Note: Descriptions are shown in the official language in which they were submitted.
133~89S
HEAVY DUTY LIQUID LAUNDRY DETERGFNTS
CONTAINING ANIONIC AND NONIONIC SURFACTANT,
BUILDER AND PROTEOLYTIC ENZYME
TECHNICAL FIELD
The present invention relates to heavy duty liquid laundry
detergent compositions containing synthetic anionic and
ethoxylated nonionic surfactant, detergency builder, specific
proteolytic enzyme, an enzyme stabilization system, and water.
The compositions have a pH in a 10% by weight solution in water at
20C of between about 7.0 and 9.0, a Critical Micelle
Concentration of less than or equal to about 200 ppm, and an
air/water Interfacial Tension above the Critical Micelle
Concentration of less than or equal to about 32 dynes/cm at 35 C
in distilled water. The compositions are preferably clear,
homogeneous, and stable and provide good cleaning performance,
particularly through-the-wash on enzyme-sensitive stains.
BACKGROUND OF THE INVENTION
Laundry detergents containing high levels of anionic sur-
factant and builder, and capable of providing superior cleaningperformance, are currently on the market. Some of these
compositions contain enzymes to enhance removal of
enzyme-sensitive stains. The stabilization of enzymes is
particularly difficult in these compositions because anionic sur-
factants, especially alkyl sulfates, tend to denature enzymes andrender them inactive. Detergency builders can also sequester the
calcium ion needed for enzyme activity and/or stability.
There is a continuing need for the development of new enzymes
that provide improved performance and better stability in heavy
duty liquid detergent compositions, particularly those containing
high levels of anionic surfactant and builder. Once these enzymes
- 1336895
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are developed, it is then difficult to formulate a composition
containing them that is clear, homogeneous and phase stable,
maintains enzyme stability over time in product, and is an
excellent fabric cleaner.
European Patent Application 130,756, Bott et al., published
January 9, 1985, discloses specific proteolytic enzymes and
methods for their preparation. The enzymes of this reference are
said to be useful in laundry detergents, both liquid and granular.
They can be combined with surfactants (including anionics),
builders, bleach and/or fluorescent whitening agents.
European Patent Application Serial No. 199,404, Venegas,
published October 29, 1986, discloses heavy duty liquid laundry
detergents containing a specific protease referred to as "Protease
A", anionic surfactant, detergency builder, and calcium ion. The
compositions provide improved cleaning performance, particularly
through-the-wash, of enzyme-sensitive stains such as grass, blood,
gravy and chocolate pudding.
European Patent Application Serial No. 199,405, Venegas,
published October 29, 1986, discloses liquid detergent
compositions containing synthetic surfactant, the same Protease A,
boric acid or a boron compound capable of forming boric acid in
the composition, and calcium ion. The compositions exhibit
improved enzyme stability because the boric acid stabilizes the
Protease A to a greater degree than it does other proteolytic
enzymes. Preferred laundry detergent compositions containing
anionic surfactant and detergency builder also provide improved
cleaning performance, particularly through-the-wash, on enzyme-
sensitive stains.
An improved proteol~vtic enzyme referred to herein as "Protease B" is
described in European Patent Publication No. EP-A 251446, published November
23, 1988. Protease B differs from the above cited Protease A in that it has a
leucine substituted for the tyrosine in position 217 on the protein backbone.
~.~
13~689~
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U.S. Patent 4,507,219, Hughes, issued March 26, 1985,
discloses heavy duty liquid laundry detergents which may contain
proteolytic enzyme along with anionic surfactant, optional
quaternary ammonium, amine or amine oxide surfactants, saturated
fatty acid, polycarboxylate builder, a neutralization system, and
a solvent system. The compositions are isotropic liquids.
International Patent Publication No. W087/04461, Stabinsky,
published July 30, 1987, discloses a specific enzyme and methods
for its preparation. The difference between the European
application enzyme structure and the present enzyme structure is
- replacement of the asparagine residue in the 218 position on the
protein backbone with serine, valine, threonine, cysteine,
glutamine or isoleucine. Said replacement is claimed to impart
improved pH and heat stability to the enzyme.
U.S. Patent 4,670,179, Inamorato et al., issued June 2, 1987;
UK Patent Application 2,178,054, published February 4, 1987; UK
Patent Application 2178055, published February 4, 1987; U.S.
Patent 4,661,287, Crossin, issued April 28, 1987; U.S. Patent
4,529,525, Dormal et al., issued July 16, 1985; and U.S. Patent
4,652,394, Inamorato et al., issued March 24, 1987, disclose
stabilized, single-phase liquid detergent compositions containing
proteolytic enzymes, an enzyme stabilization system, nonphosphate
builder salts, and/or polymeric soil removal/release systems.
U.S. Patent 4,608,189, Koch et al., issued August 26, 1986,
discloses aqueous detergent compositions, essentially free of
inorganic builder salts, which contain proteolytic enzymes and
polyoxyethylene surfactants.
The following references disclose various stabilization
systems in liquid detergent compositions containing enzymes: U.S.
Patent 4,261,868, Hora et al, issued April 14, 1981; U.S. Patent
4,404,115, Tai, issued September 13, 1983; U.S. Patent 4,318,818,
Letton et al., issued March 9, 1982; U.S. Patent 4,243,543,
Guilbert et al, issued January 6, 1981; U.S. Patent 4,529,525,
133689~
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Dormal et al., issued July 16, 1985; and U.S. Patents 4,537,706
and 4,537,707, both Severson, Jr., issued August 27, 1985.
