; -CONH2; -CONHR9; -CONR92; wherein R9 is C 1-C 12
linear or branched alkyl), -S03- M+, -OS03- M+, -N(R10)2, and -N+(R1 ~)3X-
wherein
each R1~ is independently hydrogen, C1-C4 alkyl, or mixtures thereof; and
mixtures
thereof, R~ and Rg are preferably hydrogen, C1-C6 alkyl, -C02-M+, -S03- M+, -
OS03-
M+, and mixtures thereof; more preferably R~ or Rg is hydrogen and the other
moiety is
C 1-C6; wherein M is hydrogen or a water soluble cation and X is chlorine,
bromine,
iodine, or other water soluble anion. Examples of other water soluble anions
include
organic species such as fumarate, succinate, tartrate, oxalate and the like,
inorganic
species include sulfate, hydrogen sulfate, phosphate and the like.
For the purposes of the present invention substituted or unsubstituted
alkylenearyl
units are defined as moieties having the formula:
R~
-(C H2)p
v s
R
wherein R~ and Rg are each independently hydrogen, hydroxy, C 1-C4 alkoxy,
nitrilo,
halogen, vitro, carboxyl (-CHO; -C02-M+; -C02R9; -CONH2; -CONHR9; -CONR92;
wherein R9 is C 1-C 12 linear or branched alkyl), amino, alkylamino, and
mixtures
thereof, p is from 1 to about 14; M is hydrogen or a water soluble cation.
For the purposes of the present invention substituted or unsubstituted
alkyleneoxyaryl units are defined as moieties having the formula:
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/01632
R~
-(CH2)q0
Rg
wherein R~ and Rg are each independently hydrogen, hydroxy, C1-C4 alkoxy,
nitrilo,
halogen, nitro, carboxyl (-CHO; -C02-M+; -C02R9; -CONH2; -CONHR9; -CONR9~;
wherein R9 is C 1-C 12 linear or branched alkyl), amino, alkylamino, and
mixtures
thereof, q is from 1 to about 14; M is hydrogen or a water soluble cation.
J3-Ketoesters
The compositions according to the present invention may comprise one or more
(3-ketoesters having the formula:
O
R1
'R
R2
R3
wherein R is alkoxy derived from a fragrance raw material alcohol. Non-
limiting
examples of preferred fragrance raw material alcohols include 2,4-dimethyl-3-
cyclohexene-1-methanol (Floralol), 2,4-dimethyl cyclohexane methanol (Dihydro
floralol), 5,6-dimethyl-I-methylethenylbicyclo[2.2.1]hept-S-ene-2-methanol
(Arbozol),
a,a,-4-trimethyl-3-cyclohexen-1-methanol (a-terpineol), 2,4,6-trimethyl-3-
cyclohexene-
1-methanol (Isocyclo geraniol), 4-{1-methylethyl)cyclohexane methanol (Mayol),
a-3,3-
trimethyl-2-norborane methanol, 1, I -dimethyl-1-(4-methylcyclohex-3-
enyl)methanol, 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-[i-
norbornane
ethanol (patchomint), 2-methyl-2-cyclohexylethanol, 1-(4-isopropylcyclohexyl)-
ethanol,
1-phenylethanol, 1,1-dimethyl-2-phenylethanol, 1,1-dimethyl-2-(4-methyl-
phenyl)ethanol, 1-phenylpropanol, 3-phenylpropanol, 2-phenylpropanol
(Hydrotropic
Alcohol), 2-(cyclododecyl)propan-1-of (Hydroxy-ambran), 2,2-dimethyl-3-(3-
methylphenyl}-propan-I-of (Majantol), 2-methyl-3-phenylpropanol, 3-phenyl-2-
propen-
1-0l (cinnamyl alcohol), 2-methyl-3-phenyl-2-propen-1-of {methylcinnamyl
alcohol), a-
n-pentyl-3-phenyl-2-propen-I-of (a-amyl-cinnamyl alcohol), ethyl-3-hydroxy-3-
phenyl
propionate, 2-(4-methylphenyl)-2-propanol, 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-1-of (prenol), 2-methyl-4-
(2,2,3-
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WO 99/21954 PCT/IB98I01632
trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, ethyl 3-hydroxybutyrate, 4-phenyl-
3-buten-
2-0l, 2-methyl-4-phenylbutan-2-ol, 4-(4-hydroxyphenyl)butan-2-one, 4-(4-
hydroxy-3-
methoxyphenyl}-butan-2-one, 3-methyl-pentanol, 3-methyl-3-penten-1-ol. 1-(2-
propenyl)cyclopentan-1-of (plinol), 2-methyl-4-phenylpentanol (Pamplefleur), 3-
methyl-
~-phenylpentanol (Phenoxanol), 2-methyl-S-phenylpentanol, 2-methyl-~-(2,3-
dimethyltricycio[2.2.1.0~-'~6~Jhept-3-yl)-2-penten-1-of (santalol), 4-methyl-1-
phenyl-2-
pentanol, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-oI (sandalore},
(1-
methyl-bicyclo[2.1.1]hepten-2-yl)-2-methylpent-1-en-3-ol, 3-methyl-1-
phenylpentan-3-
ol, 1,2-dimethyl-3-(1-methylethenyl}cyciopentan-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
(calrvenol), 6-
methyl-3-isopropenylcyclohexan-1-of (dihydrocarveol), 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
(rootanol), 4-
isopropyl-cyclohexanol, 4-methyl-1-(1-methylethyl)-3-cyclohexen-1-oi, 2-(5,6,6-
trimethyl-2-norbornyl)cyclohexanol, isobornylcyclohexanol, 3,3,5-
trimethylcyclohexanol, 1-methyl-4-isopropylcyclohexan-3-ol, 1-methyl-4-
isopropylcyclohexan-8-of (dihydroterpineol), 1,2-dimethyl-3-(1-
methylethyl)cyclohexan-
1-0l, heptanol, 2,4-dimethylheptan-1-ol, 6-heptyl-5-hepten-2-of (isolinalool),
2,4-
dimethyl-2,6-heptandienol, 6,6-dimethyl-2-oxymethyl-bicyclo[3.1.1 ]hept-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-ol, 2,6-
dimethylheptan-2-of (dimetol), 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-oI (citronellol), 3,7-dimethyl-2,6-octadien-1-of (geranioI), 3,7-dimethyl-
2,6-octadien-1-
ol (nerol), 3,7-dimethyl-7-methoxyoctan-2-of (osyrol), 3,7-dimethyl-1,6-
octadien-3-of
(linalool), 3,7-dimethyloctan-1-of (pelargol), 3,7-dimethyloctan-3-of
(tetrahydrolinalool),
2,4-octadien-1-o1, 3,7-dimethyl-6-octen-3-o1 (dihydrolinalool), 2,6-dimethyl-7-
octen-2-of
(dihydromyrcenol), 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-ol, 3,6-
dimethyloctan-
3-0l, 2,6-dimethyl-7-octen-2-ol, 2,6-dimethyl-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-
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I-ol, 3,7-dimethyl-1,6-nonadien-3-ol, decanoI, 9-decenol, 2-benzyl-M-dioxa-S-
ol, 2-
decen-1-ol, 2,4-decadien-I-ol, 4-methyl-3-decen-S-ol, 3,7,9-trimethyl-1,6-
decadien-3-of
(isobutyl linalool), undecariol, 2-undecen-1-ol, 10-undecen-I-ol, 2-dodecen-1-
ol, 2,4-
dodecadien-1-ol, 2,7,I I-trimethyl-2,6,10-dodecatrien-I-of (farnesol), 3,7,11-
trimethyl-
1.6,10.-dodecatrien-3-of (nerolidol), 3,7,11,IS-tetramethylhexadec-2-en-I-of
(phytol),
3,7,11, I S-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 saIicylate, n-hexyl salicylate,
2-methyl-S-
isopropylphenol, 4-ethyl-2-methoxyphenol, 4-allyl-2-methoxyphenol (eugenol), 2-
methoxy-4-(1-propenyl)phenol (isoeugenol), 4-allyl-2,6-dimethoxy-phenol, 4-
tert-
butylphenol, 2-ethoxy-4-methylphenol, 2-methyl-4-vinylphenol, 2-isopropyl-S-
methylphenol (thymol), pentyl-ortho-hydroxy benzoate, ethyl 2-hydroxy-
benzoate,
methyl 2,4-dihydroxy-3,6-dimethylbenzoate, 3-hydroxy-S-methoxy-1-
methylbenzene, 2-
tert-butyl-4-methyl-I-hydroxybenzene, 1-ethoxy-2-hydroxy-4-propenylbenzene, 4-
hydroxytoluene, 4-hydroxy-3-methoxybenzaldehyde, 2-ethoxy-4-
hydroxybenzaldehyde,
decahydro-2-naphthol, 2,S,S-trimethyl-octahydro-2-naphthol, 1,3,3-trimethyl-2-
norbornanol (fenchol), 3a,4,S,6,7,7a-hexahydro-2,4-dimethyl-4,7-methano-1 H-
inden-S-
ol, 3a,4,S,6,7,7a-hexahydro-3,4-dimethyl-4,7-methano-IH-inden-S-ol, 2-methyl-2-
vinyl-
S-(I-hydroxy-1-methylethyl)tetra-hydrofuran, [i-caryophyllene alcohol,
vanillin, ethyl
vanillin, and mixtures thereof.
