Note: Descriptions are shown in the official language in which they were submitted.
~ WO 96/10671 2 2 0 ~ 3 ~ 9 PCT/US95/11172
BLOCK COPOLYMERS FOR IMPROVFD VISCOSITY STABILITY
IN CONCENTRATED FABRIC SOFTENERS
Technical field
The present invention relates to fabric softener
compositions to be used during the rinse cycle of a textile
laundering operation to provide fabric softening/static
control benefits.
The fabric softening compositions comprise beyond the
conventional softener ingredients one or ~ore polymers having
a hydrophobic backbone with one or more hydrophilic side
chains and are characterized by excellent storage stability
and viscosity characteristics.
Background of the Invention
Fabric softener compositions, especially concentrated
and/or superconcentrated, are dispersions of positively
charged vesicles containing the softener active. These
vesicles are believed to be comprised of alternating
concentric layers of water and lamellar cationic bilayers,
.
WO96110671 PCT~S95/11172 ~
so-called lamellar droplets. The presence of lamellar
droplets in a fabric-softening composition can be detected by
methods known to persons skilled in the art like optical
techniques, rheometrical measurements, X-ray diffraction and
electron microscopy. The droplets consist of an onion-like
configuration of, as pointed out above, concentric bilayers
of molecules of fabric-softening material with entrapped
water or electrolyte solution, the so-called aqueous phase.
A well-appreciated fabric softener product exists of physical
stability and desirable flow properties combined in one
system.
However, upon storage the dispersions above-mentioned are
thickening and eventually gelling. The reason for this
phenomenon is not yet clear. There are, at least, two
theoretical possibilities : the lamellar vesicles are
increasingly interconnecting with time and eventually ~l)
form an infinitely inter-connected vesicle network or gel, or
(2) change from a lamellar vesicle to a two-phase lamellar
phase in which gelation may occur.
Regardless of the mechanism, gelation probably will be
avoided as long as the vesicles are kept separated from each
other.
It is well-known that two factors mainly determine the
viscosity and stability of the fabric softening composition.
First of all, it is the volume (fraction) 5cf the dispersed
lamellar phase in the composition and secondly it depends on
the state of aggregation of these droplets. In general, the
higher the volume (fraction) of the droplets (dispersed
lamellar phase), the higher the viscosity which, if too high,
results in an unpourable product. One way to solve this
problem is using electrolytes whereby apparently the size of
the lamellar vesicles is reduced and, as such, increases the
inter-vesicle distances preventing aggregation/gelation.
However, the stability of other components in the fabric-
softener composition is affected using higher electrolyte
levels.
~ WO96/10671 ~2 ~ 0 1 3 2 9 PCT/US95~ 72
So there are limits to~ the amount of fabric softening
material and electrolyte to be used whilst still having an
acceptable product. There is a continued need for more
concentrated, sometimes superconcentrated, fabric softening
compositions for convenience and cost reduction purposes. The
problem to be solved is that these high concentrations of
softener active in the compositions must have an acceptable
stability and at the same time pourability upon use.
Summary of the Invention
We have now found that, with respect to the stability
and viscosity requirements especially at elevated
temperature, a fabric softening composition having
conventional softener ingredients can be surprisingly
favourable influenced by incorporating a block copolymer
comprising a hydrophobic backbone with one or more
hydrophilic side chains in the presence of a non-ionic water
soluble polymer. These polymeric materials reduce the
viscosity of concentrated dispersions of cationic softener
actives in lamellar vesicles and improves unexpected the
stabilizing properties of the fabric softening compositions.
As such, they prevent these types of formulations from
gelling or solidifying. Another practical benefit of these
materials is that they prevent skin formation and dispenser
residue upon use.
Furthermore, we have found that the use of a block
copolymer with a hydrophobic backbone and one or more
hydrophilic side chains according to the invention in a
fabric softener composition, reduces the viscosity of the
composition at low and high temperature as well.
; ~ 2 ~
WO96/10671 PCT~S95111172 ~
Detailed description of the invention
The objective of polymer stabilization in concentrated
fabric softener formulations is to maintaln low viscosity
upon storage at low (oC! and high (50C) temperatures
without affecting the softening performance. It appears that
so-called di- and tri-block copolymers of the types A-B and
A-B-A, respectively, and preferably tri-block copolymers with
highly water-soluble blocks (A) and an insoluble or partially
water-soluble blocks (B) in combination with a very water-
soluble polymer (cloud point larger than 90C) provides
excellent viscosity stabilization of concentrated
compositions. The block copolymers are defined as : (a)
separated polymer blocks (of more than two units) of the same
kind separated by, at least, one monomer of another kind, (b)
different kinds of polymer blocks of more than two monomers
that are chemically connected. Probably a mixed
depletion/steric stabilization phenomenon is likely to be
responsible for this behavior. Key parameters in the
structure of these materials are (l) the chain lengths of the
blocks, (2) the water-solubility of the blocks, and (3) the
specific interactions of the B blocks with the lamellar
vesicles. In addition, we have also found that said di- or
tri-block copolymers without the water-soluble polymer
provide excellent viscosity stabilization especially at high
elevated temperature.
