Note: Descriptions are shown in the official language in which they were submitted.
~2~2 ~ 5
- 1 -
DETERGENT COMPOSITIONS CONTAINING ALKYL ETHOXY
CARBOXYLATES AND POLYHYDROXY FATTY ACID AMIDES
TECHNICAL FIELD
The present invention relates to detergent compositions comprising
alkyl ethoxy carboxylates and polyhydroxy fatty acid amides. In
particular, it relates to detergent compositions which posses desirable
cleaning and sudsing properties, and are especially suitable for use in
dishwashing applications.
BACKGROUND OF THE INVENTION
Alkyl ethoxy carboxylates, and their use in detergent compositions,
are known in the art. Canadian Patent No. 2,012,172 of Rodney M. Wise and
Thomas A. Cripe, discloses such carboxylates and their use in detergent
compositions. While these carboxylates provide improved cleaning
performance, the suds they produce generally have poor initial volume and
poor stability. This poor suds volume and stability may cause an
incorrect perception on the part of the consumer that the detergent
compositions provide inferior cleaning performance. Therefore, it would
be desirable to combine such carboxylates with a component or components
which provide improved sudsing performance. It has been found that the
compositions claimed in the present invention provide this desired effect.
The polyhydroxy fatty acid amide component contained in the
composition of the present invention is known in the art, as are several
of its uses.
N-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 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
-
wo 92/06157 2 ~ 9 2 1 8 5 - 2 - pc~r/us91/o6983
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 Com-
pounds, a New Class of Non-Ionic Detergents For Membrane Biochemis-
try," Biochem. J. (1982), 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 constit-
uents 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 condensa-
tion 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 WO 83/04412, published December
22, 1983, by J. Hildreth, relates to amphiphilic compounds contain-
ing 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 dispensing agents for
medicines, and in biochemistry for solubilizing membranes, whole
cells, or other tissue samples, and for preparing liposomes.
Included in this disclosure are compounds of the formula
R'CON(R)CH2R" and R"CON(R)R' wherein R is hydrogen or an organic
~0~2i ~
W o 92/06157 ~ P ~ /US91/06983
- 3 -
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 (prefer-
ably 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 N-acyl-
polyhydroxyalkyl-amine of the formula R1C(O)N(R2)CH2(CHOH)nCH20H,
wherein R1 is a C1-C3 alkyl, R2 is a C10-c22 alkyl, and n is 3 or 4.
The N-acylpolyhydroxyalkyl-amine is added as a soil suspending
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
W O 92/06157 2 0 9 Z 1 8 S P ~ /US91/06983
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nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl
polyhydroxyalkyl compound of the formula RlN(Z)C(O)R2 wherein Rl is
a Clo-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(CHOH)m-
CH2OH where m is 3 or 4.
U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, etal., relates to skin treating cosmetic compositions containing
N-polyhydroxyalkyl-amines which include compounds of the formula
RlN(R)CH(CHOH)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 CH2OH or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial
Solvents Corporation, relates to solutions of formaldehyde stabi-
lized 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.B. Patent 745,036, published February lS, 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.
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
WO 92/06157 ~ ' ~ PCI'/US91/06983
209218~
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.
However, none of these references teach combining an alkyl
ethoxy carboxylate and a polyhydroxy fatty acid amide in a detergent
composition. Furthermore, nothing in the art teaches the unexpected
improved sudsing characteristics and improved cleaning properties,
especially grease cleaning properties, of such detergent composi-
tions.
There is also nothing in the art which teaches the mildness to
the hand exhibited by such detergent compositions.
It is therefore an object of the present invention to provide
for detergent compositions containing an alkyl ethoxy carboxylate
and a polyhydroxy fatty acid amide which exhibit improved sudsing
and cleaning properties, and are mild to the skin.
It is still another object of the present invention to provide
a method for cleaning soiled dishes by treating said dishes with the
particular detergent compositions described herein.
These objects are realized by the present invention.
SUMMARY OF THE INVENTION
The present invention is directed to detergent compositions
comprising from about 1%, preferably about 5%, to about 65% by
weight of a surfactant mixture comprising:
(a) from about 5% to about 95% by weight of one or more alkyl
ethoxy carboxylates having the general formula
RO(CH2CH2O)kCH~COO-M+
wherein R is a Cg-C22 alkyl group, k is an integer ranging
from O to 10, and M is a cation;
(b) from about 5% to about 95% by weight of one or more
polyhydroxy fatty acid amides having the general formula
O Rl
R2-C-N-Z
wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl, or mixtures thereof, R2 is a Cs-C31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
WO 92/06157 2 0 9 Z 1 8 5 PCl'/US91/06983
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linear hydrocarbyl chain with at least 3 hydroxyl groups
directly connected to the chain, or an alkoxylated deriva-
tive thereof.
The present invention is also directed toward a method for
cleaning soiled dishes, said method comprising treating said dishes
with the detergent compositions claimed herein.
DETAILED DESCRIPTION OF THE INVENTION
The detergent compositions of the present invention are prefer-
ably liquid or gel detergent compositions, more preferably light-
duty liquid detergent compositions, most preferably light-duty
liquid dishwashing detergent compositions. These detergent composi-
tions comprise from about 5% to about 65% by weight, preferably from
about 10% to about 50% by weight, most preferably from about 20% to
about 40% by weight of a surfactant mixture comprising one or more
alkyl ethoxy carboxylates and one or more polyhydroxy fatty acid
amides. These and other optional ingredients typically found in
detergent compositions are set forth below.
Alk~l EthoxY CarboxYiate ComDonent
The surfactant mixture of the present invention comprises from
about 5% to about 95% by weight, preferably from about 20% to about
80% by weight, more preferabiy from about 40% to about 60% by weight
of one or more alkyl ethoxy carboxylates having the general formula
RO(CH2CH2O)kCH2COO-M+ (I)
wherein R is a Cg-C22 alkyl group, preferably a C12-C14 alkyl group,
k is an integer ranging from O to 10, preferably from 1 to 5, and M
is a cation, preferably an alkali metal, alkaline earth metal,
ammonium, lower alkanol ammonium, and mono-, di-, and tri-
ethanolammonium, more preferably sodium, potassium and ammonium,
most preferably sodium and potassium, and mixtures thereof with
magnesium and calcium ions. The number of carbon atoms on the R
group and the value of the integer k are interrelated in that if the
number of carbon atoms on the R group is increased, then it is
preferable that the value of the integer k be correspondingly
increased to preserve the solubility of the detergent compound.
Typically, when R is a C12-C14 alkyl group, k will be in the range
of from about 1 to about 4, when R is a C12-C1g alkyl group, k will
be in the range of from about 1 to about 6, and when R is a Cg-C12
alkyl group, k will be in the range of from 0 to about 3.