More preferably, the fragrance raw material alcohol is selected from the group
consisting of cis-3-hexen-1-ol, hawthanol [admixture of 2-(o-methylphenyl)-
ethanol, 2-
(m-methylphenyl)ethanol, and 2-(p-methylphenyl)ethanol], heptan-1-ol, decan-1-
ol, 2,4-
dimethyl cyclohexane methanol, 4-methylbutan-1-ol, 2,4,b-trimethyl-3-
cyclohexene-1-
methanol, 4-(1-methylethyl)cyclohexane methanol, 3-(hydroxy-methyl)-2-
nonanone,
octan-1-ol, 3-phenylpropanol, Rhodinol 70 [3,7-dimethyl-7-octenol, 3,7-
dimethyl-6-
octenol admixture], 9-decen-1-ol, a.-3,3-trimethyl- 2-norborane methanol, 3-
cyclohexyipropan-1-ol, 4-methyl-1-phenyl-2-pentanol, 3,6-dimethyl-3-vinyl-S-
hepten-2-
ol, phenyl ethyl methanol; propyl benzyl methanol, 1-methyl-4-
isopropenylcyclohexan-
3-0l, 4-isopropyl-1-methylcyclohexan-3-of (menthol), 4-tent-butyicyclohexanol,
2-tert-
butyl-4-methylcyclohexanol, 4-isopropylcyclo-hexanoI, traps-decahydro-[3-
naphthol, 2-
tert-butylcyclohexanol, 3-phenyl-2-propen-1-ol, 2,7,11-trimethyl-2,6,10-
dodecatrien-1-
ol, 3,7-dimethyl-2,6-octadien-I-of (geraniol), 3,7-dimethyl-2,6-octadien-1-of
(nerol), 3,7-
dimethyl-1,6-octadien-3-of (linalool), 3,7-dimethyloctan-3-of
(tetrahydrolinalool), 2,4-
octadien-I-ol, 3,7-dimethyl-6-octen-3-of (dihydrolinalool), 2,6-dimethyl-7-
octen-2-of
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(dihydromyrcenol), 4-methoxybenzyl alcohol, benzyl alcohol, 4-allyl-2-
methoxyphenol,
2-methoxy-4-( I -propenyl)phenol, vanillin, and mixtures thereof.
RI, R2, and R3 are each independently hydrogen, CI-C30 substituted or
unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched
alkyl, C~-C30
substituted or unsubstituted cyclic alkyl, C~-C30 substituted or unsubstituted
linear
alkenyl, C3-C3p substituted or unsubstituted branched alkenyl, C3-C30
substituted or
unsubstituted cyclic alkenyl, C~-C3p substituted or unsubstituted linear
alkynyl, C3-C30
substituted or unsubstituted branched alkynyl, C6-C30 substituted or
unsubstituted aryl,
C~-C20 substituted or unsubstituted alkyleneoxy, C3-C20 substituted or
unsubstituted
alkyleneoxyalkyl, C~-C2p substituted or unsubstituted alkylenearyl, C6-C20
substituted
or unsubstituted alkyleneoxyaryl, and mixtures thereof; provided at least one
RI, R2, or
R3 is a unit having the formula:
O
R4
RS R6
wherein R4, R5, and R6 are each independently hydrogen, Cl-C30 substituted or
unsubstituted linear alkyl, C3-C30 substituted or unsubstituted branched
alkyl, C3-C3p
substituted or unsubstituted cyclic alkyl, C I -C30 substituted or
unsubstituted linear
alkoxy, C3-C3p substituted or unsubstituted branched alkoxy, C3-C3p
substituted or
unsubstituted cyclic alkoxy, C2-C30 substituted or unsubstituted linear
alkenyl, C3-C30
substituted or unsubstituted branched alkenyl, C3-C30 substituted or
unsubstituted cyclic
alkenyl, C~-C30 substituted or unsubstituted linear alkynyl, C3-C30
substituted or
unsubstituted branched alkynyl, C6-C30 substituted or unsubstituted
alkylenearyl, C6-
C3p substituted or unsubstituted aryl; or R4, R5, and R6 can be taken together
to form
C6-C3p substituted or unsubstituted aryl; and mixtures thereof.
In one preferred embodiment of ~i-ketoesters at least two R2, or R3 units are
hydrogen and R4, R5, and R6 units are each hydrogen. In another preferred
embodiment two R4, R5, and R6 units are hydrogen and the remaining unit is C 1-
C20
substituted or unsubstituted linear alkyl, C3-C20 substituted or unsubstituted
branched
alkyl, C3-C20 substituted or unsubstituted cyclic alkyl; more preferably
hexyl, heptyl,
octyl, nonanyl, w-hexenyl, w-heptenyl, c.~-octenyl, w-nonenyl, and mixtures
thereof.
Also preferably R4, R5, and R6 are taken together to form a C6-C30 substituted
or
unsubstituted aryl unit, preferably substituted or unsubstituted phenyl and
naphthyl.
Also preferred embodiments include providing R2 and R3 moieties which provide
CA 02307892 2000-04-28
WO 99!21954 PCT/IB98/01632
14
increased fabric substantivity or which facilitate the rate at which fragrance
raw materials
are released.
Non-limiting examples of ketones which are releasable by the (3-ketoester pro-
accords of the present invention are a-damascene, (3-damascene, 8-damascene,
[i-
damascenone, muscone, 3,3-dimethylbutanone, methyl phenyl ketone
(acetophenone), 4-
phenylbutan-2-one (benzyl acetone), 2-acetyl-3,3-dimethyl norbornane (camek
dh), 6,7-
dihydro-1,1,2,3,3-pentamethyl-4(SH) indanone (cashmeran), 4-(1,3)-benzodioxol-
5-yl 3-
buten-2-one (cassione), 4-(3,4-methylenedioxyphenyl)-2-butanone (dulcinyl), 3-
octanone, 6-acetyl-1,2,3,4-tetrahydronaphthalene ketone (florantone t), ethyl-
2-n-hexyl
acetoacetate (gelsone), 2,6-dimethylundeca-2,6-dien-I 0-one, 6,10-dimethyl-5,9-
undecadien-2-one, 3,3-dimethylcyclohexyl methyl ketone (herbac), 4-(2,6,6-
trimethyl-I-
cyclohexen-1-yl)-3-buten-2-one ([i-ionone), 4-(2,6,6-trimethyl-2-cyclohexen-1-
yl)-3-
buten-2-one (a-ionone), 3-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-3-buten-
2-one
(8-methyl ionone), 4-(2,6,6-trimethyl--2-cyclohexen-I-yl)-3-methyl-3-buten-2-
one (y-
methyl ionone), 3-methyl-4-(2,6,-trimethyl-2-cyclohexen-I-yI)-3-buten-2-one
(irisantheme), 4-(2,3,5-trimethyl-4-cyclohexen-1-yl)-3-buten-2-one (iritone),
4-methyl-
(2,5,6,6-tetramethyl-2-cyclohexen-1-yl)-3-buten-2-one (a-ionone),
1,2,3,4,5,6,7,8-
octahydro-2,3,8,8-tetramethyl-2-acetonaphthone (iso cyclomone e), 7-acetyl-
1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyI naphthalene (Iso E Super~),
acetyl
diisoamylene (Koavone~), methyl amyl ketone, 2-acetonaphthone cedr-8-enyl
methyl
ketone (methyl cedrylone), 2,3,6-trimethyl-cyclohexen-4-yl-1-methyl ketone
(methyl
cycle citrone), hexahydroacetophenone (methyl cyclohexyl ketone), 6-methyl-3,5-
heptadien-2-one, 6-methyl-5-hepten-2-one, 2-octanone, 3-(hydroxymethyl)-2-
nonanone,
4-acetyl-1,1-dimethyl-6-tert-butyl indane (musk indanone), 2,6-dinitro-3,5-
dimethyl-4-
acetyl-tert-butyl benzene (musk ketone), 1-para-menthen-6-y1 propanone
(nerone), para-
methoxy acetophenone (acetanisole), 6-acetyl-1,1,2,3,3,5-hexamethyl indan
(Phantolid~), 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin (Tonalid~, Musk Plush),
5-
acetyl-3-isopropyl-1,1,2,6-tetr3methyl indane (Traseolide 70~), methyl-2,6,10-
trimethyl-
2,5,9-cyclododecatriene-1-yl ketone (Trimofix O~), methyl cedrylone (Vertofix
Coeur~), 4-(4-hydroxy-3-methoxyphenyl)-2-butanone, cis jasmone,
dihydrojasmone, a-
ionone, /3-ionone, dihydro-(3-ionone, 4-(4-hydroxyphenyl)butan-2-one, I-
carvone, 5-
cyclohexadecen-I-one, decatone, 2-[2-(4-methyl-3-cyclohexenyl-1-
y1)propyl]cyclopentan-2-one, 2-sec-butylcyclohexanone, ally! ionone, a-cetone,
geranyl
acetone, I-(2-methyl-5-isopropyl-2-cyclohexenyl)-I-propanone, acetyl
diisoamylene,
methyl cyclocitrone, 4-t-pentyl cyclohexanone, p-t-butylcyclohexanone, o-t-
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l~
butylcyclohexanone, menthone, methyl-7,3-dihydro-2H-l,~-benzodioxepine-3-one,
fenchone, methyl hydroxynaphthyl ketone, and mixtures thereof.
Examples of preferred pro-fragrances which comprise the fragrance delivery
systems of the present invention include 2,6-dimethyl-7-octen-2-yl 3-(4-
methoxyphenyl)-3-oxo-propionate, 2,6-dimethyl-7-octen-2-yI 3-(4-nitrophenyl)-3-
oxo-
propionate, 2,6-dimethyl-7-octen-2-yl 3-(~i-naphthyl)-3-oxo-propionate, 3,7-
dimethyl-
1,6-octadien-3-yl 3-(4-methoxyphenyl)-3-oxo-propionate, (a,a-4-trimethyl-3-
cyclohexenyl)methyl 3-(~i-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-
octadien-3-yl 3-
(a-naphthyl)-3-oxo-propionate, cis 3-hexen-1-yl 3-(~i-naphthyl)-3-oxo-
propionate, 9-
decen-I-yl 3-(~i-naphthyl)-3-oxo-propionate, 3,7-dimethyl-1,6-octadien-3-yl 3-
(nonanyl)-
3-oxo-propionate, 2,6-dimethyl-7-octen-2-yl 3-(nonanyl)-3-oxo-propionate, 2,6-
dimethyl-7-octen-2-yl 3-oxo-butyrate, 3,7-dimethyl-1,6-octadien-3-yI 3-oxo-
butyrate,
2,6-dimethyl-7-octen-2-yl 3-(~i-naphthyl)-3-oxo-2-methylpropionate, 3,7-
dimethyl-1,6-
octadien-3-yl 3-((3-naphthyl)-3-oxo-2,2-dimethyipropionate, 3,7-dimethyl-1,6-
octadien-
3-yl 3-(~3-naphthyl)-3-oxo-2-methylpropionate, 3,7-dimethyl-2,6-octadienyl 3-
(~i-
naphthyl)-3-oxo-propionate, 3,7-dimethyl-2,6-octadienyl 3-heptyl-3-oxo-
propionate, and
mixtures thereof.