The following five general polymer structures (I-V) provide
above-mentioned viscosity stabilization :
(I) polymers that are likely to adhere physically to the
positively charged vesicle surface : C-(A)x-(B)y-D and
C-(A)x-(B)y-(A)z-D, where the monomers A and B are water
soluble and partially water insoluble respectively, and
C and D are end groups or a hydrogen atom. Typical end
groups are hydroxyl, acetate, methyl amine or quaternary
amine.
2~ ~329
~ WO96/10671 PCT~S95/11172
(II) Polymers that are likely to be incorporated into the
lamellar vesicles : D-(A)x-R-~A)z-C, where R is a
polymer of B monomers as defined above, or preferably a
fatty alcohol or acid of which one carbon atom is
substituted with polymer blocks. For instance, the mono
fatty ester of ethoxylated glycerol.
(III)Combinations of polymers of type (I) and (II) with
nonionic water soluble polymers, such as polyvinyl
pyrrolidone, polyvinyl pyridine-N-oxide, polyethylene
glycol, and substituted poly alcohol.
Further details about these polymer structures are
described below.
(IV) Polymer combinations amongst type (I), amongst type (II)
and mixed type (I) + type (II) combinations.
(V) Combinations of (III) and (IV).
In EP 458 599, an attempt is made to solve the problem
of stability and acceptable viscosity of the finished
product. A fabric treatment composition is disclosed therein
comprising an aqueous base, one or more, fabric-softening
materials and an emulsion component. The composition has a
structure of lamellar droplets of the fabric-softening
material in combination with an emulsion, said composition
also comprises a deflocculating polymer of a hydrophilic
backbone and one or more hydrophobic sidechains.
However, it appears that using these types of polymers (block
copolymers), the pressumed right system for ideal steric
stabilization is not created. This steric stabilization
mechanism requires that the polymer chains, which are soluble
in the continuous phase, are physically or chemically grafted
onto the particle surface. The remaining part of the polymer
(the stabilizing polymer chain) is, ideally, pointing away
from the particle surface. In a sterically stabilized
dispersion of particles, these stabilizing polymer chains are
rejecting each others presence in the continuous phase. The
WO96/10671 2 ~ PCT~S95/11172 ~
following mechanlsm is generally accepted for steric
stabilization. When the polymer-water (continuous phase) and
water-water molecular interactions are much higher than the
polymer-polymer interactions (water solubility requirements)
there occurs some kind of microphase separation. Of course,
there are not two separate phases present, but at the
molecular level the polymer molecules remain separated. If,
on the other hand, polymer-polymer interactions are larger
than polymer-water interactions, the polymer chains of
different particles will attract each other, and will cause
destabilization of the dispersion. The phenomenon appears as
a repulsive interaction between the polymer chains (steric
stabilization).
Key parameters for this type of stabilization are :
(a)the stabilizing polymer chains must be very soluble in the
continuous phase, while the attached part of the polymer
must be insoluble;
(b)the stabilizing polymer chain must be of a minimt7m (and
optimum) length in order to stabilize the dispersion
efficiently.
Both conditions are not met by applying the polymers as
described in EP 458, 599.
We have found that block copolymers with cloud points ranging
from 40C and higher are able to stabilize aqueous
dispersions of lamellar vesicles. The cloud point dependence
is caused by the chain length of the water-soluble and
insoluble blocks, as well as the ratio of the two chain
lengths. The insoluble blocks may be as hydrophobic as poly
propylene oxide (PO) ranging from aliphatic/aromatic
polyesters to aliphatic chains. When the chain lengths are
too short, e.g. (A)x blocks with xc20 and (B)y blocks with
y=3, the opposite of viscosity stabilization occurs; extreme
thickening or even gelation takes place.
The level of these types of polymers ranges from 0.1-10%,
preferably 0.1-5%, and even more preferable 0.5-2%.
~ WO96/10671 2 ~ O ~ 3 2 9 PCT~S95111I72
In EP 0 185 427 (Gossellnk) these polymers are described in
the context of soil release polymer in fabric softening
composition. We have found a new use of these polymers viz.
the reduction of viscosity of the compos~tion at low and
elevated temperature. Surprisingly the compositions remain
stable with respect to the viscosity as well.
In addition, these polymers prevent skin formation. This
occurs through specific complexation of water molecules with
the water-soluble polymer blocks. This complexation with
water reduces the vapour pressure of water, which slows down
or even prevents skin formation. Examples of such cases are
block copolymers with poly ethoxylate, polyvinyl pyrrolidone,
and polyvinyl pyridine-N-oxide (ethoxylated and/or partially
cationic) blocks. The best molecular weight range of the
water-soluble blocks for m;n-m~lm skin formation ranges from
100-20000, preferably from 2000-8000.
The polymers may be added at any point in the process.
