Note: Descriptions are shown in the official language in which they were submitted.
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WO 01/42412 PCT/US00/32873
METHOD FOR PROVIDING IN-WEAR COMFORT
FIELD OF THE INVENTION
The present invention relates to a method for providing good in-wear comfort,
in
particular on the skin contacted with the treated fabric.
BACKGROUND OF THE INVENTION
Softening compositions have long been known in the art and are widely utilized
by consumers during for example the rinse cycles of automatic laundry
operations. The term "fabric softening" as used herein and as known in the art
refers to a process whereby a desirably soft hand and fluffy appearance are
imparted to fabrics. Typical of such softening compositions comprise softening
compounds like ditallowdimethylammonium chloride, and di-(tallowyloxyethyl)
dimethyl ammonium chloride.
Hence, the conventionally known softening compositions have been used to
reduce the harshness and wearing-out after multiple cycle to reduce the side
effect of the laundry process coupled with environmental effects, e.g. water
hardness. By use of such softening composition, the softness of the garment
and consequently the reduction of the mechanical friction between the garment
and dry skin is obtained.
Whilst these softening compositions are beneficial to the softness of the
treated
garment, it has now been found that a problem associated with these laundry
processes/applications delivering effective softness is that these also
hydrophobilise the fabric surface, thereby resulting in the loss of the
fabric's
ability to absorb water. As a result, the thermophysiological aspects of
clothes is
affected as well as is increased the friction on wetted skin. These are
perceived
as being detrimental to the in-wear comfort of the consumer.
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WO 01/42412 CA 02391904 2002-05-16 pCT~S00/32873
The detergent formulator is thus faced with the challenge of formulating a
product which provide good in-wear comfort, that is which maximises the
thermophysiological aspect of the clothes but minimises the friction on wetted
skin, i.e. minimises the hydrophobilisation of the treated fabric surface
whilst still
providing a good softness perception of the fabric to the consumer.
Indeed, it has been found that good in-wear comfort in clothing is governed by
the principle that your skin should be at it's natural moisture and
temperature
(i.e. thermophysiological aspect) coupled with reduced mechanical friction
between the treated fabric and the skin. Indeed, excessive moisture on the
skin
reduces the comfort in clothing by two fold: first by deviating it from the
natural
moisture balance on the skin and secondly by increasing the skin friction with
the clothing.
Accordingly, by "in-wear-comfort", it is meant that the softening compound
substantially maintains the natural moisture and temperature of the skin with
reduced mechanical friction between the fabric treated with the softening
compound and the skin contacted with the treated fabric upon Wearing. By
"substantially", it is meant that the maintenance of the natural moisture and
temperature of the skin upon wearing is of at least 80% identical to that of
the
natural moisture and temperature without contact with fabric. Stated
otherwise,
the softening compound maintains the balance between the air, heat (or
temperature) and moisture on the skin, thereby delivering a better climate
control for the clothes as well as for the skin (body) that are contacted with
the
treated fabric. Consequently, the skin can breathe and so does the cloth as
the
cloth absorb moisture away from the skin, i.e. the treated fabric provides a
thermal absorbency that reacts to the body's changing needs.
Whilst reducing the level of the softening compound employed in the rinse
tends
to ameliorate these problems, this is accompanied by a marked negative effect
on the softness perception.
Accordingly, there is need for a compound or composition that fulfills such a
need.
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WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
Recently, a new type of conditioning compound, namely the softening
compound having a transition temperature of less then 30°C, have found
increasing use in the domestic treatment of fabrics in order to provide clear
softening composition. Disclosure of such compounds can be found in recently
filed applications WO 98/47991 as well as in W097/03169 page 17-24, both
incorporated herein by reference.
It has now been found that the use of such softening compound fulfills such a
need by providing good in-wear comfort, in particular onto the skin.
SUMMARY OF THE INVENTION
The present invention relates to the use of a softening compound having a
transition temperature of less than 30°C for providing good in-wear
comfort.
In another aspect of the invention, there is provided a method for providing
in-
wear comfort to the skin contacted with treated fabrics, which comprises the
steps of contacting the fabric with a softening compound or composition as
defined herein.
These and other objects, features, and advantages will become apparent to
those of ordinary skill in the art from a reading of the following detailed
description and the appended claims. All percentages, ratios and proportions
herein are by weight, unless otherwise specified. All temperatures are in
degrees Celsius (o C) unless otherwise specified. All documents cited are in
relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
The following is a description of the essential element of the present
invention.
Softening compound having a transition temperature of less than
30°C
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Fabric softening actives having a transition temperature of less than
30°C are
an essential element of the invention compositions.
By "transition temperature", it is meant that the temperature at which the
physical state of the softener active changes from crystalline into liquid
crystalline when in contact with water, as measured by e.g. running
Differential
Scanning Calorimetry with a DSC apparatus ex TA Instruments, on a dispersion
of the softener active in water.
The preferred fabric softening actives according to the present invention are
amines having the formula:
~R)3_m N~OH2)n-Q-R
m
quaternary ammonium compounds having the formula:
(R)øm N ~(CH2)n-Q-R' I X
--'' m
or
~R)4-m N ~CH2)n- CH CH2 - Q - R~ X_
m
R~
and mixtures thereof, wherein each R is independently C1-C6 alkyl, C1-C6
hydroxyalkyl, benzyl, and mixtures thereof; R1 is preferably C11-C22 linear
alkyl, C11-C22 branched alkyl, C11-C22 linear alkenyl, C11-C22 branched
alkenyl, and mixtures thereof; Q is a carbonyl moiety independently selected
from the group consisting of esters, secondary amides, tertiary amides,
carbonate, mono carbonyl substituted alkylene, poly carbonyl substituted
alkylene, and mixtures thereof, preferably ester or secondary amide; X is a
softener compatible anion; the index m has a value of from 1 to 3; the index n
has a value of from 1 to 4, preferably 2 or 3, more preferably 2.
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WO 01/42412 CA 02391904 2002-05-16 pCT~S00/32873
In the above fabric softener example, the unit -OC(0)R1 represents a fatty
acyl
unit which is typically derived from a triglyceride source. The triglyceride
source
is preferably 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. Preferably, the
source of
triglyceride is selected from canola oil, partially hydrogenated canola oil,
and
mixtures thereof.
The following are non-limiting examples of preferred softener actives
according
to the present invention.
N,N-di(oleyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(oleyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(oleylamidoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl
sulfate;
N,N-di(2-oleyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-canolyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;
N,N-di(2-oleyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N,N-di(2-canolyloxyethylcarbonyloxyethyl)-N,N-dimethyl ammonium
chloride;
N-(2-oleyloxy-2-ethyl)-N-(2-oleyloxy-2-oxo-ethyl)-N, N-dimethyl
ammonium chloride;
N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N, N-dimethyl
ammonium chloride;
N,N,N-tri(oleyl-oxy-ethyl)-N-methyl ammonium chloride;
N,N,N-tri(canolyl-oxy-ethyl)-N-methyl ammonium chloride;
N-(2-oleyloxy-2-oxoethyl)-N-(oleyl)-N,N-dimethyl ammonium chloride;
N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dimethyl ammonium
chloride;
1,2-dioleyloxy-3-N,N,N-trimethylammoniopropane chloride; and
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WO 01/42412 PCT/US00/32873
1,2-dicanolyloxy-3-N,N,N-trimethylammoniopropane chloride;
and mixtures of the above actives.
A typical description of these softening ingredients is given in WO 98/47991
as
well as in as described in W097/03169 page 17-24.
A further description of fabric softening agents useful herein are described
in
U.S. 5,643,865 Mermelstein et al., issued July 1, 1997; U.S. 5,622,925 de
Buzzaccarini et al., issued April 22, 1997; U.S. 5,545,350 Baker et al.,
issued
August 13, 1996; U.S. 5,474,690 Wahl et al., issued December 12, 1995; U.S.