7 ~ 2 7 8 ~
The alkyl ethoxy carboxylate component of the present invention may
be prepare by methods known in the art. One preferred method is
disclosed in Cripe, Canadian Patent No. 2,012,171.
The alkyl ethoxy carboxylate component of the present invention may
comprise a distribution of alkyl ethoxy carboxylates. When the
composition of the present invention does comprise such a distribution,
the ethoxylate distribution will be such that, on a weight basis, the
amount of material where k is 0 is less than about 20%, preferably less
than about 15%, most preferably less than about 10%, and the amount of
material where k is greater than 7 is less than about 25%, preferably less
than about 15%, most preferably less than about 10%. The average k will
fall in the range of from 1 to 4 when the average R is C13 or less, and the
average k will fall in the range of from 2 to 6 when the average R is
greater than Cl3. Such a distribution, and its preparation, is described
in greater detail in Canadian Patent No. 2,012,172. When the compositions
of the present invention are comprised of a distribution of ethoxy
carboxylates, the desired distribution of carboxylates may be derived by
reacting a corresponding distribution of ethoxylated alcohol precursors.
It has been found that the presence of divalent cations with the
alkyl ethoxy carboxylates in the compositions of the present invention
greatly improves the cleansing of greasy soils. This is especially true
when the composition is used in74 softened water that contains few
divalent ions. It is believed that divalent ions increase the packing of
the alkyl ethoxy carboxylates at the oil/water interface, thereby
producing reduced interfacial tension and improved grease cleaning.
However, liquid detergent compositions used in dishwashing applications
which contain alkyl ethoxy carboxylates and which do not conform to the
narrow definition of this invention will benefit less from the addition of
divalent ions and, in many cases, will actually exhibit reduced cleaning
performance upon the addition of divalent cations.
- 8 - ~ 8 ~
~hen included in the compositions of the present invention, the
divalent ions are preferably added as a chloride, sulfate salt, or a
hydroxide, most preferably the chloride salt, to compositions cor,-
taining alkali metal or ammonium salts of the alkyl ethoxy carboxyl-
ates, most pre~erably sodium or potassium salts, after the composi-
tion has been neutralized with a strong base. The concentration of
divalent ion is typically in the range of from 0% to about 1.5%,
preferably from about 0.2% to about 1%, most preferably from about
0.3% to about 0.8~/. by weight. Magnesium and calcium ions are
particularly preferred divalent ions.
Depending upon the preparation method utilized to prepare the
alkyl ethoxy carboxylate component of the present invention, and the
method of preparation of the compositions of the present invention,
such compositions may also contain from O~~. to about 5.0%, preferably
less than 4.0%~ more preferably less than 2.5% by weight of alcohol
ethoxylates of the formula
R O(CH2CH2O)WH (II)
wherein R is a C12-C16 alkyl group and w is in the range of from 0
to about 10, with the average w being less than 6.
The uncarboxylated alcohol ethoxylates of structure (II) are a
detriment to the alkyl ethoxy carboxylate-containing compositions of
the present invention. Therefore, it is critical that such composi-
tions contain no more than about 5.0% by weight of the alcohol
ethoxylates from which the alkyl ethoxy carboxylates are derived.
Although commercially available alkyl ethoxy carboxylates contain
10% or more of alcohol ethoxylates, there are known routes to obtain
the desired high purity alkyl ethoxy carboxylates. For example,
unreacted alcohol ethoxylates can be removed by steam distillation,
U.S. Pat. No. 4,098,818 (Example I), or by recrystallization of the
alkyl ethoxy carboxylate, British Pat. No. 1,027,481 (Example I).
Other routes to the desired carboxylates are the reaction of sodium
hydroxide or sodium metal and monochloracetic acid, or its salt,
with alcohol ethoxylates under special pressure and temperature
conditions, as described in U.S. Pat. Nos. 3,992,443 and 4,098,818;
and Japanese Patent Application No. 50-24215.
~ ~,
g - ~ ~ g ~ ~ 8 ~
Other routes to high purity alkyl ethoxy carboxylates are disclosed
in Canadian patent No. 2,012,172, already referred to herein.
Pol~hydrox~ Fatty Acid Amide ComPOnent
The surfactant mixture of the present invention further com-
prises from about 5% to about 95% by weight, preferably from about
20% to about 80~/. by weight, more preferably from about 20% to about
60% by weight of one or more polyhydroxy fatty acid amides having
the formula
O Rl
(I) R2 - C - N - Z
wherein: Rl is H, Cl-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, preferably Cl-C4 alkyl, more prefer-
ably C1 or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2
is a Cs-C3l hydrocarbyl, preferably straight chain C7-Clg alkyl or
alkenyl, more preferably straight chain Cg-Cl7 alkyl or alkenyl,
most preferably straight chain Cll-Cl7 alkyl or alkenyl, or mixture
thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydro-
carbyl chain with at least 3 hydroxyls directly connected to the
chain, or an anhydro derivative derived by dehydration of such
polyhydroxyhydrocarbyl, 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 corn syrup can be utilized as well as the
individual sugars listed above. These corn syrups may yield a mix
of sugar components for Z. It should be understood that it is by no
means intended to exclude other suitable raw materials. Z prefer-
ably will be selected from the group consisting of -CH2-(CHOH)n-
CH20H, -CH(CH20H)-(CHOH)n l-CH20H, -CH2-(CHOH)2(CHOR")(CHOH)-CH20H,
where n is an integer from 3 to 5, inclusive, and R" is H or a
cyclic or aliphatic monosaccharide, and alkoxylated derivatives
thereof. Most preferred are glycityls wherein n is 4.
In Formula (I), Rl can be, for exa~ple, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy
propyl.
"
- 10 ~ g~
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.
The most preferred polyhydroxy fatty acid amide has the generalformula
O CH3
R2 - C - N - CH2 - (CHOH)4 - CH2OH
wherein R2 js a straight-chain C11-C17 alkyl or alkenyl group.
Methods for making polyhydroxy fatty acid amides are known in
the art. In general, they can be made by reacting an alkyl amine
with a reducing sugar in a reductive amination reaction to form a
corresponding N-alkyl polyhydroxyamine, and then reacting the
N-alkyl polyhydroxyamine with a fatty aliphatic ester or triglycer-
ide in a condensation/amidation step to form the N-alkyl, N-
polyhydroxy fatty acid amide product. Processes for making composi-
tions 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 2,965,576,
issued December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798,
Anthony M. Schwartz, issued March 8, 1955, and U.S. 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-
hydroxy-propyl, 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 presence
of a catalyst selected from the group consisting of trilithium
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,
WO 92/06157 ~ 0 9 2 1 8 ~ PCI/US91/06983
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 X to about 50 mole %, more preferably
from about 2.0 mole % to about 10 mole 7O7 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
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
polyethoxylates, alkylpolyglucosides, linear glucamide 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 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 section entitled
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-
petrochemical feedstocks and are degradable. They also exhibit low
toxicity to aquatic life.
