Note: Descriptions are shown in the official language in which they were submitted.
W O 92/19708 2 1 0 9 5 2 5 P ~ /US92/03373-
LIQUID DETERGENTS WITH AROMATIC BORATE ESTER
TO INHIBIT PROTEOLYTIC ENZYME
Field of the Invention
This invention relates to liquid detergent compositions comprising anionic
or nonionic surfac;ant, proteolytic enzyme, second enzyme, and an aromatic
borate ester.
Back~round of the invention
A commonly encountered problem with protease-cont~inine liquid detergents is
the degradation of second enzymes in the composition by the proteolytic
enzyme. The stability of the second enzyme upon storage in product and its
effect on cleaning are impaired by the proteolytic enzyme.
Boric acid and boronic acids are known to reversibly inhibit proteolytic
enzymes. A discussion of the inhibition of one serine protease, subtilisin,
by boronic acid is provided in Philipp, M. and Bender, M.L., "Kinetics o~
Subtilisin and Thiosubtilisin", Molecular & Cellular Biochemistry, vol. 51,
pp. 5-32 (1983).
One type of boronic acid, peptide boronic acid, is discussed as an inhibitor
of trypsin-like serine proteases, especially in pharmaceuticals, in European
Patent Application 0 293 881, Kettner et al., published December 7, 1988.
German Patent 3 918 761, published June 28, 1990 discloses liquid enzyme
concentrate which is said to be usable as a raw material solution for making
W O 92/19708 2 1 0 Y 5 2 ~ P ~ /US92/03373
liquid detergents and the like. The concentrate contains hydrolase,
propylene glycol and boric acid or its salt.
U.S. Patent 4,537,707, issued August 27, 1985 describes heavy duty liquid
detergents contAinine anionic surfactants, fatty acid, builder, proteolytic
enzyme, boric acid, calcium ions and sodium formate. The combination of
boric acid and sodium formate is claimed to provide improved proteolytic
enzyme stability in this composition, especially in the presence of a
polyol. These compositions are free of lipase.
European Patent Application 0 080 223, published June 1, 1983 describes
detergent compositions contAinine a polyfunctional amino compound or a
polyol together with a reducing alkali metal salt.
Similarly in GB 2 079 305, publlshed January 20, 1982, it is disclosed that
enhanced enzyme stability can be obtained in a built liquid detergent by
inclusion of boric acid, a polyol in the ratio of polyol to boric acid more
than 1:1, and a cross-linked polyacrylate polymer. These compositions
contain no lipase.
In European Application 0 381 262, Aronson et al., published August 8, 1990,
mixtures of proteolytic and lipolytic enzymes in a liquid medium have been
disclosed. The stability of lipase is claimed to be improved by the
addition of boron compound and a polyol having vicinal hydroxyl groups.
It has now been found that certain aromatic borate esters are especially
effective in reversibly inhibiting protease, in a HDL which also comprises
detergency ingredients and a second enzyme.
Vpon dilution, such as under typical wash conditions, the proteolytic enzyme
is no longer inhibited and can function (e.g. to remove protease-sensitive
stains from fabrics in the wash).
W O 92/19708 2 1 Q~ P ~ /US92/03373
Summary of the invention
The present invention relates to a liquid detergent composition containing :
a. an aromatic borate ester formed by the complexation of boric acid
with an aromatic reagent of the structure:
~Y
zi
Wherein:
-X is OH, SH, or NH2;
Y is CO2H, substituted or unsubstituted CH2OH,
CH2SH. CH2NH2 or C-NH2,
o
-each Z is H or a substituted or unsubstituted Cl-
C6 alkyl, alkenyl, alkynyl or an aryl chain, OH
or -O-R, wherein R is a Cl-C6 alkyl chain, or
an electron withdrawing group such as CN, NO2
CHO, SO3H, COOR wherein R is H or a Cl-C6 alkyl
chain;
-i is an integer of from 1 to 4,
b. from about 0.0001 to 1 % of active proteolytic enzyme;
c. a performance-enhancing amount of a detergent-compatible second
enzyme;
d. from about 1 to 80 weight % of anionic or nonionic surfactant.
Description of the invention
The present liquid detergent compositions contain certain essential
ingredients : (a) an aromatic borate ester formed by the complexation of an
aromatic reagent described herein after with boric acid or its derivatives;
(b) proteolytic enzyme; (c) detergent-compatible second enzyme; (d) anionic
and/or nonionic detersive surfactant.
21D952~
W O g~/19708 P ~ /US92/03373-
These compositions will most commonly be used for cleaning of laundry,
fabrics, textiles, fibers, and hard surfaces. Heavy duty liquid laundry
detergents are the preferred liquid detergent compositions herein.
(a) Aromatic borate ester
The present liquid detergent compositions contain an aromatic borate ester
formed by the complexation of an aromatic reagent such as described herein
after with boric acid or its derivatives.
The aromatic borate ester can either be formed prior to incorporation in the
detergent composition, or it can be formed in situ, by simply adding boric
acid and the aromatic reagent in the detergent composition at any stage in
its manufacturing process, or on top of the finished product.
From about 0.1 to 20 %, preferably about 0.2 to 10~ weight ~ of the aromatic
borate ester can be used in the liquid detergent composition. The molar
ratio of boric acid or its derivatives to aromatic reagent is preferably
between about 20:1 and 1:20, more preferably between about 10:1 and 1:10,
most preferably between 5:1 and 1:5.
The aromatic reagent
The aromatic reagent has the following structure:
~Y
zi
Wherein:
-X is OH, SH, or NH2;
Y is CO2H, substituted or unsubstituted CH2OH, CH2SH.
CH2NH2 or C-NH~;
o
-each Z is H or a substituted or unsubstituted Cl-
C6 alkvl, alkenvl, alkvnyl or an arvl chain. OH or -O-R
21~952~
W O 92/19708 P ~ /US92/03373
wherein R is a Cl-C6 alkyl chain, or an electron
withdrawing group such as CN, CHO, SO3H, NO2 or COOR
wherein R is H or a Cl-C6 alkyl chain,
-i is an integer of from l to 4; i.e there can be up to
four substituents per aromatic ring.
Preferably, there will be one substituent per aromatic ring ti.e.
i l) ; preferably, this substituent will be an electron withdrawing group,
as defined hereinabove; preferably this electron withdrawing group will be
in para position vs the X substituent.
Preferred aromatic reagents according to the invention are substituted or
unsubstituted 2-hydroxybenzylalcohol or 2-hydroxybenzoic acid, more
preferably 2-hydroxybenzylalcohol, 2,6-dihydroxybenzylalcohol, 2-
hydroxybenzoic acid, 2,6- dihydroxybenzoic acid.
From about 0.05 to about 20%, most preferably about 0.2 to 10% weight % of
aromatic reagent is preferred in the present liquid detergent compositions.
Boric Acid
The boric acid or its derivatives used in the mixture can be boric acid,
borax, boric oxide, polyborates, orthoborates, pyroborates, metaborates, or
mixtures thereof. Boric acid salts are of course included.
In the present liquid detergent compositions, from about 0.00l to 20, more
preferably about 0.02 to lO, most preferably 0.05 to 5, weight ~ of boric
acid or derivatives is incorporated.
