Note: Descriptions are shown in the official language in which they were submitted.
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1
HEAVY DUTY L1QUTD DETERGENT COMPOSITIONS COMpRiSMG SALTS OF ALPHA SUL-
FONATED FATTY ACID METfiYL ESTERS AND USE OF ALPHA-SULPHONATED FATTY ACID
SALTS TO tNHIBTT RBDEPOSITtON OF SOTL ON FABRIC
Field of the Invention
The gresent invention relates to detergent compositions
comprising one or more anionic sulfate or sulfonate surfactants.
More particularly, the invention relates to heavy duty liquid
detergent compositions comprising a sulfonated. alkyl ester, at
least one primary anionic surfactant, and nonionic surfactant. It
relates to detergent compositions which possess desirable clearing
and sudsing properties, are mild, and are especially suitable for
use in manual and machine laundry applications.
DescriRtion of the Related Art
Heavy duty liquid (HDL) detergent compositions are intended
to. clean clothes made of cotton, polyester, wool, cotton/polyester
blends, silk, etc. HDL detergents typically fall into one of
three categories: built detergents, unbuilt detergents, and
detergents for fine fabric cold water washing.
Unbuilt products, ie., those containing no builder, are
composed of anionic surfactants, typically linear alkyl benzene
sulfonates (LAS), ether sulfate, and a nonionic surfactant
typically a fatty alcohol ethoxylate. The function of anionic
surfactants is to remove and suspend particulate sail while
nonionic solubilizes, disperses and emulsifies oily soil. The
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systems utilizing LAS usually have poor cleaning performance, this
is especially true in hard water.
Built HDL systems, "i.e., detergents having builders, contain
surfactants in addition to a certain level of builder. Builders
function to protect the surfactant, in particular LAS, alkyl
sulfate, and alpha olefin sulfonate, from precipitating in dilute
or hard water. In addition, builders are good sources of
alkalinity and help improve cleaning performance. Despite
incorporation of builders in such compositions, their
cost/performance efficiency has major shortfall.
To minimize the shelf space required for displaying detergent
products, many attempts have been made to prepare cost efficient,
highly concentrated detergents having good cleaning at use
concentration.
Preparation of concentrated products having high levels of
surfactants requires higher levels of hydrotrope to fluidize the
composition. However, concentrating product via incorporation of
high levels of builder into the detergent increases the cost of
manufacturing as well as increases the difficulty of dispersion
and disolution especially in cold water. Some highly built
products are in the form of structured liquid and have an
appearance similar to that of fabric softeners.
Thus, there exists a need for highly concentrated heavy duty
liquid detergent compositions that do not require the presence of
builder for cleaning efficiency or classical hydrotrope for
fluidity and that are capable of providing good cleaning of
fabrics at low use concentrations and especially in cold to warm
temperature washing conditions.
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An object of the present invention is to provide heavy duty liquid detergent
compositions
comprising salts of alpha sulfonated fatty acid methyl esters and use of alpha-
sulfonated fatty acid
salts to inhibit redeposition of soil on fabric. In accordance with an aspect
of the present invention
there is provided, in a detergent composition comprising:
(a} from about 2 to 35% of an a-sulfonated alkyl ester of a
fatty acid having an average of about 12-16 carbon atoms;
(b) from about 2% to 25% by weight of an anionic surfactant;
and
(c) from about 2.0 to 40% by weight of a nonionic surfactant,
the sum of the concentrations of a-sulfonated alkyl ester, anionic
surfactant, and nonionic surfactant in a washing solution being from
about 0.05% to about 3.0% by weight.
In accordance with another aspect of the invention, there is provided an
improved detergent
composition comprising:
(a) from about 2 to 25% of an a-sulfonated alkyl ester of a
fatty acid having an average of about 12-16 carbon atoms;
(b) from about 2% to 40% by weight of a linear alkyl benzene
sulfonate; and
(c} from about 2.0 to 40% by weight of a nonionic surfactant.
In accordance with yet another aspect of the invention, there is provided an
improved
detergent composition comprising:
(a) from about 2 to 25% of an a-sulfonated alkyl ester of a
fatty acid having an average of about 12-16 carbon atoms;
(b) from about Z% to 40% by weight of a alkyl ether sulfate;
and
(c) from about 2.0 to 40% by weight of a nonionic surfactant.
In accordance with a further aspect of the invention, there is provided an
improved detergent
composition comprising:
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(a) from about 2 to 25~ of an a-sulfonated alkyl ester of a
fatty acid having an average of about 12-16 carbon atoms;
(b) from about 2~ to 40~ by weight of a alkyl sulfate; and
(c) from about 2.0 to 40; by weight of a nonionic surfactant.
In accordance with yet a further aspect of the invention, there is provided a
method for
inhibiting redeposition of soil on fabric during treatment of the fabric with
a detergent comprising
treating a fabric with a detergent comprising an amount of salt of an a-
sulfonated fatty acid having
from about 8-22 carbon atoms effective to inhibit redeposition of soil on the
fabric.
In accordance with a further aspect of the invention, there is provided a
method for inhibiting
redeposition of soil on fabric during treatment of the fabric with a detergent
comprising treating a
fabric with a detergent mixture comprising from about 0.001 to 10.0% by weight
of the detergent
mixture of a salt of an a-sulfonated fatty acid having from about 8-22 carbon
atoms.
In accordance with yet a further aspect of the invention, there is provided a
method for
inhibiting redeposition of soil on fabric during treatment of the fabric with
a detergent comprising
treating a fabric with a detergent mixture prepared by diluting a detergent
concentrate comprising
from about 0.1 to 10.0% by weight of the detergent concentrate of a salt of an
a-sulfonated fatty acid
having from about 8-22 carbon atoms.
The compositions of the present invention are cost efficient
unbuilt concentrated heavy duty liquid detergents with high
cleaning efficacy comprising:
(a) a salt of sulfonated alkyl ester;
(b) an anionic surfactant; and
(c) a nonionic surfactant.
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The invention provides HDL detergents that do not require the
presence of builders for improved cleaning efficiency. The
invention further provides fluid HDL detergents that do not
require the addition of classical hydrotopes. The inventive
highly concentrated, stable fluid compositions are highly surface
active and very effective in cleaning a variety of fabrics with
different types of soils at a low use concentration in water and
perform extremely well even under cold temperature washing
conditions. The compositions of the present invention show anti-
redeposition properties which makes them especially useful for
cleaning non-polar synthetic fabrics and blends of synthetic and
natural fabrics. In addition, the inventive compositions when
combined with silicone, fatty acid soaps and EO/PO/EO or PO/EO/PO
block copolymer defoamers are very useful in front loading
European style washing machines. Furthermore, the inventive
compositions exhibit excellent surface activity and extremely low
CMC'a (critical micelle concentration) which demonstrates synergy
between the sulfonated alkyl esters and the other surfactants.
This synergistic behavior of the inventive compositions
contributes towards significant improvement in cleaning efficiency
at equal surfactant concentrations when compared under similar
conditions with state-of-the art commercial products. When used
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at lower active concentrations, these inventive compositions give
equal performance to the state-of-the art commercial products thus
realizing significant cost savings.
The inventive concentrated compositions have suitable
viscosities and are clear liquids in the concentrated and diluted
forms.
The invention also provides concentrated compositions having
an amount of a disalt a-sulfonated alkyl acid effective to
provide for improved cleaning efficacy with respect to
antiredeposition of soils, etc. In this context, the compositions
comprising disalts of alpha sulfonated fatty acids act as
antiredeposition cleaning compositions.
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DETAILED DE8CRrpTrnwr pF THE INVENTrnu
The invention provides detergent compositions comprising a
salt of an alpha sulfonated alkyl ester of a fatty acid, an
anionic surfactant, and a nonionic surfactant. The anionic
surfactant is selected from the group consisting of linear alkyl
benzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates, alpha-
olefin sulfonates, paraffin sulfonates, alkyl glyceryl ether
sulfonates, secondary alkane sulfonates, acyl-N-(C1-C9 alkyl) or
-N-(C2-C4 hydroxyalkyl) glucamine sulfates, C$-Cle alkyl
sulfoacetates and C8-C18 secondary alcohol sulfates and mixtures
thereof. In the detergent mixture, a combination of methyl ester
sulfonate and an anionic surfactant and are normally present at
ratios of from about nil to nonionic 4:1 to 1:4.
The nonionic surfactant is typically an amide, alkyl n-methyl
glucamine, amine oxide, CB-C1g fatty alcohol ethoxylates,
ethoxylated methyl esters, nonyl phenyl ethoxylates or mixtures
thereof .
It has been unexpectedly discovered that when an alpha
sulfonated alkyl ester of a fatty acid is combined in a detergent
composition with an anionic surfactant and a combination of
sulfonated methyl ester and an nonionic surfactant at a weight
ratio of total anionic surfactant to nonionic of 5:1 to 1:3, the
composition demonstrates surprisingly efficient cleaning at dilute
concentrations and is fluid at high concentrations.
It has further been discovered that when the alpha sulfonated
alkyl ester component includes a certain amount of a disalt of
' alpha sulfonated fatty acid, the formulation provides improved
cleaning of substrates in terms of less redeposition of the soils,
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grease, etc. to be removed. In this context, the disalts of alpha
sulfonated fatty acids act as antiredeposition agents.