Orthoesters
Another class of compounds useful as pro-accords according to the present
invention are orthoesters having the formula:
ORl
R-C-OR2
I
OR3
wherein typically hydrolysis of the orthoester releases fragrance raw material
components according to the following scheme:
O
R-CR10R2 --~. II I + 2 3
I R-C-OR R OH + R OH
OR3
wherein R is hydrogen, C 1-Cg linear alkyl, C4-C2p branched alkyl, C6-C2p
cyclic alkyl,
C6-C2p branched cyclic alkyl, C6-C2p linear alkenyl, C6-C2p branched alkenyl,
C6-C20
cyclic alkenyl, C6-C2p branched cyclic alkenyl, C6-C2p substituted or
unsubstituted
aryl, preferably the moieties which substitute the aryl units are alkyl
moieties, and
mixtures thereof, preferably R is hydrogen, methyl, ethyl, and phenyl. R1, R2
and R3
are independently C1-C2p linear, branched, or substituted alkyl; C2-C2p
linear,
CA 02307892 2000-04-28
WO 99J21954 PCT/IB98/01632
16
branched, or substituted alkenyl; CS-C2p substituted or unsubstituted cyclic
alkyl; C6-
C2p substituted or unsubstituted aryl, C2-C4p substituted or unsubstituted
alkyleneoxy;
C3-C4p substituted or unsubstituted alkyIeneoxyalkyl; C6-C4p substituted or
unsubstituted alkylenearyl; C6-C32 substituted or unsubstituted aryloxy; C6-
C40
substituted or unsubstituted alkyleneoxyaryl; C6-C4p oxyalkylenearyl; and
mixtures
thereof.
Orthoester Releasable Components: Hydrolysis of the orthoesters of the present
invention have two types of releasable components, namely alcohols and esters.
Hydrolysis of an orthoester will yield two equivalents of releasable alcohol,
preferably a
primary or secondary alcohol and one equivalent of releasable ester. The
released ester,
when taken together with the released alcohol, forms a binary fragrance
accord. For
example tri-geranyl orthoformate releases the binary accord geraniol/geranyl
formate.
Preferred esters which are releasable components of the orthoesters of the
present
invention included but are not limited to geranyl formate, citronellyl
formate,
phenylethyl formate, phenoxyethyl formate, traps-2-hexenyI formate, cis-3-
hexenyl
formate, cis-6-nonenyl formate, 9-decenyl formate, 3,5,5-trimethylhexyl
formate, 3-
methyl-5-phenylpentanyl formate, 6-methylheptan-2-yl formate, 4-(2,2,6-
trimethyl-2-
cyclohexen-1-yl)-3-buten-2-yl formate, 3-methyl-5-(2,2,3-trimethyl-3-
cyclopenten-1-yl)-
4-penten-2-yl formate, 4-isopropylcyclohexyleth-2-yl formate, 6,8-
dimethylnonan-2-yl
formate, decahydro-~i-naphthyl formate, 4-isopropylcyclohexylmethyl formate,
linalyl
formate, lavandulyl formate, citronellyl formate, a-terpinyl formate, nopyl
formate,
isobornyl formate, bomyl formate, isobornyl formate, guaiyl formate, 2-tert-
butylyclohexyl formate, 4-tert-butylcyclohexyi formate, decahydro-[3-naphthyl
formate,
menthyl formate, p-menthanyl formate, neryl formate, cinnamyl fotmate, ethyl
acetate,
butyl acetate, isoamyl acetate, hexyl acetate, 3,5,5-trimethyihexyl acetate,
geranyl
acetate, citronellyl acetate, phenylethyl acetate, phenoxyethyl acetate, traps-
2-hexenyl
acetate, cis-3-hexenyl acetate, cis-6-nonenyl acetate, 9-decenyl acetate, 3-
methyl-5-
phenylpentanyl acetate, 6-methyl-heptan-2-yl acetate, 4-{2,2,6-trimethyl-2-
cyclohexen-1-
yl)-3-buten-2-yl acetate, 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-
penten-2-yl
acetate, decahydro-~3-naphthyl acetate, menthyl acetate, benzyl acetate, 4-
isopropylcyclohexyleth-2-yl acetate, 6,8-dimethylnonan-2-yl acetate, 1-
phenylethyl
acetate, 4-isoproylcyclo-hexylmethyl acetate, linalyl acetate, lavandulyl
acetate,
citronellyl acetate, a-terpinyl acetate, nopyl acetate, isobomyl acetate,
bornyl acetate,
isobornyl acetate, guaiyl acetate, 2-tert-butylyclohexyl acetate, 4-tert-
butylcyclohexyl
acetate, decahydro-(3-naphthyl acetate, menthyl acetate, p-menthanyl acetate,
neryl
acetate, cinnamyl acetate, ethyl propionate, ethyi butyrate, butyl butyrate,
isoamyl
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WO 99/21954 PCT/IB98/01632
17
butyrate, hexyl butyrate, cis-3-hexenyl butyrate, cis-3-hexenyl isobutyrate,
ethyl
isovalerate, 2-methylbutyrate, ethyl hexanoate, 2-propenyl hexanoate, ethyl
heptanoate,
'_'-propenyl heptanoate, ethyl octanoate, ethyl 2-traps-4-cis-decadienoate,
methyl 2-
nonynoate, benzyl propionate, benzyl isovalerate, phenylethyl isobutyrate,
phenylethyl
isovalerate, a,a-dimethyl phenylethyl butyrate, methyl benzoate, hexyl
benzoate, benzyl
benzoate, ethyl phenylacetate, geranyl phenylacetate, 1-phenylethyl
phenylacetate,
methyl cinnamate, benzyl cinnamate, phenylethyl cinnamate, geranyl propionate,
geranyl
isobutyrate, geranyl isovalerate, linalyl propionate, linalyl butyrate,
Iinalyl isobutyrate,
citronellyl propionate, citronellyl isobutyrate, citronellyl isovalerate,
citronellyl tiglate,
allyl 3-cyclohexylpropionate, methyl dihydrojasmonate, methyl 2-hexyl-3-
oxocyclopentane-carboxylate, and mixtures thereof.
Examples of alcohols suitably released by the hydrolysis of the orthoester pro-
accords are the same as those listed herein above under (3-ketoesters.
Non-limiting examples of orthoester pro-fragrances according to the present
invention are tris-geranyl orthofonnate, tris(cis-3-hexen-1-yl) orthoformate,
tris(phenylethyl) orthoformate, bis(citronellyl) ethyl orthoacetate,
tris(citronellyl)
orthoformate, tris(cis-6-nonenyl) orthofotmate, tris(phenoxyethyl)
orthoformate,
tris(geranyl, neryl) orthoformate (70:30 geranyl:neryl), tris(9-decenyl)
orthoformate,
tris(3-methyl-5-phenylpentanyl) orthoformate, tris(6-methylheptan-2-yl)
orthoformate,
tris([4-(2,2.6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-yl] orthoformate, tris[3-
methyl-5-
(2,2,3-trimethyl-3-cyclopenten-I-yl)-4-penten-2-yl] orthoformate, trismenthyl
orthoformate, tris(4-isopropylcyclohexylethyl-2-yl) orthoformate, tris-(6,8-
dimethylnonan-2-yl) orthoformate, tris-phenylethyl orthoacetate, tris(cis-3-
hexen-1-yl)
orthoacetate, tris(cis-6-nonenyl) orthoacetate, tris-citronellyl orthoacetate,
bis(geranyl)
benzyl orthoacetate, tris(geranyl) orthoacetate, tris(4-
isopropylcyclohexylmethyl)
orthoacetate, tris(benzyl) orthoacetate, tris(2,6-dimethyl-S-heptenyl)
orthoacetate,
bis(cis-3-hexen-1-yl) amyl orthoacetate, and neryl citronellyl ethyl
orthobutyrate.
Acetals and ketals
A further class of compound useful as pro-accords according to the present
invention are acetals and ketals having the formula:
R1
R-C-OR2
I
OR3
wherein hydrolysis of the acetal or ketal releases one equivalent of aldehyde
or ketone
and two equivalents of alcohol according to the following scheme:
CA 02307892 2000-04-28
WO 99121954 PCTIIB98I01632
18
R1 O
R-C-OR'- - ---~ R-C-R1 + R2pH + R30H
OR3
wherein R is CI-C2p linear alkyl, C4-C2p branched alkyl, C6-C2p cyclic alkyl,
C6-C2p
branched cyclic alkyl, C6-C2p linear alkenyl, C6-C2p branched alkenyl, C6-C2p
cyclic
alkenyl, C6-C2p branched cyclic alkenyl, C6-C2p substituted or unsubstituted
aryl,
preferably the moieties which substitute the aryl units are alkyl moieties,
and mixtures
thereof. R1 is hydrogen, R, or in the case wherein the pro-accord is a ketal,
R and RI
can be taken together to fonm a ring. R2 and R3 are independently selected
from the
group consisting of C~-C2p linear, branched, or substituted alkyl; C4-C2p
linear,
branched, or substituted alkenyl; CS-C2p substituted or unsubstituted cyclic
alkyl; C6-
C2p substituted or unsubstituted aryl, C2-C4p substituted or unsubstituted
alkyleneoxy;
C3-C4p substituted or unsubstituted alkyleneoxyalkyl; C6-C4p substituted or
unsubstituted alkylenearyl; C6-C32 substituted or unsubstituted aryloxy; C6-
C40
substituted or unsubstituted alkyleneoxyaryl; C6-C4p oxyalkylenearyl; and
mixtures
thereof.
Acetal Releasable Components: The acetals of the present invention have two
types of releasable components, namely alcohols and aldehydes. Hydrolysis of
an acetal
will yield two equivalents of releasable alcohol and one equivalent of
releasable
aldehyde. The released aldehyde, when taken together with the released
alcohol, forms a
binary fragrance accord. For example bis(cis-3-hexenyl) vanillin acetal
releases the
binary accord vanillin/cis-3-hexenol.