B. Proteolytic Enzvme
A second essential ingredient in the present liquid detergent
compositions is from about 0.000l to l.0, preferably about 0.0005
to 0.5, most preferably about 0.002 to 0.l, weight % of active proteolytic
enzyme. Mixtures of proteolytic enzyme are also included. The proteolytic
enzyme can be of animal, vegetable or microorganism (preferred) origin.
More preferred is serine proteolytic enzyme of bacterial origin. Purified
or nonpurified forms of this enzyme may be used. Proteolytic enzymes
produced by chemically or genetically modified mutants are included.
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Particularly preferred is bacterial serine proteolytic enzyme obtained from
Bacillus Subtillis and/or Bacillus Licheniformis.
Suitable proteolytic enzymes include AlcalaseR, EsperaseR , SavinaseR
(preferred); MaxataseR, MA~e~lR (preferred), and Maxapem 15R (protein
engineered M~c~lR); and subtilisin BPN and BPN'(preferred); which are
commercially available. Preferred proteolytic enzymes are also modified
bacterial serine proteases, such as those described in European Patent
Application Serial Number 87303761.8, published April 28, 1987(particularly
pages 19, 24 and 98), and which is called herein "Protease B", and in
European Patent Application 199,404, Venegas, published October 29, 1986,
which refers to a modified bacterial serine proteolytic enzy-me which is
called "Protease A" herein. Preferred proteolytic enzymes, then, are
selected from the group consisting of SavinaseR, M~Y~e~lR, BPN', Protease A
and Protease B, and mixtures thereof. Protease B is most preferred.
C. Second EnzYme
The third essential ingredient in the present liquid compositions is
a performance-enhancing amount of a detergent-compatible second enzyme. By
"detergent-compatible" is meant compatibility with the other ingredients of
a liquid detergent composition, such as detersive surfactant and detergency
builder.
These second e~y ?S are preferably selected from the group consisting of
lipase, amylase, cellulase, and mixtures thereof.
The term "second enzyme" excludes the proteolytic enzymes discussed above,
so each composition herein contains at least two kinds of enzyme, including
at least one proteolytic enzyme.
The amount of second enzyme used in the composition varies according
to the type of enzyme and the use intended. In general, from about 0.0001
to 1.0, more preferably 0.001 to 0.5, weight % on an active basis of these
second enzymes are preferably used.
Mixtures of enzymes from the same class (e.g. lipasej or two or more
classes (e.g. cellulase and lipase) may be used. Purified or non-purified
forms of the enzyme may be used.
Any lipase suitable for use in a liquid detergent composition can be
used herein. Suitable lipases for use herein include those of bacterial and
fungal origin. Second enzymes from chemically or genetically modified
t~nts are included.
Suitable bacterial lipases include those produced by Pseudomonas,
such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent
21 095~5
1,372,034. Suitable lipases include those which show a positive
immunological cross-reaction with the antibody of the lipase produced
by the microorganism Pseudomonas fluorescens IAM 1057. This lipase
and a method for its purification have been described in Japanese
Patent Application No. 53-20487, laid open on February 24, 1978.
This lipase is available under the trade mark Lipase P "Amano",
hereinafter referred to as "Amano-P". Such lipases should show a
positive immunological cross-reaction with the Amano-P antibody,
using the standard and well-known immunodiffusion procedure according
to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These
lipases, and a method for their immunological cross-reaction with
Amano-P, are also described in U.S. Patent No. 4,707,291, Thom et
al., issued November 17, 1987. Typical examples thereof are the
Amano-P lipase, the lipase ex Pse~domonAq fraai FERM P 1339
(available under the trade mark Amano-B), lipase ex Pseudomonas
nitroreducens var. lipolyticum FERM P 1338 (available under the trade
mark Amano-CES), lipases ex Chromobacter viscosum, e.g. Chromobacter
viscosum var. lipolyticum NRRLB 3673, and further Chromobacter
viscosum lipases, and lipases ex Pseudomonas qladioli. Other lipases
of interest are Amano AKG and Bacillis Sp lipase (ex. Solvay enzyme).
Suitable fungal lipases include those producible by Humicola
lanuqinosa and Thermomyces lanuqinosus. Most preferred is lipase
obtained by cloning the gene from Humicola lanuqinosa and expressing
the gene in AsPerqillus oryzae as described in European Patent
Application No. 0 258 068, commercially available under the trade
mark LipolaseR.
From about 2 to 20,000, preferably about 10 to 6,000, lipase
units of lipase per gram (LU/g) of product can be used in these
compositions. A lipase unit is that amount of lipase which produces
1 ~mol of titratable butyric acid per minute in a pH stat, where pH
is 9.0, temperature is 30~C, and substrate is an emulsion of 3.3 wt
of tributyrin and 3.3~ of gum arabic, in the presence of 2.2 ~mol/l
Ca++ and 50 ~mol/l NaCl in 5 ~mol/l phosphate.
Any cellulase suitable for use in a liquid detergent
composition can be used in these compositions. Suitable cellulase
enzymes for use herein include those of bacterial and fungal origins.
Preferably, they will have a pH optimum of between 5 and 9.5. From
about 0.0001 to 1.0, preferably 0.001 to 0.5, weight ~ on an active
enzyme basis of cellulase can be used.
~B
2 1 0~525
Suitable cellulases are disclosed in U.S. Patent No. 4,435,307,
Barbesgaard et al, issued March 6, 1984, which discloses fungal cellulase
produced from Humicola insolens. Suitable cellulases are also disclosed in
GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of
Humicola insolens (Humicola qrisea var. thermoidea), particularly the
Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N
or a cellulase 212-producing fungus belonging to the genus Aeromonas, and
cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella
Auricula Solander).
Any amylase suitable for use in a liquid detergent composition can be
used in these compositions. Amylases include, for example, amylases
obtained from a special strain of B.licheniforms, described in more detail
in British Patent Specification No. 1,296,839. Amylolytic proteins
include, for example, Rapidase~, Maxamyl~ and Termamyl~.
From about 0.0001~ to 1.0, preferably 0.0005 to 0.5, weight ~ on an
active enzyme basis of amylase can be used.
D. Detersive Surfactant
From about 1 to 80, preferably about 5 to 50, most preferably about
10 to 30, weight ~ of detersive surfactant is the fourth essential
ingredient in the present invention. The detersive surfactant can be
selected from the group consisting of anionics, nonionics, cationics,
ampholytics, zwitterionics, and mixtures thereof. Anionic and nonionic
surfactants are preferred.
Heavy duty liquid laundry detergents are the preferred liquid
detergent compositions herein. The particular surfactants used can vary
widely depending upon the particular end-use envisioned. These
compositions will most commonly be used for cleaning of laundry, fabrics,
textiles, fibers, and hard surfaces.
The benefits of the present invention are especially pronounced in
compositions containing ingredients that are harsh to enzymes such as
certain detergency builders and surfactants. Preferably the anionic
surfactant comprises C12 to C20 alkyl ether sulfate and Cg to C20 linear
alkylbenzene sulfonate. Suitable surfactants are described below.