It should be recognized that along with the polyhydroxy fatty
- 35 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
WO 92/06157 PCI/US91/06983
2092185 - 12-
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-con-
taining composition added to the detergent contains less than about
2%, preferably less than about 0.5%, of cyclic polyhydroxy fatty
acid amide. The preferred processes described above are advanta-
geous in that they can yield rather low levels of by-products,
including such cyclic amide by-product.
ODtional Inqredients
Liauid Carrier
In a preferred embodiment, the detergent compositions of the
present invention are liquid detergent compositions. These pre-
ferred liquid detergent compositions comprise from about 95% to
about 35% by weight, preferably from about 90% to about 50% by
weight, most preferably from about 80% to about 60% by weight of a
liquid carrier, e.g., water, preferably a mixture of water and a
C1-C4 monohydric alcohol (e.g., ethanol, propanol, isopropanol,
butanol, and mixtures thereof), with ethanol being the preferred
alcohol.
20 comDos i tion DH
The liquid 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 8 and about 10, more
preferably between about 8.5 and about 9.5. Liquid product formula-
25 tions of the present invention are prepared at a pH in the range offrom about 7.0 to about 11 . 0, preferably from about 8.5 to about
10.5, more preferably from about 8.8 to about 10Ø The liquid
detergent compositions may be adjusted to these pH levels using
methods known to those skilled in the art, for example by adding a
base to the compositions. Traditionally, liquid dishwashing compo-
sitions have a pH of about 7. It has been found that when in the
form of a liquid detergent, the compositions of the present inven-
tion exhibit greatly improved grease cleaning if formulated at an
alkaline pH, as compared to a pH of below 7. This cleaning benefit
3s appears to be unique to liquid detergent compositions containing the
present alkyl ethoxy carboxylate component. Surprisingly, the
compositions of this invention are still very mild to the hand at
this alkaline pH.
- 13 -
It is desirable to include a buffering agent in order to
prepare liquid detergent compositions having enhanced pH stability.
Examples of typical buffering agents include, but are not neces-
sarily limited to, glycine (preferred), N,N-bis(2-hydroxyethyl)gly-
cine (preferred), tris(hydroxymethyl)aminomethane, triethanolamine,monoethanolamine, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-
1,3-propanediol, N-methyl diethanol amine, 1,3-diamino-2-hydroxy-
propane, and mixtures thereof. When included in the liquid composi-
tions prepared in accordance with the present invention, such
buffering agents are typically present at a level of from about 0.1%
to about 15~o by weight, preferably from about 1% to about 7% by
weight, most preferably from about 1.5~. to about 5% by weight.
Thickeninq Aqent
The detergent compositions of the present invention may also be
in the form of a gel. Such compositions are typically formulated in
the same manner as liquid detergent compositions, except they
contain an additional thickening agent.
Any material or materials which can be admixed with the aqueous
liquid to provide shear-thinning compositions having sufficient
yield values can be used in the compositions of this invention.
Materials such as colloidal silica, particulate polymers, such as
polystyrene and oxidized polystyrene, combinations of certain
surfactants, and water-soluble polymers such as polyacrylate are
known to provide yield values.
A preferred thickening agent useful in the compositions of the
present invention is a high molecular weight polycarboxylate polymer
thickener. By "high molecular weight" it is meant from about
500,000 to about 5,000,000, preferably from about 750,000 to about
4,000,000.
The polycarboxylate polymer may be a carboxyvinyl polymer. Such
compounds are disclosed in U.S. Patent 2 798 053.
A carboxyvinyl polymer is an interpolymer of a monomeric
mixture comprising a monomeric olefinicall~ unsaturated carboxylic
acid, and from about 0.1% to about 10% by weight of the total
monomers of a polyether of a polyhydric alcohol, which polyhydric
W O 92/06157 PCT/US91/06983
2092185 - 14 -
alcohol contains at least four carbon atoms to which are attached at
least three hydroxyl groups, the polyether containing more than one
alkenyl group per molecule. Other monoolefinic monomeric materials
may be present in the monomeric mixture if desired, even in predomi-
nant proportion. Carboxyvinyl polymers are substantially insoluble
in liquid, volatile organic hydrocarbons and are dimensionally
stable on exposure to air.
Preferred polyhydric alcohols used to produce carboxyvinyl
polymers include polyols selected from the class consisting of
oligosaccharides, reduced derivatives thereof in which the carbonyl
group is converted to an alcohol group, and pentaerythritol; more
preferred are oligosaccharides, most preferred is sucrose. It is
preferred that the hydroxyl groups of the polyol which are modified
be etherified with allyl groups, the polyol having at least two
allyl ether groups per polyol molecule. When the polyol is sucrose,
it is preferred that the sucrose have at least about five allyl
ether groups per sucrose molecule. It is preferred that the poly-
ether of the polyol comprise from about 0.1% to about 4% of the
total monomers, more preferably from about 0.2% to about 2.5%.
Preferred monomeric olefinically unsaturated carboxylic acids
for use in producing carboxyvinyl polymers used herein include
monomeric, polymerizable, alpha-beta monoolefinically unsaturated
lower aliphatic carboxylic acids; more preferred are monomeric
monoolefinic acrylic acids of the structure
R
CH2 = C - COOH
wherein R is a substituent selected from the group consisting of
hydrogen and lower alkyl groups; most preferred is acrylic acid.
Carboxyvinyl polymers useful in formulations of the present
invention have a molecular weight of at least about 750,000. Pre-
ferred are highly cross-linked carboxyvinyl polymers having a
molecular weight of at least about 1,250,000. Also preferred are
carboxyvinyl polymers having a molecular weight of at least about
3,000,000, which may be less highly cross-linked.
Various carboxyvinyl polymers are commercially available from
B. F. Goodrich Company, New York, N.Y., under the trade name
Carbopol. Carboxyvinyl polymers useful in formulations of the
present invention include Carbopol 910 having a molecular weight of
W O 92/06157 PC~r/US91/06983 - 15 - ~0~21 ~
about 750,000; preferred is Carbopol 941 having a molecular weight
of about 1,250,000, and more preferred are Carbopols 934 and 940
having molecular weights of about 3,000,000 and 4,000,000,
- respectively.
s Carbopol 934 is a very slightly cross-linked carboxyvinyl
polymer having a molecular weight of about 3,000,000. It has been
described as a high molecular weight polyacrylic acid cross-linked
with about 1% of polyallyl sucrose having an average of about 5.8
allyl groups for each molecule of sucrose.
