Note: Descriptions are shown in the official language in which they were submitted.
, CM-I74~
- ~ ~.z73~S7
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DISPERSIBLE FABRIC SOFTENF~5
James Charle6 Th~ophile Roger BURCKETT St. LAURENT
Alfred BUS~H
- Technical Field
The pre6ent invention ~elates to means of treating ~
fibers and fabric6, vhere~n a sub-~toichiometric complex
of amine6 and phosphate ester~ is used to provide softness
and anti-~tatic benefits. Detergent compositions
containing said amine-phosphate e6ter 60ftener6 are
/0 disclosed. The composition6 herein can be used to soften
f abr iC6 .
Backqround
~ The use of softener~ to treat fabrics a~ter a washing
¦ operation i8 a well-known laundering practice. Fabric
ofteners are, in the main, water-insoluble cationic
materials that are incompatible with anionic detersive
surfactants used in most fabric washing compositions. For
that reason, the softening operation is
~r
~273~5 ~'
generally carried-out in the laundry rinse bath after the
surfactant has been removed from the washing machine.
This entails additional work for the user.
Formulators of fabric laundering compositions have
long sought means whereby fabric washing and softening
could be done concurrently. Laundering methods employ-
ing clay softeners, mixtures of clays and various amine
materials and the like, are described in the following
patents: EP 0,011,340 published May 28, 1980; DE
2,857,163 published January 10, 1979; DE 2,439,541
published March 6, 1975; DE 2,334,899 published Jan~ary
24, 1974; EP 0,023,367 published February 4, 1981; EP
0,026,528 published April 8, 1981 and EP 0,028,432
published May 13, 1981. The use of mixtures of amines
and soaps (salt of fatty acids) as through-the-wash
softeners is disclosed in U.K. Patent 1,514,276.
The prior art also describes the use of various
cationic materials in sheet form. See U.S. Patent
4,220,562.
The prior art also teaches the softener use of al-
kyl phosphonate and quaternary ammonium compounds. EP
0,006,268 published January 9, 1980.
The prior art also teaches various mixtures of
phosphate esters in detergents with fabric softening
action - BE 802,679.
The present invention employs amine-phosphate ester
softeners in laundry compositions to provide cleaning and
softening concurrently. The softeners herein provide
softening and anti-static benefits, especially when used
with clay softeners. Importantly, the use of phosphate
esters in sub-stoichiometric quantities with the amines
in the manner disclosed herein advantageously enhances
deposition of the amines on fabrics by as much as 1.5- or
2-fold, as compared with prior art amine fabric softening
compositions.
, s
"j, ~.
12~31S7
Summary of the Inventlon
The present invention encompasses a method for softening
fabrics by contacting same with sub-stoichiometric, water-
insoluble, water-dispersible complexes of amine and phosphate
ester (as described more fully, hereinafter) in the presence
of water. The method can be carried out, for example, by
tumbling damp fabrics with said complexes in a hot air
clothes dryer. In another mode, said complexes can be used
in an aqueous rinse bath, for example, in a laundry rinse.
In still another mode, the method can be carried-out concur-
rently with a fabric cleansing treatment, for example, in a
detergent-containing laundry liquor, to soften fabrics.
The invention also encompasses detergent compositions
(preferably granular) which may be described succinctly as
containing conventional detergent ingredients such as deter-
sive surfactants (including anionics), detergency builders,
optical brighteners, detersive enzymes, fabric bleaches, and
the like, all at rather conventional levels, as well as clay
fabric softeners (preferably, smectite clays), said composi-
tions being characterized in that they contain at least 0.1%
(preferably 1.0~ to 15~) of the aforesaid sub-stoichiometric,
water-insoluble, water-dispersible amine-phosphate ester
softeners. The most preferred compositions with clay are
formulated to contain not more than ~% (preferably not more
than 1%-2%) of a nonionic detersive surfactant.
