Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1 31 563~ 6~3~)]-1~23
Background of the Invention and Prior ~rt
The present invention relates to novel heavy duty
softergent liquid eompositions comprising at least 10% nonionie
surfactant, and preferably about 6-9~ of higher alkyl dimethyl
2-ethyl hexyl quaternary softening compound in conjunetion with
about 0.1-l~ of an anionie optical brightener, to improve low
temperature produet stability and softening properties. It is
preferable to add an anionie surfactant in the molar ratio of
l:l anionic surfactant:cationic softening compound, and about
4-8% by weight of a lower mono-or di-hydric aleohol.
3~
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; . ;' ' ~
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1 3 1 5~3~
'I'h~ u.~e o~ cationic quaternary ammonium compoun~ as
softeners Eor text;le products is ~ery well known in the art. ~t
is also well known to employ such materials for their softening
e~fe~ts during the laundering operation and particularly in the
r inse cyc le o~ the launderillg process. This latter technique has
heen necessitated by the fact that the aforesaid quaternary
compounds hereLofore employed, being mainly cationic in nature,
form a complex with the anionic detergent, one of the major types
of detergents used in the washing cycle. However, the use of the
quaternary softening agent in the rinse cycle is burdensome to the
consumer. Consequently, detergents have been combined with the
compatible fabric softeners for use in the wash cycle of ths
laundering operation.
It is also known that the cationic softening compounds
interfere with the brightenin8 activity as well as the cleaning
efficiency of the detergent. As a result, the prior art has used
nonionic surfactants in order to overcome this interference with
brightening activity and cleaning efficacy, as shown in U.S.
Patents 4,264,457; 4,239,659; 4,259,217, 4222,905, etc.
Another problem associated with the presence of said cationic
agents in liquid softergent compositions containing anionic
optical brightener is product instability, particularly at low
temperatures (about 40 F), due to the tendency of the quaternary
compounds to form a complex with the optical brightener which
does not resolubllize in the aqueous media.
--2--
1 31 563~
IJ.~. Pat~nt No. '~,134,83~ dlscloses a fabrLc conditi(7rling
coml)osition comprising a softenin~ agent which inclu-le prlor ar~
cationic quaternary ammonium compounds such as di-~allow dimethyl
anionic~chloride and trimethyl tallow ammoni~m chloride, and a
~eodorant pe~fume to which may be added water soluble detergent
actives well known in the art such as anionic, nonionic, etc.;
inorganic or organic detergent builders; optical brighteners; oils
and fragrances; antistatic agents; germicides; bodying agents;
soil ~elease agents; ironing aids; bleaches; enzymes; etc. The
conditioning compound may be in the form of a soLid or liquid
composition. The illustrated aqueous liquid ~abric conditioning
compositions conta~n a maximum of 6% by ~eight of the cationic
softening agent ( xample 1).
U.S. Patent No. 4,341~644 discloses a textile softener
composition comprising a quaternary ammonit~ salt mixture
dispersed in an aqueous medium where the 4 radicals contain a
total of 40-75~ saturated aliphatic straight chains, 5-45%
unsaturated aliphatic chains and 3-55% branched aliphatic chains.
European Patent No. 0,074,056 discloses a liquid
softening¦rinsing agent ~or laundry consisting of an aqueous
solution or dispersion of a quaternary ammonit~ compolmd, wherein
two of the radicals are methyl-branched alkyl or alkenyl radicals
having 12-30 carbons~ and the other two radicals are Cl-C4 alkyl
groups.
U.S. Patent Number 4,569,800 and 4,675,118 disclose a fabric
soEtenLng composition comprising a quaternary ammonlum compound,
--3--
'
',
1 3 1 563~
wherein one radical is a lligher aliphatic radical, aoother radical
is 2-ethyl hexyl, and the ~emaining two radicals are methyl
radicals, dissolved in ethanol, water, isopropyl alcohol and
blends thereof.
However, none of the cited prior ar~ references dtsclose a
stable heavy duty liquid softergent composition for si~ultaneously
cleaning and softening fabrics comprising a higher alkyl 2-ethyl
hexyl dimethyl quaternary ammonium compounds as the softening
agent, an anionic optical brightener, at least 10% nonionic
sur~actant dissolved in an aqueous medium.