It is an object of this invention to provide heavy duty
liquid detergent compositions comprising a proteolytic enzyme
which have improved cleaning performance.
It is also an object of this invention to provide heavy duty
liquid detergent compositions comprising a proteolytic enzyme
which are clear, homogeneous suspensions that are stable at room
temperature.
It is further an object of this invention to provide heavy
duty liquid detergent compositions comprising a proteolytic enzyme
which have improved enzyme stability.
It is yet another object of this invention to provide heavy
duty liquid detergent compositions comprising a proteolytic enzyme
which clean enzyme-sensitive stains, such as grass, blood, gravy
and chocolate pudding stains, as well as or better than currently
available heavy duty liquid detergent compositions comprising
proteolytic enzymes.
These and other objects are attained as a result of
formulating certain levels of Protease B, synthetic anionic
surfactant, ethoxylated nonionic surfactant, detergency builder, a
conventional enzyme stabilization system, and water at a pH in a
10% by weight solution in water at 20-C of between about 8.0 and
8.5. This composition is preferably clear, homogeneous, and phase
stable, and has good cleaning performance and enzyme stability.
SUMMARY OF THE INVENTION
The present invention relates to a heavy duty liquid laundry
detergent composition comprising, by weight:
(a) from about 10% to about 50% of a synthetic anionic
surfactant;
(b) from about 2% to about 14% of an ethoxylated nonionic
surfactant;
(c) from about 5% to about 20% of a detergency builder;
133689~
(d) from about 0.01% to about 5% of the proteolytic enzyme
characterized by the following amino acid sequence:
Ala Gln Ser Val Pro Tyr Gly Val Ser Gln Ile Lys Ala Pro
Ala Leu His Ser Gln Gly Tyr Thr Gly Ser Asn Val Lys Val
30 40
Ala Val Ile Asp Ser Gly Ile Asp Ser Ser His Pro Asp Leu
Lys Val Ala Gly Gly Ala Ser Met Val Pro Ser Glu Thr Asn
. 60 70
Pro Phe Gln Asp Asn Asn Ser His Gly Thr His Val Ala Gly
Thr Val Ala Ala Leu Asn Asn Ser Ile Gly Val Leu Gly Val
Ala Pro Ser Ala Ser Leu Tyr Ala Val Lys Val Leu Gly Ala
100 110
Asp Gly Ser Gly Gln Tyr Ser Trp Ile Ile Asn Gly Ile Glu
120
Trp Ala Ile Ala Asn Asn Met Asp Val Ile Asn Met Ser Leu
130 140
Gly Gly Pro Ser Gly Ser Ala Ala Leu Lys Ala Ala Val Asp
150
2Lys Aia Val Ala Ser Gly Val Val Val Val Ala Ala Ala Gly
160
Asn Glu Gly Thr Ser Gly Ser Ser Ser Thr Val Gly Tyr Pro
170 180
Gly Lys Tyr Pro Ser Val Ile Ala Val Gly Ala Val Asp Ser
190
Ser Asn Gln Arg Ala Ser Phe Ser Ser Val Gly Pro Glu Leu
200 210
Asp Val Met Ala Pro Gly Val Ser Ile Gln Ser Thr Leu Pro
220
Gly Asn Lys Tyr Gly Ala Leu Asn Gly Thr Ser Met Ala Ser
133~89~
230
Pro His Val Ala Gly Ala Ala Ala Leu Ile Leu Ser Lys His
240 250
Pro Asn Trp Thr Asn Thr Gln Val Arg Ser Ser Leu Glu Asn
260
Thr Thr Thr Lys Leu Gly Asp Ser Phe Tyr Tyr Gly Lys Gly
270 275
Leu Ile Asn Val Gln Ala Ala Ala Gln; (referred to herein as
Protease B)
(e) from about 0.5% to about 1570 of an enzyme stabilization
system; and
(f) from about 30% to about 80% of water;
said composition containing (a) and (b) in a ratio of from 1:1 to
5:1; having a pH, in a 10% by weight solution in water at 20-C, of
from about 7.0 to about 9.0; and having a Critical Micelle
Concentration of less than or equal to about 200 ppm, and an
air/water Interfacial Tension above the Critical Micelle
Concentration of less than or equal to about 32 dynes/cm at 35-C
in distilled water.
DESCRIPTION OF THE INVENTION
The instant compositions contain six essential ingredients
which are: (1) synthetic anionic surfactant, (2) ethoxylated
nonionic surfactant, (3) detergency builder, (4) a specific
proteolytic enzyme, (5) an enzyme stabilization system, and (6)
water. The weight ratio of synthetic anionic surfactant to
ethoxylated nonionic surfactant is from about 1:1 to about 5:1.
The compositions have a pH in a 10% by weight solution in water at
20 C of from about 7.0 to about 9.0, a Critical Micelle
Concentration of less than or equal to about 200 ppm, and an
air/water Interfacial Tension at the Critical Micelle
Concentration of less than or equal to about 32 dynes/cm at 35 C
in distilled water. The compositions are preferably clear,
homogeneous and phase stable, and have good cleaning performance
and enzyme stability.
