Note: Descriptions are shown in the official language in which they were submitted.
;;
LIQUID DETER~;ENT/SOFTENER COMPOS ITIONS
Larry ~. Hughe
.. . . .. . .. . ... . . .. . . .
,., .~. .... , ~ .
Summary of The Invent1on
The present invention relates to hea~-duty, essen-
tially unbuilt~ stable liquid laundry detergent compositions,
especially beneficial for clean.ing and softening fabrics.
The compositions are heavy-duty liquid detergent comp-
ositions comprising:
(1) from about 5~ to about 20~ of ethoxylated nonionic
detergent surfactant;
; (2) from about 5% to about 20% of a cosurfactant
selected from the group of semipolar nonionic detergent
surfactant, zwitterionic detergent surfactant, and mixtures
thereof;
,, . ~$
~ ~7~2~(D3
- 2 -
(3) from about 2~ to about ~0~, preferably no more
than about 10%, of a cationic -urfactant capable of im-
parting softness andfor antistatic benefits to fabrics;
~ 4) from about 2% to about 10% of a pH buffering agent
to provide a product pH of from about 9.5 to about 12; and
(5) the balance water, perfumes, brighteners, etc.
the total of (1), (2) and (3) being in excess of about
20%, the ratio of (1) to (2) being from about 3:1 to about
1:3, pre~erably from about 1:1 to about 1:2, and the compo- ~
sition containing less than about 5% calcium ion sequester- ii
ing or precipitating detergency builder. -~
~isclosur_ of- The Invention ~-
The compositions of the present inven-tion comprise~ by
weight, from about 15~ to about 70%, prefexably rom about
20~ to about 50%, and mos~ preferably ~rom about 20~ to
abvut 30%, of a mixture of particularly de~ined nonionic,
semipolar or zwitterionic, and cationic suractants in ~he
ratios stated herein. Preferred compositions contain at
least about 3~ of the cationic component, ikself, in order
2~ to assure the presence of a suficient amount to provide the
desired cleaning and ~a~ ic conditioning benefits.
_
The compositions of the present invention contain the
nonionic and semipolar or zwitterionic cosurfactants,
defined more precisely hereinafter, within ratios of non-
ionic to cosurfac-tant of from about 3:1 to about 1:3,
preferably from about 1:1 to about 1:2, most preEerably
about 1:1 in or~er to achieve the best de-~ergency and
softening performance. Preferred composltions may also
contain mixed nonionic surfactant systems.
It is preferred that the compositions of the present
inven-tion are formulated so as to have a pH of at least
about 9.5, preferably from about 10 to about 11, preferably
less than about 12, in the product in order to optimize
their overall cleaning performance. The cleaning results
follow product pH even when the organic buffering capacity
is relati~ely constant. The organic buffering agent is
essential to th~ stability of the product~ Higher pH's
( - 11) do not provide any cleaning improvement while
~f
~il'7~L6D3
-- 3 -- -
increasing safety risks. Alkalinity sources, such as
potassium hydroxide, potassium carbonate, potassium bicar-
bonate, sodium hydroxide, sodium carbonate and sodium
bicarbonate, may be included in the compositions to adjust
the product pH. However, it is essential that the major
alkalinity source comprise an organic buffering agent~
preferably mono-, di-, or triethanolamine, more preferably
monoetha,nola~ine. Monoethanolamine provides a benefit by
its superior ability to solubilize the acids in body soils.
In these systems, surprisingly, overall performance may be
enhanced by varying th~ pH of the product despit~ a rela-
ti~ely constant pH during the laundering p~ocess~ Particu-
larly preferred compositions hava a pH of at least ab~ut 1
in order to optimize the removal of greasy/oil~ and body
soils. In addition to the higher pH in the product, t~ese
preferred compositions should also have the abilit~ to
maintain a pH in the laundry solution o from about 7.5 to
about 10 throughout the washing operation (reserve alkalin-
ity). Such a reserve alkalinity may be obtained by incor-
porating the preferred organic compounds which buffer atpH's of from about 8 to~l, such as monoethanolaminet
diethanolamine or trie-t~anolamine. ~ -
Preerred composltqons of the present in~ention arealso essentially free of oily hydrocarbon materials and
sol~ents, such as mineral oil, paraffin oil and kerosene,
since thesè materials f which are themselves oil~ by nature,
load the washing li~uor with excessive oily material,
thereby diminishing the cleaning effectiveness of the
compositions.
Monionic Component
.
The nonionic detergent surfactants used in the composi-
tions of the present invention are conventional in the art.
Preferred nonionic detergent surfactants are biodegradable
and have the formula R(OC~H4)nOH, wherein R is a primary
alkyl chain containing an average of from about 10 to about
18, preferably from about 10 to abou~ 16, carbon atoms, and
n is an average of from about 2 to about 9, preferably from
about 2 to about 7~ These nonionic surfactants have an HLB
thydrophilic-lipophilic balance) of from ahout 5 to about
.' ~ . .. "
" ,
. . _ _ _ _ _ _ . _ _ _ . _ ~ , _ , _ _ _ . _ _ _ . _ . _ _ . . ~ _ . . . . , , . . . . . . . . . _ . . . _ . , . _ , . , . . . _ . _ , _ _ . _ _ , .