However, this is dependent on the formulation matrix. Three
points of addition are preferred : (l) to the water seat, (2)
on top of the formulation before or after the perfume
addition (hot or cold), (3) a combination of (l) and (2).
Preferred is the point of addition (l) which, probably
assists the incorporation of the polymer in the vesicle
structure. The best ways of addition are via the water seat
or afterwards while hot (40-90C) or ambient.
Type I polymers
The polymers of type I likely to adhere to the positively
charged vesicle surface have the general formula (l)
C-(A)x-(B)y-D and formula (2) C-(A)x-(B)y-(A)z-D respectively
viz. so-called di- and triblock copolymers.
The monomers A and B are water soluble and partially
water insoluble groups, respectively. The degrees of
polymerization x and z are preferably of the same order of
magnitude. The structural parameters x and z are from 1-200,
preferably 30-60; y ranges from 1-70, preferably from 3-40.
; 2~32~
WO96/10671 PCT~S95/11172
C and D are end groups and may be selected form the same
series of groups. However, some situations require them to be
different.
Possible types of monomers for A (water-soluble as polymers):
Ethylene oxide
Vinylpyrrolidone
Vinyl 2- and 4-pyridine
Vinyl 2- and 4-pyridine-N-oxide
Cationic 2- and 4-vinyl pyridine :
- CH2-CH -
~,
N
Rl
Rl = alkoxylate - (CrH2rO)q-, where r = 1-6,
pref. 1-3; and q = 1-80, pref. 2-60. This
includes ethoxylated 2- and 4-vinyl pyridine.
The counter ion may be halide ions, methyl
sulphate, acetates, sulphates.
VinyI alcohol
Acrylamides
Cationic acrylamides,
-CHR-(CH2)n-O- where R= -(CH2)m-CH3,-OH, pyrrolidone,
2- and 4-pyridine-N-oxide, cationic 2-
and 4-pyridine, ethoxylated 2- and 4-
pyridine.
Saccharides
Aminoacids
-(CH2)n-Z(AA)- where AA is any amino acid that is
bound via the carboxylic acid group.
The amino acid may be made cationic or
amine oxidized when a nitrogen in a
ring structure is used (e.g.tryptophan
and histidine). Z may be a =CH, =CH-
COO, or =CH-O- group. n = l-l0,
preferably 1-4.
WO96/10671 ~ 3 2 9 PCT~S~S/11172
Possible types of monomers B for the following polymers
(partially water-soluble to insoluble as polymers):
Poly(alkylene terephthalate) where the alkylene group may be
C1-C10, preferably C2-C4.
Aliphatic polyesters, -0-(CH2)n-C0-, where n = 1-10,
preferably 1-4.
Polybutadiene
Hydroxylated polybutadiene
Straight saturated and unsaturated aliphatic chains, carbon
chain length C4-50, preferably C4-20.
Poly (3-hydroxybutyric acid), degrees of polymerization of 4-
50, preferably 4-30.
Aliphatic/aromatic or mixed carbonates
Esterified polysaccharides
Polysiloxanes
Polyurethanes
Polyacrylates
Cellulose derivatives, such as chitosans.
Possible end groups C and D:
Hydrogen atoms
Hydroxyl groups
Alkoxy groups, -O-R-, where R = H, saturated or partially
unsaturated aliphatic alkanes
Methyl groups
Alkyl groups
-CH(CH3)2, -CH2(CH3), -C(CH3)3
Alkyl chains
straight chain saturated and unsaturated fatty
alcohol/acid, chain length C4-50, preferably C4-
20.
Cationic end groups, such as -CH2-C0-N+(CH3)3 X-, where X is
a halide ion, methyl, sulphate or acetate.
-O-CO-(CH2)n-CH3, where n = 2-30, preferably 2-20.
Sulphonate groups
2 ~ ~ ~ 3 ~ ~
WO96/10671 PCT~S95/11172
Type II polymers
These polymers are likely to be partially incorporated into
the posivitely charged vesicle and have the following general
structure of formula (3) :
D-(A)x-R-(A)z-C
or
/(A)x-C
R-P
\(A)z-D
A,x,z,C, and D are defined as in type I polymers.
P is a glycerol or other polyalcohol unit such as poly
(vinyl)alcohol or polysaccharides or the one shown below.
HO ~ CH2 - C(OH)-CH2 - O ~ H
polyglycerol
Other types of polymers that are likely to be partially
incorporated in the lamellar vesicles when stabilizing
dispersions are shown below (a substituted polyglycerol).
HO ~ CH2 - C(OH)-CH2 - O ) (CH2- C(R)-CH2- O ~ H
In these polymer types, R can be a polymer of the
monomers of type B, but is prefe~red to be a saturated or
unsaturated fatty acid, n = l-l0, preferably 1-8, and m = l-
l0, preferably 1-5. The hydroxyl end groups may be replaced
by the end groups C and D, as defined in the previous polymer
types.
Improved viscosity stabilization at low and elevated
temperature as well occurs by using mixtures of completely
water-soluble polymers and di- or tri-block copolymers
according to the invention.
