Note: Descriptions are shown in the official language in which they were submitted.
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.' TEXTILE TREATMENT CO~POSITIONS
. .
The present invention relates to textile treatment
compositions. In particular, it relates to aqueous
~ composi~isns suitable for use in the rinse cycle of a
,~,3.'. 5 textile laundering op~ration to provide so~tening/static
control benefits, the compositions being characterised ~y
excellen~ physical cha~acteristics on storage.
Textile treatment compositions suitable for providing
~abric softening and static control bene~its during
launderin~ are well-known in the ar~ and have found wide
- scale comme~cia1 application. Co~ventionally, rinse-added
fabric softening compositions contain, as the active
softening component, substantially water-insoluble cationic
materials having two long alkyl chains. Typical of such
~aterials are di-stearyl dimethyl ammonium chloride and
: imidazolinium compounds substituted with two stearyl gro~lps.
~owever, although the above mentioned cationic
compounds are highly effective so~teners when applied in a
rinse solution, there are certain disadv~ntages associated
with th~ir use. For example, the cationic compounds havin~
long alkyl chains are very sensitiYe to carry over of
anionic detergent into the~rînse. Thus, carr~ over of
;~ anionic detergent tends to neutralize the softening effect
~ecause ~he anionic-cationic complex tends to precipitate
ou~ of solution. Also, certain cationic surfactant
compounas are expensive ~nd in short supply and it is
therefore desirable, for commercial reasons, to provide
&oftening compositions having a redu~ed amount o~ cationic
; ~urfac~ant compound.
While certain ~later-insoluble nonionic compounds have
been propo~ed as ~abric softening agents, these are found to
; deposi~ only very inefficiently from aqueous solu~ion
because of ~heir lack of positive charge and so they must be
u~ed in con~unctlon ~7ith a cationic surfactan~ m~l~erial to
act as "carriern. ~uch composi~ions containing mixtures of
~rater-in~olu~le catiC~nic ant3 noni.onic material6 have to be
., .
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3;
;
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formulated with great care to ensure that the compositions
will have the necessary phase stability and viscosity
characteristics over prolonged periods of storage under both
low and high temperature conditions. In particular, the
s viscosity of the product must be neither too high as to lead
to problems with pourability or gel ~orma ion, nor too low
as to lead to poor consumer impression, and of course the
viscosity must be s~able within the appropriate range over
long term storage and under varying temperature conditions.
British Patents 1550205 and 1550206 disclose the use
!, of certain cationic surfactants for enhancing the deposition
of fatty acid ester softening materials onto fabrics. U.SD
Paten~ 4233164 discloses the use of a protonated di-poly-
ethoxy monoalkylamine for improving the freeze-thaw recovery
of a fabric conditioning composition containing cationic
fabric conditioner and a atty aci~ ester. There is a
- continuing need, however, for textile treatment compositions
having excellent softening/antistatic benefits, combined
with optimum viscosity and phase stability characteristics.
~be present invention thus provides textile treatment
compositions having improved softening characte~istics,
particularly under hard water wash/rinse conditions, and
improved formulation viscosity characteristics under long
term storage together with excellent phase stability
characteristics.
Accordinglyr the present invention provides an aqueous
textile treatment ~omposition charac~erized by from ~% to
11% of an active mixture comprising
; (a) from 1~ to 10o of a substantially wa~er-insoluble
cAtionic fabric ~of~ener having the ~eneral formula I
_ ~ R
M Y. I
\~
~ ~2 R~
~2~
. ~ .
.. . ,, . . . . . : , . . . . .... . .... .. . .... . .... .
.
-- 3 --
,,
-` wherein Rl and R2 represent alkyl or alkenyl
~ groups of from 12 to 24 carbon atoms; R3 and R4
; represent hydrogen or alkyl, alkenyl or h~droxyalk~l
groups containing from 1 to 4 carbon atoms;
(b) ~rom 0.1% to 2~ of an alkoxylated ammonium surfactant
having the general formula II
, . ~ .