Anionic Surfactants
One type of anionic surfactant which can be utilized is alkyl ester
sulfonates. These are desirable because they can be made with renewable
B'
W O 92/19708 2 1 0 9 5 2 ~ P ~ /US92/03373-
non-petroleum resources. Preparation of the alkyl ester sulfonate
surfactant component is according to known methods disclosed in the
technical literature. For instance, linear esters of C8-C20 carboxylic
acids can be sulfonated with gaseous SO3 according to "The Journal of the
American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting
materials would include natural fatty substances as derived from tallow,
palm, and coconut oils, etc.
The preferred alkyl ester sulfonate surfactant, especially for
laur.dry applications, comprises alkyl ester sulfonate surfactants of the
structural formula:
R3 - CH - C - OR
I
SO3M
wherein R is a C8-C20 hydrocarbyl, preferably an alkyl, or combination
thereof, R is a Cl-C6 hydrocarbyl, preferably an alkyl, or combination
thereof, and M is a soluble salt-forming cation. Suitable salts include
metal salts such as sodium, potassium, and lithium salts, and substituted or
unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and
quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl
piperydinium, and cations derived from alkanolamines, e.g. monoethanolamine,
diethanolamine, and triethanolamine.
Preferably, R is ClO-Cl6 alkyl, and R is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates wherein R is Cl4-Cl6
alkyl.
Alkyl sulfate surfactants are another type of anionic surfactant of
importance for use herein. In addition to providing excellent overall
cleaning ability when used in combination with polyhydroxy fatty acid amides
(see below), including good grease/oil cleaning over a wide range of
temperatures, wash concentrations, and wash times, dissolution of alkyl
sulfates can be obtained, as well as improved formulability in liquid
W 0 92/19708 2 10 9 5 2 5 PCT/US92/03373
detergent formulations are water soluble salts or acids of the formula
ROS03M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or
hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18
alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation
(e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium
cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary
ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and
cations derived from alkanolamines such as ethanolamine, diethanolamine,
triethanolamine, and mixtures thereof, and the like. Typically, alkyl
chains of C12 16 are preferred for lower wash temperatures (e.g., below
about 50~C) and C16 18 alkyl chains are preferred for higher wash
temperatures (e.g., above about 50~C).
Alkyl alkoxylated sulfate surfactants are another category of useful
anionic surfactant. These surfactants are water soluble salts or acids
typically of the formula RO(A) S03M wherein R is an unsubstituted C10-C24
alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a
C12-C20 alkyl or hydroxyalkyl, more preferably C12-C18 alkyl or
hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,
typically between about 0.5 and about 6, more preferably between about 0.5
and about 3, and M is H or a cation which can be, for example, a metal
cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well
as alkyl propoxylated sulfates are contemplated herein. Specific examples
of substituted ammonium cations include methyl-, dimethyl-, trimethyl-
ammonium and quaternary ammonium cations, such as tetramethyl-~mmonium,
dimethyl piperdinium and cations derived from alkanoll in~S, e.g.
monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof.
Exemplary surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate, C12-
C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0)
sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is
conveniently selected from sodium and potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive purposes can also be
included in the compositions hereof. These can include salts (including,
for example, sodium, potassium, ammonium, an' substituted ammonium salts
such as mono-, di- and triethanolamine saltsJ of soap, Cg-C20 linear
alkylben enesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-
C24 olefinsulphonates, sulphonated polycarboxylic acids prepared bv
21 OqS~
sulphonation of the pyrolyzed product of alkaline earth metal
citrates, e.g., as described in British Patent Specification No.
1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates,
fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether
sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as
the acyl isethionates, N-acyl taurates, fatty acid amines of methyl
tauride, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated Cl2-C1g
monoesters) diesters of sulfosuccinate (especially saturated and
unsaturated C6-C14 diesters), N-acyl sarcossinates, sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the
nonionic nonsulfated compounds being described below), branched
primary alkyl sulfates, alkyl polyethoxy carboxylates such as those
of the formula RO(CH2CH2O)kCH2COO-M~ wherein R is a C8-C22 alkyl, k is
an integer from 0 to 10, and M is a soluble salt-forming cation, and
fatty acids esterified with isethionic acid and neutralized with
sodium hydroxide. Resin acids and hydrogenated resin acids are also
suitable, such as rosin, hydrogenated rosin, and resin acids and
hydrogenated resin acids present in or derived from tall oil.
Further examples are given in "Surface Active Agents and Detergents"
(Vol. I and II by Schwartz, Perry and Berch). A variety of such
surfactants are also generally disclosed in U.S. Patent No.
3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23,
line 58 through Column 29, line 23.
Nonionic Deterqent Surfactants
Suitable nonionic detergent surfactants are generally disclosed
in U.S. Patent No. 3,929,678, Laughlin et al., issued December 30,
1975, at Column 13, line 14 through Column 16, line 6. Exemplary,
non-limiting classes of useful nonionic surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
condensates are preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from about
6 to about 12 carbon atoms in either a straight chain or branched
chain configuration with the alkylene oxide. In a preferred
embodiment, the ethylene oxide is present in an amount equal
to from about 5 to about 25 moles of ethylene oxide per mole
of alkyl phenol. Commercially available nonionic surfactants
of this type include Igepal~ C0-630, marketed by the
~ ~ .
~ D
W 0 92/19708 2 1 0 9 5 2 5 P ~ /US92/03373-
12
GAF Corporation; and Triton X-45, X-114, X-100, and X-102, all marketed by
the Rohm & Haas Company. These compounds are commonly referred to as alkyl
phenol alkoxylates, (e.g., alkyl phenol ethoxylates).
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or secondary,
and generally contains from about 8 to about 22 carbon atoms. Particularly
preferred are the condensation products of alcohols having an alkyl group
cont~inine from about 10 to about 20 carbon atoms with from about 2 to about
18 moles of ethylene oxide per mole of alcohol. Examples of commercially
available nonionic surfactants of this type include Tergitol M 15-S-9
(the condensation product of Cll-C15 linear secondary alcohol with 9 moles
ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of C12-C14
primary alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both marketed by Union Carbide Corporation; Neodol 45-9
(the conden-sation product of C14-C15 linear alcohol with 9 moles of
ethylene oxide), Neodol 23-6.5 (the condensation product of C12-C13 linear
alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the condensation
product of C14-C15 linear alcohol with 7 moles of ethylene oxide),
Neodol 45-4 (the condensation product of C14-C15 linear alcohol with 4
moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro
EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene
oxide), marketed by The Procter & Gamble Company. This category of
nonionic surfactant is referred to generally as "alkyl ethoxylates."
3. The condensation products of ethylene oxide with a hydrophobic
base formed by the condensation of propylene oxide with propylene glycol.
The hydrophobic portion of these compounds preferably has a molecular weight
of from about 1500 to about 1800 and exhibits water insolubility. The
addition of polyoxyethylene moieties to this hydrophobic portion tends to
increase the water solubility of the molecule as a whole, and the liquid
character of the product is retained up to the point where the
polyoxyethylene content is about 50% of the total weight of the condensation
product, which corresponds to condensation with up to about 40 moles of
ethylene oxide. Examples of compounds of this type include certain of the
commercially-available Plùronic surfactants, marketed by BASF.