3 2 9
WO96/10671 PCT~S95/11172
11
The viscosity stabilizing properties of di-and tri-block
copolymers of the types I and II, or polymers mentioned in EP
o 185 427 (E.P. Gosselink), or mixtures thereof, can be
improved by addition of small amounts of completely water-
soluble polymers (cloud point larger than 90C), such as poly
vinyl pyrrolidone, polyvinyl pyridine-N-oxide, polyethylene
glycol, substituted poly glycerols. The weight % of di-or
tri-block copolymers in the formulation ranges from O.l-lO~,
preferably from 0.2-6%. The weight % of completely water-
soluble non-ionic polymers in the formulation ranges from
0.1-10%, preferably from 0.2-6%.
Fabric conditioning compositions, in particular fabric
softening compositions to be used in the rinse cycle of
laundry washing processes, are well known.
The fabric softening materials may be selected from
cationic, nonionic, amphoteric or anionic fabric softening
material.
Compositions of the present invention preferably comprise
from l to 80% by weight of fabric softening active, more
preferably from 2 to 70% by weight, most preferably from 5 to
50% by weight of the composition.
Typically, such compositions contain a water-insoluble
quaternary-ammonium fabric softening active, the most
commonly used having been di-long alkyl chain ammonium
chloride.
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 traditionaly used di-long chain ammonium
chlorides. Such quaternary ammonium compounds contain long
chain alk(en)yl groups interrupted by functional groups such
as carboxy groups.
220 ~3~ ~
WO96/10671 PCT~S95/11172
12
Said materials and fabric softening compositions
containing them are disclosed in numerous publications such
as EPA 040 562, and EPA 239 910.
In EPA 239 9lO, it has been disclosed that a pH range of
from 2.5 to 4.2 provides optimum storage stability to said
rapidly biodegradable ammonium compounds.
The quaternary ammonium compounds and amine precursors
herein have the formula (I) or (II), below :
R / R2 R /R3
X I (CH2) - Q-T1 or I - (CH2~ - ICH-ClH2 X
Rl Tl T2
(I) (II)
O O O O O
Il 11 11 11 11
Q is -0-C- or -C-0- or -O-C-0- or -NR4-C- or -C-NR4-;
Rl is (CH2)n-Q-T2 or T3;
R2 is (CH2)m-Q-T4 or T5 or R3;
R3 is Cl-C4 alkyl or Cl-C4 hydroxyalkyl or H;
R4 is H or Cl-C4 alkyl or Cl-C4 hydroxyalkyl;
Tl, T2, T3, T4, T5 are (the same or different) Cll-C22 alkyl
or alkenyl;
n and m are integers from l to 4; and
X~ is a softener-compatible anion.
The alkyl, or alkenyl, chain Tl, T2, T3, T4, T5 must contain
at least ll carbon atoms, preferably at least 16 carbon atoms.
The chain may be straight or branched.
Tallow is a convenient and inexpensive source of long chain
alkyl and alkenyl material. The compounds wherein Tl, T2, T3,
T4, T5 represents the mixture of long chain materials typical
for tallow are particularly preferred.
~ WO96110671 ~ ~ ~ O ~ 3 2 9 PCT~S95/11172
13
Specific examples of quaternary ammonium compounds suitable
for use in the aqueous fabric softening compositions herein
include :
l) N,N-di(tallowoyl-oxy-ethyl)-N,N-dimethyl ammonium chloride;
2) N,N-di(tallowoyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl);
3) N,N-di(2-tallowyloxy-2-oxo-ethyl)-N,N-dimethyl ammonium
chloride;
4) N,N-di(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dimethyl
ammonium chloride;
5) N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)
-N,N-dimethyl ammonium chloride;
6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;
7) N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl-N,N-dimethyl-
ammonium chloride; and
8) l,2-ditallowyl oxy-3-trimethylammoniopropane chloride.; and
mixtures of any of the above materials.
Of these, compounds 1-7 are examples of compounds of Formula
(I); compound 8 is a compound of Formula (II).
Particularly preferred is N,N-di(tallowoyl-oxy-ethyl)-N,N-
dimethyl ammonium chloride, where the tallow chains are at
least partially unsaturated.
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 lO0 with two categories of compounds being
distinguished, having a IV below or above 25.
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
about 30/70, preferably greater than about 50t50 and more
preferably greater than about 70/30 provides optimal
concentrability.
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.
r 2 ;~ (i3 'I 3 ~ ~
WO96/10671 PCT~S95/11172
14
Other examples of suitable quaternary ammoniums of Formula
(I) and (II) are obtained by, e.g. :
- 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;
- replacing "methyl" in the above compounds with ethyl,
ethoxy, propyl, propoxy, isopropyl, butyl, isobutyl or t-
butyl;
- replacing "chloride" in the above compounds with bromide,
methylsulfate, formate, sulfate, nitrate, and the like.
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 claimed pH values.