In one embodiment, the invention comprises detergent
compositions which comprise:
(a) a mono-salt of an alpha-sulfonated methyl ester of a
fatty acid having from 8-20 carbon atoms and a di-salt of an ,
alpha-sulfonated fatty acid, the ratio of mono-salt to di-salt
being at least about 2:1;
(b) an anionic surfactant selected from the group consisting
of linear alkyl benzene sulfonates where the alkyl portion has
from about 8 to 15 carbon atoms, alkyl sulfate where the alkyl
portion has from about 8 to 18 carbon atoms, alkyl ethoxy sulfates
where the alkyl portion has from about 8 to 18 carbon atoms and
the average degree of ethoxylation is from about 1 to 7, alpha
olefin sulfonates where the olefin portion is a straight or
branched chain unsaturated hydrocarbon having from 8 to 24 carbon
atoms, paraffin sulfonate having from 8 to 18 carbon atoms, C9-CZo
alkyl glyceryl ether sulfonates, CB-C18 secondary alkane
sulfonates, C9-C1, acyl-N-(C1-CQ alkyl) or -N-(CZ-CQ hydroxyalkyl)
glucamine sulfates, C$-Cl$ alkyl sulfoacetates and C8-Cls secondary
alcohol sulfates and mixtures thereof; and
(c) a nonionic surfactant.
In certain embodiments of the invention, the detergent
compositions comprise:
(a) a salt of a alpha-sulfonated methyl ester of a fatty
acid having from about 8 to 18 carbon atoms;
(b) a salt of a alkyl ethoxy sulfate where the alkyl portion
has about 8 to 18 carbon atoms and the average degree of
ethoxylation is from about 1 to 7 ; and
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(c) a nonionic surfactant where the composition comprises at
least about 3.5:1 by weight of surfactant.
Aloha-Sulfonated Aiky~ ester
The alpha-sulfonated alkyl ester is present in the inventive
' S concentrated compositions at concentrations of from about 1-50% by
weight. Preferred compositions contain about 2-35% by weight
sulfonated alkyl ester and more preferred compositions contain
about 2-20% by weight of the sulfonated alkyl ester.
The alpha-sulfonated alkyl ester employed in the inventive
compositions may be pure alkyl ester or a blend of (1) a mono-salt
of an alpha-sulfonated alkyl ester of a fatty acid having from 8
carbon atoms where the alkyl portion forming the ester is
straight or branched chain alkyl of 1-6 carbon atoms and (2) a di
salt of an alpha-sulfonated fatty acid, the ratio of mono-salt to
15 di-salt being at least about 2:1, and up to about 25:1. The
alpha-sulfonated alkyl esters used in the invention are typically
prepared by sulfonating an alkyl ester of a fatty acid with a
sulfonating agent such as 503. When prepared in this manner, the
alpha-sulfonated alkyl esters normally contain a minor amount,
20 typically not exceeding 33% by weight, of the di-salt of the
alpha-sulfonated fatty acid which results from hydrolysis of the
ester. Preferred alpha-sulfonated alkyl esters contain less than
about 10% by weight of the di-salt of the corresponding alpha-
sulfonated fatty acid.
Preferred compositions according to the invention comprise a
mixture of mono-salt and di-salt of the alpha sulfonated fatty
acid. Most preferred compositions contain about 4-10% by weight
of the mono-salt of methyl alpha sulfonated fatty ester. The
compositions preferably contain from about 0.01-20%, more
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preferably 0.2-10%, and most preferably 0.3-5%, by weight of the
di-salt of the alpha-sulfonated fatty acid.
In particularly preferred compositions comprising such
mixtures, the amount of mono-salt should be sufficient to
solubilize the di-salt. Alternatively, the di-salt may be
solubilized using other surfactants, e.g., anionic or nonionic
surfactants, or traditional hydrotropes, although heating may be
required during manufacture. In such compositions, the dissolved
di-salt of the alpha sulfonated fatty acid functions as an
antiredeposition agent.
The alpha-sulfonated alkyl esters, i-, alkyl ester
sulfonate surfactants, include linear esters of Ce-CZO carboxylic
acid (i.e., fatty acids) which are sulfonated with gaseous S03
according to the "The Journal of American Oil Chemists Society,"
52 (1975), pp. 323-329. Suitable starting materials would include
natural fatty substances as derived from tallow, palm oil, coconut
etc.
The preferred alkyl ester sulfonate or fatty acid alpha
sulfonate surfactants comprise alkyl sulfonate surfactants of the
structural formula:
0
~OR4
S03M
wherein R3 is a CB-CZO hydrocarbyl, preferably an alkyl, or
combination thereof, RQ is hydrogen or a straight or branched chain
C1-C6 hydrocarbyl, preferably an alkyl, or combination thereof, and
M is a cation which forms a water soluble salt with the alkyl '
ester sulfonate. Suitable salt-forming cations include metals
such as calcium, magnesium, sodium, potassium, and lithium, and
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substituted or unsubstituted ammonium cations, such as monoethanol
amine, diethanolamine, and triethanolamine. Preferably, R3 is Clo-
C16 alkyl, and R9 is methyl, ethyl or isopropyl. More preferred
are alpha-sulfonated methyl esters of mixtures of fatty acids
S having an average of from 12 to 16 carbon atoms. Most preferred
are alpha-sulfonated methyl and ethyl esters of mixtures of fatty
acids having an average of from about 12 to 14 carbon atoms. A
particularly preferred mixture has an average of about 13.6 carbon
atoms in the fatty acid portion. When R4 is hydrogen in the above
formula, the formula represents a di-salt of an alpha sulfonated
fatty acid.
~r~On?C Surfaetan
Anionic surfactants can be selected from the following: alkyl
benzene sulfonates, alkyl sulfates, alkyl ethoxy sulfates,
paraffin sulfonates, monoalkane sulfonates, olefin sulfonates, and
alkyl glyceryl sulfonates. The anionic surfactant is present in
the detergent at concentrations of from 1-50%, preferably from
about 2-30%, and most preferably from about 2-25%, by weight of
the detergent composition.
Alkyl benzene sulfonates useful in compositions of the
present
invention are those in which the alkyl group, which is
substantially linear, contains 8-15 carbon atoms, preferably 10-13
carbon atoms, a material with an average carbon chain length of
about 11.5 being most preferred. The phenyl isomer distribution,
i.e., the point of attachment of the alkyl chain to the benzene
nucleus, is not critical, but alkyl benzenes having a high 2-
phenyl isomer content are preferred.
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Suitable alkyl sulfates are primary alkyl sulfates in which
the alkyl group contains 8-18 carbon atoms, more preferably an
average of 12-14 carbon atoms preferably in a linear chain. Clo Cls
alcohols, derived from natural fats, or Ziegler olefin build-up,
or OXO synthesis, form suitable sources for the alkyl group.
Examples of synthetically derived materials include Dobanol 23
(RTM) sold by Shell Chemicals (UK) Ltd., Ethyl 24 sold by the
Ethyl Corporation, a blend of C13-C15 alcohols in the ratio 67~ C13.
33% Cls sold under the trade name Lutensol by BASF GmbH and
Synperonic (RTM) by ICI Ltd., and Lial 125 sold by Liquichimica
Italina. Examples of naturally occurring materials from which the
alcohols can be derived are coconut oil and palm kernel oil and
the corresponding fatty acids.
Alkyl ethoxy sulfate surfactants comprise a primary alkyl
ethoxy sulfate derived from the condensation product of a C8-CZZ
alcohol with an average of up to 25 ethylene oxide groups. The CB-
C22 alcohol itself can be obtained from any of the sources
previously described for the alkyl sulfate component. C12-Czs alkyl
ethoxy sulfates are preferred as primary anionic surfactants where
the average degree of ethoxylation is about 3.
Conventional base-catalyzed ethoxylation processes to produce
an average degree of ethoxylation of 12 result in a distribution
of individual ethoxylates ranging from 1 to 15 ethoxy groups per
mole of alcohol, so that the desired average can be obtained in a
variety of ways. Blends can be made of material having different
degrees of ethoxylation and/or different ethoxylate distributions
arising from the specific ethoxylation techniques employed and '
subsequent processing steps such as distillation. In preferred
compositions in accordance with the present invention as alkyl
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ethoxy sulfate is used 'with has an average degree of ethoxylation
of from 0.4 to 6.5, more preferably~from 2 to 4.
Paraffin sulfonatea are also useful in the present invention
and have from 8 to 18 carbon atoms per molecule, more desirably 13
to 16 carbon atoms per molecule. These sulfonates are preferably
prepared by subjecting a cut of paraffin, corresponding to the
chain length specified above, to the action of sulfur dioxide and
oxygen in accordance w~Lth the well-known sulfoxidation process.
The product of this reaction is a secondary sulfonic acid which is
then neutralized with a suitable base to provide a water-soluble
secondary alkyl sulfonate. Similar secondary alkyl sulfonates may
be obtained by other methods, i.e. by the sulfochlorination method
in which chlorine and sulfur dioxide are reacted with paraffins in
the presence of actinic. light, the resulting sulfonyl chlorides
being hydrolyzed and neutralized to form the secondary alkyl
sulfonates. Whatever technique is employed, it is normally
desirable to produce the sulfonate as the monosulfonate, having no
unreacted starting hydrocarbon or having only a limited proportion
thereof present and with little or no inorganic salt by-product.
Similarly, the proportions of disulfonate or higher sulfonated
material will be minimized, although some may be present. The
monosulfonate may be terminally sulfonated or the sulfonate group
may be joined on the 2-carbon or other carbon of the linear chain.
Similarly, any accompanying disulfonate, usually produced when an
excess of sulfonating agent is present, may have the sulfonate
groups distributed over different carbon atoms of the paraffin
base, and mixtures of the monosulfonates and disulfonates may be
present.