5,417,868 Turner et al., issued January 27, 1994; U.S. 4,661,269 Trinh et al.,
issued April 28, 1987; U.S. 4,439,335 Burns, issued March 27, 1984; U.S.
4,401,578 Verbruggen, issued August 30, 1983; U.S. 4,308,151 Cambre, issued
December 29, 1981; U.S. 4,237,016 Rudkin et al., issued October 27, 1978;
U.S. 4,233,164 Davis, issued November 11, 1980; U.S. 4,045,361 Watt et al.,
issued August 30, 1977; U.S. 3,974,076 Wiersema et al., issued August 10,
1976; U.S. 3,886,075 Bernadino, issued May 6, 1975; U.S. 3,861,870 Edwards
et al., issued January 21 1975; and European Patent Application publication
No.
472,178, by Yamamura et al., all of said documents being incorporated herein
by reference.
OPTIONAL INGREDIENTS
The fabric softening active as above defined may suitably be incorporated into
a
composition. Accordingly, the fabric care compositions of the present
invention
will typically comprise at least about 0.05%, preferably at least about 1 %,
more
preferably from about 10%, more preferably from about 20% to about 80%, more
preferably to about 60%, most preferably to about 45% by weight, of the
composition of one or more fabric softener actives having a transition
temperature of less than 30°C, preferably below 15°C.
Preferably, the
composition may then comprises a liquid carrier as well as any of the
following
optional ingredients.
Liauid Carrier
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WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
Suitable liquid carriers are selected from water, organic solvents and
mixtures
thereof. The liquid carrier employed in the instant compositions is preferably
at
least primarily water due to its low cost relative availability, safety, and
environmental compatibility. The level of water in the liquid carrier is
preferably
at least 50%, most preferably at least 60%, by weight of the carrier. Mixtures
of
water and low molecular weight, e.g., <200, organic solvent, e.g., lower
alcohol
such as ethanol, propanol, isopropanol or butanol are useful as the carrier
liquid. Low molecular weight alcohols include monohydric, dihydric (glycol,
etc.)
trihydric (glycerol, etc.), and higher polyhydric (polyols) alcohols.
Principal solvent
The compositions defined herein, preferably the isotropic liquid
embodiments thereof, may also optionally comprise a principal solvent. The
level of principal solvent present in the compositions of the present
invention is
typically less than about 95%, preferably less than about 50%, more preferably
less than about 25%, most preferably less than about 15% by weight. Some
embodiments of isotropic liquid embodiments of the present invention may
comprise no principal solvent but may substitute instead a suitable nonionic
surfactant.
The principal solvents for use herein are primarily used to obtain liquid
compositions having sufficient clarity and viscosity. Principal solvents must
also
be selected to minmize solvent odor impact in the composition. For example,
isopropyl alcohol is not an effective principal solvent in that it does not
serve to
produce a composition having suitable viscosity. Isopropanol also fails as a
suitable principal solvent because it has a relatively strong odor.
Principal solvents are also selected for their ability to provide stable
compositions at low temperatures, preferably compositions comprising suitable
principal solvents are clear down to about 4o C and have the ability to fully
recover their clarity if stored as low as about 7° C.
The principal solvents for use herein are selected base upon their
octanol/water partition coefficient (P). The octanol/water partition
coefficient is a
measure of the ratio of the concentrations of a particular principal solvent
in
octanol and water at equilibrium. The partition coefficients are conveniently
expressed and reported as their logarithm to the base 10; IogP.
The IogP of many principal solvent species has been reported; for
example, the Ponmona92 database, available from Daylight Chemical
W~ X1/42412 CA 02391904 2002-05-16 PCT/US00/32873
Information Systems, Inc.(Daylight CIS), contains many, along with citations
to
the original literature.
However, the IogP values are most conveniently calculated by the
"CLOGP" program, also available from Daylight CIS. This program also lists
experimental IogP values when they are available in the Pomona92 database.
The "calculated 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. Ransden, Eds., p. 295,
Pergamon Press, 1990, incorporated herein by reference). The fragment
approach is based on the chemical structure of each HR species, and takes into
account the numbers and types of atoms, the atom connectivity, and chemical
bonding. CIogP values are the most reliable and widely used estimates for
octanol water partitioning. It will be understood by those skilled in the art
that
experimental log P values could also be used. Experimental log P values
represent a less preferred embodiment of the invention. Where experimental
log P values are used, the one hour log P values are preferred. Other methods
that can be used to compute CIogP include, e.g., Crippen's fragmentation
method as disclosed in J. Chem. Inf. Comput. Sci., 27a,21 (1987);
Viswanadhan's fragmentation method as disclosed in J. Chem. Inf. Comput.
Sci., 29; 163 (1989); and Broto's method as disclosed in Eur. J. Med. Chem. -
Chim. Theor., 19, 71 (1984).
The principal solvents suitable for use herein are selected from those
having a CIogP of from about 0.15 to about 1, preferably from about 0.15 to
about 0.64, more preferably from about 0.25 to about 0.62, most preferably
form
about 0.4 to about 0.6. Preferably the principal solvent is at least to some
degree an asymmetric molecule, preferably having a melting, or solidification
point which allows the principal solvent to be liquid at or near room
temperature.
Low molecular weight principal solvents may be desirable for some
embodiments. More preferred molecules are highly asymmetrical.
A further description of principal solvents suitable for use in the isotropic
liquid compositions of the present invention are thoroughly described in WO
97/03169 "Concentrated, Stable Fabric Softening Composition", published
January 30, 1997 and assigned to the Procter & Gamble Co.; WO 97/03170
"Concentrated, Water Dispersible, Stable, Fabric Softening Composition",
published January 30, 1997 and assigned to the Procter & Gamble Co.; and
WO 97/34972 "Fabric Softening Compound/Composition", published September
s
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WO 01/42412 PCT/US00/32873
25, 1997 and assigned to the Procter & Gamble Co. all included herein by
reference.
Dye fixing agent
Dye fixing agent is an optional component of the composition. Dye fixing
agents,
or "fixatives", are well-known, commercially available materials which are
designed to improve the appearance of dyed fabrics by minimizing the loss of
dye from fabrics due to washing. Not included within this definition are
components which are fabric softeners or those described hereinafter as amino-
functional polymers.
Many dye fixing agents are cationic, and are based on various quaternized or
otherwise cationically charged organic nitrogen compounds. Cationic fixatives
are available under various trade names from several suppliers. Representative
examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and
CROSCOLOR NOFF (January 1988, Code No. 8544) from Crosfield; INDOSOL
E-50 (February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) from
Sandoz; SANDOFIX TPS, which is also available from Sandoz and is a
preferred polycationic fixative for use herein and SANDOFIX SWE (cationic
resinous compound), REWIN SRF, REWIN SRF-O and REWIN DWR from
CHT-Beitlich GMBH, Tinofix~ ECO, Tinofix~FRD and Solfin~ available from
Ciba-Geigy.
Other cationic dye fixing agents are described in "Aftertreatments for
improving
the fastness of dyes on textile fibres" by Christopher C. Cook (REV. PROG.
COLORATION Vol. 12, 1982). Dye fixing agents suitable for use in the present
invention are ammonium compounds such as fatty acid - diamine condensates
e.g. the hydrochloride, acetate, metosulphate and benzyl hydrochloride of
oleyldiethyl aminoethylamide, oleylmethyl-diethylenediaminemethosulphate,
monostearyl-ethylene diaminotrimethylammonium methosulphate and oxidized
products of tertiary amines; derivatives of polymeric alkyldiamines, polyamine-
cyanuric chloride condensates and aminated glycerol dichlorohydrins.
