1299962
LIQUID DETERGENT COMPOSITION
Eugene J. Pancheri
Young S. Oh
and
Rodney M. Wise
Technical Field and Background Art
The invention relates to aqueous high sudsing liquid deter-
gent compositions containing specified amounts and types of
surfactants especially useful in the washing of tableware,
kitchenware and other hard surfaces.
~he compositions of this invention have superior ability to
handle grease.
The performance of a deterger~t con position for cleaning
tableware and kitchen utensils is evaluated by its ability to
handle grease. The detergent solution shou~d readily remove
grease and minimize its redeposition.
There is continuing need for impro~lred compositions and
- - methods wmch can be emplayed during, dlshwashing operations to ~
- ~ - improve the appearance o~ kitchen-utensifs and articles. Such
compositions and methods should provide improved removal of
grease in conventional dishwashing soil removal operations while
maintaining the sudsing attributes of an acceptable dishwashing
detergent composition.
Summary of the Invention
The present invention comprises a high sudsing liquid deter-
gent composition containing by weight:
(a) from about 5% to about 50% anionic surfactant;
(b) from about 0.19~ to about 12% of polymeric surfactant
having the formula sel,ected from,the group consisting -
- of AnBAm, BnP~Bm, BA, B and mixtures- thereof
- 30 wherein each B Is a hydrophobic group, each A is a
- ~ hydrophi!ic group; each n and m are either 0 or an
integer from one to about 50; the sum of n + m is from
one to about 50; the molecule contains from about 5 to
about 1,000 ether linkages; when the formula is BA, B
contains from about 5 to about 500 ether linkages; when
the formula is B, the ratio of -CH2- groups to ether
.,
- 1299962
linkages is at least about 2.1:1 and less than about
3:1; the molecular weight is from about 400 to about
60 000; and the percentage of tC2H4O~ groups in the
molecule is less than about 90%;
s (c) from 0% to about 10~ of a suds stabllizlng nonionic
surfactant selected from the group consistlng of fatty
acid amides trialkyl amine oxides and mixtures thereof;
(d ~ from 0% to about 10% of a detergency builder selected
from inorganic phosphates inorganic polyphosphates
inorganic silicates and inorganic carbonates organic
carboxylates organic phosphonates and mixtures
thereof;
le) from 096 to about 15% alkanol containing from one to
about six carbon atoms; and
(f) from about 20~ to about 90% water said composition
containing sufficient magnesium ions to neutralize at least.
- ~ about 10% of said anionic-surfactant when less than-about ~0%
of the anionic surfactant is an~ alkylpolyethoxylate sulfate
surfactant containing from about ~ to about ten ethoxy
groups per molecule on the average (or there is no betaine
surfactant present); said composition having a pH of greater
than about six when the composition contains said
alkylpolyethoxylate sulfate surfactant; said composition
having a viscosity of greater than about 100 cps or being
substantially free of alkylpolyethoxylate detergent
surfactants when the amount of anionic surfactant is less
than about 20% (and there is no betaine surfactant present).
Dishware glassware and ~ther tableware and icitchenware
are . washed in water- soluttons of the detergent composition -
- 30 generally at a weight concentration of from~aboutØ05% to.about
0.4% of tfie composition in water at-a temperaturq of from about
60F to about 120F.
Detailed Descri tion of the Invention
P
The liquid detergent compositions of the present invention
contain two essential components:
1299962
-- 3 --
(a) anionic surfactant which when there is no betaine
surfactant present is either a magnesium salt andl or
an alkylpolyethoxylate sulfate containing an average of
from about ~ to about ten ethoxy groups per molecule,
said average being computed herein by treating any
alkyl sulfate surfactant as an alkylpolyethoxylate sulfate
containing 0 ethoxy groups, as described hereinbefore,
to provide good sudsing, and preferably a low
interfacial tension; and
(b~ the polymeric surfactant, which improves grease
handling .
Optional ingredients can be added to provide various perfor-
mance and aesthetic characteristics.
Anionic Surfactant
The compositions of this invention contain from about 5% to
about 50% by weight of an anionic surfactant or mixtures thereof
- - ~ preferably~con,srising at least ~about-5%,-more preferably- at~least
about 8%, and most preferably more than about 1096 of an alkyl
polyethoxylate (polyethylene oxide) sulfate having from about 10
to about 20, preferably from about 10 to about 16 carbon atoms in
the alkyl group and containing from about ~ to about t0,
preferably from about 1 to about 8, most preferably from about 1
to about 6 ethoxy groups on the average. Preferred compositions
contain from about 20% to about 40% of anionic surfactant by
weight.
Most anionic detergents can be broadly described as the
water-soluble salts, particularly the alkali metal, alkaline earth
- metal, ammonium or amine ~ salts, of organic sulfuric reaction
products having In their molecular structure an~ alkyl radical
~ 30 containing from about 8 to about 22 carbon atoms and a radical
- selected from the group consisting of sulfonic acid and sulfuric
acid ester radicals. Included in the term alkyl is the alkyl
portlon of acyl radicals. Examples of the anionic synthetic deter-
gents which can form the surfactant component of the composi-
tions of the present invention are the salts of compatible cations,
i299962
-- 4 --
e.g. sodium, ammonium, monoethanolammon3um,
diethanolammonium, triethanolammonium, potassium and/or,
especially, magnesium cations with: alkyl sulfates, especially those
obtained by sulfating the higher alcohols (C8-C18 carbon atoms),
5 alkyl benzene, or alkyl toluene, sulfonates, in which the alkyl
group contains from about 9 to about ~ 5 carbon atoms, the ali~yl
radical being either a straight or branched aliphatic chain;
paraffin sulfonates or olefin sulfonates in which the alkyl or
alkenyl group contains from about 10 to about 20 carbon atoms;
10 sodium C10 20 alkyl glyceryl ether sulfonates, especially those
ethers of alcohols derived from tallow and coconut oil; coconut oil
fatty acid monoglyceride sulfates and sulfonates;
alkylphenolpolyethylene oxide ether sulfates with from about 1 to
about 10 units of ethylene oxide per molecule on the average in
15 which the alkyl radicals contain from 8 to about 12 carbon atoms;
- the reaction prpducts of fatty acids esterified with is~th\onic acid
--- ~ where-, for=example, the fatty acids are deri~ed from coconut oil,
fatty acid amides of~a methyl tauride in which the fatty acids, for
example, are derived from coconut oil; and beta-acetoxy- or
20 beta-acetarrido-alkanesulfonates where the alkane has from 8 to 22
carbon atoms.
Specific examples of alkyl sulfate salts which can be em-
ployed in the instant detergent compositions include sodium,
potassiùm, ammonium, monoethanolammonium, diethanolammonium,
25 triethanolammonium, and magnesium: lauryl sulfates, stearyl
sulfates, palmityl sulfates, decyl sulfates, myristyl sulfates,
tallow alkyl sulfates, coconut alkyl sulfates, C12 15 alkyl sulfates
- and mixtures of these surfactants. Preferred alkyl sulfates
- Include the C12_15 alkyl sulfates.
