Note: Descriptions are shown in the official language in which they were submitted.
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LIQUID DETERGENT COMPOSITIONS
HAVI NG H l GH RESERVE ALKALI N ITY
Darrei D. Kokx
Ronald L. Jacobsen
Technical Fie!d
The present invention relates to heavy-duty liquici detergent
compositions containing an amine oxide or amide surfactant, an
alcohol polyethoxylate sulfate surfactant, an anlonic sulfonate
surfactant, a water-soluble detergency builder and water. The
compositions herein have a reserve alkalinity, defined as the
equivalent grams of caustic as sodium hydroxide exceeding pH 9.5
per 100 gran~s of composition, of greater than about 2.5. At this
high reserve al)calinity, the compositions provide superior cleaning
of greasy/oily soils and stains from ~abrics.
lS Heavy-duty liquid detergents formulated to maintain a high
wash water pH are desired to enhance detergency performance on
body soils. It is believed these fatty soils are saponified to more
soluble species (e.g., soaps), which can be more readily removed
r from fabrics, at the high pH. However, it has been Found that
high wash water pH's generally decrease removal of greasy/oily
soils from fabrics. Thus, there is a continuing need for liquid
detergents capable of providing improved cleaning of greasy/oily
soils at high wash qvater pl l's.
Background Art
U.S. Patent 4,284,532, I,eikhim et al, issued August 18,
1981, discloses stable liquid detergents containing amine oxides,
ethoxylated nonionic surfactants, and water-soluble detergency
bui Iders .
U.S. Patent No. 4,436,653, Jacobsen et al, iss,ued
March 13, 1984, discloses stable liquid detergents
containing amine oxides, ethoxylated nonionic surfactants, alcohol
poh~ethoxylate su!fate surfactants, and water-soluble detergency
bui Iders .
U.S. Patent No. 4,438,024, DelGreco et al, issued
March 20, 1984, discloses stable liquid detergents con-
taining amine oxides, alcohol polyethoxylate sulfate surfactants,
water-soluble detersency builders, and alkanolarnines.
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Summary of the I nvention
The present invention encompasses heavy-duty liquid deter-
gent compositions comprising:
(a) frorn about 1% to about 10% by weight of a nonionic
surfactant selected frorn the group consisting of:
(i) amine oxide surfactants of the formula
R2
R ~OC2H4)nl ~ O
R3
wherein R is an alkyl, hydroxyalkyl, alkoxyhydroxypropyl,
alkoxyhydroxyethyl, alkyl amido or alkyl carboxylate radical in
which the alkyl and alkoxy portions contain frorn about 8 to about
15 18 carbon atoms, R2 and R3 are selected from the group consist-
ing of me-thyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hy-
droxypropyl and 3-hydroxypropyl, or are joined together to form
a cyclic structure containing the nitrogen atom and from 4 to 6
carbon atoms, and n is from 0 to about 10; and
(ii) amide surfactants of.the formula
o R2
R1 C- I -R3
wherein R1 jS an allcyl, hydroxyalkyl or alkenyl radical containing
from about 8 to about 20 carbon atoms, and R2 and R3 are selected
from the group consisting of hydrogen, methyl, ethyl, propyl,
isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,
and said radicals additionally containing up to about 5 ethylene
oxide units, or are joined together to form a cyclic structure
containing the nitrogen atom and from 4 to 6 carbon atoms;
(b) an alcohol polyethoxylate sulfate surfactant of the
formula
R ~C2H4)mS3M
wherein R is an allcyl or hydroxyalkyl radical containing from
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3 --
about 10 to about 18 carbon atoms, m is from about 0 . 5 to about
5, and M is a compatible cation;
~c) an anionic sulfonate surfactant;
(d) from about 10~d to about 25% by weight of a water-
5 soluble polycarboxylate, polyphosphonate, or polyphosphatedetergency builder capable of sequestering calcium and magnesium
ions in water solution;
le) from about 0% to about 25% by weight of a hydrotrope;
and
(f) from about 4096 to about 70~ by weight of water;
said composition con;3ining from about 5% to about 209~ by weight
of the alcohol polyethoxylate sulfate and anionic sulfonate sur-
factants in a weight ratio of alcohol polyethoxylate suifate to
anionic sulfonate surfactant of from about 0.5 to about 10, and
15 having a reserve alkalinity, defined as the equivalent grams of
caustic as sodium hydroxide exceeding pH g.5 per 100 grams of
composition, of greater than about 2.5.