Preferred dye fixing agents are the cellulose reactive dye fixing agents.
The term "cellulose reactive dye fixing agent" is defined herein as "a dye
fixative
agent which reacts with the cellulose fibers upon application of heat or upon
a
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WO 01/42412 PCT/US00/32873
heat treatment either in situ or by the formulator". The cellulose reactive
dye
fixing agents suitable for use in the present invention can be defined by the
following test procedure.
Cellulose Reactivity Test (CRT)
Four pieces of fabric which are capable of bleeding their dye (e.g. 10 x 10 cm
of
knitted cotton dyed with Direct Red 80) are selected. Two swatches are used as
a first control and a second control, respectively. The two remaining swatches
are soaked for 20 minutes in an aqueous solution containing 1 % (w/w) of the
cellulose reactive dye fixing agent to be tested. The swatches are removed and
thoroughly dried. One of the treated swatches which has been thoroughly dried,
is passed ten times through an ironing calender which is adjusted to a "linen
fabric" temperature setting. The first control swatch is also passed ten times
through an ironing calender on the same temperature setting.
All four swatches ( the two control swatches and the two treated swatches, one
of each which has been treated by the ironing calender) are washed separately
in Launder-O-Meter pots under typical conditions with a commercial detergent
used at the recommended dosage for '/2 hour at 60°C, followed by a
thorough
rinsing of 4 times 200 ml of cold water and subsequently line dried.
Color fastness is then measured by comparing the DE values of a new
untreated swatch with the four swatches which have undergone the testing. DE
values, the computed color difference, is defined in ASTM D2244. In general,
DE values relate to the magnitude and direction of the difference between two
psychophysical color stimuli defined by tristimulus values, or by chromaticity
coordinates and luminance factor, as computed by means of a specified set of
color-difference equations defined in the CIE 1976 CIELAB opponent-color
space, the Hunter opponent-color space, the Friele-Mac Adam-Chickering color
space or any equivalent color space. For the purposes of the present
invention,
the lower the DE value for a sample, the closer the sample is to the un-tested
sample and the greater the color fastness benefit.
As the test relates to selection or a cellulose reactive dye fixing agent, if
the DE
value for the swatch treated in the ironing step has a value which is better
than
the two control swatches, the candidate is a cellulose reactive dye fixing
agent
for the purposes of the invention.
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WO 01/42412 PCT/LJS00/32873
Typically cellulose reactive dye fixing agents are compounds which contain a
cellulose reactive moiety, non limiting examples of these compounds include
halogeno-triazines, vinyl sulphones, epichlorhydrine derivatives,
hydroxyethylene urea derivatives, formaldehyde condensation products,
polycarboxylates, glyoxal and glutaraldehyde derivatives, and mixtures
thereof.
Further examples can be found in "Textile Processing and Properties", Tyrone
L. Vigo, at page 120 to 121, Elsevier (1997), which discloses specific
electrophilic groups and their corresponding cellulose affinity.
Preferred hydroxyethylene urea derivatives include
dimethyloldihydroxyethylene, urea, and dimethyl urea glyoxal. Preferred
formaldehyde condensation products include the condensation products derived
from formaldehyde and a group selected from an amino-group, an imino-group,
a phenol group, an urea group, a cyanamide group and an aromatic group.
Commercially available compounds among this class are Sandofix WE 56 ex
Clariant, Zetex E ex Zeneca and Levogen BF ex Bayer. Preferred
polycarboxylates derivatives include butane tetracarboxilic acid derivatives,
citric acid derivatives, polyacrylates and derivatives thereof. A most
preferred
cellulosic reactive dye fixing agents is one of the hydroxyethylene urea
derivatives class commercialized under the tradename of Indosol CR ex
Clariant. Still other most preferred cellulosic reactive dye fixing agents are
commercialized under the tradename Rewin DWR and Rewin WBS ex CHT R.
Beitlich.
The compositions defined in the present invention optionally comprise from
about 0.01 %, preferably from about 0.05%, more preferably from about 0.5% to
about 50%, preferably to about 25%, more preferably to about 10% by weight,
most preferably to about 5% by weight, of one or more dye fixing agents.
Crystal Growth Inhibitor
The compositions defined in the present invention optionally comprise
from about 0.005%, preferably from about 0.5%, more preferably from about
0.1 % to about 1 %, preferably to about 0.5%, more preferably to about 0.25%,
most preferably to about 0.2% by weight, of one or more crystal growth
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WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
inhibitors. The following "Crystal Growth Inhibition Test" is used to
determine
the suitability of a material for use as a crystal growth inhibitor.
Crystal Growth Inhibition Test (CGIT)
The suitability of a material to serve as a crystal growth inhibitor
according to the present invention can be determined by evaluating in vitro
the
growth rate of certain inorganic micro-crystals. The procedure of Nancollas et
al., described in "Calcium Phosphate Nucleation and Growth in Solution", Prog.
Crystal Growth Charact., Vol 3, 77-102, (1980), incorporated herein by
reference, is a method which is suitable for evaluating compounds for their
crystal growth inhibition. The graph below serves as an example of a plot
indicating the time delay (t-lag) in crystal formation afforded by a
hypothetical
crystal growth inhibitor.
Volume of
base added
(mL)
t-lag
TIME
The observed t-lag provides a measure of the compound's efficiency with
respect to delaying the growth of calcium phosphate crystal. The greater the t-
lag, the more efficient the crystal growth inhibitor.
Exemplary Procedure
Combine in a suitable vessel, 2.1 M KCI (35 mL), 0.0175M CaClz (50mL),
0.01 M KH2P04 (50mL), and de-ionized water (350mL). A standard pH electrode
equipped with a Standard Calomel Reference electrode is inserted and the
temperature adjusted to 37° C while purging of the solution of oxygen.
Once the
temperature and pH are stabilized, a solution of the crystal growth inhibitor
to be
test is then added. A typical inhibitor test concentration is 1 x 106 M. The
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W~ X1/42412 CA 02391904 2002-05-16 PCT/LTS00/32873
solution is titrated to pH 7.4 with 0.05M KOH. The mixture is then treated
with 5
mL's of a hydroxyapatite slurry. The hydroxyapatite slurry can be prepared by
digesting Bio-Gel~ HTP hydroxyapatite powder (100 g) in 1 L of distilled water
the pH of which is adjusted to 2.5 by the addition of sufficient 6N HCI and
subsequently heating the solution until all of the hydroxyapatite is dissolved
(heating for several days may be necessary). The temperature of the solution
is
then maintained at about 22° C while the pH is adjusted to 12 by the
addition of
a solution of 50% aqueous KOH. Once again the solution is heated and the
resulting slurry is allowed to settle for two days before the supernatant is
removed. 1.5 L of distilled water is added, the solution stirred, then after
settling
again for 2 days the supernatant is removed. This rinsing procedure is
repeated
six more time after which the pH of the solution is adjusted to neutrality
using 2N
HCI. The resulting slurry can be stored at 37°C for eleven months.
Crystal growth inhibitors which are suitable for use in the present
invention have a t-lag of at least 10 minutes, preferably at least 20 minutes,
more preferably at least 50 minutes, at a concentration of 1 x 10-6M. Crystal
growth inhibitors are differentiated form chelating agents by the fact that
crystal
growth inhibitors have a low binding affinity of heavy metal ions, i.e.,
copper.
For example, crystal growth inhibitors have an affinity for copper ions in a
solution of 0.1 ionic strength when measured at 25° C, of less than 15,
preferably less than 12.
The preferred crystal growth inhibitors for use herein are selected from
the group consisting of carboxylic compounds, organic diphosphonic acids, and
mixtures thereof. The following are non-limiting examples of preferred crystal
growth inhibitors.