- 30 Suitable alkylbenzene, or alkyltoluene, sulfonates include the-
alkall metàl (llthiun~, sodium, andlor potassium), alkaline earth
(preferably magnesium), ammonium and/or alkanolàmmonium salts
of straight, or branched-chain, alkylbenzene, or alkyltoluene,
sulfonic acids. Alkylbenzene sulfonic acids useful as precursors
35 for these surfactants include decyl benzene sulfonic acid, undecyl
129~962
benzene sulfonic acld, dodecyl benzene sulfonlc acld, tridecyl
benzene sulfonic acid, tetrapropylene benzene sulfonic acid and
mixtures thereof. Preferred sulfonic acids as precursors of the
alkyl-benzene sulfonates useful for compositions herein are those
s in which the alkyl chain is linear and averages about 11 to 13
carbon atoms in length. Examples of commercially avallable alkyl
benzene sulfonic acids useful in the present invention include
"Conoco"SA 515 and SA 597 marketed by the Continental Oil Com-
pany and "Calsoft LAS 99" marketed by the Pilot Chemical Compa-
10 ny.
The preferred anionic surfactants herein, which are essentialif there are no, e.g., magnesium ions or betaine surfactant
present, are alkylpolyethoxylate sulfates having the formula
RO(C2H4O)xSO3M wherein R is alkyl, or alkenyl, of from about
15 10 to about 20 carbon atoms, x is rom about ~ to about ten on
- the average, treating alkyl suifates as if they had 0 ethoxy
- - groups, pre~erabiy fronr about ~ to about eight-, most preferabiyfr~m about one to about six, and M is a water-soluble compatible
cation such as those disclosed hereinbefore. The
20 alkylpolyethoxylate sulfates useful in the present invention are
sulfates of condensation products of ethylene oxide and mono-
hydric alcohols having from about 10 to about 20 carbon atoms.
Preferably, R has 10 to 16 carbon atoms. The alcohols can be
derived from natural fats, e.g., coconut oil or tallow, or can be
25 synthetic. Such alcohols can be reacted with from about ~ to
about 20, especially from about one to about 14, and more
especially from about one to about eight, molar proportions of
ethylene oxide and the resulting n~ixture of molecular species is
- sulfated and neutralized. - -
There should be more than about 10%, preferably more than
about 15% of such molecules~ containing one to lO ethoxilate
groups calculated as a percehtage of the total anionic surfactant
in the composition. When these molecules are mixed with alkyl
sulfates which are treated as containing 0 ethoxylate groups, the
35 computed average degree of ethoxylation should be more than
A * Trademark
** Trademark
~;~99962
about 0. 5, preferably more than about 0. 6 . One can use a
similar approach in computing the minimum desired amount of the
alkyl polyethoxylate sulfate which should be present when ad-
mixed with any anionic surfactant. E.g. the other anionic sur-
5 factant can be treated as if it were an alkyl sulfate to computethe average degree of ethoxylation.
Specific examples of alkylpolyethoxylate sulfates of the
present invention are sodium coconut alkylpolyethoxylate (3) ether
sulfate, magnesium C12 15 alkylpolyethoxylate (3) ether sulfate,
10 and sodium tallow alkylpolyethoxylate (6) ether sulfate. A
particularly preferred example is a water soluble, e.g.
magnesium~ C12_13 alkylpolethoxylate (1) ether sutfate.
Preferred alkyl polyethoxylate sulfates are those comprising a
mixture of individual compounds, said mixture having an average
15 alkyl chain length of from about 10 to 16 carbon atoms and an
- - average deg-ree. of ethoxylation of from about 1 to about 8 -moles - -
of ethylene oxide. : - ~ ~ ~ ~ -
For use in completely soft water, the compositions should
contain magnesium ions, and/or at least about 10~, preferably at
20 least about 1596 by weight of the anionic surfactant, of the
preferred alkyl polyethoxylate sulfates described hereinbefore. It
is preferred that the compositions of this invention, including
those that contain the preferred alkylpolyethoxylate sulfates, also
contain magnesium and/or calcium ions, most preferably magnesium
25 ions, to act as cations for a portion of the anionic surfactant. If
the composition is to be used primarily in water containin~3 more
than about 2 grains/gal, of hardness, added magnesium may not
be essential. In use, from about- 10% to about 100~, preferably
- ~- from about 20~ to~about 90%, of the anionic surfactant ~hould-be 30 the magnesium salt.
The formulation of anionic surfactant systems that will re-
duce the interfacial tension is well within the skill of the typical
detergent formulator. For the purposes of this invention, the
surfactant system minus the polymeric surfactant should pre-
35 ferably reduce the interfacial tension to below about 2~ dynelcm,
-~ 1299962
,
preferably below about 2 dyneslcm, agalnst triolein at a concen-
tration of o. 2% and a temperature of 115F (46C) in a spinning
drop Tensiometer. Interfacial tension is lowered by any deter-
gent surfactant, but the efflciency can be improved by selection
5 of surfactants which have longer alkyl chain lengths, use of
cations such as magnesium which mlnimize charge effects when
anionic surfactants are used, and use of anionic surfactants
combined with cosurfactants like trialkylamine oxides which form
cornplexes with the anionic surfactant. A more complete
10 discussion of such effects can be found in Milton J. Rosen,
Surfactants and Interfacial Phenomena, 149-17~ (1978)
The Polymeric Surfactant
Preferably, the compositions of the present invention contain
15 from about 0.1% to about 10%, more preferably frorn about ~% to
- about 4~, and most preferably from abPut 1/2%to about 2~ of the
polymeric surfactant descri~ed generically: hereinbefore and
discussed in detail hereinafter.
In the generic formula for the polymeric surfactant set forth
20 hereinbefore, B is preferably a polypropylene oxide group,
containing more than about 5 propylene oxide groups, which can
contain some ethylene oxide groups, n and m are preferably from
about 1 to about 2 and the sum of n+m is from about 2 to about
4, the molecule contains from about 20 to about 500 ether
25 linkages, and the molecular weight is from about 1000 to about
40, 000.
The polymeric surfactant is preferably represented by the
' - ' formula~
I R1 ~R2Otn ~R3O~mly[ R~] ~
30 wherein each R is selected from t~e group conslsting of
hydrogen, alkyl groups containing from one to about' 18 carbon
atoms, acyl groups containing from two to about 18 carbon atoms,
-SO"M, -SO3M, -COOM, -N(RS)2 -- O, -N(R5)3~1, amide groups,
pyrrolidone groups, saccharide groups, and hydroxy groups in
35 which each M is a compatible cation and each R5 is either an alkyl
A
1299962
or hydroxy alkyl group containing from one to about four carbon
atoms; wherein each R2 or R3 is an alkylene group containing
from two to about six carbon atoms with no more than about 9o~
of said molecule comprising R2 and R3 groups containing two
carbon atoms; wherein R4 is selected from the group consisting of
alkylene groups containing from one to about 18 carbon atoms and
having from two to about six valences, polyhydroxyalkylene oxide
groups wherein each alkylene group has from one to about six
hydroxy groups and contains from three to about eight carbon
atoms and there are from two to about 50 hydroxyalkylene oxide
groups and ~rom two to about 50 hydroxy groups, (=NR2N=),
hydrogen, =NtR2NH~X, polyester groups containing from one to
about 20 ester linkages and each ester group containing from
about 4 to about 18 carbon atoms; wherein n is from o to about
500, m is from 0 to about 500, n + m is from about 5 to about
1000, x is from a~out 2 to-about 50, and y is-from one to about
- ~ 50 and equal to the valences of ~ R~: wherein the molecular v~eight
.
is from about 400 to about 60,000; and wherein the tR2O~ and the
~R30t groups are interchangeable;
While not wishing to be bound by theory, it is believed that
the polymeric surfactant functions by forming complexes with the
hydrophilic portions of the anionic surfactants, thereby minimizing
the ability of the anionic surfactants to leave a micelle or other
interfacial region once formed. Therefore, long terminal
hydrocarbon groups are not preferred, and are not acceptable
when the formula is of the BA type. Long terminal hydrocarbons
pu!l the polymer into any oil phase, thereby minimizing the
number of anionic surfactant molecules that~ arc stabJlized.