Detailed Description of the Invention
-The liquid detergent compositions herein comprise a nonionic
20 surfactant, which can be an amine oxide or amide, an alcohol
polyethoxylate sulfate surfactant, an anionic sulfonate surfactant,
a water-soluble deter!,ency builder and water. The compositions
also have a reserve alkalinity, defined as the equivalent grams of
caustic as sodium hydroxide exceeding pH 9.5 per 100 grams of
25 composition, of greater than about 2.5. As used herein, reserve
alkalinity is determined by acid (HCI) titration of a solution
composed of 25 grams of the detergent composition diluted to 100
cm with distilled water.
The high reserve alkalinity of the compositions allows for the
30 formulation of liquid detergents capable of maintaining a high
wash water pH t preferably from about 9 . 0 to about 11 . 0, more
pre~erably from about 9.2 to about 10.5) in the presence of soil
loads and hardness levels typically encountered during the laun-
clering operation. As previously mentioned, the high wash water
35 pH enhances removal of body soils from fabrics. Surprisingly,
the addition of the anionic sulfonate surfactant to compositions
herein containing only the nonionic and polyethoxylate sulfate
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surfactants results in superior cleaning of greasy/oily soils and
stains at the high ~Nash water pH . The reserve alkalini ty should
be greater than about 2.5 to maintain the high wash water pH
and provide the superior greasy/oily soil cleaning. It preferably
is from about 2.6 to about 6, more preferably from about 2.8 to
about 3 . 8 .
The required reserve alkalinity can be provided by any
suitable caustic materia~, including carbonate, bicarbonate or
silicate salts, aikali metal and alkaline earth metal hydroxides,
~preferably sodium or potassium hydroxide), monoethanolamine or
diethanolamine. Monoethanolamine is a highly preferred alkalinity
source. The compositions preferably contain from about 4% to
ab~ut 8~ by weight of free monoethanolamine.
Nonionic Surfactant
The compositions of the present invention contain ~rom about
1% to about 1 Og~, preferably from about 3% to about 7%, by weight
of a nonionic surfactant, which can be an amine oxide, amide, or
mixtures thereof.
Amine oxide surfactants herein are of the formula
F;~2
R (OC2~14 ) n~ ~
wherein R1 jS an alkyl, hydroxyalkyl, alkoxyhydroxypropyl,
alt<oxyhydroxyethyl, alkyl amido or alkyl carboxylate radical in
which the alkyl and alkoxy, respectively, contain from about 8 to
about 18 carbon atoms, R2 and R3 are selected from the group
consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl,
2-hydroxypropyl and 3-hydroxypropyl, or are joined together to
form a cyclic structure containing -the nitrogen atom and from 4 to
~ carbon atoms (e.g., morpholine, piperidine or pyridine), and n
is from 0 to about lO.
Specific examples of the above amine oxide surfactants
include: dimethyldodecylamine oxide, dimethyltetradecylamine
oxide, ethylmethyltetraclecylamine oxide, cetyldimethylamine oxide,
cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyl-
tetradecylamine oxide, dipropyldodecylamine oxide, bis-~2-hy-
droxyethyl)dodecylamine oxide, bis~2-hydroxyethyl)-3-dodecyloxy-
1~0~9~
2-hydroxypropylamine oxide, ~2-hydroxypropyl)methyltetradecyl-
amine oxide, dimethyl-~7-hydroxydodecyl)amine oxide, C8 16 alkyl
alpha-dimethylamine oxide carboxylates, and the corresponding
decyl and hexadecyl homologs of the above compounds. A particu-
larly preferred rnaterial is C12 16 alkyi dimethylamine oxide.
Amide s~rfactants herein are of the formula
o R2
R C-N-R
wherein R is an alkyl, hydroxyalkyl or alkenyl radical containing
from about 8 to about 20 carbon atoms, and RZ and R3 are selected
from the group consisting of hydrogen, methyl, ethyl, propyl,
isopropyl, 2-hydroxyethyl, 2-hydroxypropyl ~ 3-hydroxypropyl,
and said radicals additionally containing up to about 5 ethylene
oxide units, or are joined together to form a cyclic structure
containin~ the nitrogen atom and from 4 to 6 carbon atoms.
Preferred amides are the C8-C20 fatty acid alkylol amides in
whicn each alkylol group contains from 1 to 3 carbon atoms, and
additionally can contain up to about 2 ethylene oxide units.
Particularly preferred are the C1 2-C1 6 alkyl monoethanol and
2 0 diethanol amides .