Additional polycarboxylate polymers useful in the present
invention are Sokolan PHC-25R, a polyacrylic acid available from
BASF Corp., and GantrezR a poly(methyl vinyl ether/maleic acid)
interpolymer available from GAF Corp.
Preferred polycarboxylate polymers of the present invention are
non-linear, water-dispersible, polyacrylic acid cross-linked with a
polyalkenyl polyether and having a molecular weight of from about
750,000 to about 4,000,000.
Highly preferred examples of these polycarboxylate polymer
thickeners are the Carbopol 600 series resins available from B. F.
Goodrich. Especially preferred are Carbopol 616 and 617. It is
believed that these resins are more highly cross-linked than the 900
series resins and have molecular weights between about 1,000,000 and
4,000,000. Mixtures of polycarboxylate polymers as herein described
may also be used in the present invention. Particularly preferred
is a mixture of Carbopol 616 and 617 series resins.
The polycarboxylate polymer thickener is utilized preferably
with essentially no clay thickening agents. In fact, it has been
found that if the polycarboxylate polymers of the present invention
are utilized with clay in the composition of the present invention,
a less desirable product, in terms of phase instability, results.
In other words, the polycarboxylate polymer is preferably used
instead of clay as a thickening/stabilizing agent in the present
compositions.
The polycarboxylate polymer also provides a reduction in what
is commonly called "bottle hang-up". This term refers to the
inability to dispense all of the dishwashing detergent product from
its container. Without intending to be bound by theory, it is
believed that the thickened compositions of the present invention
WO 92/06157 PCI/US91/06983
209218~ - 16 -
provide this benefit because the force of cohesion of the composi-
tion is greater than the force of adhesion to the container wall.
With clay thickener systems, which most commercially available
products contain, bottle hang-up can be a significant problem under
certain conditions.
Without intending to be bound by theory, it is also believed
that the long chain molecules of the polycarboxylate polymer thick-
ener help suspend solids in the thickened detergent compositions of
the present invention and help keep the matrix expanded. The
polymeric material is also less sensitive than clay thickeners to
destruction due to repeated shearing, such as occurs when the
composition is vigorously mixed.
If the polycarboxylate polymer is used as a thickening agent in
the compositions of the present invention, it is typically present
at a level of from about 0.1% to about 10%, preferably from about
0.2% to about 2% by weight.
The thickening agents are used to provide a yield value of from
about 50 to about 350 and most preferably from about 75 to about
250.
Yield Value AnalYsis
The yield value is an indication of the shear stress at which
the gel strength is exceeded and flow is initiated. It is measured
herein with a Brookfield RVT model viscometer with a T-bar B spindle
at 25~C utilizing a Helipath drive upward during associated read-
ings. The system is set to 0.5 rpm and a reading is taken for thecompositicn to be tested after 30 seconds or after the system is
stable. The system is stopped and the rpm is reset to 1.0 rpm. A
reading is taken for the same composition after 30 seconds or after
the system is stable. Stress at zero shear is equal to two times
the 0.5 rpm reading minus the reading at 1.0 rpm. The yield value
is calculated as the stress at zero shear times 18.8 (conversion
factor).
Other Surfactants
Other surfactants, such as anionic, nonionic, ampholytic and
zwitterionic surfactants may also be incorporated into the detergent
compositions of the present invention.
WO 92/06157 PCI/US91/06983
- 17- 209218S
Anionic Surfactants
One type of anionic surfactant which can be utilized encom-
passes alkyl ester sulfonates. Alkyl ester sulfonate surfactants
hereof include linear esters of Cg-C20 carboxylic acids (i.e., fatty
5 acids) which are sulfonated with gaseous S03 according to "The
Journal of the American Oil Chemists Society," 52 (1975J, pp.
323-329. Suitable starting materials would include natural fatty
substances as derived from tallow, palm oil, 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
503M
15 wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or combina-
tion 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 monoethanol-
amine, diethanolamine, and triethanolamine. Preferably, R3 is
C14-C16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially
preferred are the methyl ester sulfonates wherein R3 is C14-C16
alkyl.
25 AlkYl Sulfate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts or
acids of the formula ROS03M wherein R preferably is a Clo-C24
hydrocarbyl, preferably an alkyl or hvdroxyalkyl having a Clo-C20
alkyl component, more preferably a Cl~-Clg 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 tetramethylammonium and dimethyl piper-
dinium cations and quaternary ammonium cations derived from alkyla-
mines such as ethylamine, diethylamine, triethylamine, and mixturesthereof, and the like). Typically, alkyl chains of C12 16 are
preferred for lower wash temperatures (e.g., below about 50~C) and
W O 92/06157 PC~r/US91/06983
2092185 - 18 -
C14 18 alkyl chains are preferred for higher wash temperatures
(e.g., above about 50-C).
AlkYl AlkoxYlated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mSO3M wherein R is an unsubsti-
tuted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C24 alkyl
component, preferably a C12-C20 alkyl or hydroxyalkyl, more prefer-
ably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit,
m is greater than zero, typically between about 0.5 and about 6,
more preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperdinium cations and those
derived from alkylamines such as ethylamine, diethylamine, triethyl-
amine, mixtures thereof, and the like. Exemplary surfactants are
Cl2-cl8 alkyl polyethoxylate (1-0) sulfate (C12-c18E(l-0)M)~ C12-C18
alkyl polyethoxylate (2.25) sulfate (C12-ClgE(2.25)M), C12-Clg alkyl
polyethoxylate (3.0) sulfate (C12-ClgE(3.0)M), and C12-Clg alkyl
polyethoxylate (4.0) sulfate (C12-ClgE(4.0)M), wherein M is con-
veniently selected from sodium and potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive purposes can
also be included in the compositions hereof. These can include
salts (including, -for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine
salts) of soap, Cg-C20 linear alkylbenzenesulfonates, Cg-C22 primary
or secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed
product of alkaline earth metal citrates, e.g., as described in
British patent specification No. 1,082,179, Cg-C24 alkylpolyglycol-
ethersulfates (containing up to 10 moles of ethylene oxide); alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin sulfonates, alkyl phosphates, isethionates such as the acyl
- 19 -
isethionates, acyl taurates, fatty acid amides of methyl tauride, alkyl
succinamates and sulfosuccinates, monoesters of sulfosuccinates
(especially saturated and unsaturated C12-C18 monoesters), diesters of
sulfosuccinates (especially saturated and unsaturated C6-Cl2diesters), acyl
sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
below), Cg-Cl7 acyl-N-(Cl-C4 alkyl) or -N-(C2-C4 hydroxyalkyl) glucamine
sulfates, branched primary alkyl sulfates, 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 Detergents" (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.