~ ~ Rs ~7
;: \ /
` - N ~ ~ : X - II-
. / \
R6 R8
.: _
wherein R5 represents an alkyl or alkenyl group of rom 12
to 24 carbon atoms, and R6, R7 and R8 independentl~
represent an alkyl group having 1 to 4 carbon atoms, an a~yl
- group~ or ~CDB2nO)yH wherein n is ~ or 3 and y is a
number average in the range from 0 to 9, and wherein the SUTn
total of CnH2nO groups in the molecule is in the range
from 1 to 9, and X is as defined above; and
(c~ from 0.5% to 5% of a substantially ~qater-insoluble
~ nonionic fabric softener selected from C10-C2~
-~~ non-cyclic hydrocarbons and fatty acid esters, having
a total of from 10 to 40 carbon atoms.
All percentages and ratios herein are specified by
weight o~ total compositiont unless otherwise indicated.
Preferabl~, the textile treatment compositions contain
~rom about 2% to about 8%, more preferably from 2.5~ to
about 6% o~ the cationic fabric softener, from about 0.~% to
about 1.5%, Tnore preerably from about 0.5~ to abo~lt 1.2~ of
thè alkoxylated ammonium surfactant, and from abollt 1~ to
about 3%, more pref~rably from about 1~ to about 2% of ~he
nonionic fabric softener. '~hese levels of active matérials
are pre~erred from the vie-,1point of obtaining optimal
product visco~it~ and stability characteristics.
~.
'..f,,.?'
In a preferred embodiment, the alkoxylated a1nmonium
surfactant component has the general formula III
R5 (~nH2n)x
.. \ / .
` N X III
. / \
H ~ ~ ~CnH2n)yH
.,~ , , .
wherein R5 is a Cl6-C2~ alkyl or alkenyl group, n is 2
`~ S and x t Y are each a number average in ~he range from 0 to 6,
preferably 0 to 3, and the sum total of x and y is in the
range from l to 6~ preferably l to 3-and wherein X is as
defined above. By 'nurnber average' is meant that x, y each~
represent the weight averaged rlumber of moles of alkylene
lo oxide in the corresponding polyoxyalkylene moiety of the
surfactantO
.. . .
Note that, depending on the precise pB of the textile
treatment composition, alkoxylated surfactant o~ a
non-~uaternary ammonium type, may be present in the
composition in partially deprotonated form. In such cases,
all weight percentages and ratios herein are expressed in
terms of the corresponding^fully protonated salt.
The compositions of the invention are generally
formulated so as to have a slightly acidic pH, pr~ferably
2~ from about 3.5 to 7, mor~ preferably from about 4 to 6;
moreover, it is desirable that the final formulation pH be
lo~er than the acidity constant (pKa) of the amine so that
the amine exists predominantly in the form of its protonated
or ammonium derivative. Physically, the compositions take
the form of a particula~e disper~ion of the cationic and
nonionic fabric softeners in an aqueous continuum containin~
at least sorne of the alkoxylated ammonium ~urfactant.
A hiyhl~ prefer~ed composition coTnprises:
~a) ~rom abou~ 2~ to abvut 8~ of the ca~ionic fak,ric
softener having gen~ral formula I,
~2~
-- 5 --
(b) from about 0~% to about 1.5% of the al~oxylated
ammonium surfactant having general formula II wherein
the weight ratio o~ (a) to (b~ is in the range from
about 6:1 to about 3-1, ana
(c) frorn about 1% to about 3% of the nonionic ~abric
sof~enerjwherein the weight ratio of [(a)~b)l to (c)
is in the range from about 6:1 to about 1.5~
The nonionic fabric softener materials herein are
C10-C~4 non-cyclic hydrocarbons and fatty acid esters
having a total of 10 to 40 carbon atoms~ A-particularly
preferred material is glyceryl monostearate.