Alcohol Polyethoxylate Sulfate Surfactant
The compositions herein also contain an alcohol polyethoxyl-
ate sulfate surfactant of the formula R O~C2H4O)mSO3M, wherein
R is an alkyl or hydroxyalkyl radical containing from about lO to
about 18 carbon atoms, m ~the average number of ethylene oxide
units) is from abou-t 0.5 to about 5, and M is a compatible cation.
Preferred alcohol polyethoxylate sulfate surfactants of the
above formula are those wherein the R substituent is an alkyl
radical containin~ from about 12 to about 18 carbon atoms and m
is from about 0.6 to about 2.5, more pr~ferably from about 0.7 to
about 1.5. Examples of such materials are Cl2 15 alkyl poly-
ethoxylate ~1.1) sulfate ~CI2_l5 E1 15); Cl4_15E2 2S; C12-13E1S;
Cl6 l8E4S; Cl4 l5Eo 7S; and mixtures thereof. The sodium,
potassium, and monoethanolamine salts of the above are preferred.
~L2~0~9
Anionic Sulfonate Surfactant
Any anionic sulfonate surfactant known ~or use in detergent
cor:-positions can be used in the present invention. Examples of
such materials include those described in U.S. Patent 3,963,649,
Spadini et al, issued June 15, 1976, and in U.5. Patent
3,929,678, Laughlin et al, issued December 30, 1975,
Preferred sulfonates are alkylbenzene sulfonates in which the
alkyl group contains from about 9 to about 15 carbon atoms, in
straight chain or branched chain configuration; C12 18 paraffin
12-18 olefin sulfonates; C12_18 alkyl glyceryl ether
sulfonates; -sulfonated fatty acid esters conta;ning from about 12
to 18 carbon atoms in the fatty acid group and from about 1 to 10
carbon atoms in the ester group; 2-acyloxy-alkane-1-sulfonates
containing from about 2 to 9 carbon atoms in the acyl group and
from about 12 to 1~ carbon atoms in the alkane moiety; and
~-alkyloxy alkane sulfonates containing from about l to 3 carbon
atorns in the alkyl group and about 12 to 18 carbon atoms in the
alkane moiety.
Particularly preferred are the alkali metal, ammonium or
substituted ammonium salts of linear alkylbenzene sulfonates
containing from about 11 to 14 carbon atoms in the alkyl chain.
The compositions of the present invention contain from about
5% to about 20%, preferably from about 7% to about 15%, by weight
of the above-described alcohol polyethoxylate sulfate and anionic
sulfonate surfactants, in a weight ratio of sulfate to sulfonate
surfactant of from about O.S to about 10, preferably from about 1
to abo~st 7, and more preferably from about 1.5 to about 4.
Water-Soluble Det_rgency Builder
The compositions also contain from about 10% to about 25~6,
preferably from about 15~6 to about 22g6, by weight of a
water-soluble polycarboxylate, polyphosphonate, or polyphosphate
detergency builder capable of sequestering calcium or magnesium
ions in water solution. Sequestration i5 the formation of coor-
dination complexes with metallic ions to prevent or inhibit pre-
cipitation or other interfering reactions. The phenomenon is also
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called chelation if certain structural criteria are met by the
coordination complex.
Suitable polycarboxylate builders herein include the various
aminopolycarboxylates, cycloalkane polycarboxylates, ether poly-
carboxylates, alkyl polycarboxylates, epoxy polycarboxyla-tes,
tetrahydrofuran polycarboxylates, benzene polycarboxylates, and
polyacetal polycarboxylates.
Examples of such polycarboxylate builders are sodium and
potassium ethylenediaminetetraacetate: sodium 'and potassium
~o nitrilotriacetate: the water-soluble salts of phytic acid, e.g.,
sodium and potassium phytates, disclosed in U . S. Patent
2,739,942, Eckey, issued March 27, 1956
the polycarboxylate materials described in U . S . Patent
3,364,103, - and the water
soluble salts of polycarboxylate polymers and copolymers describ
ed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967,
Useful detergent builders include the water-soluble salts of
polymeric aliphatic polycarboxylic acids having the following
~o structural and physical characteristics: (a) a minimum molecular
weight of about 350 calculated as to the acid form; ~b) an equi-
valent weight of about 50 to about 80 calculated as to acid form;
(3) at least 45 mole percent of the monomeric species having at
least two carboxyl radicals separated from each other by not more
than two carbon atoms; ~d) the site of attachment of the polymer
chain of any carboxyl-containing radical being separated by not
more than three carbon atoms along the polymer chain from the
site of attachment of the next carboxyl-containing radical.
