Note: Descriptions are shown in the official language in which they were submitted.
WO 92/06162 2 ~ 9 2 ~ 5 ~ PCI/US91/0702~
I
D~TERGENT CONTAINING ALKYL SULFATE AND
POLYHYDROXY FATTY ACID AMIDE SURFACTANTS
FIELD OF TNVENTTON
This invention pertains to alkyl sulfate surfactant-containing
laundry detergent compositions. More particularly, this invention
pertains to laundry detergent compositions containing mixtures of
alkyl sulfate and certain polyhydroxy fatty acid amide surfactants.
BACKGROUND OF THE INVENTION
The ability of laundry detergent compositions to provide good
overall cleaning for a large variety of soils and stains from the
multitude of fabrics that can be present in a typical load of
laundry is of high importance in the evaluation of such detergents.
Mixtures of linear alkylbenzene sulfonates (~LAS~) and alkyl sulfate
(rAS~) surfactants have been used in granular detergent compositions
with great effectiveness for overall laundry cleaning ability in
both cold and hot water wash conditions. The LAS surfactants have
been utilized frequently for their ability to provide execellent
cleaning of grease and oil stains. Combinations of LAS with AS are
desirable because they combine the excellent grease and oil cleaning
of LAS (along with good cleaning across a broad range of stain-
types) with the excellent particulate soil removal performance of A5
surfactants. Whereas AS surfactants are readily derived from
renewable resources, it would be desirable to provide a detergent
composition that could provide comparable or improved cleaning
performance wherein the LAS was either partially or completely
replaced with surfactant that could easily be made from natural,
renewable, non-petroleum raw materials.
It would also be desirable to effectively incorporate certain
AS surfactants into heavy duty liquid detergents, in order to
benefit from their good overall cleaning ability, especially their
excellent particulate soil cleaning ability. Whereas the lower
alkyl chain alkyl sulfate surfactants can easily be incorporated
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into light duty liquid detergents, practitioners in the art have
experienced difficulty in incorporating C1~ and longer alkyl sulfate
surfactants into liquid detergents. It is these longer chain
surfactants that are generally preferred for laundry and other
textile cleaning applications.
Additionally, for granular detergents, it would be desirable to
enhance the solubility and dissolution of the alkyl sulfate
surfactants in aqueous solutions, especially those alkyl sulfates
having C14 and longer alkyl chains.
This invention provides detergent compositions that contain
alkyl sulfates and that can have reduced concentration of, or
elimination of, LAS, while providing excellent overall cleaning
performance, including grease/oil stains. This invention provides
detergent compositions that can be in granular form, and further
provides detergent compositions that can be in liquid form including
C1~ and higher alkyl sulfate surfactants. The inclusion of such
polyhydroxy fatty acid amides in granular detergent compositions can
increase the solubility and dissolution of alkyl sulfate surfactants
in aqueous solutions.
The invention further encompasses novel detersive particles for
providing alkyl sulfate and polyhydroxy fatty acid amide surfactant
in granular form wherein the detersive particles comprise a mixture
of the two surfactants and a third ingredient for further enhancing
dissolution in aqueous solutions. These detersive particles are
advantageous in that they provide improved means for delivery
polyhydroxy fatty acid amide to granular detergent formulations in a
non-tacky form, without resorting to the use of substantial
quantities of inert, and therefore cost-ineffective, ingredients.
Ordinarily, the polyhydroxy fatty acid amides exhibit a tacky or
sticky property which is undesirable in granular formulations.
Furthermore, these detersive particles can exhibit improved
dissolution in aqueous solutions, particularly in automatic laundry
washing machines.
BACKGROUND ART
A variety of polyhydroxy fatty acid amides have been described
in the art. H-acyl, N-methyl glucamides, for example, are disclosed
by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The
Thermotropic Liquid-Crystalline Properties of Some Straight Chain
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Carbohydrate Amphiphiles," Liquid Crystals, 1988, Volume 3, No. 11,
pp 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R.
Hilgenfeld in "Molecular and Crystal Structure of a Nonionic
Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun.,
1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants
has been of substantial interest recently for use in biochemistry,
for example in the dissociation of biological membranes. See, for
example, the journal article "N-D-Gluco-N-methyl-alkanamide
Compounds, a New Class of Non-Ionic Detergents For Membrane
Biochemistry," Biochem. J. (1982J, Vol. 207, pp 363-366, by J. E. K.
Hildreth.
The use of N-alkyl glucamides in detergent compositions has
also been discussed U.S. Patent 2,965,576, issued December 20,
1960 to E. R. Wilson, and G.B. Patent 809,060, published February
18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent
compositions containing anionic surfactants and certain amide
surfactants, which can include N-methyl glucamide, added as a low
temperature suds enhancing agent. These compounds include an N-acyl
radical of a higher straight chain fatty acid having 10-14 carbon
atoms. These compositions may also contain auxiliary materials such
as alkali metal phosphates, alkali metal silicates, sulfates, and
carbonates. It is also generally indicated that additional
constituents to impart desirable properties to the composition can
also be included in the compositions, such as fluorescent dyes,
bleaching agents, perfumes, etc.
U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz,
relates to aqueous detergent compositions containing the
condensation reaction product of N-alkyl glucamine and an aliphatic
ester of a fatty acid. The product of this reaction is said to be
useable in aqueous detergent compositions without further
purification. It is also known to prepare a sulfuric ester of
acylated glucamine as disclosed in U.S. Patent 2,717,894, issued
September 13, 1955, to A. M. Schwartz.
PCT International Application W0 83/04412, published December
22, 1983, by ~. Hildreth, relates to amphiphilic compounds
containing polyhydroxyl aliphatic groups said to be useful for a
variety of purposes including use as surfactants in cosmetics,
drugs, shampoos, lotions, and eye ointments, as emulsifiers and
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? Q ~! ~ 3 5 8 4
dispensing agents for medicines, and in biochemistry for
solubilizing membranes, whole cells, or other tissue samples, and
for preparation of liposomes. Included in this disclosure are
compounds of the formula R'CON(R)CH2R" and RnCON(R)R' wherein R is
hydrogen or an organic grouping, R' is an aliphatic hydrocarbon
group of at least three carbon atoms, and R" is the residue of an
aldose.
European Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty
acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a
C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C1g
(preferably C1-C6) alkyl, or an alkylene oxide, and X is a
polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl,
coconut fatty acid glucamide. The thickening properties of the
amides are indicated as being of particular use in liquid surfactant
systems containing paraffin sulfonate, although the aqueous
surfactant systems can contain other anionic surfactants, such as
alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half
ester salts, and fatty alcohol ether sulfonates, and nonionic
surfactants such as fatty alcohol polyglycol ether, alkylphenol
polyglycol ether, fatty acid polyglycol ester, polypropylene
oxide-polyethylene oxide mixed polymers, etc. Paraffin
sulfonate/N-methyl coconut fatty acid glucamide/nonionic surfactant
shampoo formulations are exemplified. In addition to thickening
attributes, the N-polyhydroxy alkyl fatty acid amides are said to
have superior skin tolerance attributes.
U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al.,
relates to detergent bars containing urea, sodium lauryl sulfate
anionic surfactant, and an N-alkylglucamide nonionic surfactant
which is selected from N-methyl,N-sorbityl lauramide and N-methyl,
N-sorbityl myristamide.
Other glucamide surfactants are disclosed, for example, in DT
2,226,872, published December 20, 1973, H. W. Eckert, et al., which
relates to washing compositions comprising one or more surfactants
and builder salts selected from polymeric phosphates, sequestering
agents, and washing alkalis, improved by the addition of an
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N-acylpolyhydroxyalkyl-amine of the formula RlC(0)N(R2)CH2(CHOH)n-
CH20H, wherein Rl is a Cl-C3 alkyl, R2 is a Clo-C22 alkyl, and n is
3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a soil sus-
pending agent.
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert,
et al., relates to detergent compositions comprising at least one
surfactant selected from the group of anionic, zwitterionic, and
nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl
polyhydroxylalkyl compound of the formula RlN(Z)C(O)R2 wherein Rl is
a C10-C22 alkyl, R2 is a C7-C21 alkyl, Rl and R2 total from 23 to 39
carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CH0H)m-
CH20H where m is 3 or 4.
U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, et
al., relates to skin treating cosmetic compositions containing
N-polyhydroxylalkyl-amines which include compounds of the formula
RlN(R)CH(CH0H)mR2 wherein Rl is H, lower alkyl, hydroxy-lower alkyl,
or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as
Rl but both cannot be H, and R2 is CH20H or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial
Solvents Corporation, relates to solutions of formaldehyde
stabilized against polymerization with the addition of amides of the
formula RC(O)N(Rl)G wherein R is a carboxylic acid functionality
having at least seven carbon atoms, Rl is hydrogen or a lower alkyl
group, and G is a glycitol radical with at least 5 carbon atoms.
German Patent 1,261,861, February 29, 1968, A. Heins, relates
to glucamine derivatives useful as wetting and dispersing agents of
the formula N(R)(Rl)(R2) wherein R is a sugar residue of glucamine,
Rl is a Clo-C20 alkyl radical, and R2 is a Cl-Cs acyl radical.
G.8. Patent 745,036, published February 15, 1956, assigned to
Atlas Powder Company, relates to heterocyclic amides and carboxylic
esters thereof that are said to be useful as chemical intermediates,
emulsifiers, wetting and dispersing agents, detergents, textile
softeners, etc. The compounds are expressed by the formula
N(R)(Rl)C(O)R2 wherein R is the residue of an anhydrized hexane
pentol or a carboxylic acid ester thereof, Rl is a monovalent
hydrocarbon radical, and -C(O)R2 is the acyl radical of a carboxylic
acid having from 2 to 25 carbon atoms.
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U.S. Patent 3,312,627, issued April 4, 1967 to D. T. Hooker,
discloses solid toilet bars that are substantially free of anionic
detergents and alkaline builder materials, and which contain lithium
soap of certain fatty acids, a nonionic surfactant selected from
certain propylene oxide-ethylenediamine-ethylene oxide condensates,
propylene oxide-propylene glycol-ethylene oxide condensates, and
polymerized ethylene glycol, and also contain a nonionic lathering
component which can include polyhydroxyamide of the formula
RC(O)NR1(R2) wherein RC(O) contains from about 10 to about 14 carbon
atoms, and Rl and R2 each are H or C1-C6 alkyl groups, said alkyl
groups containing a total number of carbon atoms of from 2 to about
7 and a total number of substituent hydroxyl groups of from 2 to
about 6. A substantially similar disclosure is found in U.S. Patent
3,312,626, also issued April 4, 1967 to D. T. Hooker.
SUMMARY OF THE INVENTION
In one aspect, this invention provides a low sudsing laundry
detergent composition useful for cleaning fabrics in automatic
washing machines, said composition comprising:
(a) at least about 1% by weight of a polyhydroxy fatty acid
amide compound of the formula:
o R1
R2 - C - N - Z
wherein R1 is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, R2 is Cs-C31 hydrocarbyl, and Z is a
polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxys directly connected to the chain, or an alkoxylated
derivative thereof;
(b) at least about 1% by weight of an alkyl sulfate
surfactant; and
(c) a suds suppressing amount of a suds suppressor, preferably
selected from the group consisting of monocarboxylic fatty
acids and salts thereof, silicone suds suppressors,
monostearyl di-alkali metal alkyl phosphates and phosphate
esters, and hydrocarbon suds suppressors, and mixtures
thereof;
wherein the weight ratio of polyhydroxy fatty acid amide to alkyl
sulfate surfactant is from about 1:10 to about 10:1, preferably
about 1:6 to about 6:1, more preferably from about 1:4 to about 3:1,
most preferably from about 1:4 to about 1 1.
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In another aspect, this invention provides detergent
compositions containing alkyl sulfate surfactant and polyhydroxy
fatty acid amide wherein the weight ratio of alkyl sulfate to
polyhydroxy fatty acid amide is from about 1.25:1 to about 6:1,
preferably from about 1.25:1 to about 4:1, more preferably from
about 1.25:1.0, wherein the polyhydroxy fatty acid amide is of the
formula:
O Rl
R2 - C - N - Z
wherein Rl is methyl, R2 is Cg-C17 alkyl or alkenyl, and Z is a
glycityl derived from a reducing sugar, or an alkoxylated
derrivative thereof.
In yet another aspect, this invention provides a liquid
detergent composition comprising:
(a) at least about 1% by weight of a polyhydroxy fatty acid
amide compound of the formula:
O Rl
R2 - C - N - Z
wherein Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, R2 is Cs-C31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl with at least 3
hydroxys directly connected to the chain, or an alkoxylated
derivative thereof;
(b) at least about 1% by weight of a C14 or higher alkyl
sulfate surfactant;
(c) a liquid carrier;
wherein said composition has a weight ratio of polyhydroxy fatty
acid amide to the higher alkyl sulfate surfactant is from about 1:10
to about 10:1, preferably from about 1:6 to about 6:1, more
preferably about 1:4 to about 3:1, most preferably from about 1:4 to
about 1:1.
In still another aspect, this invention provides detersive
particles useful for utilization in granular detergent compositions,
said detersive particles comprising an intimate mixture of:
(a) from about 5% to about 90% (preferably 50%), by weight, of
a polyhydroxy fatty acid amide compound of the formula:
O Rl
R2 - C - N - Z
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2 ~ ~ ~i5 ~ 8 - 8 -
wherein Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, R2 is Cs-C31 hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxys directly connected to the chain, or an alkoxylated
derivative thereof; and
(b) from about 10% (preferably 50%) to about 95%, by weight,
of an alkyl sulfate surfactant;
wherein the ratio of (b):(a) is from about 20:1 to about 1:1.
DETAILED DESCRIPTION OF THE INVENTION
In one aspect, this invention provides a low sudsing laundry
detergent composition useful for cleaning fabrics in automatic
washing machines, said composition comprising:
(a) at least about 1% by weight of a polyhydroxy fatty acid
amide compound of the formula:
o R1
R2 C N Z
wherein Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, R2 is Cs-C31 hydrocarbyl, and Z is a
polyhydroxy hydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxys directly connected to the chain, or an alkoxylated
derivative thereof;
(b) at least about 1% by weight of an alkyl sulfate
surfactant; and
(c) a suds suppressing amount of a suds suppressor preferably
selected from the group consisting of monocarboxylic fatty
acids and salts thereof, silicone suds suppressors,
monostearyl di-alkali metal alkyl sulfates, and
hydrocarbon suds suppressors, and mixtures thereof;
wherein the weight ratio of polyhydroxy fatty acid amide to alkyl
sulfate surfactant is from about 1:10 to about 10:1, preferably
about 1:6 to about 6:1, more preferably from about 1:4 to about 3:1,
most preferably from about 1:4 to about 1:1.
AlkYl Sulfate Surfactant
The compositions hereof will cor,tâ,r, at least abûu~ i-^io, by
3~ weight, preferably from about 3% to about 50%, more preferably from
about 5% to about ~0%, of alkyl sulfate surfactant.