Carboxylic Compounds
Non-limiting examples of carboxylic compounds which serve as crystal
growth inhibitors include glycolic acid, phytic acid, polycarboxylic acids,
polymers and co-polymers of carboxylic acids and polycarboxylic acids, and
mixtures thereof. The inhibitors may be in the acid or salt form. Preferably
the
polycarboxylic acids comprise materials having at least two carboxylic acid
radicals which are separated by not more than two carbon atoms (e.g.,
methylene units). The preferred salt forms include alkali metals; lithium,
sodium, and potassium; and alkanolammonium. The polycarboxylates suitable
for use in the present invention are further disclosed in U.S. 3,128,287, U.S.
3,635,830, U.S. 4,663,071, U.S. 3,923,679; U.S. 3,835,163; U.S. 4,158,635;
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U.S. 4,120,874 and U.S. 4,102,903, each of which is included herein by
reference.
Further suitable polycarboxylates include ether hydroxypolycarboxylates,
polyacrylate polymers, copolymers of malefic anhydride and the ethylene ether
or vinyl methyl ethers of acrylic acid. Copolymers of 1,3,5-trihydroxybenzene,
2,
4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid are also useful.
Alkali
metal salts of polyacetic acids, for example, ethylenediamine tetraacetic acid
and nitrilotriacetic acid, and the alkali metal salts of polycarboxylates, for
example, mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid,
benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, are suitable
for
use in the present invention as crystal growth inhibitors.
The polymers and copolymers which are useful as crystal growth
inhibitors have a molecular weight which is preferably greater than about 500
daltons to about 100,000 daltons, more preferably to about 50,000 daltons.
Examples of commercially available materials for use as crystal growth
inhibitors include, polyacrylate polymers Good-Rite~ ex BF Goodrich, Acrysol0
ex Rohm & Haas, Sokalan~ ex BASF, and Norasol~ ex Norso Haas. Preferred
are the Norasol~ polyacrylate polymers, more preferred are Norasol~ 410N
(MW 10,000) and Norasol~ 440N (MW 4000) which is an amino phosphoric
acid modified polyacrylate polymer, and also more preferred is the acid form
of
this modified polymer sold as Norasol~ QR 784 (MW 4000) ex Norso-Haas.
Polycarboxylate crystal growth inhibitors include citrates, e.g., citric acid
and soluble salts thereof (particularly sodium salt), 3,3-dicarboxy-4-oxa-1,6-
hexanedioates and related compounds further disclosed in U.S. 4.566,984
incorporated herein by reference, C5-C20 alkyl, C5-C20 alkenyl succinic acid
and salts thereof, of which dodecenyl succinate, lauryl succinate, myristyl
succinate, palmityl succinate, 2-dodecenylsuccinate, 2-pentadecenyl succinate,
are non-limiting examples. Other suitable polycarboxylates are disclosed in
U.S. 4,144,226, U.S. 3,308,067 and U.S. 3,723,322, all of which are
incorporated herein by reference.
Organic Phosphoric Acids
Organic diphosphonic acid are also suitable for use as crystal growth
inhibitors.
For the purposes of the present invention the term "organic diphosphonic acid"
is defined as "an organo-diphosphonic acid or salt which does not comprise a
nitrogen atom". Preferred organic diphosphonic acids include C,-Cg
diphosphonic acid, preferably Cz diphosphonic acid selected from the group
14
CA 02391904 2002-05-16
WO 01/42412 PCT/US00/32873
consisting of ethylene diphosphonic acid, a-hydroxy-2 phenyl ethyl
diphosphonic acid, methylene diphosphonic acid, vinylidene-1,1-diphosphonic
acid , 1,2-dihydroxyethane-1,1-diphosphonic acid, hydroxy-ethane 1,1
diphosphonic acid, the salts thereof, and mixtures thereof. More preferred is
hydroxyethane-1,1-diphosphonic acid (HEDP). A preferred is phosphonic acid
is 2-phosphonobutane-1,2,4-tricarboxylic acid available as BAYHIBIT AM~ ex
Bayer.
Fabric Abrasion Reducing Polymers
The herein disclosed polymers provide for decreased fabric abrasion as
well as providing a secondary benefit related to dye transfer inhibition. The
compositions cf the present invention comprise from about 0.01 %, preferably
from about 0.1 % to about 20%, preferably to about 10% by weight, of a fabric
abrasion reducing polymer.
The prefered reduced abrasion polymers for the present invention are
water-soluble polymers. For the purposes of the present invention the term
"water-soluble" is defined as "a polymer which when dissolved in water at a
level
of 0.2% by weight, or less, at 25° C, forms a clear, isotropic liquid".
The fabric abrasion reducing polymers useful in the present invention
have the formula:
~_P(D)m_~n
wherein the unit P is a polymer backbone which comprises units which are
homopolymeric or copolymeric. D units are defined herein below. For the
purposes of the present invention the term "homopolymeric" is defined as "a
polymer backbone which is comprised of units having the same unit
composition, i.e., formed from polymerization of the same monomer. For the
purposes of the present invention the term "copolymeric" is defined as "a
polymer backbone which is comprised of units having a different unit
composition, i.e., formed from the polymerization of two or more monomers".
P backbones preferably comprise units having the formula:
-[CRZ-CR2]- or [(CRZ);~ L]-
wherein each R unit is independently hydrogen, C,-C,2 alkyl, C6-C,Z aryl, and
D
units as described herein below; preferably C,-C4 alkyl.
Each L unit is independently selected from heteroatom-containing
moieties, non-limiting examples of which are selected from the group
consisting
of:
WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
R1 O O O O
I II II II II
-N- -O- -O-C- -C-O-O-C-O- -C
> > > > >
O O O O O
II II II II II
-S- -S- S- -O-S- -S-O- -O-S-O
' ' II ' II II ' II
O O O O
polysiloxane having the formula:
R2
I
-0 Si-O
Rz
P
units which have dye transfer inhibition activity:
R4 0 0
I II II
-N- -N-C- -C-N
Rs . R3
and mixtures thereof; wherein R' is hydrogen, C,-C,z alkyl, C6-C,z aryl, and
mixtures thereof. Rz is C,-C,z alkyl, C,-C,z alkoxy, Cs-C,z aryloxy, and
mixtures
thereof; preferably methyl and methoxy. R3 is hydrogen C,-C,z alkyl, C6-C,z
aryl,
and mixtures thereof; preferably hydrogen or C,-C4 alkyl, more preferably
hydrogen. R4 is C,-C,z alkyl, C6-C,z aryl, and mixtures thereof.
The backbones of the fabric abrasion reducing polymers of the present
invention comprise one or more D units which are units which comprise one or
more units which provide a dye transfer inhibiting benefit. The D unit can be
part of the backbone itself as represented in the general formula:
~_P~D~m_~n
or the D unit may be incorporated into the backbone as a pendant group to a
backbone unit having, for example, the formula:
-[CR-CRz]- or -[(CR), L]
D D
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WO 01/42412 CA 02391904 2002-05-16 pCT~S00/32873
However, the number of D units depends upon the formulation. For example,
the number of D units will be adjusted to provide water solubility of the
polymer
as well as efficacy of dye transfer inhibition while providing a polymer which
has
fabric abrasion reducing properties. The molecular weight of the fabric
abrasion
reducing polymers of the present invention are from about 500, preferably from
about 1,000, more preferably from about 100,000 most preferably from 160,000
to about 6,000,000, preferably to about 2,000,000, more preferably to about
1,000,000, yet more preferably to about 500,000, most preferably to about
360,000 daltons. Therefore the value of the index n is selected to provide the
indicated molecular weight, and providing for a water solubility of least 100
ppm,
preferably at least about 300 ppm, and more preferably at least about 1,000
ppm in water at ambient temperature which is defined herein as 25°C.