When R1 is hydrogen the pro-accords are capable of releasing an aldehyde
component. Preferred aldehydes which are releasable components of the acetals
of the
present invention include but are not limited to phenylacetaldehyde, p-methyl
phenylacetaldehyde, p-isopropyl phenylacetaldehyde, methylnonyl acetaldehyde,
phenylpropanal, 3-(4-t-butylphenyl)-2-methyl propanal (Lilial), 3-(4-t-
butyIphenyl)-
propanal (Bourgeonal), 3-(4-methoxyphenyl)-2-methylpropanal (Canthoxal), 3-(4-
isopropylphenyl)-2-methylpropanal (Cymal), 3-(3,4-methylenedioxyphenyl)-2-
methylpropanal (Helional), 3-(4-ethylpheny)-2,2-dimethylpropanal
(Floralozone),
phenylbutanal, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-
enal,
heptanal, cis-4-heptenal, 2-ethyl-2-heptenal, 2,6-dimethyl-5-heptenaI
(Melonal), 2,4-
heptadienal, octanal, 2-octenal, 3,7-dimethyloctanal, 3,7-dimethyl-2,6-
octadien-1-al, 3,7-
dimethyl-1,6-octadien-3-al, 3,7-dimethyl-6-octenal (citronellal), 3,7-dimethyl-
7-
hydroxyoctan-1-al (hydroxy citronellal), nonanal, 6-nonenal, 2,4-nonadienal,
2,6-
nonadienal, decanal, 2-methyl decanal, 4-decenal, 9-decenal, 2,4-decadienal,
undecanal,
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19
2-methyldecanal, ?-methylundecanal, 2,6,10-trimethyl-9-undecenal (Adoxal),
undec-10-
enyl aldehyde, undec-8-enanal, dodecanal, tridecanal, tetradecanal,
anisaldehyde,
bourgenonal, cinnamic aldehyde, a-amylcinnam-aldehyde, a-hexyl cinnamaldehyde,
methoxy-cinnamaldehyde, isocyclocitral, citronellyl oxyacet-aldehyde,
cortexaldehyde,
cumminic aldehyde, cyclamen aldehyde, florhydral, heliotropin, hydrotropic
aldehyde,
vanillin, ethyl vanillin, benzaldehyde, p-methyl benzaldehyde, 3,4-
dimethoxybenzaldehyde, 3- and 4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexene-1-
carboxaldehyde (Lyral), 2,4-dimethyl-3-cyclohexene-1-carboxaldehyde (Triplal),
1-
methyl-3-(4-methylpentyl)-3-cyclohexencarboxaldehyde (Vernaldehyde), p-
methylphenoxyacetaldehyde (Xi aldehyde), and mixtures thereof.
More preferably the aldehydes released by the acetals of the present invention
are
4-(4-hydroxy-4-methylpentyl}-3-cyclohexene-1-carboxaldehyde (Iyral),
phenylacetaldehyde, methylnonyl acetaldehyde, 2-phenylpropan-1-al
(hydrotropaldehyde), 3-phenylprop-2-en-1-al (cinnamaldehyde), 3-phenyl-2-
pentylprop-
2-en-1-al (a-amylcinnamaldehyde), 3-phenyl-2-hexylprop-2-enal (a-
hexylcinnamaldehyde), 3-(4-isopropylphenyl)-2-methylpropan-I-al (cyclamen
aldehyde), 3-(4-ethylphenyl)-2,2-dimethylpropan-I-al (floralozone), 3-(4-tert-
butylphenyl}-2-methylpropanal, 3-(3,4-methylenedioxyphenyl)-2-methylpropan-I-
al
(helional), 3-(4-ethylphenyl)-2,2-dimethylpropanal, 3-(3-isopropylphenyl)butan-
I-al
(flohydral), 2,6-dimethylhep-5-en-I-al (melonal), n-decanal, n-undecanal, n-
dodecanal,
3,7-dimethyl-2,6-octadien-I-al (citral), 4-methoxybenzaldehyde (anisaldehyde),
3-
methoxy-4-hydroxybenzaldehyde (vanillin), 3-ethoxy-4-hydroxybenzaldehyde
(ethyl
vanillin), 3,4-methylenedioxybenzaldehyde (heiiotropin), 3,4-
dimethoxybenzaldehyde
Ketal Releasable Components: The ketals of the present invention have two
types of releasable components, namely alcohols and ketones. Hydrolysis of a
ketal will
yield two equivalents of releasable alcohol and one equivalent of releasable
ketone. The
released ketone, when taken together with the released alcohol, forms a binary
fragrance
accord. For example di-linalyl ~i-ionone ketal releases the binary accord
IinalooU~i-
ionone.
When RI is a moiety as described herein above other than hydrogen, the pro-
accords are capable of releasing an ketone component. Preferred ketones which
are
releasable components of the ketals of the present invention include but are
not limited to
a-damascone, (3-damascone, 8-damascone, ~i-damascenone, muscone, 6,7-dihydro-
1,1,2,3,3-pentamethyl-4(SH)-indanone (cashmeran), cis jasmone, dihydrojasmone,
a-
ionone, ~3-ionone, dihydro-(3-ionone, y-methyl ionone, a-iso-methyl ionone, 4-
(3,4-
methylenedioxyphenyl)butan-2-one, 4-(4-hydroxyphenyl)butan-2-one, methyl ~3-
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naphthyl ketone, methyl cedryl ketone, 6-acetyl-1,1,2,4,4,7-hexamethyltetralin
(tonalid),
I-carvone, 5-cyclohexadecen-1-one, acetophenone, decatone, 2-[2-(4-methyl-3-
cyclohexenyl-1-yl)propyI]cyclopentan-2-one, 2-sec-butylcyclohexa.none, (3-
dihydro
ionone, allyl ionone, a-irone, a-cetone, a-irisone, acetanisole, geranyl
acetone, 1-(2-
methyl-5-isopropyl-2-cyclohexenyl)-1-propanone, acetyl diisoamylene, methyl
cyclocitrone, 4-t-pentyl cyclohexanone, p-t-butylcyclohexanone, o-t-
butylcyclohexanone,
ethyl amyl ketone, ethyl pentyl ketone, menthone, methyl-7,3-dihydro-2H-1,5-
benzodioxepine-3-one, fenchone, and mixtures thereof.
More preferably the ketones which are released by the ketals of the present
invention are a-damascone, (3-damascone, 8-damascone, (3-damascenone, muscone,
6,7-
dihydro-1,1,2,3,3-pentamethyl-4(SH)-indanone (cashmeran), cis jasmone,
dihydrojasmone, a-ionone, [i-ionone, dihydro-[3-ionone, y-methyl ionone, a-iso-
methyl
ionone, 4-{3,4-methylenedioxyphenyl)butan-2-one, 4-(4-hydroxyphenyl)-butan-2-
one,
methyl (3-naphthyl ketone, methyl cedryl ketone, 6-acetyl-1,1,2,4,4,7-
hexamethyltetralin
(tonalid), I-carvone, 5-cyclohexadecen-1-one, and mixture thereof.
Examples of alcohols suitably released by the hydrolysis of the orthoester pro-
accords are the same as those listed herein above under (3-ketoesters.
Orthocarbonates
Another class of compounds useful as pro-accords according to the present
invention are orthocarbonates having the formula:
ORS
R40-C-OR2
I
OR3
wherein hydrolysis of the orthoester releases the fragrance raw material
components
according to the following scheme:
R40-OR OR2 ~ R4 ~ 1 + R2 + R30H
I O-C-OR OH
OR3
wherein R1, R2, R3, and R4 are independently C1-C2p linear, branched, or
substituted
alkyl; C2-C2p linear, branched, or substituted alkenyl; CS-C2p substituted or
unsubstituted cyclic alkyl; C6-C2p substituted or unsubstituted aryl, C2-C40
substituted
or unsubstituted alkyleneoxy; C3-C4p substituted or unsubstituted
alkyleneoxyalkyl; C6-
C4p substituted or unsubstituted alkylenearyl; C6-C32 substituted or
unsubstituted
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21
aryloxy; C6-C4p substituted or unsubstituted alkyleneoxyaryl; C6-C.~p
oxyalkylenearyl:
and mixtures thereof. By the term "substituted" herein is meant "compatible
moieties
which replace a hydrogen atom". Non-limiting examples of substituents are
hydroxy,
nitrilo, halogen, nitro, carboxyl (-CHO; -C02H; -C02R'; -CONH2; -CONHR'; -
CONR'~; wherein R' is C 1-C 12 linear or branched alkyl), amino, C 1-C 12 mono-
and
dialkylamino, and mixtures thereof.
In addition to the releasable alcohols listed herein above under (3-
ketoesters,
orthocarbonates according to the present invention are also cyclic
orthocarbonates which
are comprised from at least one diol having the formula:
to Rll
Rg R9
'n
OH OH
wherein R8, R9, R1 p, and R11 are each independently hydrogen, C 1-C2p linear
or
branched alkyl, C1-C2p linear or branched alkenyl, Cl-Cep linear, branched or
cyclic
alkylenecarboxy, Cl-C2p linear, branched, or cyclic carboxyalkyl, Cl-Cep
linear or
branched alkyleneamino, C 1-C2p linear or branched aminoalkyl, C 1-C2p linear,
branched, or cyclic alkylenecarboxamido, C1-C2p linear or branched
carboxamidoalkyl,
alkyleneoxy having the formula:
R13
-(OCH2CH}X(CH2~,Rl 2
wherein R12 is hydrogen or methyl; R13 is hydrogen or Cl-C2 alkyl; n is from 0
to 4, x
is from 1 to about 20, y is from 0 to about 20.
In addition to the initial release of two equivalents of alcohol and one
equivalent
of carbonate by the scheme depicted herein above, the carbonate pro-fragrances
which
are released by the orthocarbonates can continue to hydrolyze and further
release two
equivalents of one or more fragrance raw material alcohol according to the
following
scheme:
O
II
R O-C-OR1 ~ R40H + R10H
thereby providing up to four equivalents of fragrance raw material alcohol per
equivalent
of delivered orthocarbonate. The carbonate pro-fragrance which is released by
the
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WO 99!21954 PCTlIB98/01632
orthocarbonate may itself be a fragrance raw material in addition to being a
pro-
fragrance, preferably the carbonate which is released serves as a fragrance
raw material.
An orthocarbonate which comprises four different fragrance raw materials will
always
release a carbonate that is a pro-accord (hydrolyzes to release a binary
accord) in addition
to any further fragrance properties attributable to the carbonate.
Examples of alcohols suitably released by the hydrolysis of the orthoester pro-
accords are the same as those listed herein above under ~3-ketoesters.