Alkyl sulfate surfactants are well known to those in the art
The alkyl sulfate surfactants hereof are water soluble salts or
SIJ~S 111 ~ITE SHEEl'
WO 92/06162 2 ~ ~ 2 5 5 8 PCr/US91/0702~
g
acids of the formula ROS03M wherein R is a C1o or higher hydrocar-
byl, preferably a C1o-C24 hydrocarbyl, preferably an alkyl or
hydroxyalkyl having a C1o-C20 alkyl component, more preferably a
C14-C1g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an
alkali metal cation (e.g., sodium, potassium, lithium), or ammonium
or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl
ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperdinium cations and quaternary
ammonium cations derived from alkylamines such as ethylamine,
diethylamine, triethylamine, and mixtures thereof, and the like. In
general, C14 and higher alkyls are preferred for detergent composi-
tion to be used for laundry applications. Typically, for laundry
applications (especially for use in automatic washing machines),
alkyl chains of C12 16, especially C14 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).
Polvhvdroxv Fatty Acid Amide Surfactant
The compositions hereof will comprise at least about 1%,
typically from about 3% to about 50%, preferably from about 3% to
about 30%, of the polyhydroxy fatty acid amide surfactant described
below.
The polyhydroxy fatty acid amide surfactant component of the
present invention comprises compounds of the structural formula:
O Rl
(I) R2 - C - N - Z
wherein: Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, preferably C1-C4 alkyl, more
preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl);
and R2 is a Cs-C31 hydrocarbyl, preferably straight chain C7-C1g
alkyl or alkenyl, more preferably straight chain Cg-C17 alkyl or
alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or
mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain with at least 3 hydroxys directly connected to the
.haill, 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 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
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- 10 -
cornn 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 sùitable raw materials. Z preferably will be selected fr~m
the group consisting of -CH2^(CHOH)n-CH2OH, -CH(CH20H)-(CHOH)n ~-
CH2OH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, where n is an integer from 3
to S, inclusive, and R' is H or a cyclic or aliphatic monosacchar-
ide, and alkoxylated derivatives thereof. Most preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2OH.
In Formula (I), Rl can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy
propyl.
R2-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-deoxymalto-
triotityl, etc.
~ ethods 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-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 809,060, published
February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent
2,g65,576, issued December 20, 1960 to E. R. Wilson, and U.S. Patent
2,703,798, Anthony M. Schwartz, issued March 8, 1g5~, and U.S
3~ Patent 1,985,424, issued December 25, 1934 to Piggott.
In one process for producing N-alkyl or N-hydroxyalkyl,
N-deoxyglycityl fatty acid amides wherein the glycityl component is
derived from glucose and the N-alkyl or N-hydroxyalkyl~ functionality
is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or
N-hydroxypropyl, the product is made by reacting N-alkyl- or
N-hydroxyalkyl-glucamine with a fatty ester selected from fatty
methyl esters, fatty ethyl esters, and fatty triglycerides in the
._~
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presence of a catalyst selected from the group consisting of tri-
lithium phosphate, trisodium phosphate, tripotassium phosphate,
tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium
hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide,
lithium carbonate, sodium carbonate, potassium carbonate, disodium
tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium
citrate, tripotassium citrate, sodium basic silicates, potassium
basic silicates, sodium basic aluminosilicates, and potassium basic
aluminosilicates, and mixtures thereof. The amount of catalyst is
preferably from about 0.5 mole % to about 50 mole %, more preferably
from about 2.0 mole % to about 10 mole %, on an N-alkyl or
N-hydroxyalkyl-glucamine molar basis. The reaction is preferably
carried out at from about 138-C to about 170-C for typically from
about 20 to about 90 minutes. When triglycerides are utilized in
1~ the reaction mixture as the fatty ester source, the reaction is also
preferably carried out using from about 1 to about 10 weight % of a
phase transfer agent, calculated on a weight percent basis of total
reaction mixture, selected from saturated fatty alcohol polyethoxyl-
ates, alkylpolyglycosides, linear glycamide surfactant, and mixtures
thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138-C to about 170-C;
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the
heated fatty acid ester and mixing to the extent needed to form a
two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and
(d) stirring for the specified reaction time.
Also preferably, from about 2% to about 20% of preformed linear
N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide product
is added to the reaction mixture, by weight of the reactants, as the
phase transfer agent if the fatty ester is a triglyceride. This
seeds the reaction, thereby increasing reaction rate. A detailed
experimental procedure is provided below in the Experimental.
The polyhydroxy "fatty acid" amide materials used herein also
offer the advantages to the detergent formulator that they can be
prepared wholly or primarily from natural, renewable, non-petro-
chemical feedstocks and are degradable. They also exhibit lowtoxicity to aquatic life.
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2 ~ 8 - 12 -
It should be recognized that along with the polyhydroxy fatty
acid amides of Formula (I), the processes used to produce them will
also typically produce quantities of nonvolatile by-product such as
esteramides and cyclic polyhydroxy fatty acid amide. The level of
these by-products will vary depending upon the particular reactants
and process conditions. Preferably, the polyhydroxy fatty acid
amide incorporated into the detergent compositions hereof will be
provided in a form such that the polyhydroxy fatty acid amide-
containing composition added to the detergent contains less than10 about lOZ, preferably less than about 4%, of cyclic polyhydroxy
fatty acid amide. The preferred processes described above are
advantageous in that they can yield rather low levels of
by-products, including such cyclic amide by-product.
Suds SuPDressors
As discussed above, compounds for reducing or suppressing the
formation of suds can be incorporated into the compositions of the
present invention. The incorporation of such materials, hereinafter
"suds suppressors," are desirable because the 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 high
sudsing surfactant in combination with the polyhydroxy fatty acid
amide surfactant. Suds suppression is particularly 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 suppressors can also
be of particular importance under hot water washing conditions and
under high surfactant concentration conditions.
A wide variety of materials may be used as suds suppressors in
the compositions hereof. Suds suppressors 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 suppressor of particular interest encompasses
monocarboxylic fatty acids and soluble salts thereof. These
materials are discussed in U.S. Patent 2,954,347, issued September
SU~STITUTE SHEET
-- - 13 - 20~2558
27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts
thereof, for use as suds suppressor 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
lithium salts, and ammonium and alkanolammonium salts. These materials
are a preferred category of suds suppressor for detergent compositions.
The detergent compositions may also contain non-surfactant suds
suppressors. These include, for example, list: high molecular weight
hydrocarbons such as paraffin and haloparaffin, fatty acid esters (e.g.,
fatty acid triglycerides), fatty acid esters of monovalent alcohols,
aliphatic C18-C40 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 (e.g, monostearyl
di-alkali metal (e.g., K, Na, Li) phosphate esters) and monostearyl di-
alkali (e.g., K, Na, Li) metal phosphates. 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 -40C and about 5C, and
a minimum boiling point not less than about 110C (atmospheric pressure).
It is also known to utilize waxy hydrocarbons, preferably having a melting
point below about 100C. The hydrocarbons constitute a preferred category
of such suppressor for detergent compositions. Hydrocarbon suds
suppressors are described, for example, in U.S. Patent 4,265,779, issued
May 5, 1981 to Gandolfo, et al. The 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 suppressor discussion, is intended to
include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane oils, such as polydimethylsiloxane, dispersions
- 2 ~ ~ 2 5 5 8
- 14 -
or emulsions of polyorganosiloxane oils or resins, and combinations of
polyorganosiloxane with silica particles wherein the polyorganosiloxane is
chemisorbed of fused onto the silica. Silicone suds suppressors are well
known in the art and are, for example, disclosed in U.S. Patent 4,265,779,
issued May 5, 1981 to Gandolfo et al. and European Patent Publication EP-A
354016, published February 7, 1990, by Starch, M.S.
Other silicone suds suppressors 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 German Patent Application DOS 2,124,526. 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, Baginski 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
20 cs. to about 1500 cs. at 25C;
20 (ii) from about 5 to about 50 parts per 100 parts by weigh of (i)
of siloxane resin composed of (CH3)3 SiO,~ units of SiO2 units
in a ratio of from (CH3)3 SiOI~ units and to SiO2 units of from
about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of (i)
of a solid silica gel.
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.
B~
i
w o 92/06162 2 ~ 9 2 ~ ~ 8 P ~ /US91/0702~
- 15 -
For example, with high sudsing surfactants, relatively more of the
suds controlling agent is used to achieve the desired suds control
than with 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 50X 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.
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 weight, of the detergent composition,
although higher amounts may be used. This upper limit is practical
in nature, due primarly to concern with keeping costs minimized and
effectiveness of lower amounts for effectively controlling sudsing.
Preferably from about .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 2X~
by weight, of the composition.
Hydrocarbon suds suppressors are typically utilized in amounts
ranging from about .01% to about 5.0%, although higher levels can
be used.
~ he detergent composition can further include an auxiliary
surfactant component which can comprise anionic and nonionic
surfactants other than the above-described alkyl sulfate and
polyhydroxy fatty acid amide, and other types surfactants.
If present, such auxiliary surfactants will typically by
present an amounts at least about 1%, by weight, of the detergent
composition, preferably from about 3% to about 30%.
SlJtJ~ ITE SHEET
w o 92/06162 pcT/~lssl/o7o2~
20~'~5~ - 16 -
Certain types of auxiliary surfactants, when utilized in the
compositions hereof, can contribute to further surprisingly improved
cleaning performance. These auxiliary surfactants include alkyl
ethoxylated sulfates, alkyl ethoxylates, and alkyl ester sulfonates
(especially methyl ester sulfonates), and mixtures thereof. Prefer-
ably, the weight ratio of the polyhydroxy fatty acid amide to these
auxiliary surfactants is from about 1:10 to about 10:1, more prefer-
ably from about 5:1 to about l:S, even more preferably from about
1:4 to about 4:1.
Without limiting the invention, other auxiliary surfactants
which can be desirable for inclusion in the compositions hereof
include paraffin sulfonates, alkyl benzene sulfonates, alkyl
polyglycosides (especially alkyl polyglucosides), and alkyl phenol
alkoxylates.
Auxiliary surfactants that can be used are discussed in more
detail below.
AuxiliarY Anionic Surfactants
Alkyl ester sulfonate surfactants hereof include linear esters
of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated
with gaseous S03 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
laundry applications, comprise alkyl ester sulfonate surfactants of
the structural formula:
o
R3 - CH - C - oR4
S03M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a Cl-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 sodium, potassium, and lithium, and
substituted or unsubstituted ammonium cations, such as methyl-,
dimethyl, -trimethyl, and quaternary ammonium cations, e.g.
tetramethyl-ammonium and dimethyl piperdinium, and cations berived
SUtsS~ ITE SHEET
~0!~25S8
w o 92/06162 PCT/US91/0702
from alkanolamines, e.g. monoethanolamine, diethanolamine, and
triethanolamine. Preferably, R3 is Clo-C16 alkyl, and R4 is methyl,
ethyl or isopropyl. Especially preferred are the methyl ester
sulfonates wherein R3 is C14-C16 alkyl-
Alkyl alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M wherein R is an
unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C24
alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-Clg 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-ammonium, dimethyl piperdinium cations, and cations
derived from alkanolamines, e.g. monoethanolamine, diethanolamine,
and triethanolamine, and mixtures thereof. Exemplary surfactants
are C12-Clg alkyl polyethoxylate (1.0) sulfate, C12-Clg alkyl
polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0)
sulfate, and C12-Clg alkyl polyethoxylate (4.0) sulfate, wherein M
is conveniently selected from sodium and potassium.
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, and
substituted ammonium salts such as mono-, di- and triethanolamine
salts) of soap, alkyl benzene sulfonates (especially Cg-C20 linear
alkylbenzenesulphonates), Cg-C22 primary or secondary alkanesulphon-
ates, Cg-C24 olefinsulphonates, sulphonated polycarboxylic acids
prepared by 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, isethi-
onates- such as the acyl isethionates, N-acyl taurates, fatty acid
amides of methyl tauride, alkyl succinamates and sulfosuccinates,
SU~ JTE SHEEr
- 2QQ255~
- 18 -
monoesters of sulfosuccinate (especially saturated and unsaturated
C12-C1g monoesters), diesters of sulfosuccinate (especially satur-
ated and unsaturated C6-C14 diesters), N-acyl sarcosinates, 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(CH2CH20)kCH2C00-M+ wherein R is a Cg-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 described in "Surface Active Agents and Deter-
gents" (Vol. I and II by Schwartz, Perry and Berch). A variety of
such surfactants are also generally disclosed in U.S. Patent
3,929,678, issued December 30, 1975 to Laughlin, et al. at Column
23, line 58 through Column 29, line 23.
AuxiliarY Nonionic Deterqent Surfactants
Suitable nonionic detergent surfactants are generally disclosed
in U.S. Patent 3,929,678, Laughlin et al., issued December ~0, 1975,
at column 13, line 14 through column 16, line 6, incorporated herein
by reference. 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 IgepalTM C0-6~0, marketed by the GAF Corporation;
and TritonTM X-45, X-114, X-100, and X-102, all marketed by the Rohm
& Haas Company. These compounds can be referred to as alkyl phenol
alkoxylates, e.g., alkyl phenol ethoxylates.
B~`
w o 92/06162 2 0 ~ 2 5 5 8 PCT/~'S91/0702~
- 19 -
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 containing 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 TergitolTM lS-S-9 (the condensation
product of Cll-Cls linear secondary alcohol with 9 moles ethylene
oxide), TergitolTM 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;
NeodolTM 45-9 (the condensation product of C14-Cl~ linear alcohol
with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation
product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide),
NeodolTM 45-7 (the condensation product of C14-Cls linear alcohol
with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation
product of C14-Cls linear alcohol with 4 moles of ethylene oxide),
marketed by Shell Chemical Company, and KyroTM EOB (the condensation
product of C13-Cls alcohol with 9 moles ethylene oxide), marketed by
The Procter & Gamble Company. These surfactants can be referred to
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 PluronicTM surfactants,
marketed by BASF.
4. The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
SU~ ITE SHEEl-
w o 92/06162 pcT/~is9l/n7o2
9 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 40X to about 80X 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 TetronicTM 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 10 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 alkyl
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 1 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 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
0
R3(oR4)x~(R5)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or
mixtures thereof containing from about 8 to about 22 carbon atoms;
R4 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 R5 is an alkyl or hydroxyalkyl group containing from about
1 to about 3 carbon atoms or a polyethylene oxide group containing
from about 1 to about 3 ethylene oxide groups. The R5 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-C18
alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl
amine oxides.
SlJ~S ~ JTE SHEET'
2U~2~58
w o 92/06162 pcT/ussl/o7o2
- 21 -
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
about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglycoside, 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 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 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 containing 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 hexaglucosides.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(91YCosyl )x
wherein R2 is selected from the group consisting of alkyl, alkyl-
phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof inwhich 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 O to about 10, preferably 0; and x is from about 1.3 to
Sl~ JTE SHEET
w o 92/06162 P ~ /US91/0702~
2~55~ - 22 -
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 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
l-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:
0
R6 - C - N(R7)2
wherein R6 is an alkyl group containing from about 7 to about 21
(preferably from about 9 to about 17) carbon atoms and each R7 is
selected from the group consisting of hydrogen, Cl-C4 alkyl, Cl-C4
hydroxyalkyl, and -(C2H40)XH where x varies from about 1 to about 3.
Preferred amides are Cg-C20 ammonia amides, monoethanolamides,
diethanolamides, and isopropanolamides.