Specific examples of such builders are the pobymers and copoly~
~c~ mers of itaconic acid, aconitic acid, maleic acid, mesaconic acid,
fumaric acid, methylen~ malonic acid, and citraconic acid.
Other suitable polycariooxylate builders include the water-
soluble salts, especially the sodium and potassium salts, of mellitic
acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid,
oxydiacetic acid, carboxymethyloxysuccinic acid, carboxymethyl-
oxymalonic acid, cis-cyclohexanehexacarboxylic acid, cis-cyclo-
pentanetetracarboxylic ac;d and oxydisuccinic acid.
.. . . .
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Other polycarboxylates for use herein are the polyacetal
carboxylates described in U.S. Patent 4,144,226, issued March 13,
1979 to Crutchfield et al, and in U.S. Patent 4,146,495, issued
March 27, 1979 to Crutchfield et al,
Sodium and potassium nitrilotriacetates are highly preferred
builders for use in the present compositions.
Polyphosphonate builders useful herein are disclosed in U.S.
Patent 3,213,030, Diehl, issued October 19, 1965, U.S. Patent
3,433,021, Roy, issued January 14, 1968, U.S. Patent 3,2g2,121,
Gedge, issued January 9, 1969 and U.S. Patent 2,599,807, Bers-
worth, issued June 10, 1952, ~`~~~~
Preferred polyphosphonate builders are the sodium and potassium
salts of ethylene diphosphonic acid, ethane l-hydroxy~ diphos-
15 phonic acid, and ethane-l,i,2-triphosphonic acid.
Preferred aminopolyphosphonate builders ara the sodium and
potassium salts of diethylenetriaminepentamethylenephosphonic
acid, hexamethylenediaminetetramethylenephosphonic acid, diethyl-
enediaminetetramethylenephosphonic acid, and nitrilotrimethylene-
20 phosphonic acid.
Polyphosphates useful herein include the water soluble
tripolyphosphates, pyrophosphates, and the polymeric metaphos-
phates having a degree of polymerization of from about 6 to 21.
However, the tripolyphosphates and metaphosphates tend to
25 hydrolyze to a mixture of orthophosphate and pyrophosphate with
prolonged storage in aqueous solutions. 5ince the orthophos-
phates precipitate but do not sequester water-hardness ions, the
pyrophosphates are the preferred polyphosphates for use in the
present invention. Particularly preferred is potassium pyrophos-
30 phate since sodium pyrophosphate has a tendency to precipitatefrom concentra~ed solutions at low storage temperatures.
It is to be understood that while the alkali metal (and par-
ticularly the sodium and potassium) salts of the foregoing deter-
gency builders are preferred for use herein frorn economic and
35 solubility standpoints, the ammonium, alkanolammonium, e.g.,
.. . . .... . ... ... . . . . . ... . .. ..
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monoethanolamine, diethanolamine, and the like, water-soluble
salts of any of the foregoing buiiders can be used.
H ydrotrope
The compositions herein can contain from about 0% to about
25~o, preferably from about 2% to about 15%, most preferably from
about 4% to about 10%, by weight of a hydrotrope. The hydro-
tropè helps to solubilize the surfactants and builders in the water
phasè under a wide variety of conditions. The types and levels
of hydrotrope needed for optimum product phase stability and
viscosity will be dependent on the types and levels of the other
components used herein.
The hydrotropes of the present invention are water soluble
and preferably have an HLB value above about 14. Suitable
hydrotropes have shorter alkyl chain lengths than the correspon-
ding surfactants typically used in detergent compositions~ For
example, the soluble salts, particularly the sodium and potassium
salts, of toluene sulfonate, xylene sulfonate, and cumene sul-
fonate are preferred hydrophilic stabilizing a~ents in the practice
of the invention. The cations are the same as or compatible with
those of the anionic alcohol polyethoxylate sulfa~e surfactants
herein .
Phosphate esters, particulariy those with a predominance of
single alkyl groups and designated primary esters, can have the
hydrophilic characteristics necessary to assist in the formation of
an isotropic liquid detergent composition. 'Emphos' PS-413 and
PS-236 ~Yitco Chemical Company) and 'Gafac PE-510' ~CAF C:orpor-
ation) are commercially available phosphate materials suitable as
the hydrotrope in the practice of the invention. Preferred phos-
phate esters will contain a high proportion of monoalkyl phosphate
esters and can be of the type consisting of the condensation
product of the reaction of R(OC2H4~xOH and a phosphoric or
polyphosphoric acid, R being an alkyl or alkyl phenyl group, said
alkyl containing from about 4 to about 18 carbon atoms and x
being 0 to 20.