The most preferred orthocarbonate pro-accords of the present invention have
each
of the R1, R2, R3, and R4 moieties derived from a fragrance raw material
alcohol,
thereby the preferred pro-fragrances have a molecular weight which is at least
4 times the
molecular weight of the lowest "fragrance raw material alcohol" which
comprises the
orthocarbonate pro-accord. Further, the preferred orthocarbonate pro-accords
have a
molecular weight which is greater than or equal to 350 g/mol.
Non-limiting examples of most preferred orthocarbonate pro-accords according
to
the present invention include: tetra-geranyl orthocarbonate, tetra-phenylethyl
orthocarbonate, tetrakis(3-methyl-5-phenylpentyl) orthocarbonate, tetrakis(cis-
3-
hexenyl) orthocarbonate, bis(geranyl) bis(cis-3-hexenyl) orthocarbonate,
bis(phenylethyl) bis(cis-3-hexenyl) orthocarbonate, tetrakis(citronellyl)
orthocarbonate,
tetrakis(linalyl) orthocarbonate, bis(linallyl) bis(geranyl) orthocarbonate,
tetrakis(myrcenyl) orthocarbonate, tetrakis(cinnamyl) orthocarbonate.
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 ~i-citronellol or cephrol, comprises a pair of
optical isomers, R-
(+)-(3-citronellol and S-{-)-(3-citronellol. Each of these materials
separately or as a
racemic pair are suitable for use as fragrance raw materials in the present
invention.
However, those skilled in the art of fragrances, by utilization of the present
invention,
should not disregard the olfactory differences that individual optical
isomers, admixtures
of optical isomers or admixtures of positional isomers impart. By way of
example,
carvone, 2-methyl-5-(1-methylethenyl}-2-cyclohexene-I-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 scent
or fragrance than one which releases 1-carvone. The same applies to 1-carvone.
In
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?3
addition, isomers such as cisltrans isomers, for example, nerol (3,7-dimethyl-
cis-2,6-
octadien-1-ol) and geraniol (3,7-dimethyl-traps-2.6-octadien-1-ol), are well
known to
those skilled in the art of.perfumery and these two terpene alcohols, which
commonly
occur as an admixture, have different fragrance characteristics. Therefore,
when
formulating fragrance raw materials which comprise mixtures of isomers such as
nerol/geraniol, the formulator must also take into account whether different
sources of
raw material have different ratios of isomers.
The formulator is not limited to the delivery of one type of fragrance, for
example
a top, middle, or base fragrance raw material note. Instead a mixture of top
notes, a
mixture of top and middle notes, or any combination of top, middle and base
notes may
be delivered in any suitable proportion.
As described herein above, those skilled in the art of preparing fragrance-
containing compositions have categorized fragrances into three types based on
their
relative volatility; top, middle, and base notes. In addition, fragrances are
categorized by
the odor they produce; some of these descriptors are broad and others are
relatively
specific. For example, "floral" is a term which connotes odors associated with
flowers
while the term "lilac" is more specific. Descriptors used by those skilled in
the art of
perfumes and fragrances are inter alia "rose", "floral", "green", "citrus",
"spicy",
"honey", and "musk". The sources of these notes are not limited to one
chemical class;
alcohols can produce "rose", "green", and "musk" scents, while "rose" scents
can
comprise alcohols, ketones, terpenes, aldehydes, etc.
Top, middle, and base notes each serve a different purpose in the blending of
fragrances and when properly formulated produce a "balanced fragrance"
composition.
Based on volatility, these notes are described by those skilled in the art as:
the base notes
having the most long lasting aroma; the middle notes, have a medium
volatility; and the
top notes are the most volatile. The compositions described herein below, as
well as
others chosen by the formulator, comprise a fragrance delivery system which
utilizes the
pro-fragrances of the present invention to successfully deliver a "balanced
fragrance"
profile.
It is also recognized by those skilled in the art that descriptors which
relate to
aesthetic perceptions such as "top", "middle" and "base" notes are relative
terms. A
fragrance raw material categorized as a top note by one formulator usually has
the
identical classification among most other Perfumers. The same is true for the
middle and
base notes, however, occasionally one formulator may classify a given
fragrance raw
material as a middle note rather than a top note, or vice versa, but this fact
does not
diminish the utility of a given compound or its absolute identity. Top, middle
and base
CA 02307892 2000-04-28
WO 99121954 PCT/IB98/01632
74
notes are now combined in a reproducible manner to produce perfumes, colognes,
after-
shave lotions, eau de toilettes, etc. for application to skin, which have
unique and
pleasant odor characteristics. Yet apart from this pleasant fragrance, a
fragrance delivery
system which is used to deliver a scent to a laundry detergent composition
must meet a
number of technical requirements. It must be sufficiently strong, it must be
persistent,
and it must retain its "essential character" throughout its period of
evaporation and
fragrance raw material release.
The compositions of the present invention comprise at least an effective
amount
of one or more pro-fragrances or pro-accords as described herein above. What
is meant
herein by "an effective amount" of a pro-accord or pro-fragrance is defined as
"at least
about 0.01 %, preferably from about 0.01 % to about 15%, more preferably from
about
0. I % to about 5%, most preferably from about 0.1 % to about 1 % by weight,
of a pro-
accord as described herein above".
An example of a preferred pro-accord is 3,7-dimethyl-1,6-octadien-3-yl 3-(~i-
naphthyl)-3-oxo-propionate having the formula:
O O
/ \ \/ ~O \/ \//\
\ /
which releases at least the fragrance raw material alcohol, linalool, having
the formula:
HO I v vi w
and the fragrance raw material ketone, methyl naphthyl ketone, having the
formula:
O
/ \ \
\ /
A further example of a pro-accord is tris(phenylethyl) orthoacetate which
releases
a binary accord having a "rose" characteristic comprising 2 parts phenylethyl
alcohol and
I part phenylethyl acetate according to the following scheme:
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98101632
\ \
- HO
O I phenylethyl alcohol
H3C-C-O /
O \
\ H3C-O-O
tris(phenylethyl) orthoacetate phenylethyl acetate
A further example of a pro-accord is di-citronellyl benzyl acetate capable of
releasing the binary fragrance accord of citronellol/citronellyl acetate
having a "rose"
characteristic together with the benzyl alcohol/benzyl acetate "jasmin"
modifiers
according to the following scheme:
HO
citroneilol
n n O
CH3-C-O
citronellyl acetate
O
CH3-C-O
benryl acetate
HO
bis(citronellyl) benryl orthoacetate
benryl alcohol
The formulator may therefore deliver one fragrance or a complex accord to
suitably mask the malodors which may form in the laundry detergent or fabric
softener
compositions.
Materials Comprising Laundry and Fabric Conditionin~positions
Surfactant s std
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,
arnpholytic and zwitterionic surface active agents. Preferably the solid (i.e.
granular) and
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WO 99121954 PCTI1B98/01632
26
viscous semi-solid (i.e. gelatinous, pastes, etc.) systems of the present
invention,
surfactant is preferably present to the extent of from about 0. I % 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 C 11-C 1 g alkyl benzene
sulfonates ("LAS") and primary, branched-chain and random C 1 p-C20 alkyl
sulfates
("AS"), the C l 0-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 1 p-C 1 g alkyl alkoxy sulfates ("AEXS"; especially 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 1 ~-C
1 g
betaines and sulfobetaines ("sultaines"), C 10-C 1 g amine oxides, and the
like, can also be
included in the overall compositions. The C 10-C 1 g N-alkyl polyhydroxy fatty
acid
amides are highly preferred, especially the C 12-C 1 g N-methylgiucamides. See
WO
9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid
amides, such as C 10-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl through
N-
hexyl C 12-C 1 g glucamides can be used for low sudsing. C 10-C20 conventional
soaps
may also be used. If high sudsing is desired, the branched-chain C 10-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-
18 carbon
atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or
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WO 99/21954 PCTlIB98/01632
27
potassium alkyl benzene sulfonates, in which the alkyl group contains from
about 9 to
about 15 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
1 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
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, Morris, 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.
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WO 99/21954 PCT/IB98/01632
28
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 1 ~-C
1 g alkyl
ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and
C6-C 1 ~
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 oxidelpropylene 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.
More preferred nonionic surfactants are the polyhydroxy fatty acid amides
having the formula:
O R8
R7-C-N-Q
wherein R7 is C5-C31 alkyl, preferably straight chain C7-C 1 g alkyl or
alkenyl, more
preferably straight chain Cg-C 17 alkyl or alkenyl, most preferably straight
chain C 11-
C 15 alkyl or alkenyl, or mixtures thereof; R8 is selected from the group
consisting of
hydrogen, Cl-C4 alkyl, Cl-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 com 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~CH20H, -
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.
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/01632
29
RICO-N< can be, for example, cocamide, stearamide, oleamide, lauramide,
myristamide, capricamide, palmitamide, taIlowamide, etc.
Rg 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, 1-deoxylactityl,
1-
deoxygalactityl, 1-deoxymannityl, 1-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 11-C I ~), R8, is methyl and Q is I -deoxyglucityl.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid
amides, such as C I p-C 1 g N-(3-methoxypropyl) glucamide. The N-propyl
through N-
hexyl C 12-C 1 g glucamides can be used for low sudsing. C 1 p-C2p
conventional soaps
may also be used. If high sudsing is desired, the branched-chain C I p-C 16
soaps may be
used.
Ouaternary Ammonium Fabric Softenin D Active Compounds (DEOA's)
The preferred fabric softening actives according to the present invention have
the
formula:
(R)4-m N (CH2)n-Q-RI X
m
wherein each R is independently C 1-C6 alkyl, C I -C6 hydroxyalkyl, benzyl,
and mixtures
thereof; Rl is preferably C11-C22 alkyl, Cl 1-C22 alkenyl, and mixtures
thereof; Q is a
carbonyl moiety having the formula:
O O R2 O O R2
-O-C- -C-O- -N-C- -C-N-
> > > ,
O
O R3 O O-C-Rl O
-O-C-O- , -CH-O-C- , -CH-CH2-O-C-
wherein R2 is hydrogen, Cl-C4 alkyl, preferably hydrogen; R3 is C1-C4 alkyl,
preferably hydrogen or methyl; preferably Q has the formula:
CA 02307892 2000-04-28
WO 99/21954 PCTIIB98I01632
O O
-O-C- or -NH-C-
X is a softener compatible anion, preferably the anion of a strong acid, for
example,
chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures
thereof, more
preferably chloride and methyl sulfate. The anion can also, but less
preferably, carry a
double charge, in which case X(') represents half a group. The index m has a
value of
from 1 to 3; the index n has a value of from 1 to 4, preferably 2 or 3, more
preferably 2.