~ Simibrly, if the hydrophillc portion of the molecule is too hydr-
30 ophilic, the molecu~e is pulled into the aqueous phase too far.
The molecu1e should be balanced between hydrophobicity and
hydrophilicity and have enough ether and/or amine linkages
~299962
g
spread throughout the structure to complex the anlonic
surfactant. The anionic surfactant also must be one that wlll
form the complex. Magnesium cations, ether linkages, and amine
or ammonium groups form stable complexes with the polymerlc
5 surfactants.
Preferably the surfactant contains a hydrophillc group
comprising polyethylene oxide andlor ethylenelmlne groups
containing from about 1 to about 500 ethylene oxlde and/or
ethyleneimine derived moieties. Sulfonate or sulfate groups, can
10 also be present. The polymeric surfactant also contains at least
one hydrophobic group, preferably comprising polyalkylene oxide
groups wherein the alkylene contains from three to about six,
most preferably three, carbon atoms and the molecular weight is
from about 400 to about 60,000. The alkylene groups containing
fronm about 7 to about 18, preferably fro~. about 10 to about 18,
- carbon atoms can also be used,- b~t preferably only short chain
- relatively nonoieophilic~alkyl or ~cyl groups containing iess tt~n
about ten carbon atoms are pendant on the polymeric surfactant.
Preferred surfactants are block copolymers comprising one or
20 more groups that are hydrophilic and which contain n-ostly
ethylene oxide groups and one or more hydrophobic groups which
contain mostly propylene oxide groups attached to the residue of
a compound that contained one or more hydroxy or amine groups
onto which the respective alkylene oxides were polymerized, said
25 polymers having molecular weights of from about 400 to about
60,000, an ethylene oxide content of from about 10% to about 90%
by weight and a propylene oxide content of from about 10% to
~ :about iO~ by weight. ~
- Preferred surfactants are those in which propylene oxlde is-
30 condensed with an amine, especlally ethylenediamlne,to provide a
~ hydrophobic base having a molecular welght of from about 350 to-
about 55,000, preferably from about 500 to about 40,000. This
hydrophobic base is then condensed wlth ethylene oxide to pro-
vide from about 10% to about 90%, preferably from about 20% to
35 about 80% ethylene oxide. Reverse structures in which the
A
~29996Z
- lo -
ethylene oxide Is condensed first are also deslrable. These
structures are especially easy to formulate Into desirable single
phase liquid compositions.
Similar structures in which the ethylenediamine is replaced
5 by a polyol, especially propylene glycol, or glycerine, or
condensation products of glycerine, are also deslrablq.
In similar compositions, the polypropylene glycol portion can
be replaced by an alkyl, or alkylene group containing from about
S to about 18, preferably from about 8 to about 16 carbon atoms
lo and the polyethylene oxide groups can be replaced either totally,
or, preferably in part, by other water solubilizing groups,
especially sulfate and sulfonate groups.
Specific examples of such compounds include:
A. R tOCH2CH~ R2 tOCH2CH2t~0Rl
15 where: - R is H, or CH3, or CH3(CH2)n, or unsaturated
- analogues ~
- - where - n=i-17 ~~ ~~
- x ,y=2-500
- R2=nothing or O(CH2)z or unsaturated analogues of
these where z=1-18
B. CH
R3R4toCH2CHtAR4R3
where: - R is sulfate or sulfonate
- R4 is nothing; ~OCH2CH2tB; or other groups
capable of bonding to propylene oxide, including
sulfate or sulfonate groups.
- A is 5-500
- B ~ A12
- Specific preferred examples of such compounds include:
2CH23~0(CH2~tOCH2CH2~H
3~CH2~(OCH2CH21x+y O(CH2) CH3
C. C~H3
NaO3S~OCH2CHtA OS03NacH
NaO3S~OCH2CH2tB (OCH2CH~A (CH2cH2~53Na
where: - x, y, z, n, A, B are as previously defined.
A
1299962
Suds Stabilizing Nonionic Surfactant
The compositions of this invention contain from 09~ to about
1096, preferably from about 1% to about 8%, of suds stabilizing
nonionic surfactant or mixtures thereof.
Suds stabilizing nonionic surfactants operable in the instant
compositions are of two basic types: fatty acid amides and the
trialkyl amine oxide semi-polar nonionics.
The amide type of nonionic surface active agent includes the
ammonia, monoethanol and diethanol amides of fatty acids having
an acyl moiety of from about 8 to about 18 carbon atoms and
represented by the general formula:
Rl-CO-N(H)m(R OH)2_m
wherein R1 iS a saturated or unsaturated, aliphatic hydrocarbon
radical having from 7 to 21, preferably from 11 to 17 carbon
ator.~s; R2 represents a methylene or ethylene group; and m is 1
or 2. SQecific examples of said amides are co~onut fatty acid
-- - - monoethanol am,de and dodecyl fatty acid diet~anol amide. T~ese
acyl moieties may be derived from naturally occurring glycerides,
e.g., coconut oil, palm oil, soybean oil and tallow, but can be
derived synthetically, e.g., by the oxidation of petroleum, or
hydrogenation of carbon monoxide by the Fischer-Tropsch
process . The monoethanol amides and diethanolamides of C1 2 14
fatty acids are preferred.
Amine oxide semi-polar nonionic surface active agents com-
prise compounds and mixtures of compounds having the formula:
R
Rl (C2H40)nN ~0
R3
- - whereirl Rl is an alkyl, i-hydroxyalkyl, 3-hydroxyalkyl, - or
3Q 3-alkoxy-2-hydroxypropyl radical in whiclr the alkyi and alkoxy,
respectively, contain from about 8 to about 18 carbon atoms, R2
and R3 are each a methyl, ethyl, propyl, isopropyl,
2-hydroxyethyl, 2-hydroxypropyl, or 3-hydroxypropyl radical and
n is from 0 to about lO. Particularly preferred are amine oxides
of the formula:
-~ 1299962
R2 - 12 -
R1 _ N ~0
R3
wherein R1 ;5 a C10 14 alkyl and R2 and R3 are methyl or ethyl.
The preferred sudsing characteristics of the compositions of
the invention are those which will provide the user of the product
with an indication of cleaning potential in a dishwashing solution.
