U.S. patent application number 10/924539 was filed with the patent office on 2005-01-27 for wrinkle resistant composition.
This patent application is currently assigned to The Procter & Gamble Company. Invention is credited to Altmann, Markus Wilhelm, Goossens, Els, Hubesch, Bruno Albert Jean, Soyez, Heidi Simonne Mariette.
Application Number | 20050015888 10/924539 |
Document ID | / |
Family ID | 34081837 |
Filed Date | 2005-01-27 |
United States Patent
Application |
20050015888 |
Kind Code |
A1 |
Altmann, Markus Wilhelm ; et
al. |
January 27, 2005 |
Wrinkle resistant composition
Abstract
There is provided a composition comprising a lubricant,
preferably a water-soluble one, and components having a deviation
of fabric wrinkle recovery angle versus water of at least +15,
whereby the combination imparts in-wear wrinkle resistance to the
fabric treated therewith.
Inventors: |
Altmann, Markus Wilhelm;
(Brussels, BE) ; Hubesch, Bruno Albert Jean;
(Neerijse-Huldenberg, BE) ; Goossens, Els; (Puurs,
BE) ; Soyez, Heidi Simonne Mariette; (Oostende,
BE) |
Correspondence
Address: |
THE PROCTER & GAMBLE COMPANY
INTELLECTUAL PROPERTY DIVISION
WINTON HILL TECHNICAL CENTER - BOX 161
6110 CENTER HILL AVENUE
CINCINNATI
OH
45224
US
|
Assignee: |
The Procter & Gamble
Company
|
Family ID: |
34081837 |
Appl. No.: |
10/924539 |
Filed: |
August 24, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10924539 |
Aug 24, 2004 |
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10111491 |
Apr 25, 2002 |
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10111491 |
Apr 25, 2002 |
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PCT/US00/29769 |
Oct 27, 2000 |
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Current U.S.
Class: |
8/115.51 |
Current CPC
Class: |
D06M 13/2243 20130101;
D06M 13/224 20130101; D06M 15/267 20130101; D06M 15/564 20130101;
D06M 15/53 20130101; D06M 2200/40 20130101; D06M 15/647 20130101;
D06M 15/263 20130101; D06M 7/00 20130101; D06M 15/03 20130101; D06M
23/06 20130101; D06M 15/285 20130101; D06M 2200/20 20130101; D06M
15/3562 20130101 |
Class at
Publication: |
008/115.51 |
International
Class: |
D06M 010/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 27, 1999 |
EP |
99870223.7 |
Claims
What is claimed is:
1. A domestic fabric wrinkle reducing composition comprising a
water-soluble lubricant and a component having a deviation of
fabric Wrinkle Recovery Angle (WRA) versus water of at least +15,
wherein said composition is contained in a device selected from the
group consisting of a spray dispenser, an aerosol dispenser, a foam
dispenser, an iron, and a refill cartridge thereof.
2. A composition according to claim 1, wherein said water-soluble
lubricant is selected from the group consisting of nonionic
silicone containing surfactants and ethoxylated sorbitan
esters.
3. A composition according to claim 1, wherein said water-soluble
lubricant is present in an amount of from 0.1% to 70% by weight of
said composition.
4. A composition according claim 1, wherein said component having a
deviation of fabric WRA versus water of at least +15 is a material
selected from the group consisting of shape retention polymers,
polymers comprising at least one unit which provide a dye transfer
inhibiting benefit, urethane polymers, isomalto oligosaccharide,
polyvinylamine polymers, amphoteric polymers, aminosilicones,
curable silicones, and mixtures thereof.
5. A composition according to claim 1, wherein said component
having a deviation of fabric WRA versus water of at least +15 is
present in an amount of at least about 0.01% by weight of the
composition.
6. A composition according to claim 1, wherein said water-soluble
lubricant and said component having a deviation of fabric WRA
versus water of at least +15 are present in a weight ratio of from
10:1 to 1:1.
7. A composition according to claim 1, wherein said composition is
a liquid composition.
8. A domestic article of manufacture comprising a fabric wrinkle
reducing composition comprising a water-soluble lubricant and a
component having a deviation of fabric Wrinkle Recovery Angle (WRA)
versus water of at least +15 wherein said article is selected from
the group consisting of an aerosol dispenser, a spray dispenser, an
iron, a foam dispenser, and a refill cartridge thereof.
9. The article of manufacture of claim 8, wherein said article is a
spray dispenser selected from the group consisting of spray
dispenser comprising battery operated pump, spray dispenser
comprising a trigger spray device, spray dispenser comprising a
pressurized aerosol spray dispenser, and spray dispenser comprising
a non-manually operated spray dispenser.
10. A method for treating fabrics domestically which comprises the
step of contacting fabrics with a fabric wrinkle reducing
composition comprising a water-soluble lubricant, said composition
being dispensed from a device selected from the group consisting of
a spray dispenser, an aerosol dispenser, a foam dispenser, an iron,
and a refill cartridge thereof.
11. A method according to claim 10, wherein said method provides a
reduction of the time and/or effort involved to iron fabrics.
12. A method according to claim 10, wherein said method increases
the fabric WRA.
13. A method according to claim 10, wherein said method provides
in-wear resistance to treated fabrics.
14. A method according to claim 10, wherein said method is
performed in an in-home dewrinkling apparatus.
15. A method according to claim 10, wherein said composition is
sprayed onto said fabric and said fabric is ironed.
16. A domestic article of manufacture comprising a container and a
fabric reducing composition, said fabric reducing composition
comprising a water-soluble lubricant, wherein said container is
selected from the group consisting of a spray dispenser, an aerosol
dispenser, a foam dispenser, an iron, and a refill cartridge
thereof, in association with instructions to use an effective
amount of said composition on fabric to provide at least one
benefit selected from the group consisting of: reducing wrinkles;
reducing the time and/or effort involved to iron fabrics, imparting
in-wear resistance to fabrics.
Description
CROSS REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent
application Ser. No. 10/111,491, filed Apr. 25, 2002, the
disclosure of which is incorporated by reference herein.
TECHNICAL FIELD OF THE INVENTION
[0002] 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 in-wear wrinkle
resistance.
BACKGROUND OF THE INVENTION
[0003] Wrinkles in textile 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 yam and fabrics.
[0004] 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 laundering. Further, it
is well-known that alternating cycles of using and laundering
fabrics and textiles, such as articles of worn clothing and
apparel, will inevitably adversely affect the appearance and
integrity of the fabric and textile items so used and laundered.
Fabrics and textiles simply wear out over time and with use.
Laundering of fabrics and textiles is necessary to remove soils and
stains which accumulate therein and thereon during ordinary use.
However, the laundering operation itself, over many cycles, can
accentuate and contribute to the deterioration of the integrity and
the appearance of such fabrics and textiles. Accordingly, this has
brought additional pressure to bear on textile technologists to
produce a product that will sufficiently reduce wrinkles in
fabrics, especially clothing, whilst still producing a good
appearance through a simple, convenient application of a
product.
[0005] The prior art contains numerous examples of compositions for
reducing wrinkles. U.S. Pat. No. 5,532,023, discloses aqueous
wrinkle control compositions containing non-volatile silicone and
film-forming polymer. Preferred silicones include reactive
silicones and amino-functional silicone, known as "amodimethicone".
The composition containing such silicones is applied to fabric from
a spray dispenser. It is found that in the spray treatment, an
appreciable amount of the aqueous composition misses the fabric,
and instead falls on flooring surfaces, such as rugs, carpets,
concrete floors, tiled floors, linoleum floors, bathtub floors,
which leaves a silicone layer that is accumulated on and/or cured
on and/or bonded to the flooring surfaces. Such silicones that are
accumulated on such surfaces, and especially those that are bonded
to such surfaces are difficult to remove. Flooring surfaces thus
become slippery and can present a safety hazard to the household
members. U.S. Pat. No. 5,573,695 discloses an aqueous wrinkle
removal composition containing a vegetable oil based cationic
quaternary ammonium surfactant, and an anionic fluorosurfactant.
Similarly, U.S. Pat. No. 4,661,268 discloses a wrinkle removal
spray comprising an aqueous alcoholic composition containing a
dialkyl quaternary ammonium salt and a silicone surfactant and/or a
fluoro surfactant. U.S. Pat. No. 5,100,566 discloses a method of
reducing wrinkles in fabric by spraying the fabric with an aqueous
alcoholic solution of an anionic siliconate alkali metal salt. U.S.
Pat. No. 4,806,254 discloses fabric wrinkle removal aqueous
alcoholic solution containing glycerine and a nonionic surfactant.
WO98/04772 provides the treatment of fabric against fabric creasing
by application of a composition comprising a polycarboxylic acid or
derivative thereof; and then curing the composition using a
domestic process. Starch is also a conventional ingredient of
dewrinkling compositions. However, while starch provides a suitable
visual benefit onto the treated fabrics, it also gives fabric with
an undesired stiff or starchy feeling. These patents are
incorporated herein by reference.
[0006] Accordingly, the domestic treatment of fabric is a problem
known in the art to the formulator of laundry compositions.
Therefore, there is a need for a wrinkle reducing composition which
reduces the above mentioned negatives.
[0007] Further, most of the focus in the dewrinkling area has been
on providing compositions with instant dewrinkling. However, with
the current trends of reducing the labor involved in ironing, it
has now been found that there is a need for a composition that
would additionally provide in-wear wrinkle resistance, i.e. a
composition that would provide long-lasting benefit upon ironing,
and wearing.
[0008] Moreover, there is also a need for an efficient and
economical composition.
[0009] It has now surprisingly been found that the combination of a
lubricant, preferably a water-soluble one, and component having a
deviation of fabric Wrinkle Recovery Angle (WRA) versus water of at
least +15 fulfill such a need. This finding is particularly
surprising, especially when the component providing such deviation
is a polymer. Indeed, it is known that the combination of a
lubricant, especially a water-soluble one, with polymer is often
the cause of phase separation. Further, often the addition of
polymer like starch on top of composition comprising a lubricant,
preferably a water-soluble one, was found to give even worse
results on the in-wear performance. Surprisingly, it has been found
that the addition of a component providing a deviation of fabric
WRA of at least +15 overcome such problems.
[0010] Accordingly, the present invention reduces wrinkles in
fabrics, including clothing, dry cleanables, linens, bed clothes,
and draperies, by ironing. The present invention can be used on
damp or dry clothing to relax wrinkles and give clothes a ready to
wear look with lasting benefits that is demanded by today's fast
paced world.
[0011] In a preferred aspect, an additional benefit of the
composition of the present invention is an improved garment shape,
body and crispness.
[0012] The composition of the present invention acts as an
excellent ironing aid. The present invention makes the task of
ironing easier and faster by creating less iron drag. The
compositions of the present invention help produce a crisp, smooth
appearance.
SUMMARY OF THE INVENTION
[0013] The present invention is a wrinkle reducing composition
comprising a lubricant, preferably a water-soluble one, and a
component having a deviation of fabric Wrinkle Recovery angle (WRA)
versus water of at least +15.
[0014] In another aspect of the invention, there is provided an
article of manufacture comprising the composition of the invention,
such as a sprayer, an aerosol, a foam dispenser, an iron, a refill
cartridge thereof which contains the composition.
[0015] Still in a further aspect of the invention, there is
provided a method of treating fabrics for imparting benefits
selected from the group consisting of: reducing wrinkles and
imparting in-wear resistance to fabrics. In a preferred method, the
composition is sprayed onto a fabric and the fabric is ironed.
[0016] In a further aspect of the invention, there is provided an
article of manufacture comprising a container and the composition
of the invention in association with usage instructions, in
particular, instructions to use in a method where the composition
is sprayed onto the fabric and the fabric is ironed.
DETAILED DESCRIPTION OF THE INVENTION
[0017] 1)-lubricant:
[0018] One essential component of the invention is a lubricant,
preferably a water-soluble one. By means of this component, the
composition provides an ease of ironing whilst still avoiding the
staining of fabric and/or presenting safety hazard to the household
members.
[0019] For the purposes of the present invention the term
"water-soluble" is defined as "a component which when dissolved in
water at a level of 0.2% by weight, or less, at 25.degree. C.,
forms a clear, isotropic liquid".
[0020] Typical water-soluble lubricants include components selected
from nonionic silicone containing surfactants, sorbitan esters,
ethoxylated sorbitan esters, and mixtures thereof. The
water-soluble lubricants are preferably present in an amount of
from 0.1% to 70% by weight of the composition, more preferably of
from 1 to 10% % by weight of the composition for diluted
composition and of from 20 to 50% by weight of the composition for
concentrated compositions.
[0021] A preferred class of nonionic silicone containing
surfactants are the polyalkylene oxide polysiloxanes having a
dimethyl polysiloxane hydrophobic moiety and one or more
hydrophilic polyalkylene side chains, and having the general
formula:
R1--(CH3)2SiO--(CH3)2SiO]a--[(CH3)(R1)SiO]b--Si(CH3)2--R1
[0022] wherein a+b are from about 1 to about 50, preferably from
about 1 to about 30, more preferably from about 1 to about 25, and
each R1 is the same or different and is selected from the group
consisting of methyl and a poly(ethyleneoxide/propyleneoxide)
copolymer group having the general formula:
--(CH2)n O(C2 H4 O)c (C3 H6 O)d R2
[0023] with at least one R1 being a poly(ethyleneoxy/propyleneoxy)
copolymer group, and wherein n is 3 or 4, preferably 3; total c
(for all polyalkyleneoxy side groups) has a value of from 1 to
about 100, preferably from about 6 to about 100; total d is from 0
to about 14, preferably from 0 to about 3; and more preferably d is
0; total c+d has a value of from about 5 to about 150, preferably
from about 7 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. Each polyalkylene oxide polysiloxane has at least one
R1 group being a poly(ethyleneoxide/propyleneoxide) copolymer
group.
[0024] Nonlimiting examples of this type of surfactants are the
Silwet.RTM. surfactants which are available OSI Specialties Inc., a
Division of Witco, Danbury, Connecticut. Representative Silwet.RTM.
surfactants which contain only ethyleneoxy (C2H4O) groups are as
follows.
1 Name Average MW Average a + b Average total c L-7608 600 1 8
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 L-7622
10,000 88 75
[0025] Nonlimiting examples of Silwet.RTM. surfactants which
contain both ethyleneoxy (C2 H4 O) and propyleneoxy (C3 H6 O)
groups are as follows.
2 Name Average MW EO/PO ratio L-720 12,000 50/50 L-7001 20,000
40/60 L-7002 8,000 50/50 L-7210 13,000 20/80 L-7200 19,000 75/25
L-7220 17,000 20/80
[0026] 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 (--C2H4O) in the polyether chain (R1) must be
sufficient to render the polyalkylene oxide polysiloxane
water-soluble. If propyleneoxy groups are present in the
polyalkylenoxy chain, they can be distributed randomly in the chain
or exist as blocks. Mixtures of Silwet.RTM. surfactants which
contain both ethyleneoxy and propyleneoxy groups, are also
preferred. Preferred Silwet.RTM. surfactants are the L-7001,
L-7087, L-7200, L-7280, L-7600, L-7608, L-7622, L-7657.
[0027] The preparation of polyalkylene oxide polysiloxanes is
well-known in the art. Polyalkylene oxide polysiloxanes of the
present invention can be prepared according to the procedure set
forth in U.S. Pat. No. 3,299,112, incorporated herein by reference.
Typically, polyalkylene oxide polysiloxanes of the surfactant blend
of the present invention are readily prepared by an addition
reaction between a hydrosiloxane (i.e., a siloxane containing
silicon-bonded hydrogen) and an alkenyl ether (e.g., a vinyl,
allyl, or methallyl ether) of an alkoxy or hydroxy end-blocked
polyalkylene oxide). The reaction conditions employed in addition
reactions of this type are well-known in the art and in general
involve heating the reactants (e.g., at a temperature of from about
85.degree. C. to 110.degree. C.) in the presence of a platinum
catalyst (e.g., chloroplatinic acid) and a solvent (e.g.,
toluene).
[0028] Still other preferred water-soluble lubricants of the
nonionic type are those from the class of sorbitan esters and/or
alkylethoxylate sorbitan ester. These ethoxylated sorbitan esters
are formed by ethoxylation of sorbitan or its cyclic derivative
sorbitan, followed by esterification of one of the available
hydroxy groups to introduce one long chain alkyl or alkenyl group,
leaving the remaining hydroxy groups free. Compounds of this type
are included in the range commercially available under the
Registered Trade Mark TWEEN from Aldrich and from ICI United States
Inc, but are also available from other suppliers e.g Radiasurf 7137
(Polyethoxylated (20 moles) sorbitan monolaurate), Radiasurf 7147
(Polysorbate 60), Radiasurf 7157 (Polysorbate 80) commercially
available from FINA and Tween 65 (Polyethoxylated (20 moles)
sorbitan tristearate), Tween 20 (Polyethoxylated (20 moles)
sorbitan monolaurate, Tween 21 (Polyethoxylated (4 moles) sorbitan
monolaurate), Tween 40 (Polyethoxylated (20 moles) sorbitan
palmitate), commercially available from Aldrich.