More particularly the composition of the invention
comprises: (a) at least 0.1% of a sub-stoichiometric,
water-dispersible amine-phosphate ester softener complex
which is prepared separately from the balance of the
composition and consists essentially of: (i) an amine of the
formula RlR2R3N, where Rl is C6 to C20 alkyl, R2 is C
to C20 alkyl or hydrogen, and R3 is Cl to Cl0 alkyl or
hydrogen; and (ii) a phosphate ester of the formula
O O
RO - P - OH or HO - P - OH
OR' OR'
1273157
- 3a -
where R and R' are Cl-C20 alkyl or ethoxylated alkyl
groups of the formula Cl-C20 alkyl -(OCH2CH~)y~ and y is an
integer of from l to 15 in a weight ratio of amine:phosphate
ester of at least 2:1; (b) at least 1% of a clay fabric
softener; and (c) at least 1% of a detersive surfactant
selected from the group consisting of: alkyl benzene sulfon-
ates, alkyl- and alkylether sulfates, paraffin sulfonates,
olefin sulfonates, alpha-sulfonates of Patty acids and of
fatty acid esters.
The invention also encompasses an article for use in a
laundry bath or rinse bath, or in a laundry dryer, comprising
the aforesaid sub-stoichiometric amine-phosphate ester
softeners releasably affixed to a water-insoluble carrier,
for example, a sheet of paper or fabric. Such compositions
are optionally formulated to
12'73157
-- 4 --
contain a bleach activator and such activator containing
compositions are especially useful in laundry baths.
The ingredients and means for preparing the compositions
are disclosed more fully hereinafter. All weights and
proportions are by weight, unless otherwise specified.
Detailed Description of the Invention
As noted hereinafter, the compositions of this invention
comprise, in major part, conventional ingredients that are
quite familiar to formulators of laundry compositions. One
of the major advantages of the amine-phosphate softeners
used herein is that they are entirely compatible with such
conventional laundry ingredients, used at conventional
concentrations.
Amines - The amines employed herein are of the formula
RlR2R3N where Rl is C6 to C20, R2 is Cl to
C20 or hydrogen, and R3 is Cl to C10 or hydrogen.
Preferably, the amines have both Rl and R2 as
C6-C20 alkyl, with C16-C18 being most preferred, and
with R3 as Cl-C3 alkyl. Mixed amines, such as
dicoconutalkyl- and ditallowalkyl-methyl amines can be
used. Such materials are commercially available under Trade
Marks such as "Armeen".
Phosphate Ester - The phosphate esters which are critical to
the practice of this invention are commercially available
materials of the general formulae:
O O
RO - P - OH and HO - P - OH
OR' OR'
wherein R and R' are Cl-C20 alkyl or (preferably)
ethoxylated alkyl groups of the general formulae:
~273~5~
-- 5
alkyl-(OCH2CH2)y, wherein the alkyl substituent is
Cl-C20, preEerably C8-C16 and ~ is an integer of 1
to 15, preferably 2-lO, most preferably 2-5. Such compounds
are prepared by known methods from phosphorus pentoxide,
phosphoric acid or phosphorus oxy halide and alcohols or
ethoxylated alcohols.
It will be appreciated that the formulae depicted
represent mono- and di-esters, and commercial phosphate
esters will generally comprise mixtures of the mono- and
di-esters, together with some proportion of tri-ester.
Typical commercial esters are available under the Trade
Marks Phospholan" PDB3 (~iamond Shamrock1 and "Servoxyl"
VPAZ (Servo).
Amine-Phosphate Ester Softeners - The prior art describes
various phosphate ester-amine compounds - see U.S. Patent
3.364.192 - some of which have been disclosed for use as
fiber-finishing agents - see U.S. Patents 3.434.874;
3.428.481; and 3.560.382. However, the prior art
compositions generally involve 1:1 (mole basis) compounds or
complexes, i.e., compounds or complexes from stoichiometric
mixtures. Suprisingly, such stoichiometric complexes are of
no use in the present invention, apparently because they
form unstable dispersions prone to aggregation. In
contrast, the sub-stoichiometric mixtures herein are
extremely well dispersed in water, but are not water-soluble.
While not intending to be limited by theory, it is
instructive to consider the physico-chemical behaviour of
the amine-phosphate ester softeners herein, inasmuch as this
can be of assistance to the formulator.
It will be appreciated that the amines used herein and
in art-disclosed compositions exist in aqueous solutions as
fairly coarse particles, or oily globules, having a spectrum
of sizes. It appears that attachment of such particles to
fabrics to provide the desired softening action can be
~.f~:73~57
-- 6 --
considerably enhanced by reduction of their average size;
coarser material being rinsed away by mechanical action. On
the other hand, complete solubilization or micellization is
to be avoided since this also leads to inadequate attachment
of the amine to fabrics.