The presen~ invention also provides a method of making
the textile treatment compositions generally described above
by the s~eps of:
(a) preparing a molten premix of the water-insoluble
cationic fabric softener, the water-soluble
alkoxylated surfactant and the water-insoluble
nonionic fabric softener~
~b) intimately mixing the molten premix with water at a
temperature above the melting point of the premix to
form an aqueous dispersion, and
(c) cooling the dispersion.
Tl~e compositions of ~he invention preferably are
stable to separation in a centrifuge at 3000 r.p.m. for 16
hours and have a dynamic viscosity in the range from about
350 cp ~O.35 Pa.s) to about 70 cp (0.07 Pa.s), preferably
from a~out 200 cp (0.~ Pa.s) to about 100 cp (0.1 Pa.s)
measured in a Brookfield Viscometer, using Spindlle No. 2 at
6~ r.p.m. and at 21C.
The variou5 ingredients of the compositions of the
invention ~lill no~7 be discussed in detail.
~he ~ater-insoluble cationic ~abric softener is
preferabl~ a fabric-substantive cationic compound which, in
pure form a~ a stron~ acid salt [e.g. chloride), has a
solubilit~ in diskilled ~later at p~l 2.5 and 20C of less
than 1~/1, or can be a mixture of ~uch compounds. In this
Z
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.
.
,
context, the soluble ~raction of the surfactant is taken to
be that material which cannot be separated from water by
centrifugal action and which passes a 100 nm ~uclepore
filte~ (Registered Trade Mark)~ In addition, the cationic
softener desirably has a monomer solubility ~as measured by
; critical micelle concentration or ~.M.C.) such that the
: C.M.C. of the material under the conditions defined above is
less than about ~0 p.p.m, preerahly less than about 20
p.pOm. Literature C.M.C. values are taken where possible,
1~ especially surface tension~ conductimetric or dye adsorption
values.
The substantially water-insoluble cationic fabric
softeners are the quaternary ammonium and amine salt
compounds having the formula:-
1 ~ 3
. , \ /
N \ X
R~ R4
wherein Rl and R2 represent alkyl or alkenyl groups of
:~ from about 12 to about 24 carbon atoms, R3 and R4
represent hydrogen, alkyl, alkenyl or hydroxyalkyl groups
containing from 1 to about 4 carbon atoms; and X is the salt
counteranior~, preferably selected EroJn halide, methylsulfate, ethyl sulfate, benzoatel aceta~e, propionate and
phosphate radicals. ~epresentative examples o~ these
quaternary softeners include ditallow dimethyl ammonium
chloride; ditallow dimethyl ammonium methyl sulfclte;
; 25 di.hexadecyl dime~hyl atnrnoniurn chloride; dithydroqenated
tallo~ alkyl) dimethyl amrnonium chloride; dioctacleoyl
-~ dimethyl amJnonium chloride; dieicosyl dirnethyl anionic
chloride; didscosyl dimethyl ammoniurn chloride; cli
(hydrogenated tallo~l) dimethyl arnrnonium rnethyl sulfate;
dihe%ade(yl diethyl arnrnoni~lrrl ch:Loride; di~c~corlut: alkyl~
dirnethyl an-l~noniurn chloride, and di~coconut alkyl~ dirnethyl
., i, :
,~, ,.
~,-
~2~
.. . .. .. . .. . . .. . .. .. . . . .. . . .
amrnonium methosulfate. Of these ditallow dimethyl ammonium
chloride and di(hydrogenated tallow alkyl) dimethyl ammonium
chloride are preferred~
- With respect to-the alkoxylated ammonium surfactant
; 5 component, this includes both quaternary and non-quaternary
ammonium species although the latter are pre~erred ~rom the
viewpoint of providing optimum viscosity and stabilit~
characteristics. Suitable surfactants of the
non-quaternized variety include protonated mono- or
di-polyethoxy primary alkyl amines wherein the amine
contains from abou~ 16 ~o about 22 carbon atoms in the alk~l
chain, and wherein the average number of ethoxy c~roups per
polyethoxy chain is from 0 to about 6, preferabl~ from about
0 to about 3, and wherein the sum to~al of polyethoxy yroups
per molecule is from 1 to about 6, pxeferably rom 1 to
about 3. ~ighly preferred amines have an alk~l group
derived from hardened or unhardened tallsw or stearyl and
are ethoxylated with an average of about 2 moles of ethylene
oxide per mole of amine (referriny to Formula III, x=y=l~.