Cationic Surfactants
Cationic detersive surfactants can also be included in
detergent compositions of the present invention as auxiliary
surfactants. Cationic surfactants include the ammonium surfactants
such as alkyldimethylammonium halogenides, and those surfactants
having the formula:
[R2(oR3)y] [R4(0R3)y]2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to
about 18 carbon atoms in the alkyl chain, each R3 is selected from
the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH20H)-,
-CH2CHzCH2-, and mixtures thereof; each R4 is selected from the
group consisting of Cl-C4 alkyl, Cl-C4 hydroxyalkyl, benzyl ring
structures formed by joining the two R4 groups,
-CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
polymer having a molecular weight less than about 1000, and hydrogen
when y is not 0; R5 is the same as R4 or is an alkyl chain wherein
the total number of carbon atoms of R2 plus R5 is not more than
about 18; each y is from 0 to about 10 and the sum of the y values
is from 0 to about 15; and X is any compatible anion.
SU~STITUTE SHEEl-
~Q~5 5~1
- - 23 -
Other cationic surfactants useful herein are also described in U.S.
Patent 4,228,044, Cambre, issued October 14, 1980.
Other Auxiliary 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 an anionic water-
solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No.
3,929,678 to Laughlin et al., isued 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.
In another aspect, this invention provides a detergent composition
having a critical selection of alkyl sulfate to polyhydroxy fatty acid
amide ratio for improved cleaning performance. In particular, this aspect
of the invention provides a detergent composition comprising:
(a) at least about 1% by weight of a polyhydroxy fatty acid amide
compound of the formula:
O
R2 C - IN - Z
wherein R1 is methyl, R2 is Cg-Cl7 alkyl or alkenyl, preferably C11-C17 alkyl
or alkenyl, and Z is a glycityl derived from a reduced sugar, or an
alkoxylated derivative thereof; and
~æ ~
WO 92/06162 PCl~ S91/0702-
358 - 24 -
(b) at least about 1% by weight of an alkyl sulfate
surfactant;
wherein the weight ratio (b) : (a) is from about 1.25:1 to about
1:6.
Preferably the above ratio is from about 1.25:1 to about 1:4,
more preferably from about 1.25:1.0 to about 1.0:1.25.
Surprisingly, good overall cleaning performance, especially
grease/oil cleaning, can be obtained for these compositions over a
wide variety of cleaning conditions, especially in view of their
relatively high polyhydroxy fatty acid amide to alkyl sulfate weight
ratios.
In yet another aspect, this invention provides a liquid
detergent composition comprising:
(a) at least about 1% by weight of a polyhydroxy fatty acid
amide compound of the formula:
O Rl
R2 - C - N - Z
wherein Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, R2 is Cs-C31 hydrocarbyl, and Z is a
polyhydroxhydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxys directly connected to the chain, or an alkoxylated
derivative thereof;
(b) at least about 1% by weight of a C14 or higher alkyl
sulfate surfactant;
(c) a liquid carrier;
wherein said composition has a weight ratio of polyhydroxy fatty
acid amide to C14 or higher alkyl sulfate surfactant from about 1:10
to about 10:1, preferably from about 1:6 to about 6:1, more
preferably from about 1:3 to about 3:1.
Traditionally, incorporation of C14 and higher alkyl sulfate
surfactants into liquid detergent compositions has been difficult.
This is due, at least in part, to the highly crystalline nature of
these surfactants. This is unfortunate because C14 and higher alkyl
sulfate surfactants are highly desirable detersive surfactants in
laundry detergents, even for detergents intended for use at wash
temperatures below about 50-C, which will generally also contain C12
alkyl sulfate surfactant. However with the use of the polyhydroxy
fatty acid amide surfactants hereof, the C14 and higher alkyl
SU~:j 111 UTE SHE61'
5 5 ~
- 25 -
~ sulfate surfactants can be incorporated into liquid detergent
formulations with much greater ease.
Preferably said comppsition comprises from about 3% to about
30X of polyhydroxy fatty acid amide and from about 3% to about 30
of said alkyl sulfate. The liquid composition hereof can optionally
contain alkyl sulfate surfactants with alkyl chains lower than C14
as well.
In still another aspect, this invention provides detersive
particles useful for utilization in granular detergent compositions,
said detersive particles comprising an intimate mixture of:
(a) from about 5% to about 50%, by weight, of a polyhydroxy
fatty acid amide compound of the formula:
O Rl
R2 e N - Z
wherein Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, R2 is Cs-C31 hydrocarbyl, and Z is a
polyhydroxylhydrocarbyl having a linear hydrocarbyl chain with at
least 3 hydroxys directly connected to the chain, or an alkoxylated
derivative thereof; and
Z (b) from about 50% to about 95%, by weight, of an alkyl
sulfate surfactant;
wherein the ratio of (b):(a) is from about 20:1 to about 1:1. For
mixtures of C12-C14 alkyl sulfate surfactants, the alkyl sulfate to
polyhydroxy fatty acid-amide weight ratio is prefera~ly from about
20:1 to about 4:1; for C14-C16 alkyl sulfates, about 20:1 to about
3:1; and for C16-C1g alkyl sulfates, about 20:1 to about 1:1.
The detersive particles can comprise an auxiliary solubilizing
agent to further enhance dissolution of the particle in aqueous
solution. Suitable solublilizing agents can be selected from the
group consisting of anionic sulfonate surfactants, ethoxylated
surfactants having a degree of ethoxylation of at least about 0.5,
cyclic polyhydroxy fatty acid ~amides, alkylpolyglycosides,
polyethylene glycol polymers, and poly(acrylic acid) polymers, and
mixtures thereof. Preferred solubilizing agents comprise alkyl
ethoxylates, alkyl ethoxylated sulfates, alkyl ester sulfonates,
cyclic polyhydroxy fatty acid amides, alkyl polyglycosides, or
polyethylene glycol or poly(acrylic acid) polymers, or a mixture
thereof. Other materials which can increase solubility or
E~
w o 92/06162 PCT/~IS91/0702
- 26 -
0 9 2 ~ 5 8 dissolution of the alkyl sulfate polyhydroxy fatty acid amide
particles can also be used.
The level of auxiliary solubilizing agent can vary from 0% to
preferably no more than about 30~., by weight, of the detersive
particle.
By "intimate mixture" of the alkyl sulfate and polyhydroxy
fatty acid amide, and any optional auxiliary solubilizing agent,
what is meant is that the ingredients are well mixed prior to or
simultaneously with formation of the detersive particles, although
the particles need not be precisely homogeneous. Techniques for
forming particles from intimate mixtures of detersive ingredients
are known in the art, and include, for example, the use of high
energy or high shear mixing equipment. A process for forming the
detersive particles is exemplified in the Examples. The sizes of
the particles can vary according to the desires of the formulator.
Generally, for granular compositions, the detersive particles hereof
should be similarly sized relative to other particles in the
composition. Typically, the particles will range in size from about
100 to about 1000 microns in diameter.
The detersive particle may also contain other ingredients for
detersive, processing, aesthetic, or other purposes.
The detersive particles can be used alone and can be included
in granular detergent compositions containing additional detergent
ingredients. Typically such detergent composition will comprise at
least about 5%, by weight, of the detersive particles.
Builders
Detergent compositions of the present invention can comprise
inorganic or organic detergent builders to assist in mineral
hardness control.
The level of builder can vary widely depending upon the end use
of the composition and its desired physical form. Liquid
formulations typically comprise at least about 1%, more typically
from about 5% to about 50%, preferably about 5% to about 30%, by
weight of detergent builder. Granular formulations typically
comprise at least about 1%, more typically from about 10% to about
80%, preferably from about 15% to about 50% by weight of the
detergent builder. Lower or higher levels of builder, however, are
not meant to be excluded.
SU~ lTE SHEEr
~ ~ ~ 2 ~ ~ ~
- 27 -
Inorganic detergent 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 50C,
especially less than about 40C.
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 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.
Aluminosilicate builders are especially 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(zAl 2 ySi 2)
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.
D
- 2 ~ ~ ~ 5 ~ 8
- - 28 -
Preferred aluminosilicates are zeolite builders which have the
formula:
Naz[(A102)z (Sio2)y]-xH2o
wherein z and y are integers of at least 6, the molar ratio of z to
y i s i n 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 aluminostlicates can be crystalline or amorphous
in structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 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
15 preferred embodiment the crystalline aluminosilicate ion exchange
material has the formula:
Nal2~(A102)12(SiO2)12] XH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Preferably, the aluminosilicate has
20 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 orthophosphate, sodium polymeta phosphate in which the
25 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, 1-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, 196~, 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
~2 -
5 ~
- - 29 -
issued September 3 1968, and January 14 1969 to Quimby.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, 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. ~hen utilized in salt form, alkali metals, such
as sodium, potassium, and lithium salts, especially sodium salts, or
ammonium and substituted ammonium (e.g., 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 haYe been disclosed for use as
detergent builders. Examples of useful ether polycarboxylates
include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,I28,287,
issued April 7, 1964, and Lamberti et al., U.S. Patent ~,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 ;s oxydissuccinic acid and its
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 2~:8~. These builders are
disclosed in U.S. Patent 4,663,071, issued to 8ush et al., on May 5,
19~37.
'Q '
a ~ s ~
- - 30 -
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,63~; 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)-0]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, C1 4 alkyl or Cl 4 substituted alkyl (preferably R is
hydrogen).
Still other ether polycarboxylates include copolymers of maleic
anhydride with ethylene or vinyl methyl ether, 1, 3, ~-trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid.
Organic polycarboxylate builders also include the various
alkali metal, ammonium and substituted ammonium salts of polyacetic
acids. Examples of polyacetic acid builder salts are the sodium,
potassium, lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid,
and soluble salts thereof.
Citric builders, e.g., citric acid and soluble salts thereof,
is a polycarboxylate builder of particular importance for heavy duty
liquid detergent formulations, but can also be used in granular
compositions. Suitable salts include the metal salts such as
sodium, lithium, and potassium salts, as well as ammonium and
substituted ammonium salts. - -
Other carboxylate builders include the carboxylated
carbohydrates disclosed in U.S. Patent 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
i ~
a ~
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the C5 - C20 alkyl succinic
acids and salts thereof. A particularly preferred compound of this type
is dodecenylsuccinic acid. Alkyl succinic acids typically are of the
general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid,
wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C12-C16
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
86200690.5/0,200,263, published November 5, 1986.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-
cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-
soluble polyacrylates (these polyacrylates having molecular weights toabove 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 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.
B~
2 ~
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Polycarboxylate builders are also disclosed in U.S. Patent
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
Clo-C20 are typically utilized. The hydrocarbyls can be saturated
or unsaturated.
EnzYmes
Detersive enzymes can be included in the detergent formulations--
for a variety of purposes including removal of protein-based,
carbohydrate-based, or triglyceride-based stains, and for prevention
of refugee dye transfer, for example. The enzymes to be
incorporated include proteases, amylases, lipases, cellulases, and
peroxidases, as well as mixtures thereof. They may be of any
suitable origin, such as vegetable, animal, bacterial, fungal and
yeast origin. However, their choice is governed by several factors
such as pH-activity and/or stability optima, thermostability,
stability versus active detergents, builders and so on. In this
respect bacterial or fungal enzymes are preferred, such as bacterial
amylases and proteases, and fungal cellulases.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and B.licheniforms.
Another suitable protease is obtained from a strain of Bacillus,
having maximum activity throughout the pH range of 8-12, developed
and sold by Novo Industries A/S under the registered trade name
Esperase~. The preparation of this enzyme and analogous enzymes is
described in British patent specification No. 1,243,784 of Novo.
Proteolytic enzymes suitable for removing protein-b~sed stains that
are commercially available include those sold under the tradenames
ALCALASETM and SAVINASETM by Novo Industries A/S (Denmark) and
MAXATASETM by International Bio-Synthetics, Inc. (The Netherlands).
$
.
~ao~2~ ~ ~
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- 33 -
Of interest in the category of proteolytic enzymes, especially for
liquid detergent compositions, are enzymes referred to herein as Protease
A and Protease B. Protease A and methods for its preparation are
described in European Patent Application 130,756, published January 9,
1985. Protease B is a proteolytic enzyme which differs from Protease A in
that it has a leucine substituted for tyrosine in position 217 in its
amino acid sequence. Protease B is described in European patent
Publication EP-A 251446, published January 7, 1988. Methods for
preparation of Protease B are also disclosed in European Patent
Application 130,756, Bott et al., published January 9, 1985.
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 tNovo). Amylolytic proteins include, for
example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo
Industries.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH optimum of
between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent
4,435,307, Barbesgoard 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 grisea 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 heptaopancreas of a marine mullusc
(Dolabella Auricula Solander).
Suitable lipase enzymes for detergent usage include those produced
by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in British Patent No. 1,372,034. Suitable
lipases include those which show a positive immunological cross-reaction
with the antibody of the lipase, produced by the microorganism
~B
z~ ~ ~
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- Pseudomona5 fluorescens IAM 1057. This lipase and a method for its
purification have been described in Japanese Patent Application No.
53-20487, laid open to public inspection on February 24, 1978. This
lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,
Japan, under the trade name Lipase P nAmano," hereinafter referred
to as ~Amano-P. n Such lipases of the present invention should show
a positiYe immunological cross reaction with the Amano-P antibody,
using the standard and well-known immunodiffusion procedure
according to Ouchterlony (Acta. ~ed. 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
4,707,291, Thom et al., issued November 17, 1987, incorporated
herein by reference. Typical examples thereof are the Amano-P
lipase, the lipase ex Psevdomonas fragi FERM P 1339 (available under
the trade name Amano-B), lipase ex Psuedomonzs nitroreducens var.
1ipo1yticum FERM P 1338 (available under the trade name Amano-CES),
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
1ipo1ytic~m NRRL8 3673, commercially available from Toyo Jozo Co.,
Tagata, Japan; and further Chromobacter viscosum 1 ipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and
lipases ex Pseudomonas g12dio1i.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc.
They are used for "solution bleaching,~ i.e. to prevent transfer of
dyes or pigments removed from substrates during wash operations to
other substrates in the wash solution. Peroxidase enzymes are known
in the art, and include, for example, horseradish peroxidase,
ligninase, and haloperoxidases such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for
example, in PCT International Application WO 89/099813, published
October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation
into synthetic detergent granules is also disclosed~in U.S. Patent
3 553 139 issued January 5 1971 to McCarty et al. Enzymes are further
disclosed in U.S. Patent No. 4 101,457, Place et al. issued July 18
1978 and in U.S. Patent 4.507 219, Hughes issued March 26 1985 both
~ O ~ 2 5 5 8
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-
Enzyme materials useful for liquid detergent formulations, and their
incorporation into such formulations, are disclosed in U.S. Patent
4,261,868, Hora et al., issued April 14, 1981.
Enzymes are normally incorporated at levels sufficient to provide
up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of
active enzyme per gram of the composition.
For granular detergents, the enzymes are preferably coated or
prilled with additives inert toward the enzymes to minimize dust formation
and improve storage stability. Techniques for accomplishing this are well
known in the art. In liquid formulations, an enzyme stabilization system
is preferably utilized. Enzyme stabilization techniques for aqueous
detergent compositions are well known in the art. For example, one
technique for enzyme stabilization in aqueous solutions involves the use
of free calcium ions from sources such as calcium acetate, calcium
formate, and calcium propionate. Calcium ions can be used in combination
with short chain carboxylic acid salts, preferably formates. See, for
example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1982. It
has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-
alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with
polyfunctional aliphatic amines (e.g., alkanolamines such as
diethanolamine, triethanolamine, di-isopropanolamine, etc.), and boric
acid or alkali metal borate. Enzyme stabilization techniques are
additionally disclosed and exemplified in U.S. Patent 4,261,868, issued
April 14, 1981 to Horn, et al., U.S. Patent 3,600,319, issued August 17,
1971 to Gedge, et al., and European Patent Application Publication No. 0
199 405, Application No. 86200586.5, published October 29, 1986, Venegas.