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Mixtures of monoalkane sulfonates wherein the alkanes are of
14 and 15 carbon atoms are particularly preferred wherein the
sulfonates are present in the weight ratio of C19-Cls paraffins in
the range of 1:3 to 3:1.
Olefin sulfonates useful in the present invention are
mixtures of alkene-1-sulfonates, alkene hydroxysulfonates, alkene
disulfonates and hydroxydisulfonates, and are described in the
commonly assigned U.S. Patent 3,332,880, issued to P.F. Pflauner
and A. Kessler on July 25, 1967.
Suitable alkyl glyceryl ether sulfonates are those derived
from ethers of coconut oil and tallow.
Other sulfate surfactants include the Ce-Cl~ acyl-N-(C ~-C 9
alkyl) -N-(Cl-CZ hydroxyalkyl) glucamine sulfates, preferably those
in which the C8-C1-, acyl group is derived from coconut or palm
kernel oil. These materials can be prepared by the method
disclosed in U.S. Patent 2,717,894, issued September 13, 1955 to
Schwartz.
The counterion for the anionic surfactant component may be
any cation capable of forming a water soluble salt.
Representative counterions include, for example, Na+, K+, divalent
cations such as Mg++ and Ca +; A1 3; ammonium and substituted
ammonium such as alkanolammonium. Suitable alkanolammonium ions
include those formed from mono-, di-, and triethanolamines.
Preferred counterions are divalent cations, such as, for example,
magnesium and calcium. Magnesium is a particularly preferred
counterion for the anionic surfactant.
Non~on~c Surfactant
The detergent compositions of the present invention also
comprise from about 1% to about 50~, preferably from about 2~
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(more preferably 8 to 20%) to about 40% by weight of a foam
stabilizing surfactant selected from the group consisting of
amides, amine oxides, ethoxylated fatty acids, Cg-C18 fatty alcohol
ethoxylates, alkyl polyglycosides, alky n-methyl glucamides, nonyl
' S phenyl ethoxylates, methyl eater ethoxylates and mixtures thereof.
Amine oxides useful in the present invention include long
chain alkyl amine oxides, ,i.~., those compounds having the formula
0
R3(OR4~X-N-' ~R')2
wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropyl
and alkyl phenyl group, or mixtures thereof, containing from 8 to
26 carbon atoms, preferably 8 to 16 carbon atoms; R~ is an alkylene
or hydroxyalkylene group containing from 2 to 3 carbon atoms,
preferably 2 carbon atoms, or mixtures thereof; x is from 0 to 3,
preferably 0; and each RS is an alkyl or hydroxyalkyl group
containing from 1 to 3, preferably from 1 to 2 carbon atoms, or a
polyethylene oxide group containing from 1 to 3 , preferably 1,
ethylene oxide groups. The RS 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 Clo-Cls
alkyl dimethyl amine oxides and Ce-C12 alkoxy ethyl dihydroxyethyl
amine oxides. Examples of such materials include
dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-
hydroxyethyl)dodecylamine oxide, dimethyldodecylamine oxide,
dodecylamidopropyl dimethylamine oxide and dimethyl-2-
hydroxyoctadecylamine oxide. Preferred are Clo-C18 alkyl
dimethylamine oxide, and Clo-C18 acylamido alkyl dimethylamine
oxide.
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The nonionic surfactant may also be a fatty acid amide
surfactant. Preferred amides are Cs-CZO alkanol amides,
monoethanolamides, diethanolamides, and isopropanolamides. A'
particularly preferred amide is a mixture of myristic
monoethanolamide and lauric monoethanolamide. This preferred
amide is sold by Stepan Company, Northffield, Illinois as Ninol
LMP.
Other suitable nonionic detergent surfactants are generally
disclosed in U.S. Patent 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 6 to 12 carbon atoms in either a straight-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 Igepah'" CO-630, marketed by the GAF Corporation;
and Triton T'~' X-45, X-114, X-100, and X-102, all marketed by the
Roha i Haas Company.
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 8 to 22 carbon
atoms. Particularly preferred are the condensation products of
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alcohols having an alkyl group containing from about 10 to about
20 carbon atoms with from about 2 to about 10 moles of ethylene
oxide per mole of alcohol. Examples of commercially available
nonionic surfactants of this type include TergitolT"' 15-S-9 (the
S condensation product of C11-Cls linear alcohol with 9 moles ethylene
- oxide) , TergitolT"' 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; NeodolT"" 45-9 (the condensation product Of C19-Cls
linear alcohol with 9 moles of ethylene oxide) , NeodolT"' 23-6.5
(the condensation product of C12-C13 linear alcohol with 6.5 moles
of ethylene oxide), NeodolT"" 45-7 (the condensation product of Clq-
C15 linear alcohol with 7 moles of ethylene oxide), NeodolT'" 45-4
(the condensation product of C1q-C15 linear alcohol with 4 moles of
ethylene oxide), marketed by Shell Chemical Company, and KyroT"" EOB
(the condensation product C13-Cls alcohol with 9 moles ethylene
oxide), marketed by The Procter & Gamble Company.
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide
2o 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 polyoxyethvlene
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
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include certain of the commercially-available PluronicT"'
surfactants, marketed by BASF.
4. The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine. The 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
propyloxyethylene 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 TetronicT"" 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 10 to 18 carbon atoms and 2
moieties selected from the group consisting of alkyl groups and
hydroxyalkyl groups containing from 1 to 3 carbon atoms; and
water-soluble sulfoxides containing one alkyl moiety of from 10 to
18 carbon atoms and a moiety selected from the group consisting of
alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants. These amine oxide surfactants in particular
include Clo-C18 alkyl dimethyl amine oxides and Cs-C12 alkoxy ethyl
dihydroxy ethyl amine oxides. -
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, '
Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from
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about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglucoside, hydrophilic group containing 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
' 5 saccharide containing 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
intersaccharide 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
polyalkyleneoxide 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 containing from
8 to 18, preferably from 12 to 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
preferably derived from glucose. To prepare these compounds, the
alcohol or alkylpolethoxdy alcohol is formed first and then
reacted with glucose, or a source of glucose, to form the
glucoside (attachment at the 1-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.
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CA 02205592 2000-09-11
Optional ingredients include detergency builders, either of
the organic or inorganic type, although such builders in general
are not preferred for use in the composition of the present
invention. Examples of water-soluble inorganic builders which can
be used, either alone or in admixture with themselves or with
organic alkaline sequentrant builder salts, are glycine, alkyl and
alkenyl succinates, alkali metal carbonates, alkali metal
bicarbonates, phosphates, polyphosphates, and silicates. Specific
examples of such salts are sodium tripolyphosphate, sodium
carbonate, potassium carbonate, sodium bicarbonate, potassium
bicarbonate, sodium pyrophosphate, potassium pyrophosphate.
Examples of organic builder salts which can be used alone, or in
admixture with each other, or with the preceding inorganic
alkaline builder salts, are alkali metal polycarboxylates,
examples of which include but are not limited to, water-soluble
citrates such as sodium and potassium citrate, sodium and
potassium tartrate, sodium and potassium
ethylenediaminetetracetate, sodium and potassium N-(2-
hydroxyethyl)-nitrilo triacetates, sodium and potassium N-(2-
hydroxyethyl)-nitrilo diacetates, sodium and potassium
oxydisuccinates, and sodium and potassium tartrate mono- and di-
succinates, such as those described in U.S. Patent 4,663,071 (Bush
et al., issued May 5, 1987)v
Other organic detergency builders, such as
water-soluble phosphonates, can be used in the compositions of the
present invention. However, detergency builders in general have
limited value when the compositions of the present invention are
in the form of heavy-duty liquid or light-duty liquid dishwashing
detergent compositions. If included in the compositions of the
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WO 97/11143 PCT/US96/14889
present invention, these optional builders are typically present
at a concentration of from about 1.0% to about 10%, preferably
from about 2% to about 5% by weight.
Other optional ingredients include diluents, solvents, dyes,
perfumes and hydrotropes. Diluents can be inorganic salts, such
as sodium and- potassium sulfate, ammonium chloride, sodium and
potassium chloride, sodium bicarbonate, etc. Diluents useful in
the compositions of the present invention are typically present at
levels of from about 1% to about 10%, preferably from about 2% to
about 5% by weight.
Solvents useful herein include water and lower molecular
weight alcohols, such as ethyl alcohol, isopropyl alcohol, etc.
Solvents useful in the compositions of the present invention are
typically present at levels of from about 1% to about 60%,
preferably from about 5% to about 50% by weight.
Traditional hydrotropes such as sodium and potassium toluene
sulfonate, sodium and potassium xylene sulfonate, sodium and
potassium cumene sulfonate, trisodium and tripotassium
sulfosuccinate, and related compounds (as disclosed in U.S. Patent
3,915,903, the disclosure of which is incorporated herein) can be
utilized in the compositions. Although such hydrotropes may be
used, they are not normally needed in the inventive compositions.
Preferred compositions do not include traditional hydrotropes
since they do not contribute towards the cleaning and grease-
cutting capabilities of the compositions. Thus, preferred
compositions are substantially free from traditional hydrotropes
based on (1) aromatic sulfonates and (2) sulfonated carboxylic
acids.