[0029] Water-insoluble lubricants are also useful herein. Suitable
water-insoluble lubricants include cationic fabric softeners,
silicones, and aliphatic and cycloaliphatic hydrocarbons.
[0030] Suitable cationic fabric softening components for use herein
include the water-insoluble quaternary-ammonium fabric softeners,
the most commonly used having been di-long alkyl chain ammonium
chloride or methyl sulfate.
[0031] Preferred cationic softeners among these include the
following:
[0032] 1) ditallow dimethylammonium chloride (DTDMAC);
[0033] 2) dihydrogenated tallow dimethylammonium chloride;
[0034] 3) dihydrogenated tallow dimethylammonium methylsulfate;
[0035] 4) distearyl dimethylammonium chloride;
[0036] 5) dioleyl dimethylammonium chloride;
[0037] 6) dipalmityl hydroxyethyl methylammonium chloride;
[0038] 7) stearyl benzyl dimethylammonium chloride;
[0039] 8) tallow trimethylammonium chloride;
[0040] 9) hydrogenated tallow trimethylammonium chloride;
[0041] 10) C.sub.12-.sub.14 alkyl hydroxyethyl dimethylammonium
chloride;
[0042] 11) C.sub.12-.sub.18 alkyl dihydroxyethyl methylammonium
chloride;
[0043] 12) di(stearoyloxyethyl) dimethylammonium chloride
(DSOEDMAC);
[0044] 13) di(tallowoyloxyethyl) dimethylammonium chloride;
[0045] 14) ditallow imidazolinium methylsulfate;
[0046] 15) 1-(2-tallowylamidoethyl)-2-tallowyl imidazolinium
methylsulfate.
[0047] However, in recent years, the need has arisen for more
environmentally-friendly materials, and rapidly biodegradable
quaternary ammonium compounds have been presented as alternatives
to the traditionally used di-long alkyl chain ammonium chlorides
and methyl sulfates. Such quaternary ammonium compounds contain
long chain alk(en)yl groups interrupted by functional groups such
as carboxy groups. Said materials and fabric softening compositions
containing them are disclosed in numerous publications such as
EP-A-0,040,562, and EP-A-0,239,910.
[0048] The quaternary ammonium compounds and amine precursors
herein have the formula (I) or (II), below: 1
[0049] wherein Q is selected from --O--C(O)--, --C(O)--O--,
--O--C(O)--O--, --NR.sup.4--C(O)--, --C(O)--NR.sup.4--;
[0050] R.sup.1 is (CH.sub.2).sub.n-Q-T.sup.2 or T.sup.3;
[0051] R.sup.2 is (CH.sub.2)m-Q-T.sup.4 or T.sup.5 or R.sup.3;
[0052] R.sup.3 is C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4
hydroxyalkyl or H;
[0053] R.sup.4 is H or C.sub.1-C.sub.4 alkyl or C.sub.1-C.sub.4
hydroxyalkyl;
[0054] T.sup.1, T.sup.2, T.sup.3, T.sup.4, T.sup.5 are
independently C.sub.6-C.sub.22 alkyl or alkenyl;
[0055] n and m are integers from 1 to 4; and
[0056] X.sup.- is a softener-compatible anion.
[0057] Non-limiting examples of softener-compatible anions include
chloride or methyl sulfate.
[0058] The alkyl, or alkenyl, chain T.sup.1, T.sup.2, T.sup.3,
T.sup.4, T.sup.5 must contain at least 6 carbon atoms, preferably
at least 11 carbon atoms, more preferably at least 16 carbon atoms.
The chain may be straight or branched.
[0059] Tallow is a convenient and inexpensive source of long chain
alkyl and alkenyl material. The compounds wherein T.sup.1, T.sup.2,
T.sup.3, T.sup.4, T.sup.5 represents the mixture of long chain
materials typical for tallow are particularly preferred.
[0060] Specific examples of quaternary ammonium compounds suitable
for use in the aqueous fabric softening compositions herein
include:
[0061] 1) N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium
chloride;
[0062] 2) N,N-di(tallowoyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)
ammonium methyl sulfate;
[0063] 3) N,N-di(2-tallowoyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium
chloride;
[0064] 4)
N,N-di(2-tallowoyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethyl
ammonium chloride;
[0065] 5)
N-(2-tallowoyl-oxy-2-ethyl)-N-(2-tallowyl-oxy-2-oxo-ethyl)-N,N-d-
imethyl ammonium chloride;
[0066] 6) N,N,N-tri(tallowoyl-oxy-ethyl)-N-methyl ammonium
chloride;
[0067] 7)
N-(2-tallowoyl-oxy-2-oxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammoniu- m
chloride; and
[0068] 8) 1,2-ditallowoyl-oxy-3-trimethylammoniopropane chloride;
and mixtures of any of the above materials.
[0069] Of these, compounds 1-7 are examples of compounds of Formula
(I); compound 8 is a compound of Formula (II).
[0070] Particularly preferred is
N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride, where
the tallow chains are at least partially unsaturated.
[0071] The level of unsaturation of the tallow chain can be
measured by the Iodine Value (IV) of the corresponding fatty 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.
[0072] Indeed, for compounds of Formula (I) made from tallow fatty
acids having a IV of from 5 to 25, preferably 15 to 20, it has been
found that a cis/trans isomer weight ratio greater than 30/70,
preferably greater than 50/50 and more preferably greater than
70/30 provides optimal concentrability.
[0073] For compounds of Formula (I) made from tallow fatty acids
having a IV of above 25, the ratio of cis to trans isomers has been
found to be less critical unless very high concentrations are
needed. Other examples of suitable quaternary ammoniums of Formula
(I) and (II) are obtained by, e.g.:
[0074] replacing "tallow" in the above compounds with, for example,
coco, palm, lauryl, oleyl, ricinoleyl, stearyl, palmityl, or the
like, said fatty acyl chains being either fully saturated, or
preferably at least partly unsaturated;
[0075] replacing "methyl" in the above compounds with ethyl,
ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl or t-butyl;
[0076] replacing "chloride" in the above compounds with bromide,
methylsulfate, formate, sulfate, nitrate, and the like.
[0077] In fact, the anion is merely present as a counterion of the
positively charged quaternary ammonium compounds. The nature of the
counterion is not critical at all to the practice of the present
invention. The scope of this invention is not considered limited to
any particular anion. By "amine precursors thereof" is meant the
secondary or tertiary amines corresponding to the above quaternary
ammonium compounds, said amines being substantially protonated in
the present compositions due to the pH values.
[0078] Still other water-insoluble lubricants include polyalkyl or
polyaryl siloxanes with the following structure: 2
[0079] the alkyl or aryl groups substituted on the siloxane chain
(R) or at the ends of the siloxane chains (A) can have any
structure as long as the resulting silicones remain fluid at room
temperature. Preferably, the silicones are hydrophobic, are neither
irritating, toxic, nor otherwise harmful when applied to fabrics or
when they come in contact with human skin, are compatible with
other components of the composition, are chemically stable under
normal use and storage conditions, and are capable of being
deposited on fabric.
[0080] The R group preferably is a phenyl, a hydroxy, an alkyl or
an aryl. The two R groups on the silicone atom can represent the
same group or different groups. More preferably, the two R groups
represent the same group preferably a methyl, an ethyl, a propyl, a
phenyl or a hydroxy group, q is prereably an integer from about 7
to about 8,000.
[0081] "A" represents groups which block the ends of the silicone
chains. Suitable A groups include hydrogen, methyl, methoxy,
ethoxy, hydroxy, propoxy, and aryloxy. The preferred silicones are
polydimethyl siloxanes; more preferred silicones are polydimethyl
siloxanes having a viscosity of greater than about 10 000
centistokes (cst) at 25.degree. C.
[0082] Suitable methods for preparing these silicone materials are
disclosed in U.S. Pat. Nos. 2,826,551 and 3,964,500, incorporated
herein by reference. Silicones useful in the present invention are
also commercially available. Suitable examples include silicones
offered by Dow Corning Corporation.
[0083] Still other water-insoluble lubricants for use herein are
hydrocarbons. Suitable hydrocarbons for use herein include, in
particular, linear or branched C.sub.8-C.sub.40 paraffin
hydrocarbons or mixtures of different hydrocarbons. An important
factor in the selection of suitable hydrocarbons is that they
should have a liquid to at most wax-like consistency at room
temperature.
[0084] 2)-component having a deviation of fabric WRA versus water
of at least +15:
[0085] A component having a deviation of fabric WRA of at least +15
is another essential component of the invention. Typically, these
components are present in an amount of at least about 0.01%,
preferably from about 0.1% to about 20% by weight of the
composition, preferably to about 4% by weight of the diluted
composition, preferably to about 12% by weight of the concentrated
composition.
[0086] The WRA Test method is taken from the AATCC 66-1990. This
method is an American National Standard method designed for the
determination of the wrinkle recovery of woven fabrics, whereby a
test specimen, creased and compressed under controlled conditions
of time and load, is suspended in the test instrument for a
controlled recovery period, after which the recovery angle is
measured. Experimental detail on how to measure this WRA is given
in AATCC 66-1990, incorporated herein by reference. The WRA method
is tested on 100% cotton, woven Oxford pinpoint fabric, free from
wrinkles, cut in twelve specimens of 0.59 inch.times.1.57 inch, six
with their long dimension parallel to the warp, and six with their
long dimensional parallel to the filling. The test is carried out
on cloth conditioned for 24 hours at 21.degree. C. (70.degree. F.)
and 65% RH. Three specimens from each set are creased on one side
and three on the other. Tweezers are used to place the test
specimen between the leaves of the specimen holder (2 superimposed
leaves 0.63 inch wide, but of different lengths and fastened
together at one end) with one end directly under the 0.71-inch
mark. With the tweezers, the exposed end of the specimen is lifted
over and looped back to the 0.71-inch mark on the shorter, thin
metal leaf and held with the left thumbnail. The holder with the
specimen is inserted into a plastic press (2 superimposed leaves of
equal length (3.74 inch) and 0.79 inch wide, fastened together at
one end ) and a weight of 500 g is applied for 5 minutes so that a
crease is formed. The plastic press can then be removed and the
specimen holder combination can be inserted in the tester with the
exposed end of the specimen holder in the mount on the face of the
tester. The crease should line up with a spot at the center of the
tester disk, and the dangling specimen leg should be lined up
immediately with the vertical guide line. In order to eliminate
gravitation effects, keep the dangling specimen leg aligned with
the vertical guide line during the 5-min recovery period. Adjust
every 15 seconds for the first minute, and once a minute
thereafter. Five minutes after the removal of the creasing load,
the wrinkle recovery value is read to the nearest degree from the
scale. The sum is taken of the average recovery for all warp
readings and all filling readings and compared with a cloth treated
with water.
[0087] Components defined by their WRA are well-known in the art.
For example, in JAPS, Vol.15, pp.341-349 (1971) as well as in
Textile Research Journal, pp. 199-201, February 1970, are given
various examples of components defined by a WRA, all of which are
included within the scope of the present invention.
[0088] The fabric WRA obtained with the tested component is
compared with the fabric WRA obtained with water, thereby giving a
deviation .DELTA.. A component which provide a .DELTA. of at least
positive(+)15, preferably having a .DELTA. within the range of
15-30 is a component suitable for the invention.
[0089] The following represents the WRA deviation versus water of
different polymers suitable for use in the present invention and
according to the above procedure. In each case, numbers are
arithmetic averages of 9 replicates and the results are
statistically significantly different at 95% confidence level:
3 Polymer .DELTA.WRA IMO 900 19 Avalure AC 120 21 Luviquat FC 905
15 IMO 900: Isomaltose Oligosaccharide cx. Showa Sangyo Co. Avalure
AC 120: Polyacrylate ex. BF Goodrich Luviquat FC 905: copolymer
Vinylimidazolium methochloride & Vinylpyrrolidone ex. BASF
[0090] IMO 900: Isomaltose Oligosaccharide ex. Showa Sangyo Co.
[0091] Avalure AC 120 :Polyacrylate ex. BF Goodrich
[0092] Luviquat FC 905 :copolymer Vinylimidazolium methochloride
& Vinylpyrrolidone ex. BASF
[0093] Preferred components which have a deviation of fabric WRA
versus water of at least 15 are selected from a) shape retention
polymers, b) polymers comprising at least one unit which provide a
dye transfer inhibiting benefit, c) polyurethanes, d)
Isomaltooligosaccharide, e) polyamine polymers, f) amphoteric
polymers, g) aminosilicones, h) curable silicones and mixtures
thereof. Most preferred are the polymers which are water-soluble.
Furthermore, as used herein, the word "component" is meant to
include compounds having a WRA deviation versus water of at least
15, mixtures of such components as well as mixtures of components
which per se do not have a WRA deviation versus water of at least
15 but which, in combination do have a WRA deviation versus water
of at least 15. One such component is disclosed and claimed in
co-pending application EP 99870222.9-2413.
[0094] a)-Shape Retention Polymer
[0095] Suitable shape retention polymers can be natural, or
synthetic, and can act by forming a film, and/or by providing
adhesive properties. E.g., the present invention can optionally use
film-forming and/or adhesive polymer to impart shape retention to
fabric, particularly clothing. By "adhesive" it is meant that when
applied as a solution or a dispersion to a fiber surface and dried,
the polymer can attach to the surface. The polymer can form a film
on the surface, or when residing between two fibers and in contact
with the two fibers, it can bind the two fibers together. Other
polymers such as Isomaltose Oligosaccharide can form a film and/or
bond the fibers together when the treated fabric is pressed by a
hot iron. Such a film will have adhesive strength, cohesive
breaking strength, and cohesive breaking strain.
[0096] Nonlimiting examples for natural polymers are Isomaltose
Oligosaccharide and their derivatives, and chitins and their
derivatives.
[0097] The synthetic polymers useful in the present invention are
comprised of monomers. Some nonlimiting examples of monomers which
can be used to form the synthetic polymers of the present invention
include: low molecular weight C.sub.1-C.sub.6 unsaturated organic
mono-carboxylic and polycarboxylic acids, such as acrylic acid,
methacrylic acid, crotonic acid, maleic acid and its half esters,
itaconic acid, and mixtures thereof; esters of said acids with
C.sub.1-C.sub.12 alcohols, such as methanol, ethanol, 1-propanol,
2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol,
3-pentanol, 2-methyl-1-butanol, 1-methyl-i-butanol,
3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-i-pentanol,
3-methyl-i-pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol,
neodecanol, 3-heptanol, benzyl alcohol, 2-octanol,
6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,
3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, and the like,
and mixtures thereof. Nonlimiting examples of said esters are
methyl acrylate, ethyl acrylate, t-butyl acrylate, methyl
methacrylate, hydroxyethyl methacrylate, methoxy ethyl
methacrylate, and mixtures thereof; amides and imides of said
acids, such as N,N-dimethylacrylamide, N-t-butyl acrylamide,
maleimides; low molecular weight unsaturated alcohols such as vinyl
alcohol (produced by the hydrolysis of vinyl acetate after
polymerization), allyl alcohol; esters of said alcohols with low
molecular weight carboxylic acids, such as, vinyl acetate, vinyl
propionate; ethers of said alcohols such as methyl vinyl ether;
aromatic vinyl such as styrene, alpha-methylstyrene,
t-butylstyrene, vinyl toluene, polystyrene macromer, and the like;
polar vinyl heterocyclics, such as vinyl pyrrolidone, vinyl
caprolactam, vinyl pyridine, vinyl imidazole, and mixtures thereof;
other unsaturated amines and amides, such as vinyl amine,
diethylene triamine, dimethylaminoethyl methacrylate, ethenyl
formamide; vinyl sulfonate; salts of acids and arnines listed
above; low molecular weight unsaturated hydrocarbons and
derivatives such as ethylene, propylene, butadiene, cyclohexadiene,
vinyl chloride; vinylidene chloride; and mixtures thereof and alkyl
quaternized derivatives thereof, and mixtures thereof. Preferably,
said monomers are selected from the group consisting of vinyl
alcohol; acrylic acid; methacrylic acid; methyl acrylate; ethyl
acrylate; methyl methacrylate; t-butyl acrylate; t-butyl
methacrylate; n-butyl acrylate; n-butyl methacrylate; isobutyl
methacrylate; 2-ethylhexyl methacrylate; dimethylaminoethyl
methacrylate; N,N-dimethyl acrylamide; N,N-dimethyl methacrylamide;
N-t-butyl acrylamide; vinylpyrrolidone; vinyl pyridine; adipic
acid; diethylenetriamine; salts thereof and alkyl quaternized
derivatives thereof, and mixtures thereof.