Soils encountered in dishwashing act as suds depressants and the
presence or absence of suds from the surface of a dishwashing
solution is a convenient guide to product usage. ~ixtures of
anionic surfactants and suds stabilizing nonionic surfactants are
utilized in the compositions of the invention because of their high
sudsing characteristics, their suds stability in the presence of
food soils and their ability to indicate accurately an adequate
level of product usage in the presence of soil.
- - In preferred embodiments of the invention, the ratio of
anionic surfactants to suds stabilizing nonionic surfactants in the
composition will be in a molar ratio of fro~ about 11-:1 to about
1:1, and more preferably from about 8:1 to about 3:1.
Other Optional Surfactants
The compositions of the invention can desirably contain
optional surfactants, especially ampholytic andlor zwitterionic
surfactants. However, when the level of anionic surfactant is
less than about 20%, the composition should not contain any
substantial an~unt of conventional nonionic surfactant, e.g., an
alkylpolyethoxylate, in addition to the polymeric surfactant.
Large amounts of conventional nonionic surfactants, e.g., more
than about three or four percent, tend to harm the slldsing
ability of the composition. ~ ~ - - ~
When larger amounts ( ~ 20%) of anionic swfactan~s are
present it is sometimes deslrable to have a low level, up to about
5%, of conventional nonionic surfactants "conventional nonionic
surfactants- are, e.g., C8_18 alkyl polyethoxylates (4-15) or
C8_15 alkyl phenol polyethoxylates (4-15).
i299962
- 13 -
An;pholytic surfactants can be broadly described as deriva-
tives of aliphatic amines which contain a long chain of about 8 to
18 carbon atoms and an anionic water-solubilizing group, e.g.
carboxylate, sulfonate or sulfate. Examples of compounds falling
within this definition are sodlum-3-dodecylamino propane
sulfonate, and dodecyl dimethylammonium hexanoate.
Zwitterionic surface active agents operable in the Instant
compositlon are broadly described as internally-neutralized deriva-
tives of aliphatic quaternary amnlonium and phosphoniun;. and
tertiary sulfonium compounds in which the aliphatic radical can be
- straight chain or branched, and wherein one of the aliphatic
substituents contains from about 8 to 18 carbon aton s and one
contains an anionic water solubilizing group, e . g ., carboxy,
sulfo, sulfato, phosphato, or pnosphono.
Highly preferred are betaine detergent surfactants which
- - - synerqistically interact -with the polyrr,eric surfactant to_ provide- -
in-.proved~grease handling. ~ ~ ~-
The Betaine Detergent Surfactant
The betaine detergent surfactant has the general formula:
(+) (~)
R-N(R6)2R7Coo
wherein R is a hydrophobic group selected from the group con-
sisting of alkyl groups containing from about 10 to about 22
carbon atoms, preferably from about 12 to about 18 carbon atoms,
25 alkyl aryl and aryl alkyl groups containing a similar number of
carbon atoms with a benzene ring being treated as equivalent to
about 2 carbon atoms, and simtlar structures interrupted by amido
or ether llnkages: each R6-is an-alkyl~group contiining from one :
to about 3 carbon atoms; and R -Is an-alkylene group containing
30 -from one to about 6 carbon atoms.
Examples of preferred betaines are dodecylamidopropyl
dimethylbetaine; dodecyldimethylbetaine; tetradecyldin~ethyl-
betaine; cetyldimethylbetaine; cetylamidopropyldimethylbetaine,
tetradecyldimethylbetaine, tetradecylamidopropyldimethylb~etaine,
3s and docosyldimethylammonium hexanoate and mixtures thereo~.
129996Z
- 14 -
8etaine surfactants are unique ingredlents that provide
exceptional benefits. When betaine surfactant and polymeric
surfactant are combined with any anionic surfactant with, or
without magnesium ions being present, superior grease holding
5 benefits are provided.
Betaines containing a C1 2 14 alkyl provide a much bigger
benefit when combined with polymeric surfactant than when used
by themselves.
The betaine is preferably present at a level of from about ~%
10 to about 15% by weight of the formula, preferably from about 1~
to about 10%, most preferably from about 196 to about 8~. The
ratio of anionic detergent surfactants to the betaine is from about
1 to about 80, preferably from about 1 to about 40, more
preferably from about 2 to about 40.
When betaines are present, the composition should preferably
have a ratio ~f betaine to polymeric surfactant of more than about -
- 7:1,~preferably more than~abo~t 9:1. ~ ~ ~ ~ --
Solvents
Alcohols, such as ethyl alcohol, and hydrotropes, such as
20 sodium and potassium toluene sulfonate, sodium and potassium
xylene sulfonate, trisodium sulfosuccinate and related compounds
(as disclosed in U.S. Patent 3,915,903) and urea,
can be utilized in the interests of achieving
a desired product phase stability and viscosity. Alicanols
25 containing from one to about six carbon atorr.s, especially two,
and especially ethyl alcohol can be present. Ethyl alcohol at a
level of fronm 0% to about 15%, preferably from about 1% to about
1- 6%, and potasslum andlor sodlum toluene! xylene, andlor cumene
sulfonates at- a level of from about 1% to-abo~t ~6% can be-used In
- 30 the colr.positions of the~ invention. The viscosity should be
greater than about 100 centipolse; more preferably more than 150
centipoise, most preferably more than about 200 centipoise for
consumer acceptance.
However the polymeric surfactant can be used to reduce the
35 viscosity and provide phase stability, e.g., when either the
A
. .
1299962
- 15 -
preferred alkyl polyethoxylate sulfate or magnesium ions are
present in the composition. For viscosity reduction, the
percentage of ethylene oxide in the polymer should be less than
about 70~, preferably less than about 50~. Preferred
5 compositlons contain less than about 2g~ alcohol and less than
about 3% hydrotrope and preferably essentlally none while
maintaining a viscosity of from about 150 to about 500 centipoise,
preferably from about 200 to about 400 centipoise. If viscosity
reduction is not desired the percentage of ethylene oxide in the
10 polymer should be more than about 5096, preferably more than
- about 70%. The polymeric surfactant reduces viscosity ~or all
water soluble anionic surfactants.
The compositions of this invention contain from about 20% to
about 90~, preferably from about 30~ to about 80%, water.
15Additional Optional Ingredients
- The compositions of this invention ca~ contain up to about
~ t0%, by weight~ of-deterge'ncy~builders e;ther of the organic or
lnorganic type. Examples of water-soluble inorganic builders
which can be used, alone or in admixture with themselves and
20 organic alkaline sequestrant builder salts, are alkali metal
carbonates, phosphates, polyphosphates, and silicates. Specific
examples of such salts are sodium tripolyphosphate, sodium
carbonate, potassium carbonate, sodium pyrophosphate, potassium
pyrophosphate, and potassium tripolyphosphate. Examples of
25 organic builder salts which can be used alone, or in admixture
with each other or with the preceding inorganic alkaline builder
salts, are alkali metal polycarboxylates, e.g., water-soluble
citrates,'tartrates, etc. s'uch as sodiu~i~ and:potassium citrate and
- - - -sodium and potasslum tartrate. ln general, l~owever, detergency
30 bullders have lin~ited value In dishwashing detergent compositlons
and use at levels above about 10% can restrict formulation flexibil-
ity in liquid compositions because'of solubliity and phase stability'
considerations. It is preferred that any builder used be
relatively specific to control of calcium as opposed to magnesium.