In addition to size of the dispersed amine particles,
their phase structure is of importance since this will
influence their effective spreading after attachment to
fiber or fabric surfaces. Phase structure influences also
the stability of amine dispersions.
Consideration of these factors apparently explains why,
on one hand, amines untreated with phosphate ester and on
the other hand, stoichiometric amine-ester complexes are of
very low effectiveness relative to the sub-stoichiometric
mixtures of amine-phosphate ester now disclosed.
It has now been discovered that sub-stoichiometric
mixtures of amine-phosphate ester exist as aqueous
dispersions whose particles readily deposit on, spread on,
and soften, fibers and fabrics.
By "sub-stoichiometric" herein is meant that there is an
excess of amine relative to phosphate ester. In general,
there are at least about two parts amine (on a weight basis)
per one part ~weight) of phosphate ester, but this will, of
course, vary with the molecular weights of the amine and
ester, respectively. The objective is to have a
readily-dispersible (in water) mixture, but not one that is
water-soluble.
Useful amine-phosphate esters can easily be observed by
a simple test. The amines herein, suspended in water, form
a generally greasy-appearing, non-homogenous mixture. By
contrast, the sub-stoichiometric amine-phosphate ester
mixtures used in this invention form stable "milky"
suspensions in water. Laboratory estimates of the particle
sizes of these suspensions indicate that 60 % to 80 ~ of the
particles fall within the size range of .1 to 8 micrometers;
~,f,:
~ 273~57
-- 7
20 ~ to 4~ % within the range 8 to 20 micrometers; and
essentially all the particles are below 40 micrometers in
diaMeter .
For the preferred sub-stoichiometric amine-phosphate
ester softeners herein, the weight ratio of amine:phosphate
ester is above 5:1, yenerally 7:1 to 15:1, most preferably
10:1. Again, such softeners are selected to be
water-dispersible, not water soluble.
In general terms, the amine-phosphate ester softeners
are prepared separately from the balance of the
compositions, and are preferably then added to the other
conventional ingredients to provide the final formulations.
This can most conveniently be done by preparing a melt of
the phosphate ester and the amine and maintaining the melt
stage for a few minutes. The melt can then be layered onto
a sheet substrate to prepare, for example, a dryer-added
fabric softener. To prepare a detergent, the melt can be
solidified and comminuted to the desired particles size
(e.g., in an extruder), and dry-mixed with a granular
detergent composition. The melt may also be sprayed onto
detergent granules. The melt may also be dispersed into a
stirred, aqueous crutcher mix comprising the balance of the
detersive ingredients, and spray-dried in standard fashion.
This crutcher-addition is less preferred, as it leads to
some decomposition of the complex. Simply adding the amine
and phosphate ester, individually, to a detergent crutcher
mix does not secure the intended benefits of this invention.
An especially preferred softener herein is prepared by
melting together ten parts by weight of di-C12-C14 alkyl
monomethyl amine and one part by weight of a mono -
[C12-C14 (EO)l 5] ester of phosphoric acid, sold under
the Trade Mark "Servoxyl VPAZ n .
The amine-phosphate ester softeners will generally be
used at levels of at least 0.1%, preferably 1% to 15~, in
detergent composltions; at
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lZ~3~7
-- 8 --
levels of at least 1%, preferably 1% to 25% in rinse-added
fabric softeners; and at levels of 2% to 60% in dryer- and
wash machine- added sheets (where the balance of the
composition mainly comprises the weight of th~ sheet
substrate).
Softener Clay - The above-disclosed amine-phosphate ester
softeners are preferably used in granular detergent
compositions, where they are most preferably used in
combination with a detergent-compatible clay-fabric
softener. Such clay softeners are well-known in the
detergency patent literature and are in broad commercial
use, both in Europe and in the United States. Included
among such clay softeners are various heat-treated kaolins
and various multi-layer smectites. Preferred clay softeners
are smectite softener clays that are described in German
patent document 23 34 899 and in U.K. Patent 1.400.898 which
can be referred to for details. Softener clays are used in
the preferred compositions at levels of at least 1%,
generally 1-20%, preferably 2~7%.