Nonionic Deterqent Surfactants
Suitable nonionic detergent surfactants are generally disclosed in
U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at
Column 13, line 14 through Column 16, line 6. Exemplary, non-limiting
classes of useful nonionic surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
condensates are preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from 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 bout 25
moles of ethylene oxide per mole of alkyl phenol. Commercially available
nonionic surfactants of this type include IgepalTM C0-630, marketed by the
GAF Corporation; and TritonTM X-45, X-114, X-100, and X-102, all marketed
by the Rohm & Haas Company.
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of the
WO 92/06157 PCT/US91/06983
209~ 20-
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 10 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 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
distributionJ, both marketed by Union Carbide Corporation; NeodolTM
45-9 (the condensation product of C14-Cls 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
20 The Procter & Gamble Company.
3. The condensation products of ethylene oxide with a hydro-
phobic 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
25 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 prod-
uct, which corresponds to condensation with up to about 40 moles ofethylene 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
35 product resulting from the reaction of propylene oxide and ethylene-
diamine. 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.
WO 92/06157 PCr/US91/06983
- 2l -2~9~
This hydrophobic moiety is condensed with ethylene oxide to the
extent that the condensation product contains from about 40% to
about 80% by weight of polyoxyethylene and has a molecular weight of
from about 5,000 to about 11,000. Examples of this type of nonionic
surfactant include certain of the commercially available 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 consist-
ing of alkyl and hydroxyalkyl moieties of from ab~ut 1 to about 3
carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
o
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-Clg
alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl
amine oxides.
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group con-
taining from about 6 to about 30 carbon atoms, preferably from about
W O 92/06157 ~ 0 9 21~ ~ - 22 - P ~ /US91/06983
10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglyco-
side, 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 galacto-
syl moieties can be substituted for the glucosyl moieties. (Option-
ally the hydrophobic group is attached at the 2-, 3-, 4-, etc.
positions thus giving a glucose or galactose as opposed to a gluco-
side 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 unsatu-
rated, 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 polyalkyl-
eneoxide 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(91YC~sYl )x
wherein R2 is selected from the group consisting of alkyl, alkyl-
phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in
which the alkyl groups contain from about 10 to about 18, preferably
from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2;
t is from O to about 10, preferably O; and x is from about 1.3 to
about 10, preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived from
glucose. To prepare these compounds, the alcohol or alkylpolyethoxy
alcohol is formed first and then reacted with glucose, or a source
- 23 - ~ $ ~
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:
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 C8-C20 ammonia amides, monoethanolamides,
diethanolamides, and isopropanolamides.
AmPholYtic 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 8 carbon atoms, typically
from 8 to 18 carbon atoms, and at least one contains an anionic
water-solubilizing group, e.g., carboxy, sulfonate, sulfate. See
U.S. Patent No. 3,92g,678 to Laughlin et al., issued December 30,
1975 at column 19 lines 18-35 for examples of ampholytic surfactants.
Zwitterionic 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, deriva-
tives 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 l9, 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.
- 24 -
Preferred additional surfactants are anionic and nonionic
surfactants, with Cll27 alkyl ester sulfonates, C822 primary and secondary
alkane sulfonates, Cl0l8 alkyl dimethyl amine oxides, alkylpolysaccharides,
and mixtures thereof being most preferred.
If included in the compositions of the present invention, these
optional additional surfactants are typically present at a concentration
of from about 1.0% to about 10%, preferably from about 2% to about 5% by
weight.
Other Optional In~redients
Other optional ingredients include detergency builders, either of
the organic or inorganic type, although such builders in general are not
preferred for use in the composition of the present invention. Examples
of water-soluble inorganic builders which can be used, either alone or in
admixture with themselves or with organic alkaline sequestrant builder
salts, are glycine, alkyl and alkenyl succinates, alkali metal carbonates,
phosphates, polyphosphates, and silicates. Specific examples of such
salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate,
sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate,
and sodium hexametaphosphate. Examples of organic builder salts which can
be used alone, or in admixture with each other, or with the preceding
inorganic alkaline builder salts, are alkali metal polycarboxylates,
examples of which include, but are not limited to, water-soluble citrates
such as sodium and potassium citrate, sodium and potassium tartrate,
sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-
(2-hydroxyethyl)-ethylene diamine triacetates, sodium and potassium
nitrilo triacetates, sodium and potassium N-(2-hydroxy- ethyl)-nitrilo
diacetates, sodium and potassium oxydisuccinates, and sodium and potassium
tartrate mono- and disuccinates, such as those described in U.S. Patent
4,663,071 (Bush et al., issued May 5, 1987). Other organic detergency
builders, such as water-soluble phosphonates, can be used in the
compositions of the present invention. However, detergency builders in
general have limited value when the compositions of the present invention
are in the form of light-duty liquid dishwashing detergent compositions.
If included in the compositions of the present invention, these optional
,~ ,
- 25 -
builders are typically present at a concentration of from about 1.0% to
about 10%, preferably from about 2% to about 5% by weight.
Other desirable ingredients include diluents, solvents, dyes,
perfumes and hydrotropes (preferred). Diluents can be inorganic salts, such
as sodium and potassium sulfate, ammonium chloride, sodium and potassium
chloride, sodium bicarbonate, etc. Diluents useful in the compositions of
the present invention are typically present at levels of from about 1% to
about 10%, preferably from about 2% to about 5% by weight.
Solvents useful herein include water and lower molecular weight
alcohols, such as ethyl alcohol, isopropyl alcohol, etc. Solvents useful
in the compositions of the present invention are typically present at levels
of from about 1% to about 60%, preferably from about 5% to about 50% by
weight.
Hydrotropes such as sodium and potassium toluene sulfonate, sodium
and potassium xylene sulfonate, sodium and potassium cumene sulfonate,
trisodium and tripotassium sulfosuccinate, and related compounds (as
disclosed in U.S. Patent 3,915,903) can be utilized in the interests of
achieving a desired product phase stability and viscosity. It has been
found that the hydrotropes can have a positive effect on the suds benefit
of the present invention. While not intending to be bound by theory, it is
believed that this benefit is due to the viscosity characteristics of such
hydrotropes. Hydrotropes useful in the compositions of the present
invention are typically present at a level of from about 1% to about 10% by
weight, preferably from about 2% to about 5% by weight.