The quaternary ammonium or amine precursors compounds herein
are present at levels of from about 1% to about 80~ of
compositions herein, depending on the composition execution
which can be dilute with a preferred level of active from
about 5% to about 15%, or concentrated, with a preferred level
of active from about 15% to about 50%, most preferably about
15% to about 35%.
Optional Ingredients
Fully formulated fabric softening compositions preferably
contain, in addition to the compounds of Formula I or II
herein, one or more of the following ingredients:
Firstly, the presence of polymer having a partial or net
cationic charge, can be useful to further increase the
cellulase stability in the compositions herein. Such polymers
2 2 0 1 3 2 9
WO96/10671 PCT~S95/11172
can be used at levels of from 0.001% to 10~, preferably 0.01
to 2% by weight of the compositions.
Such polymers having a partial cationic charge can be
polyamine N-oxide containing polymers which contain units
having the following structure formula (A):
p
(A) Ax
I
R
wherein P is a polymerisable unit, whereto the R-N~0 group
can be attached to or wherein the R-N~O group forms part of
the polymerisable unit or a combination of both.
O O O
Il 11 11
A is -NC-, -C0-, -C-, -0-, -S-, -N- ; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any combination thereof
whereto the nitrogen of the N~O group can be attached or
wherein the nitrogen of the N~O group is part of these
groups.
The N~0 group can be represented by the following general
structures :
O O
~R~ $ ~)Y =N ff R)x
~)Z
wherein R1, R2, and R3 are aliphatic groups, aromatic,
heterocyclic or alicyclic groups or combinations thereof, x
or/and y or/and z is 0 or 1 and wherein the nitrogen of the N
~O group can be attached or wherein the nitrogen of the N~0
group forms part of these groups.
The N~0 group can be part of the polymerisable unit (P) or
can be attached to the polymeric backbone or a combination of
both.
-
~ ~ ~ 1 3 2 ~
WO96/10671 PCT~S95/11172
16
Suitable polyamine N-oxides wherein the N~O group forms
part of the polymerisable unit comprise polyamine N-oxides
wherein R ls selected from aliphatic, aromatic, alicyclic or
heterocycllc groups.
One class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N~O group
forms part of the R-group. Preferred polyamine N-oxides are
those wherein R is a heterocyclic group such as pyrridine,
pyrrole, imidazole, pyrrolidine, plperidine, quinoline,
acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group
of polyamine N-oxides wherein the nitrogen of the N~O group
is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides
whereto the N~O group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the
polyamine N-oxides having the general formula (A) wherein R is
an aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N~O functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is
a heterocyclic compound such as pyrridine, pyrrole, imidazole
and derivatives thereof.
Another preferred class of polyamine N-oxides are the
polyamine oxides having the general formula (A) wherein R are
aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N~O functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein R
groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide
polymer formed is water-soluble and has dye transfer
inhibiting properties. Examples of suitable polymeric
backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures
thereof.
The amine N-oxide polymers useful herein typically have a
ratio of amine to the amine N-oxide of about 10:1 to about
1:1000000. However the amount of amine oxide groups present in
2 2 ~ 1 3 2 9
PCT~S95/11172
17
the polyamine N-oxide containing polymer can be varied by
appropriate copolymerization or by appropriate degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide is
from about 2:3 to about 1:1000000. More preferably from about
1:4 to about 1:1000000, most preferably from about 1:7 to
about 1:1000000. The polymers of the present invention
actually encompass random or block copolymers where one
monomer type is an amine N-oxide and the other monomer type is
either an amine N-oxide or not. The amine oxide unit of the
polyamine N-oxides has a PKa < 10, preferably PKa < 7, more
preferred PKa < 6.
The polyamine N-oxide containing polymer can be obtained in
almost any degree of polymerisation. The degree of
polymerisation is not critical provided the material has the
desired water-solubility and dye-suspending power.
Typically, the average molecular weight of the polyamine N-
oxide containing polymer is within the range of about 500 to
about 1000,000; preferably from about 1,000 to about 50,000,
more preferably from about 2,000 to about 30,000, most
preferably from about 3,000 to about 20,000.
Such polymers having a net cationic charge include
polyvinylpyrrolidone (PVP) as well as copolymers of N-
vinylimidazole N-vinyl pyrrolidone, having an average
molecular weight range in the range about 5,000 to about
100,000,preferably about 5,000 to about 50,000; said
copolymers having a molar ratio of N-vinylimidazole to N-
vinylpyrrolidone from about 1 to about 0.2, preferably from
about 0.8 to about 0.3.
Other optional ingredients include :
Additional softening agents : which are nonionic fabric
softener materials. Typically, such nonionic fabric softener
materials have a HLB of from about 2 to about 9, more
typically from about 3 to about 7. Such nonionic fabric
softener materials tend to be readily dispersed either by
themselves, or when combined with other materials such as
single-long-chain alkyl cationic surfactant described in
detail hereinafter. Dispersibility can be improved by using
WO96/10671 ~ 3 ~ ~ PCT~S95/11172
18
more single-long-chain alkyl cationic surfactant, mixture with
other materials as set forth hereinafter, use of hotter water,
and/or more agitation. In general, the materials selected
should be relatively crystalline, higher melting, (e.g. >40C)
and relatively water-insoluble.