35 Citrates, tartrates, malates, maleates, succinates and malonates
are especially preferred.
I
1299962
-- 16 --
The detergent compositions of thls Invention can contaln, If
desired, any of the usual adjuvants, dlluents and addltlves, for
example, perfu~,es, electrolytes, enzymes, dyes, antltarnishlng
agents, antimicrobial agents, and the like, wlthout detracting
5from the advantageous properties of the compositions. Alkallnlty
sources and pH buffering agents such as monoethanolamlne,
triethanolan;ine and alkali metal hydroxides can also be utlllzed.
When the anionic surfactant is a sulfate surfactant or
alkylpolyethoxylate sulfate surfactant, the pH should be above
1 0about 6, preferably above about 7 to avold hydrolysis of the
ester linl<age. Also, it is desirable that the composition be
substantially free of antibacterial agents such as
N-trichloromethyl-thio-4-cyclohexene-1,2,dicarboximide for safety.
Eow levels of antibacterial agents that will prevent growth of
15aacteria, molds, etc. in the product, but which have essentially
- no effect in use can be desirable, especially when Jow levels of
~ ~ alcohoi are~present. ~ ~ - ~- -
All percentages and ratios herein are by weight unless
otherwise indicated.
20The following examples are given to illustrate the composi-
tions of the invention.
In the following examples, the compounds have the following
definitions. E stands for an ethoxylate group and P stands for a
propoxylate group.
25Name Formula MW HLB
Pluronic 1~38 E45,5 P17 E45.5 5000 30.5
"Pluronic"41~ E1 .5 P22 E1 .5 1~00 4
-"Pluronic"42 E3 5 P22 E3.5- 163P- 8
~ "Pluronic"45~ E13 5 P22 E13.5 2400 18-
- 30"Pluronic'47~ E36 5 P22 E36.5 4600 26
"Pluroriic"68 E76 P29 E76 8350 29
Pluronic 81 E3 P41.5 3 2750 2
~PIuronic~l82~ E7,5 P41.5 7.5 3200 6
"Pluronic"85 E26 P41.5 E26 4600 16
35"Pluronic"87 E61 P41.5 E61 7700 24
i
~A
I
i299962
- 17 -
" Pluronlc" 88 E98 P41 S E9B 10800 28
"Pluronic"108 127 5 48 E127.5 14000 27
" Pluronic" 121 E5 P;0 E5 4400 ~5
"Pluronic"122* E11 P70 E11 5 500a 4
"Pluronic"125* E51 5 P70 Es1 5 9100 15
" Pluronic" 127 Eg9 5 P70 E99 5 12500 22
"Pluronic" 17R4 P14 E24 5 P14 2700 16
"Tetronic' 504 ~E8P8 5j4(=NCH2CH2 ) 15.5
Tetronic' 702 (E4 5j14)4(=NCH2CH2
Tetronic 704 (E12.5P14)4(=NCH2CH2N=) 5500 15
Tetronic 707 ( 47,5P14)4(=NCH2CH2N=) 12000 27
Tetronic~'902* (E6P17)4(=NCH2CH2N=) 5300 6.5
Tetronic"904* (E17P17)4(=NcH2cH2N=1 7500 14.5
" Tetronic"907* (E55P17)4(=NCH2cH2N ) 13900 26
lS " Tetronic"908 (E91P17)4(=NCH2cH2N ) 20000 30.5
" Tetronic"1307 (Et4P~4)4~=~C~2C~H2N ) 18600 ~ 23.5
Tetronic 1502 (EloP31)4( NCH2CH2N-)9000 ~--
'rTetronic"1504 (E28 5P31)4(=NCH2CH2N=) 12500 13
" Tetronic' 70R4 (P~E12J5).~(=NCH2CH2N=) 5500
20 * Prepared by ~lendlng other commercially available materials.
Name Definition
Compound A Polyethyleneimine (MW=600) condensed with 42
mols of polypropylene oxide followed by 42 mols
of polyethylene oxide
Compound B Polyethyleneimine (MW=600) condensed with 14
mols of polypropylene oxide
Corr.pound C Po!yethyleneimine tMW=600) condensed with 42
- : mols of polypropylene oxide
Compound D - Polyethyleneimlne (MW=600) condensed with - 98
mols of polypropylene oxide
'hurocol" WS100 " Random" copolymer of ethylene oxide (50%) and
propylene oxide (50~) (MW=4600] lBASF)
Compound E Pluronic 81 di-sulfated and NH~4OH neutralized
Con~pound F HOtC2H4Otlg(CH2tl2O~C2HqOtl8H
PPG 4000 Polypropylene glycol MW=4000
"Pluronic" and Tetronic" are trademarks
* Trademark
-
~299962
- 18 -
PEG 6000 Polyethylene glycol MW=6000
Compound G Polyethyleneimine (MW=189) acylated wlth 2 mols
of coconut fatty acid and condensed with 80 mols
of ethylene oxide
Compound H Polyethyleneimine (MW=189) condensed with
105 mols of ethylene oxide
Compound I Methyl capped hexamethylenediamine condensed
with 60 mols of ethylene oxlde
Compound J Triethanol amine condensed with 15 mols of
ethylene oxide
Compound K Triethanol amine condensed with 33 mols of
ethylene oxide
.. "*
Compound L Dobanol 91-10
CH3tCH2~8_1 o-tCH2CH2)10
~H _
Corr,pour~d M C13H27CH CH2-CH - _
~ C~ /CH2CH2OH 11 . 8
~CH2CH2OH
Compound N CH31CH2)11_12 O-CH C~H2
OH OH
,CH3
Compound O CH3-otcH2cH2otii~tcH2cHo~H
25 HA-q30** Polyethylene glycol/polypropylene glycol heteric
block copolymer (BASF)
The base product contains about 5% magnesium C12 13 alkyl
- sulfate, about- 23% miXed magnesium and ammonium C12 13 alkyl
polyethoxylate (1) sulfate, about 2.7% C1-2_13 alkyl dimethyl amine
30 oxides about 5% ethyl alcohol, about 3% sodium toluene sulfonate,
about 60% water, and the~balance ~eing- inorganic salts, minor
ingredients, etc.
In the following examples, "grease cutting" is determined by
the following test. A preweighed 250 cc. polypropylene cup has
35 3 cc. of a melted beef grease applied to its inner bottom surface.
*Trademark
~ A* * Trademark
~299962
- 19 -
After the grease has solldlfied, the cup Is rewelghed. Then a
.4~ aqueous solutlon of the composltion to be tested is added to
the cup to completely fill it. The aqueous solutlon has a
temperature of 46C . After 15 minutes, the cup is emptied and
5 rinsed with distilled water. The eup is dried and then weighed
to determine the amount of grease removal. The amount removed
by the base product is indexed at 100.