. . . , . . _ . _ _ . .
t
4~P3
14, preferably from about 6 to about 13. HLB, an indicator
of a surfactant's hydxophilic or lipophilic nature, is
defined in detail in Nonionic Surfactants, by M.J. Schick,
Marcel Dekker, Inc., 1966, pages 6~7-613~
Preferred nonionic surfactants for use in the present
invention include the condensation product: of coconut
alcohol with 5 moles of ethylene oxide; the condensation
product of coconut alcohol with 6 moles of eth~lene oxide;
10 the condensation product of C12 15 alcohol wi~h 7 moles o~
- ethylene oxide; the condensation product of C12 15 alcohol
with 9 moles of ethylene oxide; the condensation pxoduct of
C14 15 alcohol with 2.25 moles of ethylene oxide; the
condensation product o C14 15 alcohol with 7 moles of
ethylene oxide; the condensation product of Cg_ll alcohol
with 8 moles o~ ethylene oxide, which is stripped so as to
remove unethoxylated and lower ethoxylate fractions; the
condensation prod~ct of C12 13 alcohol with 6.5 moles of
ethylene oxide, and this same alcohol ethoxylate which is
stripped so as to remove unethoxylated and lower ethoxylate
fractionsO A preferred~lass of such surfactants utilize
alcohols which contai~-~bout 20~ 2-methyl branched isomers,
and are commercially available, under the trademark"Neodol'~
from Shell Chemical Company. The condensation product of
tallow alco~ol with 9 moles of ethylene oxide is also a
preferred nonionic surfactant for use herein. Paxticularly
preferred nonionic surfactants ~or use in the compositions
of the present invention include the condensation product of
coconut alcohol with 5 moles of ethylene oxide, the conden-
30 sation product o~ C12_13 alcohol with 6.5 moles of ethylene
oxide, the condensation product of Clz_l5 alcohol with 7
moles of et~ylene oxide, the condensation pxoduct o~ C14 15
alcohol with 7 moles of ethylene oxide, and mixtures of
those surfactants. In preferred nonionic surfactants the
lower, e.g., the unethoxylated and monoethoxylated alcohols,
are stripped to provide improved performance.
The compositions of the present invention may contain
mixtures of nonionic surfactants falling within the above
nonionic surfactant~definition, such as: a mixture Qf the
... , .; .. .,, .. _ . . . .,, .. . .. . ., . . .. . ................................ , . ........ ._ .. . _ . .. _. ~
... _ .. . .. ,.. _ _ . _. , . , . , . .. . .. . . _ . ., . _ _ . ,, . ., .. , .. ._ .. ... _ . . _ .. . .. . . . .. .
. _
- ~ ,t
~ . _ .. . . , , _ _ .. , . , . _ . _, . . . .. . . . . .
~ ~72~L~3
condensation product of C12 13 alcohol with 6.5 moles of
- ethylene oxide~(Neodol 23-6.5~)~with the condensation product
of C14 15 alcohol with 7 moles of Pthylene oxidel~(Neodol
45-7)",**in a ratio o from ahout 4:1 to 1:4, a mixture of the
condensation product of Cl~ 15 alcohol with 7 moles of
ethylene oxide with'iNeodol 45-7',*~n a ratio of from about
4:1 to ~bout 1:4 preferably about 1:1; or a mixture of the
condensation product of Cg 11 alcohol with 8 moles of
ethylene oxide, stripped to remove lower ethoxylate and non-
ethoxylated fractions, with Neodol 45-7, in a ratio of
higher ethoxylate to lower ethoxylate of from about 1:6 t~ --
about 1:1, preferably about 1:3. ~he present invention can
also contain nonionic surfactants, some o~ which do not ~all
within the above preferred nonionic surfactant deflnit:ion
(such as alcohol ethoxylates having an average of greater
than about 9 ethylene oxide groups per molecule, secondary
alcohol ethoxylates, or alkyl phenol sthoxylates). It is
preerred however that a~ least one of the nonionic sur-
factants contained in the mixture falls within the above
definition of tlle prefe~rred nonionic surfactants. Where the
nonionic surfactant mix~ure-contains a nonionic surfactant
(or surfactants~ which falls outside o~ the above pre~erred
nonionic definition, it is pre~erred that the ratio of the
surfactant (or surfactants) within the definition to that
which is outside the preferred definition be within the
range of from about 1:1 to about 10:1. A specific example
of such a surfactant mixture is a mixture of the conden-
ion produc,t of C12_13 alcohol with 6.5 moles of ethyle~eoxide (e.g., Neodol 23 6.5) and the condensation product of
a secondary C15 alcohol with 9 moles of ethylene oxid~
~e.g.,~Tergitol 15-S-9),' 1n a ratio of lower ethoxylate to
higher ethoxylate nonionic of from about 1:1 to about 6:1;
or a mixture of'~eodol 23-6.5"and the condensation product
of nonyl phenol with 7 moles of ethylene oxide, having a
ratio of"Neodol"to nonyl phenol ethoxylate of a~out 4:1.
Preferred nonionic surfactant mixtures contain alkyl
glyceryl ethers in addition to the preferred nonionic
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.. .. _ ~ ... .. . _ .. ... . _ . . . . ...... _ . . . . . . . . .. _ .. . .... .. .