More preferred softener actives according to the present invention have the
formula:
+ O
(R)4_m N (CH2)n O-C-Rt X _
m
wherein the unit having the formula:
O
-O-C-Rl
is a fatty acyl moiety. Suitable fatty acyi moieties for use in the softener
actives of the
present invention are derived from sources of triglycerides including tallow,
vegetable
oils and/or partially hydrogenated vegetable oils including inter alia canola
oil, safflower
oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran
oil.
The RI units are typically mixtures of linear and branched chains of both
saturated
and unsaturated aliphatic fatty acids, an example of which (canola oil), is
described in
Table I herein below.
Table I
Fatty acyl unit
C14 0.1
C16 5.4
C 16: I 0.4
C18 5.7
C18:1 67.0
C I 8:2 13.5
C 18:3 2.7
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WO 99/21954 PCT/IB98/01632
31
C20 0.5
C20: I 4.6
The formulator, depending upon the desired physical and performance properties
of the final fabric softener active, can choose any of the above mentioned
sources of fatty
acyl moieties, or alternatively, the formulator can mix sources of
triglyceride to form a
"customized blend". However, those skilled in the art of fats and oils
recognize that the
fatty acyl composition may vary, as in the case of vegetable oil, from crop to
crop, or
from variety of vegetable oil source to variety of vegetable oil source.
DEQA's which
are prepared using fatty acids derived from natural sources are preferred.
A preferred embodiment of the present invention provides softener actives
comprising RI units which have at least about 3%, preferably at least about
5%, more
preferably at least about 10%, most preferably at least about 15% C 11-C22
alkenyl,
including polyalkenyl (polyunsaturated) units inter alia oleic, linoleic,
linolenic.
For the purposes of the present invention the term "mixed chain fatty acyl
units" is
defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains
having from
carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case
of
alkenyl chains, from one to three double bonds, preferably all double bonds in
the cis
configuration". With regard to the R1 units of the present invention, it is
preferred that at
least a substantial percentage of the fatty acyl groups are unsaturated, e.g.,
from about
25%, preferably from about 50% to about 70%, preferably to about 65%. The
total level
of fabric softening active containing polyunsaturated fatty acyl groups can be
from about
3%, preferably from about 5%, more preferably from about 10% to about 30%,
preferably to about 25%, more preferably to about 18%. As stated herein above
cis and
traps isomers can be used, preferably with a cisltrans ratio is of from 1:1,
preferably at
/east 3:1, and more preferably from about 4:1 to about 50:1, more preferably
about 20:1,
however, the minimum being 1:1.
The R1 units suitable for use in the present invention can be further
characterized by the Iodine Value (IV) of the parent fatty acid, said IV is
preferably from
about 20, more preferably from about 50, most preferably from about 70, to a
value of
about 140, preferably to about 130, more preferably to about 115. However,
formulators,
depending upon which embodiment of the present invention they choose to
execute, may
wish to add an amount of fatty acyl units which have Iodine Values outside the
range
listed herein above. For example, "hardened stock" (IV less than or equal to
about 10)
may be combined with the source of fatty acid admixture to adjust the
properties of the
final softener active. A further preferred embodiment of the present invention
comprises
DEQA's wherein the average Iodine Value for R1 is approximately 45.
CA 02307892 2000-04-28
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32
Amines which are used to prepare the preferred fabric softening actives of the
present invention have the formula:
(R)3-m N (CH2)ri Z
m
wherein R is the same as defined herein above; each Z is independently
selected from the
group consisting of -OH, -CHR30H, -CH(OH)CH20H, -NH2, and mixtures thereof;
preferably -OH, -NH2, and mixtures thereof; R3 is C 1-C4 alkyl, preferably
methyl; the
indices m and n are the same as defined hereinabove.
Non-limiting examples of preferred amines which are used to form the DEQA
fabric softening actives according to the present invention include methyl
bis(2-
hydroxyethyl)amine having the formula:
~ H3
HON OOH
methyl bis(2-hydroxypropyl)amine having the formula:
CH3
N
HO OH
methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:
i H3
HO~N~NH2
methyl bis(2-aminoethyl)amine having the formula:
CH3
H2N~N~NH2
triethanol amine having the formula:
CA 02307892 2000-04-28
WO 99/21954 PCTIIB98/01632
33
~OH
HON OOH
bis(2-aminoethyl) ethanolamine having the formula:
~OH
H~N~N~NH2
For the purposes of the present invention, R moieties which are introduced
during
the quaternization step are preferably methyl. In the case of amines having
the formula:
R-N (CH2)n-Z
2
R is preferably the same moiety (i.e. methyl) which is introduced during the
quaternization step. For example, a methyl amine having the formula:
CH3-N (CH2)ri Z
2
is preferably quaternized to the softener active having the general formula:
(CH3)2-N (CH2)n Z X
2
In one embodiment of the present invention, the fabric softening active
precursor
amine mixture is not fully quaternized, that is, some free amine having the
general
formula:
(R m N (CH2)ri Q
m
is still present in the final fabric softener mixture.
A yet further embodiment of the present invention comprises an amine of the
formula:
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/01632
34
(R)~_m N (CH~)n-Z
m
wherein not all of the Z units are fully reacted with a fatty acyl moiety
thereby leaving an
amount of amine and/or quaternized ammonium compound in the final fabric
softener
active admixture having one or more Z units unreacted and thereby not
transformed into
an ester or amide..
The following are examples of preferred softener actives according to the
present
invention.
N,N-di(tallowyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N.N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium chloride;
N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canoIyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride;
N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl}-N,N-dimethyl
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl
ammonium chloride;
N,N,N-tri(tallowyI-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tri(canolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-ditallowyloxy-3-N,N,N-trimethylammoniopropane chloride; and
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride, where the tallow chains are at least partially unsaturated and N,N-
di(canoloyl-
oxy-ethyl)-N,N-dimethyl ammonium chloride.
The amount of fabric softening active present in the compositions of the
present
invention is at least about 2%, preferably from about 2%, more preferably from
about 5%
to about 60%, more preferably to about 40% by weight, of the composition.
ADJUNCT INGREDIENTS
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WO 99/21954 PCT/IB98/01632,
3~
The following are non-limiting examples of adjunct ingredients useful in the
laundry compositions of the present invention, said adjunct ingredients
include builders,
optical brighteners, 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.
Builders - 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 I % 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 I S% 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:I and layered silicates,
such as the
layered sodium silicates described in U.S. Patent 4,664,839, issued May 12,
198? 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
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/01632
36
layered silicate for use herein, but other such layered silicates, such as
those having the
general formula NaMSix02x+1 ~yH~O 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-
Na~Si05
(NaSKS-6 form) is most preferred for use herein. Other silicates may also be
useful
such as for example magnesium 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(~02)yJ'~20
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 I S 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. I -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
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98101632
37
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 prefen:ed.
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, 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;
4,158,63; 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, S-
trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the
various alkali
metal, ammonium and substituted ammonium salts of golyacetic 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-I,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 86200690.5/0,200,263, 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.
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98101632
38
Fatty acids, e.g., C 1 ~-C 1 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.
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,I-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.
Dispersants
The compositions of the present invention may also optionally comprise at
least
about 0.1 % by weight, preferably from about 0.1 % to about 10%, more
preferably from
about 0.5% to about 5% by weight, of a water-soluble substituted or
unsubstituted,
modified or unmodified polyalkyleneimine dispersant, said dispersant comprises
a
polyamine backbone, preferably said backbone having a molecular weight of from
about
100 to about 3000 daltons having the formula:
H
fHzN'RJn+1-f~''RJrri ~'RJri NH2
wherein R is preferably C2-C6 alkylene, m is from about 3 to 70, n is from 0
to about 35,
one or more of the polyamine backbone N-H unit hydrogens are "substituted",
that is
replaced with a substituent which increases the hydrophobic or hydrophilic
dispersancy
of said polyamine, preferably one or more backbone hydrogens, more preferably
all
hydrogens are replaced by an propyleneoxy/ethyleneoxy unit having the formula:
-(CH2CHR'Oh,(CH2CH20)xH
wherein R' is methyl or ethyl, x and y are preferably from about 0 to about
50, provided x
+ y is at least 1; and wherein further each nitrogen which comprises the
polyalkyleneimine backbone may be optionally "modified" by quaternization or
by
oxidation to the N-oxide.
A further description of polyalkyleneimine dispersants is found in U.S.
4,597,898, VanderMeer, issued July 1, 1986; European Patent Application
111,965, Oh
and Gosselink, published June 27, 1984; European Patent Application 111,984,
Gosselink, published June 27, 1984; European Patent Application 112,592,
Gosselink,
published July 4, 1984; U.S. 4,548,744, Connor, issued October 22, 1985; and
U.S.
CA 02307892 2000-04-28
WO 99121954 PCTIIB98/01632
39
~,~65,145 Watson et al., issued October 1 ~, 1996; all of which are included
herein by
reference. However, any suitable clay/soil dispersent or anti-redepostion
agent can be
used in the laundry compositions of the present invention.
Soil Release Agents
Any polymeric soil release agent known to those skilled in the art can
optionally
be employed in the compositions and processes of this invention. Polymeric
soil release
agents are characterized by having both hydrophilic segments, to hydrophilize
the surface
of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments,
to deposit
upon hydrophobic fibers and remain adhered thereto through completion of
washing and
rinsing cycles and, thus, serve as an anchor for the hydrophilic segments.
This can
enable stains occurring subsequent to treatment with the soil release agent to
be more
easily cleaned in later washing procedures.
If utilized, soil release agents will generally comprise from about 0.01% to
about
10.0%, by weight, of the detergent compositions herein, typically from about
0.1 % to
about 5%, preferably from about 0.2% to about 3.0%.