Non-boric acid and borate stabilizers are preferred. Enzyme stabilization
systems are also described, for example, in U.S. Patents 4,261,868,
3,600,319, and 3,519,570.
Bleachin~ Compounds - Bleachinq Aqents and Bleach Activators
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
~'
5 ~ ~
- 36 -
~ 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 4 m 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, especially
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 herein, "substantially free of
borate and borate-forming material" shall mean that the composition
contains not more than about 2% by weight of borate-containing and
borate-forming material of any type, preferably, no more than lX,
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 monoperoxyphthal-
ate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid,
4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
Such bleaching agents are disclosed in U.S. Patent 4,483,781,
Hartman, issued November 20, 1984, U.S. Patent Application 740,446,
Burns et al., filed June 3, 1985, 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 1, 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.
'; ~ '
2~g~ 5~
- 37 -
Another category of bleaching agents that can be used encom-
~ passes the halogen bleaching agents. Examples o~ hypohalite bleach-
ing agents, for example, include trichloro isocyanuric acid and the
sodium and potassium dichloroisocyanurates and H-chloro and H-bromo
alkane sulphonamides. Such materials are normally added at 0.5-107.
by weight of the finished product, preferably 1-5% by weight.
Peroxygen bleaching agents, other than per boron compounds, can
also be used. Suitable peroxygen bleaching compounds include sodium
carbonate 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 peroxyl acid corresponding
to the bleach activator.
Preferred bleach activators incorporated into compositions of
the present invention have the general formula:
e
R - C - L
wherein R is an alkyl group containing from about 1 to about 18
carbon atoms wherein the longest linear alkyl chain extending from
and including the carbonyl carbon contains from about 6 to about 10
carbon atoms and L is a leaving group, the conjugate acid of which
has a PKa in the range of from about 4 to about 13. These bleach
activators are described in U.S. Patent 4,915,854, issued April 10,
1990 to Mao et al. and U.S. Patent 4,412,934.
~leaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated
bleaching agents such as sulfonated zinc and/or aluminum phthalocya-
nines. These materials can be deposited upon the substrate during
the washing process. Upon irradiation with light, in the presence
of oxygen, such as by nanging clothes out to dry in the daylight,
the sulfonated zinc phthalocyanine is- activated and, consequently,
the substrate is bleached. Preferred zinc phthalocyanine ~r.,i a
photoactivated bleaching process are described in U.S. Patent
1B f
'~ O ~ 2 ~
- 38 -
4 033,718, issued July 5 1977 to Holcombe et al. Typically detergent
compositions will contain about 0.025% to about 1.25% by weight of
sulfonated zinc phthalocyanine.
Polymeric Soil Release Aqent
Any polymeric soil release agents known to those skilled in 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 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.
The compositions hereof for which improved polymeric soil
release agent performance can be obtained through the use of
polyhydroxy fatty acid amide are those which contain an anionic
surfactant system, an anionic surfactant-interactive soil release
agent and a soil release agent-enhancing amount of the polyhydroxy
fatty acid amide (PFA), wherein- (I) anionic surfactant-
interaction between the soil release agent and the anionic
surfactant system of the detergent composition can be shown by a
comparison of the level of soil release agent (SRA) deposition on
hydrophobic fibers (e.g., polyester) in aqueous solution between (A)
a "Control" run wherein deposition of the SRA of the detergent
composition in aqueous solution, in the absence of the other
t
w o 92/06162 2 a 9 r~ ~ S 8 PCT/~S91/0702
- 39 -
detergent lngredients, is measured, and (B) an ~SRA/Anionic
surfactant~ test run wherein the same type and amount of the anionic
surfactant system utilized in detergent composition is combined in
aqueous solution with the SRA, at the same weight ratio of SRA to
the anionic surfactant system of the detergent composition, whereby
reduced deposition in (B) relative to (A) indicates anionic-
surfactant interaction; and (II) whether the detergent composition
contains a soil release agent-enhancing amount of polyhydroxy fatty
acid amide can be determined by a comparison of the SRA deposition
of the SRA/Anionic surfactant test run of (B) with soil release
agent deposition in (C) an "SRA/Anionic surfactant/PFA test run"
wherein the same type and level of polyhydroxy fatty acid amide of
the detergent composition is combined with the soil release agent
and anionic surfactant system corresponding to said SRA/Anionic
surfactant test run, whereby improved deposition of the soil release
agent in test run (C) relative to test run (B) indicates that a soil
release agent-enhancing amount of polyhydroxy fatty acid amide is
present. For purposes hereof, the tests hereof should be conducted
at anionic surfactant concentrations in the aqueous solution that
are above the critical micelle concentration (CMC) of the anionic
surfactant in the aqueous solution of test run (A), and preferably
above about 100 ppm. The polymeric soil release agent concentration
should be at least 15 ppm. A swatch of polyester fabric should be
used for the hydrophobic fiber source. Identical swatches are
immersed and agitated in the 35-C aqueous solutions of the respec-
tive test runs for a period of 12 minutes, then removed, andanalyzed. Polymeric soil release agent deposition level can be
determined by radiotagging the soil release agent prior to treatment
and subsequently conducting radiochemical analysis, according to
techniques known in the art.
As an alternative to the radiochemical analytical methodology
discussed above, soil release agent deposition can alternately be
determined in the above tests runs (i.e., test runs A, B, and C) by
determination of ultraviolet light (UV) absorbance of the test
solutions, according to techniques well known in the art. Decreased
UV absorbance in the test solution after removal of the hydrophobic
fiber material corresponds to increased SRA deposition. As will be
understood by those skilled in the art, UV analysis should not be
S~ JTE SHEEr
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20~5~ 40 -
utilized for test solutions containing types and levels of materials
which cause excessive UV absorbance interference, such as high
levels of surfactants with aromatic groups (e.g., alkyl benzene
sulfonates, etc.).
Thus 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
fibers, as described above, or an amount for which enhanced
grease/oil 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 O.OlY. to
about lOX, by weight, of the polymeric soil release agent, typically
from about 0.1% to about 5%, and from about 1% to about 50~., more
typically from about 4% to about 30Z 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 (i)
polyoxyethylene segments with a degree of polymerization of 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, 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
SU~STITUTE SHEET
aa~5 5~
- 41 -
_
- preferably, especially for such components having about 20 to 30
oxypropy7ene unlts, at least about 50% oxyethylene units; or (b~ one
or more hydrophobe 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 C4-C6 alkylene segments, or
mixtures thereof, (iii) poly (vinyl ester) segments, preferably
poly(vinyl acetate), having a degree of polymerization of at least
2, or (iv) Cl-C4 alkyl ether or C4 hydroxyalkyl ether substituents,
or mixtures thereof, wherein said substituents are present in the
form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellu1Ose
- derivatives, or mixtures thereof, and such cellulose derivatives are
amphiphilic, whereby they have a sufficient level of C1-C4 alkyl
ether and/or C4 hydroxyalkyl ether units to deposit upon conven-
tional polyester synthetic fiber surfaces and retain a sufficient
level of hydroxyls, once adhered to such conventional synthetic
fiber surface, to increase fiber surface hydrophilicity, or a
combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a
degree of polymerization of from 2 to about 200, although higher
levels can be used, preferably from 3 to about 150, more preferably
from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe
segments include, but are not limited to, end-caps of polymeric soil
release agents such as M03S(C~2)nOCH2CH2O-, 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.
Polymeric soil release agents useful in the present invention
include cellulosic derivatives such as hydroxyether cellulosic
polymers, copolymeric blocks of ethylene terephthalate or propylene
terephthalate with polyethylene oxide or polypropylene oxide
terephthalate, and the like. -
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 C1-C4 alkyl and C4
~,
,
~n~75~ V
- 42 -
hydroxyalkyl cellulose such as methylcellulose, ethylcellulose,
hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose. A
variety of cellulose derivatives useful as soil release polymers are
disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et
al.
Soil release agents characterized by poly(vinyl ester) hydrophobe
segments include graft copolymers of poly(vinyl ester), e.g., C1-C6 vinyl
esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide
backbones, such as polyethylene oxide backbones. Such materials are known
in the art and are described 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 SokalanTM type of material,
e.g., SokalanTM 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 comprised of
repeating units of ethylene 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, 1976. 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 ethylene terephthalate units containing 10-15% by weight
of ethylene terephthalate units together with 90-80% by weight of
polyoxyethylene 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
B,~
~ 0 9 2 ~ 5 8
- 43 -
.
are more fully 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, U.S. Serial No. 07/474,709, filed January 29, 1990.
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 Gosselink, having polyethoxy 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 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 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)(i) above. It is the polymeric soil release
agents characterized by either, or both, of these criteria
B~
J
WO 92/06162 PCr/l lS91/n702'
r~ ~S~8 44
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
O.2% to about 3.0%.
Chelatin~ Aqents
~he 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
thereot, 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,
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-hydroxyethyl-
ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine
tetraproprionates, triethylenetetraaminehexaacetates, diethylenetri-
aminepentaacetates, 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 - P3M2.
SlJ~ ITE SHEEr
2 (~ ~ 2 ~ ~ ~
- 45 -
- 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 (methylene-
phosphonates). 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
RR ~ OH
R
R
wherein at least one R is -SO3H or -COOH or soluble salts
thereof and mixtures thereof. U.S. Patent 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 dihy-
droxydisulfobenzenes 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 107. 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 Agents
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 0.01X 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:
B~
WO 92/06162 PCr/l_'S91/0702~
U,o
2 ~ J~ ~ (1) ethoxylated monoamines having the formula:
(X-L-)-N-(R2)2
(2) ethoxylated diamines having the formula:
R2-h-Rl-N-R2 (R2)2-N- IRl-N- (R2)2
I t L
X X X
or
(X-L-)2-N-Rl-N-(R2)2
(3) ethoxylated polyamines having the formula:
~R2
R3~[(Al)q~(R4)t~N~L~X]p
(4) ethoxylated amine polymers having the general formula:
R2
[(R2)2-N3W~Rl-N~x~Rl-N3y~Rl~N~L~X)z
X
and
(S) mixtures thereof; wherein Al is
O O O O O
-NC-, -NCO-, -NCN-, -CN-, -OCN~-,
R R R R R R
O O 0 00
~1 ~t ~ ,.
-CO-, -OCO-, -OC-, -CNC-,
R
or -O-; R is H or C1-C4 alkyl or hydroxyalkyl; Rl is C2-C12 alkyl-
ene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3
oxyalkylene moiety having from 2 to about 20 oxyalkylene units
provided that no O-N bonds are formed; each R2 is Cl-C4 or hydroxy-
alkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r,
-A2-(CH2)S-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2,
and r ~ s is 3 or 4; X is a nonionic group, an anionic group or
mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl,
alkenyl, aryl, or alkaryl group having substitution sites; R4 is
Ci-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene,
or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene
SlJ~ ITE SHEET
5 ~ ~
- 47 -
units provided that no O-O or O-N bonds are formed; L is a hydrophilic
chain which contains the polyoxyalkylene moiety -[(RsO)m(CH2-CHzO)n]-,
wherein Rsis C3-C4 alkylene or hydroxyalkylene and m and n are numbers such
that the moiety -(CH2CH2O)n- comprises at least about 50% by weight of said
polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, and
n is at least about 12; for said diamines, m is from 0 to about 3, and n
is at least about 6 when R1 is C2- C3 alkylene, hydroxyalkylene, or
alkenylene. and at least about 3 when Rl is other than C2-C3 alkylene,
hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m
is from 0 to about 10 and n is at least about 3; p is from 3 to 8; q is 1
or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y +
z is at least 2; and y + z is at least 2. The most preferred soil release
and anti-redeposition agent is ethoxylated tetraethylenepentamine.
Exemplary ethoxylated amines are further described in U.S. Patent
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 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 111,984, Gosselink, published June 27, 1984;
the zwitterionic 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, Connor, issued October 22, 1985.
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 ~ispersin~ A~ents
Polymeric dispersing agents can advantageously be utilized in the
compositions hereof. These materials can aid in calcium and magnesium
hardness control.
B~
~f
W O 92/06162 ~ ~ ~ 2 5 5 ~ P ~ /~'S91/0702
48 -
Suitable polymeric dispersing agents include polymeric poly-
carboxylates and polyethylene glycols, although others known in the
art can also be used.
Polymeric dispersing agents are generally used at levels of
about 0.5~ to about 5X, by weight, of the detergent composition,
more generally from about 1.0% to about 2.0~.
The polycarboxylate materials which can be employed as the
polymeric polycarboxylate dispersing agent component herein are
these polymers or copolymers which contain at least about 60Z by
weight of segments with the general formula
X Z ~ ~:
l l
-- C - C
Y COOM
-- -- n
wherein X, Y, and Z are each selected from the group consisting of
hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl;
a salt-forming cation and n is from about 30 to about 400. Prefer-
ably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is
hydrogen and M is hydrogen, alkali metal, ammonia or substitutedammonium.
Polymeric polycarboxylate materials of this type can be
prepared by polymerizing or copolymerizing suitable unsaturated
2~ monomers, preferably in their acid form. Unsaturated monomeric
acids that can be polymerized to form suitable polymeric
polycarboxylates include acrylic acid, maleic acid (or maleic
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, etc. is suitable provided that such segments do
not constitute more than about 40% by weight.
Particularly suitable poiymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are
useful herein are the water-soluble salts of polymerized acrylic
acid. The average molecular weight of such polymers in the acid
form preferably ranges from about 2,000 to 10,000, more preferably
SU~3STITUTE SHEEr
5 5 ~
- 49 -
-- from about 4,000 to 7,000 and most prefereably 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 No. 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
maleic 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 6~,000. The ratio of acrylate to maleate segments in such
copolymers will generally rnage from about 30:1 to about 1:1, more
preferably from about 10:1 to 2:1. Water-soluble salts of such
acrylic acid/maleic acid copolymers can include, for example, the
a1kali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which
are described in European Patent Application No. 66915, published
December 15, 1982.
Another polymeric material which can be included is polyethyl-
ene glycol (PEG). PEG can exhibit dispersing agent performance as
well as act as a clay soil removal/anti-redeposition 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.
Briqhtener
Any optical brighteners or other brightening or whitening
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.
B
5 ~ ~
_ - 50 -
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.
Com,mercial optical brighteners which may be usefu1 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).
- Stilbene derivatives which may be ~seful in the present
invention include, but are not necessarily limited to, derivatives
of bis(triazinyl)amino-stllbene; 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'-disulfonic 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 3- 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,
t
5 ~ 8 J
- 51 -
-
styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and
styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.
The styrylazoles can be further subclassified into
styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on
page 78 of the Zahradnik reference. 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 pages 741-749, of The Kirk-Othmer Encyclopedia of Chemical
TechnoloqY, 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 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 hetero- cycles disclosed
in the Kirk-Othmer reference. Examples of such compounds include
brighteners derived from pyrazine and brighteners derived from 4-
aminoaphthalamide.