[0098] Preferably, said monomers form homopolymers and/or
copolymers (i.e., the film-forming and/or adhesive polymer) having
a glass transition temperature (Tg) of from about -20.degree. C. to
about 150.degree. C., preferably from about -10.degree. C. to about
150.degree. C., more preferably from about 0.degree. C. to about
100.degree. C., most preferably, the adhesive polymer hereof, when
dried to form a film will have a Tg of at least about 25.degree.
C., so that they are not unduly sticky, or "tacky" to the touch.
Preferably said polymer is soluble and/or dispersible in water
and/or alcohol. Said polymer typically has a molecular weight of at
least about 500, preferably from about 1,000 to about 2,000,000,
more preferably from about 5,000 to about 1,000,000, and even more
preferably from about 30,000 to about 300,000 for some
polymers.
[0099] Some non-limiting examples of homopolymers and copolymers
which can be used as film-forming and/or adhesive polymers of the
present invention are: adipic acid/dimethylaminohydroxypropyl
diethylenetriamine copolymer; adipic acid/epoxypropyl
diethylenetriamine copolymer; poly(vinylpyrrolidone/
dimethylaminoethyl methacrylate); polyvinyl alcohol;
polyvinylpyridine n-oxide; methacryloyl ethyl betaine/methacrylates
copolymer; ethyl acrylate/methyl methacrylate/methacrylic
acid/acrylic acid copolymer; polyamine resins; and polyquaternary
amine resins; poly(ethenylformamide); poly(vinylamine)
hydrochloride; poly(vinyl alcohol-co-6% vinylamine); poly(vinyl
alcohol-co-12% vinylamine); poly(vinyl alcohol-co-6% vinylamine
hydrochloride); and poly(vinyl alcohol-co-12% vinylamine
hydrochloride). Preferably, said copolymer and/or homopolymers are
selected from the group consisting of adipic
acid/dimethylaminohydroxypropyl diethylenetriamine copolymer;
poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinyl
alcohol; ethyl acrylate/methyl methacrylate/methacrylic
acid/acrylic acid copolymer; methacryloyl ethyl
betaine/methacrylates copolymer; polyquaternary amine resins;
poly(ethenylformamide); poly(vinylamine) hydrochloride; poly(vinyl
alcohol-co-6% vinylamine); poly(vinyl alcohol-co-12% vinylamine);
poly(vinyl alcohol-co-6% vinylamine hydrochloride); and poly(vinyl
alcohol-co-12% vinylamine hydrochloride).
[0100] Preferred polymers useful in the present invention are
selected from the group consisting of copolymers of hydrophilic
monomers and hydrophobic monomers. The polymer can be linear random
or block copolymers, and mixtures thereof. Such
hydrophobicthydrophilic copolymers typically have a hydrophobic
monomer/hydrophilic monomer ratio of from about 95:5 to about
20:80, preferably from about 90:10 to about 40:60, more preferably
from about 80:20 to about 50:50 by weight of the copolymer. The
hydrophobic monomer can comprise a single hydrophobic monomer or a
mixture of hydrophobic monomers, and the hydrophilic monomer can
comprise a single hydrophilic monomer or a mixture of hydrophilic
monomers. The term "hydrophobic" is used herein consistent with its
standard meaning of lacking affinity for water, whereas
"hydrophilic" is used herein consistent with its standard meaning
of having affinity for water. As used herein in relation to monomer
units and polymeric materials, including the copolymers,
"hydrophobic" means substantially water insoluble; "hydrophilic"
means substantially water-soluble. In this regard, "substantially
water insoluble" shall refer to a material that is not soluble in
distilled (or equivalent) water, at 25.degree. C., at a
concentration of about 0.2% by weight, and preferably not soluble
at about 0.1% by weight (calculated on a water plus monomer or
polymer weight basis). "Substantially water-soluble" shall refer to
a material that is soluble in distilled (or equivalent) water, at
25.degree. C., at a concentration of about 0.2% by weight, and are
preferably soluble at about 1% by weight. The terms "soluble",
"solubility" and the like, for purposes hereof, corresponds to the
maximum concentration of monomer or polymer, as applicable, that
can dissolve in water or other solvents to form a homogeneous
solution, as is well understood to those skilled in the art.
[0101] Nonlimiting examples of useful hydrophobic monomers are
acrylic acid C.sub.1-C18 alkyl esters, such as methyl acrylate,
ethyl acrylate, t-butyl acrylate; methacrylic C.sub.1-C18 alkyl
esters, such as methyl methacrylate, 2-ethyl hexyl methacrylate,
methoxy ethyl methacrylate; vinyl alcohol esters of carboxylic
acids, such as, vinyl acetate, vinyl propionate, vinyl
neodecanoate; aromatic vinyls, such as styrene, t-butyl styrene,
vinyl toluene; vinyl ethers, such as methyl vinyl ether; vinyl
chloride; vinylidene chloride; ethylene, propylene and other
unsaturated hydrocarbons; and the like; and mixtures thereof. Some
preferred hydrophobic monomers are methyl acrylate, methyl
methacrylate, t-butyl acrylate, t-butyl methacrylate, n-butyl
acrylate, n-butyl methacrylate, and mixtures thereof.
[0102] Nonlimiting examples of useful hydrophilic monomers are
unsaturated organic mono-carboxylic and polycarboxylic acids, such
as acrylic acid, methacrylic acid, crotonic acid, maleic acid and
its half esters, itaconic acid; unsaturated alcohols, such as vinyl
alcohol, allyl alcohol; polar vinyl heterocyclics, such as vinyl
pyrrolidone, vinyl caprolactam, vinyl pyridine, vinyl imidazole;
vinyl amine; vinyl sulfonate; unsaturated amides, such as
acrylamides, e.g., N,N-dimethylacrylamide, N-t-butyl acrylamide;
hydroxyethyl methacrylate; dimethylaminoethyl methacrylate; salts
of acids and amines listed above; and the like; and mixtures
thereof. Some preferred hydrophilic monomers are acrylic acid,
methacrylic acid, N,N-dimethyl acrylamide, N,N-dimethyl
methacrylamide, N-t-butyl acrylamide, dimethylaamino ethyl
methacrylate, vinyl pyrrolidone, salts thereof and alkyl
quaternized derivatives thereof, and mixtures thereof.
[0103] Preferably, the shape retention copolymers contain
hydrophobic monomers and hydrophilic monomers which comprise
unsaturated organic mono-carboxylic and polycarboxylic acid
monomers, such as acrylic acid, methacrylic acid, crotonic acid,
maleic acid and its half esters, itaconic acid, and salts thereof,
and mixtures thereof; and optionally other hydrophilic monomers.
These preferred polymers of the current invention surprisingly
provide control of certain amine type malodors in fabrics, in
addition to providing the fabric wrinkle control benefit. Examples
of the hydrophilic unsaturated organic mono-carboxylic and
polycarboxylic acid monomers are acrylic acid, methacrylic acid,
crotonic acid, maleic acid and its half esters, itaconic acid, and
mixtures thereof. Nonlimiting examples of the hydrophobic monomers
are esters of the unsaturated organic mono-carboxylic and
polycarboxylic acids cited hereinabove with C.sub.1-C.sub.12
alcohols, such as methanol, ethanol, 1-propanol, 2-propanol,
1-butanol, 2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol,
2-methyl-i -butanol, 1-methyl-i -butanol, 3-methyl-1-butanol,
1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,
t-butanol, cyclohexanol, 2-ethyl-1-butanol, and mixtures thereof,
preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,
2-methyl-1-propanol, t-butanol, and mixtures thereof. Compositions
containing these polymers also can additionally comprise perfume,
antibacterial active, odor control agent, static control agent, and
mixtures thereof.
[0104] It is not intended to exclude the use of higher or lower
levels of the polymers, as long as an effective amount is used to
provide adhesive and film-forming properties to the composition and
the composition can be formulated and effectively applied for its
intended purpose.
[0105] Highly preferred adhesive and/or film-forming polymers that
are useful in the composition of the present invention actually
contain silicone moieties in the polymers themselves. These
preferred polymers include graft and block copolymers of silicone
with moieties containing hydrophilic and/or hydrophobic monomers
described hereinbefore. The silicone-containing copolymers in the
composition of the present invention provide shape retention, body,
and/or good, soft fabric feel.
[0106] Both silicone-containing graft and block copolymers useful
in the present invention have the following properties:
[0107] (1) the silicone portion is covalently attached to the
non-silicone portion;
[0108] (2) the molecular weight of the silicone portion is from
about 1,000 to about 50,000; and
[0109] (3) the non-silicone portion must render the entire
copolymer soluble or dispersible in the wrinkle control composition
vehicle and permit the copolymer to deposit on/adhere to the
treated fabrics.
[0110] Suitable silicone copolymers include the following:
[0111] Preferred silicone-containing polymers are the silicone
graft copolymers comprising acrylate groups described, along with
methods of making them, in U.S. Pat. No. 5,658,557, Bolich et al.,
issued Aug. 19, 1997, U.S. Pat. No. 4,693,935, Mazurek, issued
Sept. 15, 1987, and U.S. Pat. No. 4,728,571, Clemens et al., issued
Mar. 1, 1988. Additional silicone-containing polymers are disclosed
in U.S. Pat. Nos. 5,480,634, Hayama et al, issued Oct. 2, 1996,
5,166,276, Hayama et al., issued Nov. 24, 1992, 5,061,481, issued
Oct. 29, 1991, Suzuki et al., 5,106,609, Bolich et al., issued Apr.
21, 1992, 5,100,658, Bolich et al., issued Mar. 31, 1992,
5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992, 5,104,646,
Bolich et al., issued Apr. 14, 1992, all of which are incorporated
herein by reference.
[0112] These polymers preferably include copolymers having a vinyl
polymeric backbone having grafted onto it monovalent siloxane
polymeric moieties, and components consisting of non-silicone
hydrophilic and hydrophobic monomers.
[0113] The silicone-containing monomers are exemplified by the
general formula:
X(Y).sub.n Si(R).sub.3-m Z.sub.m
[0114] wherein X is a polymerizable group, such as a vinyl group,
which is part of the backbone of the polymer; Y is a divalent
linking group; R is a hydrogen, hydroxyl, lower alkyl (e.g.
C.sub.1-C.sub.4), aryl, alkaryl, alkoxy, or alkylamino; Z is a
monovalent polymeric siloxane moiety having an average molecular
weight of at least about 500, is essentially unreactive under
copolymerization conditions, and is pendant from the vinyl
polymeric backbone described above; n is 0 or 1; and m is an
integer from 1 to 3.
[0115] The preferred silicone-containing monomer has a weight
average molecular weight of from about 1,000 to about 50,000,
preferably from about 3,000 to about 40,000, most preferably from
about 5,000 to about 20,000.
[0116] Nonlimiting examples of preferred silicone-containing
monomers have the following formulas: 3
[0117] In these structures m is an integer from 1 to 3, preferably
1; p is 0 or 1; q is an integer from 2 to 6; n is an integer from 0
to 4, preferably 0 or 1, more preferably 0; R.sup.1 is hydrogen,
lower alkyl, alkoxy, hydroxyl, aryl, alkylamino, preferably R.sup.1
is alkyl; R" is alkyl or hydrogen; X is
CH(R.sup.3).dbd..dbd.C(R.sup.4)--
[0118] R.sup.3 is hydrogen or --COOH, preferably hydrogen; R.sup.4
is hydrogen, methyl or --CH.sub.2COOH, preferably methyl; Z is
[0119] R.sup.5--[Si(R.sup.6)(R.sup.7)].sub.r
[0120] wherein R.sup.5, R.sup.6, and R.sup.7, independently are
lower alkyl, alkoxy, alkylamino, hydrogen or hydroxyl, preferably
alkyl; and r is an integer of from about 5 to about 700, preferably
from about 60 to about 400, more preferably from about 100 to about
300. Most preferably, R.sup.5, R.sup.6, and R.sup.7 are methyl,
p=0, and q=3.
[0121] Silicone-containing adhesive and/or film-forming copolymers
useful in the present invention comprise from 0% to about 90%,
preferably from about 10% to about 80%, more preferably from about
40% to about 75% of hydrophobic monomer, from about 0% to about
90%, preferably from about 5% to about 80% of hydrophilic monomer,
and from about 5% to about 50%, preferably from about 10% to about
40%, more preferably from about 15% to about 25% of
silicone-containing monomer.
[0122] The composition of any particular copolymer will help
determine its formulation properties. In fact, by appropriate
selection and combination of particular hydrophobic, hydrophilic
and silicone-containing components, the copolymer can be optimized
for inclusion in specific vehicles. For example, polymers which are
soluble in an aqueous formulation preferably contain from 0% to
about 70%, preferably from about 5% to about 70% of hydrophobic
monomer, and from about 30% to about 98%, preferably from about 30%
to about 80%, of hydrophilic monomer, and from about 1% to about
40% of silicone-containing monomer. Polymers which are dispersible
preferably contain from 0% to about 70%, more preferably from about
5% to about 70%, of hydrophobic monomer, and from about 20% to
about 80%, more preferably from about 20% to about 60%, of
hydrophilic monomer, and from about 1% to about 40% of
silicone-containing monomer.
[0123] The silicone-containing copolymers preferably have a weight
average molecular weight of from about 10,000 to about 1,000,000,
preferably from about 30,000 to about 300,000.
[0124] The preferred polymers comprise a vinyl polymeric backbone,
preferably having a Tg or a Tm as defined above of about
-20.degree. C. and, grafted to the backbone, a polydimethylsiloxane
macromer having a weight average molecular weight of from about
1,000 to about 50,000, preferably from about 5,000 to about 40,000,
most preferably from about 7,000 to about 20,000. The polymer is
such that when it is formulated into the finished composition, and
then dried, the polymer phase separates into a discontinuous phase
which includes the polydimethylsiloxane macromer and a continuous
phase which includes the backbone. Exemplary silicone grafted
polymers for use in the present invention include the following,
where the composition of the copolymer is given with the
approximate weight percentage of each monomer used in the
polymerization reaction to prepare the copolymer:
N,N-dimethylacrylamide/isobutyl methacrylate/(PDMS macromer -20,000
approximate molecular weight) (20/60/20 w/w/w), copolymer of
average molecular weight of about 400,000;
N,N-dimethylacrylamide/(PDMS macromer -20,000 approximate molecular
weight) (80/20 w/w), copolymer of average molecular weight of about
300,000; and t-butylacrylate/N,N-dimethylacryla- mide/(PDMS
macromer -10,000 approximate molecular weight) (70/10/20),
copolymer of average molecular weight of about 400,000.
[0125] Highly preferred shape retention copolymers of this type
contain hydrophobic monomers, silicone-containing monomers and
hydrophilic monomers which comprise unsaturated organic mono- and
polycarboxylic acid monomers, such as acrylic acid, methacrylic
acid, crotonic acid, maleic acid and its half esters, itaconic
acid, and salts thereof, and mixtures thereof. These preferred
polymers surprisingly provide control of certain amine type
malodors in fabrics, in addition to providing the fabric wrinkle
control benefit. A nonlimiting example of such copolymer is
n-butylmethacrylate /acrylic acid/(polydimethylsiloxane macromer,
20,000 approximate molecular weight) copolymer of average molecular
weight of about 100,000, and with an approximate monomer weight
ratio of about 70/10/20. A highly preferred copolymer is composed
of acrylic acid, t-butyl acrylate and silicone-containing monomeric
units, preferably with from about 20% to about 90%, preferably from
about 30% to about 80%, more preferably from about 50% to about 75%
t-butyl acrylate; from about 5% to about 60%, preferably from about
8% to about 45%, more preferably from about 10% to about 30% of
acrylic acid; and from about 5% to about 50%, preferably from about
10% to about 40%, more preferably from about 15% to about 30% of
polydimethylsiloxane of an average molecular weight of from about
1,000 to about 50,000, preferably from about 5,000 to about 40,000,
most preferably from about 7,000 to about 20,000. Nonlimiting
examples of acrylic acid/tert-butyl acrylate/polydimethyl siloxane
macromer copolymers useful in the present invention, with
approximate monomer weight ratio, are: t-butylacrylate/acrylic
acid/(polydimethylsiloxane macromer, 10,000 approximate molecular
weight) (70/10/20 wlwiw), copolymer of average molecular weight of
about 300,000; t-butyl acrylate/acrylic acid/(polydimethylsiloxane
macromer, 10,000 approximate molecular weight) (63/20/17),
copolymer of average molecular weight of from about 120,000 to
about 150,000; and n-butylmethacrylate/acrylic acid/
(polydimethylsiloxane macromer -20,000 approximate molecular
weight) (70/10/20 wlwiw), copolymer of average molecular weight of
about 100,000. A useful and commercially available copolymer of
this type is Diahold.RTM. ME from Mitsubishi Chemical Corp., which
is a t-butyl acrylate/acrylic acid/ (polydimethylsiloxane macromer,
12,000 approximate molecular weight) (60/20/20), copolymer of
average molecular weight of about 128,000.
[0126] Silicone Block Copolymers
[0127] Also useful herein are silicone block copolymers comprising
repeating block units of polysiloxanes.