The claimed compositions of the present invention are beneficial in
that they provide unexpected improved sudsing performance when the
particular polyhydroxy fatty acid amide is combined with the alkyl ethoxy
carboxylate. While not intending to be bound by theory, it is believed that
the compositions of the present invention offer the additional benefits of
improved cleaning performance and are mild to the skin, even when formulated
as a liquid and having a high alkaline pH. Again, while not intending to
be bound by theory, it is further believed that an additional benefit of the
compositions of the present invention is that they clean dishes without
imparting a "greasy" feel to the finish product. This is
wog2/O61572o9~l8S PCI/US91/06983
- 26 -
especially important in consumer markets where the cleanliness of a
dish is judged by the lack of such a "greasy" feel. Additionally,
it is believed that the compositions of the present invention offer
the further benefit of a reduced "slippery" feel typically associ-
ated with detergent compositions. This is especially important inconsumer markets where such a feeling is not favored and is viewed
as incomplete rinsing of surfactants from the dish surface.
In the method aspect of this invention, soiled dishes are con-
tacted with an effective amount, typically from about 0.5 ml. to
about 20 ml. (per 25 dishes being treated), preferably from about 3
ml. to about 10 ml., of the composition of the present invention.
The actual amount of liquid detergent composition used will be based
on the judgement of user, and will typically depend upon factors
such as the particular product formulation of the composition,
including the concentration of active ingredient in the composition,
the number of soiled dishes to be cleaned, the degree of soiling on
the dishes, and the like. The particular product formulation, in
turn, will depend upon a number of factors, such as the intended
market (i.e., U.S., Europe, Japan, etc.) for the composition prod-
uct. The following are examples of typical methods in which the
detergent compositions of the present invention may be used to clean
soiled dishes. These examples are for illustrative purposes and are
not intended to be limiting.
In a typical U.S. application, from about 3 ml. to about 15
ml., preferably from about 5 ml. to about 10 ml. of a liquid deter-
gent composition is combined with from about 1,000 ml. to about
10,000 ml., more typically from about 3,000 ml. to about 5,000 ml.
of water in a sink having a volumetric capacity in the range of from
about S,000 ml. to about 20,000 ml., more typically from about
10,000 ml. to about 15,000 ml. The detergent composition has a
surfactant mixture concentration of from about 21% to about 44% by
weight, preferably from about 25% to about 40% by weight. The
soiled dishes are immersed in the sink containing the detergent
composition and water, where they are cleaned by contacting the
soiled surface of the dish with a cloth, sponge, or similar article.
The cloth, sponge, or similar article may be immersed in the deter-
gent composition and water mixture prior to being contacted with the
dish surface, and is typically contacted with the dish surface for a
W O 92/06157 PC~r/US91/06983 2032~5
- 27 -
period of time ranging from about 1 to about 10 seconds, although
the actual time will vary with each application and user. The
contacting of the cloth, sponge, or similar article to the dish
surface is preferably accompanied by a concurrent scrubbing of the
dish surface.
In a typical European market application, from about 3 ml. to
about 15 ml. preferably from about 3 ml. to about 10 ml. of a liquid
detergent composition is combined with from about 1,000 ml. to about
10,000 ml., preferably from about 3,000 ml. to about 5,000 ml. of
water in a sink having a volumetric capacity in the range of from
about 5,000 ml. to about 20,000 ml., more typically from about
10,000 ml. to about 15,000 ml. The detergent composition has a
surfactant mixture concentration of from about 21% to about 44% by
weight, preferably from about 25% to about 35% by weight. The
soiled dishes are immersed in the sink containing the detergent
composition and water, where they are cleaned by contacting the
soiled surface of the dish with a cloth, sponge, or similar article.
The cloth, sponge, or similar article may be immersed in the deter-
gent composition and water mixture prior to being contacted with the
dish surface, and is typically contacted with the dish surface for a
period of time ranging from about 1 to about 10 seconds, although
the actual time will vary with each application and user. The
contacting of the cloth, sponge, or similar article to the dish
surface is preferably accompanied by a concurrent scrubbing of the
dish surface.
In a typical Latin American and Japanese market application,
from about 1 ml. to about 50 ml., preferably from about 2 ml. to
about 10 ml. of a composition is combined with from about 50 ml. to
about 2,000 ml., more typically from about 100 ml. to about 1,000
ml. of water in a bowl having a volumetric capacity in the range of
from about 500 ml. to about 5,000 ml., more typically from about 500
ml. to about 2,000 ml. The detergent composition has a surfactant
mixture concentration of from about 5% to about 40% by weight,
preferably from about 10% to about 30% by weight. The soiled dishes
are cleaned by contacting the soiled surface of the dish with a
cloth, sponge, or similar article. The cloth, sponge, or similar
article may be immersed in the detergent composition and water
mixture prior to being contacted with the dish surface, and is
W O 92/06157 ~ t ~ 5 - 28 - PCT/US91/06983
typical~y~- eo~t~ ~ 5d with the dish surface for a period of time
ranging from about 1 to about 10 seconds, although the actual time
will vary with each application and user. The contacting of the
cloth, sponge, or similar article to the dish surface is preferably
accompanied by a concurrent scrubbing of the dish surface.
Another method of use will comprise immersing the soiled dishes
into a water bath which is absent any liquid dishwashing detergent.
A device for absorbing liquid dishwashing detergent, such as a
sponge, is placed directly into a separate quantity of undiluted
liquid dishwashing composition for a period of time typically
ranging from about 1 to about 5 seconds. The absorbing device, and
consequently the undiluted liquid dishwashing composition, is then
contacted individually to the surface of each of the soiled dishes
to remove said soiling. The absorbing device is typically contacted
with each dish surface for a period of time range from about 1 to
about 10 seconds, although the actual time of application will be
dependent upon factors such as the degree of soiling of the dish.
The contacting of the absorbing device to the dish surface is
preferably accompanied by concurrent scrubbing.
EXPERIMENTAL
This exemplifies a process for making a N-methyl, 1-deoxy-
glucityl lauramide surfactant for use herein. Although a skilled
chemist can vary apparatus configuration, one suitable apparatus for
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 is important 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 ("Variac")
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 (195 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
W o 92/06157 P ~ /US91/06983
- 29 - ~ 0 9 2 1 ~ ~
under a nitrogen sweep to form a melt ~(approximately 25 minutes).
~hen 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 give 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
The following examples illustrate the practice of the present
invention, but are not intended to be limiting thereof.
EXAMPLE I
The following three formulations A, B and C of the present
invention are prepared according to the description set forth below:
Formulation A is made by initially combining an alkyl ethoxy
carboxylate detergent mixture with a C12 14 fatty acid N-methyl
glucamide to form a mixture. Ethanol, sodium chloride and sodium
xylene sulfonate are then added to this mixture. Any desired
remaining surfactants are then added. Glycine is added and the pH
is adjusted to about 9.0 with sodium hydroxide. Finally, magnesium
chloride is added, which reduces the pH accordingly. Final viscos-
ity and pH adjustments can be made at this time, followed by the
addition of perfume and dye. The balance is water.