4. The condensation products of ethylene oxide with the product
resulting from the reaction of propylene oxide and ethylenediamine. The
W O 92/19708 2 1 0'~ ~ ~ 5 P ~ /US92/03373
hydrophobic moiety of these products consists of the reaction product of
ethylenediamine and excess propylene oxide, and generally has a molecular
weight of from about 2500 to about 3000. This hydrophobic moiety is
condensed with ethylene oxide to the extent that the condensation product
contains from about 40~ to about 80% by weight of polyoxyethylene and has a
molecular weight of from about 5,000 to about 11,000. Examples of this type
of nonionic surfactant include certain of the commercially available
Tetronic compounds, marketed by BASF.
5. Semi-polar nonionic surfactants are a special category of
nonionic surfactants which include water-soluble amine oxides containing one
alkyl moiety of from about lO to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-soluble phosphine
oxides containing one alkvl moiety of from about 10 to about 18 carbon atoms
and 2 moieties selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from about l to about 3 carbon atoms; and
water-soluble sulfoxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and a moiety selected from the group consisting of
alkyl and hydroxyalkyl moieties of from about l to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide
surfactants having the formula
3 0R4 1 R5
( )x ( )2
wherein R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures
thereof containing from about 8 to about 22 carbon atoms; R is an alkylene
or hydroxyalkYlene group containing from about 2
to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and
each R is an alkvl or hvdroxyalkyl group containing from about l .o about 3
carbon atoms or a polvethylene oxide group containing from about 1 to about
3 ethylene oxide groups. The R groups can be attached to each other, e.g.,
through an oxygen or nitrogen atom. to form a ring structure.
These amine oxide surfactants in particular include C10-Cl8 alkyl
dimethyl amine oxides and C8-C12 alkoxy ethvl dihydroxy ethvl amine
oxides.
wo g2/l9708 2 1 ~0 9 5 2 ~ P ~ /US92/03373-
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group cont~ining from
about 6 to about 30 carbon atoms, preferably from about 10 to about 16
carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group
cone~ining from about 1.3 to about 10, preferably from about 1.3 to about
3, most preferably from about 1.3 to about 2.7 saccharide units. Any
reducing saccharide cont~ininE 5 or 6 carbon atoms can be used, e.g.,
glucose, galactose and galactosyl moieties can be substituted for the
glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-,
3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a
glucoside or galactoside.) The inters~cch~ride bonds can be, e.g., between
the one position of the additional saccharide units and the 2-, 3-, 4-,
and/or 6- positions on the preceding saccharide units.
Optionally, and less desirably, there can be a polyalkylene-oxide
chain joining the hydrophobic moiety and the polysaccharide moiety. The
preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups
include alkyl groups, either saturated or unsaturated, branched or
unbranched con~ining from about 8 to about 18, preferably from about 10 to
about 16, carbon atoms. Preferably, the alkyl group is a straight chain
saturated alkyl group. The alkyl group can contain up to about 3 hydroxy
groups and/or the polyalkyleneoxide chain can contain up to about 10,
preferably less than 5, alkyleneoxide moieties. Suitable alkyl
polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-,
and hexaglucosides, galactosides, lactosides, glucoses, fructosides,
fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di-,
tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexa-
glucosides.
The preferred alkylpolyglycosides have the formula
R O(cn~2nO)t(glycosyl)x
wherein R is selected from the group consisting of alkyl, alkyl-phenyl,
h~Lo~yalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl
groups contain from about 10 to about 18, preferably from about 12 to about
14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3
to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is
21'0~2~
W O 92/19708 P ~ /US92/03373
pre- ferably derived from glucose. To prepare these compounds, the alcohol
or alkylpolyethoxy alcohol is formed first and then reacted with glucose,
or a source of glucose, to form the glucoside (attachment at the l-
position). The additional glycosyl units can then be attached between their
1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position,
preferably predominately the 2-position.
7. Fatty acid amide surfactants having the formula:
R6 C - N(R )2
wherein R is an alkyl group containing from about 7 to about 21 (preferably
from about 9 to about 17) carbon atoms and each R is selected from the
group consisting of hydrogen, Cl-C4 alkyl, C1-C4 hydroxyalkyl, and -
(C2H4O) H where x varies from about 1 to about 3.
Preferred amides are C8-C20 ammonia amides, monoethanol- amides,
diethanolamides, and isopropanolamides.
Cationic Surfactants
Cationic detersive surfactants can also be included in detergent
compositions of the present invention. Cationic surfactants include the
ammonium surfactants such as alkyldimethylammonium halogenides, and those
surfactants having the formula:
[R2(oR3) ][R (OR ~y~2R N X
wherein R is an alkyl or alkyl benzyl group having from about 8 to about
18 carbon atoms in the alkyl chain, each R is selected from the group
consisting of -CH2CH2 , -CH2CH(CH3)-, -CH2GH(CH2OH)-, ~
CH2CH2CH2-, and mixtures thereof; each R is selected from the group
consisting of Cl-C4 alkyl, C1-C4 hydroxyalkyl, benzyl, ring structures
formed by joining the two R groups, -CH2CHOH-CHOHCOR CHOHCH2OH wherein R
is any hexose or hexose polymer having a molecular weight less than about
1000, and hydrogen when y is not O; R is the same as R or is an alkyl
chain wherein the total number of carbon atoms of R plus R is not more
than about 18; each y is from 0 to about lO and the sum of the ,v values is
from 0 to about 15; and X is any compatible anion.
2 1 095~5
16
Other cationic surfactants useful herein are also described in
U.S. Patent No. 4,228,044, Cambre, issued October 14, 1980.
Other Surfactants
Ampholytic surfactants can be incorporated into the detergent
compositions hereof. These surfactants can be broadly described as
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which
the aliphatic radical can be straight chain or branched. One of the
aliphatic substituents contains at least about 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at least one
contains can anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al,
issued December 30, 1975 at Column 19, lines 18-35 for examples of
ampholytic surfactants.
Zwitterionic surfactants can also be incorporated into the
detergent compositions hereof. These surfactants can be broadly
described as derivatives of secondary and tertiary amines,
derivatives of heterocyclic secondary and tertiary amines, or
derivatives of quaternary ammonium, quaternary phosphonium or
tertiary sulfonium compounds. See U.S. Patent No. 3,929,678 to
Laughlin et al., issued December 30, 1975 at Column 19, line 38
through Column 22, line 48 for examples of zwitterionic surfactants.
Ampholytic and zwitterionic surfactants are generally used in
combination with one or more anionic and/or nonionic surfactants.
Polyhydroxy Fatty Acid Amide Surfactant
~ The liquid detergent compositions hereof preferably contain an
"enzyme performance-enhancing amount", of polyhydroxy fatty acid
amide surfactant. By "enzyme-enhancing" is meant that the formulator
of the composition can select an amount of polyhydroxy fatty acid
amide to be incorporated into the composition that will improve
enzyme cleaning performance of the detergent composition. In
general, for conventional levels of enzyme, the incorporation of
about 1~, by weight, polyhydroxy fatty acid amide will enhance enzyme
performance.