SUMMARY OF_TIE INVENTION
It has now been disclosed that the use of a C6-C18 alkyl -
ethyl hexyl dimethyl quaternary ammonium salt as a softening
agent in a liquid softergent composition compriæing an anionic
optical brightener and a nonionic or nonionic-anionic surfactant
system provides product stability at low temperatures (40F) as
well as at room temperature and provides increased softening
propertles to fabrics treated therewith. The advantage of this
compound is that it improves low temperature stability of
softergent formulations while softening as effectively or more so
then a mono tallow trimethylammonium salt. Historically,
softergents have been troubled by low temperature stability when
quaternary ammonium salts were present in con~unction with anionic
optical brighteners. This new quaternary alleviates this problem.
Optical brighteners have a tendency to form complexes with
. .
--4--
`' ~' ':; , ~'
- 1 31 563~
62301-1523
quaternaries. It is believed ~hat because of increased stearic
hindrance in the ammonium salt, it i5 more difficult for any
other anionic molecule to approach, thereby, slowiny down or
preventing complex formation. Low temperature instability is
not seen until levels of brighteners and/or quaternary ammonium
salt get to be quite high.
Accordingly, the instant invention seeks to provide a
stable liquid softergent composition having improved softening
efficacy in the presence of C6-C18 alkyl 2-ethyl he~yl dimethyl
quaternary ammonium softening compounds.
The invention also seeks to provide a stable heavy
duty liquid softergent composition, that simultaneously
cleanses and softens fabrics during the laundering process
comprising an anionic optical brighkener, a C6-C18 alkyl
2-ethyl hexyl dimethyl qua~ernary ammonium softening compound,
and a nonionic surfactant in an aqueous medium.
The invention further ~eeks to provide a stable
liquid softergent formulation having improved cleaning and
fabric softening properties, due to the presence of a C6-C18
alkyl 2-ethyl hexyl dimethyl ammonium quaternary softening
compound in a composition comprising an optical brightener, a
nonionic surfactant, and preferably an anionic surfactant in a
ltl molar ratio with said quaternary compound.
A`"~ 5
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62301-15~3
Additional advankages and novel features of the
invention will be se~ for~h in part in the description which
follows~ and in par~ will become apparen~ to those skllled in
the art upon examination of the following specification or may
be learned by practice of this invention.
To achieve ~he foregoing in accordance with the
present invention, as embodied and broadly described herein,
the liquid softergent composition for laundering fabrics of
this invention comprises an effective amount of a higher alkyl
2-ethyl hexyl dimethyl quaternary ammonium softening compound
to provide produc~ stability and softening properties in the
presence of an anionic optical brightener, and a surfactant
system comprising at least 10% by weight of a nonionic
surfactant in an aqueous carrier, preferably con~aining about
4-8% by weight of a lower mono- or di-hydric alcohol; and the
method of simultaneously cleansing and softening fabrics
without reducing softening, brightener and detergency -`
performance which comprises trea~ing fabrics with said
composition during the wash cycle of the laundering operation.
~0 More specifically, present invention relates to a
stable heavy duty liquid softergent composition comprising
preferably about 6-9% by weight of a C6-C18 alkyl 2-ethyl hexyl
dimethyl quaternary ammonium softening compound, about 0.1-1%
by weight of an anionic optical brightener, a surfactant system
comprising about 10-30% by weight of a nonionic surfactant, and
pre~erably a lesser amount of an anionic surfactant preferably
in a 1:1 molar ratio with said quaternary compound, in an
aqueous vehicle, preferably containing about 4-8% by weight of
a lower mono- or di-hydric aleohol. Although the most
preferred molar ratio is 1~1 anionic to cationic, minor
variations thereof may be used with large amoun~s of
brighteners to obtain stability properties.
A
` 1 31 563~3
Detailcd D_scription of the Invention
In ac~ordance with this invention, the nonionic s~rfactants
~or use as the fabric detergent are commercially well known and
include the ethoxyLates and glycosides and mixtures thereof, such
as the pri~ary aliphatic alcohol ethoxylates, secondary aliphatic
alcohol ethoxylates, alkylphenol ethoxylates, the alcohol
ethylene oxide-propylene oxide condensates such as ~lurafacs
(Wyandotte), C1-30 alkyl monoglycosides and polyglycosides, and
mixtures thereof. The nonionic synthetic organic detergents are
generally the condensation product of an organic aliphatic or
alkyl aromatic hydrophobic compound and hydrophillc ethylene oxide
group, or a hydrophilic glycoside g~oup containlng 1 to about 10
saccharide radicals. Practically any hydrophobic compound having
a carboxy, hydroxy, amido or amino group with a free hydrogen
attached to the nitrogen can be condensed with ethylene oxide or
with the polyhydration product thereof, polyethylene glycol, to
Form a nonionic detergent. Further, the length of the
polyethenoxy chain can be adjusted to achieve the desired balance
between the hydrophobic and hydrophilic elements.