~ 724~P~
-- 6 --
suractant. Particularly pre~erred are glyceryl ethers
having the formulae
R-OCH2-C~-C~2OH and R-O(CH2cH2O]ncH2cHcH2OH
OE~ . O~I
wherein R is an alkyl or alkenyl group of from about 8 to
about 18, preferably about 8 to 12, carbon atoms or an
al~a~yl group having from about 5 to 14 carbon in the alkyl
chain, and n is from 1 to about 6, togeth~r with the non-
ionic surfactant component of the present i~vention, in a
ratio o~ noni.onic surfactant to glyceryl ether of rom about
1:1 to about 4:1, particularly about 7:3. Glyceryl ethers
of the type useful in the present invention are aisclosed in
U.S. Patent 4,0~8,713, ~ones, issued July 4, 1978a
Other ~onionic surfactants well known in the detergency.
arts may be used, either alone or in combination with one or
more of the preferre~ nionic suractants. Examples of
such surfactants are Lis~ed in U.S~ Patent No. 3,717,630,
Booth, issued February~-20, 1973, and U.S. Patent No. 3,332,880,
Kessler et al, issued July 25, lg67~
Nonlimiting examples of
suitable nonionic surfac~ants which may be used in conjunc-
tion with the required nonionic surfactants, deined above,
axe: polyethyiene oxide condensates o alkyl phenols, such
as thel'Igepal~surfactants, marketed by the GAF Corporation,
and the"Triton"surfactants, marketed by the Rohm and Haas
Coinpany; condensation products o aliphatic alcohols with
from a~out 10 to about 25 moles o~ ethylene oxide, where
those alcohols are o~ a prlmary, branched or secondary alkyl
chain structure; condensation products o ethylene oxide -
with a hydrophobic base formed by the condensation of
propylene oxide with propylene glycol, such as the"Pluronic"***.
surfactants, marketed by Wyandotte Chemical Corpo~ation; and
condensation products o ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylene
`~ * Trademark
** Trademark
*** Trademark
_ .. _, . . .. , .. . , .. _ , .,, , ._ _ _ . _ , . . .. ., . ., .. _ _ . _ _, ,,,, ;,
'
3 ~ ~29~3
-- 7 --
diamine, such as the"Tetronic"surfactants, marketed by
Wyandotte Chemical Corporation.
Another pre~erred group of nonionic surfactants useful
herein comprises a mixture of "surfactant'l and ethoxylated
nonionic "cosurfactant", containing at least one nonionic
surfactant falling within ~he definition of the preferred
nonionic surfactants useful herein, as described in
Canadian Patent No. 1,059,865, Collins, issued
August 7, 1979.
Another preferred mixture o~ nonionic surfactants
omPriSeS C12~13E6.5 a~d C14_1sEO7 in a ratio of 4 1 to
1:4 This mixture pxovides a desirable suds pattern during
the wash and during rinsing as compared to either surfactant
by itself.
Preferred compositions o the present invention are
substantially free (less than about 2~, preferably less than
about 1~, more preferably none) of fatty acid polyglycol
ether di-ester compounds, such as polyethylene glycol-600-
dioleate or polyethylen~glycol 80~-distearate. Such
additives offer no ad~a~tage, and possibly even result in a
disadvantage, in terms-~f achieving the particulate soil
removal and fabric conditioning benefits provided by the
present in~ention.
The Cosurfactant
~a) Zwitterionic detergent surfactant
Zwitterionic surfactants include derivatives of alipha~
tic quaternary ammonium, phosphonium, and sulfonium com-
pounds in which the aliphatic moieties can be straight o~
branch chain~ wherein one of the aliphatic su~stituents
contains from about 8 to 18 carbon atoms and one contains an
anionic, p~eferably carboxylate or sulfonate, water-solubil-
izing gxoup. Particulaxly preferred zwitterionic materials
are the ethoxylated ammonium sulfonates and sulfates dis-
35 closed in U.5. Patent 3,92~,262, Laughlin et alf issued
December 9, 1975; U.S. Patent 3,929,~78, Laughlin et al,
issued December 30, 1975-o
* Trademark
.. , . . . .. , .. . _, _ . .. .. .. ... _ . .. . . . . . _ ........... ... . _, _ _ _,
. .. .
1~7Z~3
8 --
The inclusion
_ .
of these surfactants in the compositions s~lpplement the
excellent clay soil removal performan~e with good body soil
removal and improved softening performance.
Preerred zwitterionic detergents have th~ fonmula:
~2 R2
Rl- N~CH2R S03~ and Rl-N~-CH2R4Coo
R3 13
wherein Rl is an alkyl radical containing ~xom about 10 to
about 18 carbon atoms, R2 and R3 are each selected from the
group consisting o~ methyl, ethyl and hydroxy ethyl xadicals,
R4 is selected from the group consisting o~ alkylene, poly-
alkoxy, and hydroxy alk ~ ne radicals, preferably methylene~
ethylene, polyethoxy, ~y~roxy ethylene and propylene rad-
icals and said hydroxyL~groups are attached only to second-
ary carbon atoms.
23 Specific examples include:
(a) Betaine examples include N-coconut alkyl betaine;
N-hexadecylbetaine; 6(N-hexadecyl-N,N-dimethylammonio)-
hexanoate; N-(2-coconutamido)ethylbetaine; and (N-hexadecyl-
N,N-dimethylammonio)-3,6-dioxa-nonanoate.
(b) Sultaine detergents of particular interest are
those in which the long alkyl chain (Rl) is a speci~ic C10-
C18 alkyl or a mixture of alkyl chains derived from natur-
ally occurring substances, whether hydrogenated or not~ and
the short alkyl chains are methyl gxoups. Fox instance,
where Rl is derived from tallow or coconut oil, R4 is an
ethylene radical with a hydrox~l group substituted on the
middle carbon atoms of the CH2R4 ~rouping, and R2 and R3 are
methyl groups, the sultaine detergent is of particular
interest. Other specific éxamples o~ preferred sultaine
, . .... ...............