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The cleaning compositions may also contain one or more
polyhydroxy fatty acid amides having the structural formula:
0
R2 %~ N / R~
~Z
wherein: R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy ,
propyl, or a mixture thereof, preferably C1-C4 alkyl, more
preferably C1 or CZ alkyl, most preferably C1 alkyl (i.e. , methyl) ;
and RZ is a CS-C31 hydrocarbyl, preferably straight-chain C~-Cl9
alkyl or alkenyl, more preferably straight-chain C9-Cl, alkyl or
alkenyl, most preferably straight-chain Cll-Cl, alkyl or alkenyl,
or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkylated derivative (preferably
ethoxylated or propoxylated) thereof. Z preferably will be
derived from a reducing sugar in a reductive amination reaction;
more preferably Z is 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 syrups 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 -CHZ-
(CHOH) n CH20H, -CH (CHZOH) - (CHOH) n_1_CHZOH, -CHZ- (CHOH) 2 (CHOR ~ ) -
CH~OH,
where n is an integer from 3 to 5, inclusive, and Rl is H or a
cyclic or aliphatic monosaccharide, and alkoxylated derivatives
thereof. Most preferred are glycityls wherein n is 4,
particularly -CHI-(CHOH)4-CHZOH.
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R1 can be, for example, N-methyl, N-ethyl, N-propyl, N-
isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
RZ-CO-N< can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide,
etc. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,
. 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1
deoxymaltotriotityl, etc.
The detergent compositions hereof may contain bleaching
agents or bleaching compositions containing bleaching agent and
one or more bleach activators. When present bleaching compounds
will typically be present at levels of from about 1% to about 20%,
more typically from about 1% to about 10%, of the detergent
composition. In general, bleaching compounds are optional
components in non-liquid formulations, e.g., granular detergents.
If present, the amount of bleach activators will typically be from
about 0.1% to about 60%, more typically from about 0.5% to about
40% of the bleaching composition.
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other
bleaching agents. For wash conditions below about 50°C, especiallv
below about 40°C, it is preferred that the compositions hereof not
contain borate or material which can form borate in situ (i.e.,
borate-forming material) under detergent storage or wash
conditions. Thus it is preferred under these conditions that a
' non-borate, non-borate-forming bleaching agent is used.
Preferably, detergents to be used at these temperatures are
substantially free of borate and borate-forming material. As used
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herein, "substantially free of borate and borate-forming material"
shall mean that the composition contains no more than about 2~ by
weight of borate-containing and borate-forming material of any
type, preferably, no more than 1~, more preferably 0~.
One category of bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium
monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybu~yric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed
in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
Patent 4,634,551, issued January 6, 1987 to Burns et al.,
European Patent Application 0,133,354, Banks et al., published
February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued
November l, 1983,
Highly preferred bleaching agents also include 6-
nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent
4,634,551, issued January 6, 1987 to Burns, et al.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of hypohalide
bleaching agents, for example, include trichloro isocyanuric acid
and the sodium and potassium dichloroisocyanurates and N-chloro
and H-brono alkane sulphonamides. Such materials are normally
added at 0.5-1D~ by weight of the finished product, preferably 1-
5~ by weight.
Peroxygen bleaching agents can also be used. Suitable
peroxygen bleaching compounds include sodium carbonate
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CA 02205592 2001-05-10
peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea
peroxyhydrate, and sodium peroxide.
Peroxygen bleaching agents are preferably combined with
bleach activators, which lead to the in situ production in aqueous
solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator.
Pref erred bleach activators for incorporation into
compositions of the present invention are described in U.S. Patent
4,915,854, issued April 10, 1990 to Man, et al.,
!, 10 and U.S. Patent 4,412,934.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type-of
nonoxygen bleaching agent of particular interest includes
photoactivated bleaching agents such as the sulfonated zinc and/or
aluminum phthalocyanines. These materials can be deposited upon
the substrate during the washing process. Upon irradiation with
i
light, in the presence of oxygen, such as by hanging clothes out
to dry in the daylight, the sulfonated zinc phthalocyanine is
activated and, consequently, the substrate is bleached. Preferred
zinc phthalocyanines and a photoactivated bleaching process are
described in U.S. Patent 4, 033,718, issued July 5, 1977 to
Holcoabe et al., Typically,
detergent compositions will contain about 0.025 to about 1.25; by
weight, of sulfbnated zinc phthalocyanine.
Any polymeric soil release agents known to those skilled in
i the art can be employed in the practice of this invention.
Polymeric soil release agents are characterized by having both
hydrophilic segments, to hydrophilize the surface of hydrophobic
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WO 97/11143 PCT/US96/14889
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.
By "soil release agent-enhancing amount" of polyhydroxy fatty
acid amide is meant an amount of such surfactant that will enhance
deposition of the soil release agent upon hydrophobic grease/oil
l0 cleaning performance can be obtained for fabrics washed in the
detergent composition hereof in the next subsequent cleaning
operation.
The amount of polyhydroxy fatty acid amide needed to enhance
deposition will vary with the anionic surfactant selected, the
amount of anionic surfactant, the particular soil release agent
chosen, as well as the particular polyhydroxy fatty acid amide
chosen. Generally, compositions will comprise from about 0.01% to
about 10%, by weight, of the polymeric soil release agent,
typically from about 0.1% to about 5%, and-from about 4% to about
50%, more typically from about 5% to about 30% of anionic
surfactant. Such compositions should generally contain at least
about 1%, preferably at least about 3%, by weight, of the
polyhydroxy fatty acid amide, though it is not intended to
necessarily be limited thereto.
The polymeric soil release agents for which performance is
enhanced by polyhydroxy fatty acid amide in the presence of
anionic surfactant include those soil release agents having: (a)
one or more nonionic hydrophile components consisting essentially
of (1) polyoxyethylene segments with a degree of polymerization of
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WO 97!11143 PCT/US96/14889
at least 2, or (ii) oxypropylene or polyoxypropylene segments with
a degree of polymerization of from 2 to 10, wherein said
hydrophile segment does not encompass any oxypropylene unit unless
it is bonded to adjacent moieties at each end by ether linkages,
b or (iii) a mixture of oxyalkylene units comprising oxyethylene and
from 1 to about 30 oxypropylene units wherein said mixture
contains a sufficient amount of oxyethylene units such that~the
hydrophile component has hydrophilicity great enough to increase
the hydrophilicity of conventional polyester synthetic fiber
surfaces upon deposit of the soil release agent on such surface,
said hydrophile segments preferably comprising at least about 25%
oxyethylene units and more preferably, especially for such
components having about 20 to 30 oxypropylene units, at least
about 50% oxyethylene units; or (b) one or more hvdronhobe
components comprising (i) C3 oxyalkylene terephthalate segments,
wherein, if said hydrophobe components also comprise oxyethylene
terephthalate, the ratio of oxyethylene terephthalate: C3
oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6
alkylene or oxy C9-C6 alkylene segments, or mixtures thereof, (iii)
poly (vinyl ester) segments, preferably polyvinyl acetate),
having a degree of polymerization of at least 2, or (iv) C1-C9
alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures
thereof, wherein said substituents are present in the form of C1-C9
alkyl ether or C9 hydroxyalkyl ether cellulose derivatives, or
mixtures thereof, and such cellulose derivatives are amphiphilic,
whereby they have a sufficient level of C1-C9 alkyl ether and/or
C9 hydroxyalkyl ether units to deposit upon conventional polyester
synthetic fiber surfaces and retain a sufficient level of
hydroxyls, once adhered to such conventional synthetic fiber
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CA 02205592 2000-09-11
surface, to increase fiber surface hydrophilicity, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have
i
a degree of polymerization of from 2 to about 200, although higher
levels can be used, preferably from 3 to about 150, more
i preferably from 6 to about 100. Suitable oxy C,-C6 alkylene
i
hydrophobe segments include, but are not limited to, end-caps of
I
polymeric soil release agents such as Mo,s(CHZ)nOCH2CH20-, Where M
is sodium and n is an integer from 4-6, as disclosed in U.S.
Patent 4,721,580, issued January 26, 1988 to Gosselink.
i' Polymeric soil release agents useful in the present invention
i include cellulosic derivatives such as h dro
y xyether cellulosi.~
i
polymers, copolymeric blocks of ethylene terephthalate or
r
propylene terephthalate with polyethylene oxide or polypropylene
i oxide terephthalate, and the like.
i
Cellulosic derivatives that are functional as soil release
agents are commercially available and include hydroxyethers of
cellulose such as MethocelR (Dow).
Cellulosic soil release agents for use herein also include
those selected from the group consisting of C~-C, alkyl and C,
hydroxyalkyl cellulose such as methylcellulose, ethylcellulose,
hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose.
A variety of cellulose derivatives useful as soil release polymers
are disclose3 in U.S. Patent 4,000,093, issued December 28, 1976
to Nicol, et al.
Soil release agents characterized by polyvinyl ester)
hydrophobe segments include graft copolymers of polyvinyl ester),
e.g., Cl-C6 vinyl esters, preferably polyvinyl acetate) grafted
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CA 02205592 2000-09-11
i
onto polyalkylene oxide backbones, such as polyethylene oxide
backbones. Such materials are known in the art and are desribed
in European Patent Application 0 219 048, published April 22, 1987
by Kud, et al. Suitable commercially available soil release
agents of this kind include the SOKALAN type of material, e.g.,
SOK,AL,AN HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer
having random blocks of ethylene terephthalate and polyethylene
oxide (PEO) terephthalate. More specifically, these polymers are
:..:
:l0 comprised of repeating units of ehtylene terephthalate and PEO
terephthalate in a mole ratio of ethylene terephthalate units to
PEO terephthalate units of from about 25:75 to about 35:65, said
PEO terephthalate 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 3,959,230 to
Hays, issued May 25, 197 6
See also U.S. Patent 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 ehtylene terephthalate units containing 10-
15~ by weight of ethylene terephthalate units together with 90-80%
by weight of polyoxyethylene terephthalate units, derived from a
polyoxyathylene glycol of average molecular weight 300-5,000, and
the mole ratid 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 ZELCON 5126 (from DuPont) and MILEASE T (from ICI).