l336~9~
A. SYnthetic Anionic Surfactant
The compositions of the present invention contain from about
10% to about 50%, preferably from about 15% to about 50%, more
preferably from about 20% to about 40%, and most preferably from
about 20% to about 30%, by weight of a synthetic anionic
surfactant. Suitable synthetic anionic surfactants are disclosed
in U.S. Patent 4,285,841, Barrat et al., issued August 25, 1981,
and in U.S. Patent 3,929,678, Laughlin et al., issued December 30,
lg75
Useful anionic surfactants include the water-soluble salts,
particularly the alkali metal, ammonium and alkylolammonium (e.g.,
monoethanolammonium or triethanolammonium) salts, of organic
sulfuric reaction products having in their molecular structure an
alkyl group containing from about lO to about 20 carbon atoms and
a sulfonic acid or sulfuric acid ester group. (Included in the
term "alkyl" is the alkyl portion of aryl groups.) Examples of
this group of synthetic surfactants are the alkyl sulfates,
especially those obtained by sulfating the higher alcohols (Cg-Clg
carbon atoms) such as those produced by reducing the glycerides of
tallow or coconut oil; and the alkylbenzene sulfonates in which
the alkyl group contains from about 9 to about l5 carbon atoms, in
straight chain or branched chain configuration, e.g., those of the
type described in U. S. Patents 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkylbenzene sul-
fonates in which the average number of carbon atoms in the alkyl
group is from about 11 to 14.
Other anionic surfactants herein are the water-soluble salts
of: paraffin sulfonates containing from about 8 to about 24 (pre-
ferably about 12 to 18) carbon atoms; alkyl glyceryl ether sul-
fonates, especially those ethers of Cg 18 alcohols (e.g., those
derived from tallow and coconut oil); alkyl phenol ethylene oxide
ether sulfates containing from about l to about 4 units of
ethylene oxide per molecule and from about 8 to about 12 carbon
atoms in the alkyl group; and alkyl ethylene oxide ether sulfates
133689S
containing about 1 to about 4 units of ethylene oxide per molecule
and from about 10 to about 20 carbon atoms in the alkyl group.
Other useful anionic surfactants include the water-soluble
salts of esters of alpha-sulfonated fatty acids containing from
about 6 to 20 carbon atoms in the fatty acid group and from about
1 to 10 carbon atoms in the ester group; water-soluble salts of
2-acyloxy- alkane-l-sulfonic acids containing from about 2 to 9
carbon atoms in the acyl group and from about 9 to about 23 carbon
atoms in the alkane moiety; water-soluble salts of olefin
sulfonates containing from about 12 to 24 carbon atoms; and
beta-alkyloxy alkane sulfonates containing from about 1 to 3
carbon atoms in the alkyl group and from about 8 to 20 carbon
atoms in the alkane moiety.
Preferred anionic surfactants are the Clo-Clg alkyl sulfates
and alkyl ethoxy- sulfates containing an average of up to about 4
ethylene oxide units per mole of alkyl sulfate, Cll-C13 linear
alkylbenzene sulfonates, and mixtures thereof.
B. EthoxYlated Nonionic Surfactant
A second essential ingredient is from about 2% to about 14%,
preferably from about 2% to about 8%, most preferably from about
3% to about 5% by weight, of an ethoxylated nonionic surfactant.
The weight ratio of synthetic anionic surfactant (on an acid
basis) to nonionic surfactant is from about 1:1 to about 5:1,
preferably from about 2:1 to about 5:1, most preferably from about
3:1 to about 4:1. This is to ensure the formation and adsorption
of sufficient hardness surfactants at the air/water interface to
provide good greasy/oily soil removal.
The ethoxylated nonionic surfactant is of the formula
Rl(OC2H4)n0H, wherein Rl is a C10-cl6 alkyl group or a Cg-C12
alkyl phenyl group, n is from about 3 to about 9, and said
nonionic surfactant has an HLB (Hydrophilic-Lipophilic Balance) of
from about 6 to about 14, preferably from about 10 to about 13.
These surfactants are more fully described in U.S. Patents
4,285,841, Barrat et al., issued August 25, 1981, and 4,284,532,
Leikhim et al., issued August 18, 1981. Particularly
preferred are condensation products of
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.9
C12-C1s alcohols with from about 3 to about 8 moles of ethylene
oxide per mole of alcohol, e.g., C12-C13 alcohol condensed with
about 6.5 moles of ethylene oxide per mole of alcohol.
' - C. Optional Cosurfactants
Optional cosurfactants for use with the above ethoxylated
nonionic surfactants include amides of the formula
O R2
Rl - C - N - R3
wherein Rl is an alkyl, 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, provided at least one of R2 and R3 contains a hydroxyl
group.
Preferred amides are the Cg-C20 fatty acid alkylol amides in
which 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 C12-C16 fatty acid monoethanol and
diethanol amides.
If used, amides are preferably present at a level such that
the above ethoxylated nonionic surfactant and amide surfactant is
in a weight ratio of from about 4:1 to 1:4, preferably from about
3:1 to about 1:3.
Preferred and optional cosurfactants, used at a level of from
about 0.15% to about 1%, are the quaternary ammonium, amine and
amine oxide surfactants described in U.S. Patent 4,507,219,
Hughes, issued March 26, 1985.
Of the above, the Clo-C14 alkyl trimethylammonium salts are
preferred, e.g., decyl trimethylammonium methylsulfate, lauryl
trimethylammonium chloride, myristyl trimethylammonium bromide and
coconut trimethylammonium chloride and methylsulfate. From about
1336895
- 10
0.2% to about 0.8% of monoalkyl trimethylammonium chloride is
preferred.