The level of optional nonionic softener in the compositions
herein is typically from about 0.1% to about 10%, preferably
from about 1% to about 5~.
Preferred nonionic softeners are fatty acid partial esters
of polyhydric alcohols, or anhydrides thereof, wherein the
alcohol, or anhydride, contains from 2 to 18, preferably from
2 to 8, carbon atoms, and each fatty acid moiety contains from
12 to 30, preferably from 16 to 20, carbon atoms. Typically,
such softeners contain from one to 3, preferably 2 fatty acid
groups per molecule.
The polyhydric alcohol portion of the ester can be ethylene
glycol, glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or
hexa-) glycerol, xylitol, sucrose, erythritol,
pentaerythritol, sorbitol or sorbitan. Sorbitan esters and
polyglycerol monostearate are particularly preferred.
The fatty acid portion of the ester is normally derived from
fatty acids having from 12 to 30, preferably from 16 to 20,
carbon atoms, typical examples of said fatty acids being
lauric acid, myristic acid, palmitic acid, stearic acid and
behenic acid.
Highly preferred optional nonionic softening agents for use
in the present invention are the sorbitan esters, which are
esterified dehydration products of sorbitol, and the glycerol
esters.
Commercial sorbitan monostearate is a suitable material.
Mixtures of sorbitan stearate and sorbitan palmitate having
stearate/palmitate weigt ratios varying between about lO:l and
about l:lO, and l,5-sorbitan esters are also useful.
Glycerol and polyglycerol esters, especially glycerol,
diglycerol, triglycerol, and polyglycerol mono- and/or di-
esters, preferably mono-, are preferred herein (e.g.
polyglycerol monostearate with a trade name of Radiasurf
7248).
~ ~ 0 1 3 2 9
WO96/10671 PCT~S95/11172
19
Useful glycerol and polyglycerol esters include mono-esters
with stearic, oleic, palmitic, lauric, isostearic~ myristic,
and/or behenic aclds and the diesters of stearic, oleic,
palmitic, lauric, isostearic, behenic, and/or myristic acids.
It is understood that the typical mono-ester contains some di-
and tri-ester, etc.
The "glycerol esters" also include the polyglycerol, e.g.,
diglycerol through octaglycerol esters. The polyglycerol
polyols are formed by condensing glycerin or epichlorohydrin
together to link the glycerol moieties via ether linkages.
The mono- and/or diesters of the polyglycerol polyols are
preferred, the fatty acyl groups typically being those
described hereinbefore for the sorbitan and glycerol esters.
Surfactant/Concentration Aids
Although as stated before, relatively concentrated
compositions of the unsaturated material of Formula tI) and
(II) above can be prepared that are stable without the
addition of concentration aids, the concentrated compositions
of the present invention may require organic and/or inorganic
concentration aids to go to even higher concentrations and/or
to meet higher stabillty standards depending on the other
ingredients.
Surfactant concentration aids are typically selected from
the group consisting of single long chain alkyl cationic
surfactants; nonionic surfactants; amine oxides; fatty acids;
or mixtures thereof, typically used at a level of from 0 to
about 15% of the composition.
Such mono-long-chain-alkyl cationic surfactants useful in
the present invention are, preferably, quaternary ammonium
salts of the general formula :
[R2N+R3 ] X-
wherein the R2 group is Clo-C22 hydrocarbon group, preferably
Cl2-Clg alkyl group of the corresponding ester linkage
interrupted group with a short alkylene (Cl-C4) group between
the ester linkage and the N, and having a similar hydrocarbon
group, e.g., a fatty acid ester of choline, preferably Cl2-Cl4
=
WO 96/10671 2 2 ~ ~ 3 ~ 9 PCT/US95/11172 ~,,
(coco) choline ester and/or C16-C1g tallow choline ester at
from about 0.1% to about 20~ by weight of the softener active.
Each R is a C1-C4 alkyl or substituted (e.g., hydroxy) alkyl,
or hydrogen, preferably methyl, and the counterion X~ is a
softener compatible anion, for example, chloride, bromide,
methyl sulfate, etc.
Other cationic materials with ring structures such as alkyl
imidazoline, imidazolinium, pyridine, and pyridinium salts
having a single C12-C30 alkyl chain can also be used. Very
low pH is required to stabilize, e.g., imidazoline ring
structures.
Some alkyl imidazolinium salts and their imidazoline
precursors useful in the present invention have the general
formula :
CH2 CH2
N~ ,N C2H4- Y-R X
C \R6
R
wherein y2 is -C(O)-O-, -O-(O)C-, -C(o)-N(R5)-, or
-N(R5)-C(o)- in which R5 is hydrogen or a C1-C4 alkyl radical;
R6 is a C1-C4 alkyl radical or H (for imidazoline precursors);
R7 and R8 are each independently selected from R and R2 as
defined hereinbefore for the single-long-chain cationic
surfactant with only one being R2.