[0128] Examples of silicone-containing block copolymers are found
in U.S. Pat. No. 5,523,365, to Geck et al., issued Jun. 4, 1996;
U.S. Pat. No. 4,689,289, to Crivello, issued Aug. 25, 1987; U.S.
Pat. No. 4,584,356, to Crivello, issued Apr. 22, 1986;
Macromolecular Design, Concept & Practice, Ed: M. K. Mishra,
Polymer Frontiers International, Inc., Hopewell Jct., N.Y. (1994),
and Block Copolymers, A. Noshay and J. E. McGrath, Academic Press,
N.Y. (1977), which are all incorporated by reference herein in
their entirety. Other silicone block copolymers suitable for use
herein are those described, along with methods of making them, in
the above referenced and incorporated U.S. Pat. No. 5,658,577.
[0129] The silicone-containing block copolymers useful in the
present invention can be described by the formulas A-B, A-B-A, and
--(A-B).sub.n-- wherein n is an integer of 2 or greater. A-B
represents a diblock structure, A-B-A represents a triblock
structure, and --(A-B).sub.n-- represents a multiblock structure.
The block copolymers can comprise mixtures of diblocks, triblocks,
and higher multiblock combinations as well as small amounts of
homopolymers.
[0130] The silicone block portion, B, can be represented by the
following polymeric structure
--(SiR.sub.2O).sub.m--,
[0131] wherein each R is independently selected from the group
consisting of hydrogen, hydroxyl, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, C.sub.2-C.sub.6 alkylamino, styryl, phenyl,
C.sub.1-C.sub.6 alkyl or alkoxy-substituted phenyl, preferably
methyl; and m is an integer of about 10 or greater, preferably of
about 40 or greater, more preferably of about 60 or greater, and
most preferably of about 100 or greater.
[0132] The non-silicone block, A, comprises monomers selected from
the monomers as described hereinabove in reference to the
non-silicone hydrophilic and hydrophobic monomers for the silicone
grafted copolymers. Vinyl blocks are preferred co-monomers. The
block copolymers preferably contain one or more non-silicone
blocks, and up to about 50%, preferably from about 10% to about
20%, by weight of one or more polydimethyl siloxane blocks.
[0133] Also useful herein are sulfur-linked silicone containing
copolymers, including block copolymers. As used herein in reference
to silicone containing copolymers, the term "sulfur-linked" means
that the copolymer contains a sulfur linkage (i.e., --S--), a
disulfide linkage (i.e., --S--S--), or a sulfhydryl group (i.e.,
--SH).
[0134] These sulfur-linked silicone-containing copolymers are
represented by the following general formula: 4
[0135] wherein
[0136] each G.sub.5 and G.sub.6 is independently selected from the
group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,
fluoroalkyl, hydrogen, and --ZSA, wherein A represents a vinyl
polymeric segment consisting essentially of polymerized free
radically polymerizable monomer, and Z is a divalent linking group
(Useful divalent linking groups Z include but are not limited to
the following: C.sub.1 to C.sub.10 alkylene, alkarylene, arylene,
and alkoxyalkylene. Preferably, Z is selected from the group
consisting of methylene and propylene for reasons of commercial
availability.);
[0137] each G.sub.2 comprises A;
[0138] each G.sub.4 comprises A;
[0139] each R.sub.1 is a monovalent moiety selected from the group
consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,
fluoroalkyl, hydrogen, and hydroxyl (Preferably, R.sub.1 represents
monovalent moieties which can independently be the same or
different selected from the group consisting of C.sub.1-4 alkyl and
hydroxyl for reasons of commercial availability. Most preferably,
R.sub.1 is methyl.);
[0140] each R.sub.2 is a divalent linking group (Suitable divalent
linking groups include but are not limited to the following:
C.sub.1 to C.sub.10 alkylene, arylene, alkarylene, and
alkoxyalkylene. Preferably, R.sub.2 is selected from the group
consisting of C.sub.13 alkylene and C.sub.7-C.sub.10 alkarylene due
to ease of synthesis of the compound. Most preferably, R.sub.2 is
selected from the group consisting of --CH.sub.2--, 1,3-propylene,
and 5
[0141] each R.sub.3 represents monovalent moieties which can
independently be the same or different and are selected from the
group consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,
fluoroalkyl, hydrogen, and hydroxyl (Preferably, R.sub.3 represents
monovalent moieties which can independently be the same or
different selected from the group consisting of C.sub.1-4 alkyl and
hydroxyl for reasons of commercial availability. Most preferably,
R.sub.3 is methyl.);
[0142] each R.sub.4 is a divalent linking group(Suitable divalent
linking groups include but are not limited to the following:
C.sub.1 to C.sub.10 alkylene, arylene, alkarylene, and
alkoxyalkylene. Preferably, R.sub.4 is selected from the group
consisting of C.sub.1-3 alkylene and C.sub.7-C.sub.10 alkarylene
for ease of synthesis. Most preferably, R.sub.4 is selected from
the group consisting of --CH.sub.2--, 1,3-propylene, and 6
[0143] x is an integer of 0-3;
[0144] y is an integer of 5 or greater(preferably y is an integer
ranging from about 14 to about 700, preferably from about 20 to
about 200); and
[0145] q is an integer of 0-3;
[0146] wherein at least one of the following is true:
[0147] q is an integer of at least 1;
[0148] x is an integer of at least 1;
[0149] G.sub.5 comprises at least one--ZSA moiety; or
[0150] G.sub.6 comprises at least one--ZSA moiety.
[0151] As noted above, A is a vinyl polymeric segment formed from
polymerized free radically polymerizable monomers. The selection of
A is typically based upon the intended uses of the composition, and
the properties the copolymer must possess in order to accomplish
its intended purpose. If A comprises a block in the case of block
copolymers, a polymer having AB and/or ABA architecture will be
obtained depending upon whether a mercapto functional group --SH is
attached to one or both terminal silicon atoms of the mercapto
functional silicone compounds, respectively. The weight ratio of
vinyl polymer block or segment, to silicone segment of the
copolymer can vary. The preferred copolymers are those wherein the
weight ratio of vinyl polymer segment to silicone segment ranges
from about 98:2 to 50:50, in order that the copolymer possesses
properties inherent to each of the different polymeric segments
while retaining the overall polymer's solubility.
[0152] Sulfur linked silicone copolymers are described in more
detail in U.S. Pat. No. 5,468,477, to Kumar et al., issued Nov. 21,
1995, and PCT Application No. WO 95/03776, assigned to 3M,
published Feb. 9, 1995, which are incorporated by reference herein
in their entirety.
[0153] b)- Polymers Comprising at Least One Unit which Provide a
Dye Transfer Inhibiting Benefit
[0154] The preferred polymers comprising at least one unit which
provide a dye transfer inhibiting benefit are water-soluble
polymers.
[0155] The polymers comprising at least one unit which provide a
dye transfer inhibiting benefit useful in the present invention
have the formula:
[--P(D).sub.m--].sub.n
[0156] 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".
[0157] P backbones preferably comprise units having the
formula:
[--CR.sub.2--CR.sub.2]-- or --[(CR.sub.2).sub.x--L]--
[0158] wherein each R unit is independently hydrogen,
C.sub.1-C.sub.12 alkyl, C.sub.6-C.sub.12 aryl, and D units as
described herein below; preferably C.sub.1-C.sub.4 alkyl.
[0159] Each L unit is independently selected from
heteroatom-containing moieties, non-limiting examples of which are
selected from the group consisting of: 7
[0160] polysiloxane having the formula: 8
[0161] wherein the index p is from 1 to about 6; units which have
dye transfer inhibition activity: 9
[0162] and mixtures thereof; wherein R.sup.1 is hydrogen, C.sub.1l
-C.sub.12 alkyl, C.sub.6-C.sub.12 aryl, and mixtures thereof.
R.sup.2 is C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy,
C.sub.6-C.sub.12 aryloxy, and mixtures thereof; preferably methyl
and methoxy. R.sup.3 is hydrogen C.sub.1-C.sub.12 alkyl,
C.sub.6-C.sub.12 aryl, and mixtures thereof; preferably hydrogen or
C.sub.1-C.sub.4 alkyl, more preferably hydrogen. R.sup.4 is
C.sub.1-C.sub.12 alkyl, C.sub.6-Cl.sub.2 aryl, and mixtures
thereof.
[0163] The backbones of the 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).sub.m--].sub.n
[0164] or the D unit may be incorporated into the backbone as a
pendant group to a backbone unit having, for example, the formula:
10
[0165] 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. The molecular weight of the polymers of the present
invention are from about 500, preferably from about 1,000, more
preferably from about 10,000 most preferably from 200,000 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 at 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.degree.
C.
[0166] 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
polyvinylpyrrolidone having the formula: 11
[0167] polyvinyloxazolidone having the formula: 12
[0168] polyvinylmethyloxazolidone having the formula: 13
[0169] polyacrylamides and N-substituted polyacrylamides having the
formula: 14
[0170] wherein each R' is independently hydrogen, C.sub.1-C.sub.6
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: 15
[0171] wherein each R' is independently hydrogen, C.sub.1-C.sub.6
alkyl, or both R' units can be taken together to form a ring
comprising 4-6 carbon atoms; poly(N-acrylylglycinamide) having the
formula: 16
[0172] wherein each R' is independently hydrogen, C.sub.1-C.sub.6
alkyl, or both R' units can be taken together to form a ring
comprising 4-6 carbon atoms; poly(N-methacrylylglycinamide) having
the formula: 17
[0173] wherein each R' is independently hydrogen, C.sub.1-C.sub.6
alkyl, or both R' units can be taken together to form a ring
comprising 4-6 carbon atoms; polyvinylurethanes having the formula:
18
[0174] wherein each R' is independently hydrogen, C.sub.1-C.sub.6
alkyl, or both R' units can be taken together to form a ring
comprising 4-6 carbon atoms.
[0175] 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: 19
[0176] wherein the index n indicates the number of monomer residues
present.
[0177] The amino-functional polymers of the present invention can
comprise any mixture of dye transfer inhibition units which
provides the product with suitable properties.
[0178] 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. 1, CRC Press, (1983) included herein by
reference.
[0179] 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. PVP is readily
soluble in aqueous and organic solvent systems. PVP is available ex
ISP, Wayne, New Jersey, and BASF Corp., Parsippany, N.J., 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:
4 PVP viscosity average molecular weight (in thousands of daltons)
K-12 K-15 K-25 K-30 K-60 K-90 2.5 10 24 40 160 360
[0180] PVP K-12, K-15, and K-30 are also available ex Polysciences,
Inc. Warrington, Pa., PVP K-15, K-25, and K-30 and
poly(2-ethyl-2-oxazoline) are available ex Aldrich Chemical Co.,
Inc., Milwaukee, Wis. 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-dimethylamin-
oethylmethacrylate, commercially available ex ISP in a quaternised
form under the tradename Gafquat.RTM. or commercially available ex
Aldrich Chemical Co. having a molecular weight of approximately
1.0MM; copolymer of 3-methyl-1-vinyl-1H-imidazolium chloride and
1-vinyl-2-pyrrolidone (30:70) ex BASF under the tradename Luviquat
FC370, polyvinylpyrrolidone-co-vinyl acetate, available ex BASF
under the tradename Luviskol.RTM., available in
vinylpyrrolidone:vinylacetate ratios of from 3:7 to 7:3;
polyvinylpyrrolidine-co-vinylimidazoliumquat, commercially
available ex BASF under the tradename Luviquat.RTM..
[0181] Another D unit which provides dye transfer inhibition
enhancement to the polymers described herein, are N-oxide units
having the formula: 20
[0182] wherein R.sup.1, R.sup.2, and R.sup.3 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, 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.
[0183] 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 Pk.sub.a 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 polymers is from about 500
daltons, preferably from about 10,000 daltons, more preferably from
about 20,000 daltons to about 6,000,000 daltons, preferably to
about 2,000,000 daltons, more preferably to about 360,000
daltons.
[0184] A further example of 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.
[0185] c)-Urethanes Polymers
[0186] Polymers of the urethane type are also suitable components
for use herein. A typical disclosure of polyurethane polymer can be
found in EP844274A1 as well as in EP839903.
[0187] d)-Isomaltooligosaccharide
[0188] Isomaltooligosaccharides (IMO) (including mixtures), the
individual components of said mixtures, substituted versions
thereof, derivatised versions thereof, and mixtures thereof are
suitable components for use herein. Currently IMO is used as corn
syrup. These components are particularly suitable where cellulosic
fibers/fabrics are used, such as cotton, rayon, ramie, jute, flax,
linen, polynosic-fibers, Lyocell (Tencel.RTM.), polyester/cotton
blends, other cotton blends, and the like, especially cotton,
rayon, linen, polyester/cotton blends, and mixtures thereof.
[0189] Suitable fabric improving actives that are useful in the
present invention include oligosaccharides with a degree of
polymerization (DP) of from about 1 to about 15, preferably from
about 2 to about 10, and wherein each monomer is selected from the
group consisting of reducing saccharide containing 5 and/or 6
carbon atoms, including isomaltose, isomaltotriose,
isomaltotetraose, isomaltooligosaccharide, fructooligosaccharide,
levooligosaccharides, galactooligosaccharide, xylooligosaccharide,
gentiooligosaccharides, disaccharides, glucose, fructose,
galactose, xylose, mannose, arabinose, rhamnose, maltose, sucrose,
lactose, maltulose, ribose, lyxose, allose, altrose, gulose, idose,
talose, trehalose, nigerose, kojibiose, lactulose,
oligosaccharides, maltooligosaccharides, trisaccharides,
tetrasaccharides, pentasaccharides, hexasaccharides,
oligosaccharides from partial hydrolysates of natural
polysaccharide sources, and the like, and mixtures thereof,
preferably mixtures of isomaltooligosaccharides, especially
mixtures including isomaltooligosaccharides, comprising from about
3 to about 7 units of glucose, respectively, and which are linked
by 1,2-.alpha., 1,3-.alpha., 1,4-.alpha.- and 1,6-.alpha.-linkages,
and mixtures of these linkages. Oligosaccharides containing
b-linkages are also preferred. Preferred oligosaccharides are
acyclic and have at least one linkage that is not an
.alpha.-1,4-glycosidic bond. A preferred oligosaccharide is a
mixture containing IMO: from 0 to about 20% by weight of glucose,
from about 10 to about 65% of isomaltose, from about 1% to about
45% of each of isomaltotriose, isomaltetraose and isomaltopentaose,
from 0 to about 3% of each of isomaltohexaose, isomaltoheptaose,
isomaltooctaose and isomaltononaose, from about 0.2% to about 15%
of each of isomaltohexaose and isomaltoheptaose, and from 0 to
about 50% by weight of said mixture being isomaltooligosaccharides
of 2 to 7 glucose units and from 0 to about 10% by weight of said
mixture being isomaltooligosaccharides of about 7 to about 10
glucose units. Other nonlimiting examples of preferred acyclic
oligosaccharides, with approximate content by weight percent,
are:
5 Isomaltooligosaccharide Mixture I Trisaccharides (maltotriose,
panose, isomaltotriose) 40-65% Disaccharides (maltose, isomaltose)
5-15% Monosaccharide (glucose) 0-20% Higher branched sugars (4 <
DP < 10) 10-30% Isomaltooligosaccharide Mixture II
Trisaccharides (maltotriose, panose, isomaltotriose) 10-25%
Disaccharides (maltose, isomaltose) 10-55% Monosaccharide (glucose)
10-20% Higher branched sugars (4 < DP < 10) 5-10%
Isomaltooligosaccharide Mixture III Tetrasaccharides (stachyose)
10-40% Trisaccharides (raffinose) 0-10% Disaccharides (sucrose,
trehalose) 10-50% Monosaccharide (glucose, fructose) 0-10% Other
higher branched sugars (4 < DP < 10) 0-5%
[0190] Oligosaccharide mixtures are either prepared by enzymatic
reactions or separated as natural products from plant materials.
The enzymatic synthesis of oligosaccharides involves either adding
monosaccharides, one at a time, to a di- or higher saccharide to
produce branched oligosaccharides, or it can involve the
degradation of polysaccharides followed by transfer of saccharides
to branching positions. For instance, Oligosaccharide Mixtures I
and II are prepared by enzymatic hydrolysis of starch to
maltooligosaccharides, which are then converted to
isomaltooligosaccharides by a transglucosidase reaction.
Oligosaccharide Mixture III, for example, is a mixture of
oligosaccharides isolated from soybean. Soybean oligosaccharides
such as Mixture III, are of pure natural origin.