The detergent compositions hereof will typically comprise at
least about 1 weight ~ polyhydroxy fatty acid amide surfactant and
preferably will comprise from about 3~ to 50~, most preferably from
about 3~ to 30~ of the polyhydroxy fatty acid amide.
~B
210952~
W O 92/19708 PCT/US92/03373
17
The polyhydroxy fatty acid amide surfactant component comprises
compounds of the structural formula:
O R
(I) R2 C - N - Z
wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or
a mixture thereof, preferably Cl-C4 alkyl, more preferably Cl or C2 alkyl,
most preferably Cl alkyl (i.e., methyl); and R is a C5-C3l hydrocarbyl,
preferably straight chain C7-Clg alkyl or alkenyl, more preferably straight
chain C9-Cl7 alkyl or alkenyl, most preferably straight chain Cll-Cl5 alkyl
or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly connected to
the chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing sugar
in a reductive amination reaction; more preferably Z will be a glycityl.
Suitable reducing sugars include glucose, fructose, maltose, lactose,
galactose, mannose, and xylose. As raw materials, high dextrose corn syrup,
high fructose corn syrup, and high maltose corn syrup can be utilized as
well as the individual sugars listed above. These corn syr~ps may yield a
mix of sugar components for Z. It should be understood that it is by no
means intended to exclude other suitable raw materials. Z preferably will
be selected from the group consisting of -CH2-(CHOH) -CH2OH, -CH(CH2OH)-
(CHOH)n l- CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, and alkoxylated
derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is
H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls
wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
In Formula (I), R' can be, for example, N-methyl, N-ethyl, N-propyl,
N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyi.
R2-CO-N can be, for example, cocamide, stearamide, oleamide,
lauramide. myristamide, capricamide, palmitamide~ tallowamide. etc.
Z can be l-deoxyglucityl, 2-deoxyfructityl, l-deoxymaltityl, l-
deoxylactityl, l-deoxygalactityl, l-deoxymannityl, l-deoxymalto-triotityl,
etc.
Methods for making polyhydroxy fatty acid amides are known in the
art. In general, they can be made by reacting an alkyl amine with a
reducing sugar in a reductive amination reaction to form a corresponding N-
k '"
2 1 09S25
18
alkyl polyhydroxyamine, and then reacting the N-alkyl
polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty
acid amide product. Processes for making compositions containing
polyhydroxy fatty acid amides are disclosed, for example, in G.B.
Patent Specification No. 809,060, published February 18, 1959, U.S.
Patent No. 2,965,576, issued December 20, 1960 to E.R. Wilson, and
U.S. Patent No. 2,703,798, Anthony M. Schwartz, issued March 8, 1955,
and U.S. Patent No. 1,985,424, issued December 25, 1934 to Piggott.
E. Optional Inqredients
Deterqency Builders
From 0 to about 50, preferably about 3 to 30, more preferably
about 5 to 20, weight ~ detergency builder can be included herein.
Inorganic as well as organic builders can be used.
Inorganic detergency builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of
polyphosphates (exemplified by the tripolyphosphates, pyrophosphates,
and glassy polymeric meta-phosphates), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. Borate builders, as well as
builders containing borate-forming materials that can produce borate
under detergent storage or wash conditions (hereinafter, collectively
"borate builders"), can also be used. Preferably, non-borate
builders are used in the compositions of the invention intended for
use at wash conditions less than about 50~C, especially less than
about 40~C.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na2O ratio in the range 1.6:1 to
3.2:1 and layered silicates, such as the layered sodium silicates
described in U.S. Patent No. 4,664,839, issued May 12, 1987 to H.P.
Rieck. However, other silicates may also be useful such as for
example magnesium silicate, which can serve as a crispening agent in
granular formulations, as a stabilizing agent for oxygen bleaches,
and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and
sesquicarbonate and mixtures thereof with ultra-fine calcium
carbonate as disclosed in German Patent Application No. 2,321,001
published on November 15, 1973.
i' ~ ,
~ 1 ~95~5
Aluminosilicate builders are useful in the present invention.
Aluminosilicate builders are of great importance in most currently
marketed heavy duty granular detergent compositions, and can also be
a significant builder ingredient in liquid detergent formulations.
Aluminosilicate builders include those having the empirical formula:
Mz(zAlo2 ysio2)
wherein M is sodium, potassium, ammonium or substituted ammonium, z
is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate.
Preferred aluminosilicates are zeolite builders which have the
formula:
Naz[(Alo2)z(sio2)y] xH2o
wherein z and y are integers of at least 6, the molar ratio of z to y
is in the range from 1.0 to about 0.5, and x is an integer from about
15 to about 264.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or
synth~etically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent No. 3,985,669,
Krummel, et al., issued October 12, 1976. Preferred synthetic
crystalline aluminosilicate ion exchange materials useful herein are
available under the designations Zeolite A, Zeolite P (B), and
Zeolite X. In an especially preferred embodiment, the crystalline
aluminosilicate ion exchange material has the formula:
Nal2 [ (Al~2) 12 (si~2) 12] xH2~
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Preferably, the aluminosilicate has
a particle size of about 0.1-10 microns in diameter.
Specific examples of polyphosphates are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and potassium
B
-- 2 1 0~525
orthophosphate, sodium polymetaphosphate in which the degree of
polymerization ranges from about 6 to about 21, and salts of phytic
acid.
Examples of phosphonate builder salts are the water-soluble
salts of ethane 1-hydroxy-1, l-diphosphonate particularly the sodium
and potassium salts, the water-soluble salts of methylene
diphosphonic acid e.g. the trisodium and tripotassium salts and the
water-soluble salts of substituted methylene diphosphonic acids, such
as the trisodium and tripotassium ethylidene, isopyropylidene
benzylmethylidene and halo methylidene phosphonates. Phosphonate
builder salts of the aforementioned types are disclosed in U.S.
Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and
October 19, 1965, to Diehl; U.S. Patent No. 3,422,021 issued January
14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 issued
September 3, 1968, and January 14, 1969 to Quimby.
Organic detergent builders preferred for the purposes of the
present invention include a wide variety of polycarboxylate
compounds. As used herein, "polycarboxylate" refers to compounds
having a plurality of carboxylate groups, preferably at least 3
carboxylates.
Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such as
sodium, potassium, and lithium, or alkanolammonium salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates. A
number of ether polycarboxylates have been disclosed for use as
detergent builders. Examples of useful ether polycarboxylates
include oxydisuccinate, as disclosed in Berg, U.S. Patent No.
3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent No.
3,635,830, issued January 18, 1972.
A specific type of ether polycarboxylates useful as builders in
the present invention also include those having the general formula:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or
a salt-forming cation. For example, if in the above general formula
A and B are both H, then the compound is oxydisuccinic acid and its
~'
2 1 09~5
water-soluble salts. If A is OH and B is H, then the compound is
tartrate monosuccinic acid (TMS) and its water-soluble salts. If A
is H and B is -O-CH(COOX)-CH2(COOX), then the compound is tartrate
disuccinic acid (TDS) and its water-soluble salts. Mixtures of these
builders are especially preferred for use herein. Particularly
preferred are mixtures of TMS and TDS in a weight ratio of TMS to TDS
of from about 97:3 to about 20:80. These builders are disclosed in
U.S. Patent No. 4,663,071, issued to Bush et al., on May 5, 1987.