Polymers Comprising Amide Units
Non-limiting examples of preferred D units are D units which comprise an
amide moiety. Examples of polymers wherein an amide unit is introduced into
the polymer via a pendant group includes polyvinylpyrr olidone having the
formula:
- [CH- CHZ]"
N
~~ 0
polyvinyloxazolidone having the formula:
- [CH- CH2]"
N
~O
0
polyvinylmethyloxazolidone having the formula:
- [CH- CHZ]n
N
~0
0
HOC
polyacrylamides and N-substituted polyacrylamides having the formula:
17
WO 01/42412 CA 02391904 2002-05-16 PCT/LTS00/32873
[CH-CHZ]n
C=0
I
N(R)2
wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be
taken together to form a ring comprising 4-6 carbon atoms;
polymethacrylamides and N-substituted polymethacrylamides having the
general formula:
CHI
[C-CHZ]n
C=O
I
N(R)
wherein each R' is independently hydrogen, C,-C6 alkyl, or both R' units can
be
taken together to form a ring comprising 4-6 carbon atoms; poly(N-
acrylylglycinamide) having the formula:
- [CH- CH2]"
C=O O
I II
NH-CHI-C-N(R')2
wherein each R' is independently hydrogen, C,-Cs alkyl, or both R' units can
be
taken together to form a ring comprising 4-6 carbon atoms; poly(N-
methacrylylglycinamide) having the formula:
CH3
[~-CHZ]n
C=0 0
I II
NH-CHI-C-N(R')2
wherein each R' is independently hydrogen, C,-Cs alkyl, or both R' units can
be
taken together to form a ring comprising 4-6 carbon atoms; polyvinylurethanes
having the formula:
[CH-CH2]n
0
I
C=0
I
N(R')z
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CA 02391904 2002-05-16
WO 01/42412 PCT/US00/32873
wherein each R' is independently hydrogen, C,-Cs alkyl, or both R' units can
be
taken together to form a ring comprising 4-6 carbon atoms.
An example of a D unit wherein the nitrogen of the dye transfer inhibiting
moiety is incorporated into the polymer backbone is a poly(2-ethyl-2-
oxazoline)
having the formula:
[CHZ-CHZ-Nln-
C=O
I
CHZCH3
wherein the index n indicates the number of monomer residues present.
The fabr is abrasion reducing polymers for the present invention can
comprise any mixture of dye transfer inhibition units which provides the
product
with suitable properties.
The preferred polymers which comprise D units which are amide moieties are
those which have the nitrogen atoms of the amide unit highly substituted so
the
nitrogen atoms are in effect shielded to a varying degree by the surrounding
non-polar groups. This provides the polymers with an amphiphilic character.
Non-limiting examples include polyvinyl-pyrrolidones, polyvinyloxazolidones,
N,N-disubstituted polyacrylamides, and N,N-disubstituted polymethacrylamides.
A detailed description of physico-chemical properties of some of these
polymers
are given in "Water-Soluble Synthetic Polymers: Properties and Behavior",
Philip Molyneux, Vol. I, CRC Press, (1983) included herein by reference.
The amide containing polymers may be present partially hydrolyzed
and/or crosslinked forms. A preferred polymeric compound for the present
invention is polyvinylpyrrolidone (PVP). This polymer has an amphiphilic
character with a highly polar amide group conferring hydrophilic and polar-
attracting properties, and also has non-polar methylene and methine groups, in
the backbone and/or the ring, conferring hydrophobic properties. The rings may
also provide planar alignment with the aromatic rings in the dye molecules.
PVP
is readily soluble in aqueous and organic solvent systems. PVP is available ex
ISP, Wayne, New Jersey, and BASF Corp., Parsippany, New Jersey, as a
powder or aqueous solutions in several viscosity grades, designated as, e.g.,
K-
12, K-15, K-25, and K-30. These K-values indicate the viscosity average
molecular weight, as shown below:
19
WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
PVP viscosity average K-12 K-15 K-25 K-30 K-60 K-90
molecular
weight (in thousands 2.5 10 24 40 160 360
of
daltons)
PVP K-12, K-15, and K-30 are also available ex Polysciences, Inc. Warrington,
Pennsylvania, PVP K-15, K-25, and K-30 and poly(2-ethyl-2-oxazoline) are
available ex Aldrich Chemical Co., Inc., Milwaukee, Wisconsin. PVP K30
(40,000) through to K90 (360,000) are also commercially available ex BASF
under the tradename Luviskol or commercially available ex ISP. Still higher
molecular PVP like PVP 1.3MM, commercially available ex Aldrich is also
suitable for use herein. Yet further PVP-type of material suitable for use in
the
present invention are polyvinylpyrrolidone-co-dimethylaminoethylmethacrylate,
commercially available commercially ex ISP in a quaternised form under the
tradename Gafquat~ or commercially available ex Aldrich Chemical Co. having
a molecular weight of approximately 1.OMM; polyvinylpyrrolidone-co-vinyl
acetate, available ex BASF under the tradename Luviskol~, available in
vinylpyrrolidone:vinylacetate ratios of from 3:7 to 7:3.
Polymers Comprising N-oxide Units
Another D unit which provides dye transfer inhibition enhancement to the
fabric abrasion reducing polymers described herein, are N-oxide units having
the formula:
O
Ry ~ - R3
RZ
wherein R', R2, and R3 can be any hydrocarbyl unit (for the purposes of the
present invention the term "hydrocarbyl" does not include hydrogen atom
alone).
The N-oxide unit may be part of a polymer, such as a polyamine, i.e.,
polyalkyleneamine backbone, or the N-oxide may be part of a pendant group
attached to the polymer backbone. An example of a polymer which comprises
an the N-oxide unit as a part of the polymer backbone is polyethyleneimine N-
oxide. Non-limiting examples of groups which can comprise an N-oxide moiety
include the N-oxides of certain heterocycles inter alia pyridine, pyrrole,
imidazole, pyrazole, pyrazine, pyrimidine, pyridazine, piperidine,
pyrrolidine,
W~ 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
pyrrolidone, azolidine, morpholine. A preferred polymer is poly(4-
vinylpyriding
N-oxide, PVNO). In addition, the N-oxide unit may be pendant to the ring, for
example, aniline oxide.
N-oxide comprising polymers of the present invention will preferably have
a ratio of N-oxidized amine nitrogen to non-oxidized amine nitrogen of from
about 1:0 to about 1:2, preferably to about 1:1, more preferably to about 3:1.
The amount of N-oxide units can be adjusted by the formulator. For example,
the formulator may co-polymerize N-oxide comprising monomers with non N-
oxide comprising monomers to arrive at the desired ratio of N-oxide to non N-
oxide amino units, or the formulator may control the oxidation level of the
polymer during preparation. The amine oxide unit of the polyamine N-oxides of
the present invention have a Pka less than or equal to 10, preferably less
than or
equal to 7, more preferably less than or equal to 6. The average molecular
weight of the N-oxide comprising polymers which provide a dye transfer
inhibitor
benefit to reduced fabric abrasion polymers is from about 500 daltons,
preferably from about 100,000 daltons, more preferably from about 160,000
daltons to about 6,000,000 daltons, preferably to about 2,000,000 daltons,
more
preferably to about 360,000 daltons.
Polymers Comprising Amide Units and N-oxide Units
A further example of polymers which are fabric abrasion reducing
polymers which have dye transfer inhibition benefits are polymers which
comprise both amide units and N-oxide units as described herein above. Non-
limiting examples include co-polymers of two monomers wherein the first
monomer comprises an amide unit and the second monomer comprises an N-
oxide unit. In addition, oligomers or block polymers comprising these units
can
be taken together to form the mixed amide/N-oxide polymers. However, the
resulting polymers must retain the water solubility requirements described
herein above.