Some alkyl pyridinium salts useful in the present invention
have the general formula :
.
R - N 9 X
.
wherein R2 and X- are as defined above. A typical material
of this type is cetyl pyridinium chloride.
Nonionic Surfactant fAlkoxylated Materials)
Suitable nonionic surfactants for use herein include
addition products of ethylene oxide and, optionally, propylene
oxide, with fatty alcohols, fatty acids, fatty amines, etc.
1 3 2 9
WO 96/10671 PCTJUS95J11172
21
Suitable compounds are substantially water-soluble
surfactants of the general ~ormula :
R2 -- y - (C2H40) z - C2H40H
wherein R2 is selected from the group consisting of primary,
secondary and branched chain alkyl and/or acyl hydrocarbyl
groups; primary, secondary and branched chain alkenyl
hydrocarbyl groups; and primary, secondary and branched chain
alkyl- and alkenyl-substituted phenolic hydrocarbyl groups;
said hydrocarbyl groups having a hydrocarbyl chain length of
from 8 to 20, preferably from 10 to 18 carbon atoms.
Y is typically -O-, -C(O)O-, -C(O)N(R)-, or -C(O)N(R)R-,
in which R2 and R, when present, have the meanings given
hereinbefore, and/or R can be hydrogen, and z is at least 8,
preferably at least 10-11.
The nonionic surfactants herein are characterized by an ~LB
(hydrophilic-lipophilic balance) of from 7 to 20, preferably
from 8 to 15.
Examples of particularly suitable nonionic surfactants
include
Straight-Chain, Primary Alcohol Alkoxylates such as tallow
alcohol-EO(11), tallow alcohol-EO(18), and tallow alcohol-
EO(25);
Straight-Chain, Secondary Alcohol Alkoxylates such as 2-
C16EO(11); 2-C2oEO(11); and 2-C16EO(14);
Alkyl Phenol Alkoxylates, such as p-tridecylphenol EO(11)
and p-pentadecylphenol EO(18), as well as
Olefinic Alkoxylates, and Branched Chain Alkoxylates such as
branched chain primary and secondary alcohols which are
available from the well-known "OXO" process.
,~
Amine Oxides
Suitable amine oxides include those with one alkyl or
hydroxyalkyl moiety of 8 to 28 carbon atoms, preferably from 8
to 16 carbon atoms, and two alkyl moieties selected from the
WO96/10671 2 ~ PCT~S95111172
22
group consisting of alkyl groups and hydroxyalkyl groups wlth
l to 3 carbon atoms.
Examples include dimethyloctylamine oxide, diethyldecylamine
oxide, bis-(2-hydroxyethyl)dodecylamine oxlde,
dlmethyldodecyl-amlne oxlde, dlpropyltetradecylamine oxide,
methylethylhexadecylamine oxide, dimethyl-2-
hydroxyoctadecylamlne oxlde, and coconut fatty alkyl
dimethylamlne oxlde.
Fatty Acids
Suitable fatty acids include those containing from 12 to 25,
preferably from 16 to 20 total carbon atoms, with the fatty
moiety containing from lO to 22, preferably from lO to 14 (mid
cut), carbon atoms. The shorter moiety contains from l to 4,
preferably from l to 2 carbon atoms.
Electrolyte Concentration Aids
Inorganic viscosity 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
obtiain 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 ll,000
ppm, by weight of the composition.
2 2 û ~ 3 2 9
~, WO 961106~ PCT/US95~11172
23
Alkylene polyammonlum 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.
Specific examples of alkylene polyammonium salts include 1-
lysine monohydrochloride and 1,5-diammonium 2-methyl pentane
dihydrochloride.
Another optional 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 alcohol such as
ethanol, propanol, isopropanol or butanol are useful as the
carrier liquid. Low molecular weight alcohols include
monohydric, dihydric (glycol, etc.) trihydric (glycerol,
etc.), and higher polyhydric (polyols) alcohols.
Still other optional ingredients are stabilizers, such as
well known antioxidants and reductive agents, Soil Release
Polymers, bacteriocides, colorants, perfumes, preservatives,
optical brighteners, anti ionisation agents, antifoam agents,
enzymes and the like.
The invention will be further illustrated by means of the
following examples.
-
-
Wo96llo67l~ 3 2 9 PCT~S95/11172
24
Examples
General molecular structures: C - (A)x - (B)y - (A)z - D
A. Effect of a water-soluble non-block copolymer (PVP) on the
viscosity of block copolymer-stabilized lamellar droplet
dispersions:
Polymer used:
Polymer C and D A B x y z
P-1 methyl ethoxy PPT 45 5 45
P-2 Poly vinyl pyrrolidone (PVP)
Storage viscosities:
Content / ~ of 7 day storage viscosity at:
P-1 P-2 4 10 RT 35 50
0.33 - S >20000 1210 570 1730
- 0.33 S S S 720 1230
0.33 0.33 S 6800 328 155 320
0.33 1.0 S 4500 700 323 530
0.33* 1.0* S 19300 560 435 1670
0.66 1.0 S >20000 413 225 303
1.0 1.0 S 15200 385 200 230
* Means that both polymers have been added to the water seat.