The following, all included herein by reference, describe soil release
polymers
suitable for use in the present invention. U.S. 3,959,230 Hays, issued May 25,
1976;
U.S. 3,893,929 Basadur, issued July 8, 1975; U.S. 4,000,093, Nicol, et al.,
issued
December 28, 1976; U.S. Patent 4,702,857 Gosselink, issued October 27, 1987;
U.S.
4,968,451, Scheibel et al., issued November 6; U.S. 4,702,857, Gosselink,
issued
October 27, 1987; U.S. 4,711,730, Gosselink et al., issued December 8, 1987;
U.S.
4,721,580, Gosselink, issued January 26, 1988; U.S. 4,877,896, Maldonado et
al., issued
October 31, 1989; U.S. 4,956,447, Gosselink et al., issued September 11, 1990;
U.S.
5,415,807 Gosselink et al., issued May 16, 1995; European Patent Application 0
219
048, published April 22, 1987 by Kud, et al..
Further suitable soil release agents are described in U.S. 4,201,824, Violland
et
al.; U.S. 4,240,918 Lagasse et al.; U.S. 4,525,524 Tung et al.; U.S.
4,579,681, Ruppert et
al.; U.S. 4,240,918; U.S. 4,787,989; U.S. 4,525,524; EP 279,134 A, 1988, to
Rhone-
Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 to Unilever N.
V.,
1974 all incorporated herein by reference.
Commercially available soil release agents include the METOLOSE SMI00,
METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN type
of material, e.g., SOKALAN HP-22, available from BASF (Germany), ZELCON 5126
(from Dupont) and MILEASE T (from ICI).
Solvents and Carrier
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/01632
The fabric softener compositions of the present invention may be liquid in
form
and, therefore be formulated into an aqueous system or optionally be
formulated with a
solvent-water system as the liquid carrier. For the liquid fabric softeners of
the present
invention containing solvents, the solvent preferably comprises less than
about 40%.
preferably from about 10% to about 35%, more preferably from about 12% to
about
25%, and even more preferably from about 14% to about 20%, by weight of the
composition. The solvent is selected to minimize solvent odor impact in the
composition
and to provide a low viscosity to the final composition. For example,
isopropyl alcohol
is not very effective and has a strong odor. n-Propyl alcohol is more
effective, but also
has a distinct odor. Several butyl alcohols also have odors but can be used
for effective
clarity/stability, especially when used as part of a solvent system to
minimize their odor.
The alcohols are also selected for optimum low temperature stability, that is
they are able
to form compositions that are liquid with acceptable low viscosities and
translucent,
preferably clear, down to about 40°F (about 4.4°C) and are able
to recover after storage
down to about 20°F (about 6.7°C).
The suitability of any solvent for the formulation of the liquid,
concentrated,
preferably clear, fabric softener compositions herein with the requisite
stability is
surprisingly selective. Suitable solvents can be selected based upon their
octanol/water
partition coefficient (P). Octanol/water partition coefficient of a solvent is
the ratio
between its equilibrium concentration in octanol and in water. The partition
coefficients
of the solvent ingredients of this invention are conveniently given in the
form of their
logarithm to the base 10, loge.
The loge of many ingredients has been reported; for example, the Pomona92
database, available from Daylight Chemical Information Systems, Inc. (Daylight
CIS),
Irvine, California, contains many, along with citations to the original
literature.
However, the loge values are most conveniently calculated by the "CLOGP"
program,
also available from Daylight CIS. This program also lists experimental IogP
values
when they are available in the Pomona92 database. The "calculated loge"
(ClogP) is
determined by the fragment approach of Hansch and Leo (cf., A. Leo, in
Comprehensive
Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A.
Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by
reference). The
fragment approach is based on the chemical structure of each ingredient, and
takes into
account the numbers and types of atoms, the atom connectivity, and chemical
bonding.
These ClogP values, which are the most reliable and widely used estimates for
this
physicochemical property, are preferably used instead of the experimental IogP
values in
the selection of the solvent ingredients which are useful in the present
invention. Other
CA 02307892 2000-04-28
WO 99121954 PCTIIB98/01632
41
methods that can be used to compute CIogP include, e.g., Crippen's
fragmentation
method as disclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987);
Viswanadhan's
fragmentation method as disclose in J. Chem. In~ Comput. Sci., 29, 163 (
1989); and
Broto's method as disclosed in Eur. J. Med. Chem. - Chim. Theor., 19, 71 (
1984).
The solvents herein are selected from those having a ClogP of from about 0.15
to
about 0.64, preferably from about 0.25 to about 0.62, and more preferably from
about
0.40 to about 0.60, said solvent preferably being at least somewhat
asymmetric, and
preferably having a melting, or solidification, point that allows it to be
liquid at, or near
room temperature. Solvents that have a low molecular weight and are
biodegradable are
also desirable for some purposes. The more asymmetric solvents appear to be
very
desirable, whereas the highly symmetrical solvents such as 1,7-heptanediol, or
1,4-
bis(hydroxymethyl) cyclohexane, which have a center of symmetry, appear to be
unable
to provide the essential clear compositions when used alone, even though their
ClogP
values fall in the preferred range.
Operable solvents are disclosed and listed below which have ClogP values which
fall within the requisite range. These include mono-ols, C6 diols, C7 diols,
octanediol
isomers, butanediol derivatives, trimethylpentanediol isomers,
ethylmethylpentanediol
isomers, propyl pentanediol isomers, dimethylhexanediol isomers,
ethylhexanediol
isomers, methylheptanediol isomers, octanediol isomers, nonanediol isomers,
alkyl
glyceryl ethers, di(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic
glyceryl
ethers, alicyclic diols and derivatives, C3C7 diol alkoxylated derivatives,
aromatic diols,
and unsaturated diols. Particularly preferred solvents include hexanediols
such as 1,2-
Hexanediol and 2-Ethyl-1,3-hexanediol and pentanediols such as 2,2,4-Trimethyl-
1,3-
pentanediol.
Perfumes
The products herein can also contain from about 0. I % to about 60%,
preferably
from about 1 % to about 50%, cycIodextrin/perfiime 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 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
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98/01632
42
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/BanksBenvegnu, issued
Aug. 3, 1993, said patent being incorporated herein by reference, by adjusting
the levels
of free perfume and perfumeICD 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 0.035% to about 0.1 % for antioxidants, and more
preferably
from about O.OI % to about 0.2% for reductive agents. These assure good odor
stability
under long term storage conditions for the compositions and compounds stored
in molten
form. The use of antioxidants and reductive agent stabilizers is especially
critical 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 and Tenox S-
1; a
mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole),
propyl
gallate, and citric acid, available from Eastman Chemical Products, Inc.,
under the trade
name Tenox-6; butylated 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;
CA 02307892 2000-04-28
WO 99!21954 PCTIIB98/01632
43
long chain esters (Cg-C~~) of gallic acid, e.g., dodecyl gallate; Irganox~
1010; Irganox
~ 1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; Irganox~ 3125; and
mixtures thereof; preferably Irganox~ 3125, Irganox~ 1425, Irganox~ 3114. and
mixtures thereof; more preferably Irganox~ 312 alone or mixed with citric acid
and/or
other chelators such as isopropyl citrate, Dequest~ 2010, available from
Monsanto with
a chemical name of 1-hydroxyethylidene-1, 1-diphosphonic acid (etidronic
acid), and
Tiron~, available from Kodak with a chemical name of 4,5-dihydroxy-m-benzene-
sulfonic acid/sodium salt, EDDS, and DTPA~, available from Aldrich with a
chemical
name of diethylenetriaminepentaacetic acid.
Concentration aids
Concentrated compositions of the present invention may require organic andlor
inorganic concentration aids to go to even higher concentrations and/or to
meet higher
stability standards depending on the other ingredients. Surfactant
concentration aids are
typically selected from the group consisting of single long chain alkyl
cationic
surfactants; nonionic surfactants; amine oxides; fatty acids; or mixtures
thereof, typically
used at a level of from 0 to about 1 S% of the composition.
Inorganic viscosity/dispersibility control agents which can also act like or
augment the effect of the surfactant concentration aids, include water-
soluble, ionizable
salts which can also optionally be incorporated into the compositions of the
present
invention. A wide variety of ionizable salts can be used. Examples of suitable
salts are
the halides of the Group IA and IIA metals of the Periodic Table of the
Elements, e.g.,
calcium chloride, magnesium chloride, sodium chloride, potassium bromide, and
lithium
chloride. The ionizable salts are particularly useful during the process of
mixing the
ingredients to make the compositions herein, and later to obtain the desired
viscosity.
The amount of ionizable salts used depends on the amount of active ingredients
used in
the compositions and can be adjusted according to the desires of the
formulator. Typical
levels of salts used to control the composition viscosity are from about 20 to
about
20,000 parts per million (ppm), preferably from about 20 to about 11,000 ppm,
by weight
of the composition.
Other Adiunct Ingredients
The present invention can include other adjunct components (minor components)
conventionally used in textile treatment compositions, for example, colorants,
preservatives, optical brighteners, opacifiers, anti-shrinkage agents, anti-
wrinkle agents,
fabric crisping agents, spotting agents, germicides, fungicides, anti-
corrosion agents,
antifoam agents, and the like.
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WO 99/21954 PCT/IB98/O1632
44
For examples of other suitable ingredients useful in fabric softener
containing
compositions see WO 97/03169 included herein by reference.
METHOD OF USE
The present invention to methods for providing a laundry detergent composition
having reduced malodor, comprising the step of adding a effective amount of a
pro-
accord to a laundry detergent composition comprising:
a) 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;
b) 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.