These polymers and methods of their preparation are more fully
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CA 02205592 2001-05-10
described in U.S. Patent 4,702,857, issued October 27, 1987 to
Gosselink,.
Another preferred polymeric soil release agent is a
sulfonated product of a substantially linear ester oligomer
comprised of an oligomeric ester backbone of terephthaloyl and
oxyalkyleneoxy repeat units and terminal moieties covalently
attached to the backbone, said soil release agent being derived
from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2
propylene diol, wherein after sulfonation, the terminal moieties
of each oligomer have, on average, a total of from about 1 to
about 4 sulfonate groups. These soil release agents are described
fully in U.S. Patent 4,968,451 , issued November 6, 1990 to J.J.
Scheibel and E.P. Gosselink,
Other suitable polymeric soil release agents include the
ethyl- or methyl-capped 1,2-propylene terephthalate-
polyoxyethylene terephthalate polyesters of U.S. Patent 4,711,730,
issued December 8, 1987 to Gosselink et al., the anionic end-
capped oligomeric esters of U.S. Patent 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 4,702,857,
issued October 27, 1987 to Gasselink, having polyethoxy end-caps
of the formula X-(OCH,CH~)~- wherein n is from 12 to about 43 and
X is a Cl-C,
alkyl, or preferably methyl.
Additional polymeric soil release agents include the soil
release agents of U.S. Patent 4,877,896, issued October 31, 1989
-28-
CA 02205592 2000-09-11
to Maldonado et al, which discloses anionic, especially
sulfoaruyl, end-capped terephthalate esters.
The terephthalate esters contain
unsymmetrically substituted oxy-1,2-alkylenoxy units. Included
;' S among the soil release polymers of U.S. Patent 4,877,896 are
materials with polyoxyethylene hydrophile components of Cj
oxyalkylena terephthalate (propylene terephthalate) repeat units
within the sco a of the h dro hobs com
p y p ponents of (b)(i) above. It
is the polymeric soil release agents characterized by either,
or
both, 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 f~ra~a
about 0.01% to about 10.0%, by weight, of the detergent
compositions herein, typically from about 0.1% to about 5%,
i preferably from about o.2% to about 3.0%.
i
t
i
i
ng Agen
s
Cb~lat
The detergent compositions herein may also optionally contain
one or more iron and manganese chelating agents as a builder
ZO adjunct material. Such chelating agents can be selected from
the
group consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and
''~
~' I mixtures thereof, all as hereinafter defined. Without-intending
to ba bound by theory, it is believed that the benefit of these
materials is due in part to their exceptional ability to remove
' from and manganese ions from washing solutions by formation of
i
soluble chelates.
Amino carboxylates useful as optional chelating agents in
compositions of the invention include, for example,
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WO 97/11143 PCT/US96114889_
a t h y 1 a n a d i a m i n a t a t-r a a c a t a t a s , N -
hydroxyethylethyleneiaminetriacetates, nitrilotriacetates,
a t h y 1 a n a d i a m i n a t a t r a p r o p r i o n a t a s ,
t r i a t h y 1 a n a t a t r a a m i n a h a x a a c a t a t a s ,
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. Suitable amino phosphonates for use in the
inventive compositions and include ethylenediaminetetrakis
(methylenephosphonates), nitrilotris (methylenephosphorates) 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. U.S. Patent 3,812,044,
issued May 21, 1974, to Connor et al, incorporated herein by
reference, 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-disulfobenzene. Alkaline detergent compositions
can contain these materials in the form of alkali metal, ammonium
or substituted ammonium (e. g. mono-or triethanol-amine) 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
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CA 02205592 2001-05-10
comprise from about 0.1% to about 3.0% by weight of such
compositions.
The compositions of the present invention can also optionally
contain water-soluble ethoxylated amines having clay soil removal
and anti-redeposition properties. Granular detergent compositions
which contain these compounds typically contain from about 0.01%
to about 10.0% by weight of the water-soluble ethoxylated amines;
liquid detergent compositions, typically about 0.01% to about 5%.
These compounds are selected preferably from the group
consisting of:
(1) ethoxylated monoamines;
(2) ethoxylated diamines;
(3) ethoxylated polyamines;
(4) ethoxylated amine polymers; and
(5) mixtures thereof.
The most preferred soil release and anti-redeposition agent
is ethoxylated tetraethylanepentamine. Exemplary ethoxylated
amines are further described in U.S. Patent 4,597,898, VanderMeer,
issued July 1, 1986, incorporated herein by reference. Another
group of preferred clay soil removal/antiredeposition agents are
the cationic compounds disclosed in European Patent Application
111,965, Oh and Gosselink, published June 27, 1984.
Other clay soil removal/antiredeposition
agents which can be used include the ethoxylated amine polymers
disclosed' ih European Patent Application 111,984, Gossellink,
published June 27, 1984; the awitterionic polymers disclosed in
European Patent Application 112,592, Gosselink, published July 4,
1984; and the amine oxides disclosed in U.S. Patent 4,548,744,
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WO 97/11143 PCT/US96/14889
Connor, issued October 22, 1985, all of which are incorporated
herein by reference.
Other clay soil removal and/or anti redeposition agents known
in the art can also be utilized in the compositions hereof.
Another type of preferred anti-redeposition agent includes the
carboxy methyl cellulose (CMC) materials. These materials are
well known in the art.
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. It is
believed, though it is not intended to be limited by theory, that
polymeric dispersing agents enhance overall detergent builder
performance, when used in combination with other builders
(including lower molecular weight polycarboxylates) by crystal
growth inhibition, particular soil release peptization, and anti-
redeposition.
Polycarboxylate materials which can be employed as the
polymeric dispersing agent herein can be prepared by polymerizing
or copolymerizing suitable unsaturated monomers, preferably in
their acid form. Unsaturated monomeric acids that can be
polymerized to form suitable polymeric polycarboxylates include
acrylic acid, malefic acid (or malefic anhydride), fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no '
carboxylate radicals such as vinylmethyl ether, styrene, ethylene,
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CA 02205592 2000-09-11
etc. is suitable provided that such segments do not constitute
more than about 40$ by weight.
Particularly suitable polymeric polycarboxylates can be
derived from acrylic acid. Such acrylic acid-based polymers which
are useful herein are the water-soluble salts of polymerised
acrylic acid. The average molecular weight of such polymers in
the acid form preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000 and most preferably from
about 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble polymers'of this type are
known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S-
Patent 3,308,067, issued March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a
preferred component of the dispersing/anti-redeposition agent.
Such materials include the water-soluble salts of copolymers of
acrylic acid and malefic acid. The average molecular weight of
such copolymers in the acid form preferably ranges from about
2,000 to 100,000, more preferably from about 5,000 to 75,000 most
preferably from about 7,000 to 65,000. The ratio of acrylate to
maleate segments in such copolymers will generally range from
about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
Water-soluble silts of such acrylic acid/maleic acid copolymers
can include, far example, the alkali metal, ammonium and
substituted ammonium salts. Soluble acrylate/maleate copolymers
of this type are known materials which are described in European
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CA 02205592 2001-05-10
Patent Application No. 66915, published December 15, 1982.
Another polymeric material which can be included is
polyethylene glycol (PEG). PEG can exhibit dispersing agent
performance as well as act as a clay soil removal/antiredeposition
agent. Typical molecular weight ranges for these purposes range
from about 500 to about 100,000 preferably from about 1,000 to
about 50,000, more preferably from about 1,500 to about 10,000.
Any optical brightenero or other brightening or whitening
l0 agents known in the art can be incorporated into the detergent
compositions hereof.
The choice of brightener for use in detergent compositions
will depend upon a number of factors, such as the type of
detergent, the nature of other components present in the detergent
composition, the temperatures of wash water, the degree of
agitation, and the ratio of the material washed to tub size.
The brightener selection is also dependent upon the type of
material to be cleaned, e.g., cottons, synthetics, etc. Since
most laundry detergent products are used to clean a variety of
fabrics, the detergent compositions should contain a mixture of
brighteners which will be effective for a variety of fabrics. It
is of course necessary that the individual components of such a
brightener mixture be compatible.
Coamercial 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, cumarin, carboxylic acid, methinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Examples of such
-34-
CA 02205592 2001-05-10
brighteners are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by John
Wiley & Sons, New York (1982),
Stilbene derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
of bis-(triazinyl)amino-stilbene; bisacylamino derivatives of
stilbene; triazole derivatives of stilbene; oxadiazole derivatives
of stilbene' oxazole derivatives of stilbene; and styryl
derivatives of stilbene. Certain derivatives of
bis(triazinyl)aminostilbene which may be useful in the present
invention may be prepared from 4,4'-diamine-stilbene-2,2'-
disultonic acid.
Coumarin derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
substituted in the 3-position, in the 7-position, and in the S
and 7-positions.
Carboxylic acid derivatives which may be useful in the
present invention include, but are not necessarily limited to,
fumaric acid derivatives; benzoic acid derivatives; p-phenylene
bis-acrylic acid derivatives; naphthalenedicarboxylic acid
derivatives; heterocyclic acid derivatives; and cinnamic acid
derivatives.
Cinnamic acid derivatives which may be useful in the present
invention can be further subclassified into groups which include,
but are not necessarily limited to, cinnamic acid derivatives,
styrylazoles, styrylbenzofurans, styryloxadiazoles,
styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of
the Zahradnik reference.
-35-
CA 02205592 2000-09-11
The styrylazoles can be further subclassified into
styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as
disclosed on page 78 of the Zahradnik refe
rence. It will be
understood that these three identified subclasses may not
necessarily reflect an exhaustive list of subgroups into which
styrylazoles may be subclassified.