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-pyrenetri- sulphonic acid: 2,4-dimethoxy-1,3,5-
triazin-6-yl-pyrene; 4,5-di- phenylimidazolone-disulphonic 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 Wixon on December 13, 1988. These brighteners include the
PhorwhiteTM series of brighteners from Verona. Other brighteners
disclosed in this reference include: Tinopal UNPA, Tinopal CBS
and Tinopal 5BM; available from Ciba-Geigy; Arctic White
2 5 ~ ~
- 52 -
CC and Artic ~hite 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)-stil- benes; 4,4'-bis(styryl)bisphenyls;
and the y-aminocoumarins. Specific examples of these brighteners
include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-
2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)-
thiophene; 2-styryl-naphth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-
2H-naphtho- [1,2-d]triazole.
Other optical brighteners which may be useful in the present
10invention include those disclosed in U.S. Patent 3,646,015, issued
February 29, 1972 to Hamilton.
Other Ingredients
A wide variety of other ingredients useful in detergent
compositions can be included in the compositions hereof, including
15other 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
20are 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.
25The 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 about 11, 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
30about 7.5 and 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 ihvention further provides a method for improving the
performance of granular and liquid detergents containing alkyl
35sulfate surfactant by incorporating into such composition, either
separately or in detersive particles also containing alkyl sulfate
D~-
WO 92/06162 2 Q ~ ~ 5 ~ 8 PCr/US91/070t~
- 53 -
surfactant, polyhydroxy fatty acid amide surfactant as described
above.
This invention further provides a method for cleaning
substrates, such as fibers, fabrics, hard surfaces, skin, etc., by
contacting said substrate with a detergent composition comprising at
least about 1% surfactant and at least 1% of the polyhydroxy fatty
acid amide, wherein a) the composition also includes i) a suds
suppressing amount of a suds suppressor, or ii) at least about 1%,
preferably from about 3% to about 30% of an auxiliary surfactant
selected from the group consisting of alkyl ethoxylates, alkyl
ethoxylated sulfates, alkyl ester sulfonates, or mixtures thereof,
wherein the weight ratio of alkyl sulfate surfactant to polyhydroxy
fatty acid amide is from about 1:10 to about 10:1, or preferably
within the previously stated preferred weight ratios, or b) wherein
the composition comprises alkyl sulfate surfactant and polyhydroxy
fatty acid amide wherein Rl is methyl, R2 is a Cg-C17 alkyl or
alkenyl, and Z is derived from a reducing sugar, preferably a
glycoside, more preferably a glucoside, and the weight ratio of
alkyl sulfate to polyhydroxy fatty acid amide, is from about 1.25:1
to about 1:6, preferably from about 1.25:1 to about 1:4, more
preferably from about 1.25:1.0 to about 1.0:1.25. Agitation is
preferably provided for enhancing cleaning. Suitable means for
providing agitation include rubbing by hand or preferably with the
aid of a brush, or other cleaning device, automatic laundry washing
machines, automatic dishwashers, etc.
EXPER~MENTAL
This exemplifies a process for making a N-methyl, l-deoxyglu-
cityl lauramide surfactant for use herein. Although a skilled
chemist can vary apparatus configuration, one suitable apparatus for
~o use herein comprises a three-liter four-necked flask fitted with a
motor-driven paddle stirrer and a thermometer of length sufficient
to contact the reaction medium. The other two necks of the flask
are fitted with a nitrogen sweep and a wide-bore side-arm (caution:
a wide-bore side-arm t; impGrtant in case of very rapid methanol
evolution) to which is connected an efficient collecting condenser
and vacuum outlet. The latter is connected to a nitrogen bleed and
vacuum gauge, then to an aspirator and a trap. A 500 watt heating
mantle with a variable transformer temperature controller ("Yariac")
SU~ JTE SHEET
2~06162 PCT/US91 /0702
- 54 -
used to heat the reaction is so placed on a lab-jack that it may be
readily raised or lowered to further control temperature of the
reaction.
N-methylglucamine (l9S 9., 1.0 mole, Aldrich, M4700-0) and
methyl laurate (Procter ~ Gamble CE 1270, 220.9 9., 1.0 mole) are
placed in a flask. The solid/liquid mixture is heated with stirring
under a nitrogen sweep to form a melt (approximately 25 minutes).
When the melt temperature reaches 145- C, catalyst (anhydrous
powdered sodium carbonate, 10.5 9., 0.1 mole, J. T. Baker) is added.
The nitrogen sweep is shut off and the aspirator and nitrogen bleed
are adjusted to giYe 5 inches (5/31 atm.) Hg. vacuum. From this
point on, the reaction temperature is held at 150- C by adjusting
the Variac and/or by raising or lowering the mantle.
Within 7 minutes, first methanol bubbles are sighted at the
meniscus of the reaction mixture. A vigorous reaction soon follows.
Methanol is distilled over until its rate subsides. The vacuum is
adjusted to give about 10 inches Hg. (10/31 atm.) vacuum. The
vacuum is increased approximately as follows (in inches Hg. at
minutes): 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of
methanol evolution, heating and stirring are discontinued
co-incident with some foaming. The product is cooled and
solidifies.
The following examples are meant to exemplify compositions of
the present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention, said scope being
determined according to claims which follow.
EXAMPLES 1-6
These examples show preferred compositions containing alkyl
sulfates and polyhydroxy fattty acid amides for washing preferably
above about 40-C, at concentrations of about 6000 - 8000 ppm, wash
water weight basis.
Base Granule i 2 3
C14 15 Alkyl Sulfate 4.6 4.6
Ci6 i8 Alkyl Sulfate 2.4 2.4 2.4
Linear C12 Alkylbenzene Sulfonate 7.6
C16 18 Alkyl Ethoxylate (11 mole) 1.1 1.1 1.1
Zeolite 22.0 24.0 21.3
Acrylate/maleate copolymer (60000 MW) 4.3 5.6 4.3
SU~ ITE SHEEr
w 0 s2/06l6~ 2a~3~8 PCT/US91/0702~
Water and Miscellaneous 9.4 9.2 lo.
Admix and SPrav-on
N-Methyl N-l-Deoxyglucityl Cocoamide 7.0
N-Methyl N-l-Deoxyglucityl Oleamide 7.0 4.0
Sodium Citrate 8.0 8.0
Sodium Carbonate 17.5 17.3 17.5
Sodium Silicate (SiO2/Na20=1.6) 3.5 3.0 3.5
Perfume 0.4 0.4 0.4
Silicone Fluid 0.5 0.5 0.5
Miscellaneous (filler salts, enzymes,
bleach, soil release polymers, etc) 19.3 26.8 19.4
100.0 100.0 100.0
The compositions of Examples 1-3 are preferably utilized at
concentrations of about 6000 ppm, wash water weight basis, at a
lS temperature of from about 30 C to 95-C. These compositions are made -
by slurrying the base granule ingredients and spray drying to about
9% moisture content. Remaining dry powdered or granular ingredients
are admixed followed by spray-on addition of the final liquid
ingredients.
Base Granule 4 5 6
Linear C12 Alkylbenzene Sulfonate 5.9
N-Methyl N-l-Deoxyglucityl
Tallow Fatty Amide 7.1
C14 15 Alkyl Sulfate 5.9 S.9
C16 18 Alkyl Sulfate 2.5 2.5 2.5
2eolite 20.5 14.0 20.5
Polyacrylate (4500 MW) 3.9 3.9 3.9
Sodium Citrate 6.0
Sodium Carbonate 12.7 16.0 12.7
Water and Miscellaneous 8.1 8.2 8.7
Admix and SDrav-on
N-Methyl N-l-Deoxyglucityl Lauramide 7.1
N-Methyl N-l-Deoxyglucityl Cocoamide 6.6
Miscellaneous (bleach, filler salts,
builder salts, enzymes, etc) 39.3 36.9 38.7
100.0 100.0 100.0
Examples 4-6 show standard density heavy duty granular
detergent compositions for wash temperatures between about 30-C to
SU13STITlJTE SHEEr
w o 92/06162 pcT/~lssl/o7o2~
2 ~ 3 - 56 -
gS-C, at concentrations of about 8000 ppm, wash water weight basis.
The compositions are prepared by spray drying a slurry of the base
granule ingredients to about 10-13% moisture, adding additional dry
powdered ingredients, such as bleach, activators, and other
adjuncts, and spraying on liquids such as perfume, nonionics, or
suds suppressor fluids.
EXAMPLES 7-20
These examples show heavy duty granular detergent compositions
containing polyhydroxy fatty acid amide, alkyl sulfates and suds
suppressors.
Base Granule 7 8 9 10
C14 15 Alkyl Sulfate 18.7 10.1 11.3
C14 15 Alkyl Ethoxy (2.25) Sulfate 5.6
C12 18 Alkyl Sulfate 16.9
Linear C12 Alkylbenzene Sulfonate 10.1
N-Methyl N-l-Deoxyglucityl
Cocoamide 3.8 2.4 5.6 5.6
Zeolite A 30.1 18.8 18.8 30.1
Sodium Citrate 11.3 11.3
Sodium Carbonate 16.9 16.9 16.9 16.9
Sodium Silicate 3.1 2.5 2.5 2.5
Sodium Sulfate 15.0 15.0 15.1 15.1
Tallow Fatty Acid 1.1 1.1 1.1
Miscellaenous 3.1 3.2 2.7 4.4
Admix and SDraY-on
Miscellaneous 2.5 3.5 3.5 2.5
Suds Suppressor Flake* 0.5 0.5 1.0
Residual Water 5.0 5 0 5.0 5.0
100.O 100.O 100.O 100.O
30 *Suds Suppressor Flake contains approximately 5% of a silica/sili-
cone oil dispersion encapsulated in a flake containing primarily
polyethylene glycol ("PEG," 8000 MW), at greater than 80%, and minor
optional water soluble ingredients.
Examples 7-lQ exemplify formlllations for preferred use of abcut
1400 ppm, wash water weight basis, for temperatures below about
50-C. The above examples are made by combining the base granule
ingredients as a slurry, and spray drying to about 4-8% residual
moisture. The remaining dry ingredients are admixed in granular or
SlJEs;~ JTE SHEET
W O 92/06162 ~ Q ~ 2 ~ 5 8 PCT/US91/0702'
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powder form with the spray dryed granule in a rotary mixing drum,
and the liquid ingredients (nonionic surfactant and perfume) sprayed
on.
Base Granule 11 12
Linear C12 Alkylbenzene Sulfonate 7.6
C14 15 Alkyl Sulfate 3-3
Tallow Fatty Acid 3.0
Zeolite A 13.4 19.8
Polyacrylate (4500 MW) 3.5 4.5
Polyethylene Glycol (8000 MW) 2.0 2.0
Sodium Silicate (SiO2/Na20=1.6) 2.0 2.0
Sodium Carbonate 15.0 15.0
Sodium Sulfate 12.0 6.0
Miscellaneous 1. 5 1.0
Admix and SDraY-on
Detersive Particle of Example 29 14.3
Detersive Partcile of Example 30 30.0
Zeolite A 5.0 5.0
Sodium Citrate 5.0
Suds Suppressor Flake* 0.5 0.5
Miscellaneous 7.1 5.0
Residual Water 7. 8 6.2
100.0 100.0
*Suds Suppressor Flake contains about 5% of a silica/silicone oil
dispersion encapsulated in a flake of PEG (8000 MW), at 85%, and
about 10% of tallow fatty acid.
Examples 11 and 12 are preferably utilized at about 1000 ppm,
wash water weight basis, at temperature less than about 50-C. These
ane made by slurrying and spray drying the base granule ingredients
to about 7-10% moisture, and admixing or spraying on the remaining
ingredients.
Base Granule 13 .14 15
C14 15 Alkyl Sulfate 4.3 6.0
C16 18 Fatty Acid 2.2 2.2
Zeolite A 7.0 7.0 7.0
Polyacrylate (4500 MW) 3.3 3.3 3.3
Polyethylene Glycol (8000 MW) 1.3 1.3 1.3
Sodium Carbonate 10.7 10.7 10.7
SU~S 111 ~JTE SHEEr
w o 92/06162 pcT/~lss1/o7o2
2 ~ ~ 8 - 58 -
Sodium Sulfate 5.0 5.0 5.0
Sodium Silicate (SiO2/Na20=2) 5.0 5.0 5.0
Miscellaneous 7.1 7.1 7.1
Admix and SpraY-on
S Zeolite A 5.0 5.0 5.0
N-Methyl N-l-Deoxyglucityl Cocoamide 6.4 6.4
Detersive Particle of Example 28 21.3
C12 18 Alkyl Sulfate 13.1 13.1
C12-18 Alkyl Ethoxy (2) Sulfate 6.0
Suds Suppressor Flake * 1.0 0.5
Optional admixed ingredients 17 . 2 17 . 2 16.5
C12 13 Alkyl Ethoxylate (6.5 mole) 2.0 2.0 2.0
Perfume 0.5 0.5 0.5
Water and Miscellaneous 8.2 9 4 8.4
Totals 100.0 100.0 100.0
* Suds Suppressor Flake contains approximately 5% of a silica/sili-
cone oil dispersion encapsulated in a flake containing primarily PEG
(8000 MW), at greater than 80%, and minor optional water soluble
ingredients.
The compositions of Examples 13-15 represent condensed granular
formulations prepared by slurrying and spray drying the base granule
ingredients to a moisture of about 5%, and mixing in the additional
or powdered dry ingredients. The resulting mixture is dedusted by
spraying on the liquid ingredients. The product is intended for use
at about 1000 ppm concentration, at wash temperatures less than
about 30-C.
Base Granule 16 17
C14 15 Alkyl Sulfate 4.6
C16 18 Alkyl Sulfate 2.4 2.4
Linear C12 Alkylbenzene Sulfonate 7.6
C16 18 Alkyl Ethoxylate (11 mole) 1.1 1.1
Tallow Fatty Acid 1.1 1.1
Zeolite 21.3 22.0
Acrylate/maleate copolym.er ~60000 Mh') 4.3 5.6
Water and Miscellaneous 10.1 9.2
Admix and SPraY-on
N-Methyl N-l-Deoxyglucityl Cocoamide 7.0
N-Methyl N-1-Deoxyglucityl Tallow Fatty Amide 4.0
SU~ lTE SHEEl-
2 0 ~
W O 92/06162 PCT/US91/0702'
- 5g -
Sodium Citrate 8.0
Sodium Carbonate 17.5 17.3
Sodium Silicate (1.6r) 3.5 3.0
Perfume 0.4 0.4
Silicone Fluid 0.5 0.5
Miscellaneous (bleach, filler salts, enzymes,
builder salts, etc) 18.3 25. 7
100.0 100.0
The compositions of Examples 16 and 17 are preferably utilized
at concentrations of about 6000 ppm, wash water weight basis, at
temperature of from about 30-C to 95-C. These compositions can be
made by slurrying the base granule ingredients and spray dried to
about 9% moisture content. Remaining dry powdered or granular
ingredients are added and mixed in a rotary mix drum, followed by
spray on addition of the final liquid ingredients.