The corresponding polyal~oxylated ~uaternary ammonium
surfactants are also suitable, for instance, (referring to
Formula II) t those species in ~hich R5 is Cls~C22
alkyl or alkenyl, R6 is methyl or ethyl, and R7 and R~
-;~ are groups of formula (C2H40)xH, (C2H40)yE3,
respectively wherein x, y are each rom 0 ~o abou~ 6,
; preferably 0 to about 3 and the sum total of x and y is from
1 to about 6, preferably from 1 to about 3. In a specific
e~ample, R5 is tallowyl, R6 is methyl, and x, y are each
about 1.
Pre~erred water-insoluble nonionic abric soteners o~
the fatty acid ester cla~s are C10-C2~ ~atty acid esters
of mono- or poly-hydroxy alcohol~ con~ainin~ 1 ~o ahout 12
carbon atorn~. Preferably the alcohol has ~rom 1 to about ~
carbon alvms, and th~ ~atty acid est~r has at leas~ 1, more
3~r~ preferabl~ at least 2, frQe ~i.e., unes~eAri~ied) ~lydro~yl
c~roupc; ~
~-2~
.. . .... .. . . ... ... .
.,
-- 8 --
The moro or poly-hydric alcohol portion of the ester
can be represented by methanol, isobutanol, 2-ethyl-hexanol,
isopropanol~ ethylene glycol and polyethylene glycol with a
maximum of ~ ethylene glycol units, ylycerol, dig~ycerol,
polyglycerol, xylitol~ erythritol, pentaerythritol, sorbitol
~, or sorbitan, sugars such as glucose, fructose, galactose,
~annose, xylose, arabinose, ribose, 2-dPoxy-ribose,
sedoheptulose and sucrose. Ethylene glycol, glycerol, and
sor~itan esters are particularly preferred, especially the
monoesters of glycerol~
'!`~ The fat~y acid portion of the ester n~rmally comrrise-~ a fa~t~ acid having from lO ~o 24 (preferably 12 to 22)
carbon atoms, typical examples being lauric acid, m~ristic
: acid, palmitic acid, stearic acid, arachidic acid, be~enic
acid, oleic acid and linoleic acid.
The glycerol esters are very hiyhly preferred. These
are the mono-, di- or tri-esters of glycerol and ~at~y acids
o~ the class described above. Commercial glyceryl
mono-stearate, which may contain a proportion of di- and
~ ~ri-stearate, is suitable. Also useful are mixtures of
` saturiated and unsaturated esters of gl~cerol derived from
- mixed saturated and unsaturated fatty acids.
Another suitable group of nonionic fabric conditioning
agents are the ClO to C24 fatty acid es~ers of sorbitan
~5 such a~ those described in l~urphy et al., US Pa~ent
4,085,052 issued April 18, 1978. Sorbitan mono- and
di-esters of lauric, myristic, palmitic1 stearic, arachidic
or behenic, ol~ic or linoleic acids are particularly useful
as ~oftening agents and can also provide antistatic
benefits. Sorbitian esters are commercially available, for
instance, under the trademark "Span". For the purpose of the
present invention, it is preferred that a signiflcian~ amount
of di~ and tri~sorbitan esters are present in ~he ester
~Z~67QS
mixture. Ester mixtures having from 20~ - 50~ mono-esterr
25~ - 50% di~ester and 10~ - 35% of tri- and tetra-esters
are preferred.