The nonionic detergents include the polyethylene oxide
condensate of one mole of alkyl phenol containing from about 6 to
12 carbon atoms in a straight-or branched-chain configuration with
about S to 30 moles of ethylene oxide, for example, nonyl phenol
condensed with 9 moles of ethylene oxide, dodecyl phenol condensed
with 15 moles of ethylene oxide. Condensation products of the
corresponding alkyl thiophenols with 5 to 30 moles of ethylene
oxide are also suitable.
~ 7 RftD ~
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1 3 1 563~
Also iocLIlded in t:he nonionic detergent class are the
con~ellsatioll products of a higher alcohol (e.g. an alkanol
contain;ng about 8 to 18 carbon atoms in a straight or branched-
chain configuration) condensed with about 4 to 30 moles of
ethvlene oxide, for example, lauryl-myristyl alcohol condensed
with about 16 moles of ethylene oxide. A commercially available
preferred group is the narrow range ethoxylate nonionics known as
Tergitol provided by Union Carbide, wherein the ethylene oxidé
chain (including the terminal ethanol) i5 of such narrow
distribution that at leas 80% and preferably 85-90% of the
nonionic detergent contains an average of 4-lZ and preferably 6-7
ethylene oxides.
The alkyl glycosides may be represented by the following
formula, RO(R'O) z , wherein R is a Cl-C30 alkyl radical, (R'0) is
an ethoxy, propoxy or glyceryl group, X has a numerical value of
0-10 and preferably 0, Z is a reducing saccharide containing 5 or
6 carbon atoms, and n has a numerical value of 1-10 and preferably
1 to 3. l'he hydrophobic alkyl group may be saturated or
unsaturated, branched or straight chain, preferably saturated and
linear, containing 1 to 30 carbon atoms, preferably 8 to 23
carbon atoms. Suitable alkyl polyglycosides include methyl,
ethyl, propyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,
tetradecyl, hexdecyl, heptadecyl, octadecyl and mixtures thereof,
monoglycosides, diglycosidesj trlglycosides, tetraglycosides,
~enta-glycosides, hexaglycosides, etc. The glycoside units may
be glucose, galactose, mannose, lactose and/or fructose. Methods
~P~n~R/~
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1 31 563~ 6~301-1523
of preparing the foregoiny glycosides are disclosed in U.S.
Patents 3,598,865; 3,707,535; 3,839,318; 3,772,269; 3,219,656
Another preferred group of nonionic surfactants are
the Neodol ethoxylates (Shell Co.), which are higher alipha~ic
alcohol ethoxylates having about 5 ~o 20 ethyleno~y groups per
mole of aliphatic alcohol containing about 10-18 carbon atoms,
such as C12-C13 alkanol condensed with 6.5 moles ethylene
oxide, C12-C15 alkanol condensed with 12 moles ethylene oxide,
C14-C15 alkanol condensed with 13 moles ethylene oxide, and the
like.
It has been found that the nonionic surfactants
improve oily soil detergency and provide low temperature (40F)
stability to the softergent composition. Ethoxamers having a
HLB (hydrophobic lipophilic balance) value of about 8-15 gives
good O/W emulsification, whereas ethoxamers with low HLB values
(Below 8) contain less than 5 ethylenoxy groups, and are poor
emulsifiers and poor nonionic detergents. The amount of
nonionic detergent constitutes the major detergent component in
this softergent, about 10-30% and preferably 15-25% by wt. of
~0 the composition.