Otherwise the polymers have been added after the perfume when
still hot.
The viscosity has been measured using a Brookfield Viscometer.
The method used is the standard method known by persons
skilled in the art.
2 ~0 ~ 32 9
WO96/10671 PCT~S9S/llI72
B. Effect of hydrophillc and hydrophobic block lengths of
EO/PO/EO triblock copolymers on the viscosity of lamellar
droplet dispersions:
- A is an ethoxy unit (EO) and B is a relatively hydrophobic
unit like propoxy (PO) or propylene terephthalate
(PPT).
- C and D, as well as x and z, are the same. They are all
hydroxyl groups, except for the reference polymer which has
methyl end groups.
Polymer # EO~s # PO's F~* Cps after storage:
3 day~ at RTl 10 days at RT2
Reference 80 5** 1425 S 470
Synperonic L35 22 16 608 S
Synperonic F38 88 16 1664 S
6200
Synperonic F87 120 39 6201 115
Synperonic F88 206 39 9555 180
Synperonic F108 297 56 19768 180
Pluronic PE 10400 5056 5936 50 73
Pluronic PE 10500 7456 7280 333 83
* The numbers 1 and 2 stand for the reduced and the full
matrix, respectively. The difference between the two is that
in the reduced matrix some of the emulsifiers/dispersants have
been omitted.
** PPT units, length equivalent to 15PO units.
WO96/10671~ 1 3 2 9 PCT~S95/11172
26
C. Effect of the center block chemistry on the viscosity of
lamellar droplet dispersions:
- C and D are end groups, A is an ethoxy unit and B is a
relatively hydrophobic unit like propoxy (PO), propylene
terephthalate (PPT), n-butoxy (BuO), hexadecylene (C16), or
dodecylene (C12).
- C and D, as well as x and z, are the same.
Center C x y Viscosity (cps) after 7 days
block storage:
4 10 RT 3550C
PPT methyl 45 5 630 120 35 3560
PO methyl 55 17 >20000 360 45 45 72
PO methyl 63 13 >20000 290 40 43 68
PO hydroxyl 40 16 >20000 342 35 35 43
BuO methyl 43 9 1780 160 35 4060
BuO methyl 50 14 7700 265 36 3858
C16 methyl 75 1 1260 223 38 4045
C12 methyl 60 1 1146 238 52 5054
WO96110671 2 2 ~ 1 3 2 9 PCT~S95111172
27
D. Effect of end-groups on the viscosity of lamellar droplet
dispersions:
- C and D are end groups, A is an ethoxy unit and B is
a relatively hydrophobic unit
like propoxy ~PO) or propylene terephthalate (PPT).
- C and D, as well as x and z, are the same.
End group B x y Viscosity (cps) after 7 days
storage:
functionallity 10 RT 35 50~C
Methyl PPT 40 5 >20000 128 40 85
Hydroxyl PO 40 15 S >20000 43 80
Methyl PO 55 17 360 45 45 72
Methyl PO 63 13 290 40 43 68
Hydroxyl PO 40 16 342 35 35 43
Acetate PO 40 15 S 7800 98 193
Trimethyl PO 40 16 328 43 40 43
-amido chloride
Hydroxyl PO 14 30 S S 4600 14400
Methyl PO 14 30 S S 5600 9400
S = solid, RT = room temperature/C
W096,l067l - 2 ~ ~ 1 3 ~ 9 28 PCT~S95/11172 ~
E. Effect of a block copolymer according to the invention on
the viscosity stability as measured after 7 days storage.
Two experiments have been performed in different softener
matrices.
4C 10C RT 35C 50C
1. w/o polymer P-1* S S S S S
with 0.5% P-1 S S 88 160 235
2. w/o polymer P-1 360 123 78 113 235
with 0.5% P-1 40 40 40 68 153
* for P-1 description see Table A.
2 ~ O ~1 3 ~ ~
WO 96110671 ~CT/US95/11172
29
A typical formulation in above-mentioned examples for use
as a rinse conditioner to which the different polymers were
added, according to the lnvention comprises
weight %
Softener active24.5
PGMS 2.0
TEA 25 1.5
HCl 0.12
Antifoam agent 0.019
Blue dye 80 ppm
CaCl2 0.35
Perfume 0.90
In conclusion above results clearly show :
a. Beyond a certain length of the ethoxy side blocks the
triblock copolymers provide a reduction of the product
viscosity.
b. The more hydrophobic the center block becomes the better
the polymer stabilizes the viscosity.
c. The combination of PVP with a triblock copolymer such as
H3C-(E0)45-(PT)5-(EO)45-CH3 provides the best viscosity
stabilizing benefits. This MAY be due to PVP providing a
shield around the positive charges such that the center
block of the polymer adheres even better to the droplets.