- . ................ .. .
.. .:
_ g- ~L~72~
detergents include 3~(N,N-dimethyl-N-hexadecylammonio)-
2(polyethoxy)-ethane-1-sulonate, 3-(N,N-dimethyl-N-hexa-
decyla~onio)-propane-l-sulfonate, 2-(N-methyl-N-ethyl-N-
decylammo~io)-ethane-l-sulfonate, 4-(N,N-diethyl-N-tetra-
decylammonio)butane-l-sulfonate, 4-[N,N-di(2-hydroxyethyl)-
N-octadecylammonio]-2-hydroxy butane-l-sulfonate, 2-[N,N-
di(2-hydroxyethyl)-N dodecylammonio]-ethane-l-sulfonate, 4-
tN-methy~-N-(2-hydroxyethyl)-N-hexadecylammonio~-3-hydr
butane-1-sulfonate, and 3-(N,N-dimethyl-N-hexadecylammonio)
10 2-hydroxypropane-1-sulfonate. Other specific examples -
include compounds wherein different long alkyl chains are - -- -~
used to provide the corresponding decyl, dodecyl, tetra~-
decyl, hexadecyI, and octadecyl homologs o~ the above
compounds such as 3-~N,N dimethyl-N~tetradecylammonio)-
propane-l-sulfona~e, 3-(N,N-dimethyl-N-octadecylammonio)-
ethane~l sulfonate, etc. Still other specific examples
include compounds where the short chains substituted on the
nitrogen atom in the above compounds are replaced by the
corresponding methyl, eth~l and hydroxy ethyl groups to
2~ providè the corresponding homologs of the above compounds.
~c~ Semipolar noni ~ic suxfactants
Generically these surfactants have the formula
R (R ~n~~~~
wherein X is N, S, or P with n being 2 when X is ~ or P and
1 when X is S, Rl is a long chain hyarophobic group and each
R2 is a short chain h~drophobic or hydrophilic group.
Pre~erred are surfactants having the formula:
R6 . '.
R5-N~ O
R
wherein R is an organic radical containing from about l0 to
about 24 carbon atoms, containing from 0 to about 3 ether
linkages, containing from 0 to 1 hydroxy ~roup, and having
one alkyl moiety which contains from about 10 to about 18
carbon atoms and no ether linkages; R6 and R7 are each
~,
.. . .. . .... ,_ . . ~_ .. __ .. ,. _ .. . ... ... . .. . .... _.. _ ...... ... . . . .... ... .. . .
~t7Z4~3
-- 10 --
selected from the group consisting of me-thyl, ethyl, hydroxy
ethyl, propyl and hydroxy propyl radicals.
Specific examples include: .
dimethyldodeoylamine oxide, dimethyltetradecylamine oxide,
ethylmethyltetradecylamine oxide, cetyldimethylamine oxide,
dimethylstearylamine oxide, cetylethylpropylamine oxide,
diethyldodecylamine oxide, diethyltetradecylamine oxide,
dipropyl~odecylamine oxlde, 3,6,9-~rioxaheptacosanyldi-
methylamine oxide, b.is-(2-hydroxyethyl)dodecylamine oxide, ~.
10 an amine oxide prepared from an amine containing two 2- . -
hydroxyethyl groups and a long chain group which is derived ~
from the condensation product of coconut alcohol and three
moles o~ ethylene oxide, bis-(2-hydroxyethyl)-3-dodecoxy-2-
hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecyl-
amine oxide, dimethyloleylamine oxide, dimeth~l-(2-hydroxy-
dodecyl)amine oxide~
The C12-C14 dimethyl or bis-~2-hydroxye-thyl) homologs
of the above compounds are preferred. . Other examples
include those compounds wherein the short alkyl chains in
the above compounds are each replaced by the methyl, ethyl,
hydroxyethyl, propyl and_hydroxy propyl radicals to form
homologs of the abo~e c~mpounds. Still other examples
include those compounds wherein decyl, dodecyl, tetradecyl,
hexadecyl, and octadecyl hydrocarbon groups replace the long
alkyl chains in the above compounds to form the correspond-
ing homologs of the above compounds.
Cationic Compon~nt
The cationic surfactants used in the compositions of
the present invention are pre~erably of the di-lony chain
quaternary ammonium type, having two cha.ins each of which
contains an average of from abou-t 10 to about 22, preferably
from about 16 to about 18, carbon atoms. The remaining
groups, if any, attached to the quaternary nitrogen atom,
are preferably Cl to C4 alkyl or hydroxyalkyl groups.
35 Although it is preferred that the long chains be alkyl
groups, these chains may contain heteroatoms or other
linkages, such as hydroxy groups, double or triple carbon-
... ... .... .... . . . . ...
Z~3
carbon bonds, and ester, amide, or ether linkages, as longas each chain falls within the carbon atom ranges required
given above. Pre~erred cationic surfactants are those
having the formula
R
R4-N+-R2 X~
Rl
whçrein.the Rl and R~ groups contain an average of from
about 16 to about 22 carbon atoms, preerably as alkyl . -.
groups, and most pre~erably contain an aYerage of from about . .
16 to about 18 carbon atoms, R3 and R4 are Cl to C~ alkyl or
hydroxyalkyl groups, and X is any compatible anion, par.ticu-
larly one selected from.the group consisting oE halider
hydroxide, methylsulfate, or acetate anions.