The anionlc surfactants, which are optionally
preferred in the softergent of this invention, are commercially
well known and include alkylbenzene-sulfonic acid and its
salts, e.g. compounds of the formula alkyl-phenol -SO -M,
wherein alkyl is an alkyl radical of C8 to C22 and preferably
C10 to C18 and M is hydrogen or an alkali metal, which
compounds comprlse a well-known class of anionic detergents and
include sodium dodecyl benzene sulfonate, potassium dodecyl
benzene sulfonate, sodium l~uryl benzene sulfonate, sodium
cetylbenzene sulfonate. Others include para~fin sulfonates,
:
,
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1 3 1 5 6 3 ~ 623~1-15~3
alkyl sulfates, alcohol ether sulfate~, ole1n sulfonates and
the alkyl phenolethoxylate sulfates (e.y. sodiu~,
dinonylphenoxynonaethoxyethanol sulfate), and other equivalent
`A` 9a
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1 3 1 563~
water-soluble salts, particularly of the alkal1 metaL series.
Among the above-noted alkylbenzene-sulfonic acid and sa1ts
thereof, the preferred compounds include those which are
biodegrad~ble and which are particularly characterized by a linear
al~yl su~stituent of from C10 to C22and prefer~ly from ~12
to Cl5. I't is, of course, understood that the carbon chain
length represen~s, in general. an average chain length since the
metho-l for producing such products usually employs alkylating
reagents of mixed chain length. It is clear, however, that
substantially pure olefins as well as alkylating compounds used in
other techniques can and do give alkylated benzene sulfonates
wherein the alkyl ~oiety is substantially (i.e., at least 9~%) of
one chain length, i.e., C2 to Cl2, Cl3, Cl4 or ClS h
alkyl benzene sulfonates are further characterized by the po.sition
of the benzene rinB in the linear alkyl chain with any of the
position isomers (i.e., alpha to omega) being operable and
contemplated.
In addition to the benzene sulfonates one may also employ the
lower alkyl (Cl to C4)analog of benzene such as toluene, xylene,
the trimethyl benzenes, ethyl benzene, isopropyl benzene and the
like. The sulfonates are generally employed in the water soluble
salt form which include as the cation, the alkali metals, ammonium
and lower amine, and alkanolamine cations.
Examples of suitabie linear alkyl benzene sulfonates include:
sodium n-decyl benzene sulfonate
sodium n-dodecyl benzene sulfonate
sodium n-tetradecyl benzene sulfonate
sodium n-pentadecyl benzene sulfonate
sodium n-hexadecyl benzene sulfonate
and the corresponding lower alkyl substituted homo10gues of
benzene as well as the salts of the cations previously referred
--10-- :
1 3 1 563~
to. Mixtures of thsse .suLfonates may, of course, a.lso be use-l
with mixtures which maY incLu~le rompound5 wherein the linear alkyl
chain is smalle~ or larger than indicated herein provided that the
average chain length in the mixture conforms to the specific
~equirements of C1O to C~'2
The linear paraffin sulfonates are also a well-known group of
compounds and inc.lude water-soluble salts (alkali metal, amine,
alkallolamine, and ammonium) of:
I-decane sulfonic acid
l-dodecane sulfonic acid
l-t:ridecane sulfonic acid
l-tetradecane sulfonic acid
l-pentadecane sulfonic acid
l-hexadecarle sulEonic acid
as well as the other po.sition isomers oE the sulfonic acid group.
In a~ldition to the paraffin sulfonates illustrated above,
others with the general ranBe of C10 to C~ alkyl may be used,
with the most preferable range being from C12 to C20.
The linear alkyl sulfates which are contemplated in this
invention comprise the range of C10 to C20. Specific examples
include sodium n-decyl sulfate; sodium n-dodecyl sulfate; sodium
n-hexadecyl sulfate, sodium n-heptadecyl sulfate; sodium n-
octadecyl sulfate; and the ethoxylated (1 to 100 moles ethylene
oxide) derivatives such as the ethoxylated alcohol sulfate and,
of course, the other water-soluble salt-formlng catiolls mentioned
above.
Included in the group of anionic detergents, which have been
descrlbed above as suitabie in the present invention, are the
olefin sulfates, including long chain alkene sulfonates, long
chain hydroxyalkane sulfonates, as well as disulfonates. Examples
of suitable olefin, which are merely illustrative of the general
---`` 1 3 1 563~
class, are ~sodium dodecenyL-L sulfor~ate, sodium tetradecyl-l
sulfonate, sodium hexadecenyl-l sulfonate, and sodium octadecenyl-
I sulfonate. The amount of anionic surfactant utilized in present
composition is less than the nonionic surfactant content by wt,
and preferably in a 1:1 molar ratio with the cationic quaternary
softening agent, and cons$itutes the 3.8-7% by wt. of ths
soEtergent composition.