D. DeterqencY Builder
The compositions herein contain from about 5% to about 20%,
preferably from about 10% to about 15%, by weight of a detergency
builder which can be a fatty acid containing from about 10 to
about 18 carbon atoms and/or a polycarboxylate, polyphosphonate
and/or polyphosphate builder. Preferred are from 0 to about lO~o
(more preferably from about 3% to about 10%) by weight of sat-
urated fatty acids containing from about 12 to about 14 carbon
atoms, along with from 0 to about 10%, more preferably from about
2% to about 8%, most preferably from about 2% to about 5%, by
weight of a po1ycarboxylate builder, most preferably citric acid,
in a weight ratio of from 1:1 to 3:1.
Since the proteolytic enzymes herein appear to provide
optimum performance benefits versus other enzymes when the builder
to water hardness ratio is close to one, the compositions
preferably contain sufficient builder to sequester from about 2 to
about 10, preferably from about 3 to about 8, grains per gallon of
hardness.
Suitable saturated fatty acids can be obtained from natural
sources such as plant or animal esters (e.g., palm kernel oil,
palm oil and coconut oil) or synthetically prepared (e.g., via the
oxidation of petroleum or by hydrogenation of carbon monoxide via
the Fisher-Tropsch process). Examples of suitable saturated fatty
acids for use in the compositions of this invention include
capric, lauric, myristic, coconut and palm kernel fatty acid.
Preferred are saturated coconut fatty acids; from about 5:1 to 1:1
(preferably about 3:1) weight ratio mixtures of lauric and
myristic acid; mixtures of the above with minor amounts (e.g.,
1%-30% of total fatty acid) of oleic acid; and palm kernel fatty
acid.
The compositions herein preferably also contain the
polycarboxylate, polyphosphonate and polyphosphate builders
1336895
--11--
described in U.S. Patent 4,284,532, Leikhim et al.,
issued August 18, 1981. Water-soluble polycarboxylate
builders, particularly citrates, are preferred of this
group. Suitable polycarboxylate builders include the
various aminopolycarboxylates, cycloalkane polycar-
boxylates, ether polycarboxylates, alkyl polycarboxy-
lates, epoxy polycarboxylates, tetrahydrofuran
polycarboxylates, benzene polycarboxylates, and
polyacetal polycarboxylates.
Examples of such polycarboxylate builders are sodium
and potassium ethylenediaminetetraacetate; sodium and
potassium nitrilotriacetate; the water-soluble salts of
phytic acid, e.g., sodium and potassium phytatese,
disclosed in U.S. Patent 1,739,942, Eckey, issued
March 2i, 1956; the polycarboxylate materials described
in U.S. Patent 3,364,103; and the water-soluble salts of
polycarboxylate polymers and copolymers described in U.S.
Patent 3,308,067, Diehl, issued March 7, 1967.
Other useful detergency builders include the water-soluble
salts of polymeric aliphatic polycarboxylic acids having the
following structural and physical characteristics: (a) a minimum
molecular weight of about 350 calculated as to the acid form; (b)
an equivalent 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 polymers and copolymers
of itaconic acid, aconitic acid, maleic acid, mesaconic acid,
fumaric acid, methylene malonic acid, and citraconic acid.
Other suitable polycarboxylate builders include the
water-soluble salts, especially the sodium and potassium salts, of
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mellitic acid, citric acid, pyromellitic acid, benzene
pentacarboxylic acid, oxydiacetic acid, carboxymethyloxysuccinic
acid, carboxymethyloxymalonic acid, cis-cyclohexanehexacarboxylic
acid, cis-cyclopentanetetracarboxylic acid and oxydisuccinic acid.
Other polycarboxylates are the polyacetal carboxylates
described in U.S. Patent 4,144,226, issued March 13, 1979 to
Crutchfield et al., and U.S. Patent 4,146,495, issued March 27,
1979 to Crutchfield et al.
Other detergency builders include the aluminosilicate ion
exchange material described in U.S. Patent 4,405,483, Kuzel et
al., issued September 20, 1983.
Other preferred builders are those of the general formula
R-CH(COOH)CH2(COOH), i.e. derivatives of succinic acid, wherein R
is Clo-C20 alkyl or alkenyl, preferably C12-C16, or wherein R may
be substituted with hydroxyl, sulfo, sulfoxy or sulfone
substituents. These succinate builders are preferably used in the
form of their water soluble salts, including the sodium, potassium
2 and alkanolammonium salts. Specific examples of succinate
builders include: lauryl succinate, myristyl succinate, palmityl
succinate, 2-dodecenyl succinate, and the like.
E. Tartrate Succinate Builder
The compositions herein preferably contain from 0 to about
2 10%, preferably from 0 to about 6%, by weight on an acid basis, of
a tartrate succinate builder material selected from the group
consisting of:
i ) HOCH - CH - O - CH - CHz
COOX COOX COOX COOX
wherein X is a salt-forming cation;
ii) CH2 - CH - O - CH - CH - O - CH - CH2
COOX COOX COOX COOX COOX COOX
wherein X is a salt-forming cation; and
iii) mixtures thereof.
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The tartrate succinate compounds used herein are described in
U.S. Patent 4,663,071, Bush et al., issued May 5, 1987.
F. Neutralization SYstem
The present compositions can also optionally contain from
about 0 to about 0.04 moles, preferably from about 0.01 to about
0.035 moles, more preferably from about 0.015 to about 0.03 moles,
per 100 grams of composition of an alkanolamine selected from the
group consisting of monoethanolamine, diethanolamine, trietha-
nolamine, and mixtures thereof. Low levels of the alkanolamines,
particularly monoethanolamine, are preferred to enhance product
stability, detergency performancet and odor. However, the amount
of alkanolamine should be minimized for best chlorine bleach
compatibi-lity.