Mixtures o~ the above surfactants are also.useful in
the present invention. Other cationic sur~actants include
sulfonium, phosphonium, and mono- or tri-long chain ~uat
ernary ammonium materials, as long as the amount of required
cationic sur~actant is= ~ sent.
Examples of cationic surfactants which may be used
include those described in U.S. Patent No. 4,259,217,
Murphy, issued March 31, 1981, and Cockrell's U.S.
Patent 4,222,905 issued September 16, 980.
Preferred cationic surfactants include dital~owalkyl-
dimethyl tox diethyl ox dihydroxyethyl) ammonium chloride,
ditallowalkyldimethylammonium methyl sulfate, dihexadecyl-
alkyl (C16; also known as distearyl) dimethyl (or diethyl,
or dihydroxyethyl) ammonium chloride, dioctadecylalkyl
(C18)- dimethylammonium chloride, dieicosylalkyl-(C20)
dimethylammonium chloride, or mixtures of those sur~actants.
Particularly preferred cationic suractants are ditallow-
alkyldimethylammonium chloride, ditallowalkyldimethyl-
ammonium methyl sul~ate, and mixtures of those sur~actants,
with ditallowalkyldimethylammonium chloride being especially
preferred. ...
J`~ J
'
_ ... .. . _. .. __ ,_ _~.. __,~ __~ _ _ __.__ _ _. _ .. __ _ .. _ . ~ .. _ .. _ _ .. _.. _ .. __ _. A .. .. __ ._.. ---- -- ' --
_ .. . _ _ _. . _~ ~ __ _ .. _ ., _. ______ ._ _ _ _ _ . . _ . ... _ .. ~ .. _ .. _ . . _ ... _ .. _ __ _ _ __ _ _ _ _. _ . __ . _ _ . .. _ .. __ . _ _ _ ~ . _ .
_.. ~_
~7;~Q3
- 12 -
Another particularly useful class of cationic surfac
tant is that in which the two long chains of the cationic
surfactant contain a significant amount of unsaturation,
such as where at least about 20~/ preferably at leas* about
30%, of the long chains contain at least one double bond.
By increasing the percentage of chains containing the double
bonds, t-he performance benefits of these cationic materials
are increased. Compounds of this type have the formula
R3
R4 - N~ - R2 - ~
I
Rl
wherein Rl and R2 contain an average of from about 16 to
a~out 22 ~most preferahly from about 16 to about 18) carbon
atoms, and at least about ~0~ of these chains contain at
least one double bond; R3 and R4 are Cl to C4 alk~l or
hydroxyalkyl groups, and X is any compatible anion, particu-
larly one selected from the group consisting of halide,
hydroxide, methylsulfat ~or acetate anions. Thus, ox
example, a preferred cationic surfactant is di-partially
hydrogenated tallow dimethylammonium halide (especially
chloride or methyl sulfate), which is also known as di~
softened tallowalkyl dimethylammonium halide. A commer-
cially available compound o~ this type is Adogen 470,*sold
by ~shland Chemical Company, wherein about 30~ of the tallow
chains are oleyl in character. Another method of fo~ning
similar cationic materials is to synthesize a di-oleyl
quaternary ammonlum compound and hydragenate it to the level
of unsaturation desired. Compositions made with these
cationics show several significant advantages over those
made with more conventional cationics (such as ditallow-
alkyldimethylammonium chloride, only about 2~ of the long
chains of which contain double bonds); particularly ~hese
compositions show improved particulate soil removal,
especially at low wash temperatures, improved static control
and remain in a stable single phase at temperatures down to
about 40F.
* Trademark
i
.. ~ .. .. . , . ... . . . , ~ .. . . . ...
~1 ~7;~3
- 13 -
-
The cationics of this invention are preferably low in
unquaterni7ed amine content. ~lso, for odor reasons, it is
preferable to use a solvent f~r the amine quaternization
reaction which does not have an objectionable odor, e.g., a
liquid nonionic detergent material, ethyl alcohol, etc.
Prefexably, the compounds in the formula should be
stable, especially under the specific pH conditions.
The compositions of the present invention are prefer~
ably formulated so as to be substantially free of ethoxy-
lated cationic surfactants which contain more than anaverags of about 1~, and preferably ~ree of those which
contain more than an average of about 7, moles of ethylene
oxide per mole of surfactant. ~hese compounds tend to be
relatively non-biodegradable. It is to be noted that
polyethoxylated cationic surfactants having relatively low
le~els of ethoxylation, i-.e., those with less than 10, and
particularly less than 7, ethylene oxide groups exhibit
better biodegradability ~ aracteristics and may be advan-
tageously included in t~ co~positions of the present
invention.
The compositions of the present invention may also
contain additional ingredients generally found in laundry
detergent compositions, at their co~ventional art-estab--
lish~d levels, as long as these ingredients are compatible -^
with the nonionic and cationic components required herein.
For example, the compositions may contain up to about 15~,
prefera~ly up to about 5~, and most preferably from about
0.001 to about 2~, of a suds suppressor component. Typica-l
suds suppressors useul in the compositions of the present
invention include, but are not limitea to, those described
below.
Preferred silicone-type suds suppressing additives are
described in U.S. Patent 3,933,672, issued January 20, 1976,
Bartolotta et al. The
silicone material can be represented by alkylated poly-
siloxane materials such as silica aerogels and xerogels and
_ ._., . __ __ .. ..... _ ._ .. , . . .. . _ . , . _ _ _ , , ,, ~
.... . . .. . . . .. . .