The presence of the anionlc surfactant in the formulation
enhances detergency performance and brightening efficacy by
depositing the brightener on the ~abric more effectively.
The essential ingredient in the instant liquid softergent is
the cationic fabric softener which is an alkyl 2-ethyl hexyl
dimethyl quaternary ammonium compound represented by the
following formula:
CH3 H
R----N-----CH ------C--~ --(C~ CH3 X
~- CH3 CH~CH3
wherein R is an aliphatic straight chain, saturated and
unsaturated hydrocarbon radical having from 6 to 18 carbon atoms,
and X is a water soluble salt forming anion such as halide, i.e.
chloride~ bromide, iodide; sulfate, me$hosulfate, ethosulfate9
citrate, acetate, hydroxide, phosphate, or similar inorganic or
-12-
1 3 1 5 6 3 ~ 62301-1523
organic solubilizing radical. Preferably, the ~ radical ls
obtained from a mixture o~ long chain ~atty acids such as the
tallow or coco radicals. The tallow radical is a mix~ure o~
aliphatic saturated and unsaturated hydrocarbon radicals
containing a major amount of 16 to 18 carbon chains and a minor
amount of 12 to 14 carbon chains. The coco radical i5 a
mixture of saturated and unsaturated hydrocarbon radicals
containing a major amount of 12 to 14 carbon chains and a minor
amount of 6 to 10 and 16 to 18 carbon chains. Hydrogenated
tallow is another preferred long chain radical. Other suitable
radicals include stearyl, cetyl, lauryl, dodecyl, octadecyl,
myristyl and hexadecyl and mixtures thereof. Methods of
preparing the aforesaid quaternary ammonium compounds are
disclosed in U.S. Pa~ents No. 4,569,800 and 4,675,118.
Aforesaid alkyl 2-ethyl hexyl dimethyl quaternary ammonium
softening compounds is preferably used at levels of 6-9% by
weight of the liquid softergent but may be used at 3-4% levels
provided effective softening properties are obtained. However,
prior art quaternary softeners are conventlonally used at
concentrations of 3~. The branched alkyl radical, 2-ethyl
hexyl, provides the quaternary compound with greater solubility
in the aqueous alcoholic medlum.
It has now been found that these quaternary ammonium
softening compounds improve low temperature stability of the
softergent compositions. This may be due to the low cloud
point of the softening compound which is directly related to
its clarity at a given temperature. The cloud point of
hydrogenated tallow 2-ethyl hexyl dimethyl quaternary ammonium
chloride is 27F and cocoalkyl 2-ethylhexyl dimethylammonium
chloride has a cloud point of -10F.
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1 31 563~3
~ he stability of the liquid softergent is also a function of
the amount of the quaternary compound in relation to the anionic
optical brightener content. A greater quantity of quaternary
compcund requires a lesser amount of brightener. The anionic
optical brighteners have a tendency to form a complex with the
cationic quaternaries in an aqueous medium. However, due to the
stearic hindrance in the higher alkyl 2-ethyl hexyl dimethyl
ammonium salt, it is more difficult for any anionic molecule to
approach the cationic ammonium salt, thereby slowing down or
preventing complex formation. The use of these particular
quaternary ammonium compounds obviates the long standing low
temperature instability problem associated with compositions
containing both a quaternary compound and an anionic optical
brightener. Fabric softening, brightening and deter~ency
propsrties as well as stability of the liquid compositions has
been achieved.
Another essential lngredient in present liquid softergent is
an anionic optical brlghtener having a sulfonate moiety such as
substituted dlsulphonated diaminostilbene and triazole compounds
to provide brlghtness to the wsshed fabric, a feature found
desirable to consumers. Optical brighteners are substantive to
textiles during the laundering process and sometimes are of
comparatively low solubilities. Accordingly~ it is important that
they be maintained~in solution in the liquid softergsnt
composition and readily dispersed in the wash water in order to
produce a uniformly bright appearance. Relatively small
quantities of brighten~ should b~ ~sed s~ ~ :~ot to exceed the
( '1
. ' ~
.
l;mits of soLubility. IIoweverl ~hl ~r6es)er3ce of a catiorIic
quaternary softening compound forms a complex with th~ anionic
optical brightene~ causing low temperature instability o~ the
liquid composition. Due to the increased stearic hindrance in the
particular ~mmonium salt used in prese~t softergent composLtion,
it is ~ore difficult for ~he anionic molecule to approach, thereby
slowing down or preventing complex formation. Certain brighteners
have been found to readily dissolve in an aqueous medium and thus
are suitable for incorporation in present liquid softergent.