Molecular weight
For all the above polymer for use herein, it most preferred that they have a
molecular weight in the range as described herein above. This range is
typically
higher than the range for polymers which render only dye transfer inhibition
benefits alone. Indeed, the high molecular weight enables the abrasion
occurring subsequent to treatment with the polymer to be reduced, especially
in
a later washing procedure. Not to be bound by theory, it is believed that that
this benefit is partly due to the high molecular weight, thereby enabling the
21
WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
deposition of the polymer on the fabric surface and providing sufficient
substantivity that the polymer is able to remain adhered to the fabric during
the
subsequent use and washing of the fabric: Further, it is believed that for a
given
charge density, increasing the molecular weight will increase the
substantivity of
the polymer to the fabric surface. Ideally the balance of charge density and
molecular weight will provide both a sufficient rate of deposition onto the
fabric
surface and a sufficient adherence to the fabric during a subsequent wash
cycle. Increasing molecular weight is considered preferable to increasing
charge density as it allows a greater choice in the range of materials which
are
able to provide the benefit and avoids the negative impact that increasing
charge density can have such as the attraction of soil and residue onto
treated
fabrics. It should be noted however that a similar benefit may be predicted
from
the approach of increasing charge density while retaining a lower molecular
weight material.
Polyolefin dispersion
The compositions for the present invention optionally comprise from
about 0.01 %, preferably from about 0.1 % to about 8%, preferably to about 5%,
more preferably to about 3% by weight, of a poly olefin emulsion or suspension
in order to provide anti-wrinkle and improved lubrication benefits to the
fabrics
treated by the fabric care compositions of the present invention. Preferably,
the
polyolefin is a polyethylene, polypropylene or mixtures thereof. The
polyolefin
may be at least partially modified to contain various functional groups, such
as
carboxyl, carbonyl, ester, ether, alkylamide, sulfonic acid or amide groups.
More
preferably, the polyolefin employed in the present invention is at least
partially
carboxyl modified or, in other words, oxidized. In particular, oxidized or
carboxyl
modified polyethylene is preferred in the compositions of the present
invention.
When considering ease of formulation, the polyolefin is preferably
introduced as a suspension or an emulsion of polyolefin dispersed by use of an
emulsifying agent. The polyolefin suspension or emulsion preferably has from
1, preferably from 10%, more preferably from 15% to 50%, more preferably to
35% more preferably to 30% by weight, of polyolefin in the emulsion. The
polyolefin preferably has a molecular weight of from 1,000, preferably from
4,000 to 15,000, preferably to 10,000. When an emulsion is employed, the
emulsifier may be any suitable emulsification or suspending agent. Preferably,
the emulsifier is a cationic, nonionic, zwitterionic or anionic surfactant or
22
WO 01/42412 CA 02391904 2002-05-16 PCT/LTS00/32873
mixtures thereof. Most preferably, any suitable cationic, nonionic or anionic
surfactant may be employed as the emulsifier. Preferred emulsifiers are
cationic
surfactants such as the fatty amine surfactants and in particular the
ethoxylated
fatty amine surfactants. In particular, the cationic surfactants are preferred
as
emulsifiers in the present invention. The polyolefin is dispersed with the
emulsifier or suspending agent in a ratio of emulsifier to polyolefin of from
1:10
to 3:1. Preferably, the emulsion includes from 0.1, preferably from 1 %, more
preferably from 2.5% to 50%, preferably to 20%, more preferably to 10% by
weight, of emulsifier in the polyolefin emulsion. Polyethylene emulsions and
suspensions suitable for use in the present invention are available under the
tradename VELUSTROL exHOECHST Aktiengesellschaft of Frankfurt am Main,
Germany. In particular, the polyethylene emulsions sold under the tradename
VELUSTROL PKS, VELUSTROL KPA, or VELUSTROL P-40 may be employed
in the compositions of the present invention.
Stabi I izers
The compositions for the present invention can optionally comprise from
about 0.01 %, preferably from about 0.035% to about 0.2%, more preferably to
about 0.1 % for antioxidants, preferably to about 0.2% for reductive agents,
of a
stabilizer. The term "stabilizer," as used herein, includes antioxidants and
reductive agents. These agents assure good odor stability under long term
storage conditions for the compositions and compounds stored in molten form.
The use of antioxidants and reductive agent stabilizers is especially critical
for
low scent products (low perfume).
Non-limiting examples of antioxidants that can be added to the compositions of
this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl
gallate, ex Eastman Chemical Products, Inc., under the trade names Tenox~
PG and Tenox S-1; a mixture of BHT (butylated hydroxytoluene), BHA
(butylated hydroxyanisole), propyl gallate, and citric acid, ex Eastman
Chemical
Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene,
available from UOP Process Division under the trade name Sustane~ BHT;
tertiary butylhydroquinone, Eastman Chemical Products, Inc., as Tenox TBHQ;
natural tocopherols, Eastman Chemical Products, Inc., as Tenox GT-1/GT-2;
and butylated hydroxyanisole, Eastman Chemical Products, Inc., as BHA; long
chain esters (Cg-C22) of gallic acid, e.g., dodecyl gallate; Irganox~ 1010;
Irganox~ 1035; Irganox~ B 1171; Irganox~ 1425; Irganox~ 3114; Irganox~
23
W~ 01/42412 CA 02391904 2002-05-16 pCT~S00/32873
3125; and mixtures thereof; preferably Irganox~ 3125, Irganox~ 1425, Irganox
~ 3114, and mixtures thereof; more preferably Irganox~ 3125 alone or mixed
with citric acid and/or other chelators such as isopropyl citrate, Dequest~
2010,
ex Monsanto with a chemical name of 1-hydroxyethylidene-1, 1-diphosphonic
acid (etidronic acid), and Tiron~, ex Kodak with a chemical name of 4,5-di-
hydroxy-m-benzene-sulfonic acid/sodium salt, EDDS, and DTPA~, ex Aldrich
with a chemical name of diethylenetriaminepentaacetic acid.
Hydrophobic Dispersant
A preferred composition for the present invention comprises from about
0.1 %, preferably from about 5%, more preferably form about 10% to about 80%,
preferably to about 50%, more preferably to about 25% by weight, of a
hydrophobic polyamine dispersant having the formula:
R1 B
I I
L(R')2N-R~,~IN-RIXLN-RIyN(R')2
wherein R, R' and B are suitably described in U.S. 5,565,145 Watson et al.,
issued October 15, 1996 incorporated herein by reference, and w, x, and y have
values which provide for a backbone prior to substitution of preferably at
least
about 1200 daltons, more preferably 1800 daltons.
R' units are preferably alkyleneoxy units having the formula:
-(CH2CHR'O)m(CH2CH20)nH
wherein R' is methyl or ethyl, m and n are preferably from about 0 to about
50,
provided the average value of alkoxylation provided by m + n is at least about
0.5.
A further description of polyamine dispersants suitable for use in the
present invention is found in U.S. 4,891,160 Vander Meer, issued January 2,
1990; U.S.4,597,898, Vander Meer, issued July 1, 1986; European Patent
Application 111,965, Oh and Gosselink, published June 27, 1984; European
Patent Application 111,984, Gosselink, published June 27, 1984; European
Patent Application 112,592, Gosselink, published July 4, 1984; U.S. 4,548,744,
Connor, issued October 22, 1985; and U.S. 5,565,145 Watson et al., issued
October 15, 1996; all of which are included herein by reference. However, any
suitable clay/soil dispersent or anti-redepostion agent can be used in the
laundry compositions of the present invention.