~Z~
- 14 -
hydrophobic silicas of various types. The silicone material
can be described as a siloxane having the formula:
~ sio~
I Jx
~ R'
wherein x is from about ~0 to about 2,000, and R and R' are -~
each alkyl or aryl groups, especially methyl, ethyl r propyl,
butyl and phenyl. Polydimethylsiloxanes ~R and R' are
methyl, having a molecular weight within the xange of ~rom
ab~ut 200 to about 200,000, and higher, are all use~ul as
suds controlling agents. Additional suitable silicone
materials wherein the side chain groups R and R' are alkyl,
aryl t or mi~ed alkyl and aryl hydrocaxbyl groups exhibi~
useful suds contxolling properties. Examples of such
ingredients in~lude dieth~ -, dipxopyl-, dibutyl-, methyl-
ethyl-, phenylmethyl-pol~siloxanes and the like. Additional
useful silicone suds co~roll-ing agents can be represented
by a mixture of an alkylated siloxane, as referred to
hereinbefore, and solid silica. Such mixtures are prepared
by affixing the silicone to the surface of the solid silica~
A preferred silicone suds controlling agent is represented
by a hydrophobic silanated (most preferably trimethylsila-
nated) silica having a particle size in the range ~rom about
lO millimicrons to 20 millimicrons and a specific surface
area above about 50 m2~gm intimately admixed with dimethyl
silicone fluid having a ~olecular weight in the range from
about 500 to about 200,000 at a weight ratio of silicone to
silanated silica of from about l9:1 to about 1:2. The
silicone suds suppressing agent is ad~antageously releasab?y
incorporated in a water-soluble or water-dispersible, sub-
stantially non-surface-active, detergent-impermeable carrier.
Particularly useful suds supp~essors are the self-
emulsifying silicone suds Cuppxessors~ described in U.S.
Patent 4,136,045, Gault et al, issued Januaxy 23, 19790
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- 15 -
An example of such a
compound is DB-544* commercially available from Dow Corning,
which contains a siloxane/glycol copolymer together with
solid silica and a siloxane resin.
Microcrystalline waxes having a melting point in the
range f,rom 35C-115C and a saponiication value of less
than 100 represent additional examples o a preferred suds
regulating component for use in the subject compositions,
and are described in detail in U.S. Patent 4,056,481, Tate~
issued November 1, 1977~ r_ ~ ~
The microcrystalline waxes axe substantially water-insolu-
ble, but are watex-dispersible in the presence of organic
surfactants. Preferred microcxystalline waxes have a
melting paint from about 65C to 100C, a molecular weight
in the range fxom 400-1,000; and a penetration value oE a~
Ieast 6, measured at 77F by ASTM-D1321. Suitable examples
of the above waxes include: microcrystalline and oxidized
microcrys~alline petrolatum waxes; Fischer-Tropsch and
oxidi~ed Fischer-Trop~ç~~waxes; ozokerite; ceresin; montan
wax; beeswax; candelil~, and carnauba wax.
Alkyl phosphate esters represent an additional pre-
ferred suds suppressant for use herein. These preferred
phosphate esters are predominantly monostearyl phosphate
which, in addition thereto, can contain di- and tristearyl
phosphates and monoleyl phosphates, which can contain di-
and trioleyl phosphates.
The alkyl phosphate esters frequently contain some
trialkyl phosphate Accordingly, a preferred phosphate
ester can contain, in addition to the monoalkyl ester, e.~.
monostearyl phosphate, up to about 50 mole percent of
dialkyl phosphate and up to about 5 mole percent of trialkyl
phosphate.
Fatty acids are an additional preferred suds suppress-
ant herein. Examples include coconut, tallow, and marine
fatty acids having chain lengths of from about 10 to about
30 carbon atoms.
Other adjunct components which may be included in the
,
* Trademark
~.
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7~Q3
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compositions of the present invention, in their conventional
art-established levels for use (i.e., from about 0 to about
40%), include bleaching agents; bleach activa-tors; soil
release agents ~particula~ly copolymers of ethylene tere-
phthalate and polyethylene oxide terephthalate, such as~lilease T ~old by ICI, United Statesi as disclosed in U.S.
Patent No. 4~132l680r Nicol, issued January 2, 1979;
soil suspending
agents; corrosion inhibitors; dyes; fillers; optical bright-
eners; germicides; pH adjusting agents; alkalinity source~;hydrotxopes; enzymes; enzyme-stabilizing agents; perfumes;
solvents; carriers; suds modifiers, opacifiers; and the
like. However, because o~ the numexous and di~erse per-
, formance advantage~ of the present invention, co~ventional
components, such as hydrotropes and deter~enc~ builders,will not be necessar~, giviny the compositions of the
present invention an advantage over con~entional deter-
gent/softener compositions. In fact, the compositions o~
the present invention give outstanding cla~ removal per-
formance, even in a bu-EIder~free environment, and across a
range of water haraness-conditions. Therefore, for en-
vironmental reasons the compositions of the present inven
tion contain less than about 5% se~uestexing aetergency
builders. Preferred compositions are totally ~ree o
phosphate matexials, without decreasing the pe~formance o~
the compositions. Further, in oxder to achieve optimal
particulate soil removal performance, the compositions of
the present invention contain less than about 5%, and are
preferably substantially free of, silicate materials.