Formulation B is made by adding ethanol, sodium chloride and
sodium xylene sulfonate to an alkyl ethoxy carboxylate deter-
gent/polyhydroxy fatty acid amide mixture of the type prepared in
w 0 92/06157 P ~ /US91/06983
209218S - 30 -
Formulation A. The remaining formula components are added in the
order given in the table below.
Formulation C is made by adding ethanol, sodium chloride and
sodium xylene sulfonate to an alkyl ethoxy carboxylate deter-
gent/polyhydroxy fatty acid amide mixture of the type prepared inFormulation A. C12 14 monoethanol amide is warmed to about 65~C and
is then added to the mixture. Minor pH and viscosity adjustments
are made at this time, followed by the addition of dye, perfume and
water to bring the formulation to 100%.
% BY Weiqht
Formulation Formulation Formulation
COMPONENT A B
Sodium C12-13 alkyl ethoxy
(2.8 ave.) carboxylate* 20.0 20.0 15.0
C12 14 fatty acid N-methyl
glucamide 5.0 5.0 5.0
Clo alkyl ethoxy alcohol -- -- 5.0
Sodium C12 13 alkyl ethoxy
(0.8 ave.) sulfate 3.0 -- --
Sodium C12 14 fatty acid
~-sulfonate methyl ester -- 4.0 --
Sodium C12 13 alkyl ethoxy
(3.0 ave.) sulfate -- -- 4.0
C12-14 alkyl dimethyl betaine 3.0 --
C12 14 alkyl dimethyl
amine oxide 3.0 5.0 5.0
C12 14 fatty acid mono-
ethanol amide -- -- 4.0
Magnesium ion 0.76 0.76 0.76
(added as MgC12.6H20)
Glycine 4.0 -- --
Trisodium sulfosuccinate 2.0 2.2 2.0
Ethanol 7.5 7.0 7 o
Sodium chloride 1.5 <1 2.25
Product pH 9.0 9.0 9.0
Perfume and dye 0.15 0.15 0.15
Water Balance Balance Balance
-
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- 31 -
*The surfactant mixture containing sodium alkyl ethoxy car-
boxylate is prepared according to the process outlined below:
1. A C12 13 alkyl ethoxy (3.0 ave.) alcohol is reacted with
potassium t-butoxide and sodium chloroacetate in the ratio of
1:1.1:1.1 by first mixing the alkyl ethoxylate with the potas-
sium t-butoxide at about 60~C and about 20 mm Hg pressure for
about 1 hour. Thereafter, t-butanol is continuously removed
from the reaction mixture by distillation. The vacuum is then
broken and sodium chloroacetate is added with mixing. The
pressure is reestablished at about 18-20 mm Hg, and the reac-
tion is allowed to continue for about 3 hours. Afterwards, the
reaction pressure is brought to atmospheric level with nitro-
gen, and the steam heating coils are turned off. The reaction
mixture is left in this state overnight. The next day the
reaction mixture temperature is increased and the pressure
reduced to remove more t-butanol from the system. The reaction
mixture is then added to an aqueous solution of hydrochloric
acid containing 105% of the theoretical amount needed to
neutralize the potassium t-butoxide initially added. The acid
aqueous reaction product is heated to force phase separation of
the organic and aqueous materials. The organic phase is
collected.
2. Step 1 above is repeated using a C12 13 alkyl ethoxy (2.7 ave.)
alcohol and a ratio of this ethoxy alcohol to potassium t-
butoxide and sodium chloroacetate of 1:1.3:1.3. The potassium
t-butoxide is added to the alkyl ethoxylate, which is at a
temperature of about 32.2~C, and the reaction mixture is then
increased to about 76.7~C. The vacuum pump is then turned on
to achieve reduced pressure. The reaction temperature is
increased to about 104.4~C, and the t-butanol is pulled off and
collected over about a 30 minute period. The sodium chloro-
acetate is then added to the reaction mixture, which has been
cooled slightly to about 66~C. The reaction is mixed for about
1.5 hours, cooled, and added to an aqueous solution of suffi-
cient hydrochloric acid to achieve a pH of 3.4. Water is added
to increase the volume of the reaction mixture by about 50%,
and the mixture is then heated to about 49~C. The top organic
layer is collected, and the washing process is repeated.
WO 92/06157 PCI/US91/06983
3. The ~ Q ~ac~tan~ mixtures produced in Steps 1 and 2 above are
mixed at a ratio of 40.4 to 59.6. A portion of this larger
combined surfactant mixture is neutralized with 50% sodium
hydroxide to a pH of about 8 and diluted by about 50% with a
25/75 by volume mixture of water and ethanol. The resulting
solution is continuously extracted at room temperature with
hexanes for about four days. The lower aqueous phase is
collected, and some ethanol and water is removed by heating to
yield a paste containing the alkyl ethoxy carboxylate contain-
ing surfactant mixture described below.
In the above formulations of Example I, the surfactant portion
contains about 93.9% alkyl ethoxy carboxylates of the formula
RO(CH2CH20)xCH2COO~Na+, wherein R is a C12 13 alkyl averaging 12.5,
x ranges from O to about 10, and the ethoxylate distribution is such
that the amount of material where x is O is about 2.8% and the
amount of material where x is greater than 7 is less than about 2%
by weight of the alkyl ethoxy carboxylates. The average x in the
distribution is 2.8. The surfactant mixture also contains about
6.1% of alcohol ethoxylates of the formula RO(CH2CH20)xH with R
being a Cl2-l3 alkyl averaging 12.5 and the average x = 2.8. The
surfactant mixture contains 0% soap materials.
EXAMPLE II
The following three formulations C, D and E of the present
invention are prepared in the same manner as the formulations of
Example I:
(% By Weight)
COMPONENT C D E- E H
Sodium C12-13 alkyl ethoxy
(2.8 ave.) carboxylate* 15.0 20.0 15.0 10.0 12.0 8.0
C12 14 alkyl N-methyl
glucamide 5.0 5.0 5.0 10.0 10.0 10.0
C1o alkyl ethoxy (8 ave.)