Fortunately, these preferred brighteners include both cotton and
amide-polyester-brighteners. Accordingly, suitable co~mercial
A brighteners are used in present liquid softergents including
Tinopal UNPA, Tinopal CBS, Tinopal 5BM(Ciba-Geigy), Arctic White
CC, Arctic White CWD (Hilton Davis), and the following Phorwhites
from Veronao BIIC, BKL, BUP, B~H solution, BRV solution, DCR
liquid, DCBVF, EV liquid, DBS liquids and ANR.
The anionic optical brightener content of the liquid
softergent composition is about 0.l-lZ9 and preferably about 0.4-
0.8% by weight of the composition. Said concentrations are
soluble in the present liquid softergents and are effective in
brightening the washed laundry.
The liquid vehicle or carrier for the present liquid
softergent composition ~s primarily an aqueous medium. It is
preferable to add about 4-8Z by weight of a lower alkyl mono- or
di-hydric alcohol such as ethanol, propanol, isopropanol, butanol,
isobutanol, ethylene glycol, propylene glycol or the like, to
control the viscoslty of said clear liquid softergent composition,
when necessary or desirable.
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I'he softer~ent compositi~n of the instant invention may aLso
inc]ude minimal amoun~.s up to 5% by weight of conventional
~aundering additives such as germicides, soil suspending agents,
antiredispos;ton agents, colorin~ materials (dyes and pigments),
perfunles, hydrotropes such as sodium and potassium xylene
sulfonates, sodium and potassium tolusne sulfonates, cumene
sul~onates, ethyl ben~ene sulfonate and the like, enzymes, and
enæyme stabilizers, provided they do not interfere with the
stability, brightness, detergency and softening activity of the
composition .
The present liquid softergent compositions may be prepared by
simply admixing the various ingredients at room temperature, in an
aqueous medium until a clear liquid îs formed. The order of
addition of the ingredients may be varied without adversely
affecting the ~ormation of the single phase, clear liquid products
of instant invention.
Thè softergent composition of the present invention exhibits
many desirable characteristics with regard to both physical
propertie~ and performance in use. More specifically the liquid
compositions are clear, pourable and free-flowing from any
suitable container. They are stable upon aging at room
temperature (about 700F) as well as at low temperatures (400F)
without any appreciable preclpitation or cloudiness. The present
softerRents simultaneously and effectively clean, soften and
control the static of the different fabrics during the wash cycle
oE the laundering operation.
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Th~ following specifi~ examp1es are merely illustrative of
the iovention and are not to be constnled as limi~ing thereof.
Example 1
Liquid Softer~
InRredients %
(']2-C15 ~lcohol : 7E0 (ethylene oxide) 21.0
Dodecylben~ene sulfonate (DBS) 3.8
~allow alkyl 2-~thyl hexyl dimethyl
ammoniwn methyl sulfate (TL8-~lS)6.0
Tinopal UNPA* O.4
Ethanol 6.0
Sodium xylene sulfonate (SXS) 5.0
Water q.s.
*CAS Regi~try No. 4l93-55-9-2,Z'-(1,2-ethenediyl)bis(5-((4-
(bis(2-hydroxyathyi)amino)-6-(phenylamino)-1,3,5-triazin-2-
yl)amino)-benzene sulfonic acid, disodium salt.
This composition is prepared by mixing the above water
soluble ingredients until a homogeneous, clear liquid softergent
is formed which is stable at room temperature and at 40F.
This formulation was tested after 5 wash-dry cycles using
terry hand towels for softness and antistatic properties. Table I
compares compositions containing the prior art monotallow
~rimethyl amnonium chloride softening agent in lieu of the tallow
2-ethyl hexyl dimethyl amrnonium methyl sulfate softening agent in
Rxample 1, using liquld Bold ~containing ditallow dimethyl
arnmonium chloride) as the control ha~ing the greatest softness
(9 . S) .
Table I lists the comparative softrless ratlng which is within
a range of 1 (hardest) to 10 (softest), and the comparative
antistatic ratlng wherein ~he control exhibiL~ no sLa.lc.
nn ~ R/~
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,
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1 3 1 563~
Table I
Product SofteninR Antistatic
Example l 8.0 None
Monotallow trimethyl 5.0 Very light
ammonium chloride
~ontrol 9.S Nonc
'rha ratin~ description for the antistatic is as follows:
None-no noise/no cling
V8ry light-l or 2 items sticking together or 1 type of fabric
clinging.