Another class of optical brighteners which may be useful in
the present invention are the derivatives of dibenzothiophene-
5 " 5-dioxide disclosed at page 741-749 of The Kirk-o hm r
$~yc o~edia of Chymi~,~Tech_ho~ow, Volume 3, pages 737-750 (John
Wiley & Son, Inc., 1962).
and include 3,7-diaminodibenzothiophene-2,8-
disulfonic acid, 5,5 dioxide.
Another class of optical brighteners which may be useful in
i
the present invention include azoles, which are derivatives of 5-
membered ring heterocycles. These can be further subcategorized
into monoazoles and bisazoles. Examples of monoazoles and
bisazoles are disclosed in the Kirk-Othmer reference.
Another class of brighteners which may be useful in the
present invention are the derivatives of 6-membered-ring
heterocycles disclosed in the Kirk-othmer reference. Examples of
such compounds include brighteners derived from pyrazine and
brighten~rs derived from 4-aminonaphthalamide. -
In addition to the brighteners already described,
miscellaneous agents may also be useful as brighteners. Examples
of such miscellaneous agents are disclosed at pages 93-95 of the
Zahradnik reference, and include 1-hydroxy-3,6,8-pyrenetrisuphonic
acid; 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5
-36-
i
CA 02205592 2000-09-11
diphenylimidazolanedisulphonic acid and derivatives of pyrazoline-quinoline.
Other specific examples of optical brighteners which may be
useful in the present invention are those identified in U.S.
Patent 4,790,856, issued to Wixan on December 13, 1988
f
. These
brighteners include the PHORWHITE series of brighteners from
Verona. Other brighteners disclosed in this reference include:
Tinopal UNPA, Tinopal CBS and Tinopal SHM; available from Ciba-
. .;
Geigy; Arctic White CC and Antic White CWD, available from Hilton
Davis, located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol(1,2
d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'
bis(styryl)bisphenyls; and the y-aminocoumarins. Specific
examples of these brighteners include 4-methyl-7-diethylamino
coumarin; 1, 2-bis (-benzimidazol-2-yl) ethylene; 1, 3
i
diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl
naphth-(1,2-d]oxazole; and 2-(stilbene-4-yl)2-H-naphtho-(1,2
r d]triazole.
Other optical brighteners which may be useful in the present
invention include those disclosed in U.S. Patent 3,646,015, issued
February 29, 1972, to Hamilton.
Compounds known, or which become known, for reducing or
suppressing the formation of suds can be incorporated into the
composition of the present invention. The incorporation of such
materials, hereinafter "suds suppressors," can be desirable
because the presence of anionic surfactants with polyhydroxy fatty
acid amide surfactants hereof can increase suds stability of the
detergent compositions. Suds suppression can be of particular
importance when the detergent compositions include a relatively
-37-
CA 02205592 2000-09-11
a
high sudsing surfactant in combination with the polyhydroxy fatty
acid amide surfactants. Suds suppression is particularly
r
desirable for compositions intended for use in front loading
automatic washing machines. These machines are typically
characterized by having drums, for containing the laundry and wash
water, which have a horizontal axis and rotary action about the
axis. This type of agitation can result in high suds formation
and, consequently, in reduced cleaning performance. The use of
,.
suds suppressers can also be of particular importance under hot
v' 10 water washing conditions and under high surfactant concentration
conditions.
A wide variety of materials may be used as suds suppresors in
the compositions hereof. Suds suppressers are well known to those
skilled in the art. They are generally described, for example, in
Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,
Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One
category of suds suppresser of particular interest encompasses
monocarboxylic fatty acids and soluble salts thereof. These
materials are discussed in U.S. Patent 2,954,347, issued September
27, 1960 to Wayne St. John,
The monocarboxylic fatty acids, and salts thereof,
for use as suds suppresser typically have hydrocarbyl chains of 10
to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
Suitable salts include the alkali metal salts such as sodium,
potassium, and ~Iithium salts, and ammonium and alkanolammonium
salts. These materials are a preferred category of suds
suppresser for detergent compositions.
The detergent compositions may also contain non-surfactant
suds suppressers. These include, for example, high molecular
-38-
CA 02205592 2001-05-10
weight hydrocarbons such as paraffin, fatty acid esters (e. g.,
fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic Cta-C" ketones (e. g., stearone), etc. Other
suds inhibitors include N-alkylated amino triazines such as tri-
to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines
formed as products of cyanuric chloride with two or three moles of
a primary or secondary amine containing 1 to 24 carbon atoms,
propylene oxide, and monostearyl phosphates such as monostearyl
alcohol phosphate ester and monostearyl di-alkali metal (e.g., K,
Na, and Li) phosphates and phosphate esters. The hydrocarbons
such as paraffin and haloparaffin can be utilized in liquid form.
The liquid hydrocarbons will be liquid at room temperature and
atmospheric pressure, and will have a pour point in the range of
about -.40°C and about 5°~C, and a minimum boiling point not
less
than about 110°C (atmospheric pressure). It is also known to
utilize waxy hydrocarbons, preferably having a melting point below
about 100°C. The hydrocarbons constitute a preferred category of
suds suppresser for detergent compositions. Hydrocarbon suds
suppressers are described, for example, in U.S. Patent 4,265,779,
issued May 5, 1981 to Gandolfo, et al.
Tha hydrocarbons, thus, include aliphatic, alicyclic,
aromatic, and heterocyclic saturated or unsaturated hydrocarbons
having from about 12 to about 70 carbon atoms. The term
"paraffin," as used in this suds suppresser discussion, is
intended to include mixtures of true paraffins and cyclic
hydrocarbons.
Another preferred category of non-surfactant suds suppressers
comprises silicone suds suppressers. This category includes the
use of polyorganosiloxane oils, such as polydimethylsiloxane,
-39-
CA 02205592 2001-05-10
dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of polyorganosiloxane with silica particles wherein
the polyorganoxiloxane is chemisorbed or fused. onto the silica.
Silicone suds suppressors are well known in the art and are, for
example, disclosed in U.S. Patent 4,256,779, issued May 5, 1981 to
Gandolfo et al. and European Patent Application No. Ep 354016A2
published February 7, 1990, by Starch, M.S.
Other silicone suds suppresaors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for
defoaming aqueous solutions by incorporating therein small amounts
of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for
instance, in Genaan Patent No. DE 2124526. Silicone
defoamers and suds controlling agents in granular detergent
compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
al., and in U.S. Patent 4,652,392, Baginiski et al., issued March
24, 1987.
An exemplary silicone based suds suppressor for use herein is
a suds suppressing amount of a suds controlling agent consisting
essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from
about 2O 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 (CIi3),Si01/1 units of SiOZ
units in a ratio of from (CH3),Si01/2 units and to si02 units of
from about 0.6:i 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;
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CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889
For any detergent compositions to be used in automatic
laundry washing machines, suds should not form to the extent that
they overflow the washing machine. Suds suppressors, when
utilized, are preferably present in a "suds suppressing amount."
By "suds suppressing amount" is meant that the formulator of the
composition can select an amount of this suds controlling agent
that will sufficiently control the suds to result in a low-sudsing
laundry detergent for use in automatic laundry washing machines.
The amount of suds control will vary with the detergent
surfactants selected. For example, with high sudsing surfactants,
relatively more of the suds controlling agent is used to achieve
the desired suds control than the lesser foaming surfactants. In
general, a sufficient amount of suds suppressor should be
incorporated in low sudsing detergent compositions so that the
suds that form during the wash cycle of the automatic washing
machine (i.e., upon agitation of the detergent in aqueous solution
under the intended wash temperature and concentration conditions)
do not exceed about 75% of the void volume of washing machine's
containment drum, preferably the suds do not exceed about 50% of
said void volume, wherein the void volume is determined as the
difference between total volume of the containment drum and the
volume of the water plus the laundry.
The compositions hereof will generally comprise from 0% to
about 5% of suds suppressor. When utilized as suds suppressors,
monocarboxylic fatty acids, and salts thereof, will be present
typically in amounts up to about 5%, by weight, of the detergent
composition. Preferably, from about 0.5% to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to about 2.0% by
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CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889_
weight, of the detergent composition, although higher amounts, may
be used. This upper limit is practical in nature, due primarily
to concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from
about 0.01% to about 1% of silicone suds suppressor is used, more
preferably from about 0.25% to about 0.5%. As used herein, these ,
weight percentage values include any silica that may be utilized
in combination with polyorganosiloxane, as well as any adjunct
materials that may be utilized. Monostearyl phosphates are
generally utilized in amounts ranging from about 0.1% to about 2%,
by weight, of the composition.
Hydrocarbon suds suppressors are typically utilized in
amounts ranging from about 0.01% to about 5.0%, although higher
levels can be used.
Other Ingredients
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, 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 those containing 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. '
The detergent compositions hereof will preferably be
formulated such that during use in aqueous cleaning operations,
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WO 97/11143 PCT/LTS96/14889
the wash water will have a pH of between about 6.5 to about ll,
preferably between about 7.5 and about 10.5. Liquid product
formulations preferably have a pH between about 7.5 and about 9.5,
more preferably between about 7.5 and about 9Ø Techniques for
controlling pH at recommended 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 improving the
performance of detergents containing anionic, nonionic, and/or
l0 cationic surfactant, and detersive enzyme, by utilizing therein an
enzyme performance-enhancing amount of the polyhydroxy fatty acid
amide surfactant described above, typically at least about 1% of
such surfactant.