Preferred nonionic fahric softeners of the hydrocarbon
- 5 class are paraffins or olefins containing from about 14 to
about 22 carbon atoms. Materials known generall~ as
paraffin oil, soft paraffin wax and petrolatum are
- especially suitable. Examples of specific materials are
tetradecane, hexadecane, octadecane and octadecene.
Preerred commercially-available paraffin mixtures include
;~ spindle oil and light oil, techn7cal grade mixtures of
C14/C17 n~paraffins and C18/C20 n-paraffins and
refined white oil.
In addition to the cationic softener, nonionic
softener, and alkoxylated ammonium suractant components,
the present compositions can be supplemented by all manner
o~ optional components conventionally used in textile
, .
treatment compositivns, for example, colorants, perfumes,
preservatives, optical brighteners, opacifiers, pH buffers,
viscosity modifiers, fabric conditioning agents,
surfactants, stabilizers such as guar gum and polyethylene
glycol, anti-shrinkage agents, anti-wrinkle agents, fabric
crisping agents, nonionic softening agents, spottiny agents,
soil-release agents, germicides, fungicides, anti-oxidants
such as butylated hydroxy toluene, anti-corrosion agents
-etc. Of course, the level of these optional ingredients
should, if necessaryr be controlled so as not to
deleteriously effect the physical stability and viscosity
characteristics o~ the product.
Another optional ingredient is a water-soluble
non-al~o~ylated quaternary arnmonium surfactant havin~ the
general formula IV
.,
- t
.
~7~ ~
. . .
-- 10 --
, _
'`'` ~9 \ / 11
/ N \ X IV
R~ / \ R12
wherein R9 represents a C8~C2~ alkyl or alkenyl group,
and ~10~ Rll, Rl~ independently represent a C~L-C4
alkyl or alkenyl group or an aryl group and wherein X is as
defined earlier.
Suitable materials of this general type include the
tallow trimethyl ammonium salts, cetyl tri-methyl ammonium
salts, myristyl trimethyl ammonium salts and coconutalkyl
~rimethyl ammonium salts.
I~ addition to the above-mentioned components, the
compositions may contain other textile treatment or
conditioning agents. Such agents include silicones, as for
èxample described in German Patent Application DOS 26 31 419,
published on February 3rd, 1977. The optional silicone
comp~nent can be used in an amount of from about 0.1% to
about 6%, preferably from ~.2% to 2~ of thé softener
composition.
~nother optional ingredient of the present
.~ ~compositions is a water-soluble cationic polymer havin~ a
molecular weight in the range from about 2000 to 250,000,
preferahly from about 5000 to 150,000 and containing an
average of from about 100 to about 1000, preferab]Ly from
about 150 to 700 monomer units per molecule. Molecular weights
are ~pecified as viscosity average molecualr welghts and can
':~
il
,~,
L~
~2~'7Q~
be determined as described in F. Daniels et al''Experimental
Physical Chemistr~', pp 71-74, 242-246, McGraw-Hill l1949), -
at 25 C using an Ostwald viscometer. The po7ymers ar~
~; pxeferably soluble in aistilled water to the extent o~ ~
5 0.5~ by weight at 20C. Such polymers can provide valuable
softening robustness in the presence of anionic sur~actant
carried over from a previous cleaning operation, and also ~
^, contribute to viscosity control. Suitable polymers of
this type include polyethyleneimine having an average
," 10 molecular weight o~ from ahout 10,000 to about 35,Q00,
ethoxyla~ed polyethyleneimine wherein the weicyht ratio of
: polyethyleneim;ne to ethyleneoxide is at least 1:1 and
wherein the molecular weight is from about 20,000 to about
70,000, and quaternised polyethyleneimines sold under the
15 trademark '~lcostat"by Allied Colloids.
Suitable preservativPs for use in the present cornpo-
sitions include 2-nitro-2-bromo-propane-1,3-diol, glutar-
- aldehyde and 2-me~hyl-4-isothiazolin-3-one and its 5-chloro
derivative.