In addition, the compositions contain sodium ions, and
preferably potassium ions, at a level sufficient to neutralize the
anionic species and provide the desired product pH.
G. ProteolYtic EnzYme
The compositions of the present invention contain from about
0.01% to about 5%, preferably from about 0.1% to about 2%, by
weight of the proteolytic enzyme referred to herein as Protease B.
This proteolytic enzyme, and methods for its Preparation, is
described in European Patent Publication No. 251,446,
published January 7, 1988. Methods for its preparation
are also described in European Patent Publication
130,756, Bott et al., published January 9, 1985.
The described proteolytic enzyme is preferably
included in an amount sufficient to provide an activity
of from about 0.05 to about 1.0, more preferably from
about 0.1 to about 0.75, most preferably from about 0.125
to about 0.5, mg of active enzyme per gram of
composition.
- 14 1336895
H. EnzYme Stabilization SYstem
An enzyme stabilization system, comprising calcium ion, boric
acid, propylene glycol and/or short chain carboxylic acids, is the
fifth essential element of the instant heavy duty liquid detergent
composition. The enzyme stabilization system comprises from about
0.5% to about 15% by weight of the composition.
The composition preferably contains from about 0.01 to about
50, preferably from about 0.1 to about 30, more preferably from
0 about 1 to about 20, millimoles of calcium ion per liter. The
level of calcium ion should be selected so that there is always
some minimum level available for the enzyme, after allowing for
complexation with builders, etc., in the composition. Any water-
soluble calcium salt can be used as the source of calcium ion,
including calcium chloride, calcium formate, and calcium acetate.
A small amount of calcium ion, generally from about 0.05 to about
0.4 millimoles per liter, is often also present in the composition
due to calcium in the enzyme slurry and formula water. From about
0.03% to about 0.6% of calcium formate is preferred.
A second preferred enzyme stabilizer is polyols containing
only carbon, hydrogen and oxygen atoms. They preferably contain
from 2 to 6 carbon atoms and from 2 to 6 hydroxy groups. Examples
include propylene glycol (especially 1,2 propanediol, which is
preferred), ethylene glycol, glycerol, sorbitol, mannitol, and
glucose. The polyol generally represents from about 0.5% to about
15%, preferably from about 1.5% to about 8%, by weight of the
composition. Preferably, the weight ratio of polyol to any boric
acid added is at least 1, more preferably at least about 1.3.
The compositions preferably also contain the water-soluble,
short chain carboxylates described in U.S. Patent 4,318,818,
Letton et al., issued March 9, 1982. The formates are
preferred and can be used at levels of from about 0.05%
to about 5%, preferably from about 0.2% to about 2%, most
preferably from about 0.4% to about 1.5%, by weight of
the composition. Sodium formate is preferred.
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-
- 15 -
The compositions herein also optionally contain from about
0.25% to about 5%, most preferably from about 0.5% to about 3%, by
weight of boric acid. The boric acid may be, but is preferably
' - not, formed by a compound capable of forming boric acid in the
composition. Boric acid is preferred, although other compounds
such as boric oxide, borax and other alkali metal borates (e.g.,
sodium ortho-, meta- and pyroborate, and sodium pentaborate) are
suitable. Substituted boric acids (e.g., phenylboronic acid,
butane boronic acid, and p-bromo phenylboronic acid) can also be
used in place of boric acid.
I. Water
Finally, the compositions herein contain from about 30% to
about 80%, preferably from about 35% to about 60%, by weight of
water.
J. Suds Suppressor
Another optional component for use in the liquid detergents
herein is from 0 to about 1.5%, preferably from about 0.5% to
about 1.0%, by weight of silicone based suds suppressor agent.
Silicones are widely known and taught for use as highly
effective suds controlling agents. For example, U.S. Patent
3,455,839 relates to compositions and processes for defoaming
aqueous solutions by incorporating therein small amounts of
polydimethylsiloxane fluids.
Useful suds controlling silicones are mixtures of
silicone and silanated silica as described, for instance,
in Canadian Patent Application 947,608.
Silicone defoamers and suds controlling agents have been
successfully incorporated into granular detergent compositions by
protecting them from detergent surfactants as in U.S. Patent
3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392,
Baginski et al., issued March 24, 1987.
A preferred silicone based suds suppressor for use herein is
a suds suppressing amount of a suds controlling agent consisting
essentially of:
1336g95
- 16 -
(i) polydimethylsiloxane fluid having a viscosity of from
about 20 cs. to about 1500 cs. at 25-C;
(ii) from about 5 to about 50 parts per 100 parts by weight
of (i) of siloxane resin composed of (CH3)3 Sil/2 units
and SiO2 units in a ratio of from (CH3)3 SiOl/2 units
and to SiO2 units of from about 0.6:1 to about 1.2:1;
and
(iii)from about 1 to about 20 parts per 100 parts by weight
of (i) of a solid silica gel;
By "suds suppressing amount" is meant that the formulator of
the composition can select an amount of this suds controlling
agent that will control the suds to the extent desired. The
amount of suds control will vary with the detergent surfactant
selected. For example, with high sudsing surfactants, relatively
more of the suds controlling agent is used to achieve the desired
suds control than with low foaming surfactants.
K. Other Optional ComDonents
Other optional components for use in the liquid detergents
herein include soil removal agents, soil release polymers, antire-
deposition agents such as tetraethylene pentamine ethoxylate (from
about 0.5% to about 3%, preferably from about 1% to about 3%, by
weight), suds regulants, hydrotropes such as sodium cumene
sulfonate, opacifiers, antioxidants, bactericides, dyes, perfumes,
and brighteners known in the art. Such optional components
generally represent less than about 15%, preferably from about
0.5X to about 10%, more preferably from about 1% to about 10%, by
weight of the composition.