[0191] Substituted and/or derivatised materials of the
oligosaccharides listed hereinabove are also suitable in the
present invention. Nonlimiting examples of these materials include:
carboxyl and hydroxymethyl substitutions (e.g., glucuronic acid
instead of glucose); amino oligosaccharides (amine substitution,
e.g., glucosamine instead of glucose); cationic quaternized
oligosaccharides; C.sub.1-C.sub.6 alkylated oligosaccharides;
acetylated oligosaccharide ethers; oligosaccharides having amino
acid residues attached (small fragments of glycoprotein);
oligosaccharides containing silicone moieties. These substituted
and/or derivatised oligosaccharides can provide additional
benefits, such as: carboxyl and hydroxymethyl substitutions can
introduce readily oxidizable materials on and in the fiber, thus
reducing the probability of the fiber itself being oxidized by
oxidants, such as bleaches; amine substitution can bind and/or
condense with oxidatively damaged regions of the fiber to
rejuvenate aged fabrics; acetylated sugar ethers can serve as
bleach activators in subsequent processes where hydrogen peroxide
is present; oligosaccharides having amino acid residues can improve
delivery of fabric care benefits for fabrics containing
proteinaceous fibers, e.g., wool and silk; and silicone-derivatised
oligosaccharides can provide additional fabric softness and
lubricity. C.sub.6 alkyl oligosaccharide is disclosed (along with
other higher, viz., C.sub.6-C.sub.30, alkyl polysaccharides) in
U.S. Pat. No. 4,565,647. Typical disclosure of C.sub.1-C.sub.6
alkylated oligosaccharides can also be found in U.S. Pat. No.
4,488,981. These patents are incorporated herein by reference.
[0192] One preferred isomaltooligosaccharide is IMO 900
commercially available from Showa Sangyo Co.
[0193] e)-Polyvinylamines Polymers
[0194] Polyvinylamines polymers are also suitable component giving
a deviation of fabric WRA of at least 15. Typical polyvinylamines
polymers include the quaternized and non-quaternized
polyvinylamines having the formula: 21
[0195] wherein R is hydrogen, C1-C12 linear or branched alkyl,
benzyl, or alkyleneoxy having the formula (R1O)zY, wherein R1 is
C1-C6 linear or branched alkylene, Y is hydrogen or an anionic
unit, non-limiting examples of which include, --(CH2)fCO2M,
--C(O)(CH2)fCO2M, --(CH2)fPO3M, --(CH2)fOPO3M, --(CH2)fSO3M,
--CH2(CHSO3M)--(CH2)fSO3M, --CH2(CHSO2M)(CH2)fSO3M,
--C(O)CH2CH(SO3M)CO2M, C(O)CH2CH(CO2M)NHCH(CO2M)- CH2CO2M,
--C(O)CH2CH(CO2M)NHCH2CO2M, --CH2CH(OZ)CH2O(R1O)tZ,
--(CH2)fCH[O(R2O)tZ]CH2O(R2O)tZ, and mixtures thereof, wherein Z is
hydrogen or an anionic unit non-limiting examples of which include
--(CH2)fCO2M, --C(O)(CH2)fCO2M, --(CH2)fPO3M, --(CH2)fOPO3M,
--(CH2)fSO3M, --CH2(CHSO3M)--(CH2)fSO3M, --CH2(CHSO2M)(CH2)fSO3M,
--C(O)CH2CH(SO3M)CO2M, --C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and
mixtures thereof, M is a cation which provides charge neutrality;
and the index f is from 0 to 6, t is 0 or 1, z is from 1 to 50.
[0196] The index x has the value from about 50 to about 1,500;
preferably the index x has a value such that the resulting
polymeric suds stabilizer has an average molecular weight of from
about 2,500, preferably from about 10,000, more preferably from
about 20,000 to about 150,000, preferably to about 90,000, more
preferably to about 80,000 daltons.
[0197] Most preferred polymers for use in the present invention are
water-soluble, including IMO 900 (Isomaltose Oligosaccharide ex.
Showa Sangyo Co.), Avalure AC 120 (Polyacrylate ex. BF Goodrich),
Luviskol K30, K60 and K85 (Polyvinylpyrrolidone MW 40.000, 400.000
and 1.250.000 ex. BASF), Luvitec VPC 55K65W (copolymer
Vinylpyrrolidone & Vinylcaprolactam ex. BASF), Luvitec Quat 73W
(copolymer 1-methyl-3-vinyl-imidazolium-methy- lsulfate &
1-vinyl-2-pyrrolidone ex. BASF), Luviquat FC 905 (copolymer
Vinylimidazolium methochloride & Vinylpyrrolidone ex. BASF),
Sedipur 520 (modified Polyacrylamide ex. BASF), Chitanide 222
(Chitosan succinamide ex. MIP), Mirasil ADM-E (Aminodimethicone ex.
Rhone-Poulenc), Percol 370 (diallyl amine polymer ex. CIBA),
Amphomer HC (Acrylate/Octylacrylamide copolymer ex. National
Starch), and mixtures thereof.
[0198] More preferably, the water-soluble lubricant and the
component, preferably polymer, having a deviation of fabric WRA of
at least +15 are present in weight ratios of water-soluble
lubricant to component of from 10:1 to 1:1. Indeed, it has been
found that within these ratio ranges the resulting composition
provides best in wear wrinkle benefit.
[0199] f)-Amphoteric Polymers
[0200] Suitable for use herein are amphoteric polymers, i.e.,
polymers comprising at least one anionic moiety and one cationic
moiety, and optionally a non-ionic moiety. The anionic moiety
comprises a group which is a deprotonated anion of an acid group
when the polymer is dissolved/dispersed in water at a pH of about 7
and which can be protonated to form a nonionic acid group when the
polymer is dissolved/dispersed in water at an acidic pH.
Representative examples of such groups include carboxylate,
phosphonate, phosphate, phosphite, sulfonate, sulfate groups, and
combinations thereof.
[0201] Optionally, each moiety may be further complexed with a
separate, cationic counterion other than hydrogen. When used,
representative examples of such counterions, include Na.sup.+,
Li.sup.+, K.sup.+, NH4.sup.+ or combinations thereof.
[0202] The cationic moiety comprises a protonated cation when the
polymer is dissolved/dispersed in water at a pH of about 7 or below
and can be deprotonated to a nonionic form when the polymer is
dissolved/dispersed in water at a basic pH. Alternatively, the
cationic moiety comprises a group which is a quaternized group.
[0203] Representative examples of the protonated group include the
ammonium functionality, phosphonium functionality, sulfonium
functionality, and combinations thereof. The term ammonium refers
to a moiety including a nitrogen atom linked to a plurality of
moieties (either H, alkyl or aryl groups) by four bonds when
dissolved/dispersed in water at a pH of 7. The term sulfonium
refers to a moiety including a sulfur atom linked to three other
moieties (either H, alkyl or aryl groups) when dispersed in water
at a pH of about 7. The term phosphonium refers to a moiety
including a phosphorous atom linked to four other moieties (either
H, alkyl or aryl groups) when dispersed in water at a pH of about
7.
[0204] Examples of the ammonium, phosphonium and sulphonium
functionality may be presented by the following formulae,
respectively: 22
[0205] In these formulae, R1 represents the polymer backbone and R2
represents hydrogen, alkyl or aryl substituents. In case the
cationic moiety exists as a quaternized group, all R2 groups
represents alkyl or aryl substituents, excluding hydrogen.
[0206] As an option, each such second functional group may be
further complexed with a separate, anionic counterion. When used,
representative examples of such counterion, include chlorides,
sulfates, carbonates, nitrates, formiates, perchlorates, or
combinations thereof.
[0207] Optionally, amphoteric polymers herein comprise a non-ionic
moiety. A preferred class of amphoteric polymers for use herein are
polymers composed of both cationic and anionic vinylmonomers.
[0208] Suitable anionic vinylmonomers for use herein include salts
of acrylic acid, methacrylic acid, crotonic acid, maleic acid,
fumaric acid, itaconic acid and vinylsulphonic acid. Suitable
cationic vinylmonomers for use herein include salts of unsaturated
amines such as the hydrochloride salt of vinylamine, salts of
N,N'-dialkylaminoalkyl (meth) acrylates and N,N'-dialkylaminoalkyl
(meth) acrylamides such as the hydrochloride salt of
dimethylaminoethylmethacrylate (DMAEMA.HCl) or
dimethylaminopropylacrylamide; alkyl quaternized aminoalkyl (meth)
acrylates and aminoalky (meth) acrylamides such as
trimethylammoniumethyl methacrylatechloride,
trimethylammoniumpropyl acrylamidemethylsulfate, alkyl quaternized
polar vinyl heterocyclics such as based on pyridinium or
imidazolium such as alkylvinylpyridinium, alkylvinylimidazolium and
mixtures thereof.
[0209] Optionally, a non-ionic comonomer can be incorporated, such
as amides and imides of organic acids, such as acrylamide,
N,N-dialkylacrylarnide, N-t-butylacrylamide, maleimides,
vinylformamide, aromatic vinyl monomers such as styrene,
vinyltoluene, t-butylstyrene; polar vinyl heterocyclics such as
vinyl pyrrolidone, vinyl caprolactam, vinyl pyridine,
vinylimidazole; low molecular weight unsaturated hydrocarbons and
derivatives such as ethylene, propylene, butadiene, cyclohexadiene,
vinylchloride and mixtures thereof.
[0210] A preferred polymer of this class is based on
poly(vinylamine-co-acrylic acid), in molar ratios varying between
1:100 to 100:1, preferably 90:10 to 40:60. Polymers of this class
preferably have a molecular weight between 20.000 and 5.000.000
preferably between 30.000 and 1.000.000, more preferably between
50.000 and 300.000.
[0211] A second class of polymers which are preferred for use
herein are anionically modified polyethyleneimines. Examples of
anionically modified polyethyleneimines include polyethyleneimines
grafted with acrylic acid, methacrylic acid, maleic acid, fumaric
acid, crotonic acid, itaconic acid, or carboxymethylated.
[0212] The processes for the preparation of anionically modified
polyethyleneimines are well known. They can be prepared by reacting
.alpha.,.beta.-unsaturated carboxylic acids ( C.dbd.C--COOH) like
acrylic or maleic acid with polyethyleneimine (Michael-type
reaction) or by carboxymethylation. The carboxymethylation is
carried out by reacting polyethyleneimine either with chloroacetic
acid or with formaldehyde and sodium cyanide and subsequent
saponification of the resultant aminonitrile. The latter procedure
is well-known as the "Strecker Synthesis".
[0213] Polymers of this class have a degree of substitution of
between 5 and 95, preferably 20 and 80, and a molecular weight
between 5000 and 2 000 000, preferably 20 000 and 1 000 000.
[0214] In the present invention, the amphoteric polymers can be
provided to the clothes in amounts of from 1.times.10.sup.-7 g/g
fabric to 0.3 g/g fabric, preferably from 1.times.10.sup.-5 g/g
fabric to 0.1 g/g fabric; more preferably from 1.times.10.sup.-3
g/g fabric to 1.times.10.sup.-2 g/g fabric.
[0215] g)-Aminosilicones
[0216] Suitable for use herein are aminosilicones, preferably those
comprising an amine comprising a sterically hindered functional
group.
[0217] In the present invention, any known aminosilicone can be
used to treat clothes so as to provide the desired benefit.
Aminosilicones used in a domestic context have been described in
numerous publications, for instance U.S. Pat. No. 5,062,971 and
U.S. Pat. No. 5,064,543 as ironing aid; in WO 00/24853, WO/9201773
and EP 300 525 in fabric conditioners, EP 150 867 and EP 150 872 in
detergents and there is no need to redescribe such aminosilicones
herein.
[0218] However, a particular problem that arises with most
aminosilicones is that they eventually yellow fabrics. The
phenomenon for such yellowing is not well understood, but it does
create a practical limitation to the use of aminosilicones to treat
clothes: amino silicones can be used to treat clothes, but only in
limited amounts such that the yellowing phenomenon does not become
too visible, thereby limiting the performance of the
composition.
[0219] It has now been found that there exists a particular class
of amino silicones which is suitable for use in a domestic context
and which does not yellow fabrics. Such silicones have been
discussed in, e.g. U.S. Pat. No. 5,688,889 as well as U.S. Pat. No.
5,540,952, but only for use in an industrial context, and for a
different benefit. In particular, in example 3 of those documents,
a process is described in which fabrics are immersed in a solution
of the amino silicone in white spirit, and the fabrics are
subsequently dried at 40.degree. C. for 15 minutes in a ventilated
oven and then heated at 160.degree. C. for 30 min. This
pad-dry-cure process is a standard process in textile industry, but
it cannot be performed in a domestic context. This particular class
of amino silicones is referred throughout this description as
aminosilicones comprising a sterically hindered functional group.
Such aminosilicones have been described in U.S. Pat. No. 5,540,952,
EP 659 930, WO 00/5315, U.S. Pat. No. 5,688,889, WO 96/16110, WO
96/16124, WO 96/16127, WO 96/18667 and U.S. Pat. No. 5,792,825, the
contents of which are incorporated herein.
[0220] The present invention utilizes amino silicones comprising a
sterically hindered functional group, i.e. polyorganosiloxanes
having, per mole, at least one unit of general formula: 1 ( R ) a (
X ) b Z Si ( O ) 3 - ( a + b ) 2
[0221] in which:
[0222] The symbols R are identical or different and represent a
monovalent hydrocarbon radical chosen from linear or branched alkyl
radicals having from 1 to 4 carbon atoms, the phenyl radical, the
benzyl radical and the 3,3,3-trifluoropropyl radical;
[0223] The symbols X are identical or different and represent a
monovalent radical chosen from a hydroxyl group and a linear or
branched alkoxy radical having from 1 to 3 carbon atoms;
[0224] The symbol Z represents a monovalent group of the formula
R.sup.1--U--S in which:
[0225] R' is a divalent hydrocarbon radical chosen from:
[0226] linear or branched alkylene radicals having from 2 to 18
carbon atoms;
[0227] alkylenecarbonyl radicals in which the linear or branched
alkylene part contains 2 to 20 carbon atoms;
[0228] alkylenecyclohexylene radicals in which the linear or
branched alkylene part contains from 2 to 12 carbon atoms and the
cyclohexylene part contains an --OH group and optionally 1 or 2
alkyl radicals having from 1 to 4 carbon atoms;
[0229] radicals of the formula R.sup.2--O--R.sup.3-- in which the
radicals R.sup.2 and R.sup.3, which are identical or different,
represent alkylene radicals having 1 to 12 carbon atoms;
[0230] radicals of the formula R.sup.2--O--R.sup.3-- in which the
radicals R.sup.2 and R.sup.3 have the meanings indicated above and
one of them or both are substituted by one or two --OH
group(s);
[0231] radicals of the formula R.sup.2--COO--R.sup.3-- and
R.sup.2--OCO--R.sup.3 in which the radicals R.sup.2 and R.sup.3
have the meanings above;
[0232] radicals of the formula
R.sup.4--O--R.sup.5--O--CO--R.sup.6-- in which the radicals R.sup.4
, R.sup.5 and R.sup.6, which are identical or different, represent
alkylene radicals having 2 to 12 carbon atoms and the radical
R.sup.5 is optionally substituted by a hydroxyl group;
[0233] radicals of the formula 23
[0234] in which the radical R.sup.7 represents alkylene radicals
having 1 to 4 carbon atoms, and the radical R.sup.8 represents
linear or branched alkylene radicals having 1 to 4 carbon atoms,
the phenyl radical and the phenylalkyl radical where the linear or
branched alkyl part contains 1 to 3 carbon atoms; and where x is a
number chosen between 0, 1 and 2.
[0235] U represents --O-- or --NR.sup.9--, R.sup.9 being a radical
chosen from a hydrogen atom, a linear or branched alkyl radical
having from 1 to 6 carbon atoms, a divalent radical --R.sup.1--
having the meaning indicated above, one of the valency bonds being
connected to the nitrogen of --NR.sup.9-- and the other being
connected to a silicon atom and a divalent radical of the formula
--R.sup.10--N(R.sup.1)--S in which R.sup.1 has the meaning
indicated above, and R.sup.10 represents a linear or branched
alkylene radical having from 1 to 12 carbon atoms, one of the
valency bonds (that of R.sup.10) being connected to the nitrogen
atom of --NR.sup.9-- and the other (that of R.sup.1) being
connected to a silicon atom.
[0236] S represents a monovalent group, in which:
[0237] the free valency is a carbon atom, carrying a secondary or
tertiary amine function, comprised in a cyclic hydrocarbon chain or
in a heterocyclic chain comprising from 6 to 30 carbon atoms, in
which the two atoms of the cyclic chain in the positions .alpha.
and .alpha.' relative to the nitrogen atom, do not comprise any
hydrogen atom;
[0238] the free valency is a carbon atom, carrying a secondary or
tertiary amine function, comprised in a linear hydrocarbon chain
comprising 6 to 40 carbon atoms, in which the two atoms of the
cyclic chain in the positions .alpha. and .alpha.' relative to the
nitrogen atom, do not comprise any hydrogen atom.
[0239] Preferably, the secondary or tertiary amine function in S is
incorporated in a piperidyl group.
[0240] a is a number chosen from 0, 1 and 2;
[0241] b is a number chosen from 0, 1 and 2;
[0242] the sum a +b is not greater than 2.