Preferred compositions of the present invention are also
substantially free of carboxymethylcellulose in orde~ to
optimize the clay removal performance!of the system.
Finally, while the compositions of the present invention ca~
contain small amounts of anionic materials, such as anionic
surfactants and hydrotropes (e.g., alkali metal toluene
sulfonatesJ, it is preferred that particular anionic
materials be contained in amounts sufficiently small such
* Trademark
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7~3
- 17 -
that not more than about 50%, preferably not more than about
15%, and most preerably none o~ the cationic sur~actant,
contained in the laundry solution, is complexed by the
anionic material. Such a complexing of the anionic material
5- with the cationic surfactant, decreases the overall cleaning
and fabr,ic conditioning performance of the composition.
Compositions of the present invention may contain from
about 0.005% to about 3%, prefexably ~rom about 0.01% to
about 1%, of an optical briyhtener. Nonionic brighteners
10 .are preferred because of their compatibility with the . .
nonionic and cationlc surfactants utilized.herein. Suitable
and preferred bxlghteners are disclosed.in Coward 2t al.'s
U.S. Patent 3,537,g93 issued November 3, 1970,
i~
Nonionic brighteners include tho~e of the
coumarin and benzoxazo~.classes;-a particularly preferred
brightener being 4-me~ 7-diethyl amino coumarin, commer-
cially available under the trad~E~ks"Tinopal SWW"from Ciba-
Geigy Corp., Ardsley, N.Y.,"Hiltamine Arctic ~hite SOL',
a~ailable from Hilton-Davis Chemical Co., Cincinnati, Ohio,
and'.'Calcofluor White SD".available-from.American Cyana.mid,
2S Wayne, N.J. Other brighteners useful herein include bis-
(benzoxazol-2-yl)triophenes, 1,2-bis(benzoxazol~2-yl)ethy-
lenes, 1,4-bis~benzoxazol-2-yl)naphthalenes, 4,4'-bis
(benzoxazol-2-yl)-s~ilbenes, 2-~styxyl)benzoxazoles, 2
(styryljnaphthoxazole, or 2-(4-phen~lstilben-4'-yl)-5-
tertbutyl benzoxazole.
Preferred compositions of the pressnt invention can
contain from about 0.05% to about 1.5%, pxeferably from
about 0.05% to about 1~, and most preferably rom about 0~1%
to about 0.8%, of polyacids capable of orming water-soluble
calcium complexes, such as organo-phosphonic acids, particu-
larly alkylene-polyamino-polyalkylene phosphonic acids.
These materials include ethylenediamine tetramethylene
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- 18 - .
phosphonic acid, hexamethylene diaminetetramethylene pho~-
phonic acid, diethylene triaminepentamethylene phosphonic
acid, and aminotrimethylene phosphonic acid.
Other preferred embodiments of the present invention
include an alkaline proteolytic enzyme having an isoelectric
point of,greater than about 8. The enzyme is present in an
: amount from 0.001% to about 2%, preferably from about 0.005%
to about 0~8%, especially from about 0.02~ to about 0.2%,
and axe particularly useful.when usea in conjunction with
- . 10 the polyacids, described above~ The most preferred proteo-
: lytic enz~me preparations for use in this invention are
- derived from bacillus subtilis, such asl'~lcalase', manu-
factured by No~o Industri A/S, and"Maxatase', manufactuxed by
. GistBrocades N.~. These most preferred enzyme specie~ have
an isoelectric point in the range from about 8.5 to a:bout
9~2.
.: These polyacid and.enzyme components, as well as the
j beneits they provide, are discussed in detail in U.S~
Patent 4,100,262, ~rnau~ alï issued August 29, 1978, and
20 U.S~ Patent 4,111,855, -~rrat et al, issued September 5,
1978, - :: .
Compositions which include these components are particularly
il; .,
useful for the hand-laundering of fine fabrics, such as
- wool.
. 25 In a particularl~ preferred embodiment, the composi-
: tions of the present invention contain up to about 20% of a
lower alkyl (Cl to C4) alcohol, particularly ethanol.
The compositions of the present invention are used in
the laundering process by for~ing an aq~eous.solution con--
taining from about 0.01 (lOQ parts per million) to about
0.3% (3,000 parts per million), preferably from about 0.03~
to about 0.2%, and most pre~erably from abou~ 0.05. to about
: 0.15%, of the organic detergent surfactant mixture, and
agitating the soiled.fabrics in that solution.. The fabrics
are then rinsed and dried. When used in this manner, the
compositions of the present invention yield exceptionally
good detergency and also provide fabric softening, static
* Trademark
** Trademark.
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.
- control, color fidelity, and dye transfer inhibition to the
laundered fabrics, without requiring the use of any of the
other conventionally-used fabric softening and/or static
control laundry additives.
All percentages, parts, and ratios used herein are by
weight u,nless otherwise speciied.
The following nonlimiting examples illustxate the ,
compositions and the method of the present invention.
EXAMPLES
10 , I II III IV V VI ~II VIII
~ :;
C12 5 alkyl
polyethoxylate
(6.5) 4.5 6.0 9.012.0 13.5 9.020.0 4.5
C 2 alkyl di-
~ethylamine
oxide 13.5 12.0 9.06.0 4.5 9.020.0 4.5
Citric acid ~ 5.0 - 5.0
Ditallowalkyl-
;~ dimethyl ammon- -
ium chloride 4.0 4.0 4.04.0 4.0 4.0 4.0 4.0
Ethyl alcohol 6.0 ~ - 6.06.0 6.0 - 6.0 6.0
-; Monoethanol- -~ -
amine 3.6-3~6 3.63.6 3.6 3.6 3.6 3.6
.