In the following examples, "grease capacity" is determlned
by modifying the above grease cutting test by using 10 ml of an
10 easier to remove fat which is an 80/ 20 mixture of a solid
vegetable shortening and a liquid vegetable shortening, lowering
the detergent concentration to about 0.2%, and soaking for 30
minutes to allow equilibrium to occur.
In the Examples "~" indicates a significant difference and the
15 figures in parentheses under the headings "Grease Capacity" and
"Grease Cutting" are the number- o~ repl~cates run and averaged
to give the-indicate~ test scores. ~ -~ ~ ~
In all of the Examples, the viscosity of the composition is
greater than about 150 centipoise and less than about 500
20 centipoise.
EXAMPLE I
This test shows the improvement in grease capacity and
grease cutting obtainable with various Pluronics.
IA
Grease Grease
Capacity Cutting Total
14) (5)
Base Product 1~0 ~ 100 200 ~
" + 1.3% P!uronic-127 - - - 125*- 116* 24~*
~ " +~1.3% PJuronic q7 129* - 119~ 248*
" + 1.3% Pluronic 87 ~ 123* 111* 234*
" + 1.396 Pluronic 122 124* 108* 232*
" ~ 1.39~ Pluronic q2 128* 124* 252*
" ~ 1.34 Pluronic 82 124* 120* 244*
" + 1.3~ Pluronic 125 130* 112* 242*
+Trademark
1299962
- 20 -
+ 1,3% Pluronic 45 134* 119* 253*
" + 1,3~ Pluronic 85 129* 120* 249
LSD10 8 8 11
IB
S Grease Grease
Capacity Cutting Total
13) (3)
13aseProduct 100 100 200
"+ 1.3~ Pluronic 121 113* 104 217*
10 " + 1.3% Pluronic 81112* 106 218*
" + 1.3~ Pluronic41 109 113* 222*
" + 1.396 Pluronic 85 116* 110 226*
LSDlo 10 11 15
Grease Grease
- ~ - . Capacity ~tt7ng ~ Total - -
: - - (3} ~2)
Base Product 100 100 200
" + 1.3~ Pluronic 38 113* 102 215*
" + 1.3~ Pluronic 68 118* 101 219*
" + 1.3~ Pluronic 88 116* 93 209
" + 1.3% Pluronic 108 125* 93 218*
LSDlo 10 13 15
EXAMPLE l l
This test shows the improvement obtained with various
- "retronics"+
~ -
Grease Grease
Capacity Cutting Total
(6) (5)
Base Product 100 100 200
n + 1.3% Tetronic 504 108* lt6* 224*
I~ + 1.3% Tetronic 702113* 113* 226*
ll + 1.3% Tetronic 707108* 111* 219*
Trademark
1299962
- 21 -
" ~ 1.3% Tetronic 902 120~ 104 224*
" + 1.3% Tetronic 904 108~ 99 207
" + 1.3% Tetronic 907 113* 108~ 221
" + 1.3~ Tetronic 1502 111* 108* 219
" + 1.3~ Tetronic 1504 106* lll* 217
" + 1.3% Tetronic 1307 108* 97 205
LSDl o 6 8 10
IIB
Grease Grease
Capacity Cutting Totai
Reps (3) (2).
Base Product 100 100 200
" + 1.3% Tetronic 908121* 87 208
SD10 10 13 15
EXAMPLE l l l
- - This example demonstrates that reversing the order of - -
additlon - of the ethylene- oxi~e and propylene oxide to create a
hydrophilic center and hydrophobic ~ends provides compounds
which are equally as effective as the Pluronics or Tetronics.
Grease Grease
Capacity Cutting Total
(4) (4)
Base Product 100 100 200
" + 1.3% Pluronic 85 121* 98 219*
" + 1.3% Pluronic 17R4 125* 94 219*
" + 1.3% Tetronic 704 131~ 99 230*
" + 1.3% Tetronic 70R4 129* 96 225*
- - LSD10 - - - . 8 9 12- -
- . - - - EXAMPLE IV - - - -
- This example demonstrates.tha~ a polymeric surfactant with a
- somewhat hydrophilic center, two . or -more intermediate
hydrophobic moieties and terminal hydrophilic moieties provides
almost the same benefits as the Pluronics or Tetronics.
1 299962
G rease G rease
Capacity Cutting Total
(9) (5)
Base Product 100 100 200
s " + 1.396 Pluronic 85 108* 105 213*
" + 1.3% Tetronic 704 111* 98 210*
" + 1.3~ Compound A 116* 100 216*
LSDlo 6 9 10
EXAMPLE V
This example demonstrates that a compound with a
hydrophilic chain with grafted polypropylene oxide hydrophobic
chains can provide grease capacity and grease cutting benefits
about the same as Pluronics.
Grease Grease
Capacity Cutting Total
(5) (1~) -
~ ~ - - . Base Product ~ - - 100- ~ - 100. 200 - ~-
" + 1.3% Pluronic 85 112* 1~2 214*
" + 1.3~ Compound B111 * 92 203
" + 1.3~ Compound C109* 92 201
" + 1.3% Compound D116* 107 223*
LSDlo 7 10 12
EXAMPLE Vl
This example shows that random structures of ethylene oxide
25 and propylene oxide are as effective as their analog block
structures .
Grease Grease
. . .Capacity C~tting Total
- (4) (4)
- 30 Base Product - 100 . 100 200
- " + 1.3% Pluronic 85 115* 111* 226*
" + 1.3~ Plurocol W5100 114* 106 220*
LSDlo 8 10 13
EXAMPLE Vll
35This example shows that similar structures in which anionic
moieties substitute, at least in part, for polyethoxylate moieties or
1299962
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alkylene chains are substituted, at least in part, for
polypropoxylate moieties provide benefits similar to the Pluronics.
Grease Grease
Capacity Cutting Total
(7) (5)
Base Product 100 100 200
" + 1.3% Pluronic 65 107* 103 210
" + 1 . 3~ Compound E 114* 97 211*
" + 1 . 396 Compound F 110* 98 209
LSD10 7 9 11
EXAMPLE Vl l l
This example demonstrates that mixtures of polypropylene
glycol and polyethylene glycol, and the individual materials do not
provide the benefits.
Grease Grease
Capacity Cutting Total
(2) (2)
Base Product 100 100 200- - -
" + 0.65% PPG 4000(A) 102 106 208
" + 0.65% PEG 6000(B) 91 101 192
" ~ 0.65~ A + 0.65% B 99 101 200
" + 1 . 3% A 95 104 199
" + 1 . 3% B 89 98 187
LSDlo 12 13 18
EXAMPLE IX
This example demonstrates that excessively water-soluble
compounds and compounds which are more like conventional
- - surfactants and contaln termi~nal oleophilic hydrophobic groups do~ ~
' not provide the beneflts. ' ~ -
Grease G,rease
' ' Capacity Cunlng Total ~ ~
. (6) `(4)
Base Product 100 100 200
; " + 1.3% Compound G102 98 200
~ 35 " + 1.3% Compound H102 93 195
~ 24 -
n ~ 1.3% Compound 1 98 97 195
" + 1.3~ Compound J 99 96 195
+ 1.3~ Compound K 94 93 187
I~ + 1.3% Compound L 93 95 1a8
LSDlo 7 9 11
EXAMPLE X
This example is a continuation of Example IX.
Grease Grease
Capaclty Cuttlng Total
(3) (3)
Base Product, " 1 100 100 200
" + 1,3% Methocel A15LV 103 103 206
+ 1.3% NHq C12_13E12 4 96 98 194
~ + 1.3% NH4C12_13SO4 102 99 201
~ + 1.3~ Cl2-l3N(cH3)2 101 106 207
" +-1.3% Gelatin (Type A) 106 96- 202
- ~ LSDlo - - ~O 11 ~ ~5'
EXAMPLE Xl
This example also demonstrates that other conventional
20 surfactants do not provide the benefits.
Grease Grease
Capacity Cutting Total
(5) (3)
Base Product 100 100 200
" + 1.3% C12_13 Glucoside ~2) 102 100 202
" + 1.3% Cn monoethanol amide 104 101 205
" + 1.3~ Compound M 101 100 201
" + 1.3~"Lexaine LM ,,,2100 100 ~-200
u ~ 1.3% Compound N - 99 - 10~ -199
LSD1 0 11 12
EX~MPLE, X l l : ' -
This example shows ' that' some low molecular weight
polypropylene oxldes provide the beneflt, although they do
adversely affect sudsing.
~' 35
.,
Trademark for methylcellulose
~rademark
1299962
- 25 -
Grease Grease
Capacity Cutting T
(9) (5)
Base Product 100 100 200
" + 1.3% Pluronic 85 108* 105 213
" + 1.3% PEG 6000 105 98 203
" + 1.396 PPG 4000110* 115~ 225
LSD1o 6 9 10
EXAMPLE X l l l
This example demonstrates yet another polymeric surfactant
structure that is operable.
Grease G rease
Capacity Cutting Total
(5) (4)
Base Product 100 100 200
- - '' + 1.3% Pluronic 85 112* --102 . 214*
+-1.39~ Compound O 114* ~ -- 106 220* ~ -
~ LSD ~ ~ ~ ~ ~- 7 10 12
EXAMPLE X IV
This example demonstrates that increasing the amount of the
polymeric surfactant, a heteric block copolymer of ethyiene oxide
and propylene oxide on a glycerol base, improves Grease
Capacity, but, eventually, lowers the Grease Cutting
unacceptably. High levels above about 4%, and especially above
about 9%, lose good grease cutting when the basic formula is
optimlzed for grease cutting.
Grease Grease
Capacity Cuttina Total -
-(3) (3)
¦- 30~ Base Product 100 i00 ~ 200
, " + 1.3% HA 430 115* 113* 228*
i " I 16% HA 430 195* 29* 225*
LSDlo 10 11 15
EXAMPLE XV
This example, like Example XIV, shows the effect of
increased (Tetronic) surfactant. Again, above about 4%, there is
.
" ~Z9996Z
- 26 -
a loss which becomes substantial before a level of about 9% is
reached.
Grease Grease
CapacityCutting Total
(3) (3)
Base Product 100 100 200
" + 0.25~ Tetronic 704112* 121~ 233
" I 0.50% Tetronic 704118~ 119* 237
" + 1.0% Tetronic 704119* 120* 239*
" + 4.09~ Tetronic 704136* 96 232*
" +-8.0~ Tetronic 704 168* 74* 242*
" I 16.0% Tetronic 704221* 47* 268*
LSD1o 10 11 15
COMPARAT IVE EXAMPLE XVI
15This example shows the effect of using twice the amount of a
-- - commercial detçrgent. The Grease Capacity and Grease Cutting
- ~ - - are increased, but at~ a ~much greater cost than ~s~ociated~ with
the invention. - -~
GreaseGrease
CapacityCutting Total
Reps (4) (4)
Base Product 100 100 200
Base Product (Double Usage) 140* 130* 270*
LSD1o 8 10 13
EXAMPLE XVI I
A high sudsing, light duty liquid detergent composition is as
follows:
. % : -
Sodium C11- 8 alkylbenzene sulfonate - - : 14.8 ~-
30 Sodium C12_13 alkylioolyethoxylate (0.8) sulfate 17.3
~12 l4 alkyldimethylbetaine- - 1.5
Pluronic 64 (as hereinafter defined) 0.175
C10 alkYIpOIyethoxylate (8-10) 4.7
Coconut fatty acid monoethanol amide 3.8
Urea 5.0
I
-`` 1299962
Ethanol 6.0
Water and minors Balance
In a similar con~position the urea is replaced by 4% sodium
xylene sulfonate and the ethanol Is reduced to 3.5~.
In a similar composition the Pluronic 64 is replaced by
Pluronic 85.
EXAMPLE XVI I I
GreaseGrease
CapacityCutting Total
(2) (2)
- Base Product 100 100 200
" + 4~ Lexaine LM 134* 134* 268*
~% Pluronic 85
" + 4-3/4% Lexaine LM 98 138* 236*
~ Pluronic 85
LSD10 - ~ - - 22 10 24
- ' -'rhis ~ example - demanst~rates the excellent performance of
mixtures of betaine surfactants and the~ polymeric surfactants. At
ratios up to about 20:1 grease cutting is improved, but the
20 optimum ratio is lower, e.g. about 9:1 or less where both grease
cutting and grease capacity are improved.
EX AMPLE X I X
Viscosity Reduction
Viscosity
% Reducition
Ethoxylate (CPS)
~ ~ Base Pr'oduct (Visco'sity = 270 centieoise) Base
- - -' - " +t% Pluronic 121 - io -62
. . 30 - " +t% Pluronic 123 . 30 -40
' " +t% Pluronic 127 70 -30
" +t% Pluronic 72 20 -55
" +t% Pluronic 75 50 -41
+t% Pluronic 77 70 -31
" +t% Pluronic 61 10 -70
1299962
- 28 -
+t% Pluronic 63 30 59
" +~% Pluronic 64 40 -59
" +t% Pluronic 68 80 -20
" +~% Tetronic 1302 20 -42
" +~% ~etronic 1304 40 -32
" +~ Tetronic 1307 70 -15
This example demonstrates the large reductions in viscosity
obtained by adding the polymeric surfactant. The viscosity can
be adjusted back up by reducing alcohol andlor hydrotrope
10 levels. As can be seen, the higher the level of ethoxylate
moieties in the polymers, the less the reduction in viscosity.
Additional Materials Description
The additional polymeric surfactants not defined hereinbefore
are as follows:
Name Formula MW H LB
Pluronic 123- E4s,s P70 E45.5 ~ 8
- Pluronic 72 - E6 5 P36 E6 5 - 2750 ~ 6.5 ~-
Pluronic 75 F23.5 P36 E23.5 4150 --16.5
Pluronic 77 E52,5 P36 52.5 6600 24.5
Pluronic 61 E2,5 P29 E2,5 2000 3
Pluronic 63 Eg P29 Eg 2650 11
Pluronic 64 E13 P29 E13 2900 15
Tetronic 1302 (Eg P24)4 (=NCH2CH2N=) 7800 5.5
TetroniC 1304 (E24 P24)4 [=NCH2C 2 ) 13.5
EXAMPLE XX
Polymer compounds are added at 0.5~, 1%, and 5% to the
National Brand composition previously described, replacing water
in'~the 100-part formula. Clear solutions result.