This invention further provides a method for cleaning
substrates, such as fibers, fabrics, hard surfaces, skin, hair
etc., by contacting said substrate, with a detergent composition
comprising detersive enzyme and one or more anionic, nonionic, or
cationic surfactants wherein said detergent composition contains
an enzyme performance-enhancing amount of polyhydroxy fatty acid
amide, typically at least about 1% by weight, of the composition,
in the presence of a solvent such as water or water-miscible
solvent (e.g., primary and secondary alcohols). 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 machines, automatic dishwashers, etc.
- Mixtures of lipases, proteases, cellulases, amylases and
peroxidases are adequately stable in the presence of certain non-
alkylbenzene sulfonate surfactant systems, such that effective,
-43-
CA 02205592 2000-09-11
heavy-duty liquid detergents can be formulated. Indeed, the
formulation of stable, liquid, enzyme-containing detergent
compositions constitutes a highly advantageous and preferred
embodiment afforded by the technology of the present invention.
The preferred liquid compositions herein comprise up to about 2%,
preferably about 0.0001% to about 1%, most preferably about 0.001%
to about 0.5%, on an active basis, of detersive enzyme. These
enzymes are preferably selected from the group consisting of
protease (preferred), lipase (preferred), amylase, cellulase,
peroxidase, and mixtures thereof. Preferred are compositions with
--
two or more classes of enzymes, most preferably where one is a
protease.
' While various descriptions of detergent proteases,
cellulases, etc., are available in the literature, detergent
lipases may be somewhat less familiar. Accordingly, to assist the
formulator, lipases of interest include Amano AKG and Bacillis Sp
i
lipase (e.g., Solvay enzymes). Also, see the lipases described in
EP.A 0 399 681, published November 28, 1990, EP A 0 218, 272,
l
published April 15, 1987 and PCT/US/ 88/00177, published May 18,
I
1989
Suitable fungal lipases include those producible by Xumicola
Iaaug3nosa and Thermoncyes Zanuginoaus. Most preferred is the
lipase obtained by cloning the gene from Humico3a lanuginosa and
expressing the gene in Aspergillus oryzae, as described in
European Patent Application 0 258 058
commercially available under the trade name Lipolase.
From about 2 to about 20,000, preferably about 10 to about
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
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CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889_
lipase which produces 1 ~umol of titratable butyric acid per minute
in a pH stat, where pH is 7.0, temperature is 30°C, and substrate
is an emulsion tributyrin and gum arabic, in the presence of
and NaCl in phosphate buffer.
Representative enzymes for use in the invention include those
shown below.
Classes of d~tsrgsat enzymes
Enzyme Class Substrate Examples
Protease Proteins: Alcalase
Blood Savinase
Egg Esperase
Grass Durazyn
Human soils
Amylase Starch: g~
Cocoa Termamyl
Gravy
Oatmael
Pasta, etc.
Lipase Triglycerides: Lipolase
Vegetable oils
Fats
Human sebum
Cellulase Cellulose: Celluzyme
Microf fibrils
causing greying,
piling
All documents, Pte, patents and journal articles, cited
above or below are hereby incorporated by reference in their
entirety.
One skilled in the art will recognize that modifications may
be made in the present invention without deviating from the spirit
or scope of the invention. The invention is illustrated further
by the following examples which are not to be construed as
limiting the invention or scope of the specific procedures
described herein.
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CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889
In the following examples, all amounts are stated in percent
by weight of active material unless indicated otherwise.
Laundry detergent formulations may be prepared by adding
water to a suitable vessel equipped with mixing means. The
remaining ingredients are added in the order in which they are
listed in the formulations set forth in the following examples.
The resulting mixtures are continuously mixed until a liquid of
uniform consistency is obtained. The pH may be adjusted as needed
to about 8.5-8.8 using suitable alkaline or acidic reagents.
Alternatively, laundry detergent formulations may be prepared
by adding water to a suitable vessel equipped with mixing,
heating and cooling means, followed by the remaining ingredients
in the order in which they are listed in the formulations set
forth in the following examples. The resulting mixtures are
heated to about 140-145°F and mixed until a liquid of uniform
consistency is obtained. The pH may be adjusted as required to
about 8.5-8.8 using suitable alkaline or acidic reagents.
The test conditions for determining the detergency for
formulations set forth in the following examples are shown below.
Results for detergency are expressed as the change in reflectance
for fabric before and after washing, oR. In a detergency
determination, a higher oR value indicates better cleaning of a
fabric swatch and, thus, a better detergent composition.
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CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889_
Warm Wash
Temperature of washing solution: 100°F.
Washing Time: 10 minutes.
Temperature of rinse water: 80°F.
Rinsing time: 5 minutes.
Water hardness: 140 ppm.
Soil: dust-sebum.
Agitation: 100 rpm.
Cold Wash
Temperature of washing solution 60°F.
Temperature of rinse water 60°F .
All other parameters are the same as used for the warm wash
detergency determination.
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CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889
The test conditions for determining the antiredeposition
efficacy for formulations set forth in the following examples are
shown below. Results for antiredeposition efficacy are expressed ,
as the change in reflectance for fabric before and after washing,
i.e., oR = refectance before washing - reflectance after washing. ,
Reflectance is measured for three (3) sets of clean sample 3"
x 4" swatches (3 cotton, 3 cotton/polyester and 3 polyester).
Three (3) soiled (dust-sebum or clay) swatches and 3 clean
swatches of each fabric type are washed together using the
following conditions at 0.2% detergent concentrations. Washing is
repeated 3 times in the same surfactant solution, each time
introducing a new set of 3 soiled swatches with the original set
of clean swatches while removing the washed soiled swatches.
Reflectance determinations are then made for original set of clean
swatches. In redeposition determinations, lower oR values
indicate less redeposition of soil onto a fabric swatch and, thus,
better antiredeposition agents.
Warm Wash
Temperature of washing solution: 100°F.
Washing cycle: 10 minutes.
Temperature of rinse water: 80°F.
Rinsing cycle: 5 minutes.
Water hardness: 140 ppm.
Agitation: 100 rpm.
Temperature of washing solution 60°F.
Temperature of rinse water 60°F .
All other parameters are the same as used for the warm wash
detergency determination.
Detergent concentration equals total surfactant
concentration. Surfactant concentration does not include non-
surfactants such as traditional hydrotropes.
-48-
CA 02205592 1997-OS-16
WO 97/11143
PCT/US96/14889
_
For m W n No
a+-;
o
Com onents 1 2
3 4 5 6 7
Alpha-Step MC-48Z 18.08
10.07 10.07 10.07
Sodium Lauryl Sulfate
18.08 8
00
Sodium Lauryl(3E0) .
18.08 8.00
ether sulfate
Sodium LAS'
18.08 8.00
Neodol 25-7~
9.03 9.03 9.03 9.03 9.03 9.03 9
03
TEA 1.00 1.00 1.00 1.00 1 .
00
. 1.00 1.00
DI Water
All to 100
are
Q.S.
%Active Surfactant 27.1 27 27
1 1
. . 27.1 27.1 27.1 27.1
Appearance
ClearClear Clear Clear Clear Clear Clea
r
pH 8.8 8.8 8.8 8.8 8
8
. 8.8 8.8
CMCS
29.0 41.0 30.4 50.0 28.6 28.4 28.4
Deter enc chan in reflectance, oR
a
Warm Wash D t o ~n ~r G -;
Tes d:
+
on n_n,~
0.2% active surfactant
Cotton Fabric 16.1 15.4 13 16
9 3
. . 17.4 17.4 18.1
Cotton/poly. 12
8
. 14.0 14.0 15.1 16.1 16.1 16.4
2 0 Fabric
0.5% active surfactant
Cotton Fabric 18.8 16.4 16 18
5 2
. . 18.7 18.4 20.1
Cotton/poly. 16
8
. 15.5 14.6 15.0 17.7 16.7 17.9
Fabric
2 5 fold Wash DeteQencv nnri r,
Tef' n W
;
0.2% active surfactant
Cotton Fabric 17.8 18.2 16 16
8 4
. . 20.3 19.8 18.1
Cotton/poly. 15
0
. 13.5 14.3 13.6 15.4 16.2 15.5
Fabric
3 0 0.5% active surfactant
Cotton Fabric 18.4 19.0 18 20
7 4
. . 20.7 20.8 21.9
Cotton/poly. 15
7
. 14.2 16.2 15.6 15.9 17.9 17.3
Fabric
~MPh E 2
FOrm»1_g~io, ri Np
35 Components 8 9 10
Sodium salt of methyl ester of a-sulfonated fatt C
Y iz-i9
acid and Disodium salt of a-sulfonated ClZ_1~ fatty acid, mono:di
ratio of about 5:1
Linear alkyl benzene sulfonate having an average of
11.5 carbon atoms in alkyl portion.
4 Clz-~s alcohol ethoxylated with 7 moles of ethylene
oxide.
s Critical micelle concentration (mg of surfactant/mL).
-49-
CA 02205592 1997-OS-16
PCT/US96/14889_
WO 97/11143
DI Water Q.S. to Q.S. to Q.S. to-
100.00 100.00 100.00
Sodium Sulfate 2.00 2.00 2.00
Alpha-Step MC-48 12.30 12.30 12.30
Na6 Lauryl (3) Ether 19.90
Sulfate ,
Na LAS 19.90
Na Lauryl Sulfate 19.90
Neodol 25-7 22.80 22.90 22.90
TEA 99$ 2.00 2.00 2.00
weight ~ Active 55.0 55.0 55.0
Surfactant
Appearance Clear Clear Clear
Viscosity @ 25C 550 460 500
(cps)
pH 8.8 8.8 8.8
Detergency @0 047 Active(change in
reflectance,
oR)
jgjQrm Wash DeterqenC~est Condit?ons
T
Cotton Fabric 15.6 13.2 14.2
Cotton/Polyester 13.2 11.2 12.5
Fabric
Na refers to Sodium.