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WO 01/42412 CA 02391904 2002-05-16 pCT~S00/32873
Electrolyte
The fabric softening embodiments of the compositions of the present
invention, especially clear, isotropic liquid fabric softening compositions,
may
also optionally, but preferably comprise, one or more electrolytes for control
of
phase stability, viscosity, and/or clarity. For example, the presence of
certain
electrolytes inter alia calcium chloride, magnesium chloride may be key to
insuring initial product clarity and low viscosity, or may affect the dilution
viscosity of liquid embodiments, especially isotropic liquid embodiments. Not
wishing to be limited by theory, but only wishing to provide an example of a
circumstance wherein the formulator must insure proper dilution viscosity,
includes the following example. Isotropic or non-isotropic liquid fabric
softener
compositions can be introduced into the rinse phase of laundry operations via
an article of manufacture designed to dispense a measured amount of said
composition. Typically the article of manufacture is a dispenser which
delivers
the softener active only during the rinse cycle. These dispensers are
typically
designed to allow an amount of water equal to the volume of softener
composition to enter into the dispenser to insure complete delivery of the
softener composition. An electrolyte may be added to the compositions of the
present invention to insure phase stability and prevent the diluted softener
composition from "gelling out" or from undergoing an undesirable or
unacceptable viscosity increase. Prevention of gelling or formation of a
"swelled", high viscosity solution insures thorough delivery of the softener
composition.
However, those skilled in the art of fabric softener compositions will
recognize that the level of electrolyte is also influenced by other factors
inter alia
the type of fabric softener active, the amount of principal solvent, and the
level
and type of nonionic surfactant. For example, triethanol amine derived ester
quaternary amines suitable for use as softener actives according to the
present
invention are typically manufactured in such a way as to yield a distribution
of
mono-, di-, and tri- esterified quaternary ammonium compounds and amine
precursors. Therefore, as in this example, the variability in the distribution
of
mono-, di-, and tri- esters and amines may predicate a different level of
electrolyte. Therefore, the formulator must consider all of the ingredients.
namely, softener active, nonionic surfactant, and in the case of isotropic
liquids,
the principal solvent type and level, as well as level and identity of adjunct
ingredients before selecting the type and/or level of electrolyte
WO 01/42412 CA 02391904 2002-05-16 PCT/US00/32873
A wide variety of ionizable salts can be used. Examples of suitable salts
are the halides of the Group IA and IIA metals of the Periodic Table of the
elements, e.g., calcium chloride, sodium chloride, potassium bromide, and
lithium chloride. The ionizable salts are particularly useful during the
process of
mixing the ingredients to make the compositions herein, and later to obtain
the
desired viscosity. The amount of ionizable salts used depends on the amount of
active ingredients used in the compositions and can be adjusted according to
the desires of the formulator. Typical levels of salts used to control the
composition viscosity are from about 20 to about 10,000 parts per million
(ppm),
preferably from about 20 to about 5,000 ppm, of the composition.
Alkylene polyammonium salts can be incorporated into the composition to
give viscosity control in addition to or in place of the water-soluble,
ionizable
salts above, In addition, these agents can act as scavengers, forming ion
pairs
with anionic detergent carried over from the main wash, in the rinse, and on
the
fabrics, and can improve softness performance. These agents can stabilized
the viscosity over a broader range of temperature, especially at low
temperatures, compared to the inorganic electrolytes. Specific examples of
alkylene polyammonium salts include L-lysine, monohydrochloride and 1,5-
diammonium 2-methyl pentane dihydrochloride.
Cationic Charge Boosters
The compositions for the present invention may optionally comprise one
or more cationic charge boosters, especially to the rinse-added fabric
softening
embodiments of the present invention. Typically, ethanol is used to prepare
many of the below listed ingredients and is therefore a source of solvent into
the
final product formulation. The formulator is not limited to ethanol, but
instead
can add other solvents inter alia hexyleneglycol to aid in formulation of the
final
composition. This is especially true in clear, translucent, isotropic
compositions.
The preferred cationic charge boosters of the present invention are
described herein below.
i) Quaternary Ammonium Compounds
A preferred composition for the present invention comprises at least
about 0.2%, preferably from about 0.2% to about 10%, more preferably from
about 0.2% to about 5% by weight, of a cationic charge booster having the
formula:
26
CA 02391904 2002-05-16
WO 01/42412 PCT/US00/32873
R2
+ _
Rl -N R3
X
R4
wherein R1, R2, R3, and R4 are each independently C1-C22 alkyl, C3-C22
alkenyl, R5-Q-(CH2)m-, wherein R5 is C1-C22 alkyl, and mixtures thereof, m is
from 1 to about 6; X is an anion.
Preferably R1 is Cg-C22 alkyl, C6-C22 alkenyl, and mixtures thereof,
more preferably C11-C1g alkyl, C11-C1g alkenyl, and mixtures thereof; R2, R3,
and R4 are each preferably C1-C4 alkyl, more preferably each R2, R3, and R4
are methyl.
The formulator may similarly choose R1 to be a R5-Q-(CH2)m- moiety
wherein R5 is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms,
preferably the alkyl or alkenyl moiety when taken together with the Q unit is
an
acyl unit derived preferably derived from a source of triglyceride selected
from
the group consisting of 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 thereof.
An example of a fabric softener cationic booster comprising a R5-Q-
(CH2)m- moiety has the formula:
CH3
~ +N-CH3
CI CH
3
wherein R5-Q- is an oleoyl units and m is equal to 2.
X is a softener compatible anion, preferably the anion of a strong acid, for
example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and
mixtures thereof, more preferably chloride and methyl sulfate.
ii) Polyvinyl Amines
A preferred embodiment for the present invention contains at least about
0.2%, preferably from about 0.2% to about 5%, more preferably from about 0.2%
to about 2% by weight, of one or more polyvinyl amines having the formula
27
CA 02391904 2002-05-16
WO 01/42412 PCT/US00/32873
CHI-CH
I
NHZ
wherein y is from about 3 to about 10,000, preferably from about 10 to about
5,000, more preferably from about 20 to about 500. Polyvinyl amines suitable
for use in the present invention are available from BASF.
Optionally, one or more of the polyvinyl amine backbone -NH2 unit
hydrogens can be substituted by an alkyleneoxy unit having the formula:
(R1 O~XR2
wherein R1 is C2-C4 alkylene, R2 is hydrogen, C1-C4 alkyl, and mixtures
thereof; x is from 1 to 50. In one embodiment or the present invention the
polyvinyl amine is reacted first with a substrate which places a 2-
propyleneoxy
unit directly on the nitrogen followed by reaction of one or more moles of
ethylene oxide to form a unit having the general formula:
CH3
(CH2CH0)(CH2CH20}xH
wherein x has the value of from 1 to about 50. Substitutions such as the above
are represented by the abbreviated formula PO-EOx-. However, more than one
propyleneoxy unit can be incorporated into the alkyleneoxy substituent.
Polyvinyl amines are especially preferred for use as cationic charge
booster in liquid fabric softening compositions since the greater number of
amine moieties per unit weight provides substantial charge density. In
addition,
the cationic charge is generated in situ and the level of cationic charge can
be
adjusted by the formulator.
iii) Poly-Quaternary Ammonium Compounds
A preferred composition for the present invention comprises at least
about 0.2%, preferably from about 0.2% to about 10%, more preferably from
about 0.2% to about 5% by weight, of a cationic charge booster having the
formula:
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CA 02391904 2002-05-16
WO 01/42412 PCT/US00/32873
Rl R1
+I I+ _
R2-N-R-N-R2 2 X
Rl Rl
wherein R is substituted or unsubstituted C2-C12 alkylene, substituted or
unsubstituted C2-C12 hydroxyalkylene; each R1 is independently C1-C4 alkyl,
each R2 is independently C1-C22 alkyl, C3-C22 alkenyl, R5-Q-(CH2)m-,
wherein R5 is C1-C22 alkyl, C3-C22 alkenyl, and mixtures thereof; m is from 1
to about 6; Q is a carbonyl unit as defined hereinabove; and mixtures thereof;
X
is an anion.