Water and
minors Balance
;~ The compositions of Examples I, III, IV, and V were
tested in a conventional top-loading automatic washing
; machine using 5-1/2 pounds of soiled laundry and test
; swatches in 17-1/2 gallons of water at 95F. One set of
swatches was washed in water with 2 grains hardness and
another set was washed in water of 6 grains hardness and the
results averaged.
The clay removal grades given are the average of the
two hardnesses and three fabric swatch types (cotton,
~ 35 polyester and polyester/cotton~ in Hunter Whiteness units
; versus a control which con-tained 24% of a mixture of non-
io~ic surfactantS (C12~13 E6,5 and C14-15 E7)
the cationic surfactant.
~ The facial soil removal grades are the average of the
':~
.. . . . . .
~ . _
.
il~ 3
- 20 -
.
different hardness treatments in which the swatches are
split and one half is washed in the treatment while the
other half is washed in the control product. Skilled
graders compare the two ~alves using a 0-4 scale in which 0
represents no di~ference and 4 represents a very large
difference.
Sof-tness is ranked against the control by skilled
graders using the same 0-4 scale.
The results are as follows:
Nonionic to Clay Facial Soil Fabric -~-
Fxample Ratio ~emoval Removal Softness
V 3:1 -G.60 -0.96 ~0.73
III 1:1 -0.30 ~1.23 ~1~62
II 1:2 -6.25 ~0.44 ~2~01
I 1:3 -9.25 ~0.72 ~2.37
Reads: (-), test pxoduct was poorer than control
~+), test product was better than control
, . . .
As can be seen fr ~ the above, increasing the semipolar
nonionic surfactant (or_~zwitterionic surfactant) improves
the facial swatch cleaning and so~tening despite the use of
less cationic surfactant. However, surprisîngly, the lower
levels give the same superior clay removal and the highex
levels (~1:1) do not give an unacceptable reduc-tion in clay
removal.
When, in the above example, 3(lauryldimethylammonio)-2-
hydroxypropane-1-sulfonate is substituted for the amine
: oxide Ind/or diethanolamine or txiethanolamine is substi--
tuted for the monoethanolamine, substantially equivalent
results are obtained.
Similar cleaning results are obtained when the cationic
suractant in Compositions I-VXII is replaced, in whole or
; in part, by ditallowalkyldimethylammonium methyl sulfater
ditallowalkyldime-thylammonium iodide, dihexadecylalkyl-
dimethylammonil~m chloride, dihexadecyla~kyldihydroxylethyl-
ammonium methyl sulfate, dioctadecylalkyldimethylammonium
chloride, dieicosylalkyl methyl ethyl ammonium chloride,
. .. . ..... . . . . ...... .. ....
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- 21 -
dieicosylalkyl dimethylammonium bromide, or mixtures of
these surfactants.
Substantially similar results are also obtained where
the nonionic surfactant in Compositions I-VIIX is replaced,
in whole or in part, by the condensation product of C14 15
alcohol with 2.25 moles of ethylene oxide; the condensation
product of C14 15 alcohol with 7 moles of ethylene oxide;
the condensation product of C12 15 alcohol with 9 moles of
ethylene oxide; the condensation product of C12 13 alcohol -
with 6O5 moles of eth~lene oxide, which is stripped so as to
remove lower ethoxylate and nonethoxylated ractions; the
condensation pxoduct of coconu-t alcohol with 5 moles o~
ethylene oxide; the condensation product of coconut alcohol
with 6 moles of ethylene oxide; the condensation product of
C12 15 alcohol with 7 moles of ethylene oxide; the conden-
sation product of tallow alcohol with 9 moles of ethylene
oxide; a 1:1 by weight mixture o the condensation product
of C12 15 alcohol with 7 moles of ethylene oxide and the
; condensation product of ~l4 15 alcohol with 7 moles of
ethylene oxide; and othe=r mixtures of those surfactants.
Similar performanc~ is also obtained where there is
about 1% of a suppressor component in the above compbsition
selected from the group consisting of dimethyl-, diethyl-,
dipropyl-, dibutyl-, methyle-thyl-, phenylmethyl polysil-
oxane, and mixtures thereof; a petrolatum or oxidized
petrolatum wax; a Fischer-Txopsch or oxidized Fischer-
Tropsch wax; ozokerite; ceresin; montan wax; beeswax;
candelilla; or carnauba wax.
EXAMPLE IX
The product oE Example III was formulated at product
pH's of 7.5, 8.5, 9.5, 10.5, and 11~5 using acetic acid and
NaOH to adjust the pH. These products were tested as
hereinbefore described. For facial swatch soil, the results
were as follows, with the product having a pH of 7.5
arbitrarily assigned the role of the control.
Facial Soil
Removal
- 7.5- 0 -
.. ... ___. _~_._ .. _ .. _ ... . _ .. . . . . ......... .,.. _ .. . . .... .... . _ _ _ _ . .. .... .. . . ....
2~!~P3
- 22 -
,
8.5 ~0.30
9.5 ~0.90
:~ 10.5 ~1,88
11~5 ~1.83
Softening results and clay c:Leaning were essentially
unaffected and stains were affected in various ways with the
overall result being an improvement with pH on stains
considered more important.
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