Detersive Surfactants - The detergent compositions of this
invention will contain organic surface-active agents
("surfactants") to provide the usual cleaning benefits
associated with the use of such materials.
Detersive surfactant useful herein inlcude well-known
synthetic anionic, amphoteric and zwitterionic surfactants.
Typical of these are the alkyl benzene sulfonates, alkyl-
and alkylether sulfates, paraffin sulfonates, olefin
sulfonates, amine oxides, a-sulfonates of fatty acids and of
fatty acid esters, and the like, which are well-known from
the detergency art. In general, such detersive surfactants
contain an alkyl group in the C9-C18 range; the anionic
detersive surfactants can be used in the form of their
sodium, potassium or triethanolammonium salts. U.S. patent
'~.
',,~
1273~S7
_ 9 _
4.111.855 contains detailed listings of such typical
detersive surfactants Cll-C16 alkyl benzene sulfonates,
C12-C18 paraffin-sulfonates and alkyl sulfates are
especially preferred in the compositions of the present type.
Also useful herein as the surfactant are the
water-soluble soaps, e.g. the common sodium and potassium
coconut or tallow soaps well-known in the art.
It is to be understood that the use of typical
alkoxylated nonionic surfactants (e.g. the Cg-Cl~3 alkyl
alcohols and alkyl phenols with 5 to 20 ethoxyl groups) are
preferably limited in the practice of this invention to
levels of not more than about 5%, preferably not more than
2%, most preferably 0-1%, of the compositions when clay is
present as a co-softener, since alkoxylates can interfere
lS with the softening properties of clay. In clay-free
compositions, the alkoxylated nonionics can be used at any
desired level.
The surfactant component clan comprise as little as 1~ of
the laundry detergent compositions herein, but generally the
20 compositions will contain 5% to 40%, preferably 6% to 30%,
of surfactant. Mixtures of the anionics, such as the alkyl
benzene sulfonates, alkyl sulfates and paraffin sulfonates
are preferred for through-the-wash cleansing of a broad
spectrum of soils and stains from fabric.
Detersive Adjuncts - The compositions herein can contain
other ingredients which aid in their cleaning
performance. For example, it is highly preferred that
through~the-wash detergent compositions contain a
detergent builder and/or metal ion sequestrant. Compounds
classifiable and well-known in the art as detergent builders
include the nitrilotriacetates, polycarboxylates,
1273~S7
-- 10 --
citrates, water-soluble phosphates such as tri-
polyphosphate and sodium ortho- and pyro-phosphates,
silicates, and mixtures thereof. Metal ion sequestrants
include all of the above, plus materials like ethylene
diaminetetraacetate, the amino-polyphosphonates and
phosphates (DEQUEST*) and a wide variety of other poly-
functional organic acids and salts too numerous to mention
in detail here. See U.S. Patent 3,579,454 for typical
examples of the use of such materials in various cleaning
compositions. In general, the builder/sequestrant will
comprise 0.5% to 45% of the composition. The 1-10 micro-
meter size zeolite (e.g. zeolite A) builders disclosed in
German Patent 24 22 655 are especially preferred for use
in low-phosphate compositions which contain the softeners
described herein.
The laundry compositions herein also preferably con-
tain enzymes to enhance their through-the-wash cleaning
performance on a variety of soils and stains. Amylase
and protease enzymes suitable for use in detergents are
well-known in the art and in commercially available liquid
and granular detergents. Commercial detersive enzymes
tPreferably a mixture of amylase and protease) are typi-
cally used at levels of 0.001% to 2%, and higher, in the
present compositions.
Moreover, the compositions herein can contain, in
addition to ingredients already mentioned, various other
optional ingredients typically used in commercial products
to provide aesthetic or additional product performance
benefits. Typical ingredients include pH regulants,
perfumes, dyes, bleaches, optical brighteners, soil
suspending agents, hydrotropes and gel-control agents,
freeze-thaw stabilizers, bactericides, preservatives,
suds control agents, bleach activators and the like.
* Trade Mark
~27~157
The compositions can further contain a peroxygen bleach
activator, particularly tetraacetyl ethylenediamine (TAED),
typically from 0.1% to 5%, preferably from 0.5% to 2.5%.