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Patent Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether
hydroxypolycarboxylates represented by the structure:
HO-[C (R) (COOM) -C (R) (COOM) -O] n~H
wherein M is hydrogen or a cation wherein the resultant salt is
water-soluble, preferably an alkali metal, ammonium or substituted
ammonium cation, n is from about 2 to about 15 (preferably n is from
about 2 to about 10, more preferably n averages from about 2 to about
4) and each R is the same or different and selected from hydrogen,
C14 alkyl or C14 substituted alkyl (preferably R is hydrogen).
Still other ether polycarboxylates include copolymers of maleic
anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy
benzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid.
Organic polycarboxylate builders also include the various
alka~i metal, ammonium and substituted ammonium salts of polyacetic
acids. Examples include the sodium, potassium, lithium, ammonium and
substituted ammonium salts of ethylenediamine tetraacetic acid, and
nitroltriacetic acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-
tricarboxylic acid, and carboxymethyloxysuccinic acid, and soluble
salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders of
particularimportance for heavy duty liquid detergent formulations,
but can also be used in granular compositions.
D
D
- 2 1 0~52S
Other carboxylate builders include the carboxylated
carbohydrates disclosed in U.S. Patent No. 3,723,322, Diehl, issued
March 28, 1973.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the
related compounds disclosed in U.S. Patent No. 4,566,984, Bush,
issued January 28, 1986. Useful succinic acid builders include the
Cs-C20 alkyl succinic acids and salts thereof. A particularly
preferred compound of this type is dodecenylsuccinic acid.
Alkyl succinic acids typically are of the generally formula
R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is
hydrocarbon, e.g., Cl0-C20 alkyl or alkenyl, preferably Cl2-Cl6 or
wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone
substituents, all as described in the above-mentioned patents.
The succinate builders are preferably used in the form of their
water-soluble salts, including the sodium, potassium, ammonium and
alkanolammonium salts.
Specific examples of succinate builders include:
laurylsuccinate, myristylsuccinate, palmitylsuccinate,
2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the
like. Laurylsuccinates are the preferred builders of this group, and
are described in European Patent Application No. 86200690.5/
0,200,263, published November 5, 1986.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo-
hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-
soluble polyacrylates (these polyacrylates having molecular weights
to above about 2,000 can also be effectively utilized as
dispersants), and the copolymers of maleic anhydride with vinyl
methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal carboxylates
disclosed in U.S. Patent No. 4,144,226, Crutchfield et al., issued
March 13, 1979. These polyacetal carboxylates can be prepared by
bringing together, under polymerization conditions, an ester of
glyoxylic acid and a polymerization initiator. The resulting
polyacetal carboxylate ester is then attached to chemically stable
end groups to stabilize the polyacetal carboxylate against rapid
depolymerization in alkaline solution, converted to the corresponding
salt, and added to a surfactant.
~r~ D
2 1 09525
23
Polycarboxylate builders are also disclosed in U.S. Patent
No. 3,308,067, Diehl, issued March 7, 1967. Such materials include
the water-soluble salts of homo- and copolymers of aliphatic
carboxylic acids such as maleic acid, itaconic acid, mesaconic acid,
fumaric acid, aconitic acid, citraconic acid and methylenemalonic
acid.
Other organic builders known in the art can also be used. For
example, monocarboxylic acids, and soluble salts thereof, having long
chain hydrocarbyls can be utilized. These would include materials
generally referred to as "soaps". Chain lengths of C,0-C20 are
typically utilized. The hydrocarbyls can be saturated or
unsaturated.
Soil Release Aqent
Any soil release agents known to those skilled in the art can
be employed in the practice of this invention. Preferred polymeric
soil release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hydrophobic fibers, such as
polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the
hydrophilic segments. This can enable stains occurring subsequent to
treatment with the soil release agent to be more easily cleaned in
later washing procedures.
~ Whereas it can be beneficial to utilize polymeric soil release
agents in any of the detergent compositions hereof, especially those
compositions utilized for laundry or other applications wherein
removal of grease and oil from hydrophobic surfaces is needed, the
presence of polyhydroxy fatty acid amide in detergent compositions
also containing anionic surfactants can enhance performance of many
of the more commonly utilized types of polymeric soil release agents.
Anionic surfactants interfere with the ability of certain soil
release agents to deposit upon and adhere to hydrophobic surfaces.
These polymeric soil release agents have nonionic hydrophile segments
or hydrophobe segments which are anionic surfactant-interactive.
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephthalate and polyethyene oxide (PEO)
terephthalate. More specifically, these polymers are comprised of
repeating units of ethylene terepehthalate and PEO terepehthalate in
a mole ratio of ethylene terephthalate units to PEO terephthalate
units of from about 25:75 to about 35:65, said PEO terephthalate
,B
2~ 095~5
units containing polyethylene oxide having molecular weights of from
about 300 to about 2000. The molecular weight of this polymeric soil
release agent is in the range of from about 25,000 to about 55,000.
See U.S. Patent No. 3,959,230 to Hays, issued May 25, 1976 and U.S.
Patent No. 3,893,929 to Basadur issued July 8, 1975 which discloses
similar copolymers.
Another preferred polymeric soil release agent is a polyester
with repeat units of ethylene terephthalate units containing 10-15
by weight of ethylene terephthalate units together with 90-80~ by
weight of polyoxyethlyene terephthalate units, derived from a
polyoxyethylene glycol of average molecular weight 300-5,000, and the
mole ratio of ethylene terephthalate units to polyoxyethylene
terephthalate units in the polymeric compound is between 2:1 and 6:1.
Examples of this polymer include the commercially available material
ZelconR 5126 (from Dupont) and MileaseR T (from ICI). These polymers
and methods of their preparation are more fully described in U.S.
Patent No. 4,702,857, issued October 27, 1987, to Gosselink.
Other suitable polymeric soil release agents include the ethyl
or methyl-capped 1,2-propylene terephthalate-polyoxyethylene
terephthalate polyesters of U.S. Patent No. 4,711,730, issued
December 8, 1987, to Gosselink et al., the anionic end-capped
oligomeric esters of U.S. Patent No. 4,721,580, issued January 26,
1988, to Gosselink, wherein the anionic end-caps comprise sulfo-
polyethoxy groups derived from polyethylene glycol (PEG), the block
polyester oligomeric compounds of U.S. Patent No. 4,702,857, issued
October 27, 1987 to Gosselink, having polyethyoxy end-caps of the
formula X-(OCH2CH2)n- wherein n is from 12 to about 43 and X is a Cl-C4
alkyl, or preferably methyl.