Example 1 was ranked equal in softness to liquid Bold at the
99% confidence level. l'he softness Rankin8 procedure is as
follows: A panel of twenty subjects was asked to rank from
harshest to softest, terry hand towels washed 5 times in the
products being tested. More than one product can be ranked in the
same position. The results are analyzed by Friedman two way non
parametric statistical methods, M. Hollander and D.A. Wolf, J.
Wlley and Sons, 1973, page 13. The test conditions are a
temperature of 72 F and a humidity of 50~.
The detergency of this product was also tested in a
tergotometer containing 1 liter of 150 ppm (calcium) water at 120
F and 70 F, with a concentration of 0.18% softergent, and
compared to commercial detergent products which contain different
quaternary ammonium softening compounds. A fabrlc load of standard
soiled swatches of Test Fabrlc nylon (TFN) and cotton (TFC), a 65-
35% blend of polyester-cotton (PC) and 50:50% dacron:co~on (DC~
"
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1 ~1 563~
~nd EMPA 10l Cloth, was washed with the test softer~ents and dried
in electric tumble dryers. Reflectance of the soiled swatches are
read as a ~easure of deter~ency (Rd.~ The soil removal (SR) is
the sum total of the Rd readings on all the swatches, and the
soil ~emoval index (SRl) is the average of the total Rd readings
divided by the number of swatches.
Table II
SRl
Ex. 1 Liquid Fab Liquid Bold
l20F 200 219 189
70~ 20L 205 183
Example 1 exhibits superior detergency to liquid Bold. No
statistically significar.t difference in detsrgency was observed
between ~xample 1, and Liquid Fab at 120F and 70F. The
difference observed at 120F was due to a better performance of
liquid Fab on TFN and TFC fabrlcs. I~owever, performance on PC
cotton, DC and EMPA were equivalent.
A five week bundle test tested the ~xample 1 for~ulation
against liquid Bold. On Whites, Example l showed a strong win
over liquid Bold visually with a preference ratio of 2.74. On
cotton, Example 1 showed enhanced performance relative to liquid
Bold as measured instrum~ntally. Rd values for cotton for the two
products wsre not significantly different. On colors, Example 1
was visually preferred over liquid Bold at a ratio of 1.5. No
significant difference was detected Lnstrumentally. Liquid Bold
showed a strong win on whites and cottons with respect to
softness. Static clin~ evaluation showed liquid Bold to have
.: ~
~. :
~ 1 3 1 5~)3~3
nolle an~ Example l to have slight to none.
11ulti~tain tests on oily particulate, dry particulate,
oxidizable and enzyme stains conducted with the liquid softergents
o~ present invention ln the washing machine at 70F, 120F and 150
pp~ water hardness, gave favorable results.
Rxamples 2-9
Ingredients ~ ~ ~ S 6 7 8 9
% % % % % % 7O %
Cl2-15 Alcohol
7E0 21 21 21 21 21 _1 21 21
TL8-MS 6 6 6 6 6 6 6 6
Tinopal UNPA 0.1 0.2 0.3 n.4 0.5 0.6 0.8 1.0
DBS 3.8 3.8 3.B 3.8 3.8 3.8 3.8 3.8
~thanol 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
SXS 5.0 5.0 5.0 5.0 ~.0 5.0 5.0 5.0
1l20 ~ -----------balance-----------------------
Aging ti~e 4 weeks 4 4 4 4 4 2 2
~tability clear clear cle~r clear clear clr.clr. slight
precipitate
recovers at
-2a-
:
1 31 563~
These e~amples cl~rly show that 0.1 to a maximum of 1%
c)ptical brightener can ba used in a liquid softener containing the
particùlar quaternary ammonium softening cGmpounds set forth
herein and an anionic surfactanL in a 1:1. molar ratio, wlthout
interfering witll the .stabili.ty of the soft.ergent product. This
eliminates the need to limit t;he brightener content to a minimal
amount of about 0.3% or less in order to avoid or prevent
instability and the loss of brightening yroperties.