Other highly desirable detergent ingredients for use in the
detergent compositions of the present invention are
quaternary ammonium compounds of the form
R4R3R6R7N X , wherein R4 is alkyl having from
10 to 20, preferably from 12-18 carbon atoms, and R5, R6
and R7 are each cl to C4 alkyl preferably methyl x
is an anion, e.g. chloride. Examples of such quaternary
ammonium compounds include monotallowalkyl trimethyl
ammonium chloride and mono(cocoalkyl) trimethyl ammonium
methosulfate. The quaternary ammonium compounds can be used
at levels from 0.5% to 5%, preferably from, 1% to 3%.
Detergent composition containing both TAED and the mono(long
chain alkyl) tri(short chain alkyl) ammonium compound are
highly preferred.
In a through-the-wash laundry mode, the compositions are
typically used at a concentration of at least 500 ppm,
preferably 0.10% to 2.5%, in an aqueous laundry bath at pH
7-11 to launder fabrics. The laundering can be carried out
over the range from 5C to the boil, with excellent
results.
In an alternate mode, the amine-phosphate ester
softeners herein may be releasably adsorbed or releasably
coated onto a non-particulate substrate such as a non-woven
or paper sheet or flexible sponge mat, or the like. Such
sheet-form objects may be added to the laundry or rinse
bath, or to the laundry dryer, where the softener is
released to provide fabric softening. In an alternate, and
highly preferred, mode the amine-phosphate ester softener is
used in sheet form in combination with a bleach activator
(such as tetraacetyl ethylene diamine or a straight- or
~Z7~157
- 12 -
branched-chain C6-C10 oxybenzene sulfonate) as a
combined perborate activator and softener in a laundry
liquor. See, for example U.S. Patent 4.220.562.
Such sheet-form products will generally employ 1-20
grams of the amine-phosphate ester softener and 1-20 grams
of the bleach activator.
In still another mode, the amine-phosphate ester can be
formulated as a liquid fabric softener and used in a
post-laundry rinse bath. Such liquid softeners can
comprise, for example, a simple dispersion of the
amine-phosphate ester softener in water or water-alcohol.
It is to be understood that the compositions and
processes of this invention are carried out in a manner that
will, typically, deposit at least a few milligrams
(generally, at least 1-1000 mg) of the sub-stoichiometric
amine-phosphate ester softener per square meter on the
fabric being treated, as will be seen in the following
examples.
INDUSTRIAL APPLICATION
The following examples are typical of the preferred
compositions of this invention, but are not intended to
limit the scope of the invention.
EXAMPLE I
A mix of ditallow methyl amine (total 3.8% of complete
formulation after spray-drying) and monococonutalkyl-
(ethoxy)1-5 phosphoric acid ester (0.38~ of complete
formulation) are admixed, melted in a jacketed bath, and
maintained as a melt for about ten minutes. ~tirring
assures homogeneity.
~r
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~73~57
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- 13 _
.
a ~tandard ~queou6 crutcher ~x coaprising the
following ~ngredlent~ prepare~ (perc,entages iisted
relate to percent ingredient~ in the complete ormulation
- - after spray-~ry~g).~~
.
Inaredient~ ~ Percent
,, .. . , _ . . . . . . . . . .
Clî 12 alkyl ben-zene fiulfonate ~~ 6.2 ~' ~~ ~~~
Tallow alcohol ethoxylate (EOll) 1.0
Sodium perborate 20.0
Sodium tripolyphosphate 24.0
~ sodium sulfate 22.0
Sodium ~ilicate 8.0
Smectits Clay ~ 2.4
Carboxymethyl cellulo~e 0.4
Polyacryla~e (6,0il_~uspenderJ 1.7
I ~ ~nzymes ~ 0-5
Optical brightener 0.23
- Sulp~onated zinc phthalocyanins ~25 ppm
EDTA 0.2
Perfume~copper ~alts/~inors 0.5
a ~ Moisture to 100
* Natural smectite: ion exchange capacity above
50 ~eg/lOOg clay;
~* U.S. Patent 3 927 967
_ The crutcher ~ix i~ handled i~ entirely ~tandard
. a S fashion, and ~pray-dried to for~ a granular composition.
i The amine-pho~phate e6ter ~oftener is added to the
spray-dried granules as earticles o~ "prillsn.
j The composition of Example I i8 free-flowing and
i provide~ excellent cleaning and through-the-wash fabric
1 3 0 softening when used at laundry concentration of 0.1% and
¦ above.