The textile treatment compositions of the invention
can be used by adding to the rinse cycle of a convention~l
home laundry ope~ation.~ Generally, rinse ~Jater has a
temperature of from ahout 5C to about 60~C. The concen-
tration of the total active ingredients is generally from
;, ,~5 about 2 ppm to ahout 1000 ppm, preferably from about 10
ppm to about 500 ppm, by weight of the aqueous rinsing
bath.
In general, the present invention in its textile
treatment method aspect cornpr,ises (a) washing fabrics in
30 a conventional ~lashing machine ~ith a deterc~el~-t composition;
; (~) rinsing the fabxics; ~c~,adding,during 1:h~ rinsing
~tac3e o the opera~ion the above-described amounts of
cationic f~bric ~oft~ner in an aqueous liquid composition
containlny a speclicd amount of alkoxyla~ctl amine as
35 her~inl3efore describe~;and (d) drying the fabrics.
i, ,
~L2~:1467~5
. -.12 -
~ . T11e detergent composition'normally contains an
: anionic, nonionic, ~nphoteric or ampholytic surfactant
; or a mixture thereof, and requently contains in addition
an organic or inorganic builder. ,When multiple rinses
:. . 5 are used, the ~abric conditioning composition is preer-
ably aaded to the final rinse. Fabric drying can take
place either in ~he open air or in an automatic dryex.
The following examples illustrate the invention.
In the Examples, the followin~ abbreviations are used:
' 10 Ditallow dimeth~l~ammoni-~n chloride DTDMAC'
. Didocosyl dimethyl ammonium chloride .~DD~C
' Dilauryl diethyl ammonium methosulate D~DEAM
Ethox~lated tallo~7amine (2Eo7, benzoate
.' salt , TA2E0 ' .
` " ~ E~hoxylated stearylamine ~Eoi, phosphate
; - salt ~ SA5E0
' 15 .~thoxylatèd coconu~ amine (3E0~, acetate
.' salt CA3E0 .
Di(hydroxy eth~l) methyl tallo~1yl ammonium
chloride DHr~lTAC
I~10notallo~7yltrimethylammoni~n chloride. MTTMAC
Glyceryl monos,teara-te (~O~i monoestex; ''
60~ di and triesters~ GMS
.. , s , . .
Examples ~ to VI
,j 20 Aqueous ~extile ~reatment compositions are prepar'ed
having the follo~7in~ formulae:- .
III ~V V VI
~TD,~AC - 6 3 - , ~ 2~5
DDDMAC 8 - - - ' 3
25 DJJ'DE~ . 5 , _ , _
~r~2E~ , O. i -
S~5~ 2 ~
C~3Ii'0 _ ~ - 0 75
~ - 1.5 - - 0.5
~5TT~51~C . ~ ~ 0 3 ~ 0~4
....
~2~t~7(3~i
- 13 ~
GMS - . 2 1~5 1 1.5 0.5
Silicone 0.2 : - 0.1
n-C 4-C17 para-
f~ln 2.5 ~ - 0.5
Perfume, dye,
isopropanol to 100 ~ -
The compositions are prepared by forming a molten
premix of the water-insoluble cationic and nonionic fabr.ic
softeners and alkoxylated ammonium surfactants, and
where presenty silicone and non-alkoxylatea water-soluble
surfactant, at a temperature o a~out 65C.. The molten
premix is then injected into a water sea~ containing minor
: ingredients/ apart from perume, held at about ~5C and
this is stirred for about 5 minutes. Thereafter, the
. ~ dispersion is passed through a heat exchangex to bring
. the temperature down to about 25C and finally perfu~e is
adaed. . .
The products thus prepared are stable dispersions
displaying excellent viscosity characteristics at both
. lo~ and hi~h temperatures over prolonged periods of
. storage; they deliver excellent softening and antistatic
performance across the~range of natural and synthetic
fabrics in both hara and soft water and theY also display
excellent dispensins and dissolving characteristics in
. ~ cold rinse ~ater.
,~