Additional polymeric soil release agents include the soil
release agents of U.S. Patent No. 4,877,896, issued October 31, 1989
to Maldonado et al., which discloses anionic especially sulfoaroyl,
end-capped terephthalate esters. The terephthalate esters contain
unsymmetrically substituted oxy-1,2-alkyleneoxy units. Included
among the soil release polymers of U.S. Patent No. 4,877,896 are
materials with polyoxyethylene hydrophile components or C3
oxyalkylene terephthalate (propylene terephthalate) repeat units
within the scope of the hydrophobe components of (b)(1) above. It is
the polymeric soil release agents characterized by either, or both,
B'
2 1 09525
of these criteria that particularly benefit from the inclusion of the
polyhydroxy fatty acid amides hereof, in the presence of anionic
surfactants.
If utilized, soil release agents will generally comprise from
about 0.01~ to about 10.0~, by weight, of the detergent compositions
herein, typically from about 0.1~ to about 5~, preferably from about
0.2~ to about 3.0~.
Useful soil release polymers are described in U.S. Patent
No. 4,000,093, issued December 28, 1976 to Nicol et al., European
Patent Application No. 0 219 048, published April 22, 1987 by Kud et
al., U.S. Patent No. 3,959,230 to Hays, issued May 25, 1976, U.S.
Patent No. 3,893,929 to Basadur, issued July 8, 1975, U.S. Patent
No. 4,702,857, issued October 27, 1987 to Gosselink, U.S. Patent
No. 4,711,730, issued December 8, 1987 to Gooselink et al., U.S.
Patent No. 4,721,580, issued January 26, 1988 to Gosselink, U.S.
Patent No. 4,702,857, issued October 27, 1987 to Gosselink, U.S.
Patent No. 4,877,896, issued October 31, 1989 to Maldonado et al.
If utilized, soil release agents will generally comprise from
about 0.01~ to about 10.0~, by weight, of the detergent compositions
herein, typically from about 0.1~ to about 5~, preferably from about
0.2~ to about 3.0~.
Chelatinq Aqents
The detergent compositions herein may also optionally contain
one or more iron and manganese chelating agents as a builder adjunct
material. Such chelating agents can be selected from the group
consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures
thereof, all as hereinafter defined. Without intending to be bound
by theory, it is believed that the benefit of these materials is due
in part to their exceptional ability to remove iron and manganese
ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in
compositions of the invention can have one or more, preferably at
least two, units of the substructure
CH2
N - (CH2)X - COOM
/
r ~
21 0~525
wherein M is hydrogen, alkali metal, ammonium or substituted ammonium
(e.g. ethanolamine) and x is from 1 to about 3, preferably 1.
Preferably, these amino carboxylates do not contain alkyl or alkenyl
groups with more than about 6 carbon atoms. Operable amine
carboxylates include ethylenediaminetetraacetates, N-
hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates, triethylenetetr~m- n~h~
acetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts thereof and
mixtures thereof.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low levels
of total phosphorus are permitted in detergent compositions.
Compounds with one or more, preferably at least two, units of the
substructure
- CH2
N - (CH2)X - PO3M2
wherein M is hydrogen, alkali metal, ammonium or substituted ammonium
and x is from 1 to about 3, preferably 1, are useful and include
ethylenediaminetetrakis (methylenephosphonates), nitrilotris
(methylenephosphonates) and diethylenetriaminepentakis
(methylenephosphonates). Preferably, these amino phosphonates do not
contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Alkylene groups can be shared by substructures.
Polyfunctionally-substituted aromatic chelating agents are also
useful in the compositions herein. These materials can comprise
compounds having the general formula
OH
R ~ OH
R ~ R
wherein at least one R is -SO3H or -COOH or soluble salts thereof and
mixtures thereof. U.S. Patent No. 3,812,044, issued May 21, 1974, to
Connor et al., discloses polyfunctionally-substituted aromatic
chelating and sequestering agents. Preferred compounds of this type
in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-
~ D
-
2 1 0~S~5
disulfobenzene. Alkaline detergent compositions can contain these
materials in the form of alkali metal, ammonium or substituted
ammonium (e.g. mono- or triethanolamine) salts.
If utilized, these chelating agents will generally comprise
from about 0.1% to about 10% by weight of the detergent compositions
herein. More preferably chelating agents will comprise from about
0.1% to about 3.0% by weight of such compositions.
Clay Soil Removal/Anti-redeposition Aqents
The compositions of the present invention can also optionally
contain water-soluble ethoxylated amines having clay soil removal and
anti-redeposition properties. Liquid detergent compositions which
contain these compounds typically contain from about 0.01~ to 5~.
The most preferred soil release and anti-redeposition agent is
ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are
further described in U.S. Patent No. 4,597,898, VanderMeer, issued
July 1, 1986. Another group of preferred clay soil removal/anti-
redeposition agents are the cationic compounds disclosed in European
Patent Application No. 111,965, Oh and Gosselink, published June 27,
1984. Other clay soil removal/anti-redeposition agents which can be
used include the ethoxylated amine polymers disclosed in European
Patent Application No. 111,984, Gosselink, published June 27, 1984;
the zwitterionic polymers disclosed in European Patent Application
No. 112,592, Gosselink, published July 4, 1984; and the amine oxides
disclosed in U.S. Patent No. 4,548,744, Connor, issued October 22,
1985:
Other clay soil removal and/or anti-redepostiion agents known
in the art can also be utilized in the compositions hereof. Another
type of preferred anti-redeposition agent includes the
carboxymethylcellulose (CMC) materials. These materials are well
known in the art.
Polymeric Dispersinq Aqents
Polymeric dispersing agents can advantageously be utilized in
the compositions hereof. These materials can aid in calcium and
magnesium hardness control. Suitable polymeric dispersing agents
include polymeric polycarboxylates and polyethylene glycols, although
others known in the art can also be used.
Suitable polymeric dispersing agents for use herein are
described in U.S. Patent No. 3,308,067, Diehl, issued March 7, 1967,
and European Patent Application No. 66915, published December 15,
1982.
21 0{~7J3~5
28
Briqhtener
Any suitable optical brighteners or other brightening or
whitening agents known in the art can be incorporated into the
detergent compositions hereof.
Commercial optical brighteners which may be useful in the
present invention can be classified into subgroups which include, but
are not necessarily limited to, derivatives of stilbene, pyrazoline,
coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-
dioxide, azoles, 5- and 6-membered-ring heterocycles, and other
miscellaneous agents. Examples of such brighteners are disclosed in
"The Production and Application of Fluorescent Brightening Agents",
M. Zahradnik, published by John Wiley & Sons, New York (1982).
Suds Suppressors
Compounds known, or which become known, for reducing or
suppressing the formation of suds can be incorporated into the
compositions of the present invention. Suitable suds suppressors are
described in Kirk Othmer Encyclopedia of Chemical Technology, Third
Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979),
U.S. Patent No. 2,954,347, issued September 27, 1960 to St. John,
U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al., and
European Patent Application No. 89307851.9, published February 7,
1990, U.S. Patent No. 3,455,839, German Patent Application DOS
2,124,526, U.S. Patent No. 3,933,672, Bartolotta et al., and U.S.
Patent No. 4,652,392, Baginski et al., issued March 24, 1987.
~ The compositions hereof will generally comprise from 0~ to
about 5~ of suds suppressor.
Other Inqredients
A wide variety of other ingredients useful in detergent
compositions can be included in the compositions hereof, including
other active ingredients, carriers, hydrotropes, processing aids,
dyes or pigments, solvents for liquid formulations, bleaches, bleach
activators, etc.