-50-
CA 02205592 1997-OS-16
WO 97/11143 PCT/US96/14889_
Fo_rm,~1 ati on hTo
Components 11 12 13.
14
DI Water Q.S. Q.S. to Q.S. to Q.S. to
to
100.00 100.00 100.00 100.00
Sodium Sulfate 1.00 1
00
. 1.00 1.00
TEA 99% 1.00 1.00 1.00 1.00
Alpha-Step MC-48 6.06 6 6
06
. .06 6.06
Sodium Clz-is (7E0) 9.77
Ether Sulfate
Sodium Clz-1~ ( 5E0 ) 9
77
Ether Sulfate .
Sodium lauryl ether
9.77 9.77
(3E0) sulfate
Fatty acid (lauryl)
11.27
methyl ester ethoxylated
with 10.9 moles of
ethylene oxide'
Fatty acid (lauryl)
11.27
methyl ester ethoxylated
with 14.6 moles of
2 0 ethylene oxides
Neodol 25-7 11.27 11.27
% Active 27.10 27.10 27.10 27
10
Surfactant .
Appearance Clear Clear Clear Clear
2 5 Viscosity @ 25C 200 250 300
250
(cps)
pH 8.8 8.8 8.8 8.8
Deter encv @0.047% Active (change reflectance,oR)
in
Plarm Wash Det l
e
T
~'
y nnr
3 0 ncy ; f-; 16.1 16.1 16.5
est nna
Cotton Fabric 17.0
Cotton/Polyester 15.4 14.8 13.9 14
0
Fabric .
Compound has the following structure: RCOZ(CH,CH20)"CH3
where R is lauryl -and n is an average of 10.9.
Compound has the following structure: RCOZ(CHZCHZO)nCH3
where R is lauryl and n is an average of 14.6.
-51-
CA 02205592 1997-OS-16
WO 97/11143 PCT/CTS96/14889
Formulat ion No.
Components 15 16 17 18
DI Water Q.S. Q.S. to Q.S. Q.S. to
to to
100.00 100.00 100.00 100.00
Sodium Sulfate 1.00 1.00 1.00 1.00 '
TEA 99% 1.50 1.50 1.50 1.50
Na Alpha Sulfonated 14.53
Methyl Eater of
C1z Acid9
Na Alpha Sulfonated 14.53
Meth 1 Ester of
y
ACidlo
Ci2-ie
Na Alpha Sulfonated 14.53
Methyl Ester of
Cl~ Acidli
Na Alpha Sulfonated 14.53
Methyl Eater of
C16 Acidl2
Na Lauryl (3E0) 11.75 11.75 11.75 11.75
Ether Sulfate
2 Neodol 25-7 11.40 11.40 11.40 11.40
0
weight % active 37.68 37.68 37.68 37.68
Surfactant
Appearance Clear Clear Hazy Opaque
Consistency @ 25C Flowing Flowing Paste Gel/
2 (cps) Liquid Liquid Paste
5
pH 8.8 8.8 8.8 8.8
Detergency @0.047% Active change oR)
( in reflectance,
'
Warm Wash Deterq~enc~ Cond
Test _tions
Cotton Fabric 14.7 15.6 15.4 15.5
3 Cotton/Polyester 13.5 14.5 13.8 14.0
0
Fabric
Contains disalt at mono:di ratio of about 5:1.
to Contains disalt at mono:di ratio of about 5:1.
11 Contains disalt at mono:di ratio of about 5:1.
12 Contains disalt at mono:di ratio of about 5:1.
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Formula tion
Components 19 20 No 22
21
DI Water Q.S. to Q.S. to Q.S. Q.S. to
to
100.00 100.00 100.00 100.00
Sodium Sulfate 1.00 1.00 1.00 1.00
TEA 99% 1.00 1.00 1.00 1.00
,, Alpha-Step MC-48 6.01 6.01 6.01 6.01
Na Lauryl (3E0) 9,77 9.77 9.77 9
77
Ester Sulfate .
Neodol 25-7 11.27 11.27 11.27 11.27
Coco (Clz-1, ) 5.00
Fatty Acid Soap,
Na Salt
DC Silicone 0.50
Antifoam
1430
Pluronic P10413 5.00
Pluronic 178414
5.00
% Active 32.1 27.1 32.1 32
1
Surfactant .
Appearance Clear Clear Clear Clear
8.8 8 8 8 8 8 8
13 polyoxyethylene, pol ox
identifed by the Cosmetics, Toi etr propylene block copolymer
y, and Fragrance Association
as Ploxamer 334, commercially available from BASF as
Pluracare/Pluronic P104.
14 pol ox eth lene y xyp py
Y Y Y , pol o ro lene block copolymer
identifed by the Cosmetics, Toiletry, and Fragrance Association
as Ploxamer 334, commercially available from BASF as
Pluracare/Pluronic 1784.
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Procedure:
1. Prepare a 0.2% active solution of the sample liquid
detergent material in 140 ppm hardness tap water at 25 deg C.
2. Introduce 100 g of the 0.2% solution into a 500 ml
graduated cylinder, keeping foam to a minimum.
3. Shake the cylinder 20 complete times using an automatic
shake foam machine capable of keeping speed and force constant.
4. Let foam settle for 5 seconds, then measure total height
in ml, including the base of 100 ml of solution.
5. Repeat steps 1-5 seven (7) times.
The sample liquid detergent material employed in this example
is Formulation 20 from Example 5 above.
Total Number of Foam height
Shakes (ml)
100
40 100
60 100
20 80 100
100 115
120 115
140 120
160 120
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Fo_rm Llation No
1 2 3 4 5
Sodium lauryl sulfate 18.0 9.0
Sodium lauryl ether sulfate 18.0 9
0
(3 moles of ethylene oxide) .
Cll.s ca~er$~e~ alkyl benzene 18
0
sulfonate .
C12-is linear alcohol 9.0 9.0 9.0 9.0 9
0
ethoxyate (7 moles of .
ethylene oxide)
methyl ester of alpha 9.0 9
0
sulfonated Clz-19 fatty acid, .
sodium saltls
deionized water Q.S. Q.S, Q.S. ~,5. Q.S.
to to to to to
100% 100% 100% 100% 100%
pH 8.8 8.8 8.8 8.8 8.8
appearance clear clear clearclear clear
is Contains disalt of alpha sulfonated C
lz-14 fatty acid at a
ratio of methyl ester to disalt of about 5:1.
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Formulation No.
6 7 8 9
Sodium lauryl ether sulfate 18.0 16.0 8.0
(3 moles of ethylene oxide)
Cm.s c8~e=$ee~ alkyl benzene 9.0
sulf onate
Clz-is linear alcohol 9.0 9.0 ,
ethoxyate (7 moles of
ethylene oxide)
75:25 mixture of C12,19 N- 11.0 11.0
methyl glucamide
to methyl ester of alpha 9.0 8.0
sulfonated C12_19 fatty acid,
sodium saltls
disalt of alpha sulfonated 2.0
C12_1Q fatty acid
sodium xylene sulfonate 3.0
deionized water Q.S. Q.S. Q.S. Q.S. to
to to to
100 100 100% 100%
pg 8.8 8.8 8.8 8.8
appearance clear clear clear clear
is Contains disalt of alpha sulfonated C12_19 fatty acid at a
ratio of methyl ester to disalt of about 5:1.
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FormL7 err; ~., mo
1 2 3 4 5 6 7 8 g
Antirede osition Efficac chan a in reflectance, oR
Warns Wash Anti-R demos; t; on moan. r~
ond;t,nrQ
0.2% active surfactant
s
Cotton/poly. 3.6 1.8 3.9 1.9 3.5 2.0 2.0
Fabric
Pol ester Fabric 3.4 2.5 4.4 3.5 4.1 2.9 2.2
Cold Wash Anti-R d Dos; ;on T a Cond;t;r,.,Q
0.2% active surfactant
Cotton/poly. 1.8 1.0 1.8 1.4 0.8 2.0 1.5
Fabric
Pol ester Fabric 2.0 1.5 2.3 2.0 1.3 2.7 2.4
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Example 9 -
For mulationNo.
10 11 1~ 13 14
Sodium lauryl ether sulfate (3 moles 27.0 13.5
of ethylene oxide)
Cu.s ca~.r.9~~ alkyl benzene sulfonate27.0 13.5 '
Sodium salt of a-sulfonated methyl 27.0 13.5 13.5
ester of C12-1, fatty acid
w
Deionized water Q.S. Q.S. Q.S. Q.S. Q.S. to
to to to to
100.0%100.0% 100.0% 100.0% 100.0%
Anti Yedegosition Efficar,~rlchanQ,~ ; n rPfi pr.tance eR)
T°~sh Anti-Redenosition Test Conditions
0.2% active surfactant
Cotton/poly. Fabric 4.3 3.7 3.5 3.7 3.0
Polyester Fabric 5.4 4.2 3.7 4.5 3.8
~~-sh Ant:-Reds~Q~ ~'' ~n Test Condi tions
0.2% active surfactant
Cotton/poly. Fabric 4.5 4.1 3.3 3.8 3.1
Pol ester Fabric 5.8 4.5 3.7 5.1 3.9
From the foregoing it will be appreciated that, although
specific embodiments of the invention have been described herein for
purposes of illustration, various modifications may be made without
deviating from the spirit and scope of the invention.
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