[0243] The polyorganosiloxane used can additionally comprise (an)
other siloxyl unit(s).
[0244] Such amino silicones comprising a sterically hindered
functional group which are suitable for use herein are commercially
available from Rhodia under the trade name Rhodorsil .RTM., in
particular Rhodorsil .RTM. H 21645 or Rhodorsil .RTM. H 21650 or
Silicex .RTM., in particular Silicex .RTM. 263.
[0245] In the present invention, thanks to their ability not to
yellow fabrics, the aminosilicones comprising a sterically hindered
amino functional group can be provided to the clothes in amounts
from 1.times.10.sup.-7 g/g fabric to 0.3 g/g fabric, preferably
from 1.times.10.sup.-5 g/g fabric to 0.1 g/g fabric; more
preferably from 1.times.10.sup.-3 g/g fabric to 1.times.10.sup.-2
g/g fabric, i.e. in amounts which are greater than the amounts in
which other amino silicones can be used. Thus, a greater benefit
can be obtained without observing fabric yellowing.
[0246] h)-Curable Silicones
[0247] Also suitable for use herein are curable silicones.
"Curable" silicone molecules have the ability to reach one with
each other to yield a polymeric elastomer of a much higher
molecular weight compared to the original molecule. Thus, "curing"
often occurs when two curable silicone molecules or curable
silicone polymers react yielding a polymer of a higher molecular
weight. This "cure" reaction is define herein as the formation of
new silicon-oxygen, silicon-carbon, and/or carbon-carbon linkages.
Curable silicones can be cross-linked to some degree before
application. That means that the curable silicone has cured to some
degree before application but that can still further cure during
and after application. Cross-linked curable silicones are
preferred.
[0248] Examples of curable silicones are vinyl-, allyl-, silane-,
epoxy-, alkoxy-, and/or silanol-modified polydimethylsiloxanes, and
mixtures thereof. Some curable silicones may required the
cooperative use of a catalyst to induce curing, as in the case of
vinyl-,hydrogen-modified silicones which cure via a hydrosilation
process catalyzed by platinum compounds or radical catalysts. More
preferred in this invention are curable silicone able to cure
without the addition of a catalysts, such as epoxy-, alkoxy-,
and/or silanol-modified polydimethylsiloxanes. Most preferred are
silanol-stopped polydimethyl-siloxanes emulsions.
[0249] Curable silicones can have other organic group modifications
as for example, although not restricting, amino or
polyalkyleneoxide groups. Curable silicones may content reinforcing
fillers. By reinforcing fillers we mean small particles made of
inorganic or organic materials added to the curable silicone as
additives or intimately linked to silicone molecules via covalent
bonds. One example, although not restricting, are silica particles
sized from 10 to 100 nanometers present in 10% to 100% by weight
based on the weight of the silicone.
[0250] It is preferred that curable silicones are formulated as
oil-in-water emulsions. Curable silicone emulsions are commercially
available; e.g., GE-Bayer SM2112 Silicone Emulsions or Dow Corning
Syl-Off.RTM. 7922 Catalyst Emulsion.
[0251] It is believed that curable silicones cure during or/and
after application to the fabrics producing a network which will
prevent the formation of wrinkles.
[0252] Other suitable film-forming polymers for use herein are
durable press polymers. Durable press polymers are optional
components of the invention. These polymers can be a cross-linking
resin having the property of being cationic. By "cross-linking
resin having the property of being cationic", it is meant that the
resin is at least partially positively charged. It is not however
necessary that the reactive part of the molecule carries the
positive charge. Indeed, polymeric resins can be based on
positively charged monomers which help the deposition on the
fibers.
[0253] Cross-linking resins having the property of being cationic
suitable for use herein are those commonly known as having wet
strength in the paper field. At least two mechanisms have been
postulated to account for the mechanism by which wet strength resin
act. One is that wet strength resins form covalent bonds between
adjacent fibers while another is that the wet strength resin places
a layer over the hydrogen bonds formed between adjacent paper
fibers and thus prevents water from breaking the hydrogen
bonds.
[0254] Conventional wet-strength agents suitable for use herein
include compounds made of epichlorohydrin adducts of polyamine
resins, polyethyleneimine resins, cationic starch,
polydiallyldimethylammonium chloride, and mixtures thereof,
amine-aldehyde resins such as melamine-formaldehyde resin,
amide-aldehyde resins, and mixtures thereof. For use within the
meaning of the present invention, there can also be used materials
of the above-mentioned classes of substances which admittedly do
not themselves possess any outstanding wet-strength properties but,
nevertheless, have the same durable press effect as do the
wet-strength agents as described therein.
[0255] Among the class of epichlorohydrin adducts of polyamine
resins, polyethyleneimine resins, cationic starch,
polydiallyldimethylammonium chloride, and mixtures thereof, the
preferred components are the polymeric amine-epichlorohydrin resins
selected from the group consisting of a polyamide-epichlorohydrin
(PAE) resin, a polyalkylenepolyamine-epich- lorohydrin (PAPAE)
resin, and an amine polymer-epichlorohydrin (APE) resin, in which
the amine groups have been alkylated with epichlorohydrin to
produce a polyamine-epichlorohydrin resin that has azetidinium or
epoxide functionality. Preferably, for use herein, the
cross-linking resin having cationic properties is a cationic wet
strength resin that is produced by reacting a saturated aliphatic
dicarboxylic acid containing three to ten carbon atoms with a
polyalkylenepolyamine, containing from two to four ethylene groups,
two primary amine groups, and one to three secondary amine groups
(such as diethylenetriamine, triethylenetetramine and
tetraethylenepentamine), to form a poly(aminoamide) having
secondary amine groups that are alkylated with epichlorohydrin to
form a PAE resin.
[0256] These polyamide/polyamine/epichlorohydrin wet-strength
resins are fully described by Carr, Doane, Hamerstrand and
Hofreiter, in an article appearing in the Journal of Applied
Polymer Science Vol. 17, pp. 721-735 (1973). Such resins are
available as KYMENE from Hercules, Inc. A commercial synthesis of
such resins from adipic acid, diethylene triamine and
epichlorohydrin is described in the Carr et al publication, ibid.,
and is U.S. Pat. No. 2,926,154 (Feb. 23, 1960) to G. I. Keim or
U.S. Pat. No. 4,240,995. Reference can be made to these
publications for further details regarding the preparation of
polyamide/polyamine/epichlorohydrin resins.
[0257] Most preferred cross-linking resin having cationic
properties from this class are the wet strength resin Kymene 557H
(available from Hercules Incorporated), in which adipic acid is
reacted with diethylenetriamine to form a poly(aminoamide) that is
alkylated and crosslinked with epichlorohydrin to form a PAE resin.
Still another preferred cross-linking resin having cationic
properties made of epichlorohydrin are Luresin.RTM and Etadurin
which both are polyamidoamine-epichlorohydrin resins.
[0258] Amine-aldehyde resins are suitable cross-linking resins for
the present invention and are made by condensation of amine or
amide monomers with aldehydes such as formaldehyde or glyoxal.
Preferred amines are those having low molecular weight amines e.g.
melamine or polymeric amines e.g. poly-diallylamine, preferably
quarteinized. Preferred amides are those polymeric amides such as
polyacrylamide. All these suitable amine/amide monomers can also be
copolymerized with cationic monomers.
[0259] Among the class of amine-aldehyde cross-linking resin,
preferred are those from the class of melamine-formaldehyde resin.
Melamine-formaldehyde resins of this type are known as crosslinking
agents of this type in the coating industry and are also described,
for example, in German Auslegeschrift Nos. 2,457,387 (U.S. Pat. No.
4,035,213 incorporated herein by reference) and U.S. Pat. No.
1,719,324 and, in particular, in U.S. Pat. No. 3,242,230
incorporated herein by reference.
[0260] Preferred melamine-formaldehyde resin are those commercially
available under the tradenames Madurit, and Cassurit from
Clariant.
[0261] Still other preferred cross-linking resin having the
property of being cationic among the class of amine-aldehyde
cross-linking resin are the Poly(acrylamide-glyoxal) resin
commercially available under the tradename SOLIDUR1 T KM from
Clariant.
[0262] According to the present invention, there can also be used a
mixture of wet-strength agents of the above-mentioned types or
equivalent compounds.
[0263] Preferably for the purpose of the invention, the
cross-linking resin having cationic properties have a molecular
weight between 200 and 1,000,000, preferably between 500 and
100,000, most preferably between 1000 and 25,000. Cross-linking
resin having a low molecular weight are most preferred for use in
the present invention as they are more water-soluble and have a
better fiber penetration. By low molecular weight it is meant a
molecular weight within the range of from 25 to 2000, preferably
from 50 to 1000, and more preferably from 50 to 500.
[0264] It is desirable if the level of cross-linking components or
derivative thereof is present in an amount of from 0.01% to 60%,
preferably from 0.01% to 30% by weight of the total composition
[0265] It is advantageous for aldehyde containing cross-linking
resins if a catalyst is used with compositions of the invention.
Preferred catalysts includes organic acids such as citric acid,
succinic acid, and tartaric acids, as well as conventional Lewis
acid such as Al Cl.sub.3 or MgCl.sub.2, or salts thereof, or
mixtures thereof. A typical example of catalyst is the catalyst NKD
made of a mixture of salts and organic acid, and commercially
available from Hoechst.
[0266] It is preferred if the level of catalyst is from 10% to 50%,
preferably from 20 to 40% by weight of the cross-linking components
or derivative thereof.
[0267] For other cross-linking resins like the Kymene, the use of a
catalyst is not necessary.
[0268] 3)-Optionals:
[0269] The composition of the invention may also comprise one or
more of the following optional ingredients.
[0270] a) Durable Press Polymer
[0271] Durable press polymers are optional components of the
invention. These polymers can be a cross-linking resin having the
property of being cationic. By "cross-linking resin having the
property of being cationic", it is meant that the resin is at least
partially positively charged. It is not however necessary that the
reactive part of the molecule carries the positive charge. Indeed,
polymeric resins can be based on positively charged monomers which
help the deposition on the fibers.
[0272] Cross-linking resins having the property of being cationic
suitable for use herein are those commonly known as having wet
strength in the paper field. At least two mechanisms have been
postulated to account for the mechanism by which wet strength resin
act. One is that wet strength resins form covalent bonds between
adjacent fibers while another is that the wet strength resin places
a layer over the hydrogen bonds formed between adjacent paper
fibers and thus prevents water from breaking the hydrogen
bonds.
[0273] Conventional wet-strength agents suitable for use herein
include compounds made of epichlorohydrin adducts of polyamine
resins, polyethyleneimine resins, cationic starch,
polydiallyldimethylammonium chloride, and mixtures thereof,
amine-aldehyde resins such as melamine-formaldehyde resin,
amide-aldehyde resins, and mixtures thereof. For use within the
meaning of the present invention, there can also be used materials
of the above-mentioned classes of substances which admittedly do
not themselves possess any outstanding wet-strength properties but,
nevertheless, have the same durable press effect as do the
wet-strength agents as described therein.
[0274] Among the class of epichlorohydrin adducts of polyamine
resins, polyethyleneimine resins, cationic starch,
polydiallyldimethylammonium chloride, and mixtures thereof, the
preferred components are the polymeric amine-epichlorohydrin resins
selected from the group consisting of a polyamide-epichlorohydrin
(PAE) resin, a polyalkylenepolyamine-epich- lorohydrin (PAPAE)
resin, and an amine polymer-epichlorohydrin (APE) resin, in which
the amine groups have been alkylated with epichlorohydrin to
produce a polyamine-epichlorohydrin resin that has azetidinium or
epoxide functionality. Preferably, for use herein, the
cross-linking resin having cationic properties is a cationic wet
strength resin that is produced by reacting a saturated aliphatic
dicarboxylic acid containing three to ten carbon atoms with a
polyalkylenepolyamine, containing from two to four ethylene groups,
two primary amine groups, and one to three secondary amine groups
(such as diethylenetriamine, triethylenetetramine and
tetraethylenepentamine), to form a poly(aminoamide) having
secondary amine groups that are alkylated with epichlorohydrin to
form a PAE resin.
[0275] These polyamide/polyamine/epichlorohydrin wet-strength
resins are fully described by Carr, Doane, Hamerstrand and
Hofreiter, in an article appearing in the Journal of Applied
Polymer Science Vol. 17, pp. 721-735 (1973). Such resins are
available as KYMENE from Hercules, Inc. A commercial synthesis of
such resins from adipic acid, diethylene triamine and
epichlorohydrin is described in the Carr et al publication, ibid.,
and is U.S. Pat. No. 2,926,154 (Feb. 23, 1960) to G. I. Keim or
U.S. Pat. No. 4,240,995. Reference can be made to these
publications for further details regarding the preparation of
polyamide/polyamine/epichlorohydrin resins.
[0276] Most preferred cross-linking resin having cationic
properties from this class are the wet strength resin Kymene 557H
(available from Hercules Incorporated), in which adipic acid is
reacted with diethylenetriamine to form a poly(aminoamide) that is
alkylated and crosslinked with epichlorohydrin to form a PAE resin.
Still another preferred cross-linking resin having cationic
properties made of epichlorohydrin are Luresin.RTM and Etadurin
which both are polyamidoamine-epichlorohydrin resins.
[0277] Amine-aldehyde resins are suitable cross-linking resins for
the present invention and are made by condensation of amine or
amide monomers with aldehydes such as forrnaldehyde or glyoxal.
Preferred amines are those having low molecular weight amines e.g.
melamine or polymeric amines e.g. poly-diallylamine, preferably
quarternized. Preferred amides are those polymeric amides such as
polyacrylamide. All these suitable amine/amide monomers can also be
copolymerized with cationic monomers.
[0278] Among the class of amine-aldehyde cross-linking resin,
preferred are those from the class of melamine-formaldehyde resin.
Melamine-formaldehyde resins of this type are known as crosslinking
agents of this type in the coating industry and are also described,
for example, in German Auslegeschrift Nos. 2,457,387 (U.S. Pat. No.
4,035,213 incorporated herein by reference) and U.S. Pat. No.
1,719,324 and, in particular, in U.S. Pat. No. 3,242,230
incorporated herein by reference.
[0279] Preferred melamine-formaldehyde resin are those commercially
available under the tradenames Madurit, and Cassurit from
Clariant.
[0280] Still other preferred cross-linking resin having the
property of being cationic among the class of amine-aldehyde
cross-linking resin are the Poly(acrylamide-glyoxal) resin
commercially available under the tradename SOLIDUR1 T KM from
Clariant.
[0281] According to the present invention, there can also be used a
mixture of wet-strength agents of the above-mentioned types or
equivalent compounds.
[0282] Preferably for the purpose of the invention, the
cross-linking resin having cationic properties have a molecular
weight between 200 and 1,000,000, preferably between 500 and
100,000, most preferably between 1000 and 25,000. Cross-linking
resin having a low molecular weight are most preferred for use in
the present invention as they are more water-soluble and have a
better fiber penetration. By low molecular weight it is meant a
molecular weight within the range of from 25 to 2000, preferably
from 50 to 1000, and more preferably from 50 to 500.
[0283] It is desirable if the level of cross-linking components or
derivative thereof is present in an amount of from 0.01% to 60%,
preferably from 0.01% to 30% by weight of the total composition
[0284] It is advantageous for aldehyde containing cross-linking
resins if a catalyst is used with compositions of the invention.
Preferred catalysts includes organic acids such as citric acid,
succinic acid, and tartaric acids, as well as conventional Lewis
acid such as Al Cl.sub.3 or MgCl.sub.2, or salts thereof, or
mixtures thereof. A typical example of catalyst is the catalyst NKD
made of a mixture of salts and organic acid, and commercially
available from Hoechst.
[0285] It is preferred if the level of catalyst is from 10% to 50%,
preferably from 20 to 40% by weight of the cross-linking components
or derivative thereof.
[0286] For other cross-linking resins like the Kymene, the use of a
catalyst is not necessary.
[0287] b) Liquid Carrier
[0288] Another optional, but preferred, ingredient is a liquid
carrier. 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 about 50%, most
preferably at least about 60%, by weight of the carrier. Mixtures
of water and low molecular weight, e.g., <about 200, organic
solvent, e.g., lower alcohols 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.
[0289] c) Dispersibility Aids
[0290] Relatively concentrated compositions containing both
saturated and unsaturated diester quaternary ammonium compounds can
be prepared that are stable without the addition of concentration
aids. However, the compositions of the present invention may
require organic and/or inorganic concentration aids to go to even
higher concentrations and/or to meet higher stability standards
depending on the other ingredients. These concentration aids which
typically can be viscosity modifiers may be needed, or preferred,
for ensuring stability under extreme conditions when particular
softener active levels are used. The surfactant concentration aids
are typically selected from the group consisting of (1) single long
chain alkyl cationic surfactants; (2) nonionic surfactants; (3)
amine oxides; (4) fatty acids; and (5) mixtures thereof. These aids
are described in WO 94/20597, specifically on page 14, line 12 to
page 20, line 12, which is herein incorporated by reference.