Base Granule 18 19 20
Linear C12 Alkylbenzene Sulfonate 5.9
N-Methyl N-l-Deoxyglucityl
Tallow Fatty Amide 7.1
C14 15 Alkyl Sulfate 5.9 5.9
C16-l8 Alkyl Sulfate 2.5 2.5 2.5
Zeolite 20.5 14.0 20.5
Tallow Fatty Acid 1.1 1.1
Polyacrylate (4500 MW) 3.9 3.9 3.9
Citrate 6.0
Sodium Carbonate 12.7 15.6 12.7
Water and Miscellaneous 8.1 8.2 8.7
Admix and SPraY-on
N-Methyl N-l-Deoxyglucityl Lauramide 7.1
N-Methyl N-l-Deoxyglucityl Cocoamide 7.1
Perfume 0.4 0.4 0.4
Silicone Fluid 1.0 0.5 0.5
Miscellaneous (bleach, filler salts,
bu,lder salts, er,zyr~,es, etc) 36.8 34.& 37.8
100.0 100.0 100.0
Examples 18-20 show standard density heavy duty granular
detergent compositions for wash temperatures between about 30-C to
95 C, at concentrations of about 8000 ppm, wash water weight basis.
SIJ~ JTE SHEET
W o 92/06162 PCT/~'S91/0702~
~ 5~ 60 -
The compositions are prepared by spray drying a slurry of the base
granule ingredients to about 10-13% moisture, adding additional dry
powdered ingredients, such as bleach, activators, and other
adjuncts, and spraying on liquids such as perfume, nonionics, or
suds suppressor fluids.
EXAMPLES 21-27
The following examples represent heavy duty liquid compositions
containing alkyl sulfates and polyhydroxy fatty acid amides.
Inqredients 21 22 23 24
C12 14 Alkyl Sulfate 12.9 12.9 9.0 11.5
N-Methyl N-1-Deoxyglucityl
Cocoamide 8.4 8.4
N-Meth~l N-1-Deoxyglucityl
Oleamide 8.4 6.5
Oleic acid 1.8 1.8 3.5 2.0
Citric acid 4.1 4.1 10.0 9.0
Dodecenyl succinic acid 11.1 11.1 4.0 5.0
Silicone oil 0.2 0.2 0.2 0.2
Miscellaneous (e.g. solvents,
enzymes, brightener,
stabilizers, buffers) 16.1 16.1 16.6 17.7
Water 45.5 45.5 48.3 48.1
100.0 100.0 100.0 100.0
Examples 21-24 are preferably used at about 12000 ppm, wash
25 water weight basis, at temperatures from 30-95'C.
Inqredients 25 26 27
N-Methyl N-1-Deoxyglucityl Cocoamide 4.2 3.1 3.1
N-Methyl N-1-Deoxyglucityl Oleamide
C14 15 Alkyl Ethoxy (2.25) Sulfate 8.4 6.1
C14 15 Alkyl Sulfate 4.2 3.1
C12 18 Alkyl Ethoxy (2.5) Sulfate 6.2
C12 14 Alkyl Sulfate 3.1
C12 14 Alkyl Ethoxylate 3.4 0.0 0.0
Dodecyl Trimethyl Ammonium Chloride 0.5 0.0 0.0
Dodecenyl Succinate 5.0
Citrate 3.4 0.0 15.0
TMS/TDS (80/20) * 3.4 0.0 0.0
C12 14 Fatty Acid 3.0 0.0 0.0
Sl~ ITE SHEEl-
WO 92/06162 2 Q ~ ~ 5 ~ 8 PC[/US91/0702~
- 61 -
Oxydisuccinate 20.0
Ethoxylated Tetraethylene Pentamine 1.5 0.0 0.0
Polyacrylate (4500 MW) 1.5 1.5
Miscellaneous (enzymes, brighteners, 15.3 14.g 14.9
release agents, stabilizers, etc)
Water 52.7 51 2 51.2
100.0 100.0 100.0
* TMS/TDS is tartrate monosuccinate/tartrate disuccinate
Examples 25-27 are preferably used at about 2000 ppm, wash
water weight basis, for wash temperatures below about 50-C.
Examples 21-27 are prepared by combining non-aqueous solvents,
aqueous surfactant pastes or solutions, melted fatty acids, aqueous
solutions of polycarboxylate builders and other salts, aqueous
ethoxylated tetraethylenepentamine, buffering agents, caustic, and
the remaining water. The pH is adjusted using either an aqueous
citric acid solution or sodium hydroxide solution to about pH 8.5.
After pH adjustment, the final ingredients, such as soil release
agents, enzymes, colorants, and perfume, are added and the mixture
stirred until a single phase is achieved.
EXAMPLES 28-30
The following examples demonstrate detersive particles
containing alkyl sulfates and polyhydroxy fatty acid amides,
suitable for direct addition into heavy duty granular detergent
compositions.
Inaredients 28 29 30
C12 18 Alkyl Sulfate 75.0
C14 15 Alkyl Sulfate 65.0 83.0
N-Methyl N-1-Deoxyglucityl Cocoamide 18.7 21.7 12.0
Miscellaneous 1.3 8.3
Residual Water and Miscellaneous 5.0 S.O 5.0
100.0 100.0 100.0
Examples 26-28 are prepared by mixing a melt of polyhydroxy
fatty acid amide between 70-C-100-C to an alkyl sulfate paste. The
product is then allowed to dry to less than 5% moisture, and finally5 ground and sized to approximately .1-1 mm in diameter.
EXAMPLE 31
An alternate method for preparing the polyhydroxy fatty acid
amides used herein is as follows. A reaction mixture consisting of
SIJ~S ~ JTE SHEET
W o 9~l06162 PCT/~IS91/0702
2 ~ 9 ~j 5 ~ - 62 -
84.879. fatty acid methyl ester (source: Procter & Gamble methyl
ester CE1270), 759. N-methyl-D-glucamine (source: Aldrich Chemical
Company M4700-0), 1.049. sodium methoxide (source: Aldrich Chemical
Company 16,499-2), and 68.519. methyl alcohol is used. The reaction
vessel comprises a standard reflux set-up fitted with a drying tube,
condenser and stir bar. In this procedure, the N-methyl glucamine
is combined with methanol with stirring under argon and heating is
begun with good mixing (stir bar; reflux). After 15-20 minutes,
when the solution has reached the desired temperature, the ester and
sodium methoxide catalyst are added. Samples are taken periodically
to monitor the course of the reaction, but it is noted that the
solution is completely clear by 63.5 minutes. It is judged that the
reaction is, in factt nearly complete at that point. The reaction
mixture is maintained at reflux for 4 hours. After removal of the
methanol, the recovered crude product weighs 156.16 grams. After
vacuum drying and purification, an overall yield of 106.92 grams
purified product is recovered. However, percentage yields are not
calculated on this basis, inasmuch as regular sampling throughout
the course of the reaction makes an overall percentage yield value
meaningless. The reaction can be carried out at 80% and 90%
reactant concentrations for periods up to 6 hours to yield products
with extremely small by-product formation.
The following is not intended to limit the invention herein,
but is simply to further illustrate additional aspects of the
technology which may be considered by the formulator in the manufac-
ture of a wide variety of detergent compositions using the polyhy-
droxy fatty acid amides.
It will be readily appreciated that the polyhydroxy fatty acid
amides are, by virtue of their amide bond, subject to some
instability under highly basic or highly acidic conditions. While
some decomposition can be tolerated, it is preferred that these
materials not be subjected to pH's above about 11, preferably 10,
nor below about 3 for unduly extended periods. Final product pH
(liquids) is typically 7.0-9Ø
During the manufacture of the polyhydroxy fatty acid amides it
will typically be necessary to at least partially neutralize the
base catalyst used to form the amide bond. While any acid can be
SU~ ITE SHEEr
w o 92/06162 - 63 - PCT/~1S91/0702'
.
used for this purpose, the detergent formulator will recognize that
it is a simple and convenient matter to use an acid which provides
an anion that is otherwise useful and desirable in the finished
detergent composition. For example, citric acid can be used for
purposes of neutralization and the resulting citrate ion (ca. 1%) be
allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry
and be pumped into the later manufacturing stages of the overall
detergent-manufacturing process. The acid forms of materials such
as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate,
I0 tartrate/succinate, and the like, can be used similarly.
The polyhydroxy fatty acid amides derived from coconut alkyl
fatty acids (predominantly C~2-Cl~) are more soluble than their
tallow alkyl (predominantly C16-C~8) counterparts. Accordingly, the
CI2-Cl4 materials are somewhat easier to formulate in liquid compo-
sitions, and are more soluble in cool-water laundering baths.
However, the C,6-C,8 materials are also quite useful, especially
under circumstances where warm-to-hot wash water is used. Indeed,
the C16-C18 materials may be better detersive surfactants than their
C12-C14 counterparts. Accordingly, the formulator may wish to
balance ease-of-manufacture vs. performance when selecting a par-
ticular polyhydroxy fatty acid amide for use in a given formulation.
It will also be appreciated that the solubility of the polyhy-
droxy fatty acid amides can be increased by having points of unsat-
uration and/or chain branching in the fatty acid moiety. Thus,
materials such as the polyhydroxy fatty acid amides derived from
oleic acid and iso-stearic acid are more soluble than their n-alkyl
counterparts.
Likewise, the solubility of polyhydroxy fatty acid amides
prepared from disaccharides, trisaccharides, etc., will ordinarily
be greater than the solubility of their monosaccharide-derived
counterpart materials. This higher solubility can be of particular
assistance when formulating liquid compositions. Moreover, the
polyhydroxy fatty acid amides wherein the polyhydroxy group is
derived from maltose appear to fur,ctior, especial,y well dS deler-
gents when used in combination with conventional alkylbenzenesulfonate ("LAS") surfactants. ~hile not intending to be limited by
theory, it appears that the combination of LAS with the polyhydroxy
fatty acid amides derived from the higher saccharides such as
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maltose causes a substantial and unexpected lowering of interfacial
tension in aqueous media, thereby enhancing net detergency perform-
ance. (The manufacture of a polyhydroxy fatty acid amide derived
from maltose is described hereinafter.)
The polyhydroxy fatty acid amides can be manufactured not only
from the purified sugars, but also from hydrolyzed starches, e.g.,
corn starch, potato starch, or any other convenient plant-derived
starch which contains the mono-, di-, etc. saccharide desired by the
formulator. This is of particular importance from the economic
standpoint. Thus, "high glucose" corn syrup, "high maltose" corn
syrup, etc. can conveniently and economically be used.
De-lignified, hydrolyzed cellulose pulp can also provide a raw
material source for the polyhydroxy fatty acid amides.
As noted above, polyhydroxy fatty acid amides derived from the
higher saccharides, such as maltose, lactose, etc., are more soluble
than their glucose counterparts. Moreover, it appears that the more
soluble polyhydroxy fatty acid amides can help solubilize their less
soluble counterparts, to varying degrees. Accordingly, the
formulator may elect to use a raw material comprising a high glucose
corn syrup, for example, but to select a syrup which contains a
modicum of maltose (e.g., 1% or more). The resulting mixture of
polyhydroxy fatty acids will, in general, exhibit more preferred
solubility properties over a broader range of temperatures and
concentrations than would a "pure" glucose-derived polyhydroxy fatty
2~ acid amide. Thus, in addition to any economic advantages for using
sugar mixtures rather than pure sugar reactants, the polyhydroxy
fatty acid amides prepared from mixed sugars can offer very
substantial advantages with respect to performance and/or ease-of-
formulation. In some instances, however, some loss of grease
removal performance (dishwashing) may be noted at fatty acid malt-
amide levels above about 2S% and some loss in sudsing above about
33% (said percentages being the percentage of maltamide-derived
polyhydroxy fatty acid amide vs. glucose-derived polyhydroxy fatty
acid amide in the mixture). This can vary somewhat, depending on
the chain length of the fatty acid moiety. Typically, then, the
formulator electing to use such mixtures may find it advantageous to
select polyhydroxy fatty acid amide mixtures which contain ratios of
SUBSTITUTE SHEET
w o 92/06162 2 Q ~ 8 PC~r/US91/0702
- 6~ -
monosaccharides (e.g., glucose) to di- and higher saccharides (e.g.,
maltose) from about 4:1 to about 99:1.
The manufacture of preferred, uncyclized polyhydroxy fatty acid
amides from fatty esters and N-alkyl polyols can be carried out in
alcohol solvents at temperatures from about 30-C-90-C, preferably
about 50-C-80-C. It has now been determined that it may be con-
venient for the formulator of, for example, liquid detergents to
conduct such processes in 1,2-propylene glycol solvent, since the
glycol solvent need not be completely removed from the reaction
product prior to use in the finished detergent formulation. Like-
wise, the formulator of, for example, solid, typically granular,
detergent compositions may find it convenient to run the process at
30-C-90-C in solvents which comprise ethoxylated alcohols, such as
the ethoxylated (E0 3-8) C12-Cl~ alcohols, such as those available
as NEODOL 23 E06.5 (Shell). When such ethoxylates are used, it is
preferred that they not contain substantial amounts of unethoxylated
alcohol and, most preferably, not contain substantial amounts of
mono-ethoxylated alcohol. ("T" designation.)
While methods for making polyhydroxy fatty acid amides per se
form no part of the invention herein, the formulator can also note
other syntheses of polyhydroxy fatty acid amides as described
hereinafter.
Typically, the industrial scale reaction sequence for preparing
the preferred acyclic polyhydroxy fatty acid amides will comprise:
SteP 1 - preparing the N-alkyl polyhydroxy amine derivative from the
desired sugar or sugar mixture by formation of an adduct of the
N-alkyl amine and the sugar, followed by reaction with hydrogen in
the presence of a catalyst; followed by SteP 2 - reacting the
aforesaid polyhydroxy amine with, preferably, a fatty ester to form
an amide bond. While a variety of N-alkyl polyhydroxy amines useful
in Step 2 of the reaction sequence can be prepared by various
art-disclosed processes, the following process is convenient and
makes use of economical sugar syrup as the raw material. It is to
be understood thaL, for best results wnen using such syrup raw
materials, the manufacturer should select syrups that are quite
light in color or, preferably, nearly colorless ("water-white").
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Preparation of N-Alkyl Polyhydroxy Amine
From Plant-Derived Sugar Syrup
I. Adduct Formation - The following is a standard process in
which about 420 9 of about 55% glucose solution (corn syrup - about
5231 9 glucose - about 1.28 moles) having a Gardner Color of less
than 1 is reacted with about 119 9 of about 50% aqueous methylamine
(59.5 9 of methylamine - 1.92 moles) solution. The methylamine
(MMA) solution is purged and shielded with N2 and cooled to about
10-C, or less. The corn syrup is purged and shielded with N2 at a
10temperature of about 10--20-C. The corn syrup is added slowly to
the MMA solution at the indicated reaction temperature as shown.
The Gardner Color is measured at the indicated approximate times in
minutes.
TABLE 1
15Time in Minutes: 10 30 60 120 180 240
Reaction TemD. C Gardner Color (ADDroximate)
0
1 1 2 2 4 5
4 6 10
As can be seen from the above data, the Gardner Color for the
adduct is much worse as the temperature is raised above about 30-C
and at about 50-C, the time that the adduct has a Gardner Color
below 7 is only about 30 minutes. For longer reaction, and/or
holding times, the temperature should be less than about 20-C. The
Gardner Color should be less than about 7, and preferably less than
about 4 for good color glucamine.
When one uses lower temperatures for forming the adduct, the
time to reach substantial equilibrium concentration of the adduct is
shortened by the use of higher ratios of amine to sugar. With the
1.5:1 mole ratio of amine to sugar noted, equilibrium is reached in
about two hours at a reaction temperature of about 30-C. At a 1.2:1
mole ratio, under ~he same conditions, the time is at least about
three hours. For good color, the combination of amine:sug~r r~tio;
reaction temperaturei and reaction time is selected to achieve
substantially equil;brium conversion, e.g., more than about 90%,
preferably more than about 95%, even more preferably more than about
~9%, based upon the sugar, and a color that is less than about 7,
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preferably less than about 4, more preferably less than about 1, for
the adduct.