Preferably R is ethylene; R1 is methyl or ethyl, more preferably methyl; at
least one R2 is preferably C1-C4 alkyl, more preferably methyl. Preferably at
least one R2 is C11-C22 alkyl, C11-C22 alkenyl, and mixtures thereof.
The formulator may similarly choose R2 to be a R5-Q-(CH2)m- moiety
wherein R5 is an alkyl moiety having from 1 to 22 carbon atoms, preferably the
alkyl moiety when taken together with the Q unit is an acyl unit derived
preferably derived from a source of triglyceride selected from the group
consisting of 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 thereof.
An example of a fabric softener cationic booster comprising a R5-Q-
(CH2)m- moiety has the formula:
Cl CH3
O~NHj~N-CH3
O Cl CH CHs
3
wher
ein R1 is methyl, one R2 units is methyl and the other R2 unit is R5-Q-(CH2)m-
wherein R5-Q- is an oleoyl unit and m is equal to 2.
X is a softener compatible anion, preferably the anion of a strong acid, for
example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and
mixtures thereof, more preferably chloride and methyl sulfate.
Cationic Nitrocten Compounds
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WO 01/42412 PCT/LTS00/32873
The fabric enhancement compositions for the present invention may
optionally comprise from about 0.5%, preferably from about 1 % to about 10%,
preferably to about 5% by weight, of one or more cationic nitrogen containing
compound, preferably a cationic compound having the formula:
CR-N(Ri)3~ X
wherein R is C,o-C,$ alkyl, each R' is independently C,-C4 alkyl, X is a water
soluble anion; preferably R is C,z-C,4, preferably R' is methyl. Preferred X
is
halogen, more preferably chlorine.
Non-limiting examples of preferred cationic nitrogen compounds are
N,N,N-trimethyl-N-dodecyl ammonium chloride, N,N-dimethyl-(2-hydroxyethyl)-
N-dodecyl ammonium bromide, N,N-dimethyl-(2-hydroxyethyl)-N-tetradecyl
ammonium bromide. Suitable cationic nitrogen compounds are available ex
Akzo under the tradenames Ethomeen T/15~, Secomine TA15~, and
Ethoduomeen T/20~.
Of course, the composition may also comprises further optional like perfume,
cyclodextrins, chlorine scavengers, etc..
METHOD OF USE
The present invention relates to the use of the softening compound having a
transition temperature of less than 30°C or composition thereof for
providing in-
wear comfort, preferably on the skin that is contacted with the treated fabric
upon wearing.
The present invention further relates to a method for providing in-wear
comfort
to the skin contacted with treated fabrics, which comprises the steps of
contacting the fabrics with a softening compound having a transition
temperature of less than 30°C or composition thereof.
By use of this softening component, contrary to conventional softening
compound, the air is allowed to circulate and the excess moisture is allowed
to
escape. The cotton fabric treated therewith can breathe by letting the
moisture
out through the fibers, keeping it away from the skin, and therefore keeping
the
WD ~l/42412 CA 02391904 2002-05-16 PCT/US00/32873
fabric fresher for longer. As a result, the fabric (clothes) are more
comfortable to
the consumer.
Examples
The following are non-limiting examples of compositions suitable for use in
the
present invention.
TABLE I
weight
In redients 1 2 3 4
TEA Di-ester Quat (100% 35 28 - 28
active 1
DEA Di-ester Quat (100% - - 28 -
active 2
2 ro anol - - - -
Ethanol from active 3.09 2.47 2.47 2.47
Hex lene GI col from active3.09 2.47 2.47 2.47
1,2 hexanediol 14 17 -
1,2 ro anediol - - - -
TMPD 3 5 - - 3
2-Eth I- 1,3 Hexanediol - - - 2
Neodol 91-8 4 5 - - 5
Lutensol T05 5 - -
M C12 1.75 - - 1.5
CaCl2 - - - -
HCI 0-0.25 0-0.25 0-0.25 0-0.25
Perfume 2.5 1.25 1.25 2.5
Water balance balance balance balance
1. Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid, 85%
active commercially available under the tradename Rewoquat V3620 from
Witco.
2. Di(acyloxyethyl) dimethyl ammonium chloride where the acyl group is
derived from partially hydrogenated canola fatty acid, 85% active as
described in W097/03169 page 21-22.
3. 2,2,4 trimethyl 1,3 pentanediol
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WO 01/42412 PCT/CTS00/32873
4. Neodol 91-8 ex Shell
5. Lutensol T05 ex BASF
In redients 5 6 7 8
TEA Di-ester Quat (100% 28 73.5 - 60
active 1
DEA Di-ester Quat (100% - 75.8 -
active 2
2 ro anol - 12.7 -
Ethanol from active 2.47 - 11.8 5.29
Hex lene GI col from active2.47 - - 5.29
1,2 hexanediol - - - -
1,2 ro anediol - 15 - -
TMPD - - - -
2-Eth I- 1,3 Hexanediol 6 - - 14
Neodol91-8 - - - -
Lutensol T05 2 - - -
M C12 - - - -
CaCl2 0.15 - - -
HCI 0-0.25 - - 0-0.25
Perfume 2 - 12.4 2
Water + Minors balance balance balance balance
1. Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid, 85%
active commercially available under the tradename Rewoquat V3620 from
Witco.
2. Di(acyloxyethyl) dimethyl ammonium chloride where the acyl group is
derived from partially hydrogenated canola fatty acid, 85% active as
described in W097/03169 page 21-22.
3. 2,2,4 trimethyl 1,3 pentanediol
4. Neodol 91-8 ex Shell
5. Lutensol T05 ex BASF
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In redients 1 2 3 4
TEA Di-ester Quat (100%5.0 - - 10.5
active 1
DEA Di-ester Quat (100%- 5.7 10.5 -
active 2
2 ro anol - - - -
Ethanol from active 0.44 0.5 1.85 1.85
Hexylene Glycol (from 0.44 0.5 - -
active
1,2 hexanediol - - 2.5 2.2
1,2 ro anediol - - - -
CaCl2 - 0.005 0.1 0.1
HCI 0.01 0.01 0.01 0.01
Perfume 0.4 0.2 1.5 1.75
Water + Minors balance balance balance balance
1. Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid, 85%
active commercially available under the tradename Rewoquat V3620 from
Witco.
2. Di(acyloxyethyl) dimethyl ammonium chloride where the acyl group is
derived from partially hydrogenated canola fatty acid, 85% active as
described in W097/03169 page 21-22.
In redients 5 6 7
TEA Di-ester Quat (100% active)10.5 18 20
1
DEA Di-ester Quat (100% active)- - -
2
2 ro anol - 2.0 3.5
Ethanol from active 1.85 - -
Hex lene GI col from active - - -
1,2 hexanediol - - -
1,2 ro anediol 2.2 - -
CaCl2 0.1 0.25 0.3
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HCI 0.01 0.01 0.01
Perfume 1.75 1.25 1.20
Water + Minors balance balance balance
1. Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfate where the
acyl group is derived from partially hydrogenated canola fatty acid, 85%
active commercially available under the tradename Rewoquat V3620 from
Witco.
2. Di(acyloxyethyl) dimethyl ammonium chloride where the acyl group is
derived from partially hydrogenated canola fatty acid, 85% active as
described in W097/03169 page 21-22.
34