Liquid detergent compositions can contain water and other
solvents as carriers. Low molecular weight primary or secondary
alcohols exemplified by methanol, ethanol, propanol, and isopropanol
are suitable. Monohydric alcohols are preferred for solubilizing
surfactant, but polyols such as
W O 92/19708 2 1 ~ 9 5 2 ~ PCT/US92/03373
29
those cont~ining from 2 to about 6 carbon atoms and from 2 to about 6
hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine, and
1,2-propanediol) can also be used.
Liquid Com~ositions
Preferred heavy duty liquid laundry detergent compositions hereof
will preferably be formulated such that during use in aqueous cleaning
operations, the wash water will have a pH of between about 6.5 and 11.0,
preferably between about 7.0 and 9.0, most preferably between 7.5 and 8Ø
The compositions herein preferably have a pH in a 10% solution in water at
20~C of between about 7.0 to 11.0, preferably 7.0 to 8.5. Techniques for
controlling pH at rec -n~ed usage levels include the use of buffers,
alkalis, acids, etc., and are well known to those skilled in the art.
This invention further provides a method for cleaning substrate, such
as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrate,
with a liquid detergent composition comprising detersive surfactant,
proteolytic enzyme, a detergent-compatible second enzyme, and the aryl
boronic acids described above. Agitation is preferably provided for
enhancing cleaning. Suitable means for providing agitation include rubbing
by hand or preferably with use of a brush, sponge, cloth, mop, or other
cleaning device, automatic laundry washing ~chi n~S, automatic dishwashers,
etc.
Preferred herein are concentrated liquid detergent compositions. By
"concentrated" is meant that these compositions will deliver to the wash the
same amount of active detersive ingredients at a reduced dosage. Typical
regular dosage of heavy duty liquids is 118 milliliters in the U.S. (about
1/2 cup) and 180 milliliters in Europe.
Concentrated heavy duty liquids herein contain about 10 to 100
weight % more active detersive ingredients than regular heavy duty liquids,
and are dosed at less than 1/2 cup depending upon their active levels. This
invention becomes even more useful in concentrated formulations because
there are more actives to interfere with enzyme performance. Preferred are
heavy duty liquid laundry detergent compositions with from about 30 to 90,
preferably 40 to 80, most preferably 50 to 60, weight % of active detersive
ingredients.
The following examples illustrate the compositions of the present
invention. All parts, percentages and ratios used herein are by weight
unless otherwise specified.
wo 92/lg708 2 1 0 g 5 ~ ~ 3 ~ P ~ /US92/03373-
EXAMPLES
I II III
Linear alkyl benzene sulfonate 12 9 12
Sodium C12-15 alkyl sulfate 2 2 2
C14-15 alkyl 2.5 times ethoxylated sulfate O 0 2
C12 glucose amide O 0 6
C12-15 alcohol 7 times ethoxylated 8 0
C12-15 alcohol 5 times ethoxylated 0 6 0
Oleic acid 2 0 0
Citric acid 3 8 8.5
C12-14 alkenyl substituted succinic acid 10 6 8.5
Ethanol 4 4 8
1,2-propanediol 2 2 2
NaOH 6 7 9
diethylene triamine penta
(methylene phosphonic acid) 0.5 0.7
Amylase (143KNU/g) O.1 0.1 0.1
LipolaseR(lOORLU/g commercial solution) 0.2 0.2 0.3
Protease B (34mg/g commercial solution~ 0.3 0.3 0.5
Soil release polymer 0.5 0 0
2,6-dihydroxybenzylalcohol 1 0.3
CaC12 0.01 0.01 0.01
~a metaborate 2.2 3.5 4
~ater and Minors Balance to 100~
IV V VI
Linear alkyl benzene sulfonate 12 9 12
Sodium C12-15 alkyl .ulfate 2 2 2
C14-15 alkyl 2.5 times ethoxylated sulfate O 0 2
C12 glucose amide O 0 6
C12-15 alcohol 7 times ethoxylated 8 0
C12-15 alcohol 5 times e~hoxylated 0 6 0
Oleic acid 2 0 0
~_itric acid 3 5 7
C12-14 alkenyl substituted succinic acid 10 5 9
Ethanol 4 4 8
.,2-propanediol 2 2 2
~aOH 6 , 9
diethylene triamine penta
(methvlene phosphonic acid) 0.5 0.7
Amviase (143KNU/g) 0.1 0.1 0.1
LipolaseR(lOOKLU/g commercial solution) 0.2 0.2 0.3
~roeease B (34mg/g commercial solution~ 0.3 0.3 0.5
Soil release poly~er O . 5 0 0
2-hvdroxvbenzylalcohol 0.75 0.5 2
CaC12 0.01 0.01 0.01
Na ~etaborate 2.2 3.5 4
Water and ~inors Balance to 100
W 0 92/19708 2 1 0 9 ~ 2 ~ PC~r/US92/03373
31
VII VIII IX ~-
Linear alkyl benzene sulfonate 6 10 12
Sodium C12-15 alkyl sulfate 10 3 6
C14-15 alkyl 2.5 times ethoxylated sulfate O 0 2
C12 glucose amide O 0 8
C12-15 alcohol 7 times ethoxylated 8 0
C12-15 alcohol 5 times ethoxylated 0 6 0
Ol~eic acid 2 0 0
Cit~ric acid 6 8 8.5
C12-14 alkenyl substituted succinic acid 6 6 8.5
Ethanol 4 4 8
1,2-propanediol 2 2 2
NaOH 6 7 9
diethylene triamine penta
(methylene phosphonic acid) 0.5 0.7
Amylase (143KNU/g) O.1 0.1 0.1
LipolaseR(lOOKLU/~ commercial solution) 0.2 0.2 0.3
Protease B (34mg/g commercial solution) 0.3 0.3 0.5
Soil release polymer 0.5 0 0
2-hydroxybenzoic acid 1 1 2
CaC12 0.01 0.01 0.01
~la metaborate 2.2 3.5 4
Water and Minors Balance to 100~
X XI XII
Linear alkyl benzene sulfonate S 9 O
Sodium C12-15 alkyl sulfate 12 2 12
C14-15 alkyl 2.5 times ethoxylated sulfate O 0 4
C12 glucose amide O 0 6
C12-15 alcohol 7 times ethoxylated 8 0
C12-15 alcohol 5 times ethoxylated 0 6 0
Oleic acid 2 0 0
Citric acid 3 8 7
C12-14 alkenyl substituted succinic acid 10 6 ?.5
Ethanol 4 4 8
1,2-propanediol 2 2 2
~aOH 6 7 9
diethylene triamine penta
~methylene phosphonic acid) 0.5 0.7
Amylase (143KNU/g) O.1 0.1 0.1
LipolaseR(lOOKLU/g commercial solution) 0.2 0.2 0.3
Protease B (34mg/g commercial solution) 0.3 0 3 0.5
Soil release polymer 0 5 0 O
2,6-dihydroxybenzoic acid 2 0.5 2
CaC12 0.01 0.01 0.01
"a metaborate 2.2 3.5 4
'~ater and .~inors Balance to 100