The compositions may contain from 0% to about 8%, preferably
from 0% to about 5%, by weight of a C12-C14 alkenyl succinic acid
or salt thereof. These materials are of the general formual
R-CH(COOX)CH2(COOX), wherein R is a C12-C14 alkenyl group and each
X is H or a suitable cation, such as sodium, potassium, ammonium
or alkanolammonium (e.g., mono-, di-, or tri-ethanolammonium).
13368g~
- 17 -
Specific examples are 2-dodecenyl succinate (preferred) and
2-tetradecenyl succinate.
The compositions herein optionally contain from about 0.1% to
about 1%, preferably from about 0.2% to about 0.6%, by weight of
water-soluble salts of ethylenediamine tetramethylenephosphonic
acid, diethylenetriamine pentamethylenephosphonic acid, ethyl-
enediamine tetraacetic acid (preferred), or diethylenetriamine
pentaacetic acid (most preferred) to enhance cleaning performance
when pretreating fabrics.
The compositions herein preferably contaln up to about 10% of
ethanol.
L. Other Requirements
The instant composition has a pH, in a 10% by weight solution
in water at 20'C, of from about 7.0 to about 9.0, preferably from
about 8.0 to about 8.5.
The instant compositions also have a Critical Micelle
Concentration (CMC) of less than or equal to about 200 parts per
million (ppm), and an air/water Interfacial Tension above the CMC
of less than or equal to about 32, preferably less than or equal
to about 30, dynes per centimeter at 35C in distilled water.
These measurements are described in "Measurement of Interfacial
Tension and Surface Tension - General Review for Practical Man",
C. Weser, GIT Fachzeitschrift fvr das Laboratorium, 24 (1980)
642-648 and 734-742, FIT Verlag Ernst Giebeler, Darmstadt, and
Interfacial Phenomena - Equilibrium and DYnamic Effects, C.A.
Miller and P. Neogi, Chapter 1, pp. 29-36 (1985), Marcel Dekker,
Inc. New York.
Enzyme activity can be measured using the PNA assay,
according to reaction with the soluble substrate
succinyl-alanine-alanine-proline-phenylalanine-para-nitrophenol,
which is described in the Journal of American Oil Chemists
Society, Rothgeb, T.M., Goodlander, B.D., Garrison, P.H., and
Smith, L.A., JAOCS, 65, No. 5, May 1988, pages 806-810.
~,
....
__.. ...
13368~5
- 18
The following examples illustrate the compositions of the
present invention. All parts, percentages and ratios used herein
are by weight unless otherwise specified.
- EXAMPLE I
A heavy duty liquid laundry detergent composition of the
present invention is as follows:
ComPonent Active Weight %
C13 linear alkylbenzene sulfonic acid 8.00
C14 15 alkyl polyethoxylate (2.25) sulfonic acid 12.00
1,2 Propanediol 3.50
Sodium diethylenetriamine pentaacetate 0.30
Monoethanolamine 2.00
C12 13 alcohol polyethoxylate (6.5)* 5.00
Ethanol - 8.50
Sodium hydroxide ~~ 3.85
Potassium hydroxide 1.80
C12 14 fatty acid 10.00
Citric acid 4.00
20 Calcium formate 0.12
Sodium formate 0.86
C12 alkyltrimethylammonium chloride 0.50
Tetraethylene pentamine ethoxylate (15-18) 2.00
Water 37.14
Dye 0.08
Perfume 0.25
Protease~ B** 0.099
*Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (@27 mg active enzyme/g stock)
The ingredients listed above are added to a mixing tank with
a single agitator in the order in which they appear below. Before
the proteolytic enzyme, dye and perfume are added, the pH of the
mix is adjusted so that a 10% by weight solution in water at 20C
has a pH of about 8.5.
13368g5
- 19 -
Stock Material Weight Percent
C13 linear alkyl benzene sulfonic acid (96%) 8.33
Alkyl polyethoxylate paste mixture 24.80
C14 15 alkyl polyethoxylate (2-25) 48.38
sulfonic acid
Ethanol (92%) 16.20
Sodium hydroxide 5.12
Water 30.30
1,2 Propanediol
Sodium diethylenetriamine pentaacetate (41%) 0.73
Brightener premix 6.70
Brightener 3.07
Monoethanolamine 7.46
C12 13 alcohol polyethoxylate (6.5)* 29.82
Water 59.65
Monoethanolamine 1.50
C12 13 alcohol polyethoxylate (6.5)* 2.93
Sodium hydroxide (50%) 5.16
Potassium hydroxide (45%) 4.00
C12 14 fatty acid 10.00
Citric acid (50~O) 8.00
Ethanol (92%) 4.87
Calcium formate (10%) 1.20
Sodium formate (30%) 2.87
C12 alkyltrimethylammonium chloride (37%) 1.62
Tetraethylene pentamine ethoxylate (15-18)(80%) 2.50
Water 10.86
Dye 0.08
30 Perfume 0.25
Protease B** 0.099
*Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (27 mg active enzyme/g stock)
This formula is clear, homogeneous, and stable, and has a
Critical Micelle Concentration of about 200 ppm and an air/water
Interfacial Tension above this CMC of about 25 dynes/cm at 35 C in
1336895
- 20 -
distilled water. The composition with Protease~ B provides
superior cleaning of enzyme-sensitive stains, even when compared
to Protease A (described above) at 0.25 mg active enzyme/g product
-- in a 60-F (15.6C) wash at 5 grains per gallon (gpg) hardness (3:1
Ca/Mg).