The present invention also relates to methods for providing a fabric softener
composition having reduced malodor, comprising the step of adding a effective
amount
of a pro-accord to a fabric softener composition comprising:
a) at least about 2%, preferably from about 2%, more preferably from about
3% to about 60%, more preferably to about 40% by weight, of a fabric
softening active having the formula:
+ _
~)4-m N (CH2)ri Q-R~ X
m
wherein each R is independently Cl-C6 alkyl, C1-C6 hydroxyalkyl,
benzyl, and mixtures thereof; R1 is C1-C22 alkyl, C3-C22 alkenyl, and
mixtures thereof; Q is a carbonyl moiety having the formula:
CA 02307892 2000-04-28
WO 99/21954 PCT/IB98I01632
O O R~ O O R2
II II I II II I
-O-C- , -C-O- , -N-C- , -C-N- ,
O
O R3 O O-C-Rl O
-O-C-O- , -CH-O-C- , -CH-CH2-O-C-
wherein R2 is hydrogen, C 1-C4 alkyl, C 1-C4 hydroxyalkyl, and mixtures
thereof; R3 is hydrogen, C 1-C4 alkyl, and mixtures thereof; X is a
softener compatible anion; m is from 1 to 3; n is from 1 to 4; and
b) the balance Garners and adjunct ingredients, said adjunct ingredients
selected from the group consisting of nonionic fabric softening agents,
concentration aid, soil release agent, perfume, preservatives, stabilizers,
colorants, optical brighteners, opacifiers, fabric conditioning agents, anti-
shrinkage agents, anti-wrinkle agents, fabric crisping agents, spotting
agents, germicides, fungicides, anti-corrosion agents, antifoam agents,
cationic charge boosters, and mixtures thereof.
What is meant herein by "an effective amount" of a pro-accord or pro-fragrance
is
defined as "at least about 0.01 %, preferably from about 0.01 % to about 15%,
more
preferably from about 0.1 % to about 5%, most preferably from about 0.1 % to
about 1
by weight, of a pro-accord as described herein above".
The method of the present invention can be conducted in any manner suitable to
the formulator. For example, the fragrance releasing pro-accord material may
be added
at any step during formulation of the laundry detergent or fabric softening
composition,
provided that the final form of the composition allows for adequate delivery
of the
released fragrance.
EXAMPLE 1
Preparation of 3,7-dimethyl-1,6-octadien-3-y! 3-oxo-butyrate
A mixture of linalool (100 g, 0.648 mol) and 4-dimethylaminopyridine (0.40 g,
3.20 mmol) in a 500 mL three-necked round-bottomed flask fitted with a
condenser,
argon inlet, addition funnel, magnetic stirrer and internal thermometer is
heated to 55 °C.
Diketene (54.50 g, 0.648 mol) is added dropwise in the course of 30 min. The
mixture
has a slight exotherm and turns from yellow to red during this time. After
stirring an
additional hour at 50 °C, the mixture is cooled to room temperature. At
this point, NMR
analysis indicates the reaction is complete. The material from this lot is
carried onto the
next step. Purification of an earlier sample from this route by flash
chromatography
CA 02307892 2000-04-28
WO 99121954 PCT/IB98101632
46
(elution with dichloromethane) yields the desired product in 92% v_ field and
nearly
colorless.
EXAMPLE 2
Preuaration of 2,6-dimethyl-7-octen-2-yl 3-oxo-butyrate
A mixture of dihydromyrcenol (37.88 g, 0.240 mol) and 4-
dimethylaminopyridine (0.16 g, 1.30 mmol) in a 100 mL three-necked round-
bottomed
flask fitted with a condenser, argon inlet, addition funnel, magnetic stirrer
and internal
thermometer is heated to 50-60 °C. Diketene (20.16 g, 0.240 mol) is
added dropwise in
the course of 15 min. The mixture has a slight exotherm and turned from yellow
to red
during this time. After stirring an additional hour at SO °C, the
mixture is cooled to room
temperature. At this point, NMR analysis indicates the reaction is complete.
Purification
of the product mixture by flash chromatography (elution with dichloromethane)
yields
the desired product in 95% yield as a nearly colorless oil.
EXAMPLE 3
Preparation of 3,7-dimethyl-1,6-octadien-3-yl 3-(,(3-naphthyly-3-oxo-
~ro~ionate
Crude 3,7-dimethyl-1,6-octadien-3-yl 3-oxo-butyrate (154.51, 0.648 mol) from
above is placed in a 3000 mL three-necked round-bottomed flask fitted with a
condenser,
argon inlet, addition funnel, magnetic stirrer and internal thermometer. The
contents are
dissolved in 350 mL of dichloromethane and treated with powdered calcium
hydroxide
(50.44 g, 0.681 mol). The mixture is stirred at 30 °C for 30 min and
then heated to 40 °
C. 2-Naphthoyl chloride (142.12 g, 0.746 mot) dissolved in 20 mL of
dichloromethane
is added dropwise over 15 min. The mixture continues to be heated at this
temperature
for 1 h. Ammonium chloride (36.41 g, 0.681 mol) dissolved in 250 mL of water
is added
to the reaction mixture and the pH adjusted to ~9 with 28% ammonium hydroxide.
After
stirring 30 min at 35 °C the pH is adjusted to ~1 with 20% HCI. The
mixture is
transferred to a separatory funnel containing diethyl ether (500 mL) and water
(500 mL).
The layers are separated and the organic phase is washed with saturated NaHC03
solution (2 x 500 mL), dried over MgS04, filtered and concentrated by rotary
evaporation to give a yellow red oil. At this point a light yellow solid
precipitates from
the mixture. An equal volume of hexane is added and the solids is collected by
filtration
and dried. NMR analysis indicates the solid is 2-naphthoic acid. The eluent is
concentrated again by rotary evaporation to give a red oil. The oil is taken
up in an equal
volume of dichloromethane, passed through a plug of silica gel (400 g) and
eluted with
dichloromethane. The mixture is concentrated by rotary evaporation and
stripped by
Kugelrohr distillation (40 °C, 0.10 mm Hg, 30 min) to yield 173.26 g
(76.3%) of the
product as a red oil; this product is a mixture of a 1:10 molar ratio of
linalyl acetoacetate
CA 02307892 2000-04-28
WO 99121954 PCTIIB98/01632
47
to linalyl (2-naphthoyl)acetate. A portion of this material is purified by
column
chromatography (elution with 2.5% ethyl acetate in hexanes) to give the
desired product
as a light yellow oil.
The following are examples of granular detergent compositions comprising the
fragrance delivery system of the present invention.
TABLEI
weight
In reg dient 4 5 6 7
Sodium C 11-C 13 alkylbenzenesulfonate13.3 13.7 10.4 11.1
Sodium C 14-C I 5 alcohol sulfate3.9 4.0 4.5 I 1.2
Sodium C 14-C 15 alcohol ethoxylate2.0 2.0 0.0 0.0
(0.5 j 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 10.5 10.9 8.2 15.0
Sodium perborate 1.0 1.0 5.0 0.0
Poly(ethyleneglycol), MW ~--40001.7 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 polymer 1 1.5 1.5 1.5 1.5
Pro-accord 2 1.0 1.5 0.0 0.0
Pro-accord 3 0.0 0.0 2.5 1.5
Minors 4 7.0 2.1 4.1 6.3
1. Soil release polymer according to U.S. Patent 5,415,807, Gosselink, Pan,
Kellett and
Hall, issued May 16, 1995.
2. Pro-accord according to Example 1.
3. Pro-accord according to Example 3.
4. Balance to 100% can, for example, include minors like optical brightener,
perfume,
suds suppresser, soil dispersant, protease, lipase, cellulase, chelating
agents, dye
CA 02307892 2000-04-28
WO 99/21954 PC"T/IB98/01632
48
transfer inhibiting agents, additional water. and fillers, including CaC03,
talc,
silicates, etc.
The following illustrate liquid laundry detergent compositions comprising the
fragrance delivery system according to the present invention.
TABLE II
Ingredients Weight
8 9 10 11 12
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
C25 Alkyl ethoxylate sulphate19.00 19.40 19.00 17.40 14.00
C~5 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
Pro-accord 5 1.18 1.18 1.18 1.18 1.75
Soil release agent 6 0.22 0.15 0.15 0.15 0.15
Fumed silica 0.119 0.119 0.119 0.119 0.119
Minors, aesthetics, waterbalancebalancebalancebalancebalance
1. C I2-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.
CA 02307892 2000-04-28
WO 99/21954 PCTlIB98I01632
49
Pro-accord according to Example 3.
6. Terephthalate co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et
al.,
issued November 6, 1990.
TABLE III
weight
Ingredients 13 14 IS
DEQA 1 (85% active in ethanol) 19.9 -- 15.3
DEQA2 (85% active in ethanol) -- 19.9 --
DEQA3 (85% active in ethanol) 10.7 10.7 15.3
Ethanol __ __ 2
Irganox~ 3125 0.01 0.01 0.02
DTPA 0.01 0.01 0.01
1,2-Hexanediol 18 18 18
Pro-accord '* ~.~ 3.~ 1.8
HC1 (pH 2.5-4.0) 0.005 0.005 0.005
Distilled Water balancebalance balance
1. N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the
tallow
chains are at least partially unsaturated.
2. N,N-di(canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chloride.
3. N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride.
4. Pro-accord according to Example 3.
TABLE IV
weight
Ingredients 16 I7 18
DEQAI (85% active in ethanol) -- 32.5 --
DEQA2 (85% active in ethanol) 15.3 -- 32.5
DEQA3 (85% active in ethanol) 15.3 17.5 17.5
Ethanol 2 2 2
Irganox~ 3125 0.02 0.03 0.03
DTPA 0.1 0.1 0.1
1,2-Hexanediol 18 28 28
Pro-accord '~ 1.35 1.3 1.3
HCl (pH 2.5-4.0) 0.005 0.005 0.005
Distilled Water balancebalance balance
CA 02307892 2000-04-28
WO 99/21954 PCT/1B98/01632
1. N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the
tallow
chains are at least partially unsaturated.
2. N,N-di(canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chloride.
3. N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium chloride.
4. Pro-accord according to Example 1.
TABLE V
weight
Ingredients 19 20 21
DEQA 1 (85% active in ethanol/hexylene30.6 30.6 --
glycol)
DEQA~ (85% active in ethanol/hexylene__ -- 30.6
glycol 1:1)
2,2,4-Trimethylpentane-1,3-diol 15.0 -- 12.0
Irganox~ 3125 0.01 0.01 0.01
DTPA 0.01 0.01 0.01
2-Ethyl-1,3-hexanediol -- 1 S.0 --
1,4-Cyclohexanedimethanol 5.0 5.0 S.0
Pro-accord ~ 2.5 2.5 2.5
HCl (pH 2.5-4.0) 0.005 0.005 0.005
Distilled Water balance balance balance
1. N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where the
tallow
chains are at least partially unsaturated.
2. N,N-di{canoloyl-oxy-ethyl)-N,N-dimethyl ammonium chloride.
3. Tris(citronellyl) orthoformate.