Using the above process at a reaction temperature of less than
about 20-C and corn syrups with different Gardner Colors as
5 indicated, the MMA adduct color (after substantial equilibrium is
reached in at least about two hours) is as indicated.
TABLE 2
Gardner Color (ADDroximate)
Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2
As can be seen from the above, the starting sugar material must
be very near colorless in order to consistently have adduct that is
acceptable. When the sugar has a Gardner Color of about 1, the
adduct is sometimes acceptable and sometimes not acceptable. When
the Gardner Color is above 1 the resulting adduct is unacceptable.
The better the initial color of the sugar, the better is the color
of the adduct.
II. Hvdroqen Reaction - Adduct from the above having a Gardner
Color of 1 or less is hydrogenated according to the following
procedure.
About 539 9 of adduct in water and about 23.1 9 of United
Catalyst G49B Ni catalyst are added to a one liter autoclave and
purged two times with 200 psig H2 at about 20-C. The H2 pressure
is raised to about 1400 psi and the temperature is raised to about
50-C. The pressure is then raised to about 1600 psig and the
temperature is held at about 50-55-C for about three hours. The
product is about 95% hydrogenated at this point. The temperature
is then raised to about 85-C for about 30 minutes and the reaction
mixture is decanted and the catalyst is filtered out. The product,
after removal of water and MMA by evaporation, is about 95% N-methyl
glucamine, a white powder.
The above procedure is repeated with about 23.1 9 of Raney Ni
catalyst with the following changes. The catalyst is washed three
times and the reactor, with the catalyst in the reactor, is purged
twice with 200 psig H2 and the reactor is pressurized with H2 at
1600 psig for two hours, the pressure is released at one hour and
the reactor is repressurized to 1600 psig. The adduct is then
S~ JTE SHEEl-
w o 92/06162 PCT/~IS91/0702
pumped into the reactor which ls at 200 psig and 20-C, and the
reactor is purged with 200 psig ~2. etc., as above.
The resulting product in each case is greater than about 95%
N-methyl glucamine; has less than about 10 ppm Ni based upon the
glucamine; and has a solution color of less than about Gardner 2.
The crude N-methyl glucamine is color stable to about 140-C for
a short exposure time.
It is important to have good adduct that has low sugar content
(less than about 5%, preferably less than about 1%) and a good color
(less than about 7, preferably less than about 4 Gardner, more
preferably less than about 1).
In another reaction, adduct is prepared starting with about 159
g of about 50% methylamine in water, which is purged and shielded
with N2 at about 10-20-C. About 330 9 of about 70% corn syrup (near
water-white) is degassed with N2 at about 50-C and is added slowly
to the methylamine solution at a temperature of less than about
20-C. The solution is mixed for about 30 minutes to give about 95%
adduct that is a very light yellow solution.
About 190 9 of adduct in water and about 9 9 of United Catalyst
G49B Ni catalyst are added to a 200 ml autoclave and purged three
times with H2 at about 20-C. The H2 pressure is raised to about 200
psi and the temperature is raised to about 50-C. The pressure is
raised to 250 psi and the temperature is held at about 50-55-C for
about three hours. The product, which is about 95% hydrogenated at
this point, is then raised to a temperature of about 85-C for about
30 minutes and the product, after removal of water and evaporation,
is about 95% N-methyl glucamine, a white powder.
It is also important to minimize contact between adduct and
catalyst when the H2 pressure is less than about 1000 psig to
minimize Ni content in the glucamine. The nickel content in the
N-methyl glucamine in this reaction is about 100 ppm as compared
to the less than 10 ppm in the previous reaction.
The following reactions with H2 are run for direct comparison
of reaction temperature effects.
A 200 ml autoclave reactor is used following typical procedures
similar to those set forth above to make adduct and to run the
hydrogen reaction at various temperatures.
Adduct for use in making glucamine is prepared by combining
about 420 9 of about 55% glucose (corn syrup) solution (231 g
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glucose; 1.28 moles) (the solution is made using 99DE corn syrup
from CarGill, the solution having a color less than Gardner 1) and
about 119 9 of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air
Products).
The reaction procedure is as follows:
1. Add about 119 g of the 50% methylamine solution to a N2 purged
reactor, shield with N2 and cool down to less than about 10-C.
2. Degas and/or purge the 55% corn syrup solution at 10-20-C with
N2 to remove oxygen in the solution.
3. Slowly add the corn syrup solution to the methylamine solution
and keep the temperature less than about 20-C.
4. Once all corn syrup solution is added in, agitate for about 1-2
hours.
The adduct is used for the hydrogen reaction right after
making, or is stored at low temperature to prevent further
degradation.
The glucamine adduct hydrogen reactions are as follows:
1. Add about 134 g adduct (color less than about Gardner 1) and
about 5.8 9 G49B Ni to a 200 ml autoclave.
2. Purge the reaction mix with about 200 psi H2 twice at about
20-30-C.
3. Pressure with H2 to about 400 psi and raise the temperature to
about 50-C.
4. Raise pressure to about 500 psi, react for about 3 hours. Keep
temperature at about 50-55-C. Take Sample 1.
5. Raise temperature to about 85-C for about 30 minutes.
6. Decant and filter out the Ni catalyst. Take Sample 2.
Conditions for constant temperature reactions:
1. Add about 134 9 adduct and about 5.8 9 G49B Ni to a 200 ml
autoclave.
2. Purge with about 200 psi H2 twice at low temperature.
3. Pressure with H2 to about 400 psi and raise temperature to
about 50-C.
4. Raise pressure to about 500 psi, react for about 3.5 hours.
Keep temperature at indicated temperature.
5. Decant and filter out the Ni catalyst. Sample 3 is for about
50-55 C; Sample 4 is for about 75 C; and Sample 5 is for about
85-C. (The reaction time for about 85-C is about 45 minutes.)
SUE~ ITE SHEEr
w o 92/06162 PCT/US91/0702
All runs give similar purity of N-methyl glucamine (about 94%);
the Gardner Colors of the runs are similar right after reaction, but
only the two-stage heat treatment gives good color stability; and
the 85-C run gives marginal color immediately after reaction.
EXAMPLE 32
The preparation of the tallow (hardened) fatty acid amide of
N-methyl maltamine for use in detergent compositions according to
this invention is as follows.
SteD 1 - Reactants: Maltose monohydrate (Aldrich, lot
01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 50h slurry (UAD 52-73D, Aldrich, lot 12921LW).
The reactants are added to glass liner (250 9 maltose, 428 9
methylamine solution, 100 9 catalyst slurry - 50 9 Raney Ni) and
placed in 3 L rocking autoclave, which is purged with nitrogen
(3X500 psig) and hydrogen (2X500 psig) and rocked under H2 at room
temperature over a weekend at temperatures ranging from 28-C to
50-C. The crude reaction mixture is vacuum filtered 2X through a
glass microfiber filter with a silica gel plug. The filtrate is
concentrated to a viscous material. The final traces of water are
azetroped off by dissolving the material in methanol and then
removing the methanol/water on a rotary evaporator. Final drying is
done under high vacuum. The crude product is dissolved in refluxing
methanol, filtered, cooled to recrystallize, filtered and the filter
cake is dried under vacuum at 35-C. This is cut #1. The filtrate
is concentrated until a precipitate begins to form and is stored in
a refrigerator overnight. The solid is filtered and dried under
vacuum. This is cut #2. The filtrate is again concentrated to half
its volume and a recrystallization is performed. Very little
precipitate forms. A small quantity of ethanol is added and the
solution is left in the freezer over a weekend. The solid material
is filtered and dried under vacuum. The combined solids comprise
N-methyl maltamine which is used in Step 2 of the overall synthesis.
SteD 2 - Reactants: N-methyl maltamine (from Step 1); hardened
tallow methyl esters; sodium methoxide (25% in methanol); absolute
methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst
level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level
50% (wt.).
In a sealed bottle, 20.36 9 of the tallow methyl ester is
heated to its melting point (water bath) and loaded into a 250 ml
SUE3~ JTE SHEET
w o 92/06162 2 ~ S ~ PCT/~Ss1/0702
- 71 -
3-neck round-bottom flask with mechanical stirring. The flask is
heated to ca. 70-C to prevent the ester from solidifying. Separ-
ately, 25.0 g of N-methyl maltamine is combined with 45.36 g of
methanol, and the resulting slurry is added to the tallow ester with
good mixing. 1.51 9 of 25% sodium methoxide in methanol is added.
After four hours the reaction mixture has not clarified, so an
additional 10 mole Z of catalyst (to a total of 20 mole %) is added
and the reaction is allowed to continue overnight (ca. 68-C) after
which time the mixture is clear. The reaction flask is then modi-
fied for distillation. The temperature is increased to llO-C.
Distillation at atmospheric pressure is continued for 60 minutes.
High vacuum distillation is then begun and continued for 14 minutes,
at which time the product is very thick. The product is allowed to
remain in the reaction flask at llO-C (external temperature) for 60
minutes. The product is scraped from the flask and triturated in
ethyl ether over a weekend. Ether is removed on a rotary evaporator
and the product is stored in an oven overnight, and ground to a
powder. Any remaining N-methyl maltamine is removed from the
product using silica gel. A silica gel slurry in 100% methanol is
loaded into a funnel and washed several times with 100% methanol. A
concentrated sample of the product (20 9 in 100 ml of 100% methanol)
is loaded onto the silica gel and eluted several times using vacuum
and several methanol washes. The collected eluant is evaporated to
dryness (rotary evaporator). Any remaining tallow ester is removed
by trituration in ethyl acetate overnight, followed by filtration.
The filter cake is vacuum dried overnight. The product is the
tallowalkyl N-methyl maltamide.
In an alternate mode, Step 1 of the foregoing reaction
sequence can be conducted using commercial corn syrup comprising
glucose or mixtures of glucose and, typically, 5%, or higher,
maltose. The resulting polyhydroxy fatty acid amides and mixtures
can be used in any of the detergent compositions herein.
In still another mode, Step 2 of the foregoing reaction
sequence can be carried out in 1,2-propylene glycol or NEODOL. At
the discretion of the formulator, the propylene glycol or NEODOL
need not be removed from the reaction product prior to its use to
formulate detergent compositions. Again, according to the desires
of the formulator, the methoxide catalyst can be neutralized by
SU~ JTE SHEET
w o 92/06162 PCT/~IS91/0702
- 72 -
2~ 5 citric acid to provide sodium citrate, which can remain in the
polyhydroxy fatty acid amide.
Depending on the desires of the formulator, the compositions
herein can contain more or less of various suds control agents.
Typically, for dishwashing high sudsing is desirable so no suds
control agent will be used. For fabric laundering in top-loading
washing machines some control of suds may be desirable, and for
front-loaders some considerable degree of suds control may be
preferred. A wide variety of suds control agents are known in the
art and can be routinely selected for use herein. Indeed, the
selection of suds control agent, or mixtures of suds control agents,
for any specific detergent composition will depend not only on the
presence and amount of polyhydroxy fatty acid amide used therein,
but also on the other surfactants present in the formulation.
However, it appears that, for use with polyhydroxy fatty acid
amides, silicone-based suds control agents of various types are more
efficient (i.e., lower levels can be used) than various other types
of suds control agents. The silicone suds control agents available
as X2-3419 and Q2-3302 (Dow Corning) are particularly useful herein.
The formulator of fabric laundering compositions which can
advantageously contain soil release agent has a wide variety of
known materials to choose from (see, for example, U.S. Patents
3,962,152; 4,116,885; 4,2~8,531; 4,702,857; 4,721,580 and
4,877,896). Additional soil release materials useful herein include
the nonionic oligomeric esterification product of a reaction mixture
comprising a source of C1-C~ alkoxy-terminated polyethoxy units
(e.g., CH3[0CH2CH2]~60H), a source of terephthaloyl units (e.g.,
dimethyl terephthalate); a source of poly(oxyethylene)oxy units
(e.g., polyethylene glycol 1500); a source of oxyiso-propyleneoxy
units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy
units (e.g., ethylene glycol) especially wherein the mole ratio of
oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about
0.5:1. Such nonionic soil release agents are of the general formula
0 Q ~ 0
., ~ ~1 " ~ ~1
R10-(CH2CH20)x C ~ C0-CH-CH20 - C- ~ C0(CH2cH20)y
_ R2 _ m _ _ n
O O
Il t=\ ~
C~C - O (CH2CH20)x-Rl
SlJ~ JTE SHEEl-
w o 92/06162 2 ~ 9 2 5 5 ~ PCT/~IS91/0702~
- 73 -
wherein Rl is lower (e.g., Cl-C4) alkyl, especially methyl; x and y
are each integers from about 6 to about 100; m is an integer of from
about 0.75 to about 30; n is an integer from about 0.25 to about 20;
and R2 is a mixture of both H and CH3 to provide a mole ratio of
oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
Another preferred type of soil release agent useful herein is
of the general anionic type described in U.S. Patent 4,877,896, but
with the condition that such agents be substantially free of mono-
mers of the HOROH type wherein R is propylene or higher alkyl.
Thus, the soil release agents of U.S. Patent 4,877,896 can comprise,
for example, the reaction product of dimethyl terephthalate,
ethylene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid,
whereas these additional soil release agents can comprise, for
example, the reaction product of dimethyl terephthalate, ethylene
glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid. Such
agents are preferred for use in granular laundry detergents.
The formulator may also determine that it is advantageous to
include a non-perborate bleach, especially in heavy-duty granular
laundry detergents. A variety of peroxygen bleaches are available,
commercially, and can be used herein, but, of these, percarbonate is
convenient and economical. Thus, the compositions herein can
contain a solid percarbonate bleach, normally in the form of the
sodium salt, incorporated at a level of from 3% to 20% by weight,
more preferably from 5% to 18% by weight and most preferably from
8% to 15% by weight of the composition.
Sodium percarbonate is an addition compound having a formula
corresponding to 2Na2CO3. 3H202, and is available commercially as a
crystalline solid. Most commercially available material includes a
low level of a heavy metal sequestrant such as EDTA, l-hydroxy-
ethylidene l,l-diphosphonic acid (HFDP) or an amino-phosphonate,
that is incorporated during the manufacturing process. For use
hereint the percarbonate can be incorporated into detergent composi-
tions without additional protection, but preferred embodiments of
the ...ver,t,o,. util,ze â stable form of the material (FMC). hlthough
a variety of coatings can be used, the most economical is sodium
silicate of SiO2:Na20 ratio from 1.6:1 to 2.8:1, preferably 2.0:1,
applied as an aqueous solution and dried to give a level of from 2%
to 10% (normally from 3% to 5%), of silicate solids by weight of the
SU~ JTE SHEET
a~9255~ ~
- 74 -
percarbonate. Magnesium silicate can also be used and a chelant
such as one of those mentioned above can also be included in the
coating.
The particle size range of the crystalline percarbonate is from
350 micrometers to 450 micrometers with a mean of approximately 400
micrometers. When coated, the crystals have a size in the range
from 400 to 600 micrometers.
~hile heavy metals present in the sodium carbonate used to
manufacture the percarbonate can be controlled by the inclusion of
sequestrants in the reaction mixture, the percarbonate still
requires protection from heavy metals present as impurities in other
ingredients of the product. It has been found that the total level
of iron, copper and manganese ions in the product should not exceed
25 ppm and preferably should be less than 20 ppm in order to avoid
an unacceptably adverse effect on percarbonate stability.