- Viscosities are measured on these compositions at 70F with a
-~ 30 Brookfleld LyF viscometer, spindle No. 2, at 60 rpm.
' ' Results are snown for the three additives and are compared
against equal' parts of added ethanol also'replacing water in the
formula. Ethanol ts typically used to trim vtscostty and is
already present tn the formula at about 4.5 parts/100 prlor to the
added parts.
:1 .
1299962
Surprisingly, the addition of the polymers all drop the
viscoslty further than does the added ethanol The Pluronic 61 Is
even more effective at 1% than is ethanol at 5~.
Viscosity of National Brand with Added Polymers
CPS Vlscosity
Addit~ve Level: 0~ 0.5~ 1 ~ 5
Additive Type
Compound H 370 250 220 NA
Pluronic 35 370 ~A 195 113
10 Pluronic 61 370 NA 163 83
Ethanol 370 275 240 190
In a similar manner, the national brand formula is composited
with a 0.25~ level of several Pluronic polymers. Viscosities are
again read as above.
15 Additive Viscosity in Centipoise at 70F
-- - None - 320
-~- Pluronic 6~ ~ 265- ~ ~ -- - ~ ~ -
Pluronic 92 247
Pluronic 42 237
20 Pluronic 31 242
Note that the additive compounds provide different levels of
viscosity reduction. The Compound H in the first experiment is
one of the poorer (more hydrophilic) performers of Example IX
and, though effective on viscosity reduction, did not show as
25 great a benefit, The Pluronic compounds of lower HLB (lower
second digit) and moderate molecular weight (first digit) are more
effective. If the purpose for adding ti e polymer is to lower
viscosity, lower levels provide the biggest benefit per part of
~ polymer added. - - - - - - -
~ - EXAMPLE XXI
- This test was conducted in water with no hardness.
l - -Grease Grease
; CapacityCutting Total
t2) l4)
35 A. Sodium coconut alkyl sulfate 100 100 200
,j
1299962
- 30 -
B. A + 4.5~ Lexaine IM +
0~5% Pluronic 85 215~ 1'06~ 321
C. B + MgCI2 to replace the sodium 325~ 110* 435
D. 1:1 mixture of sodium coconut
s alkyl sulfate and sodium coconut
alkyl polyethoxylate(1) sulfate 96 98 194
E, D + 4.5% Lexaine LM I 0.5%
Pluronic 85 300~ 90~ 390*
F, E + MgCI2 to replace the sodium 266~ 114 380
LSD10 14 15 21
This example clearly shows that when a mixture of polymeric
surfactant and betaine is used, it is not necessary to have either
an alkyl polyethoxylate sulfate surfactant or magnesium ions
present.
EXANIPLE XXII
- . _ Grease Grease
~~~ ~-- ~ ' - - . Capacity Cutting Total - (4) (2)
National Brand 100 100 200
20 " " +1.3~ MAPEGl 6000DS 112* 99 211
+1.39v MAPEG1400 DS 107 99 206
~1,3% MAPEG1400 DL 112~ 101 213
" " +1.3~ MAPEG1400 DO 116~ 100 216*
LSD1o 8 13 15
Definition of Polymeric Surfactants
MAPEG 6000DS ldialkyl polyethoxylate) C18 E136 C18 9 %
MAPEG 400DS (dialkyl polyethoxylate) C18 Eg C18 44% E
- MAPEG 400DL (dialk'yl polyetho~ylate) C12 Eg C12 54% E
-- MAPEG 400 DO ldialkylene polyethoxyl?te) C18 Eg C~8 45% E
3~ Thls example clearly shows that alkyt groups can be used as
termirial hydrophobic groups, but do not provlde the best
results, especially when the h'ydrophilic portion of the molecule
represents less than about 45~ of the molecular welght in
compounds with saturated groups each of which Is longer than
35 about 16 carbon atoms.
A~
1 MAPEG is a Trademark
. .
. . : .
.
1299962
- 31 --
EX~IUPLE XXIII
In this example, a differcnt type of test ~vas used to
demonstrate another aspect of grease control by the detergent
composltlons. ~n most cases, ~his test S~ives a ranklng betwoen
formulations similar to that of the total Index value of the
preceeding examples.
This test de~ermines ~he off~ctiveness ~r str~ngth of the
grease emuisir~cation by ~he detergent by measuring the level of
g~ease deposltion on a hydrophobic surface a~ter Its exposure ~o
10 a detergent solution to which a grease has been added. ~his test
models the actual sltuation of redepositlon of greases onto later
washed Items, especially plastics.
For this experiment, 2 gallons of median hardness ~vater (6
gta;nslciallon) . ~ere held a~ . loS~F, a common end-of-wash
lS tempcrature for dishwater! A 0,1~ solution of the detergent
product ~as made and mlld a3itation was begun. Liquid ~e~etable
oil was added In 6cc ir~rrements. At totals of 18cc, 36ct, and
54cc, plastic items (3 for each grease level, 9 total) are dipped in
succession into the water. After drying, the mean weight gain
20 per plastic ISem unit area is calculated ~nd indexed to a reference
product.
The reference product used here is the base product. The
polymeric s~rfactant is added at ~he 1~ le~el to the base,
A "*" ihd;ca~es a statis~ically slgniflcant (L~Do5) reduction
25 In grease redep~sition compared to the Base Product.
The con~pounds tested hereln that were not previously
defined are as follows:
Formula for P-T:
O O
., ~1
CH3(ocH2c:H2)xoc~cH2)yco(a~2c~2 )X 3
P X-8, Y-4
Q X=8,Y-14
R X-43, Y-4
5 X=43, Y=14
T X-17, Y~10
' ~299962
- 32 -
FOrmUIa fOr ~ nd V:
O C~t
C~3 (OCH~C~ XO(C (~)~COC~I2~;~20)Y(CH2CH20)X 3
jJ )~-16, Y=2.75
V X=7,5, Y~2.~S
DePO5;t;0n
IndeX
BaSe PrOdUCt 1 00
I~ M~PEG 1540 DS ~
n n ~IAPEG 600 MO 76*
" " ~1~ MAPEC 600 I~O 75~ .
~1~ PIUrOn;C 85 . 84
Il n ~l9o Te~rOn;C ~04 107
~1~ MethOCe1 A15LV 8B
IS " " ~1~ CDmP~Ut d E . 84
U ~ ~1% PPG 4000 64
" " ~19~ Compound F 89
~1~ Compound i? 84
~1~ Compound C~ 80~
" " ~1~ Compound R ~07
" 1' ~1~ Comp~und S 117
Compound T 85
Compound U 71
n n ~19o Compound V 53~
Note frO~n the above that Tetronic 704 and Compound ~ did
not exc-l In ~his test, but dld PerfOrrn well in the previous
exan~ples. Again, the Nletho~el polymer does n~t provide
s-lfrlcient benefiS.
~lso, cer~a;n very hl9h n~Olecular weight compounds (R and
S) of the ABA type do not show any adv~ntage.
OtherW;Se, all are exemplary of the in~ention.