Ethoxylated nonionic surfactants with a relatively high
degree of ethoxylation and a corresponding high HLE3 value can
find use in the compositions of the present invention.
* Trademark
** Trademark
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1~1ixtures of hydrotropes, especially mixtures of lower alkyl-
benzene sulfonates, such as toluene sulfonate, and phosphate
esters, can be used, but preferably no phosphorus is present~
Water
The compositions of this invention contain from about 40% to
about 70~, preferably from about 45% to about 60%, by weight of
water .
Optional Components
The compositions of the present invention preferabiy contain
minor amounts of a suds modifying agent, such as fatty acids and
the silicone materials, microcrystalline waxes and phosphate esters
described in U.S. Patent 4,28~,532, Leikhim et al, issued August
1 8 , 1 981, particularly from Column 7 , line 25 to Column 9 , line 8~
The fat~y acld soap and ester
mixtures described in U . S . Patent 4, 017, 409, Demessemaekers et
al, issued April 12, 1g77 ~ are
also useful suds suppressors herein.
Optional components which can also be added in minor
amounts lgenerally less than about 10%, preferably less than 5%
by weight) to the compositions of the present invention include
cosurfactants; cobuilders; bleaching agents; bleach activators,
soil release agents; soil suspending agents; corrosion inhibitors;
dyes; fillers; optical brighteners; germicides; enzymes; enzyme-
stabilizing agents; perfumes; carriers; opacifiers; and the like.
All percentages, parts, and ratios used herein are by weight
unless otherwise specified.
The following nonlimiting examples illustrate the compositions
of the present invention.
.... _ . . . . , , ,, .. ... . . .. . . . .~.... . .. . .. .. . .. . , . .. . _
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EXAMPLES
Wt. %
Component I 11 111 IV V Vl
C12 16 alkyl dimethylamine 6.6 4.0 4.2
oxide
C12-16 alkyl diethanolamide 6.6 8.5 3.3
Sodium C14_15 allcyl poly- 8.1 7.0 7.8 8.1 6.8 4.2
ethoxylat0 ~x) sulfate
(x)= (0.7) (0.7)(1.1) (1.0) (1.1) (1.7)
Monoethanolamine Cl 1 13 3 9 3 . 63 . 9 3. 9 3 . 5 4. 9
linear alkylbenzene sulfonate
Sodium toluene sulfonate 8.0 8.û 6.0 5.5 6.0 6.0
Sodium nitrilotriacetate 18.2 18.2 21.0 18.2 18.2 18.2
Oleic acid 0.5 t.5
lS Monoethanolamine 5.4 5.4 6.0 3.9 4.2 5.6
Water and minors ~ -Balance to 100
Reserve alkalinity 3.0 3.0 3~5 3.0 2.9 2.7
The above compositions were prepared by mixing the compo-
nents to form single phase isotropic liquids.
Other compositions of the present invention are obtained
when the diethanolarnide in Examples IV-VI is replaced with the
corresponding monoethanolamide, with coconutalkyl monoethanol-
amide additionally containing 1 or 2 ethylene oxide units in the
ethanol group, or with oleyl diethanolamide.
When the alkylbenzene sulfonate sur~actant in the above
compositions is replaced with sodium C1 4-1 6 alkane sulfo a
sodium alpha-olefin sulfonate containing from 14 to 16 carbon
atoms, sodium 2-acetoxy-dodecane-1-sulfonate, potassium ~-meth-
oxytridecanesulfonate or sodium hexyl-~s-sulfomyristate, other
compositions within the invention are obtained.
Other compositions herein are also obtained when the sodium
nitrilotriacetate in the above compositions is replaced with sodium
citrate, potassium pyrophosphate, or with a 1:1 weight ratio
mixture of sodium nitrilotriacetate and sodium ethane 1-hydroxy-
1,1-diphosphona~e, and the monoethanolamine level is adjusted to
provicle the indicated reserve alkalinity.
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Other compositions of the present invention are obtained
when the monoethanolamine level in the above compositions is
adjusted to provide a reserve alkalinity of 2.6, 3.8 or 4.6
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