In an alternate mode, the amine-phosphate e~ter
softener can be sprayed onto the spcay-dcied granule~.
~73~S7
- 14 -
The cornposition of Exarnple I may be modified by adding
1.0% tetraacetyl ethylenediamine (TAE~ as a perborate
bleach activator. It is preferred that materials such as
bleach activators and enzymes be dry-mixed with the balance
of the composition, after spray-drying.
The composition may be modified further by adding, in
addition to TAED, 2.4~ monotallowalkyl trimethyl ammonium
chloride.
EXAMPLE II
A low-P spray-dried detergent formulation is as follows:
_gredient Percent
Zeolite A (1-10 micron) 26.0
Sodium nitrilotriacetate 5.0
Smectite clay * 3.0
Amine-phosphate Ester ** 4.1
Cll~l2 alkyl benzene sulfonate (Na) 6.5
Tallow ethoxylate (EO 9-ll) 0.5
Sodium Perborate.4H2O 20.0
Sodium silicate 8.0
CMC 1.0
Sodium sulfate 20.0
Enzymes (l:l amylase/protease) *** 1.5
Optical brightener 0.5
TAED 1.2
Water, minors to 100
* As Gelwhite GP (TM); CaCO3 ion exchange
capacity 70 Meq/100g.
** As in Example I.
*** Dry-mixed with composition.
12731';7
_ 15 -
The coapo~it~on of ~xample II iB pra~area by
sprAy-dryinq an aqueous crutcher ~ix, ln the ~anner
de~cribed ~or Example I. In use, t~e co~position gi~e~
~x~ nt cleaning,,a-n_ t-h~rou-gh-t,he-~-wash ~abric,~oftëning~-
perfor~ance.
,, ~--= ,_,,,
~ E~AMPLE III ~~` '--
A clay-free compo~ition i~ prepared by r~moving the
clay from Example I and substituting therefor an
additional softener compri~ing ~onotallowalkyl trimethyl
/~ a~monium chloride as 2.4~ of the total composition.
EXAMPLE ~V
A laundry aadit~ve,produc~ i~ prepared by waeaing 6.5g
of bi~(tetradecyl)methyl amine and 0.8g of
tetradecylphosphate to form a melt, and ~preading the melt
onto an ordinary di~pogable paper hand-towel (20x20 cm~.
4 grams of TAED powder (1-1~ ~icron~) are sprinkled onto,
and pres~çd into, the melt before it has the chance to
solidify.
The article of Example IV i~ added to a laundry liguor
a ~ containing a commercial perborate/clay detergent
composition (DASH-3; Trade Mark) to enhance
through-the-wash softening and bleaching performance.
i EXAMPLE V
The aLticle of Example IV i~ modified by deleting the
TAED and replacing the Example IV softener with 3.5g. of
' the amine-phosphate ester softener of Examples I and lI.
', The resulting article is tumbled with damp fabrics in a
standard hot air clothes dryer, wheceby the softener is
transferred to the fabrics to impart 60ftness.
~2~731~;7
. - 16 -
. .
- ~A~PL~ YI
A fine-fabric laund-e-ri-ng~compo~i'tio~ w~th~~~abr'c~'~' ~ ~~'~~''
80ftenillg prOpert-i-e'l~='f~!i8- ~oli~sw8~~
- = , . . ........ .
Incredient '~ Percent
S cl0 14 Alkyl Sulfate
Tallow alkyl benzene~~6urfo-~te~ 2~.d'l-' ~ ~~ ^~ '~~ ~ '
Coconut Soap 4.0
Glycer~ne - 3.0
- Amine-Pho~phate ester coaplex ~ 6.O
l Triethanolam~ne to pH 7.0
Perfume 0.25
~ater to 100
* Octadecyl amine (i~~pa~ts)~ -decyiphosp~ate ~ ~~~=~'' ~~'~~~-'=
- (1 part) as melt.
J The composition of ~xample ~ in the form of'a
~milky~ liguid.