[0291] When said dispersibility aids are present, the total level
is from 0.1% to 20%, preferably from 0.2% to 10%, more preferably
from 0.5% to 5%, and even more preferably from 1% to 2% by weight
of the composition. These materials can either be added as part of
the active softener raw material, (I), e.g., the mono-long chain
alkyl cationic surfactant and/or the fatty acid which are reactants
used to form the biodegradable fabric softener active as discussed
hereinbefore, or added as a separate component. The total level of
dispersibility aid includes any amount that may be present as part
of component (I).
[0292] Inorganic viscosity/dispersibility control agents which can
also act like or augment the effect of the surfactant concentration
aids, include water-soluble, ionizable salts which can also
optionally be incorporated into the compositions of the present
invention. A wide variety of ionizable salts can be used. Examples
of suitable salts are the halides of the Group IA and IIA metals of
the Periodic Table of the Elements, e.g., calcium chloride,
magnesium chloride, sodium chloride, potassium bromide, and lithium
chloride. The ionizable salts are particularly useful during the
process of mixing the ingredients to make the compositions herein,
and later to obtain the desired viscosity. The amount of ionizable
salts used depends on the amount of active ingredients used in the
compositions and can be adjusted according to the desires of the
formulator. Typical levels of salts used to control the composition
viscosity are from about 20 to about 20,000 parts per million
(ppm), preferably from about 20 to about 11,000 ppm, by weight of
the composition. 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 may improve softness performance. These agents may
stabilize the viscosity over a broader range of temperature,
especially at low temperatures, compared to the inorganic
electrolytes.
[0293] Specific examples of alkylene polyammonium salts include
1-lysine monohydrochloride and 1,5-diammonium 2-methyl pentane
dihydrochloride.
[0294] d) Stabilizers
[0295] Stabilizers can be present in the compositions of the
present invention. The term "stabilizer," as used herein, includes
antioxidants and reductive agents. These agents are present at a
level of from 0% to about 2%, preferably from about 0.01% to about
0.2%, more preferably from about 0.035% to about 0.1% for
antioxidants, and more preferably from about 0.01% to about 0.2%
for reductive agents. These assure good odor stability under long
term storage conditions for the compositions and compounds stored
in molten form. The use of antioxidants and reductive agent
stabilizers is especially critical for low scent products (low
perfume).
[0296] Examples of antioxidants that can be added to the
compositions of this invention include a mixture of ascorbic acid,
ascorbic palmitate, propyl gallate, available from Eastman Chemical
Products, Inc., under the trade names Tenox.RTM. PG and Tenox S-1;
a mixture of BHT (butylated hydroxytoluene), BHA (butylated
hydroxyanisole), propyl gallate, and citric acid, available from
Eastman Chemical Products, Inc., under the trade name Tenox-6;
butylated hydroxytoluene, available from UOP Process Division under
the trade name Sustane.RTM. 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 (C.sub.8-C.sub.22) of gallic acid, e.g.,
dodecyl gallate; Irganox.RTM. 1010; Irganox.RTM. 1035; Irganox.RTM.
B 1171; Irganox.RTM. 1425; Irganox( 3114; Irganox.RTM. 3125; and
mixtures thereof; preferably Irganox.RTM. 3125, Irganox.RTM. 1425,
Irganox@ 3114, and mixtures thereof; more preferably Irganox.RTM.
3125 alone. The chemical names and CAS numbers for some of the
above stabilizers are listed in Table II below.
6TABLE II Chemical Name used in Code of Federal Antioxidant CAS No.
Regulations Irganox .RTM. 6683-19-8
Tetrakis(methylene(3,5-di-tert-butyl-4 1010
hydroxyhydrocinnamate))methane Irganox .RTM. 41484-35-9
Thiodiethylene bis(3,5-di-tert-butyl-4- 1035 hydroxyhydrocinnamate
Irganox .RTM. 23128-74-7 N,N'-Hexamethylene
bis(3,5-di-tert-butyl-4- 1098 hydroxyhydrocinnamamide Irganox .RTM.
31570-04-4 B 1171 23128-74-7 1:1 Blend of Irganox .RTM. 1098 and
Irgafos .RTM. 168 Irganox .RTM. 65140-91-2 Calcium
bis(monoethyl(3,5-di-tert-butyl-4- 1425 hydroxybenzyl)phosphonate)
Irganox .RTM. 65140-91-2 Calcium bis(monoethyl(3,5-di-tert-butyl-4-
3114 hydroxybenzyl)phosphonate- ) Irganox .RTM. 34137-09-2
3,5-Di-tert-butyl-4-hydroxy-hydrocinnami- c 3125 acid triester with
1,3,5-tris(2-hydroxyethyl)- S-triazine-2,4,6-(1H, 3H, 5H)-trione
Irgafos .RTM. 31570-04-4 Tris(2,4-di-tert-butyl-phenyl)phosphite
168
[0297] Examples of reductive agents include sodium borohydride,
hypophosphorous acid, Irgafos.RTM. 168, and mixtures thereof.
[0298] e) Preservative
[0299] Optionally, but preferably, antimicrobial preservative can
be added to the composition of the present invention. Contamination
by certain microorganisms with subsequent microbial growth can
result in an unsightly and/or malodorous solution. Because
microbial growth in solutions is highly objectionable when it
occurs, it is highly preferable to include an antimicrobial
preservative, which is effective for inhibiting and/or regulating
microbial growth in order to increase storage stability of the
composition.
[0300] It is preferable to use a broad spectrum preservative, e.g.,
one that is effective on both bacteria (both gram positive and gram
negative) and fungi. A limited spectrum preservative, e.g., one
that is only effective on a single group of microorganisms, e.g.,
fungi, can be used in combination with a broad spectrum
preservative or other limited spectrum preservatives with
complimentary and/or supplementary activity. A mixture of broad
spectrum preservatives can also be used. In some cases where a
specific group of microbial contaminants is problematic (such as
Gram negatives), aminocarboxylate chelators, such as those
described hereinbefore, can be used alone or as potentiators in
conjunction with other preservatives. These chelators which
include, e.g., ethylenediaminetetraacetic acid (EDTA),
hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaacetic
acid, and other aminocarboxylate chelators, and mixtures thereof,
and their salts, and mixtures thereof, can increase preservative
effectiveness against Gram-negative bacteria, especially
Pseudomonas species.
[0301] Antimicrobial preservatives useful in the present invention
include biocidal compounds, i.e., substances that kill
microorganisms, or biostatic compounds, i.e., substances that
inhibit and/or regulate the growth of microorganisms. Well-known
preservatives such as short chain alkyl esters of p-hydroxybenzoic
acid, commonly known as parabens;
N-(4-chlorophenyl)-N'-(3,4-dichlorophenyl) urea, also known as
3,4,4'-trichlorocarbanilide or triclocarban;
2,4,4'-trichloro-2'-hydroxy diphenyl ether, commonly known as
triclosan are useful preservative in the present invention.
[0302] Still other preferred preservatives are the water-soluble
preservatives, i.e. those that have a solubility in water of at
least about 0.3 g per 100 ml of water, i.e., greater than about
0.3% at room temperature, preferably greater than about 0.5% at
room temperature.
[0303] The preservative in the present invention is included at an
effective amount. The term "effective amount" as herein defined
means a level sufficient to prevent spoilage, or prevent growth of
inadvertently added microorganisms, for a specific period of time.
In other words, the preservative is not being used to kill
microorganisms on the surface onto which the composition is
deposited in order to eliminate odors produced by microorganisms.
Instead, it is preferably being used to prevent spoilage of the
solution in order to increase the shelf-life of the composition.
Preferred levels of preservative are from about 0.0001% to about
0.5%, more preferably from about 0.0002% to about 0.2%, most
preferably from about 0.0003% to about 0.1%, by weight of the usage
composition.
[0304] The preservative can be any organic preservative material
which will not cause damage to fabric appearance, e.g.,
discoloration, coloration, bleaching. Preferred water-soluble
preservatives include organic sulfur compounds, halogenated
compounds, cyclic organic nitrogen compounds, low molecular weight
aldehydes, quaternary ammonium compounds, dehydroacetic acid,
phenyl and phenolic compounds, and mixtures thereof. Non-limiting
examples of preferred water-soluble preservatives for use in the
present invention can be found in U.S. Pat. No. 5,714,137,
incorporated hereinbefore by reference, as well as co-pending
application PCTJUS 98/12154 pages 29 to 36.
[0305] Preferred water-soluble preservatives for use in the present
invention are organic sulfur compounds. Some non-limiting examples
of organic sulfur compounds suitable for use in the present
invention are:
[0306] 3-Isothiazolone Compounds: A preferred preservative is an
antimicrobial, organic preservative containing 3-isothiazolone
groups. This class of compounds is disclosed in U.S. Pat. No.
4,265,899, Lewis et al., issued May 5, 1981, and incorporated
herein by reference. A preferred preservative is a water-soluble
mixture of 5-chloro-2-methyl4-isothiazolin-3-one and
2-methyl4-isothiazolin-3-one, more preferably a mixture of about
77% 5-chloro-2-methyl4-isothiazolin-3-- one and about 23%
2-methyl4-isothiazolin-3-one, a broad spectrum preservative
available as a 1.5% aqueous solution under the trade name
Kathon.RTM. CG by Rohm and Haas Company.
[0307] When Kathon.RTM. is used as the preservative in the present
invention it is present at a level of from about 0.0001% to about
0.01%, preferably from about 0.0002% to about 0.005%, more
preferably from about 0.0003% to about 0.003%, most preferably from
about 0.0004% to about 0.002%, by weight of the composition.
[0308] Other isothiazolins include 1,2-benzisothiazolin-3-one,
available under the trade name Proxel.RTM. products; and
2-methyl4,5-trimethylene4-- isothiazolin-3-one, available under the
trade name Promexal.RTM.. Both Proxel and Promexal are available
from Zeneca. They have stability over a wide pH range (i.e., 4-12).
Neither contain active halogen and are not formaldehyde releasing
preservatives. Both Proxel and Promexal are effective against
typical Gram negative and positive bacteria, fungi and yeasts when
used at a level from about 0.001% to about 0.5%, preferably from
about 0.005% to about 0.05%, and most preferably from about 0.01%
to about 0.02% by weight of the usage composition.
[0309] Sodium Pyrithione : Another preferred organic sulfur
preservative is sodium pyrithione, with water solubility of about
50%. When sodium pyrithione is used as the preservative in the
present invention it is typically present at a level of from about
0.0001% to about 0.01%, preferably from about 0.0002% to about
0.005%, more preferably from about 0.0003% to about 0.003%, by
weight of the usage composition.
[0310] Mixtures of the preferred organic sulfur compounds can also
be used as the preservative in the present invention.
[0311] f) Antimicrobial Active
[0312] 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.
[0313] 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.
[0314] Biguanides. 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 chlorhexidine is used as a sanitizer in the present invention
it is typically present at a level of from about 0.001% to about
0.4%, preferably from about 0.002% to about 0.3%, and more
preferably from about 0.01% 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.
[0315] Other useful biguanide compounds include Cosmoci.RTM.
CQ.RTM., Vantocil.RTM. 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.
[0316] As stated hereinbefore, the bis biguanide of choice is
chlorhexidine and its salts, e.g., digluconate, dihydrochloride,
diacetate, and mixtures thereof.
[0317] 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 and/or
substituted benzalkonium chlorides such as commercially available
Barquat.RTM. (available from Lonza), Maquat.RTM. (available from
Mason), Variquat.RTM. (available from Witco/Sherex), and
Hyamine.RTM. (available from Lonza); (2) dialkyl quaternary such as
Bardac.RTM. products of Lonza, (3) N-(3-chloroallyl) hexaminium
chlorides such as Dowicide.RTM. and Dowicil.RTM. available from
Dow; (4) benzethonium chloride such as Hyamine.RTM. 1622 from Rohm
& Haas; (5) methylbenzethonium chloride represented by
Hyamine.RTM. 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.
[0318] Other preservatives which are conventional in the art, such
as described in U.S. Pat. No. 5,593, 670 incorporated herein by
reference, may also be used herein.
[0319] g) Perfume
[0320] The present invention can contain a perfume. Suitable
perfumes are disclosed in U.S. Pat. No. 5,500,138, said patent
being incorporated herein by reference.
[0321] As used herein, perfume includes fragrant substance or
mixture of substances including natural (i.e., obtained by
extraction of flowers, herbs, leaves, roots, barks, wood, blossoms
or plants), artificial (i.e., a mixture of different nature oils or
oil constituents) and synthetic (i.e., synthetically produced)
odoriferous substances. Such materials are often accompanied by
auxiliary materials, such as fixatives, extenders, stabilizers and
solvents. These auxiliaries are also included within the meaning of
"perfume", as used herein. Typically, perfumes are complex mixtures
of a plurality of organic compounds.
[0322] Examples of perfume ingredients useful in the perfumes of
the present invention compositions include, but are not limited to,
hexyl cinnamic aldehyde; amyl cinnamic aldehyde; amyl salicylate;
hexyl salicylate; terpineol; 3,7-dimethyl-cis-2,6-octadien-1-ol;
2,6-dimethyl-2-octanol; 2,6-dimethyl-7-octen-2-ol;
3,7-dimethyl-3-octanol; 3,7-dimethyl-trans-2,6-octadien-1-ol;
3,7-dimethyl-6-octen-1-ol; 3,7-dimethyl-1-octanol;
2-methyl-3-(para-tert-butylphenyl)-propionaldehyde;
4-(4-hydroxy4-methylpentyl)-3-cyclohexene-1-carbox-aldehyde;
tricyclodecenyl propionate; tricyclodecenyl acetate; anisaldehyde;
2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
ethyl-3-methyl-3-phenyl glycidate;
4-(para-hydroxyphenyl)-butan-2-one;
1-(2,6,6-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one;
para-methoxyacetophenone; para-methoxy-alpha-phenylpropene;
methyl-2-n-hexyl-3-oxo-cyclopentane carboxylate; undecalac-tone
gamma.
[0323] Additional examples of fragrance materials include, but are
not limited to, orange oil; lemon oil; grapefruit oil; bergamot
oil; clove oil; dodecalactone gamma;
methyl-2-(2-pentyl-3-oxo-cyclopentyl) acetate; beta-naphthol
methylether; methyl-beta-naphthylketone; coumarin; decylaldehyde;
benzaldehyde; 4-tert-butylcyclohexyl acetate;
alpha,alpha-dimethylphenethyl acetate; methylphenylcarbinyl
acetate; Schiff's base of
4-(4-hydroxy4-methylpentyl)-3-cyclohexene-1-carboxaldehy- de and
methyl anthranilate; cyclic ethyleneglycol diester of tridecandioic
acid; 3,7-dimethyl-2,6-octadiene-1-nitrile; ionone gamma methyl;
ionone alpha; ionone beta; petitgrain; methyl cedrylone;
7-acetyl-1,2,3,4,5,6,7,-
8-octahydro-1,1,6,7-tetramethyl-naphthalene; ionone methyl;
methyl-1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone;
7-acetyl-1,1,3,4,4,6-hexamethyl tetralin;
4-acetyl-6-tert-butyl-1,1-dimet- hyl indane; benzophenone;
6-acetyl-1,1,2,3,3,5-hexamethyl indane;
5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodecanal;
7-hydroxy-3,7-dimethyl octanal; 10-undecen-1-al; iso-hexenyl
cyclohexyl carboxaldehyde; formyl tricyclodecan;
cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone;
1,3,4,6,7,8-hexahydro4,6,6,7,8,8--
hexamethylcyclopenta-gamma-2-benzopyrane; ambroxane;
dodecahydro-3a,6,6,9a-tetramethylnaphtho-[2,1b]furan; cedrol;
5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol;
2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol;
caryophyllene alcohol; cedryl acetate; para-tert-butylcyclohexyl
acetate; patchouli; olibanum resinoid; labdanum; vetivert; copaiba
balsam; fir balsam; and condensation products of:
hydroxycitronellal and methyl anthranilate; hydroxycitronellal and
indol; phenyl acetaldehyde and indol; 4-(4-hydroxy-4-methyl
pentyl)-3-cyclohexene-1-carboxaldehyde and methyl anthranilate.