A modern, condensed laundry detergent granule is as follows.
~XAMPLE 33
Inqredient Wt.~o
C14-15 alkyl alcohol sulfonic acid 13
Cl~ ls alkyl polyethoxy (2.25) sulfonic acid 5.60
C12-13 alkyl polyethoxylate (6.5) 1.45
Cl2 14 fatty acid N-methyl glucamide 2.50
Sodium aluminosil;cate (as hydrated Zeolite A) 25.2
Crystalline layered silicate builder1 23.3
25 Citric acid 10.0
Sodium carbonate To get wash pH = 9.90
Sodium polyacrylate (m.w. 2000-4500) 3.2
Diethylenetriamine pentaacetic acid 0.45
Savinase2 0.70
6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40
Sodium perborate monohydrate 2.10
Nonanoyloxybenzene sulfonic acid 5.00
Brightener - 0.10
lLayered silicate builders are known in the art. Preferred
are the layered sodium silicates. See, for example, the layered
sodium silicate builders of U.S. Patent 4,664,859, issued May 12,
1987 to H.P. Rieck. A suitable layered silicate builder is available as
SKS-6 from Hoechst.
r B -
w o 92/06162 2 0 ~ 2 5 5 8 PCT/US91/0702~
- 75 -
2Availab,e from Novo Nordisk A/S, Copenhagen.
Highly preferred granules of the foregoing types are those
which comprise from about 0.0001% to about 2% by weight of active
enzyme and at least about 1% by weight of said polyhydroxy fatty
acid amide, and, most preferably, wherein the anionic surfactant is
not an alkylbenzene sulfonate surfactant.
EXAMPLE 34
The following illustrates a perborate bleach-plus-bleach
activator detergent composition of the present invention which is
prepared by admixing the listed ingredients in a mixing drum.
In the example, Zeolite A refers to hydrated crystalline
Zeolite A containing about 20% water and having an average particle
size of 1 to 10, preferably 3 to 5, microns; LAS refers to sodium
C12.3 linear alkylbenzene sulfonate; AS refers to sodium Cl4-C1s
alkyl sulfate; nonionic refers to coconut alcohol condensed with
about 6.5 moles of ethylene oxide per mole of alcohol and stripped
of unethoxylated and monoethoxylated alcohol, also abbreviated as
CnAE6.5T.; and DTPA refers to sodium diethylenetriamine
pentaacetate.
Parts by Weight of
Final Com w sition ~O of Granules
Base Granules1 51.97 100.00
AS 9.44 18.16
LAS 2.92 5.62
Moisture 4.47 8.60
Sodium silicate (1.6 ratio) 1.35 2.60
Sodium sulfate 6.47 12.45
Sodium polyacrylate (4500 MW) 2.61 5.02
PEG 8000 1.18 2.27
Nonionic 0.46 0.89
Sodium carbonate 13.29 25.57
Brightener 0.20 0.38
Sodium aluminosilicate 9. 11 17.53
DTPA 0.27 O.i2
Perfume 0.20 0.38
NAPAA Granules2 6.09 100.00
NAPM 2.86 46.96
LAS 0.30 4 93
Sulfate and Misc. 2.93 48.11
SIJ~ 1TE SHEET
W O 92/06162 PC~r/~'S91/0702~
? ~5'~ NOBS Granules3 3.88 100.00
NOBS 3.15 81.19
LAS 0.12 3.09
PEG 8000 0.19 4.90
Misc. 0.42 10.82
Zeolite Granules~ 12.00 100.00
Sodium aluminosilicate 7.39 61.58
PEG 8000 l.SO 12.47
Nonionic 1.16 9.70
Moisture 1.66 13.83
Misc. 0.29 2.42
Admix
Sodium SKS-6
layered silicate 15.84
Protease
(0.078 mg/g activity) 0.52
Sodium perborate
monohydrate 1.33
Citric acid 6.79
Cl2-C1~ N-methyl glucamide1.58
Total of final composition 100.00
lThe base granules are produced by spray drying an aqueous
crutcher mix of the listed ingredients.
2A freshly-prepared sample of NAPAA wet cake, which typically
consists of about 60% water, about 2% peroxyacid available oxygen
(AvO) (corresponding to about 36% NAPAA), and the rest (about 4X)
unreacted starting material, is obtained. This wet cake is the
crude reaction product of NAAA (monononyl amide of adipic acid),
sulfuric acid, and hydrogen peroxide which is subsequently quenched
by addition to water followed by filtration, washing with distilled
water, phosphate buffer washing and final suction filtration to
recover the wet cake. A portion of the wet cake is air-dried at
room temperature to obtain a dry sample which typically consists of
about 5X AvQ (corresponding to about 90Y. NAPAA) and about 10%
unreacted starting material. When dry, the sample pH is about 4.5.
NAPAA granules are prepared by mixing about 51.7 parts of the
dried NAPAA wet cake (containing about 10% unreacted), about 11.1
parts of sodium Cl2.3 linear alkyl benzene sulfonate (LAS) paste
(45% active), about 43.3 parts of sodium sulfate, and about 30 parts
SUE~STITIJ~E SHEET
2~25 5~ -`
- - 77 -
- of water in a CUISINART mixer. After drying, the granules (which
contain about 47% NAPAA) are sized by passing through a No. 14 Tyler
mesh sieve and retaining all particles not passing through a ~o. 6
Tyler mesh. The average amide peroxyacid particle (agglomerate)
size is about 5-40 microns and the median particle size is about
10-20 microns, as determined by Malvern particle size analysis.
3The N08S (nonanoyloxybenzene sulfonate) granules are prepared
according to U.S. Patent 4,997,596, Bowling et al, issued March 5,
1991.
10~Zeolite granules having the following composition are made by
mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich R08 energy
intensive mixer. Parts bv Weiqht
Before DrYinq After Drvinq
Zeolite A (includes bound water) 70.00 76.99
PEG 8000 10.80 12.49
CnAE6.5T~ 8.40 9.72
Free water 10.80 0.80
The PEG 8000 is in an aqueous form containing 50% water and is
at a temperature of approximately 55-F (12.8'C). The CnAE6.5T is in
a liquid state and is held at approximately 90-F (32.2-C). The two
liquids are combined by pumping through a 12 element static mixer.
~he resulting binder material has an outlet temperature of
approximately 75-F (23.9-C) and a viscosity of approximately 5000
cps. The ratio of PEG 8000 and CnAE6.5T through the static mixer is
2~ 72:28 respectively.
The Eirich R08 energy intensive mixer is operated in a batch
type mode. First, 34.1 kg of powdered Zeolite A is weighed into the
pan of the mixer. The mixer is started by first rotating the pan in
a counterclockwise direction at approximately 75 rotations per
minute (rpm), and then rotating the rotor blade in a clockwise
direction at 1800 rpm. The binder material is then pumped from the
static mixer directly into the Eirich R08 energy intensive mixer
which contains Zeolite A. The feed rate of the binder material is
about 2 minutes. The mixer continues to mix for an additional
minute for a total batch time of approximately 3 minutes. The batch
is then discharged and collected in a fiber drum.
The batch step is repeated until approximately 22~ kg Ot wet
product has been collected. This discharged product is then dried
B'~
w o 92/06162 PCT/~'S91/0702
7J '~ln a fluid bed at 240-270-F (I16-132-C). The drying step removes
most of the free water and changes the composition as described
above. The total energy input by the mixer to the product in a
batch mode is approximately 1.31X1012 erg/kg. at a rate of approxi-
S mately 2.18X109 erg/kg-s.
The resulting free flowing agglomerates have a mean particle
size of about 450-500 microns.
EXAMPLE 35
A granular laundry detergent composition suitable for use at
the relatively high concentrations common to front-loading
automatic washing machines, especially in Europe, and over a wide
range of temperatures is as follows.
Inqredient Wt. %
SOKALAN CP5 (100% active as Na salt)1 3.52
DEQUEST 2066 (100% as acid)2 0.45
TINOPAL DMS3 0.28
MgSO, 0-49
Zeolite A (anhydrousJ 17.92
CMC (100% active)~ 0.47
Na2CO3 9.44
Citric acid 3-5
Layered Silicate SKS-6 12.9
Tallow alkyl sulfate (100% active; Na salt) 2.82
C1~-C1s alkyl sulfate (100% active; Na salt) 3.5
C12-C15 alkyl EO(3) sulfate 1.76
C16-Cl~ N-methyl glucamide 4.1
DOBANOL C12-C15 EO(3) 3-54
LIPOLASE (100,000 LU/g)5 0.42
SAVINASE (4.0 KNPU)6 1.65
Perfume 0.53
X2-34197 0.22
Starch 1.08
Stearyl alcohol 0.35
Sodium percarbonate (coated) 22.3
Tetraacetylethylenediamine (TAED) 5.9
Zinc phthalocyanin 0.02
Water (ex zeolite) Balance
SU~ ITE SHEEl-
W o 92/06162 792 Q 3 2 ~ ~ ~ P ~ /~'S91/0702
1SOKALAN is sodium poly-acrylate~maleate available from
Hoechst.
ZMonsanto brand of pentaphosphonomethyl diethylenetriamine.
30ptical brightener available from Ciba Geigy.
~Trade name FINNFIX available from Metasaliton.
sLIPOLASE lipolytic enzyme from NOVO.
sSAVINASE protease enzyme from NOVO.
'X2-3419 is a silicone suds suppressor available from Dow
Corning.
The procedure for preparing the granules comprises various
tower-drying, agglomerating, dry-additions, etc., as follows. The
percentages are based on the finished composition.
A. Crutched and Blown Throuqh the Tower
Using standard techniques the following components are crutched
and tower-dried.
SOKALAN CPS 3.52%
DEQUEST 2066 0 45%
TINOPAL DMS 0.28%
Magnesium sulfate 0.49%
ZEOLITE A as anhydrous 7.1%
CMC 0 47%
B. Surfactant Aqqlomerates
B1. Aqqlomeration of Sodium Salt of Tallow AlkYl Sulfate and
Sodium Salt of C~2 ls EO(3) Sulfate Pastes - A 50% active paste of
tallow alkyl sulfate and a 70% paste of C12-C1s EO(3) sulfate are
agglomerated with Zeolite A and sodium carbonate according to the
following formula (contribution to the detergent formulation after
the drying of the agglomerate).
Tallow alkyl sulfate 2.82%
C1z 1s EO(3) sulfate 1.18%
Zeolite A 5.3%
Sodium carbonate 4.5%
B2. A wlomerate of the C1A CI5 Alkvl Sulfate. C12 C,5 Alkvl
Ethoxv Sulfate~ DOBANOL C~2-C~5 EO(3) and Cl6-C~ N-methvl qlucose
amide - The C~6-C18 glucose amide nonionic material is synthesized
with DOBANOL C12 1sEO(3) present during the reaction of methyl ester
and N-methyl glucamine. The C12 1sEO(3) acts as a melting point
SlJ~ JTE SHEEr
wo 92/06162 PCr/~Ss1/0702
- 80 -
~y?~5~SdePressor which allows the reaction to be run without forming cyclic
glucose amides which are undesirable.
A surfactant mixture of 20% DOBANOL Cl2 1s EO(3) and 80%
Cl6-C18 N-methyl glucose amide is obtained and coagglomerated with
5 10% sodium carbonate.
Second, the above particle is then coagglomerated with a high
active paste (70%) of a sodium salt of C1~-C15 alkyl sulfate and
C12 1s EO(3) sulfate and Zeolite A and extra sodium carbonate. This
particle evidences a good dispersibility in cold water of the
10 C16-C1t N-methyl glucose amide.
The overall formulation of this particle (contribution to the
detergent formulation after the drying of the agglomerate) is:
C1~-C1e N-methyl glucose amide 4.1%
DOBANOL C1 2-15 EO(3) 0.94%
Sodium carbonate 4.94%
Zeolite A 5.3%
Na Cl~,-C15 al kyl sul fate 3.5%
Na C12-15 EO(3) sul fate 0.59%
C. DrY Additives
The following ingredients are added.
Percarbonate 22.3%
TAED (tetraacetylethylenediamine) 5.9%
Layered silicate SKS 6 from Hoechst 12.90%
Citric acid 3.5%
Lipol ase 0.42%
100,000 LU/g
SAVINASE 4.0 KNPU 1.65%
Zinc phthalocyanin (photobleach) 0.02%
D. SPraY on
DOBANOL C12-15 EO(3) 2.60%
Perfume 0.53%
E. Suds SuPPressor
The silicone suds suppressor X2-3419 (95%-97% high molecular
weight linear silicone; 3%-5% hydrophobic silica) ex Dow Corning is
35 coagglomerated with Zeolite A (2-5 ~ size), starch and stearyl
alcohol binder. This particle has the following formulation:
SUt~ ITE SHEEl'
WO 92/06162 ~ 3 9 % ~ 5 8 PCI`/US91/0702
- 81 -
Zeolite A 0.22%
Starch 1. 08%
X2-3419 0.22%
Stearyl alcohol 0.35%
The detergent preparation exhibits excellent solubility,
superior performance and excellent suds control when used in
European washing machine, e.g., using 85 9 detergent in a AEG-brand
washing machine in 30-C, 40-C, 60-C and 90-C cycles.
EXAMPLE 37
In any of the foregoing examples, the fatty acid glucamide
surfactant can be replaced by an equivalent amount of the maltamide
surfactant, or mixtures of glucamide/maltamide surfactants derived
from plant sugar sources. In the compositions the use of ethanol-
amides appears to help cold temperature stability of the finished
formulations. Moreover, the use of sulfobetaine (aka "sultaine")
surfactants provides superior sudsing.
In the event that especially high sudsing compositions are
desired, it is preferred that less than about 5%, more preferably
less than about 2%, most preferably substantially no C1~ or higher
fatty acids be present, since these can suppress sudsing. Accord-
ingly, the formulator of high sudsing compositions will desirably
avoid the introduction of suds-suppressing amounts of such fatty
acids into high sudsing compositions with the polyhydroxy fatty acid
amide, and/or avoid the formation of C1~ and higher fatty acids on
storage of the finished compositions. One simple means is to use
C12 ester reactants to prepare the polyhydroxy fatty acid amides
herein. Fortunately, the use of amine oxide or sulfobetaine
surfactants can overcome some of the negative sudsing effects caused
by the fatty acids.
The formulator wishing to add anionic optical brighteners to
liquid detergents containing relatively high concentrations (e.g.,
10% and greater) of anionic or polyanionic substituents such as the
polycarboxylate builders may find it useful to pre-mix the bright-
ener with water and the polyhydroxy fatty acid amide, and then to
add the pre-mix to the final composition.
SU~STITUTE SHEET
w o 92/06162 PCT/US91/0702
- 82 -
2~ Polyglutamic acid or polyaspartic acid dispersants can be
usefully employed with zeolite-built detergents. AE fluid or flake
and DC-544 (Dow Corning) are other examples of useful suds control
agents herein.
It will be appreciated by those skilled in the chemical arts
that the preparation of the polyhydroxy fatty acid amides herein
using the di- and higher saccharides such as maltose will result in
the formation of polyhydroxy fatty acid amides wherein linear
substituent Z is "capped" by a polyhydroxy ring structure. Such
materials are fully contemplated for use herein and do not depart
from the spirit and scope of the invention as disclosed and claimed.
SU~STITUTE SHEEr