alcohol 5.0 -- 5.0 -- 5.0 --
Sodium C12 13 alkyl ethoxy
(0.8 ave.) sulfate 3.0 -- -- 10.0 --
Sodium C12 14 fatty acid
~-sulfonate methyl ester -- 4.0 -~ 10.0
W O 92/06157 230 P~r/US91/06983
Sodium C12 13 alkyl ethoxy
(3.0 ave.) sulfate -- -- 4.0 -- --
C12 14 alkyl dimethyl
betaine 4.0 -- -- 3.0 -- --C14 16 alkyl dimethyl
betaine -- 5.0 -- -- 3.0 --C12 14 fatty acid di-
ethanol amide -- -- -- 1.0 -- 1.0
C12 14 fatty acid mono-
ethanol amide -- -- 4.0 -- -- 1.0
Magnesium ion 0.76 0.76 0.76 0.3 0.5 0.5
(added as MgCl2.6H20)
Glycine 4.0 -- -- -- -- --
N,N-bis(2-hydroxyethyl)-
glycine -- -- -- 5.0 3.0 --Methyldiethanolamine -- -- -- -- 10.0 --
Cocoamidopropyldimethyl
betaine -- -- 3.0 -- -- 3.0
C12 14 dimethyl amine oxide -- -- -- -- -- 3.0
Trisodium sulfosuccinate 2.0 2.2 2.0 -- -- --
Ethanol 7.5 7.0 7.0 5.0 5.0 5.0
Sodium chloride 1.5 c1 2.25 -- -- --
Product pH 9.0 9.0 9.0 9.0 8.0 8.0
Perfume and dye 0.15 0.15 0.15 0.15 0.15 0.15
Monoethanolamine -- -- -- 5.0 5.0 --
Triethanolamine -- -- -- 5.0 -- 4.0
Water --- balance to 100% ---
*The surfactant mixture containing sodium alkyl ethoxy carboxylate
is prepared according to the process disclosed in Example I.
EXAMPLE I r I
An alternate method for preparing the polyhydroxy fatty acid
amides used herein is as follows. A reaction mixture consisting of
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
W O 92/06157 2 0 9 218 ~ 34 PCT/US91/06983
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 fact, 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 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 insta-
bility 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
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 composit on. 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
WO92/06157 ~~~ 2~ 8~ PCI/US91/06983
- 35 -
as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate,
tartrate/succinate, and the like, can be used similarly.
The polyhydroxy fatty acid amides derived from coconut alkyl
fatty acids (predominantly C12-Cl4) are more soluble than their
5 tallow alkyl (predominantly C16-C18) counterparts. Accordingly, the
C12-C14 materials are somewhat easier to formulate in liquid compo-
sitions, and are more soluble in cool-water laundering baths.
However, the Cl6-C18 materials are also quite useful, especially
under circumstances where warm-to-hot wash water is used. Indeed,
the C16-Cl8 materials may be better detersive surfactants than their
Cl2-Cl4 counterparts. Accordingly, the formulator may wish to
balance ease-of-manufacture vs. performance when selecting a partic-
ular polyhydroxy fatty acid amide for use in a given formulation.
It will also be appreciated that the solubility of the poly-
hydroxy fatty acid amides can be increased by having points of
unsaturation 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 function especially well as deter-
gents when used in combination with conventional alkylbenzene
sulfonate ("LASn) surfactants. While 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
maltose causes a substantial and unexpected lowering of interfacial
tension in aqueous media, thereby enhancing net detergency perfor-
mance. (The manufa.ture 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
W O 92/06157 ~ 0 Y ~ 1 8 5 - 36 - P~r/US91/06983
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
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 25% 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
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 to 90-C, preferably
about 50-C-80-C. It has now been determined that it may be conve-
nient 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
W O 92/06157 37 ? 0 ~ 2 l 8 5 P~r/US91/06983
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 (EO 3-8) C12-C1~ 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:
SteD 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 SteD 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 that, for best results when using such syrup raw
materials, the manufacturer- should select syrups that are quite
light in color or, preferably, nearly colorless ("water-white").
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
231 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
temperature of about 10~-20-C. The corn syrup is added slowly to
the MMA solution at the indicated reaction temperature as shown.
W o 92/06157 ~ 0 9 2 1 8 5 - 38 - P~r/USsl/06983
The Gardner Color is measured at the indicated approximate times in
minutes.
TABLE 1
Time in Minutes: 10 30 60 120 180 240
5Reaction TemD. ~C Gardner Color (ADProximate)
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 the same conditions, the time is at least about
three hours. For good color, the combination of amine:sugar ratio;
reaction temperature; and reaction time is selected to achieve
substantially equilibrium conversion, e.g., more than about 90%,
preferably more than about 95%, even more preferably more than about
99%, based upon the sugar, and a color that is less than about 7,
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 indi-
cated, the MMA adduct color (after substantial equilibrium is
reached in at least about two hours) is as indicated.
TABLE 2
Gardner Color (Approximate)
Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2
W O 92/06157 PCT/US91/06983
39 2 ~ 3 2 1 8 5
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. HYdroqen 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 i~ 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
pumped into the reactor which is at 200 psig and 20-C, and the
reactor is purged with 200 psig H2, 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 140CC 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%J and a good color
(less than about 7, preferably less than about 4 Gardner, more
preferably less than about 1).
WO 92/061~7 PCI'/US91/06983
2~9218~) 40-
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 g of about 55% glucose (corn syrup) solution (231 9
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 9 MMA; 1.92 moles) (from Air
Products).
The reaction procedure is as follows:
1. Add about 119 9 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.
W O 92/06157 PC~r/US91/06983
~09218S
- 41 -
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 degrada-
tion.
The glucamine adduct hydrogen reactions are as follows:
1. Add about 134 9 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 g 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.
S. 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.)
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 IV
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.
W O 92/06157 ~ i 8 ~ - 42 - P~r/US91/06983
SteD 1 - Reactants: Maltose monohydrate (Aldrich, lot
01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 50% 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
SO-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 l); hardened
tallow methyl esters; sodium methoxide (25% in methanol); absolute
methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst
level 10 mole X (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
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 9 of N-methyl maltamine is combined with 45.36 9 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 % of catalyst (to a total of 20 mole %) is added
~ o 92/06157 PCT/USsl/06983
- 43 - ~ ~9218~
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
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.
WO 92/06157 PCI'/US91/06983
- 44 -
2Q92185 EXAMPLE V
In any of the foregoing examples of detergent compositions, the
fatty acid glucamide surfactant can be replaced by an equivalent
amount of the maltamide surfactant, or mixtures of glucamide/malt-
amide surfactants derived from plant sugar sources. In the composi-
tions the use of ethanolamides appears to help cold temperature
stability of the finished formulations. Moreover, the use of
sulfobetaine (aka "sultaine") surfactants provides superior sudsing.
CaCl2 can be used (ca. 1%) in the formulations to enhance greasy
soil removal from dishes. MgCl2 enhances sudsing.
Since the present invention provides especially high sudsing
compositions, it is preferred that less than about 5%, more prefer-
ably less than about 2%, most preferably substantially no C14 or
higher fatty acids be present, since these can suppress sudsing.
Accordingly, 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 amides, and/or avoid the formation of C14 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 such as cocoamidopropyl hydroxysultaine and
betaines such as cocoamidopropyl betaine 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.
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.