[0324] More examples of perfume components are geraniol; geranyl
acetate; linalool; linalyl acetate; tetrahydrolinalool;
citronellol; citronellyl acetate; dihydromyrcenol; dihydromyrcenyl
acetate; tetrahydromyrcenol; terpinyl acetate; nopol; nopyl
acetate; 2-phenylethanol; 2-phenylethyl acetate; benzyl alcohol;
benzyl acetate; benzyl salicylate; benzyl benzoate; styrallyl
acetate; dimethylbenzylcarbinol; trichloromethylphenylcarbinyl
methylphenylcarbinyl acetate; isononyl acetate; vetiveryl acetate;
vetiverol; 2-methyl-3-(p-tert-butylphenyl)-pr- opanal;
2-methyl-3-(p-isopropylphenyl)-propanal; 3-(p-tert-butylphenyl)-pr-
opanal; 4-(4-methyl-3-pentenyl)-3-cyclohexenecarbaldehyde;
4-acetoxy-3-pentyltetrahydropyran; methyl dihydrojasmonate;
2-n-heptylcyclopentanone; 3-methyl-2-pentyl-cyclopentanone;
n-decanal; n-dodecanal; 9-decenol-1; phenoxyethyl isobutyrate;
phenylacetaldehyde dimethylacetal; phenylacetaldehyde
diethylacetal; geranonitrile; citronellonitrile; cedryl acetal;
3-isocamphylcyclohexanol; cedryl methylether; isolongifolanone;
aubepine nitrile; aubepine; heliotropine; eugenol; vanillin;
diphenyl oxide; hydroxycitronellal ionones; methyl ionones;
isomethyl ionomes; irones; cis-3-hexenol and esters thereof; indane
musk fragrances; tetralin musk fragrances; isochroman musk
fragrances; macrocyclic ketones; macrolactone musk fragrances;
ethylene brassylate.
[0325] The perfumes useful in the present invention compositions
are substantially free of halogenated materials and nitromusks.
[0326] Suitable solvents, diluents or carriers for perfumes
ingredients mentioned above are for examples, ethanol, isopropanol,
diethylene glycol, monoethyl ether, dipropylene glycol, diethyl
phthalate, triethyl citrate, etc. The amount of such solvents,
diluents or carriers incorporated in the perfumes is preferably
kept to the minimum needed to provide a homogeneous perfume
solution.
[0327] Perfume can be present at a level of from 0% to 10%,
preferably from 0.1% to 5%, and more preferably from 0.2% to 3%, by
weight of the finished composition. Fabric softener compositions of
the present invention provide improved fabric perfume
deposition.
[0328] Perfume ingredients may also be suitably added as releasable
fragrances, for example, as pro-perfumes or pro-fragrances as
described in U.S. Pat. No. 5,652,205 Hartman et al., issued Jul.
29, 1997, WO95/04809, WO96/02625, PCT US97/14610 filed 19 Aug. 1997
and claiming priority of 19 Aug. 1996, EP-A-0,752,465, co-pending
application EP 98870227.0, EP 98870226.2, EP 99870026.4, and EP
99870025.6; all incorporated herein by reference.
[0329] h) Soil Release Agent
[0330] 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.
[0331] 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%.
[0332] The following, all included herein by reference, describe
soil release polymers suitable for use in the present invention.
U.S. Pat. No. 3,959,230 Hays, issued May 25, 1976; U.S. Pat. No.
3,893,929 Basadur, issued Jul. 8, 1975; U.S. Pat. No. 4,000,093,
Nicol, et al., issued Dec. 28, 1976; U.S. Pat. No. 4,702,857
Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,968,451, Scheibel
et al., issued November 6; U.S. Pat. No. 4,702,857, Gosselink,
issued Oct. 27, 1987; U.S. Pat. No. 4,711,730, Gosselink et al.,
issued Dec. 8, 1987; U.S. Pat. No. 4,721,580, Gosselink, issued
Jan. 26, 1988; U.S. Pat. No. 4,877,896, Maldonado et al., issued
Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink et al., issued
Sep. 11, 1990; U.S. Pat. No. 5,415,807 Gosselink et al., issued May
16, 1995; European Patent Application 0 219 048, published Apr. 22,
1987 by Kud, et al.
[0333] Further suitable soil release agents are described in U.S.
Pat. No. 4,201,824, Violland et al.; U.S. Pat. No. 4,240,918
Lagasse et al.; U.S. Pat. No. 4,525,524 Tung et al.; U.S. Pat. No.
4,579,681, Ruppert et al.; U.S. Pat. No. 4,240,918; U.S. Pat. No.
4,787,989; U.S. Pat. No. 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.
[0334] Commercially available soil release agents include the
METOLOSE SM100, METOLOSE SM200 manufactured by Shin-etsu Kagaku
Kogyo K. K., SOKALAN type of material, e.g., SOKALAN HP-22,
available from BASF (Germany), ZELCON 5126 (from Dupont) and
MILEASE T (from ICI).
[0335] i)-pH
[0336] An optional requirement of the compositions according to the
present invention is that the pH as measured in the neat
compositions at 20.degree. C., is greater than 3, preferably
between 3 and 12, more preferably between 4 and 8, most preferably
is of 5. This range is preferred for fabric safety. The pH of these
compositions herein can be regulated by the addition of a Bronsted
acid.
[0337] j)-Blowing Agents
[0338] Also suitable for use herein are blowing agents selected
from the group consisting of ammonium carbonate, ammonium
bicarbonate, or mixtures thereof. It is hypothesized that those
agents, when present, will generate small amounts of CO.sub.2 when
exposed to heat, such as during the ironing process. The CO.sub.2
will be released in the composition which is deposited as a film on
the fabric. The film, hence the fabric, will thus acquire more
flexibility, resulting in a better ability to resist to the dry
formation of wrinkles, when the fabric is stored or worn.
[0339] k) Void Fillers
[0340] The compositions herein may further comprise void fillers.
By fabric void filler, it is meant herein particles having the size
and shape suited to fill the structural defects in cotton, and
hereby provide lubricating properties. Cyclodextrins such as those
described in WO 99/55950 can be used as void fillers, as well as
polyolefin dispersions, such as those described in U.S. Pat. No.
6,020,302. Inorganic particles can also be used to that effect, for
instance TiO.sub.2 and Silica.
[0341] 1) Other Optional Ingredients
[0342] The present invention can include optional components
conventionally used in textile treatment compositions, for example,
humectants like diethylene glycol, and/or salts like lithium salts,
colorants, bactericides, optical brighteners, opacifiers,
anti-shrinkage agents, germicides, fungicides, anti-oxidants, color
protection agent like dye fixing agent as described in EP 931133,
enzymes, chelating agents, cyclodextrin as described in WO
98/56888, metallic salts to absorb amine and sulfur-containing
compounds and selected from the group consisting of copper salts,
zinc salts, and mixtures thereof, water-soluble polyionic polymers,
e.g., water-soluble cationic polymer like polyamines, and
water-soluble anionic polymers like polyacrylic acids, other
antistatic agent, insect and/or moth repelling agents, colorants
and dyes, anti-clogging agent, and the like; typical disclosure of
which can be found in WO 98/56888. Still other suitable optional
ingredients are ingredients which provide shield protection against
stain like hydroxypropylcellulose as well as other cellulosic
polymer like carboxymethylcellulose. 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.
[0343] 4)-Form of the Composition:
[0344] The composition of the invention may take a variety of
physical form including liquid, liquid-gel, paste-like, foam in
either aqueous or non-aqueous form, powder like granular and tablet
forms. A preferred form of the composition is in a liquid form.
[0345] When in a liquid form, the composition is preferably
dispensed by a dispensing means such as a spray dispenser, aerosol
dispenser, or refill thereof. Still another preferred dispensing
means is by incorporation of the composition of the invention in
the ironing tank per se, or via a cartridge preferably adapted for
the iron.
[0346] 5)-Spray Dispenser:
[0347] The present invention also relates to such compositions
incorporated into a spray dispenser to create an article of
manufacture that can facilitate treatment of fabric articles and/or
surfaces with the compositions according to the invention at a
level that is effective. The spray dispenser comprises manually
activated and non-manual powered (operated) spray means and a
container containing the treating composition. Typical disclosure
of such spray dispenser can be found in WO 96/04940 page 19 line 21
to page 22 line 27. Preferably, the spray dispenser is selected
from spray dispenser comprising battery operated pump, spray
dispenser comprising a trigger spray device, spray dispenser
comprising a pressurized aerosol spray dispenser.
[0348] 6)-Method of Use:
[0349] It has been found that the use of the water-soluble
lubricant provided a reduction of the WRA compared to water.
Accordingly, there is provided a method of increasing the WRA of
fabrics, which comprises the steps of contacting the fabrics with a
water-soluble lubricant as defined herein before, using a domestic
process.
[0350] It has also been found that the use of the water-soluble
lubricant or composition of the invention provides surprisingly
good benefit on the dewrinkling performance upon wearing. This
benefit is particularly achieved while spraying the compound or
composition preferably from an iron during an otherwise known
fabric ironing process. Accordingly, there is also provided a
method of treating fabrics, in particular to provide in wear
wrinkle resistance on fabrics, which comprises the steps of
contacting the fabrics with a water-soluble lubricant or
composition according to the invention, as defined herein before,
using a domestic process.
[0351] 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, and/or spraying as well as by
means of a dryer sheet onto which is adsorbed the composition.
Preferably, the contacting occurs after the laundering and optional
drying of the fabrics, e.g. by spraying the composition, more
preferably by spraying the composition from an iron spray dispenser
and/or via the vaporisation holes from an iron sole plate or foam
or sprayer which is separate from the iron. Accordingly, in this
instance, the composition of the present invention is used as an
ironing aid. An effective amount of the composition can be sprayed
onto the fabric, wherein said fabric should not be sprayed to
saturation. Still another preferred way of treating the fabrics is
when the fabric can be sprayed with an effective amount of the
composition, allowed to dry and then ironed, or sprayed and ironed
immediately.
[0352] Accordingly, in a further aspect of the invention, the
composition of the invention can also be sprayed onto the fabrics
by means of spraying means which are incorporated to an iron, and
the composition is incorporated into the iron's water tank or via a
cartridge, adapted to fit within the iron. Such irons are disclosed
for instance in WO 00/08247 and WO 99/27176. As for the method of
spraying via the iron, the spraying means should preferably be
capable of providing droplets with a weight average diameter of
from about 40 to about 200 .mu.m, preferably from about 70 to about
150 .mu.m. Preferably, the loading of moisture on fabrics made of
natural and synthetic fibers is from about 5 to about 25%, more
preferably from about 5 to about 10% by weight of the dried
fabric.
[0353] By "wrinkle reducing composition", it is meant that the
composition is tested on 100% cotton, woven Oxford pinpoint fabric
according to the procedure given in W. Garner, Textile Laboratory
Manual Vol. 6, Ed. 3, Elsevier Inc., 1967, p. 105, so called
"cylinder test". The cylinder test consists in taking a 12.times.14
inch of treated cloth, rolling it round a plastic tube, placing the
roll in a 360 ml measuring cylinder (r=0.67 inch, I=15.7 inch),
withdrawing the tube, and pushing the fabric down to occupy a
volume of about 90 ml by means of a plastic tube which is an easy
sliding fit for the cylinder. This test is carried out on cloth
conditioned for 24 hours at 21.degree. C. (70.degree. F.) and 65%
RH. The cloth is left 1 minute in the cylinder, opened immediately,
inspected visually, and then compared with a cloth only treated
with water. The results obtained are compared against fabrics which
have only been treated with water. Wrinkle reducing compositions
are compositions which provide a better crease resistance versus
water, i.e, fabrics that have been treated with a composition of
the invention show less wrinkles compared to fabrics which have
only been treated with water.
[0354] In a still further aspect of the invention, the composition
can be sprayed onto fabrics by an in-home de-wrinkling chamber
containing the fabric to be dewrinkled, thereby providing ease of
operation. Conventional personal as well as industrial de-wrinkling
apparatuses are suitable for use herein. Traditionally, these
apparatuses act by a steaming process which effects a relaxation of
the fibers. Examples of home dewrinkling chambers include shower
stalls. The spraying of the composition or compounds onto the
fabrics can then occur within the chamber of the apparatus or
before placing the fabrics into the chamber. As for the manual
method of spraying, the spraying means should preferably be capable
of providing droplets with a weight average diameter of from about
8 to about 100 .mu.m, preferably from about 10 to about 50 .mu.m.
Preferably, the loading of moisture on fabrics made of natural and
synthetic fibers is from about 5 to about 25%, more preferably from
about 5 to about 10% by weight of the dried fabric. Other
conventional steps that can be carried out in the dewrinkling
apparatus can be applied such as heating which will provide the
curing step and drying. Preferably, for optimum dewrinkling
benefit, the temperature profile inside the chamber ranges from
about 40.degree. C. to about 80.degree. C., more preferably from
about 50.degree. C. to about 70.degree. C. The preferred length of
the drying cycle is from about 15 to about 60 minutes, more
preferably from about 20 to about 45 minutes.
[0355] The steaming step in the dewrinkling apparatus can also be
eliminated if the composition is maintained at a temperature range
from about 22.degree. C. (about 72.degree. F.) to about 76.degree.
C. (170.degree. F.) before spraying.
[0356] The present invention encompasses the method of spraying a
mist of an effective amount of solution of the invention
composition onto fabric and/or fabric articles. Preferably, said
fabric and/or fabric articles include, but are not limited to,
clothes, curtains, drapes, upholstered furniture, carpeting, bed
linens, bath linens, tablecloths, sleeping bags, tents, car
interiors, etc.
[0357] The compositions herein are especially useful, when used to
treat garments for extending the time before another wash cycle is
needed, and/or even reducing the time involved in ironing. Such
garments include uniforms and other garments which are normally
treated in an industrial process, which can be dewrinkled and the
time between treatments extended.
[0358] 7)-Article of Manufacture:
[0359] Also provided herein is an article of manufacture comprising
a container and the composition of the invention in association
with a set of instructions to use the composition in an amount
effective to provide a solution to problems involving and/or
provision of a benefit related to those selected from reducing
wrinkles; imparting in-wear resistance to fabrics. It is important
that the consumer be aware of these additional benefits, since
otherwise the consumer would not know that the composition would
solve these problems and/or provide these benefits.
[0360] As used herein, the phrase "in association with" means the
set of instructions are either directly printed on the container
itself or presented in a separate manner including, but not limited
to, a brochure, print advertisement, electronic advertisement,
and/or verbal communication, so as to communicate the set of
instructions to a consumer of the article of manufacture. The set
of instructions preferably comprises the instruction to apply an
effective amount of the composition, preferably by spraying, to
provide the indicated benefit, e.g. wrinkles reduction; imparting
in-wear resistance to fabrics. The set of instructions preferably
comprises instructions to spray the composition on the fabrics and
iron the fabrics.
[0361] The invention is illustrated in the following non limiting
examples, in which all percentages are on a weight basis unless
otherwise stated.
[0362] In the examples, the abbreviated component identifications
have the following meanings:
[0363] Polymer 1: Isomalto oligosaccharide available from Showa
Sangyo Co. under the trade name IMO 900
[0364] Polymer 2: Polyvinylpyrrolidone available from BASF under
the trade name Luviskol K30
[0365] Polymer 3: Co-polymer of vinylpyrrolidone and
vinylcaprolactame available from BASF under the trade name Luvitec
VPC
[0366] Polymer 4: Co-polymer of vinylpyrrolidone and
vinylimidazolinium methachloride available from BASF under the
trade name Luviquat FC 905
[0367] Lubricant 1: Polyalkylene oxide polysiloxane commercially
available under the tradename of Silwet 7200 from OSI
Chem./Witco
[0368] Lubricant 2: Polyalkylene oxide polysiloxane commercially
available under the tradename of Silwet 7657 from OSI
Chem.[Witco
[0369] Lubricant 3: Polyethoxylated (20 moles) sorbitan monolaurate
commercially available under the tradename of Radiasurf 7137 from
FINA
[0370] Lubricant 4: Polyethoxylated (20 moles) sorbitan tristearate
commercially available under the tradename of Tween 65
[0371] Wetting agent 1: Polyalkylene oxide polysiloxane
commercially available under the tradename of Silwet 7600 from OSI
Chem./Witco
[0372] Wetting agent 1: Polyalkylene oxide polysiloxane
commercially available under the tradename of Silwet L 77 from OSI
Chem./Witco
[0373] Emulsifier 1: CAE 10 (coconut alcohol condensed with an
average of 10 moles of ethylene oxide)
7 A B C D E F Polymer #1 5% -- -- -- -- 1% Polymer #2 -- 1% -- 2%
-- -- Polymer #3 -- -- 2% -- -- -- Polymer #4 -- -- -- -- 0.5% --
Lubricant #1 14% 4% -- -- 1.5% -- Lubricant #2 -- -- 6% 2% 1.5% --
Lubricant #3 8% 2% -- -- -- 5% Lubricant #4 -- -- -- 3% -- --
Wetting agent 1 3% 0.5 -- -- 0.2% -- Wetting agent 2 -- -- 0.5% --
-- -- Dipropyleneglycol -- 0.3 -- -- -- -- Emulsifier 1 0.6% 0.2 --
-- -- -- Cyclodextrin -- 0.5 1% -- -- -- Preservative 3 ppm 3 ppm
-- 3 ppm -- -- Perfume 0.5% 0.1 0.1% -- -- 0.2% Water Balance
Balance Balance Balance Bal- Bal- ance ance
* * * * *