E~amples 10-18
11 l2 13 14 15 16 l7 18
In~radients % ~ ~ % % ~ % % %
C12-15 alcohol
7R0 71 21 21 Zl 21 Zl 21 21 21
TL8-MS 6 6 6 6 6 6 6 6 6
Tinopal ~PA 0 0.4 0.8 0 0.4 0.8 0 0.4 0.8
DBS 5.0 5.0 5.0 6.0 6.0 6.0 7.0 7.0 7.0
Ethanol 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
SXS 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
H20 ---------------balance----------------------
A8inB time
(weeks)4 4 4 4 2 4 2 2 2
tability failed clr. clr.EailedOK clr.fld. fld. fld.
cloudy cloudy
oily
-21-
- : , . .. .
- 1 31 5~3~
These examples clearly show that a Kreater amount of anionic
sllrfactallt (~x 16, 17 and 18) than the cationic quaternary ammonium
compound content, adversely affects the stability of the cvmposition. It
is further shown herein that ~he presence of the optical brightene-. is a
necessary ingredient in the present softergent composition in order to
E-rovide stability to the liquid product. The absence of the optical
brighteners in Examples 10, 13 and 16 resulted in instability.
Examples 19-2?
19 20 21 ~2 23 24 ~5 26 ~7
Ingredients % % ~ % ~ ~ % %
C12-15 Alcohol 21 21 21 21 21 21 21 21 21
1`L8-Ms 7.0 7.0 7.0 8.0 8.0 8.0 9.0 9.0 9.0
Tinopal UNPA 0.4 0.6 0.8 0.4 0.6 0.8 0.h 0.6 0.8
DBS 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8 3.8
Ethanol 6.0 6.~0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
SX~ 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0
H20 --~ -----ba]ance---------------------
Aging time 4 4 2 2 2 2 2 2 2
stability clr. clr.clr. oilyoilyoilyoilyoily oily
OK OK OK phase cldy.cloudy
~ - not stable -----------
These examples show that the alkyl 2-ethyl hexyl dimethyl
quarternary ammonium compound can be used in a liquid softergent
composition in an amount in excess of 6~ by weight, provided a
molar ratio of about 1:1 anioic:quaternary is present, contrary to
the prior art usage of a quaternary softening agent in an amount
-22-
131563~3
of about 4~ by weight, without interferLng with the stability~ofthe composition (Examples l9, 20 and 21). rhere was an
insufficient amount of anionic surfactant with reference to the
amount of the quaternary ccmpound in Examples 22-27. Composi-
tions containing 0.6~ by weight of brightener and 7.0~ by weight
quaternary are stable at 40F up to 4 weeks~
Sometlmes an oily phase is seen if excess anionic is
present, not because of an interaction with quat and brightener,
but rather because of interaction with quat and anionic. A
theoretical model of solution thereof envisions an equilibrium
between ncmer, micelle and precipitate ~cationic-quat-and
anionic-surfactant-). At high enough levels of one species,
micelles form, thereby reducing the free monomer available. This
makes the monomer unavailable for complexing with the oppositely
charged species. The theoretical model is only inadequate i~ a
region when coacervate form~ (a type of gel or oily phase). This
is what w~ see when an oily phase develops on aging when excess
anionic or quat is present. This instability is not caused by
quat brightener interaction, presumably. That is why one should
stay as close as possible to l:l molar ratio. If this ratio is
observed, then, the amount of brightener can probably be pretty
high, also the quat; bu~ the anionic has to go up correspond-
ingly.
A ccnparison of the low temperature stabllity of
compositions containing a tallow 2-ethyl hexyl dimethyl a~monium
compound or the monotallow trimethyl quaternary of the prior art
is set ~orth in Table III.
23
_
.
.
1 31 563~)
l'able III
Low Temperature Stability
TalIow 2-ethylhe~yl quat Brig}ltener Stability at 40 F
% %
6.0 0.4 Passed
6.0 0.8 Passed
7.0 0.4 Passed
7.0 0.6 Paæsed
Tallow trimethyl quat
6.5 0.2 Passed
6.5 0.3 Failed
7.0 0.2 Passed
7.0 0.3 Failed
This table clearly shows the superior stability using greater
level~ of brightener of p~esent novel compositions, heretofore
unobtainable.
It is understood that the foregoing detailed description is
given merely by way of Illustration and that variations may be
made therein without departing from the spirit of the lnvention.
The "Abstract" given above is merely for the convenience of
technical searchers an~ is not to be given any weight with respect
to the scope of the invention.
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