Protease B also shows superior enzyme stability in the
composition of Example I versus other proteolytic enzymes such as
Protease A and Alcalase~ B (Novo Industries, Copenhagen, Denmark):
10Enzyme Activity*
(after 1 week storage at 37.8C)
% ActivitY Half Life (daYs)
Protease B 58.4 9.1
Protease A 33.6 4.5
Alcalase B 13.7 2.5
*PNA assay
EXAMPLE II
A heavy duty liquid composition of the present invention is as
follows:
ComPonent Active Weight %
C13 linear alkylbenzene sulfonic acid 3.80
C11.g linear alkylbenzene sulfonic acid 3.80
C14 15 alkyl polyethoxylate (2.25) sulfonic acid 11.41
C12 1~ alkyl polyethoxylate (6.5)* 3.80
C12 alkyl trimethyl ammonium chloride 0.28
Sodium cumene sulfonate 2.38
Ethanol 2.61
1,2 Propanediol 2.85
Brightener 0.12
30 Monoethanolamine 1.66
Potassium hydroxide 0.19
Sodium hydroxide 3.85
C12 14 fatty acid 3 33
Citric acid 3.80
35 Tartrate succinate 3.80
133~8~
- 21 -
Sodium formate 0.92
Calcium formate 0.04
Tetraethylene pentamine ethoxylate (15-18) 1.66
Water 48.04
Soil release polymer 1.10
Dye 0.08
Perfume 0.30
Protease B** 0.175
*Alcohol and monoethoxylated alcohol removed
** mg active enzyme/g (@ 27 mg active enzyme/g stock)
The ingredients listed above are added to a mixing tank with
a single agitator in the order which they appear below. Before
addition of soil release polymer, dye, perfume, and proteolytic
enzyme, the pH of the mixture is adjusted such that a 10% by
weight solution in water has a pH of about 8.5.
Stock Material Weiqht Percent
Alkyl polyethoxylate paste mixture 28.28
C14 15 alkyl polyethoxylate (2.25) 40.34
sulfonic acid
Ethanol 40-b 4.98
Sodium hydroxide 5.13
1,2 Propanediol 6.89
Monoethanolamine 2.84
Sodium formate 1.65
Water 38.17
Sodium amine sulfonate (45%) 5.29
Ethanol (92%) 1.31
1,2 Propanediol o.go
Brightener premix 2.59
Brightener 4.63
Monoethanolamine 10.62
C12 13 alcohol polyethoxylate (6.5)* 42.38
Water 42.37
3 C12 13 alcohol polyethoxylate (6.5)* 2.70
133689~
- 22 -
Monoethanolamine 0.58
Potassium hydroxide (45%) 0.42
Sodium hydroxide (50%) 4.80
C13 linear alkyl benzene sulfonic acid (96X) 3.96
C11.g linear alkyl benzene sulfonic acid (97%) 3.92
C12 14 fatty acid 3 33
Citric acid 6.96
Tartrate succinates (34.3%) 11.08
Sodium formate (307O) 3.08
-Calcium formate (10Z) 0.38
C12 alkyl trimethylammonium chloride (37%) 0.76 -~
Tetraethylene pentamine ethoxylate (15-18) (80%) 2.08
Water 15.92
Soil release polymer 1.10
Dye 0.08
Perfume 0.30
Protease B** 0.175 ~`
*Alcohol and monoethoxylated alcohol removed
** mg active enzyme/g (@ 27 mg active enzyme/g stock)
The above formula is clear, stable, and homogeneous, and has
a Critical Micelle Concentration of about 100 ppm and an air/water
Interfacial Tension above that CMC of about 30 dynes/cm at 35-C in
distilled water. The composition with Protease B provides
protease-sensitive stain removal equal to that achieved with the
same formula using 0.35 mg active enzyme/g product of Protease A
(described above).
Protease B also shows superior enzyme stability in the
composition of Example II versus other proteolytic enzymes such
as Protease A and Alcalase B (Novo Industries, Copenhagent
Denmark).
Enzyme Activity*
(After 4 weeks storage at 37.8-C)
% ActivitY Half Life (daYs)
Protease B 16.2 10.7
1336895
- 23 -
Protease A 4.2 6
Alcalase B 0.00
*PNA assay
EXAMPLE III
A heavy duty liquid laundry detergent composition of the
present invention is as follows:
ComDonent Active Weiqht %
C13 linear alkylbenzene sulfonic acid 13.00
C13 14 alkyl sulfuric acid 13.00
C12 13 alcohol polyethoxylate (6.5)* 6.00
Sodium cumene sulfonate 6.30
Ethanol (92%) 2.50
1,2 Propanediol 7.50
Brightener 0.12
Monoethanolamine - Z.00
Potassium hydroxide 0.15
Sodium hydroxide 4.29
C12 14 fatty acid 1.0
20 Tartrate succinate 10.0
Citric acid 4.0
Calcium formate 0.04
Sodium formate 0.86
C12 alkyltrimethylammonium chloride 0.50
Tetraethylene pentamine ethoxylate (15-18) 1.65
Water 25.36
Soil release polymer 1.00
Dye 0.08
Perfume 0.25
30 Protease B** 0.397
*Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (@ 27 mg active enzyme/g stock)
The composition is prepared as in Example II.
