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Patent 2330473 Summary

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(12) Patent Application: (11) CA 2330473
(54) English Title: WRINKLE REDUCING COMPOSITION
(54) French Title: COMPOSITION DE REDUCTION DES PLIS
Status: Dead
Bibliographic Data
(51) International Patent Classification (IPC):
  • D06M 13/148 (2006.01)
  • C11D 3/00 (2006.01)
  • C11D 3/02 (2006.01)
  • C11D 3/20 (2006.01)
  • C11D 11/00 (2006.01)
  • D06M 11/13 (2006.01)
  • D06M 11/155 (2006.01)
  • D06M 11/56 (2006.01)
  • D06M 11/65 (2006.01)
  • D06M 11/76 (2006.01)
  • D06M 11/82 (2006.01)
  • D06M 13/17 (2006.01)
  • D06M 13/175 (2006.01)
  • D06M 13/184 (2006.01)
  • D06M 13/207 (2006.01)
  • D06M 13/224 (2006.01)
  • D06M 13/46 (2006.01)
  • D06M 13/463 (2006.01)
  • D06M 13/467 (2006.01)
  • D06M 15/03 (2006.01)
  • D06M 15/53 (2006.01)
  • D06M 15/647 (2006.01)
  • D06M 23/06 (2006.01)
(72) Inventors :
  • HUBESCH, BRUNO ALBERT JEAN (Belgium)
  • THOEN, CHRISTIAAN ARTHUR JACQUES KAMIEL (United States of America)
  • VERMOTE, CHRISTIAN LEO MARIE (Belgium)
  • WOO, RICKY AH-MAN (United States of America)
(73) Owners :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(71) Applicants :
  • THE PROCTER & GAMBLE COMPANY (United States of America)
(74) Agent: KIRBY EADES GALE BAKER
(74) Associate agent:
(45) Issued:
(86) PCT Filing Date: 1998-04-27
(87) Open to Public Inspection: 1999-11-04
Examination requested: 2000-10-26
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US1998/008125
(87) International Publication Number: WO1999/055948
(85) National Entry: 2000-10-26

(30) Application Priority Data: None

Abstracts

English Abstract




There are provided wrinkle reducing compositions and method for treating
fabrics in order to improve various properties of fabrics, in particular,
reduction or removal of unwanted wrinkles, by means of an aqueous composition
comprising a nonionic polyhydric alcohol humectant and a salt.


French Abstract

L'invention concerne des compositions de réduction des plis, et un procédé de traitement de tissus permettant d'améliorer diverses propriétés des tissus, en particulier la réduction ou l'élimination de plis indésirables, à l'aide d'une composition aqueuse comprenant un humectant à l'alcool polyhydrique non ionique et un sel.

Claims

Note: Claims are shown in the official language in which they were submitted.



57

Claims

1-A wrinkle reducing composition, comprising:
A. a wrinkle reducing active, comprising a nonionic polyhydric alcohol
humectant and a salt made of alkaline and/or earth alkaline metal,
and
B. a liquid aqueous carrier.
2-A composition according to Claim 1, wherein said nonionic polyhydric alcohol
humectant is a polyol having from 2 to 8 hydroxy groups, preferably said
humectant is selected from glycerol, ethylene glycol, propylene glycol,
diethylene
glycol, dipropylene glycol, sorbitol, erythritol or mixtures thereof.

3- A composition according to either one of Claim 1 or 2, wherein the nonionic
humectant is present in amount of from 0.1 to 10% by weight, preferably from
0.1 to 5%, more preferably from 0.1 % to 1.5% by weight of the composition.

4-A composition according to any one of Claims 1-3, wherein said salt is
selected
from salts selected from sodium, calcium, potassium, magnesium and mixtures
thereof; more preferably salt of sodium, calcium, and mixtures thereof.

5-A composition according to any one of Claim 1-4, wherein said salt is
present
in an amount of from 0.1 to 10% by weight, preferably from 0.1 to 5%, more
preferably from 0.1% to 1.5% by weight of the composition.

6-A composition according to any one of Claim 1-5, wherein the water of the
liquid aqueous carrier comprises from 50% to 95%, by weight of the
composition,
preferably from 60% to 97%, more preferably from 70% to 99%, by weight of the
composition.

7-A composition according to any one of Claim 1-6, wherein said composition
further comprises a water soluble wetting agent.

8- A composition according to Claim 7, wherein said wetting agent is a
cationic
surfactant, preferably of formula:

[R1N+R3) X-





58

wherein R1 is C10-C22 hydrocarbon group, or the corresponding ester linkage
interrupted group with a C1-C4 alkylene group between the ester linkage and
the
N, each R is a C1-C4 alkyl or substituted alkyl, or hydrogen, and the
counterion
X- is a softener compatible anion.

9- A composition according to Claim 7, wherein said cationic surfactant is a
choline ester, preferably of formula:

Image

wherein R1 is a C10-C22, preferably a C12-C14 linear or branched alkyl,
alkenyl
or alkaryl chain or M-. N+(R6R7R8)(CH2)s; X and Y, independently, are selected
from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH
and NHCOO wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or
NHCOO group; R2, R3, R4, R6, R7, and R8 are independently selected from the
group consisting of alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups
having from 1 to 4 carbon atoms and alkaryl groups; and R5 is independently H
or a C1-C3 alkyl group; wherein the values of m, n, s and t independently lie
in
the range of from 0 to 8, the value of b lies in the range from 0 to 20, and
the
values of a, u and v independently are either 0 or 1 with the proviso that at
least
one of a or v must be 1; and wherein M is a counter anion.

10-A composition according to Claim 7, wherein said wetting agent is a
nonionic
surfactant, preferably a polyalkyleneoxide polysiloxane surfactant, a block
copolymer of ethylene oxide and propylene oxide based on ethylene glycol,
propylene glycol, glycerol, trimethylolpropane, or ethylenediamine, and
mixtures
thereof.

11-A composition according to Claim 7, wherein said wetting agent is an
anionic
surfactant, preferably an alkylsulphosuccinate surfactant.





59

12-A composition according to any one of Claim 7-11, wherein said wetting
agent
is present in an amount of from 0.1 to 10% by weight, preferably from 0.1 to
5%,
more preferably from 0.1% to 1.5% by weight of the composition.

13-A composition according to any one of Claims 1-12, wherein said composition
further comprises a lubricant selected from a water-insoluble cationic
softener,
nonionic softener selected from cyclomethicones, fatty acid esters of mono- or
polyhydric alcohols or anhydride thereof containing from 1 to 8 carbon atoms.

14- A composition according to any one of Claim 1-13, wherein said composition
further comprises an uncomplexed cyclodextrin, preferably selected from
beta-cyclodextrin, alpha-cyclodextrin, gamma-cyclodextrin, derivatives of said
cyclodextrins, and mixtures thereof.

15- A composition according to any one of Claim 1-14, wherein said composition
has a fluid surface tension of from about 20 dynes/cm to about 55 dynes/cm.

16- A composition according to any one of Claim 1-15, wherein said composition
has a fluid viscosity of from about 1 cps to about 50 cps.

17-A method for reducing or removing wrinkles on fabrics which comprises the
steps of contacting the fabrics with a composition as defined in any one of
Claims
1-16.

18- A method for reducing or removing wrinkles on fabrics which comprises the
steps of contacting the fabrics with a nonionic polyhydric alcohol humectant,
preferably a nonionic polyhydric alcohol humectant as defined in Claim 2.

19- A method for reducing or removing wrinkles on fabrics and malodours on
fabrics which comprises the steps of contacting the fabrics with a composition
as
defined in Claim 14.

20-A method according to anyone of Claim 17-19, wherein the composition is
contacted with the fabrics by means of a spray dispenser.





60

21-A method according to anyone of Claim 17-20, wherein the fabrics are placed
into a dewrinkling apparatus.

22-A method according to Claim 21, wherein the apparatus comprises spraying
means capable of providing droplets with a mean diameter of 3 to 50 µm.

23-A packaged composition comprising the composition of any one of Claims
1-16, in a spray dispenser.

24-A packaged composition according to Claim 23 or method according to Claim
20, wherein said spray dispenser comprises a trigger spray device and is
capable of providing droplets with a weight average diameter of from 8 to 100
µm.


Description

Note: Descriptions are shown in the official language in which they were submitted.



CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
WRINKLE REDUCING COMPOSITION
10
Field of the invention
The present invention relates to fabric care compositions and to a method for
treating fabrics in order to improve various properties of fabrics, in
particular,
reduction or removal of unwanted wrinkles.
Background of the invention
Wrinkles in fabrics are caused by the bending and creasing of the textile
material
which places an external portion of a filament in a yarn under tension while
the
internal portion of that filament in the yarn is placed under compression.
Particularly with cotton fabrics, the hydrogen bonding that occurs between the
cellulose molecules contributes to keeping wrinkles in place. The wrinkling of
fabric, in particular clothing, is therefore subject to the inherent tensional
elastic
deformation and recovery properties of the fibers which constitute the yarn
and
fabrics.
In the modern world, with the increase of hustle and bustle and travel, there
is a
demand for a quick fix which will help to diminish the labor involved in home
laundering and/or the cost and time involved in dry cleaning or commercial


CA 02330473 2000-10-26
WO 99/55948 PCT/LTS98/08125
2
laundering. This has brought additional pressure to bear on textile
technologists
to produce a product that will sufficiently reduce wrinkles in fabrics,
especially
clothing, and to produce a good appearance through a simple, convenient
application of a product.
The present invention reduces wrinkles from fabrics, including clothing, dry
cleanables, and draperies, without the need for ironing. The present invention
can be used on damp or dry clothing to relax wrinkles and give clothes a ready
to
wear look that is demanded by today's fast paced world. The present invention
also essentially eliminates the need for touch up ironing usually associated
with
closet, drawer, and suitcase storage of garments.
When ironing is desired however, the present invention can also act as an
excellent ironing aid. The present invention makes the task of ironing easier
and
faster by creating less iron drag. When used as an ironing aid, the
composition
of the present invention produces a crisp, smooth appearance.
An additional benefit of the composition of the present invention is an
improved
garment shape, body and crispness.
A further additional benefit to invention composition is the variety of fabric
that
can be treated from the more resistant to the more delicate including fabric
made
of cotton, polycotton, polyester, viscose, rayon, silk, wool, etc...
Summary of the invention
The present invention relates to a wrinkle reducing composition, comprising:
A. a wrinkle reducing active, comprising a nonionic polyhydric alcohol
humectant and a salt made of alkaline and/or earth alkaline metal,
and
B. a liquid aqueous carrier.


CA 02330473 2000-10-26
WO 99/55948 PCTNS98/08125
3
In another aspect of the invention, there is provided a packaged composition
comprising the composition of the invention in a spray dispenser.
Still in a further aspect of the invention, there is a method of reducing the
wrinkles on fabrics which comprises the steps of contacting the fabrics with a
composition of the invention.
Detailed description of the invention
A. Wrinkle reducing actives
1- Nonionic polyhydric alcohol hum~ctant
The present invention, in one aspect uses a nonionic humectant of the
polyhydric
alcohol type. Typical of these compounds are the low molecular weight polyols.
Low molecular weight polyols with relatively high boiling points, as compared
to
water, are essential ingredients of the composition of the present invention.
By "low molecular weight", it is meant that the compounds preferably have a
molecular weight below 1000, preferably from 50 to 500, more preferably from
55
to 200.
Preferably, these polyols are short chain. By "short chain ", it is meant that
the
compounds have a carbon chain length of less than 10 carbon atoms, preferably
less than 8 carbon atoms.
Not to be bound by theory, it is believed that the incorporation of a small
amount
of nonionic polyhydric alcohol humectant into the compositions containing the
water-soluble wetting agent reinforces the hydrogen breaking process as well
as
reducing the fabric drying rate, thereby allowing more time to the fabric to
relax.
Preferred polyols for use herein are selected from polyols having from 2 to 8
hydroxy groups.


CA 02330473 2000-10-26
WO 99/55948 PCTNS98/08125
4
Preferably the glycol used is glycerol, ethylene glycol, propylene glycol,
diethylene glycol, dipropylene glycol, sorbitol, erythritol or mixtures
thereof, more
preferably diethylene glycol, ethylene glycol, propylene glycol, dipropylene
giycol
and mixtures thereof.
Some polyols, e.g., dipropylene glycol, are also useful to facilitate the
solubilization of some perfume ingredients in the composition of the present
invention. Both diethylene glycol and dipropylene glycol are favored for use
herein as it provides non-stickiness properties on hard surfaces andlor
fabrics.
The humectant is present in the composition in a sufficient amount to result
in an
amount of from 0.005% to 5%, preferably from 0.01 % to 3%, more preferably
from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Typically, the humectant is added to the composition of the present invention
at a
level of from about 0.01 % to about 10%, by weight of the composition,
preferably
from about 0.1 % to about 3%, more preferably from about 0.1 % to about 1.5%,
by weight of the composition.
2-Salt
The present invention in one aspect uses a salt to contribute to the hydrogen
bond breaking process produces by the water. It also reinforces the wetting
power of any present water-soluble surfactant, if present. The salt is further
believed to facilitate the dewrinkling action by maintaining a residual
humidity of
fibers.
The salt useful in the present invention is made of alkaline and/or earth
alkaline
metal, and is a compound that can form hydrates upon crystallization.
Typically,
the salt for use in the present invention have the following formula: AM;
wherein A is a cation. This cation is an alkaline and/or earth alkaline metal,
preferably selected from sodium, calcium, potassium, magnesium; more
preferably sodium and calcium, and
wherein M is a couteranion selected from sulfate, chloride, nitrate,
carbonate,
borate, and carboxylates.


CA 02330473 2000-10-26
WO 99/55948 PCT/US98108125
Preferred salts are salts selected from sodium, calcium, potassium, magnesium
and mixtures thereof; more preferably salt of sodium, calcium, and mixtures
thereof.
5 Particularly preferred salts for use herein are selected from sodium
sulphate,
sodium bicarbonate, sodium chloride, sodium borate, potassium sulphate,
calcium chloride, sodium citrate, magnesium sulphate, and mixtures thereof,
more preferably are selected from sodium sulphate, sodium bicarbonate,
potassium sulphate, calcium chloride, and mixtures thereof.
The salt is present in the composition in a sufficient amount to result in an
amount of from 0.005% to 5%, preferably from 0.01 % to 3%, more preferably
from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Accordingly, typical levels of the salt in the composition are from 0.01 % to
about
10%, by weight of the composition, preferably from about 0.1 % to about 3%,
more preferably from about 0.1% to about 1.5%, by weight of the composition.
B. Liquid Carrier
The liquid carrier used in the composition of the present invention is an
aqueous
system comprising water. Optionally, but not preferably, in addition to the
water,
the carrier can contain a low molecular weight organic solvent that is highly
soluble in water, e.g., C1-C4 monohydric alcohols, alkylene carbonates, and
mixtures thereof. Examples of these water-soluble solvents include ethanol,
propanol, isopropanol, etc. Water is the main liquid carrier due to its low
cost,
availability, safety, and environmental compatibility. Water can be distilled,
deionized, or tap water.
The level of liquid carrier in the compositions of the present invention is
typically
greater than 80%, preferably greater than 90%, more preferably greater than
95%, by weight of the composition. When a concentrated composition is used,
the level of liquid carrier is typically from 50% to 95%, by weight of the
composition, preferably from 60% to 97%, more preferably from 70% to 99%, by
weight of the composition.


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
6
C. Optional Ingredients
1- Water soluble wetting agent
A water-soluble wetting agent is a preferred optional ingredient of the
composition of the present invention. The wetting agent for use herein are
selected from a cationic surfactant, a nonionic surfactant and an anionic
surfactant. Further suitable wetting agents are the zwiterrionic surfactants
such
as the betaine or sulphobetaine surfactants commercially available from Seppic
and Albright 8~ Wilson respectively, under the trade name of Amonyl 265~ and
Empigen~ BB/L. These wetting agent facilitates the action of water. Indeed,
the
water penetrates into the fabric where it breaks hydrogen bonds between fibers
resulting in fiber relaxation. By use of the wetting agent, the water action
is
further facilitated via the wetting properties of the water soluble
surfactant.
By "water-soluble wetting agent", it is meant that the wetting agent forms
substantially clear, isotropic solutions when dissolved in water at 0.2 weight
percent at 25°C.
Water-soluble cationic surfactant
Any type of water-soluble cationic surfactant can be used to impart the
wetting
property. However, some water-soluble cationic surfactants and mixtures
thereof
are more preferred. Hence, it is preferred that the cationic surfactant is a
surface-
active molecule with a linear or branched hydrophobic tail and a positively
charged hydrophilic head group, more preferably, the cationic surfactant for
use
in the present invention is quaternary ammonium salt of formula:
[R'N+R3] X-
wherein the R' group is C,o-C22 hydrocarbon group, preferably C,2-C,e alkyl
group
or the corresponding ester linkage interrupted group with a short alkylene (C,-
C4)
group between the ester linkage and the N, and having a similar hydrocarbon
group, e.g., a fatty acid ester of choline, preferably C,2-C,4 (coco) choline
ester
and/or C,e-C,e tallow choline ester. The hydrocarbon group may be interrupted
by
further groups like COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and
NHCOO. Each R is a C,-C4 alkyl or substituted (e.g., hydroxy) alkyl, or


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
7
hydrogen, preferably methyl, and the counterion X- is a softener compatible
anion, for example, chloride, bromide, methyl sulfate, etc.
The long chain group R1, of the single-long-chain-alkyl surfactant, typically
contains an alkylene group having from 10 to 22 carbon atoms, preferably from
12 to about 1 fi carbon atoms, more preferably from 12 to 18 carbon atoms.
This
R1 group can be attached to the cationic nitrogen atom through a group
containing one, or more, ester, amide, ether, amine, etc., preferably ester,
linking
groups which can be desirable for increased hydrophilicity, biodegradability,
etc.
Such linking groups are preferably within about three carbon atoms of the
nitrogen atom. A preferred cationic surfactant of this type is N,N dimethyl-N-
(2-
hydroxyethyl)-N-dodecyl/tetradecyl ammonium bromide.
If the corresponding, non-quaternary amines are used, any acid (preferably a
mineral or poiycarboxylic acid) which is added to keep the ester groups stable
will also keep the amine protonated in the compositions.
Typical disclosure of these cationic surfactants suitable for use in the
present
invention are the choline ester surfactants of formula:
R2
i _
R1- (CH)n0 ___ (X)u __ ( C H 2 )m (Y)~ (C H 2 )t -N ~ R3 M
b
a I
R4
wherein R1 is a C10-C22 linear or branched alkyl, alkenyl or alkaryl chain or
M-.
N+(RgR~Rg)(CH2)s; X and Y, independently, are selected from the group
consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO
wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO
group; R2, R3, R4, R6, R7, and Rg are independently selected from the group
consisting of alkyl, alkenyl, hydroxyalkyl and hydroxy-alkenyl groups having
from
1 to 4 carbon atoms and alkaryl groups; and R5 is independently H or a C1-Cg
alkyl group; wherein the values of m, n, s and t independently lie in the
range of
from 0 to 8, the value of b lies in the range from 0 to 20, and the values of
a, a


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
8
and v independently are either 0 or 1 with the proviso that at least one of a
or v
must be 1; and wherein M is a counter anion.
Preferably M is selected from the group consisting of halide, methyl sulfate,
sulfate, and nitrate, more preferably methyl sulfate, chloride, bromide or
iodide.
A preferred choline ester surfactant is selected from those having the
formula:
R2
R5
R1 O (CH)n0 _.__._ (X) ~_ (CH2)m _._ N ~ R3 M_
b
a
R4
wherein R1 is a C10-C22, preferably a C12-C14 linear or branched alkyl,
alkenyl
or alkaryl chain; X is selected from the group consisting of COO, OCO, OCOO,
OCONH and NHCOO; R2, Rg, and R4 are independently selected from the
group consisting of alkyl and hydroxyalkyl groups having from 1 to 4 carbon
atoms; and R5 is independently H or a C1-Cg alkyl group; wherein the value of
n
lies in the range of from 0 to 8, the value of b lies in the range from 0 to
20, the
value of a is either 0 or 1, and the value of m is from 3 to 8.
More preferably R2, R3 and R4 are independently selected from a C1-C4 alkyl
group and a C1-C4 hydroxyalkyl group. In one preferred aspect at least one,
preferably only one of R2, R3 and R4 is a hydroxyalkyl group. The hydroxyalkyl
preferably has from 1 to 4 carbon atoms, more preferably 2 or 3 carbon atoms,
most preferably 2 carbon atoms. In another preferred aspect at least one of
R2,
Rg and R4 is a C2-C3 alkyl group, more preferably two C2-Cg alkyl groups are
present.
Highly preferred water soluble choline ester surfactants are the esters having
the
formula:


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
9
O CH3
~i
R1--C-O-(CH2)m.-N+-CH3 M-
CH3
where m is from 1 to 4, preferably 2 or 3 and wherein R1 is a C11-C19,
preferably a C12-C14 linear or branched alkyl chain.
Particularly preferred choline esters of this type include the stearoyl
choline ester
quaternary methylammonium halides (R1=C17 alkyl), palmitoyl choline ester
quaternary methylammonium halides (R1=C15 alkyl), myristoyl choline ester
quaternary methylammonium halides (R1=C13 alkyl), lauroyl choline ester
methylammonium halides (R1=C11 alkyl), cocoyl choiine ester quaternary
methylammonium halides (R1=C11_C1g alkyl), tallowyl choline ester quaternary
methylammonium halides (R1=C15_C1~ alkyl), and any mixtures thereof.
Most particularly preferred choline esters of this type are selected from
myristoyl
choline ester quaternary methylammonium halides, lauroyl choline ester
methylammonium halides, cocoyl choline ester quaternary methylammonium
halides, and any mixtures thereof.
Other suitable choline ester surfactants have the structural formulas below,
wherein d may be from 0 to 20.
O CH3
R -O-~-( CH )-C-O-CH CH -N~ CH M
1 2 d 2 2 I 3
CH3
CH3 O O CH3
M CH3-N ~ CH2-CH2-O-C-( CH2 ) a C-O-CH2-CH2-N~ CH3M
CH3 CH3
The particularly preferred choline esters, given above, may be prepared by the
direct esterification of a fatty acid of the desired chain length with
dimethylaminoethanol, in the presence of an acid catalyst. The reaction
product


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
is then quaternized with a methyl halide, preferably in the presence of a
solvent
such as ethanol, water, propylene glycol or preferably a fatty alcohol
ethoxylate
such as C1p-C1g fatty alcohol ethoxylate having a degree of ethoxylation of
from
3 to 50 ethoxy groups per mole forming the desired cationic material. They may
5 also be prepared by the direct esterification of a long chain fatty acid of
the
desired chain Length together with 2-haloethanol, in the presence of an acid
catalyst material. The reaction product is then quaternized with
trimethylamine,
forming the desired cationic material.
10 Still other suitable water-soluble cationic surfactants for use in the
present
invention are the cationic materials with ring structures such as alkyl
imidazoline,
imdazolinium, pyridine, and pyridinium salts having a single C,2-C3o alkyl
chain
can also be used.
Some alkyl imidazolinium salts useful in the present invention have the
general
formula:
CHZ CHZ
N N+ - C2H4 Y2 R7 X_
C R6
Rg
wherein Y2 is -C(O)-O-, -O-(O)-C-, -C(O)-N(R5), or -N(R5)-C(O)- in which R5 is
hydrogen or a C,-C4 alkyl radical; Re is a C,-C4 alkyl radical; R' and Ra are
each
independently selected from R and R2 as defined hereinbefore for the single-
long-chain cationic surfactant with only one being R2.
Some alkyl pyridinium salts useful in the present invention have the general
formula:
R2


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
11
wherein RZ and X' are as defined above. A typical material of this type is
cetyl
pyridinium chloride.
Water-soluble nonionic surfactant
Suitable wetting agents are the nonionic surfactants. Typical of these
surfactants
are the alkoxylated surfactants. It provides a low surface tension that
permits the
composition to spread readily and more uniformly on hydrophobic surfaces like
polyester and nylon. Said surfactant is preferably included when the
composition
is used in a spray dispenser in order to enhance the spray characteristics of
the
composition and allow the composition to distribute more evenly, and to
prevent
clogging of the spray apparatus. The spreading of the composition also allows
it
to dry faster, so that the treated material is ready to use sooner. For
concentrated
compositions, the surfactant facilitates the dispersion of many actives such
as
antimicrobial actives and perfumes in the concentrated aqueous compositions.
Nonlimiting examples of nonionic alkoxylated surfactants include addition
products of ethylene oxide with fatty alcohols, fatty acids, fatty amines,
etc.
Optionally, addition products of propylene oxide with fatty alcohols, fatty
acids,
fatty amines may be used.
Suitable compounds are surfactants of the general formula:
R2 - Y - (C2H40)z - C2H40H
wherein R2 is selected from the group consisting of primary, secondary and
branched chain alkyl andlor acyl hydrocarbyl groups; primary, secondary and
branched chain alkenyl hydrocarbyl groups; and primary, secondary and
branched chain alkyl- and alkenyl-substituted phenolic hydrocarbyl groups;
said
hydrocarbyl groups preferably having a hydrocarbyl chain length of from 6 to
20,
preferably from 8 to 18 carbon atoms. More preferably the hydrocarbyl chain
length is from 10 to 18 carbon atoms. In the general formula for the
ethoxylated
nonionic surfactants herein, Y is -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-, in
which R, when present, is R2 or hydrogen, and z is at least 2, preferably at
least
4, more preferably from 5 to 11.
The nonionic surfactants herein are characterised by an HLB (hydrophilic-
iipophilic balance) of from 7 to 20, preferably from 8 to 15. Of course, by
defining
R2 and the number of ethoxylate groups, the HLB of the surfactant is, in
general,


CA 02330473 2000-10-26
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12
determined. However, it is to be noted that the nonionic ethoxylated
surfactants
useful herein contain relatively long chain R2 groups and are relatively
highly
ethoxylated. While shorter alkyl chain surfactants having short ethoxylated
groups may possess the requisite HLB, they are not as effective herein.
Examples of nonionic surfactants follow. The nonionic surfactants of this
invention are not limited to these examples. In the examples, the integer
defines
the number of ethoxyl {EO) groups in the molecule.
a. Straight-Chain. Primar)i Alcohol Alkoxylates
The tri-, penta-, hepta-ethoxylates of dodecanol, and tetradecanol are useful
surfactants in the context of this invention. The ethoxylates of mixed natural
or
synthetic alcohols in the "coco" chain length range are also useful herein.
Commercially available straight-chain, primary alcohol alkoxylates for use
herein
are available under the tradename Marlipal~ 24/70, Marlipal 24/100, Marlipal
24/150 from Huls, and Genapol~ C-050 from Hoechst.
b. Straight-Chain, Secondary Alcohol Alkoxylates
The tri-, penta-, hepta-ethoxylates of 3-hexadecanol, 2-octadecanol, 4-
eicosanol,
and 5-eicosanol are useful surfactants in the context of this invention.
A commercially available straight-chain secondary alcohol ethoxylate for use
herein is the material marketed under the tradename Tergitol 15-S-7 from Union
Carbide, which comprises a mixture of secondary alcohols having an average
hydrocarbyl chain length of 11 to 15 carbon atoms condensed with an average 7
moles of ethylene oxide per mole equivalent of alcohol. Still another suitable
commercially available straight-chain secondary alcohol ethoxyiate for use
herein
is the material marketed under the tradename Softanol obtainable from BP
Chemicals Ltd. or Nippon Catalytic of Japan. Particularly useful herein are
Softanol 50, Softanol 90, which comprises a mixture of linear secondary
alcohol
having an average hydrocarbyl chain length of 11 to 16 carbon atoms condensed
with an average of 5 to 10 moles of ethylene oxide per mole equivalent of
alcohol.
c. Alkyl Phenol Alkoxvlates


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13
Suitable alkyl phenol alkoxylates are the polyethylene oxide condensates of
alkyl
phenols, e.g., the condensation products of alkyl phenols having an alkyl or
alkenyl group containing from 6 to 20 carbon atoms in a primary, secondary or
branched chain configuration, preferably from 8 to 12 carbon atoms, with
ethylene oxide, the said ethylene oxide being preferably present in amounts
equal to 3 to 11 moles of ethylene oxide per mole of alkyl phenol. The alkyl
substituent in such compounds may be derived from polymerized propylene,
diisobutylene, octane, and nonane.
Examples of this type of nonionic surfactants include Triton N-57~ a nonyl
phenol ethoxylate {5E0) from Rohm & Haas, Dowfax~ 9N5 from Dow and
Lutensol~ AP6 from BASF.
d. Olefinic Alkoxylates
The alkenyl alcohols, both primary and secondary, and alkenyl phenols
corresponding to those disclosed immediately hereinabove can be ethoxylated
and used as surfactants.
Commercially available olefinic alkoxylates for use herein are available under
the
tradename Genapol O-050 from Hoechst.
e. Branched Chain Alkoxylates
Branched chain primary and secondary alcohols ( or Guerbet alcohols) which
may be available from the well-known "OXO" process or modification thereof can
be ethoxylated.
Particularly preferred among these ethoxylates of the primary OXO alcohofs are
the surfactants marketed under the name Lutensol by BASF or Dobanol by the
Shell Chemicals, U.K., LTD. The preferred Dobanols are primary alcohols with
hydrocarbyl groups of 9 to 15 carbon atoms, with the majority having a
hydrocarbyl group of 13 carbon atoms. Particularly preferred are Dobanols with
an average degree of ethoxylation of 3 to 11, and preferably 7 on the average.
An example of this type of material is an aliphatic alcohol ethylene oxide
condensate having from 3 to less than 9 moles of ethylene oxide per mole of
aliphatic alcohol, the aliphatic alcohol fraction having from 9 to 14 carbon
atoms.
Other examples of this type of nonionic surfactants include certain of the
commercially available Dobanol~, Neodolc,~ marketed by Shell, Lutensol~ from
BASF, or Lial~ from Enichem. For example Dobanol~ 23.5 (C12-C13 E05),


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14
Dobanol~ 91.5 (C9-C11 EO 5), Neodol 45 E5, and Lial-145.7 EO (oxo C 14 15
alcohol + 7.0 mol of EO), Lial 111 EO 6 and Isalchem 123 series from Enichem.
Other suitable nonionic alkoxylated surfactants are alkyl amines alkoxylated
with
at least 5 alkoxy moieties. Typical of this class of compounds are the
surfactants
derived from the condensation of ethylene oxide with an hydrophobic alkyl
amine
product. Preferably the hydrophobic alkyl group, has from 6 to 22 carbon
atoms.
Preferably, the alkyl amine is alkoxylated with 10 to 40, and more preferably
20
to 30 alkoxy moieties.
Example of this type of nonionic surfactants are the alkyl amine ethoxylate
commercially available under the tradename Genamin from Hoechst. Suitable
example for use herein are Genamin C-100, Genamin O-150, and Genamin S-
200.
Still other suitable type of nonionic surfactant among this class are the
N,N',N'-
polyoxyethylene (12)-N-tallow 1,3 diaminopropane commercialised under the
tradename Ethoduomeen T22 from Akzo, and Synprolam from ICI.
Further suitable nonionic surfactants are the alkyl amide surfactants.
Still further nonionic surfactants which may be of use herein are the
polyhydroxyfatty acid surfactants as described in EP-A-659870.
Further nonlimiting examples of nonionic alkoxylated surfactants include the
surfactant which are cyclodextrin-compatible, that is it should not
substantially
form a complex with the cyclodextrin so as to diminish performance of the
cyclodextrin and/or the surfactant. Complex formation diminishes both the
ability
of the cyclodextrin to absorb odors and the ability of the surfactant to lower
the
surface tension of the aqueous composition. This include block copolymers of
ethylene oxide and propylene oxide. Suitable block polyoxyethylene-
polyoxypropylene polymeric surfactants, that are compatible with most
cyclodextrins, include those based on ethylene glycol, propylene glycol,
glycerol,
trimethylolpropane and ethylenediamine as the initial reactive hydrogen
compound. Polymeric compounds made from a sequential ethoxylation and
propoxylation of initial compounds with a single reactive hydrogen atom, such
as


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C12_1 g aliphatic alcohols, are not generally compatible with the
cyclodextrin.
Certain of the block polymer surtactant compounds designated Pluronic~ and
Tetronic~ by the BASF-Wyandotte Corp., Wyandotte, Michigan, are readily
available.
5
Non limiting examples of surfactants of this type include:
Pluronic Surfactants with the general formula H(EO)n(PO)m(EO)nH,
wherein EO is an ethylene oxide group, PO is a propylene oxide group, and n
10 and m are numbers that indicate the average number of the groups in the
surfactants. Typical examples of cyclodextrin-compatible Pluronic surfactants
are:


Name Average MW Average n Average m


L-44 2,200 10 23


15 L-43 1,850 6 22


F-38 4,700 43 16


P-84 4,200 19 43,


and mixtures thereof.
Tetronic Surfactants with the general formula:
H(EO)n(PO) ~ ,(p0)m(EO)nH
NCH2CH2N
H(EO)n(PO)rri ~((PO)m(EO)nH
wherein EO, PO, n, and m have the same meanings as above. Typical
examples of cyclodextrin-compatible Tetronic surfactants are:
Name Average MW Average n Average m
901 4,700 3 18
908 25,000 114 22,
and mixtures thereof.
"Reverse" Piuronic and Tetronic surfactants have the following general
formulas:
Reverse Pluronic Surfactants H(PO)m(EO)n(PO)mH


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16
Reverse Tetronic Surfactants
H(PO)n(EO)~ /(EO)m(PO)nH
NCH2CH2N
H(PO)n(EO)~i ~ (EO)m(PO)nH
wherein EO, PO, n, and m have the same meanings as above. Typical


examples of Reverse Pluronic
and Reverse Tetronic surfactants
are:


Reverse Pluronic surfactants:


Narne Average MW Average n Average m


10 R5 1,950 8 22


25 R1 2,700 21 6


Reverse Tetronic surfactants


Name Average MW Average n Average m


130 R2 7,740 9 26


70 R2 3,$70 4 13


and mixtures thereof. .


The silicone surfactants
A preferred class of nonionic alkoxylated surfactants are the
polyalkyleneoxide
polysiloxanes having a dimethyl polysiloxane hydrophobic moiety and one or
more
hydrophilic polyalkylene side chains. Examples of this type of surfactants are
the
Silwet~ surfactants which are available OSi Specialties, Inc., Danbury,
Connecticut, and have the general formula:
I H3 CH3


(CH3)3Si0-(Si0)a-(Si0)b-Si(CH3)3


CH3 Rl


wherein a + b are from about 1 to about 50, preferably from about 3 to about
30 ,
more preferably from about 10 to about 25, and R1 is mainly one or more random
poly(ethyleneoxide/propyleneoxide) copolymer groups having the general
formula:
-(CH2)n O(C2 H4 O)c (C3 H6 O)d RZ
wherein n is 3 or 4, preferably 3; total c (for all polyalkyleneoxy side
groups) has a
value of from 1 to about 100, preferably from about 6 to about 100; total d is
from


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
17
0 to about 14, preferably from 0 to about 3; and more preferably d is 0; total
c+d
has a value of from about 5 to about 150, preferably from about 9 to about 100
and each R2 is the same or different and is selected from the group consisting
of
hydrogen, an alkyl having 1 to 4 carbon atoms, and an acetyl group, preferably
hydrogen and methyl group.
Representative Silwet surfactants are as follows.
Name Average MW Average a+b Average total
c


L-7608 600 1 9


L-7607 1,000 2 17


L-77 600 1 9


L-7605 6,000 20 99


L-7604 4,000 21 53


L-7600 4,000 11 68


L-7657 5,000 20 76


L-7602 3,000 20 29


The molecular weight of the polyalkyleneoxy group (R1 ) is less than or equal
to
about 10,000. Preferably, the molecular weight of the polyalkyleneoxy group is
less than or equal to about 8,000, and most preferably ranges from about 300
to
about 5,000. Thus, the values of c and d can be those numbers which provide
molecular weights within these ranges. However, the number of ethyleneoxy
units
(-C2H40) in the polyether chain (R1 ) must be sufficient to render the
polyalkyleneoxide polysiloxane water dispersible or water soluble. If
propyleneoxy
groups are present in the polyalkylenoxy chain, they can be distributed
randomly
in the chain or exist as blocks. Preferred Silwet surfactants are L-7600, L-
7602,
L-7604, L-7605, L-7657, and mixtures thereof. Besides surface activity,
polyalkyleneoxide polysiloxane surfactants can also provide other benefits,
such
as antistatic benefits, lubricity and softness to fabrics.
The preparation of polyalkyleneoxide polysiloxanes is well known in the art.
Polyalkyleneoxide polysiloxanes of the present invention can be prepared
according to the procedure set forth in U.S. Pat. No. 3,299,112, incorporated
herein by reference. Typically, polyalkyleneoxide polysiloxanes of the
surfactant
blend of the present invention are readily prepared by an addition reaction
between a hydrosiloxane (i.e., a siloxane containing silicon-bonded hydrogen)
and an alkenyl ether (e.g., a vinyl, allyl, or methallyl ether) of an alkoxy
or


CA 02330473 2000-10-26
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18
hydroxy end-blocked polyalkylene oxide). The reaction conditions employed in
addition reactions of this type are well known in the art and in general
involve
heating the reactants (e.g., at a temperature of from about 85° C. to
110° C.) in
the presence of a platinum catalyst (e.g., chloroplatinic acid) and a solvent
(e.g.,
toluene).
The above ethoxylated nonionic surfactants are useful in the present process
invention alone or in combination, and the term "nonionic surfactant"
encompasses mixed nonionic surface active agents.
Water-soluble anionic surfactant
Still suitable wetting agents are the anionic surfactants. Suitable anionic
surfactants for the purpose of the invention include the alkyl sulphates
(RS04),
alkyl ether sulphates (R(OCH2CH2)eS04), alkyl sulphonates (RS03), alkyl
succinates (ROOCCH2CH2COOZ), alkyl carboxylates (RCOOM), alkyl ether
carboxylates (R(OCH2CH2)eCOOM). In the formulae in brackets, R is a
hydrophobic chain (Cg-C22) alkyl or alkenyl, a is from 0 to 20, Z is M or R',
M is
H or any counterion such as those known in the art, including Na, K, Li, NH4,
amine, and R' is a C1-C5 alkyl group, possibly functionalized with hydroxyl
groups, preferably C1-C3, most preferably methyl. Still other preferred
anionic
surfactants for use herein are the alkyl sulphosuccinates
(R'OOCCH2CH(SO3M)COOR') wherein R' is a hydrophobic chain (Cg-Clg,
preferably Cg-C12) linear or branched alkyl or alkenyl, and M is as defined
hereinbefore. Preferred alkyl sulphosuccinates are commercially available from
CYTEC Industries under the tradename Aerosol OT, and Aerosol AOT. Preferred
among the above described anionic surfactants are selected from the alkyl
sulphate surfactants, alkyl sulphosuccinate surfactants, and mixtures thereof.
Preferred alkyl sulphates for use herein are selected from sodium dodecyl
alkyl
sulphate, sodium tallow alkyl sulphate, sodium lauryl sulphate, sodium octyl
sulphate and mixtures thereof. Preferred commercially available compounds are
Empicol~ 02981F andlor Empimin~ LV33 from Albright and Wilson.
Still another preferred anionic surfactant for use herein has the general
formula:


CA 02330473 2000-10-26
WO 99/55948 PCT/US98108125
19
S03Na S03Na
U
R
wherein R is an alkyl group. These surfactants are preferred ingredients when
a
cyclodextrin is present since it is compatible with the cyclodextrin. Examples
of
this type of surfactants are available from the Dow Chemical Company under the
trade name Dowfax~ wherein R is a linear or branched C6-C~6 alkyl group. An
example of these anionic surfactant is Dowfax 3B2 with R being approximately a
linear Cep group. These anionic surfactants are preferably not used when the
antimicrobial active or preservative, etc., is cationic to minimize the
interaction
with the cationic actives, since the effect of both surfactant and active are
diminished.
The wetting agent is present in the composition in a sufficient amount to
result in
an amount of from 0.001 % to 5%, preferably from 0.01 % to 3%, more preferably
from 0.01 % to 1.50% by weight of active per weight of dry fabrics.
Accordingly, typical levels of the water-soluble wetting agent in the
composition
are from 0.1 to 10% by weight, preferably from 0.1 to 5%, more preferably from
0.1 % to 1.5% by weight of the composition.
2-Lubricant
In addition to the above humectants which can impart a lubrication property to
the fabrics, the composition may also optionally employ typical lubricating
compounds.
Typical lubricants are those conventionally known as softeners and include the
cationic softener and nonionic softeners.
Cationic softeners
Typical of the cationic softening components are the quaternary ammonium
compounds or amine precursors thereof as defined hereinafter.
A?-Quaternar)r Ammonium Fabric Softenina Active Compound


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(1 ) Preferred quaternary ammonium fabric softening active compound have
the formula
(R)a-m N (CH2~-Q-Rl X
m
(1)
5 or the formula:
~)a~, N W-~-~z 'Q'-R~ X
m
Q ~ Ri
(2)
wherein Q is a functional unit having the formula:
-O-O- ' -O~O- ' -O-O-O~ ' -IR2 O~ ' -O-IR2
each R unit is independently hydrogen, C1-Cg alkyl, C1-Cg hydroxyalkyl, and
mixtures thereof, preferably methyl or hydroxy alkyl; each R1 unit is
independently linear or branched C11-C22 alkyl, linear or branched C11-C22
alkenyl, and mixtures thereof, R2 is hydrogen, C1-C4 alkyl, C1-C4
hydroxyalkyl,
and mixtures thereof; X is an anion which is compatible with fabric softener
actives and adjunct ingredients; the index m is from 1 to 4, preferably 2; the
index
n is from 1 to 4, preferably 2.
An example of a preferred fabric softener active is a mixture of quaternized
amines having the formula:
+ O
R2-N (CH2~-O-C-Rl X -
2
wherein R is preferably methyl; R1 is a linear or branched alkyl or alkenyl
chain
comprising at least 11 atoms, preferably at least 15 atoms. In the above
fabric
softener example, the unit -R1 represents a fatty alkyl or aikenyl unit which
is
typically derived from a triglyceride source. The triglyceride source is
preferably


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21
derived from tallow, partially hydrogenated tallow, lard, partially
hydrogenated
lard, vegetable oils and/or partially hydrogenated vegetable oils, such as,
canola
oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall
oil, rice bran
oil, etc. and mixtures of these oils.
The preferred fabric softening actives of the present invention are the
Diester
and/or Diamide Quaternary Ammonium (DEQA) compounds, the diesters and
diamides having the formula:
+ _
(R)4_m N (CH2~-Q-Rl X
m
wherein R, R1, X, and n are the same as defined herein above for formulas (1)
and (2), and Q has the formula:
-p-O- or -N-O-
These preferred fabric softening actives are formed from the reaction of an
amine
with a fatty acyl unit to form an amine intermediate having the formula:
R N (CH2)n-Q-Rt
2
wherein R is preferably methyl, Q and R' are as defined herein before;
followed
by quaternization to the final softener active.
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:
~ Hs
HO~N~OH
methyl bis(2-hydroxypropyl)amine having the formula:


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22
CH3
N
HO OH
methyl (3-aminopropyl) (2-hydroxyethyl)amine having the formula:
CH3
HO~N~NHZ
methyl bis(2-aminoethyl)amine having the formula:
CH3
H2N ~,,/N ~'NH2
,
triethanol amine having the formula:
~OH
HON OOH
di(2-aminoethyl) ethanolamine having the formula:
~OH
H2N~NI ~NH2
The counterion, X(-) above, can be any softener-compatible anion, preferably
the anion of a strong acid, for example, chloride, bromide, methylsulfate,
ethylsulfate, sulfate, nitrate and the like, more preferably chloride or
methyl
sulfate. The anion can also, but less preferably, carry a double charge in
which
case X(-) represents half a group.
Tallow and canola oil are convenient and inexpensive sources of fatty acyl
units
which are suitable for use in the present invention as R1 units. The following
are
non-limiting examples of quaternary ammonium compounds suitable for use in
the compositions of the present invention. The term "tallowyl" as used herein
below indicates the R1 unit is derived from a tallow trigiyceride source and
is a


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23
mixture of fatty alkyl or alkenyl units. Likewise, the use of the term canolyl
refers
to a mixture of fatty alkyl or alkenyl units derived from canola oil.
In the following table are described non-limiting examples of suitable fabric
softener according to the above formula. In this list, the term "oxy" defines
a
O
-~- unit, whereas the term "oxo" defines a -O- unit.
Table II
Fabric Softener Actives
N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(canolyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium
chloride;
N,N-di(taliowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride
N,N,N-tri(tallowyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;
N,N,N-tri(canolyl-oxy-2-oxo-ethyl)-N-methyl ammonium chloride;
N-(tallowyloxy-2-oxo-ethyl)-N-(tallowyl)-N,N-dimethyl ammonium chloride;
N-(canolyloxy-2-oxo-ethyl)-N-(canolyl)-N,N-dimethyl ammonium chloride;
1,2-di(tallowyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride; and
1,2-di(canolyloxy-oxo)-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
Other examples of quaternay ammoniun softening compounds are
methylbis(tallowamidoethyl)(2-hydroxyethyl)ammonium methylsulfate and
methylbis(hydrogenated tallowamidoethyl)(2-hydroxyethyl)ammonium
methylsulfate; these materials are available from Witco Chemical Company
under the trade names Varisoft~ 222 and Varisoft~ 110, respectively.
Particularly preferred is N,N-di(tallowyl-oxy-2-oxo-ethyl)-N-methyl, N-(2-
hydroxyethyl) ammonium chloride, where the tallow chains are at least
partially
unsaturated.
The level of unsaturation contained within the tallow, canola, or other fatty
acyl
unit chain can be measured by the Iodine Value (IV) of the corresponding fatty


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
24
acid, which in the present case should preferably be in the range of from 5 to
100
with two categories of compounds being distinguished, having a IV below or
above 25.
Indeed, for compounds having the formula:
+ _
~)4_m N (CH2)ri Q-R~ X
m
derived from tallow fatty acids, when the Iodine Value is from 5 to 25,
preferably
to 20, it has been found that a cisltrans isomer weight ratio greater than
about
10 30/70, preferably greater than about 50/50 and more preferably greater than
about 70130 provides optimal concentrability.
For compounds of this type made from tallow fatty acids having a Iodine Value
of
above 25, the ratio of cis to traps isomers has been found to be less critical
unless very high concentrations are needed.
15 Other suitable examples of fabric softener actives are derived from fatty
acyl
groups wherein the terms "tallowyl" and canolyl" in the above examples are
replaced by the terms "cocoyl, palmyl, lauryl, oleyl, ricinoleyl, stearyl,
palmityl,"
which correspond to the triglyceride source from which the fatty acyl units
are
derived. These alternative fatty acyl sources can comprise either fully
saturated,
or preferably at least partly unsaturated chains.
As described herein before, R units are preferably methyl, however, suitable
fabric softener actives are described by replacing the term "methyl" in the
above
examples in Table II with the units "ethyl, ethoxy, propyl, propoxy,
isopropyl,
butyl, isobutyl and t-butyl.
The counter ion, X, in the examples of Table II can be suitably replaced by
bromide, methylsulfate, formate, sulfate, nitrate, and mixtures thereof. In
fact,
the anion, X, is merely present as a counterion of the positively charged
quaternary ammonium compounds. The scope of this invention is not considered
limited to any particular anion.
Mixtures of actives of formula (1) and (2) may also be prepared.


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
2)-Still other suitable quaternary ammonium fabric softening compounds for use
herein are cationic nitrogenous salts having two or more long chain acyclic
aliphatic Cg-C22 hydrocarbon groups or one said group and an arylalkyl group
which can be used either alone or as part of a mixture are selected from the
5 group consisting of:
(i) acyclic quaternary ammonium salts having the formula:
R4 +
Rg-N-RS A-
wherein R4 is an acyclic aliphatic Cg-C22 hydrocarbon group, R5 is a C1-C4
saturated alkyl or hydroxyalkyl group, R$ is selected from the group
consisting of
R4 and R5 groups, and A- is an anion defined as above;
(ii) diamino alkoxylated quaternary ammonium salts having the formula:
O RS O
Rj-C-NH-R2-N-R2-NH-C-R1 A
(CH2CH20~H
wherein n is equal to 1 to about 5, and R1, R2, R5 and A- are as defined
above;
(iii) mixtures thereof.
Examples of the above class cationic nitrogenous salts are the well-known
dialkyldi methylammonium salts such as ditallowdimethylammonium chloride,
ditallowdimethylammonium methylsulfate,
di(hydrogenatedtaliow)dimethylammonium chloride, distearyldimethylammonium
chloride, dibehenyldimethylammonium chloride. Di(hydrogenatedtallow)di
methyfammonium chloride and ditallowdimethylammonium chloride are preferred.
Examples of commercially available dialkyldimethyl ammonium salts usable in
the present invention are di(hydrogenatedtallow)dimethylammonium chloride
(trade name Adogen~ 442), ditallowdimethylammonium chloride (trade name
Adogen~ 470, Praepagen~ 3445), distearyl dimethylammonium chloride (trade


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
26
name Arosurf~ TA-100), all available from Witco Chemical Company.
Dibehenyldimethylammonium chloride is sold under the trade name Kemamine
Q-2802C by Humko Chemical Division of Witco Chemical Corporation.
Dimethylstearylbenzyl ammonium chloride is sold under the trade names Varisoft
~ SDC by Witco Chemical Company and Ammonyx~ 490 by Onyx Chemical
Company.
B)-Amine Fabric Softening Active Compound
Suitable amine fabric softening compounds for use herein, which may be in
amine form or cationic form are selected from:
(i)- Reaction products of higher fatty acids with a polyamine selected from
the
group consisting of hydroxyalkylalkylenediamines and dialkylenetriamines and
mixtures thereof. These reaction products are mixtures of several compounds in
view of the multi-functional structure of the polyamines.
The preferred Component (i) is a nitrogenous compound selected from the group
consisting of the reaction product mixtures or some selected components of the
mixtures.
One preferred component (i) is a compound selected from the group consisting
of substituted imidazoline compounds having the formula:
N
R~--
N
I
Rg-NH-C-R~
I
O
wherein R7 is an acyclic aliphatic C15-C21 hydrocarbon group and R8 is a
divalent C1-C3 alkylene group.
Component {i) materials are commercially available as: Mazamide~ 6, sold by
Mazer Chemicals, or Ceranine~ HC, sold by Sandoz Colors & Chemicals; stearic
hydroxyethyl imidazoline sold under the trade names of Alkazine~ ST by Alkaril
Chemicals, Inc., or Schercozoline~ S by Scher Chemicals, Inc.; N,N"-
ditallowalkoyldiethylenetriamine; 1-tallowamidoethyl-2-tallowimidazoline
{wherein
in the preceding structure R1 is an aliphatic C15-C1~ hydrocarbon group and R$
is a divalent ethylene group).


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
27
Both N,N"-ditallowalkoyldiethylenetriamine and 1-tallow(amidoethyl)-2-
tallowimidazoline are reaction products of tallow fatty acids and
diethylenetriamine, and are precursors of the cationic fabric softening agent
methyl-1-tallowamidoethyl-2-tallowimidazolinium methylsulfate (see "Cationic
Surface Active Agents as Fabric Softeners," R. R. Egan, Journal of the
American
Oil Chemicals' Society, January 1978, pages 118-121). N,N"-ditallow
alkoyldiethylenetriamine and 1-tallowamidoethyl-2-tallowimidazoline can be
obtained from Witco Chemical Company as experimental chemicals. Methyl-1-
tallowamidoethyl-2-tallowimidazolinium methylsulfate is sold by Witco Chemical
Company under the tradename Varisoft~ 475.
(ii)-softener having the formula:
N
R~
C
O (+) ->
N CSC X~
Rs
R' C G Rz
wherein each R2 is a C1_g alkylene group, preferably an ethylene group; and G
is an oxygen atom or an -NR- group; and each R, R1, R2 and R5 have the
definitions given above and A- has the definitions given above for X-.
An example of Compound {ii) is 1-oleylamidoethyl-2-oleylimidazolinium chloride
wherein R1 is an acyclic aliphatic C15-C17 hydrocarbon group, R2 is an
ethylene
group, G is a NH group, R5 is a methyl group and A- is a chloride anion.
(iii)- softener having the formula:
H H
\N-Rz-N
N~ N 2A0
R' Ri
wherein R, R1, R2, and A- are defined as above.


CA 02330473 2000-10-26
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28
An example of Compound (iii) is the compound having the formula:
H H
N CH2CH2 N ' C1
N~ N
wherein R1 is derived from oleic acid.
5
Nonionic softeners
Nonionic softener include compounds such as the fatty acid esters, preferably
a
partial ester, of mono- or polyhydric alcohols or anhydride thereof containing
from
1 to 8 carbon atoms.
It is preferred that the fatty acid ester has at least 1 free (i.e.
unesterified)
hydroxyl group and at least 1 fatty acyl group.
The mono- or polyhydric alcohol portion of the ester can be represented by
methanol, isobutanol, 2-ethyl hexanol, isopropanol, ethylene glycol and
polyethylene glycol with a maximum of 5 ethylene glycol units, glycerol,
diglycerol, xylitol, sucrose, erythritol, penta-erythritol, sorbitol or
sorbitan.
Ethylene glycol, glycerol and sorbitan esters are particularly preferred.
The fatty acid portion of the ester normally comprises a fatty acid having
from 12
to 22 carbon atoms, typical examples being lauric acid, myristic acid,
palmitic
acid, stearic acid and behenic acid.
One highly preferred group of lubricant for use in the present invention is
the
sorbitan esters, which are esterified dihydration products of sorbitol.
Sorbitol,
itself prepared by the catalytic hydrogenation of glucose, can be dehydrated
in
well known fashion to form mixtures of 1,4- and 1,5-sorbitol anhydrides and
small
amounts of isosorbides. (See Brown, U.S. Pat. No. 2,322,821, issued June 29,
1943). The foregoing type of complex mixtures of anhydrides of sorbitol are
collectively referred to herein as "sorbitan". It will be recognized that this
"sorbitan" mixture will also contain some free, uncyciized sorbitol.


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29
The lubricants of the type employed herein can be prepared by esterifying the
"sorbitan" mixture with a fatty acyl group in standard fashion, e.g. by
reaction with
a fatty acid halide or fatty acid. The esterification reaction can occur at
any of the
available hydroxyl groups, and various mono-, di-, etc., esters can be
prepared.
In fact, mixtures of mono-, di-, tri-, etc., esters almost always result from
such
reactions, and the stoichiometric ratios of the reactants can be simply
adjusted to
favor the desired reaction product.
For commercial production of the sorbitan ester materials, etherification and
esterification are generally accomplished in the same processing step by
reacting
sorbitol directly with fatty acids. Such a method of sorbitan ester
preparation is
described more fully in MacDonald; "Emulsifiers: Processing and Quality
Control:", Journal of the American Oil Chemists' Society, Volume 45, October
1968.
The mixtures of hydroxy-substituted sorbitan esters useful herein contain,
inter
alia, compounds of the following formulae, as well as the corresponding
hydroxy-
substituted di-esters:


CA 02330473 2000-10-26
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HO OH H
C - CH20 C(O)R
O
OH
CH20 C(O)R
OH
OH
HO O
O C(O)R
O
wherein the group R is a C10-C2fi, and higher, fatty alkyl residue. Preferably
this
fatty alkyl residue contains from 16 to 22 carbon atoms. The fatty alkyl
residue
5 can, of course, contain non-interfering substituents such as hydroxyl
groups.
Esterified hydroxyl groups can, of course, be either in terminal or internal
positions within the sorbitan molecule.
The foregoing complex mixtures of esterified dehydration products of sorbitol
10 (and small amounts of esterified sorbitol) are collectively referred to
herein as
"sorbitan esters". Sorbitan mono- and di-esters of lauric, myristic, palmitic,
stearic
and behenic (docosanoic) acids are particularly useful herein as softening
agents
and also can provide an anti-static benefit to fabrics. Mixed sorbitan esters,
e.g.
mixtures of the foregoing esters, and mixtures prepared by esterifying
sorbitan
15 with fatty acid mixtures such as the mixed tallow fatty acids, are useful
herein
and are economically attractive. Unsaturated C10-C22 sorbitan esters, e.g.
sorbitan monoofeate, usually are present in such mixtures in low
concentration.


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31
The term "alkyl" as employed herein to , describe the sorbitan esters
encompasses both the saturated and unsaturated hydrocarbyl ester side chain
groups.
Certain derivatives of the sorbitan esters herein, especially the "lower"
ethoxylates thereof (i.e. mono-, di- and tri-esters) wherein one or more of
the
unesterified --OH groups contain one to about 20 oxyethylene moieties
(Tweens~) are also useful in the composition of the present invention.
Therefore,
for purposes of the present invention, the term "sorbitan ester" includes such
derivatives.
Preparation of the sorbitan esters can be achieved by dehydrating sorbitol to
form a mixture of anhydrides of the type set forth above, and subsequently
esterifying the mixture using, for example, a 1:1 stoichiometry for the
esterification reaction. The esterified mixture can then be separated into the
various ester components. Separation of the individual ester products is,
however, difficult and expensive.
Accordingly, it is easier and more economical not to separate the various
esters,
using instead the esterified mixture as the sorbitan ester component. Such
mixtures of esterified reaction products are commercially available under
various
tradenames e.g. Span~ Such sorbitan ester mixtures can also be prepared by
utilizing conventional interesterification procedures.
For the purposes of the present invention, it is preferred that a significant
amount
of di- and tri-sorbitan esters are present in the ester mixture. Ester
mixtures
having from 20%-50% mono-ester, 25% to 50% di-ester and 10%-35% of tri- and
tetra-esters are preferred. The material which is sold commercially as
sorbitan
mono-ester (e.g. mono-stearate) does in fact contain significant amounts of di-

and tri-esters and a typical analysis of sorbitan monostearate indicates that
it
comprises ca.27% mono-, 32% di- and 30% tri- and tetra esters. Commercial
sorbitan mono-stearate therefore is a preferred material.
Mixtures of sorbitan stearate and sorbitan palmitate having stearatelpalmitate
weight ratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are
useful.
Both the 1,4- and 1,5- sorbitan esters are useful herein. Other useful alkyl


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32
sorbitan esters for use in the softening compositions herein include sorbitan
monolaurate, sorbitan monomyristate, sorbitan monopolmitate, sorbitan mono-
behenate, sorbitan monooleate, sorbitan dilaurate, sorbitan dimyristate,
sorbitan
dipalmitate, sorbitan
distearate, sorbitan dibehenate, sorbitan dioleate, and mixtures, thereof, and
mixed tallowalkyl sorbitan mono- and di-esters. Such mixtures are readily
prepared by reacting the foregoing hydroxy-substituted sorbitans, particularly
the
1,4- and 1,5-sorbitans, with the corresponding acid or acid chloride in a
simple
esterification reaction, It is to be recognized, of course, that commercial
materials
prepared in this manner will comprise mixtures usually containing minor
proportions of uncyclized
sorbitol, fatty acids, polymers, isosorbide structures, and the like.
It is also to be recognized that the sorbitan esters employed herein can
contain
up to about 15% by weight of esters of the C20 -C26, and higher, fatty acids,
as
well as minor amounts of C8, and lower, fatty esters.
Other fatty acid partial esters useful in the present invention are xylitol
monopalmitate, pentaerythritol monostearate, sucrose monostearate, glycerol
monostearate and ethylene glycol monostearate. As with the sorbitan esters,
commercially available mono-esters normally contain substantial quantities of
di-
or tri-esters.
The glycol esters are also highly preferred. These are the mono-, di- or tri-
esters
of glycerol and fatty acids of the class described above.
Commercial glyceryl monostearate, which may contain a proportion of the di-
and
tristearates, is especially preferred.
Another class of suitable nonionic lubricants are the cyclomethicones such as
described in EP636356.
The above-discussed nonionic compounds are correctly termed "lubricating
agents", because, when the compounds are correctly applied to a fabric, they
do
impart a soft, lubricious feel to the fabric.


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33
Additional fabric softening agents useful herein are described in U.S. Pat.
No.
4,661,269, issued April 28, 1987, in the names of Toan Trinh, Errol H. Wahl,
Donald M. Swartley, and Ronald L. Hemingway; U.S. Pat. No. 4,439,335, Burns,
issued March 27, 1984; and in U.S. Pat. Nos.: 3,861,870, Edwards and Diehl;
4,308,151, Cambre; 3,886,075, Bernardino; 4,233,164, Davis; 4,401,578,
Verbruggen; 3,974,076, Wiersema and Rieke; 4,237,016, Rudkin, Clint, and
Young; and European Patent Application publication No. 472,178, by Yamamura
et al., all of said documents being incorporated herein by reference.
Of course, the term "lubricating agent" can also encompass mixed softening
active agents.
Preferred lubricating agent among the one disclosed above are the quaternary
ammonium compound disclosed under (A) and the cyclomethicones.
The lubricating agent is present in the composition in a sufficient amount to
result
in an amount of from 0.005% to 5%, preferably from 0.01 % to 3%, more
preferably from 0.01% to 1.50% by weight of active per weight of dry fabrics.
Typically, the lubricating agent is added to the composition of the present
invention at a level of from about 0.01 % to about 10%, by weight of the
composition, preferably from about 0.1 % to about 3%, more preferably from
about 0.1 % to about 1.5%, by weight of the composition.
3-Cyclodextrin
In a preferred aspect of the invention, the composition of the invention
comprises
an optional cyclodextrin. This will impart the composition with odour
absorbing
properties, which is especially useful for application on inanimate surfaces
to
control the malodour, whilst not being detrimental to the dewrinkling
performance
of the composition.
As used herein, the term "cyclodextrin" includes any of the known
cyclodextrins
such as unsubstituted cyclodextrins containing from six to twelve glucose
units,
especiaNy, alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin andlor
their
derivatives and/or mixtures thereof. The alpha-cyclodextrin consists of six
glucose units, the beta-cyclodextrin consists of seven glucose units, and the


CA 02330473 2000-10-26
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34
gamma-cyclodextrin consists of eight glucose units arranged in donut-shaped
rings. The specific coupling and conformation of the glucose units give the
cyclodextrins a rigid, conical molecular structures with hollow interiors of
specific
volumes. The "lining" of each internal cavity is formed by hydrogen atoms and
glycosidic bridging oxygen atoms; therefore, this surface is fairly
hydrophobic.
The unique shape and physical-chemical properties of the cavity enable the
cyclodextrin molecules to absorb (form inclusion complexes with) organic
molecules or parts of organic molecules which can fit into the cavity. Many
odorous molecules can fit into the cavity including many malodorous molecules
and perfume molecules. Therefore, cyclodextrins, and especially mixtures of
cyclodextrins with different size cavities, can be used to control odors
caused by
a broad spectrum of organic odoriferous materials, which may, or may not,
contain reactive functional groups. The complexation between cyclodextrin and
odorous molecules occurs rapidly in the presence of water. However, the extent
of the complex formation also depends on the polarity of the absorbed
molecules. In an aqueous solution, strongly hydrophilic molecules (those which
are highly water-soluble) are only partially absorbed, if at all. Therefore,
cyclodextrin does not complex effectively with some very low molecular weight
organic amines and acids when they are present at low levels on wet fabrics.
As
the water is being removed however, e.g., the fabric is being dried off, some
low
molecular weight organic amines and acids have more affinity and will complex
with the cyclodextrins more readily.
The cavities within the cyclodextrin in the solution of the present invention
should
remain essentially unfilled (the cyclodextrin remains uncomplexed) while in
solution, in order to allow the cyclodextrin to absorb various odor molecules
when
the solution is applied to a surface. Non-derivatised (normal) beta-
cyclodextrin
can be present at a level up to its solubility limit of about 1.85% (about
1.85g in
100 grams of water) at room temperature. Beta-cyclodextrin is not preferred in
compositions which call for a level of cyclodextrin higher than its water
solubility
limit. Non-derivatised beta-cyclodextrin is generally not preferred when the
composition contains surfactant since it affects the surface activity of most
of the
preferred surfactants that are compatible with the derivatized cyclodextrins.
Preferably, the solution of the present invention is clear. The term "clear"
as
defined herein means transparent or translucent, preferably transparent, as in


CA 02330473 2000-10-26
WO 99/55948 PCTNS98/08125
"water clear," when observed through a layer having a thickness of less than
about 10 cm.
Preferably, the cyclodextrins for use herein are highly water-soluble such as,
5 alpha-cyclodextrin and/or derivatives thereof, gamma-cyclodextrin and/or
derivatives thereof, derivatised beta-cyclodextrins, and/or mixtures thereof.
The
derivatives of cyclodextrin consist mainly of molecules wherein some of the OH
groups are converted to OR groups. Cyclodextrin derivatives include, e.g.,
those
with short chain alkyl groups such as methylated cyclodextrins, and ethylated
10 cyclodextrins, wherein R is a methyl or an ethyl group; those with
hydroxyalkyl
substituted groups, such as hydroxypropyl cyclodextrins and/or hydroxyethyl
cyclodextrins, wherein R is a -CH2-CH(OH)-CH3 or a -CH2CH2-OH group;
branched cyclodextrins such as maltose-bonded cyclodextrins; cationic
cyclodextrins such as those containing 2-hydroxy-3-(dimethylamino)propyl
ether,
15 wherein R is CH2-CH(OH)-CH2-N(CH3)2 which is cationic at low pH; quaternary
ammonium, e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloride groups,
wherein R is CH2-CH(OH)-CH2-N+(CH3)3C1-; anionic cyclodextrins such as
carboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrin
succinylates;
amphoteric cyclodextrins such as carboxymethyl/quaternary ammonium
20 cyclodextrins; cyclodextrins wherein at least one glucopyranose unit has a
3-6-
anhydro-cyclomalto structure, e.g., the mono-3-6-anhydrocyclodextrins, as
disclosed in "Optimal Performances with Minimal Chemical Modification of
Cyclodextrins", F. Diedaini-Pilard and B. Perly, The 7th International
Cyclodextrin
Symposium Abstracts, April 1994, p. 49, said references being incorporated
25 herein by reference; and mixtures thereof. Other cyclodextrin derivatives
are
disclosed in U.S. Pat. Nos: 3,426,011, Parmerter et al., issued Feb. 4, 1969;
3,453,257; 3,453,258; 3,453,259; and 3,453,260, all in the names of Parmerter
et
al., and all issued July 1, 1969; 3,459,731, Gramera et al., issued Aug. 5,
1969;
3,553,191, Parmerter et al., issued Jan. 5, 1971; 3,565,887, Parmerter et al.,
30 issued Feb. 23, 1971; 4,535,152, Szejtli et al., issued Aug. 13, 1985;
4,616,008,
Hirai et al., issued Oct. 7, 1986; 4,678,598, Ogino et al., issued Jul. 7,
1987;
4,638,058, Brandt et al., issued Jan. 20, 1987; and 4,746,734, Tsuchiyama et
al.,
issued May 24, 1988; all of said patents being incorporated herein by
reference.
35 Highly water-soluble cyclodextrins are those having water solubility of at
least
about 10 g in 100 ml of water at room temperature, preferably at least about
20 g


CA 02330473 2000-10-26
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36
in 100 ml of water, more preferably at least about 25 g in 100 ml of water at
room
temperature. The availability of solubilized, uncomplexed cyclodextrins is
essential for effective and efficient odor control performance. Solubilized,
water-
soluble cyclodextrin can exhibit more efficient odor control performance than
non-water-soluble cyclodextrin when deposited onto surfaces, especially
fabric.
Examples of preferred water-soluble cyclodextrin derivatives suitable for use
herein are hydroxypropyl alpha-cyclodextrin, methylated alpha-cyclodextrin,
methylated beta-cyclodextrin, hydroxyethyl beta-cyclodextrin, and
hydroxypropyl
beta-cyclodextrin. Hydroxyalkyl cyclodextrin derivatives preferably have a
degree of substitution of from about 1 to about 14, more preferably from about
1.5 to about 7, wherein the total number of OR groups per cyclodextrin is
defined
as the degree of substitution. Methylated cyclodextrin derivatives typically
have
a degree of substitution of from about 1 to about 18, preferably from about 3
to
about 16. A known methylated beta-cyclodextrin is heptakis-2,6-di-O-methyl-~i-
cyclodextrin, commonly known as DIMES, in which each glucose unit has about
2 methyl groups with a degree of substitution of about 14. A preferred, more
commercially available, methylated beta-cyclodextrin is a randomly methylated
beta-cyclodextrin, commonly known as RAMEB, having different degrees of
substitution, normally of about 12.6. RAMEB is more preferred than DIMEB,
since DIMES affects the surface activity of the preferred surfactants more
than
RAMEB. The preferred cyclodextrins are available, e.g., from Cerestar USA,
Inc.
and Wacker Chemicals (USA), Inc.
It is also preferable to use a mixture of cyclodextrins. Such mixtures absorb
odors more broadly by complexing with a wider range of odoriferous molecules
having a wider range of molecular sizes. Preferably at least a portion of the
cyclodextrins is alpha-cyclodextrin and its derivatives thereof, gamma-
cyclodextrin and its derivatives thereof, and/or derivatised beta-
cyclodextrin,
more preferably a mixture of alpha-cyclodextrin, or an alpha-cyclodextrin
derivative, and derivatised beta-cyclodextrin, even more preferably a mixture
of
derivatised alpha-cyclodextrin and derivatised beta-cyciodextrin, most
preferably
a mixture of hydroxypropyl alpha-cyclodextrin and hydroxypropyl beta
cyclodextrin, and/or a mixture of methylated alpha-cyclodextrin and methylated
beta-cyclodextrin.


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37
It is further believed that a small amount of low molecular weight polyol as
defined herein before into the composition comprising the uncomplexed
cyclodextrin enhances the formation of the cyclodextrin inclusion complexes as
the fabric dries. Further, the incorporation of such polyol provides an
improved
odor control performance of the composition of the present invention
comprising
said cyclodextrin.
It is believed that the polyols' ability to remain on the fabric for a longer
period of
time than water, as the fabric dries allows it to form ternary complexes with
the
cyclodextrin and some malodorous molecules. The addition of the glycols is
believed to fill up void space in the cyclodextrin cavity that is unable to be
filled
by some malodor molecules of relatively smaller sizes.
Cyclodextrin compositions prepared by processes that result in a level of such
polyols are highly desirable, since they can be used without removal of the
polyols.
Diethylene glycol is particularly useful in the presence of the uncomplexd
cyclodextrin. Indeed, it has been found to enhance the removal of small
malodour molecules.
The preferred weight ratio of low molecular weight cyclodextrin to polyol is
from
about 50:1 to about 1:11, more preferably from about 20:1 to about 1:1, even
more preferably from about 10:1 to about 1:1, and most preferably from about
5:1 to about 1:1.
For controlling odor on fabrics, the composition is preferably used as a
spray. It
is preferable that the usage compositions of the present invention contain low
levels of cyclodextrin so that a visible stain does not appear on the fabric
at
normal usage levels. Preferably, the solution used to treat the surface under
usage conditions is virtually not discernible when dry. Typical levels of
cyclodextrin in usage compositions for usage conditions are from about 0.01 %
to
about 5%, preferably from about 0.1 % to about 4%, more preferably from about
0.2% to about 2% by weight of the composition. Compositions with higher
concentrations can leave unacceptable visible stains on fabrics as the
solution
evaporates off of the fabric. This is especially a problem on thin, colored,


CA 02330473 2000-10-26
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38
synthetic fabrics. In order to avoid or minimize the occurrence of fabric
staining,
it is preferable that the fabric be treated at a level of less than about 5 mg
of
cyclodextrin per gram of fabric, more preferably less than about 2 mg of
cyclodextrin per gram of fabric. The presence of the surfactant can improve
appearance by minimizing localized spotting.
Concentrated compositions can also be used in order to deliver a less
expensive
product. When a concentrated product is used, i.e., when the level of
cyclodextrin used is from about 3% to about 20%, more preferably from about
5% to about 10%, by weight of the concentrated composition, it is preferable
to
dilute the concentrated composition before treating fabrics in order to avoid
staining. Preferably the concentrated cyclodextrin composition is diluted with
about 50% to about 6000%, more preferably with about 75% to about 2000%,
most preferably with about 100% to about 1000% by weight of the concentrated
composition of water. The resulting diluted compositions have usage
concentrations of cyclodextrin as discussed hereinbefore, e.g., of from about
0.1 % to about 5%, by weight of the diluted composition.
4- Antimicrobial active
The composition may suitably use an optional solubilized, water-soluble
antimicrobial active, useful in providing protection against organisms that
become
attached to the treated material. The free, uncomplexed antimicrobial, e.g.,
antibacterial, active provides an optimum antibacterial performance.
Sanitization of fabrics can be achieved by the compositions of the present
invention containing, antimicrobial materials, e.g., antibacterial halogenated
compounds, quaternary compounds, and phenolic compounds.
BiQUanides. Some of the more robust antimicrobial halogenated compounds
which can function as disinfectants/sanitizers as well as finish product
preservatives (vide infra), and are useful in the compositions of the present
invention include 1,1'-hexamethylene bis(5-(p-chlorophenyl)biguanide),
commonly known as chlorhexidine, and its salts, e.g., with hydrochloric,
acetic
and gluconic acids. The digluconate salt is highly water-soluble, about 70% in
water, and the diacetate salt has a solubility of about 1.8% in water. When
chiorhexidine is used as a sanitizer in the present invention it is typically
present


CA 02330473 2000-10-26
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39
at a level of from about 0.001 % to about 0.4%, preferably from about 0.002%
to
about 0.3%, and more preferably from about 0.01 % to about 0.1 %, by weight of
the usage composition. In some cases, a level of from about 1% to about 2%
may be needed for virucidal activity.
Other useful biguanide compounds include Cosmoci~ CQ~, Vantocil~ IB,
including poly (hexamethylene biguanide) hydrochloride. Other useful cationic
antimicrobial agents include the bis-biguanide alkanes. Usable water soluble
salts of the above are chlorides, bromides, sulfates, alkyl sulfonates such as
methyl sulfonate and ethyl sulfonate, phenylsulfonates such as p-methylphenyl
sulfonates, nitrates, acetates, gluconates, and the like.
Examples of suitable bis biguanide compounds are chlorhexidine; 1,6-bis-(2-
ethylhexylbiguanidohexane)dihydrochloride; 1,6-di-(N1,N1'-phenyldiguanido-
N5,N5')-hexane tetrahydrochloride; 1,6-di-(N1,N1'-phenyl-N1,N1'-
methyldiguanido-N5,N5')-hexane dihydrochloride; 1,6-di(N1,N1'-o-
chlorophenyldiguanido-N5,N5')-hexane dihydrochloride; 1,6-di(N1,N1'-2,6-
dichlorophenyldiguanido-N5,N5')hexane dihydrochloride; 1,6-di[N1,N1'-.beta.-(p-

methoxyphenyl) diguanido-N5,N5']-hexane dihydrochloride; 1,fi-di(N1,N1'-
.aipha.-methyl-.beta.-phenyldiguanido-N5,N5')-hexane dihydrochloride; 1,6-
di(N 1,N 1'-p-nitrophenyldiguanido-N5,N5')hexane
dihydrochloride;.omega.:.omega.'-di-{N 1,N 1'-phenyldiguanido-N5,N5')-di-n-
propyl
ether dihydrochloride;.omega:omega'-di(N1,N1'-p-chlorophenyldiguanido-
N5,N5')-di-n-propylether tetrahydrochloride; 1,6-di(N1,N1'-2,4-
dichlorophenyldiguanido-N5,N5')hexane tetrahydrochloride; 1,6-di(N1,N1'-p-
methylphenyldiguanido-N5,N5') hexane dihydrochloride; 1,6-di(N1,N1'-2,4,5-
trichlorophenyldiguanido-N5,N5') hexane tetrahydrochloride; 1,6-di[N1,N1'-
.alpha.-(p-chlorophenyl) ethyldiguanido-N5,N5'] hexane
dihydrochloride;.omega.:.omega.'di(N1, N1'-p-chlorophenyl diguanido-N5,N5')m-
xylene dihydrochloride; 1,12-di(N1,N1'-p-chlorophenyl diguanido-N5,N5')
dodecane dihydrochloride; 1,10-di(N1,N1'-phenyldiguanido-N5,N5')-decane
tetrahydrochloride; 1,12-di(N1,N1'-phenyldiguanido-N5,N5') dodecane
tetrahydrochloride; 1,6-di(N1,N1'-o-chlorophenyldiguanido-N5,N5') hexane
dihydrochloride; 1,6-di(N 1,N 1'-p-chlorophenyldiguanido-N5,N5')-hexane
tetrahydrochloride; ethylene bis (1-tolyl biguanide); ethylene bis (p-tolyl
biguanide); ethylene bis(3,5-dimethylphenyl biguanide); ethylene bis(p-tert-


CA 02330473 2000-10-26
WO 99/55948 PCTNS98/08125
amylphenyl biguanide); ethylene bis(nonylphenyl biguanide); ethylene bis
(phenyl
biguanide); ethylene bis (N-butylphenyl biguanide); ethylene bis (2,5-
diethoxyphenyl biguanide); ethylene bis(2,4-dimethylphenyl biguanide);
ethylene
bis(o-diphenylbiguanide); ethylene bis(mixed amyl naphthyl biguanide); N-butyl
5 ethylene bis(phenylbiguanide); trimethylene bis(o-tolyl biguanide); N-butyl
trimethylene bis(phenyl biguanide); and the corresponding pharmaceutically
acceptable salts of all of the above such as the acetates; gluconates;
hydrochlorides; hydrobromides; citrates; bisulfites; fluorides; polymaleates;
N-
coconutalkylsarcosinates; phosphites; hypophosphites; perfluorooctanoates;
10 silicates; sorbates; salicylates; maleates; tartrates; fumarates;
ethylenediaminetetraacetates; iminodiacetates; cinnamates; thiocyanates;
arginates; pyromellitates; tetracarboxybutyrates; benzoates; glutarates;
monofluorophosphates; and perfluoropropionates, and mixtures thereof.
Preferred antimicrobials from this group are 1,6-di-(N1,N1'-phenyldiguanido-
15 N5,N5')-hexane tetrahydrochloride; 1,6-di(N1,N1'-o-chlorophenyldiguanido-
N5,N5')-hexane dihydrochloride; 1,6-di(N1,N1'-2,6-dichlorophenyldiguanido-
N5,N5')hexane dihydrochloride; 1,6-di(N1,N1'-2,4-dichlorophenyldiguanido-
N5,N5')hexane tetra hydrochloride; 1,6-di[N1,N1'-.alpha.-(p-chlorophenyl)
ethyldiguanido-N5,N5'] hexane dihydrochloride;.omega.:.omega.'di(N1, N1'-p-
20 chlorophenyldiguanido-N5,N5')m-xylene dihydrochloride; 1,12-di(N1,N1'-p-
chlorophenyldiguanido-N5,N5') dodecane dihydrochloride; 1,6-di(N1,N1'-o-
chlorophenyldiguanido-N5,N5') hexane dihydro chloride; 1,6-di(N1,N1'-p-
chlorophenyldiguanido-N5,N5')-hexane tetrahydrochloride; and mixtures thereof;
more preferably, 1,6-di(N1,N1'-o-chloraphenyldiguanido-N5,N5')-hexane
25 dihydrochloride; 1,6-di(N1,N1'-2,6-dichlorophenyldiguanido-N5,N5') hexane
dihydrochloride; 1,6-di(N1,N1'-2,4-dichlorophenyldiguanido-N5,N5')hexane
tetrahydrochloride; 1,6-di[N1,N1'-.alpha.-(p-chlorophenyl) ethyldiguanido-
N5,N5']
hexane dihydrochloride;.omega.:.omega.'di(N1, N1'-p-chlorophenyldiguanido-
N5,N5')m-xylene dihydrochloride; 1,12-di(N1,N1'-p-chlorophenyidiguanido-
30 N5,N5') dodecane dihydrochloride; 1,6-di(N1,N1'-o-chlorophenyldiguanido-
N5,N5') hexane dihydrochloride; 1,6-di(N1,N1'-p-chlorophenyldiguanido-N5,N5')-
hexane tetrahydro chloride; and mixtures thereof. As stated hereinbefore, the
bis
biguanide of choice is chlorhexidine its salts, e.g., digluconate,
dihydrochloride,
diacetate, and mixtures thereof.


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41
Quaternary Compounds. A wide range of quaternary compounds can also be
used as antimicrobial actives, in conjunction with the preferred surfactants,
for
compositions of the present invention that do not contain cyclodextrin. Non-
limiting examples of useful quaternary compounds include: (1) benzalkonium
chlorides andlor substituted benzalkonium chlorides such as commercially
available Barquat~ (available from Lonza), Maquat~ (available from Mason),
Variquat~ (available from Witco/Sherex), and Hyamine~ (available from Lonza);
(2) dialkyl quaternary such as Bardac~ products of Lonza, (3) N-(3-
chloroallyl)
hexaminium chlorides such as Dowicide~ and Dowicil~ available from Dow; (4)
benzethonium chloride such as Hyamine~ 1622 from Rohm & Haas; (5)
methylbenzethonium chloride represented by Hyamine~ 10X supplied by Rohm
& Haas, (6) cetylpyridinium chloride such as Cepacol chloride available from
of
Merrell Labs. Typical concentrations for biocidal effectiveness of these
quaternary compounds range from about 0.001 % to about 0.8%, preferably from
about 0.005% to about 0.3%, more preferably from about 0.01 % to 0.2%, by
weight of the usage composition. The corresponding concentrations for the
concentrated compositions are from about 0.003% to about 2%, preferably from
about 0.006% to about 1.2%, and more preferably from about 0.1 % to about
0.8% by weight of the concentrated compositions.
Other preservatives which are conventional in the art, such as described in US
5,593, 670 incorporated herein by reference, may also be used herein.
The surfactants, when added to the antimicrobials tend to provide improved
antimicrobial action. This is especially true for the siloxane surfactants,
and
especially when the siloxane surfactants are combined with the chlorhexidine
antimicrobial actives.
5-Perfume
The composition of the present invention can also optionally provide a "scent
signal" in the form of a pleasant odor which signals the removal of malodor
from
fabrics. The scent signal is designed to provide a fleeting perfume scent, and
is
not designed to be overwhelming or to be used as an odor masking ingredient.
When perfume is added as a scent signal, it is added only at very low levels,
e.g.,
from about 0% to about 0.5%, preferably from about 0.003% to about 0.3%,


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42
more preferably from about 0.005% to about 0.2%, by weight of the usage
composition.
Perfume can also be added as a more intense odor in product and on surfaces.
When stronger levels of perfume are preferred, relatively higher levels of
perfume
can be added. Any type of perfume can be incorporated into the composition of
the present invention.
Preferably the perfume is hydrophilic and is composed predominantly of
ingredients selected from two groups of ingredients, namely, (a) hydrophilic
ingredients having a CIogP of less than about 3.5, more preferably less than
about 3.0, and (b) ingredients having significant low detection threshold, and
mixtures thereof. Typically, at least about 50%, preferably at least about
60%,
more preferably at least about 70%, and most preferably at least about 80% by
weight of the perfume is composed of perfume ingredients of the above groups
(a) and (b).
(a). Hydrophilic Perfume Ingredients
The hydrophilic perfume ingredients are more soluble in water, have less of a
tendency to complex with the cyclodextrins, and are more available in the odor
absorbing composition than the ingredients of conventional perfumes. The
degree of hydrophobicity of a perfume ingredient can be correlated with its
octanol/water partition coefficient P. The octanol/water partition coefficient
of a
perfume ingredient is the ratio between its equilibrium concentration in
octanol
and in water. A perfume ingredient with a greater partition coefficient P is
considered to be more hydrophobic. Conversely, a perfume ingredient with a
smaller partition coefficient P is considered to be more hydrophilic. Since
the
partition coefficients of the perfume ingredients normally have high values,
they
are more conveniently given in the form of their logarithm to the base 10,
IogP.
Thus the preferred perfume hydrophilic perfume ingredients of this invention
have IogP of about 3.5 or smaller, preferably of about 3.0 or smaller.
The IogP of many perfume ingredients have 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 IogP values are most conveniently calculated
by


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43
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 IogP" (CIogP) is determined by the fragment approach of Hansch
and Leo (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch,
P. G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press,
1990, incorporated herein by reference). The fragment approach is based on the
chemical structure of each perfume ingredient, and takes into account the
numbers and types of atoms, the atom connectivity, and chemical bonding. The
CIogP values, which are the most reliable and widely used estimates for this
physicochemical property, are used instead of the experimental IogP values in
the selection of perfume ingredients which are useful in the present
invention.
Non-limiting examples of the more preferred hydrophilic perfume ingredients
are
allyl amyl glycolate, allyl caproate, amyl acetate, amyl propionate, anisic
aldehyde, anisyl acetate, anisole, benzaldehyde, benzyl acetate, benzyl
acetone,
benzyl alcohol, benzyl formate, benzyl iso valerate, benzyl propionate, beta
gamma hexenol, calone, camphor gum, laevo-carveol, d-carvone, laevo-carvone,
cinnamic alcohol, cinnamyl acetate, cinnamic alcohol, cinnamyl formate,
cinnamyl propionate, cis jasmone, cis-3-hexenyl acetate, coumarin, cuminic
alcohol, cuminic aldehyde, Cyclal C, cyclogalbanate, dihydroeuginol, dihydro
isojasmonate, dimethyl benzyl carbinol, dimethyl benzyl carbinyl acetate,
ethyl
acetate, ethyl aceto acetate, ethyl amyl ketone, ethyl anthranilate, ethyl
benzoate, ethyl butyrate, ethyl cinnamate, ethyl hexyl ketone, ethyl maltol,
ethyl-
2-methyl butyrate, ethyl methylphenyl glycidate, ethyl phenyl acetate, ethyl
salicylate, ethyl vanillin, eucalyptol, eugenol, eugenyl acetate, eugenyl
formate,
eugenyl methyl ether, fenchyl alcohol, flor acetate (tricycio decenyl
acetate),
fructone, frutene (tricyclo decenyl propionate), geraniol, geranyl
oxyacetaldehyde, heliotropin, hexenol, hexenyl acetate, hexyl acetate, hexyl
formate, hinokitiol, hydratropic alcohol, hydroxycitronellal,
hydroxycitronellal
diethyl acetal, hydroxycitronellol, indole, isoamyl alcohol, iso cyclo citral,
isoeugenol, isoeugenyl acetate, isomenthone, isopulegyl acetate, isoquinoline,
keone, ligustral, linalool, linalool oxide, linalyl formate, lyral, menthone,
methyl
acetophenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl
benzyl acetate, methyl cinnamate, methyl dihydrojasmonate, methyl eugenol,
methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methyl hexyl
ketone, methyl isobutenyl tetrahydropyran, methyl-N-methyl anthranilate,
methyl


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44
beta naphthyl ketone, methyl phenyl carbinyl acetate, methyl salicylate,
nerol,
nonalactone, octalactone, octyl alcohol (octanol-2), para-anisic aldehyde,
para-
cresol, para-cresyl methyl ether, para hydroxy phenyl butanone, para-methoxy
acetophenone, para-methyl acetophenone, phenoxy ethanol, phenoxyethyl
propionate, phenyl acetaldehyde, phenylacetaldehyde diethyl ether, phenylethyl
oxyacetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenyl ethyl
dimethyl
carbinol, prenyl acetate, propyl butyrate, pulegone, rose oxide, safrole,
terpineol,
vanillin, viridine, and mixtures thereof.
Nonlimiting examples of other preferred hydrophilic perfume ingredients which
can be used in perfume compositions of this invention are allyl heptoate, amyl
benzoate, anethole, benzophenone, carvacrol, citral, citronellol, citronellyl
nitrite,
cyclohexyl ethyl acetate, cymal, 4-decenal, dihydro isojasmonate, dihydro
myrcenol, ethyl methyl phenyl glycidate, fenchyl acetate, florhydral, gamma-
nonalactone, geranyl formate, geranyl nitrite, hexenyl isobutyrate, alpha-
ionone,
isobornyl acetate, isobutyl benzoate, isononyl alcohol, isomenthol, para-
isopropyl phenylacetaldehyde, isopulegol, linalyl acetate, 2-methoxy
naphthalene, menthyl acetate, methyl chavicol, musk ketone, beta naphthol
methyl ether, neral, nonyl aldehyde, phenyl heptanol, phenyl hexanol, terpinyl
acetate, Veratrol, yara-yara, and mixtures thereof.
The preferred perfume compositions used in the present invention contain at
least 4 different hydrophilic perfume ingredients, preferably at least 5
different
hydrophilic perfume ingredients, more preferably at least 6 different
hydrophilic
perfume ingredients, and even more preferably at least 7 different hydrophilic
perfume ingredients. Most common perfume ingredients which are derived from
natural sources are composed of a multitude of components. When each such
material is used in the formulation of the preferred perfume compositions of
the
present invention, it is counted as one single ingredient, for the purpose of
defining the invention.
(b). Low Odor Detection Threshold Perfume Ingredient
The odor detection threshold of an odorous material is the lowest vapor
concentration of that material which can be olfactorily detected. The odor
detection threshold and some odor detection threshold values are discussed in,


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e.g., "Standardized Human Olfactory Thresholds", M. Devos et al, IRL Press at
Oxford University Press, 1990, and "Compilation of Odor and Taste Threshold
Values Data", F. A. Fazzalari, editor, ASTM Data Series DS 48A, American
Society for Testing and Materials, 1978, both of said publications being
5 incorporated by reference. The use of small amounts of perfume ingredients
that
have iow odor detection threshold values can improve perfume odor character,
even though they are not as hydrophilic as perfume ingredients of group (a)
which are given hereinabove. Perfume ingredients that do not belong to group
(a) above, but have a significantly low detection threshold, useful in the
10 composition of the present invention, are selected from the group
consisting of
ambrox, bacdanol, benzyl saficylate, butyl anthranilate, cetalox, damascenone,
alpha-damascone, gamma-dodecalactone, ebanol, herbavert, cis-3-hexenyl
salicylate, alpha-ionone, beta-ionone, alpha-isomethylionone, lilial, methyl
nonyl
ketone, gamma-undecalactone, undecylenic aldehyde, and mixtures thereof.
15 These materials are preferably present at low levels in addition to the
hydrophilic
ingredients of group (a), typically less than about 20%, preferably less than
about
15%, more preferably less than about 10%, by weight of the total perfume
compositions of the present invention. However, only low levels are required
to
provide an effect.
There are also hydrophilic ingredients of group (a) that have a significantly
low
detection threshold, and are especially useful in the composition of the
present
invention. Examples of these ingredients are allyl amyl glycolate, anethole,
benzyl acetone, calone, cinnamic alcohol, coumarin, cyclogalbanate, Cyclal C,
cymal, 4-decenal, dihydro isojasmonate, ethyl anthranilate, ethyl-2-methyl
butyrate, ethyl methylphenyl glycidate, ethyl vanillin, eugenol, flor acetate,
florhydral, fructose, frutene, heliotropin, keone, indole, iso cyclo citral,
isoeugenol, lyral, methyl heptine carbonate, linalool, methyl anthranilate,
methyl
dihydrojasmonate, methyl isobutenyl tetrahydropyran, methyl beta naphthyl
ketone, beta naphthol methyl ether, nerol, para-anisic aldehyde, para hydroxy
phenyl butanone, phenyl acetaldehyde, vanillin, and mixtures thereof. Use of
low
odor detection threshold perfume ingredients minimizes the level of organic
material that is released into the atmosphere.
6- Soil Release Agent


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46
Soil Release agents are desirably used in compositions of the instant
invention.
Any polymeric soil release agent known to those skilled in the art can
optionally
be employed in the compositions 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 SM100,
METOLOSE SM200 manufactured by Shin-etsu Kagaku Kogyo K.K., SOKALAN


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47
type of material, e.g., SOKALAN HP-22, available from BASF (Germany),
ZELCON 5126 (from Dupont) and MILEASE T (from ICI).
7-Pro-perfume
The composition may also comprises ingredient useful for providing a long and
lasting release of a perfume material. Typical disclosure can be found in
W095/04809, W096/02625, PCT US97/14610 filed 19 August 1997 and
claiming priority of 19 August 1996, and EP-A-0,752,465.
Typical level of incorporation of the perfume are from 0.01 % to 15% by weight
of
the composition.
8-pH
An optional requirement of the compositions according to the present invention
is
that the pH is greater than 3, preferably between 3 and 12. This range is
preferred for fabric safety. When a lubricant of the diester quaternary
ammonium
type is used, it is most preferred to have the conventional pH range, as
measured in the neat compositions at 20 °C, of from 2.0 to 5,
preferably in the
range of 2.5 to 4.5, preferably about 2.5 to about 3.5. The pH of these
compositions herein can be regulated by the addition of a Bronsted acid.
9- Other Optional Ingredients
The present invention can include optional components conventionally used in
textile treatment compositions, for example, colorants, preservatives,
bactericides, optical brighteners, opacifiers, anti-shrinkage agents,
germicides,
fungicides, anti-oxidants, dye fixing agent, enzymes, chelating agents,
metallic
salts to absorb amine and sulfur-containing compounds and selected from the
group consisting of copper salts, zinc salts, and mixtures thereof, color
protectors
like polyethylene imine and its alkoxylated derivatives, and the like. The
compositions are preferably free of any material that would soil or stain
fabric,
and are also substantially free of starch. Typically, there should be less
than
about 0.5%, by weight of the composition, preferably less than about 0.3%,
more
preferably less than about 0.1 %, by weight of the composition, of starch
and/or
modified starch.
D. Form of the composition and compounds


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48
The composition or its individual components can be provided in any suitable
form such as spray, foam, gel or any other suitable form for liquid aqueous
compositions, preferably the composition is in the form of a spray.
Preferably,
when sprayed, the liquid composition which is applied on the fabric will have
particle sizes in the range of 8 to 100 ~,m, preferably from 10-60 ~,m (more
preferably from 20-60 Vim) for automatic sprayer, and preferably from 50-100
~m
for manually activated sprayer. Accordingly, there is provided a packaged
composition comprising the composition or compounds, in a spray dispenser.
E. Packaging
In another aspect of the invention, a packaged composition is provided that
comprises a packaged composition comprising a wrinkle reducing composition
comprising a wrinkle reducing active which contains a nonionic polyhydric
alcohol
humectant and a salt made of alkaline and/or earth alkaline metal, a liquid
carrier, and a spray dispensing device.
The dilute compositions, i.e., compositions containing from about 0.1 % to
about
5%, by weight of the composition, of wrinkle reducing active, of the present
invention are preferably sprayed onto fabrics and therefore are typically
packaged in a spray dispenser. The spray dispenser can be any of the manually
activated means for producing a spray of liquid droplets as is known in the
art,
e.g. trigger-type, pump-type, electrical spray, hydraulic nozzle, sonic
nebulizer,
high pressure fog nozzle, non-aerosol self pressurized, and aerosol-type spray
means. Automatic activated means can also be used herein. These type of
automatic means are similar to manually activated means with the exception
that
the propellant is replaced by a compressor. It is preferred that at least
about
70%, more preferably, at least about 80%, most preferably at least about 90%
of
the droplets have a particle size of smaller than about 200 microns.
The spray dispenser can be an aerosol dispenser. Said aerosol dispenser
comprises a container which can be constructed of any of the conventional
materials employed in fabricating aerosol containers. The dispenser must be
capable of withstanding internal pressure in the range of from about 5 to
about
100 p.s.i.g., more preferably from about 10 to about 60 p.s.i.g. The one
important
requirement concerning the dispenser is that it be provided with a valve
member
which will permit the wrinkle reducing composition contained in the dispenser
to


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49
be dispensed in the form of a spray of very fine, or finely divided, particles
or
droplets. The aerosol dispenser utilizes a pressurized sealed container from
which the wrinkle reducing composition is dispensed through a special
actuator/valve assembly under pressure. The aerosol dispenser is pressurized
by incorporating therein a gaseous component generally known as a propellant.
Common aerosol propellants, e.g., gaseous hydrocarbons such as isobutane,
and mixed halogenated hydrocarbons, are not preferred. Halogenated
hydrocarbon propellants such as chlorofluoro hydrocarbons have been alleged to
contribute to environmental problems. Preferred propellants are compressed
air,
nitrogen, inert gases, carbon dioxide, etc. A more complete description of
commercially available aerosol-spray dispensers appears in U.S. Pat. Nos.:
3,436,772, Stebbins, issued April 8, 1969; and 3,600,325, Kaufman et al.,
issued
August 17, 1971; both of said references are incorporated herein by reference.
Preferably the spray dispenser can be a self pressurized non-aerosol container
having a convoluted liner and an elastomeric sleeve. Said self pressurized
dispenser comprises a liner/sleeve assembly containing a thin, flexible
radially
expandable convoluted plastic liner of from about 0.010 to about 0.020 inch
thick,
inside an essentially cylindrical elastomeric sleeve. The liner/sleeve is
capable of
holding a substantial quantity of odor-absorbing fluid product and of causing
said
product to be dispensed. A more complete description of self pressurized spray
dispensers can be found in U.S. Pat. Nos. 5,111,971, Wner, issued May 12,
1992, and 5,232,126, Winer, issued Aug. 3, 1993; both of said references are
herein incorporated by reference. Another type of aerosol spray dispenser is
one
wherein a barrier separates the wrinkle reducing composition from the
propellant
(preferably compressed air or nitrogen), as is disclosed in U.S. Pat. No.
4,260,110, issued April 7, 1981, incorporated herein by reference. Such a
dispenser is available from EP Spray Systems, East Hanover, New Jersey.
More preferably, the spray dispenser is a non-aerosol, manually activated,
pump-
spray dispenser. Said pump-spray dispenser comprises a container and a pump
mechanism which securely screws or snaps onto the container. The container
comprises a vessel for containing the wrinkle reducing composition to be
dispensed.
The pump mechanism comprises a pump chamber of substantially fixed volume,
having an opening at the inner end thereof. Within the pump chamber is located


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a pump stem having a piston on the end thereof disposed for reciprocal motion
in
the pump chamber. The pump stem has a passageway there through with a
dispensing outlet at the outer end of the passageway and an axial inlet port
located inwardly thereof.
5
The container and the pump mechanism can be constructed of any conventional
material employed in fabricating pump-spray dispensers, including, but not
limited to: polyethylene; polypropylene; polyethyleneterephthalate; blends of
polyethylene, vinyl acetate, and rubber eiastomer. Other materials can include
10 stainless steel. A more complete disclosure of commercially available
dispensing
devices appears in: U.S. Pat. Nos.: 4,895,279, Schultz, issued January 23,
1990; 4,735,347, Schultz et al., issued April 5, 1988; and 4,274,560, Carter,
issued June 23, 1981; all of said references are herein incorporated by
reference.
Most preferably, the spray dispenser is a manually activated trigger-spray
dispenser. Said trigger-spray dispenser comprises a container and a trigger
both
of which can be constructed of any of the conventional material employed in
fabricating trigger-spray dispensers, including, but not limited to:
polyethylene;
polypropylene; polyacetal; polycarbonate; polyethyleneterephthalate; polyvinyl
chloride; polystyrene; blends of polyethylene, vinyl acetate, and rubber
elastomer. Other materials can include stainless steel and glass. The trigger-
spray dispenser does not incorporate a propellant gas. The trigger-spray
dispenser herein is typically one which acts upon a discrete amount of the
wrinkle reducing composition itself, typically by means of a piston or a
collapsing
bellows that displaces the composition through a nozzle to create a spray of
thin
liquid. Said trigger-spray dispenser typically comprises a pump chamber having
either a piston or bellows which is movable through a limited stroke response
to
the trigger for varying the volume of said pump chamber. This pump chamber or
bellows chamber collects and holds the product for dispensing. The trigger
spray
dispenser typically has an outlet check valve for blocking communication and
flow of fluid through the nozzle and is responsive to the pressure inside the
chamber. For the piston type trigger sprayers, as the trigger is compressed,
it
acts on the fluid in the chamber and the spring, increasing the pressure on
the
fluid. For the bellows spray dispenser, as the bellows is compressed, the
pressure increases on the fluid. The increase in fluid pressure in either
trigger


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51
spray dispenser acts to open the top outlet check valve. The top valve allows
the
product to be forced through the swirl chamber and out the nozzle to form a
discharge pattern. An adjustable nozzle cap can be used to vary the pattern of
the fluid dispensed.
For the piston spray dispenser, as the trigger is released, the spring acts on
the
piston to return it to its original position. For the bellows spray dispenser,
the
bellows acts as the spring to return to its original position. This action
causes a
vacuum in the chamber. The responding fluid acts to close the outlet valve
while
opening the inlet valve drawing product up to the chamber from the reservoir.
A more complete disclosure of commercially available dispensing devices
appears in U.S. Pat. Nos. 4,082,223, Nozawa, issued Apr. 4, 1978; 4,161, 288,
McKinney, issued Jul. 17, 1985; 4,434,917, Saito et al., issued Mar. 6, 1984;
and 4,819,835, Tasaki, issued Apr. 11, 1989; 5,303,867, Peterson, issued Apr.
19, 1994; all of said references are incorporated herein by reference.
A broad array of trigger sprayers or finger pump sprayers are suitable for use
with the compositions of this invention. These are readily available from
suppliers such as Calmar, Inc., City of Industry, California; CSI (Continental
Sprayers, Inc.), St. Peters, Missouri; Berry Plastics Corp., Evansville,
Indiana - a
distributor of Guala~ sprayers; or Seaquest Dispensing, Cary, Illinois.
The preferred trigger sprayers are the blue inserted Guala~ sprayer, available
from Berry Plastics Corp., the Calmar TS800-1A~ sprayers, available from
Calmar Inc., or the CSI T7500~ available from Continental Sprayers, Inc.,
because of the fine uniform spray characteristics, spray volume, and pattern
size.
Any suitable bottle or container can be used with the trigger sprayer, the
preferred bottle is a 17 fl-oz. bottle (about 500 ml) of good ergonomics
similar in
shape to the Cinch~ bottle. It can be made of any materials such as high
density
polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyethylene
terephthalate, glass, or any other material that forms bottles. Preferably, it
is
made of high density polyethylene or polyethylene terephthalate.


CA 02330473 2000-10-26
WO 99/55948 PCTNS98/08125
52
For smaller four fl-oz. size (about 118 ml), a finger pump can be used with
canister or cylindrical bottle. The preferred pump for this application is the
cylindrical Euromist I1~ from Seaquest Dispensing.
Regardless of the particular commercial spray nozzle used, it is preferable
for the
atomization spray nozzle to have an orifice diameter of from about 0.1 mm to
about 2 mm, and most preferably from about 0.15 mm to about 1 mm. The
spraying step is conducted for a period of time of from about 5 minutes to
about
30 minutes, more preferably from about 5 minutes to about 20 minutes. Spraying
times will vary depending upon the various operating parameters selected as
described herein.
For use herein, it is preferred that said spray dispenser comprises a trigger
spray
device. More preferably, the spray dispenser should be capable of providing
droplets with a weight average diameter of from 8 to 100 Vim, preferably from
10-
60 ~m (more preferably from 20-60 Vim) for automatic sprayer, and preferably
from 50-100 p,m for manually activated sprayer.
F. Method of use
An effective amount of the composition of the present invention is preferably
sprayed onto fabrics, particularly clothing. When the composition is sprayed
onto
fabric an effective amount should be deposited onto the fabric without causing
saturation of the fabric, typically from 3 % to 85%, preferably from 5 % to
50%,
more preferably from 5 % to 25 %, by weight of the fabric. The amount of total
active typically sprayed onto the fabric is from 0.01 % to 3 %, preferably
from
0.1 % to 2 %, more preferably from 0.1 % to 1 %, by weight of the fabric. Once
an
effective amount of the composition is sprayed onto the fabric the fabric is
optionally, but preferably stretched. The fabric is typically stretched
perpendicular to the wrinkle. The fabric can also be smoothed by hand after it
has been sprayed. The smoothing movement works particularly well on areas of
clothing that have interface sewn into them, or on the hem of clothing. Once
the
fabric has been sprayed and optionally, but preferably, stretched, it is hung
until
dry.


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
53
Accordingly, there is provided a method for reducing wrinkles on fabrics which
comprises the steps of contacting the fabrics with a composition of the
invention,
as defined herein before.
By "contacting", it is meant any steps that is suitable for providing a
contact of the
composition with the fabric. This can include by soaking, washing, rinsing,
andlor
spraying as well as by means of a dryer sheet onto which is adsorbed the
composition.
Further, the use of the nonionic humectant as defined herein has also been
found beneficial to the reduction of wrinkles upon the treatment of fabrics.
Accordingly, there is also provided use of the nonionic polyhydric alcohol
humectant for reducing wrinkles on fabrics treated therewith.
Of course, when the humectant is in individual form, it can be provided in any
suitable form for the contacting with the fabric to occur, such as in liquid
form like
aqueous form.
The composition of the present invention can also be used as an ironing aid.
An
effective amount of the composition can be sprayed onto fabric, wherein said
fabric should not be sprayed to saturation. The fabric can be ironed at the
normal
temperature at which it should be ironed. The fabric can be sprayed with an
effective amount of the composition, allowed to dry and then ironed, or
sprayed
and ironed immediately.
In a still further aspect of the invention, the composition can be sprayed
onto
fabrics by means of an in-home de-wrinkling apparatus containing the fabric to
be dewrinkled, thereby providing ease of operation. Conventional personal as
well as industrial de-wrinkling apparatus are suitable for use herein.
Traditionally,
these apparatus act by a steaming process which provides a relaxing of the
fibers. The spraying of the composition or compounds on the fabrics can then
occurs within the chamber of the apparatus or before placing the fabrics into
the
chamber. Again, the spraying means should preferably be capable of providing
droplets with a mean diameter of from 3 to 50 Vim, preferably from 5-30 prn
for
automatic sprayer, and preferably from 50-100 pm for manually activated
sprayer. Preferably, the loading of moisture on fabrics made of natural and


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
54
synthetic fibers is from 5 to 25%, more preferably from 5 to 10% by weight of
the
dried fabric. Other conventional steps for the dewrinkling apparatus can be
applied such as heating and drying. Optionally, for optimum dewrinkling
benefit,
the temperature of the conditioning composition can be heated to enhance
distribution and deposition of the conditioning composition on the garments.
In
that regard, the temperature of the conditioning composition can be as low as
room temperature, and preferably is from 35°C to 80°C, more
preferably from 40-
70°C. By having the conditioning composition at the aforementioned
elevated
temperatures, it has been found that superior de-wrinkling benefits are
achieved.
It should be understood that the temperature of the conditioning composition
can
be from about ambient (15°C) temperature to about 80°C, and
higher
temperatures generally improve de-wrinkling performance.
It has also been found that effective softening composition distribution on
the
garments, e.g inside the cabinet, can be further enhanced by optimally
selecting
the fluid surface tension of the softening composition. For example, it is
preferable for the softening composition to have fluid surface tension of from
about 5 dynes/cm to about 60 dynes/cm, more preferably of from about 20
dynes/cm to about 55 dynes/cm, and most preferably, from about 20 dynes/cm to
about 30 dynes/cm. The lower surface tension of the softening composition
improves effective distribution by improving surface absorption and spreading
of
the softening composition on the garment fabric.
Furthermore, it is preferable for the softening composition to have a fluid
viscosity
of from about 1 cps to about 100 cps, more preferably from about 1 cps to
about
50 cps, and most preferably of from about 1 cps to about 20 cps as measured by
a standard Brookfield viscometer.
In the examples, the abbreviated component identifications have the following
meanings:
Wetting agent 1: N,N dimethyl-N-(2-hydroxyethyl)-N-dodecyl/tetradecyl
ammonium bromide
Wetting agent 2: C12/C14 Choline ester
Wetting agent 3: C8/C12 dimethyl, hydroxyethyl quaternary ammonium salt
Wetting agent 4: Silwet L-7600 commercially available from OSi Specialties
Lubricant: N, N-di-(canolyl-oxy-ethyl)-N-methyl-N-(2-hydroxyethyl)


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
ammonium methyl sulfate
Cyclodextrin: Hydroxypropyl beta-cyclodextrin
preservative: Kathon
Dye fixative: Cationic dye fixing agent (50% active) available under the
5 tradename Tinofix Eco from Ciba-Geigy
Carezyme: Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO
Industries A/S and of activity mentioned above unless
otherwise specified
10 The invention is illustrated in the following non limiting examples, in
which all
percentages are on a weight basis unless otherwise stated.
Example I
A B C D E


Glycerol 0.75% 0.75% - - -


Di-ethylene - - 0.75% 0.75% 0.75%


glycol


Wetting agent 0.33% - - - -
1


Wetting agent - 0.25% 0.25% 0.25% 0.25%
4


Sodium sulphate0.75% 0.75% 0.75% - -


Calcium chloride0.75% 0.75% 0.75% 0.50% 0.75%


Lubricant - - - 0.40% -


Cyclodextrin 1.00% 1.00% - - -


Preservative 3 ppm 3 ppm - - -


Perfume 0.10% 0.10% - - -


Water Balance Balance Balance Balance Balance


20


CA 02330473 2000-10-26
WO 99/55948 PCT/US98/08125
56
F G H I


Sorbitol 0.7% - - -


Ethylene glycol - - 0.6% 1.0%


Propylene glycol - 3.0% -


Wetting agent 1 - - 1.5% -


Wetting agent 2 - 0.3% - -


Wetting agent 3 0.7% - - 0.5%


Magnesium sulphate 0.7% - 3.0% -


Sodium borate - - - 1.0%


Sodium citrate - 2.0% - -


Dye fixative - 0.5% - -


Carezyme - 0.1 % - -


Perfume 0.15% 0.3% 0.1 % 0.4%


Water Balance Balance Balance Balance



Representative Drawing

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Administrative Status

For a clearer understanding of the status of the application/patent presented on this page, the site Disclaimer , as well as the definitions for Patent , Administrative Status , Maintenance Fee  and Payment History  should be consulted.

Administrative Status

Title Date
Forecasted Issue Date Unavailable
(86) PCT Filing Date 1998-04-27
(87) PCT Publication Date 1999-11-04
(85) National Entry 2000-10-26
Examination Requested 2000-10-26
Dead Application 2006-04-27

Abandonment History

Abandonment Date Reason Reinstatement Date
2005-04-27 FAILURE TO PAY APPLICATION MAINTENANCE FEE

Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Request for Examination $400.00 2000-10-26
Registration of a document - section 124 $100.00 2000-10-26
Application Fee $300.00 2000-10-26
Maintenance Fee - Application - New Act 2 2000-04-27 $100.00 2000-10-26
Maintenance Fee - Application - New Act 3 2001-04-27 $100.00 2001-03-28
Registration of a document - section 124 $100.00 2001-04-27
Registration of a document - section 124 $100.00 2001-04-27
Maintenance Fee - Application - New Act 4 2002-04-29 $100.00 2002-03-27
Maintenance Fee - Application - New Act 5 2003-04-28 $150.00 2003-03-27
Maintenance Fee - Application - New Act 6 2004-04-27 $200.00 2004-03-26
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE PROCTER & GAMBLE COMPANY
Past Owners on Record
HUBESCH, BRUNO ALBERT JEAN
THOEN, CHRISTIAAN ARTHUR JACQUES KAMIEL
VERMOTE, CHRISTIAN LEO MARIE
WOO, RICKY AH-MAN
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Description 2000-10-26 56 2,866
Abstract 2000-10-26 1 48
Claims 2000-10-26 4 155
Cover Page 2001-02-21 1 30
Correspondence 2001-02-13 1 2
Assignment 2000-10-26 4 120
PCT 2000-10-26 16 665
Assignment 2001-04-27 4 235