l336~95
- 24 -
EXAMPLE IV
A heavy duty liquid laundry detergent composition of the
present invention is as follows:
Com w nent Active Weiqht %
C13 linear alkylbenzene sulfonic acid 4.23
C11.g alkylbenzene sulfonic acid 4.23
C14 15 alkyl polyethoxylate (2.25) sulfonic acid 8.46
C12 13 alkyl polyethoxylate (6.5)* 3.39
Sodium cumene sulfonate 5.45
Ethanol (92%) 1.18
Propanediol 2.89
Brightener 0. 11
Monoethanolamine 1.57
Tartrate succinate 9.62
15 Calcium formate 0.102
Formic acid 0.51
C12 Trimethylammonium chloride 0.51
Tetraethylene pentamine ethoxylate (15-18) 0.96
Water 55.57
20 Soil release polymer 0.90
Silicone suds suppressor 0.10
Protease B** 0.221
*Alcohol and monoethoxylated alcohol removed.
**mg active enzyme/g (@ 27 mg active enzyme/g stock)
The composition is prepared as in Example II.
The above formula is clear, stable, and homogeneous, and has
a Critical Micelle Concentration of about 100 ppm and an air/water
Interfacial Tension above that CMC of about 30 dynes/cm at 35C in
distilled water. The composition with Protease B provides
protease-sensitive stain removal equal to that achieved with the
same formula using 0.35 mg active enzyme/g product of Protease A
(described above).
Protease B also shows superior enzyme stability in the
composition of Example IY versus other proteolytic enzymes such
133~895
- 25 -
as Protease A and Alcalase B (Novo Industries, Copenhagen,
Denmark).
Enzyme Activity*
(After 2 weeks storage at 37.8-C)
% ActivitY Half Life (daYs)
Protease B 64.0 20.7
Protease A 50.0 13.8
Alcalase B --- 3.3
*PNA assay
EXAMPLE V
A heavy duty liquid laundry detergent composition of the
present invention is as follows:
ComDonent Active Weight %
C1o 15 Linear alkylbenzene sulfonic acid 12.86
Sodium C12 14 alkyl sulfate 2.00
1,2 Propanediol 2.00
Diethylenetriamine pentamethylene phosphonic acid 0.70
C14-15 alcohol polyethoxylate (E07) 7.77
20 Ethanol 4.60
Sodium hydroxide 7.00
Soil release polymer 0.46
C12 14 alkenyl succinic acid 11.44
Brightener 0.163
25 Oleic acid 1.80
Citric acid (monohydrate) 2.90
Calcium chloride 0.014
Boric acid 1.00
Silane 0.03
30 Water & miscellaneous Balance
Protease B* 0.28
*419 active enzyme/liter of enzyme
1336895
Stock Material
Premix 1
Water 23.68
Sodium hydroxide 11.50
Citric acid 5.674
Ethanol 4.00
C12 14 alkenyl succinic acid 10.74
C10 15 Linear alkylbenzene sulfonic acid 6.70
62.294
Premix 2
1,2 Propanediol 0.493
Brightener 0.163
C14 15 alcohol polyethoxylate (E07) 1.70
2.356
Premix 3
Water 4.44
Boric acid 1.0
Sodium hydroxide 2.4
Diethylene triamine pentamethylene
phosphonic aid 1.4
9.244
Premix 4
Citric acid 0.126
Calcium chloride 0.015
0.141
Premix 5
Soil release polymer 0.46
Water 0.46
0.92
Finished Product
Premix 1 62.294
1,2 Propanediol 1.507
Clo l5 Linear alkyl benzene sulfonate 6.70
3S C14 15 alcohol polyethoxylate (E07) 6.07
Premix 2 2.356
133689~
- 27 -
Premix 3 9.244
Sodium C12 14 alkyl sulfate 6.66
Oleic acid 1.80
Premix 4 0.141
Premix 5 0.92
Silane 0.03
Protease B 0.28
Water Balance
The ingredients listed above in "Finished Product" are added
to a mixing tank with a single agitator in the order in which they
appear. The pH of the mix is adjusted so that the pH is from 7.5
to 7.8.
The composition with Protease B provides 61% retained5 protease activity after three weeks storage at 35-C.
EXAMPLE VI
A heavy duty liquid laundry detergent composition of the
present invention is as follows:
Component Active Weight %
C10 lsLinear alkylbenzene sulfonic acid 10.25
Triethanolamine C12 14 alkyl sulfate 3.88
1,2 Propanediol 1.50
Diethylenetriamine pentamethylene phosphonic acid 0.765
Triethanolamine (free) 4.335
C14 15 alcohol polyethoxylate (E07) 11.620
Ethanol 5.510
Sodium hydroxide 3.400
Cg 18 fatty acid 10.68
Oleic acid 3.88
30 Citric acid (anhydrous) 0.83
Calcium chloride 0.0167
Sodium formate 0.972
Tetraethylene pentamine ethoxylate (15-18) 0.30
Dye 0.0032
35 Opacifier 0.224
Perfume 0.30
133~89S
- 28 -
Soil release polymer 0.50
N-(ethylene diaminoethyl) aminopropyltrimethoxy
silane 0.030
Silicone suds suppressor 0.0025
Brightener 0.148
Water & miscellaneous Balance
Protease B* 0.28
Amylase** 0.183
*419 active enzyme/liter of enzyme.
**125 PGU active enzyme/gram amylase solution.
The ingredients listed above are added to a mixing tank with
a single agitator. The pH of the mix is adjusted so that it is
between about 8.0 and 8.5.
WHAT IS CLAIMED IS:
