Note: Descriptions are shown in the official language in which they were submitted.
2~2~57
W o 92/061501 P ~ /VS91/07026
DETERGENT COMPOSITIONS CONTAINING POLYHYDROXY
FATTY ACID AMIDE AND ALKYL BENZENE SULFONATE
5FIELD OF INVENTION
This invention pertains to low sudsing detergent compositions
containing alkyl benzene sulfonate and polyhydroxy fatty acid amide
surfactants.
lG
BACKGROUND OF THE INVENTION
1~The ability of detergent compositions to clean a large variety
of soils and stains from the numerous types of fabrics present in
the typical load of laundry, as well as cleaning of other surfaces
(e.g., hard surfaces, hair, etc.) is of high importance in the
evaluation of detergent performance. One type of surfactant which
has been of value due to its good overall cleaning ability,
particularly its excellent grease/oil cleaning performance over a
wide temperature range (including relatively low temperatures)
encompasses the linear alkylbenzene sulfonates (nLAS"). Whereas
LAS-containing surfactant systems have performed admirably,
particularly in the area of grease/oil cleaning, alkyl sulfates,
alkyl ethoxylated sulfates, alkyl ethoxylates, and other surfactants
have commonly been added to enhance detergency over a wider range of
soils and stains (e.g., particulate soil).
It has now been found that laundry detersive surfactant systems
comprising a combination of alkyl benzene sulfonate surfactant and
certain polyhydroxy fatty acid amides can provide excellent cleaning
performance over a wide variety of soils and stains and, quite
significantly, can provide even improved cleaning of grease/oil
stains (e.g., motor oil, lipstick and cosmetics, shoe polish, etc.).
Furthermore, the polyhydroxy fatty acid amides can be derived mainly
or entirely from natural, renewable, non-petroleum raw materials.
~ ~ ~ 2 5 S ~ - 2 - PCI/US91/07026
BACKGROUND ART
A variety of polyhydroxy fatty acid amides have been described
in the art. 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
has been of substantial interest recently for use in biochemistry,
for example in the dissociation of biological membranes. See, for
example, the journal article ~N-D-Gluco-N-methyl-alkanamide
Compounds, a New Class of Non-Ionic Detergents For Membrane
Biochemistry," Biochem. J. (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
constituents to impart desirable properties to the composition can
also be included in the compositions, such as fluorescent dyes,
bleaching agents, perfumes, etc.
U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz,
relates to aqueous detergent compositions containing the
condensation reaction product of N-alkyl glucamine and an aliphatic
ester of a fatty acid. The product of this reaction is said to be
useable in aqueous detergent compositions without further
purification. It is also known to prepare a sulfuric ester of
acylated glucamine as disclosed in U.S. Patent 2,717,894, issued
September 13, 1955, to A. M. Schwartz.
w o 92/06150 _Q3~ ~ 5 7 PCT/US91/07026
PCT International Application WO 83/04412, published December
22, 1983, by J. Hildreth, relates to amphiphilic compounds
containing polyhydroxyl aliphatic groups said to be useful for a
variety of purposes including use as surfactants in cosmetics,
drugs, shampoos, lotions, and eye ointments, as emulsifiers and
dispensing agents for medicines, and in biochemistry for
solub;lizing membranes, whole cells, or other tissue samples, and
for preparation of liposomes. Included in this disclosure are
compounds of the formula R'CON(R)CH2R" and R"CON(R)R' wherein R is
hydrogen or an organic grouping, R' is an aliphatic hydrocarbon
group of at least three carbon atoms, and R" is the residue of an
aldose.
European Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty
acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a
C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C1g
(preferably C1-C6) alkyl, or an alkylene oxide, and X is a
polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl,
coconut fatty acid glucamide. The thickening properties of the
amides are indicated as being of particular use in liquid surfactant
systems containing paraffin sulfonate, although the aqueous
surfactant systems can contain other anionic surfactants, such as
alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half
ester salts, and fatty alcohol ether sulfonates, and nonionic
surfactants such as fatty alcohol polyglycol ether, alkylphenol
polyglycol ether, fatty acid polyglycol ester, polypropylene
oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/N-
n,ethyl coconut fatty acid glucamide/nonionic surfactant shampoo
formulations are exemplified. In addition to thickening attri-
butes, the N-polyhydroxy alkyl fatty acid amides are said to have
superior skin tolerance attributes.
U.S. Patent 2,982,737, issued Mzy 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.
WO 92/06150 PCT/US91/07026
20~25~ - 4 -
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-acylpolyhydroxyalkyl-amine of the formula RlC(O)N(R2)CH2(CHOH)n-
CH20H, wherein Rl is a Cl-C3 alkyl, R2 is a Clo-C22 alkyl, and n is
3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a soil sus-
pending agent.
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert,
et al., relates to detergent compositions comprising at least one
surfactant selected from the group of anionic, zwitterionic, and
nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl
polyhydroxylalkyl compound of the formula RlN(Z)C(O)R2 wherein Rl is
a 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-
CH20H where m is 3 or 4.
U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, et
al., relates to skin treating cosmetic compositions containing
N-polyhydroxylalkyl-amines which include compounds of the formula
RlN(R)CH(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 CH20H or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial
Solvents Corporation, relates to solutions of formaldehyde
stabilized against polymerization with the addition of amides of the
formula RC(O)N(Rl)G wherein R is a carboxylic acid functionality
having at least seven carbon atoms, Rl is hydrogen or a lower alkyl
group, and G is a glycitol radical with at least 5 carbon atoms.
German Patent 1,261,861, February 29, 1968, A. Heins, relates
to glucamine derivatives useful as wetting and dispersing agents of
the formula N(R)(Rl)(R2) wherein R is a sugar residue of glucamine,
Rl is a Clo-c2o alkyl radical, and R2 is a Cl-Cs acyl radical.
G.B. Patent 745,036, published February 15, 1956, assigned to
35 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
WO 92/06150 2 0 ~ ~ 5 ~ 7 PCI/US91/07026
- 5 -
N(R)(R1)C(O)R2 wherein R is the residue of an anhydrized hexane
pentol or a carboxylic acid ester thereof, R1 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
RC(O)NR1(R2) wherein RC(O) contains from about 10 to about 14 carbon
atoms, and Rl and R2 each are H or C1-C6 alkyl groups, said alkyl
groups containing a total number of carbon atoms of from 2 to about
7 and a total number of substituent hydroxyl groups of from 2 to
about 6. A substantially similar disclosure is found in U.S. Patent
3,312,626, also issued April 4, 1967 to D. T. Hooker.
SUMMARY OF THE INVENTION
In one aspect of this invention, provided is a low sudsing
laundry detergent composition comprising:
(a) at least about 1%, by weight, polyhydroxy fatty acid amide
surfactant of the formula:
O Rl
R2 - C - N - Z
wherein Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, or
2-hydroxy propyl, R2 is Cs-C31 hydrocarbyl, and Z is
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly connected to said
chain, or alkoxylated derivatives thereof;
(b) at least about 1%, by weight, alkyl benzene sulfonate
surfactant; and
(c) optionally, but most preferably, a suds suppressing amount
of a suds suppressor, preferably selected from the group
consisting of monocarboxylic fatty acids and salts
thereof, silicone suds suppressors, hydrocarbon suds
suppressors, and monostearyl phosphates such as mono-
stearyl di-alkali metal phosphates and phosphate esters,
and mixtures thereof;
W O 92/061~0 ~ P~r/US91/07026
wherein said composition is characterized by a polyhydroxy fatty
acid amide:alkyl benzene sulfonate weight ratio of from about 10:1
to about 1:10 . Preferably Rl is methyl, R2 is Cg-C17 hydrocarbyl,
and Z is glycityl derived from a reducing sugar, and the polyhydroxy
fatty acid amide: alkyl benzene sulfonate ratio is from about 5:1
to about 1:5, more preferably from about 2:1 to about 1:3.
The inclusion of a suds suppressor can be of importance in
formulating detergent compositions with alkyl benzene sulfonates and
the polyhydroxy fatty acid amides hereof because such surfactant
combination often results in an excessive level of suds, which
adversely affects cleaning performance in washing machines.
In another aspect of this invention, provided are detergent
compositions comprising polyhydroxy fatty acid amide and alkyl
benzene sulfonate surfactants, as described above, and further
comprising an auxiliary surfactant component selected from the group
consisting of alkyl sulfates, alkyl ethoxylated sulfates, alkyl
ethoxylates, and alkyl polyglycosides, and mixtures thereof. These
compositions will typically comprise from about 1% to about 25%, by
weight, of such auxiliary surfactant. In these compositions, the
polyhydroxy fatty acid:alkyl benzene sulfonate weight ratio is from
about 10:1 to about 1:10, preferably from about 5:1 to about 1:5,
more preferably from about 2:1 to about 1:3. The alkyl benzene
sulfonate to such auxiliary surfactant weight ratio is preferably
from about 5:1 to about 1:5, more preferably from about 4:1 to about
1:1. Also preferably, the alkyl ethoxylated sulfate has a degree of
ethoxylation of from about 0.5 to about 3.0, more preferably from
about 1.0 to about 3Ø
Other auxiliary surfactants may additionally be present in the
detergent compositions hereof, as well as optional detergent
adjuncts and other ingredients known in the art or otherwise
desirable for inclusion in detergent compositions.
This invention further provides a method for cleaning
substrates, such as fibers, fabrics, hard surfaces, etc., by
contacting said substrate, with a detergent composition comprising
alkyl benzene sulfonate surfactant and the polyhydroxy fatty acid
amides hereof, wherein the weight ratio of alkyl benzene sulfonate
to polyhydroxy fatty acid amide is from about 1:10 to about 10:1, in
the presence of water or water-miscible solvent (e.g., primary and
WO 92/06150 2 ~ ; 7 PCI/US91/07026
secondary alcohols). Agitation is preferably provided for enhancing
cleaning. Suitable means for providing agitation include rubbing by
hand preferably with the aid of a brush, or other cleaning device,
automatic laundry washing machines, automatic dishwashers, etc.
Surprisingly, at the high wash temperature hereof, significantly
improved cleaning performance, especially grease/oil cleaning, can
be obtained.
In the above method, the more preferred surfactant weight
ratios, as discussed herein, as well as suds suppressors, preferred,
or other optional auxiliary surfactants, and other detergent
adjuncts, can be utilized.
DETAILED DESCRIPTION OF THE INVENTION
PolyhYdroxY Fattv Acid Amide Surfactant
The compositions hereof will comprise at least about 1%,
typically from about 3% to about 50%, preferably from about 3% to
about 30%, of the polyhydroxy fatty acid amide surfactant described
below.
The polyhydroxy fatty acid amide surfactant component of the
present invention comprises compounds of the structural formula:
o R1
(I) R2 C - N - Z
wherein: Rl is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, preferably C1-C4 alkyl, more
preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e., methyl);
and R2 is a Cs-C31 hydrocarbyl, preferably straight chain C7-C1g
alkyl or alkenyl, more preferably straight chain Cg-C17 alkyl or
alkenyl, most preferably straight chain C11-C17 alkyl or alkenyl, or
mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear
hydrocarbyl chain with at least 3 hydroxyls directly connected to
the chain, or an alkoxylated derivative (preferably ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing
sugar in a reductive amination reaction; more preferably Z 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
- 8 20q2 5 57
other suitable raw materials. Z preferably will be selected from
the group consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n l-
CH20H, -cH2-(cHoH)2(cHoRl)(cHoH)-cH2oH~ where n is an integer from 3
to 5, inclusive, and R' is H or a cyclic or aliphatic monosacchar-
ide, and alkoxylated derivatives thereof. Most preferred areglycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
In Formula (I), R1 can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy
propyl.
R2-C0-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.
Methods for making polyhydroxy fatty acid amides are kno,Yn 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-polyhy-
droxy fatty acid amide product. Processes for making compositions
containing polyhydroxy fatty acid amides are disclosed, for example,
in G.B. Patent Specification 809,060, published February 18, 1959,
by ~homas 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 i5
derived from glucose and the N-alkyl or N-hydroxyalkyl functionality
is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or
N-hydroxypropyl, the product is made by reacting N-alkyl- or
N-hydroxyalkyl-glucamine with a fatty ester selected from fatty
methyl esters, fatty ethyl esters, and fatty triglycerides in the
presence of a catalyst selected from the group consisting o-~ tri-
lithium phosphate, trisodium phosphate, tripotassium phosphate,
~,
W O 92/06150 2 ~ D 2 5 ~ 7 PC~r/US91/07026
tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium
hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide,
lithium carbonate, sodium carbonate, potassium carbonate, disodium
tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium
citrate, tripotassium citrate, sodium basic silicates, potassium
basic silicates, sodium basic aluminosilicates, and potassium basic
aluminosilicates, and mixtures thereof. The amount of catalyst is
preferably from about 0.5 mole % to about 50 mole X, more preferably
from about 2.0 mole % to about 10 mole %, on an N-alkyl or
N-hydroxyalkyl-glucamine molar basis. The reaction is preferably
carried out at from about 138-C to about 170-C for typically from
about 20 to about 90 minutes. When triglycerides are utilized in
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
lS phase transfer agent, calculated on a weight percent basis of total
reaction mixture, selected from saturated fatty alcohol polyethoxy-
lates, alkylpolyglycosides, linear glycamide surfactant, and mix-
tures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138-C to about 170-C;
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the
heated fatty acid ester and mixing to the extent needed to
form a two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and
(d) stirring for the specified reaction time.
Also preferably, from about 2% to about 20% of preformed linear
N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide product
is added to the reaction mixture, by weight of the reactants, as the
phase transfer agent if the fatty ester is a triglyceride. This
seeds the reaction, thereby increasing reaction rate. A detailed
experimental procedure is provided below in the Experimental.
The polyhydroxy "fatty acid" amide materials used herein also
offer the advantages to the detergent formulator that they can be
prepared wholly or primarily from natural, renewable, non-petro-
chemical feedstocks and are degradable. They also exhibit low
toxicity to aquatic life.
WO 92/061!~9 PCI'/US91/07026
~og25~7 - lo-
It should be recognized that along with the polyhydroxy fatty
acid amides of Formula (I), the processes used to produce them will
also typically produce quantities of nonvolatile by-product such as
esteramides and cyclic polyhydroxy fatty acid amide. The level of
these by-products will vary depending upon the particular reactants
and process conditions. Preferably, the polyhydroxy fatty acid
amide incorporated into the detergent compositions hereof will be
provided in a form such that the polyhydroxy fatty acid amide-
containing composition added to the detergent contains less than
about 10%, preferably less than about 4%, of cyclic polyhydroxy
fatty acid amide. The preferred processes described herein are
advantageous in that they can yield rather low levels of
by-products, including such cyclic amide by-product.
AlkYl Benzene Sulfonate
The alkyl benzene sulfonate surfactants hereof are well known
in the art. These surfactants have Cg and higher alkyl groups,
preferably the alkyl groups are Cg-C1g alkyl groups, more preferably
linear, to provide the linear alkyl benzene sulfonate (nLASn) class
of commerical surfactants. Especially preferrred are C1o-C14 LAS
surfactant. These surfactants can be used in either the acid or
soluble salt form, with the soluble salt form being preferred.
Suitable salts include metal salts (e.g., sodium, potasssium, and
lithium) as well as substituted and unsubstituted ammonium salts
(e.g., ethanolamines).
The compositions hereof will typically comprise at least about
1%, by weight, alkyl benzene sulfonate, preferably from about 3% to
about 50%, more preferably from about 5% to about 30%.
Suds SuPDressors
The suds suppressors hereof are compounds known, or which
become known, for reducing or suppressing the formation of suds in
detergent compositions. The incorporation of such suds suppressors
can be desirable because the polyhydroxy fatty acid amide
surfactants hereof can increase suds stability of the detergent
compositions. Suds suppression can be of particular importance when
the detergent compositions include a relatively high sudsing
surfactant in combination with the polyhydroxy fatty acid amide
surfactant. Suds suppression is particularly desirable for
compositions intended for use in front loading automatic washing
- 11 2 092 5 5 7
machines. These machines are typically characterized by having
drums, for containing the laundry and wash water, which have a
horizontal axis and rotary action about the axis. This type of
agitation can result in high suds formation and, consequently, in
reduced cleaning performance. The use of suds suppressors is of
particular importance under higher temperature washing conditions
(e.g., above about 50-C) and under high surfactant concentration
conditions (e.g., from about 1000 to about 3500 ppm).
A wide variety of materials may be used as suds suppressors in
the compositions hereof. Suds suppressors are well known to those
skilled in the art They are generally described, for example, in
Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,
Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One
category of suds suppressor of particular interest encompasses
monocarboxylic fatty acids and soluble salts thereof. These materials are
discussed in U.S. Patent 2 954,347, issued September 27, 1960 to Wayne
St. John. The monocarboxylic fatty acids, and salts thereof, for
use as suds suppressor typically have hydrocarbyl chains of 10 to
about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable
salts include the alkali metal salts such as sodium, potassium, and
lithium salts, and ammonium and alkanolammonium salts. These
materials are a preferred category of suds suppressor for detergent
compositions.
The detergent compositions may also contain non-surfactant suds
suppressors. These include, for example, list: high molecular
weight hydrocarbons such as paraffin and haloparaffin, fatty acid
esters (e.g., fatty acid triglycerides), fatty acid esters of
monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
Other suds suppressors include N-alkylated amino triazines such as
tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine
chlortriazines formed as products of cyanuric chloride with two or
three moles of a primary or secondary amine containing 1 to 24
carbon atoms, propylene oxide, and monostearyl phosphates such as
monostearyl di-alkali metal (e.g., Na, K, Li) phosphates and
phosphate esters (e.g., monostearyl alcohol phosphate esters). The
hydrocarbons such as paraffin and haloparaffin can be utilized in
liquid form. The liquid hydrocarbons will be liquid at room
- 12 20 92 5 5 7
temperature and atmospheric pressure, and will have a pour point in the
range of about -40~C and about 5~C, and a minimum boiling point not less
than about 110~C (atmospheric pressure). It is also known to utilize waxy
hydrocarbons, preferably having a melting point below about 100~C. The
hydrocarbons constitute a preferred category of suds suppressor for
detergent compositions. Hydrocarbon suds suppressors are described, for
example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo, et al.
The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and
heterocyclic saturated or unsaturated hydrocarbons having from about 12
to about 70 carbon atoms. The term "paraffin," as used in this suds
suppressor discussion, is intended to include mixtures of true paraffins
and cyclic hydrocarbons.
Another preferred category of non-surfactant suds comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or
emulsions of polyorganosiloxane oils or resins, and combinations or
polyorganosiloxane with silica particles wherein the polyorganosiloxane
is chemisorbed of fused onto the silica. Silicone suds suppressors are
well known in the art and are, for example, disclosed in U.S. Patent
4,265,779, issued May 5, 1981 to Gandolfo et al. and EP 354016, published
February 7, 1990, by Starch, M.S.
Other silicone suds suppressors are disclosed in U.S. Patent
3,455,839 which relates to compositions and processes for defoaming
aqueous solutions by incorporating therein small amounts of
polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for
instance, in German Patent Application DOS 2,124,526. Silicone defoamers
and suds controlling agents in granular detergent compositions are
disclosed in U.S. patent 3,933,672, Bartolotta et al., and in U.S. Patent
4,652,392, Baginski et al., issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a
suds suppressing amount of a suds controlling agent consisting essentially
of:
'' 'B
WO 92/06150 2 ~ 9 2 5 5 ~ PCr/US91/07026
- 13 -
(i) polydimethylsiloxane fluid having a viscosity of from
about 20 cs. to about 1500 cs. at 25-C;
(ii) from about 5 to about 50 parts per 100 parts by weight of
(i) of siloxane resin composed of (CH3)3 SiO1/2 units of
SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to
SiO2 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight of
(i) of a solid silica gel;
For any detergent compositions to be used in automatic laundry
washing machines, suds should not form to the extent that they
overflow the washing machine. Suds suppressors, when utilized, are
preferably present in a "suds suppressing amount. R By "suds
suppressing amount" is meant that the formulator of the composition
can select an amount of this suds controlling agent that will
sufficiently control the suds to result in a low-sudsing laundry
detergent for use in automatic laundry washing machines. The amount
of suds control will vary with the detergent surfactants selected.
For example, with high sudsing surfactants, relatively more of the
suds controlling agent is used to achieve the desired suds control
than with lesser foaming surfactants. In general, a sufficient
amount of suds suppressor should be incorporated in low sudsing
detergent compositions so that the suds that form during the wash
cycle of the automatic washing machine (i.e., upon agitation of the
detergent in aqueous solution under the intended wash temperature
and concentration conditions) do not exceed about 75% of the void
volume of washing machine's containment drum, preferably the suds do
not exceed about 50X of said void volume, wherein-the void volume is
determined as the difference between total volume of the containment
drum and the volume of the water plus the laundry.
When utilized as suds suppressors, monocarboxylic fatty acids,
and salts thereof, will be present typically in amounts up to about
5%, by weight, of the detgerent composition. From about 5% to about
3~h of fatty monocarboxylate suds suppressor are typically utilized.
Silicone suds suppressors are typically utilized in amounts up to
about 2.0~o~ by weight, of the detergent composition, although higher
amounts may be used. This upper limit is practical in nature, due
primarly to concern with keeping costs minimized and effectiveness
of lower amounts for effectively controlling sudsing. Preferably
w o 92/06150 P ~ /US91/07026
~925~7 - 14 -
from about .0190 to about lX of silicone suds suppressor is used,
more preferably from about 0.25% to about 0.5%. As used herein,
these weight percentage values include any silica that may be
utilized in combination with polyorganosiloxane, as well as any
adjunct materials that may be utilized. Monostearyl phosphates are
generally utilized in amounts ranging from about 0.1% to about 2%,
by weight, of the composition. '
Hydrocarbon suds suppressors are typically utilized in amounts
ranging from about .01% to about 5.0%, although higher levels can
be used.
In another aspect of this invention, provided are detergent
compositions comprising polyhydroxy fatty acid amide and alkyl
benzene sulfonate surfactants, as described above, and further
comprising an auxiliary surfactant component selected from the group
consisting of alkyl sulfates, alkyl ethoxylated sulfates, alkyl
ethoxylates, and alkyl polyglycosides, and mixtures thereof. These
compositions will typically comprise from about 1% to about 25%, by
weight, auxiliary surfactant when such auxiliary surfactant is
included for detersive purposes. In these compositions, the
polyhydroxy fatty acid:alkyl benzene sulfonate weight ratio is from
about 10:1 to about 1:10, preferably from about 5:1 to about 1:5,
more preferably from about 2:1 to about 1:3. The auxiliary
surfactant of this embodiment is preferably present at a weight
ratio of polyhydroxy fatty acid amide to said auxiliary surfactant
ranging from about 10:1 to about 1:10, preferably from about 5:1 to
about 1:5. When alkyl sulfate surfactant is the auxiliary
surfactant or when alkyl ethoxylated sulfate is the auxiliary
surfactant, or combinations thereof, the alkyl benzene sulfonate to
such auxiliary surfactant weight ratio is preferably from about 4:1
to about 1:1. Al so preferably, the alkyl ethoxylated sulfate has a
degree of ethoxylation of from about 0.5 to about 3.0, more
preferably from about 1.0 to about 3Ø C16-C1g alkyl sulfates are
preferred for formulations intended to be used at wash temperatures
above about 50-C.
Other auxiliary surfactants may additionally be present in the
detergent compositions hereof, as well as optional detergent
adjuncts and other ingredients known in the art or otherwise
desirable for inclusion in detergent compositions. Such additional
- 15 - 20 q25 5 7
auxiliary surfactants will typically be present in amounts ranging
from OX to about 25%, by weight, of the detergent composition, and
can be present in the absence of any of the preferred auxiliary
surfactants discussed above. Other common auxiliary surfactants
include, but are not limited to, alkyl phenol ethoxylates, paraffin
sulfonates, and alkyl ester sulfonates. Auxiliary surfactants are
discussed in more detail below.
Anionic AuxiliarY Surfactants
Anionic auxiliary surfactants useful for detersive purposes
include salts (including, for example, sodium, potassium, ammonium,
and substituted ammonium salts such as mono-, di- and triethanola-
mine salts) of soap, Cg-C22 primary or secondary alkanesulphonates,
Cg-C24 olefinsulphonates, sulphonated polycarboxylic acids prepared
by sulphonation of the pyrolyzed product of alkaline earth metal
citrates, e.g., as described in British patent specification No.
1,082,179, alkyl glycerol sulfonates, fatty acyl glycerol sulfon-
ates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide
ether sulfates, sulfonates, alkyl phosphates, isethionates such as
the acyl isethionates, N-acyl taurates, fatty acid amides of methyl
tauride, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated C12-C1g mono-
esters), diesters of sulfosuccinates (especially C6-C14 diesters),
N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the
sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
being described below), branched primary alkyl sulfates, alkyl
polyethoxy carboxylates such as those of the formula RO(CH2CH20)k-
CH2COO-M+ wherein R is a Cg-C22 alkyl, k is an integer from O to 10,
and M is a soluble salt-forming cation, and fatty acids esterified
with isethionic acid and neutralized with sodium hydroxide. Resin
acids and hydrogenated resin acids are also suitabie, 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 Colu~n 29,
line 23.
WO 92/06150 PCr/US91/07026
- 16 -
-
o~55~ Alkyl sulfate surfactants are preferred auxiliary surfactants.
They include water soluble salts or acids of the formula ROS03M
wherein R preferably is a Clo-C24 hydrocarbyl, preferably an alkyl
or hydroxyalkyl having a Clo-C20 alkyl component, more preferably a
C12-Clg alkyl or hydroxyalkyl, and M is H or a cation, e.g., an
alkali metal cation (e.g., sodium, potassium, lithium), substituted
or unsubstituted ammonium cations such as methyl-, dimethyl-, and
trimethyl ammonium cations and quaternary ammonium, e.g.,
tetramethyl-ammonium and dimethyl piperdinium, and cations derived
from alkanolamines such as ethanamine, diethanolamine, triethanol-
amine, and mixtures thereof, and the like. Alkyl chains of C16 18
are preferred for higher wash temperatures (above about 50-C)
hereof. Alkyl chains of C12-C16 are preferred for wash temperatures
of about 50-C and lower.
Alkyl alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M 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-Clg alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit,
m is greater than zero, typically between about 0.5 and about 6,
more preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein. The alkyl
ethoxylated sulfates are preferred. Specific examples of substi-
tuted ammonium cations include methyl-, dimethyl-, trimethyl-
ammonium cations and quaternary ammonium cations, such as
tetramethyl-ammonium, dimethyl piperdinium and cations derived from
alkanolamines, e.g. monoethanolamine, diethanolamine, and trietha-
nolamine, and mixtures thereof. Exemplary surfactants are C12-C18
alkyl polyethoxylate (1.0) sulfate, C12-Clg alkyl polyethoxylate
(2.25) sulfate, C12-Clg alkyl polyethoxylate (3.0) sulfate, and
C12-Clg alkyl polyethoxylate (4.0) sulfate, wherein M is conven-
iently selected from sodium and potassium.
Alkyl ester sulfonite surfactants hereof include linear estersof Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated
with gaseous S03 according to "The Journal of the American Oil
- 17 - 20~2557
- Chemists Society," 52 (1975), pp. 323-329. Suitable starting
materials would include natural fatty substances as derived from
tallow, palm, and coconut oils, etc.
The preferred alkyl ester sulfonate surfactant, especially for
laundry applications, comprise alkyl ester sulfonate surfactants of
the structural formula:
o
R3 - CH - C - oR4
S03M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl,
or combination thereof, and M is a cation which forms a water
soluble salt with the alkyl ester sulfonate. Suitable salt-forming
cations include metals such as sodium, potassium, and lithium, and
substituted or unsubstituted ammonium cations, such as methyl-,
dimethyl, -trimethyl, and quaternary ammonium cations, e.g.
tetramethyl-ammonium and dimethyl piperdinium, and cations derived
from alkanolamines, e.g. monoethanolamine, diethanolamine, and
triethanolamine. Preferably, R3 is C10-cl6 alkyl, and R4 is methyl,
ethyl or isopropyl. Especially preferred are the methyl ester
sulfonates wherein R3 is C14-C16 alkyl.
In addition to anionic surfactants, additional nonionic
surfactants and other surfactants can be included in the
compositions.
Nonionic AuxiliarY Deteraent 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 bel~w.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols (commonly referred to as alkylphenol
alkoxylates, e.g., alkylphenol ethoxylates). 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 aikylene
W O 92/06150 PC~r/US91/07026
2~ oxide. In a preferred embodiment, the ethylene oxide is present in
an amount equal to from about 5 to about 25 moles of ethylene oxide
per mole of alkyl phenol. Commercially available nonionic
surfactants of this type include IgepalTM C0-630, marketed by the
GAF Corporation; and TritonTM X-45, X-114, X-100, and X-102, all
marketed by the Rohm & Haas Company. These surfactants are referred
to as alkyl phenol alkoxylates (e.g., alkyl phenol ethoxylates).
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or
secondary, and generally contains from about 8 to about 22 carbon
atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from about 10 to about 20
carbon atoms with from about 2 to about 18 moles of ethylene oxide
per mole of alcohol. Examples of commercially available nonionic
surfactants of this type include TergitolTM 15-S-9 (the condensation
product of C11-C1s linear secondary alcohol with 9 moles ethylene
oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14
primary alcohol with 6 moles ethylene oxide with a narrow molecular
weight distribution), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s 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-C1s linear alcohol
with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation
product of C14-C1s linear alcohol with 4 moles of ethylene oxide),
marketed by Shell Chemical Company, and KyroTM EOB (the condensation
product of C13-C1s alcohol with 9 moles ethylene oxide), marketed by
The Procter & Gamble Company. These are nonionic surfactants are
commonly referred to as "alkyl ethoxylates~.
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with
propylene glycol. The hydrophobic portion of these compounds
preferably has a molecular weight of from about 1500 to about 1800
and exhibits water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the water
solubility of the molecule as a whole, and the liquid character of
the product is retained up to the point where the polyoxyethylene
20923!~7
W O 92/06150 PC~r/US91/07026
- 19 -
content is about 50% of the total weight of the condensation
product, which corresponds to condensation with up to about 40 moles
of ethylene oxide. Examples of compounds of this type include
certain of the commercially-available PluronicTM surfactants,
marketed by BASF.
4. The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products consists
of the reaction product of ethylenediamine and excess propylene
10 oxide, and generally has a molecular weight of from about 2500 to
about 3000. This hydrophobic moiety is condensed with ethylene
oxide to the extent that the condensation product contains from
about 40% to about 80~h by weight of polyoxyethylene and has a
molecular weight of from about 5,000 to about 11,000. Examples of
15 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
20 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
25 groups containing from about 1 to about 3 carbon atoms; and
water-soluble sulfoxides containing one alkyl moiety of from about
10 to about 18 carbon atoms and a moiety selected from the group
consisting of alkyl and hydroxyalkyl moieties of from about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
o
R3(oR4)xN(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
WO 92/06150 PCr/US91/07026
- 20 -
2 ~ 9 2 ~ S l 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-Cl8
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
containing from about 6 to about 30 carbon atoms, preferably from
about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group containing from about 1.3 to about
10, preferably from about 1.3 to about 3, most preferably from about
1.3 to about 2.7 saccharide units. Any reducing saccharide
containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose
and galactosyl moieties can be substituted for the glucosyl
moieties. (Optionally the hydrophobic group is attached at the 2-,
3-, 4-, etc. positions thus giving a glucose or galactose as opposed
to a glucoside or galactoside.) The intersaccharide bonds can be,
e.g., between the one position of the additional saccharide units
and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide
units.
Optionally, and less desirably, there can be a polyalkylene-
oxide chain joining the hydrophobic moiety and the polysaccharide
moiety. The preferred alkyleneoxide is ethylene oxide. Typical
hydrophobic groups include alkyl groups, either saturated or
unsaturated, branched or unbranched containing from about 8 to about
18, preferably from about 10 to about 16, carbon atoms. Preferably,
the alkyl group is a straight chain saturated alkyl group. The
alky1 group can contain up to about 3 hydroxy groups and/or the
polyalkyleneoxide chain can contain up to about 10, preferably less
than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are
octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and
hexaglucosides, galactosides, lactosides, glucoses, fructosides,
fructoses and/or galactoses. Suitable mixtures include coconut
alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl
tetra-, penta-, and hexaglucosides.
~92~57
WO 92/06150 PCI/US91/07026
- 21 -
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 0 to about 10, preferably 0; and x is from about 1.3 to
about 10, preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived from
glucose. To prepare these compounds, the alcohol or alkylpolyethoxy
alcohol is formed first and then reacted with glucose, or a source
of glucose, to form the glucoside (attachment at the l-position).
The additional glycosyl units can then be attached between their
l-position and the preceding glycosyl units 2-, 3-, 4- and/or
6-position, preferably predominately the 2-position.
7. Fatty acid amide surfactants having the formula:
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.
Cationic Surfactants
Cationic detersive surfactants can also be included as
auxiliary surfactant in detergent compositions of the present
invention. Cationic surfactants include the ammonium surfactants
such as alkyldimethylammonium halogenides, and those surfactants
having the formula:
[R2(oR3)y][R4(OR3)y]2R5N+X~
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to
about 18 carbon atoms in the alkyl chain, each R3 is selected from
the group consisting of -CH2CH2-, -CH2CH(CH3)~-, -CH2CH(CH2OH)-,
-CH2CH2CH2-, and mixtures thereof; each R4 is selected from the
group consisting of Cl-C4 alkyl, Cl-C4 hydroxyalkyl, benzyl, ring
structures formed by joining the two R4 groups, -CH2CHOH-CHOHCOR6-
CHOHCH2OH wherein R6 is any hexose or hexose polymer having a
~- - 22 - 20 92 5 5 7
molecular weight less than about 1000, and hydrogen when y is not 0; R5
is the same as R4 or is an alkyl chain wherein the total number of carbon
atoms of R2 plus Rs is not more than about 18; each y is from 0 to about
10 and the sum of the y values is from 0 to about 15; and X is any
compatible anion.
Other cationic surfactants useful herein are also described in U.S.
Patent 4,228,044, Cambre, issued October 14, 1980.
Other AuxiliarY Surfactants
Ampholytic surfactants can be incorporated into the detergent
compositions hereof. These surfactants can be broadly described as
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which the
aliphatic radical can be straight chain or branched. One of the aliphatic
substituents contains at least about 8 carbon atoms, typically from about
8 to about 18 carbon atoms, and at least one contains an anionic water-
solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent
No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19,
lines 18-35 for examples of ampholytic surfactants.
Zwitterionic surfactants can also be incorporated into the
detergent compositions hereof. These surfactants can be broadly described
as derivatives of secondary and tertiary amines, derivatives of
heterocyclic secondary and tertiary amines, or derivatives of quaternary
ammonium, quaternary phosphonium or tertiary sulfonium compounds. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued December 30, 1975 at
column 19, line 38 through column 22, line 48 for examples of zwitterionic
surfactants.
Ampholytic and zwitterionic surfactants are generally used in
combination with one or more anionic and/or nonionic surfactants.
Builders
Detergent compositions of the present invention can comprise
inorganic or organic detergent builders to assist in mineral hardness
control.
The level of builder can vary widely depending upon the end use of
the composition and its desired physical form. Liquid formulations
typically comprise at least about 1%, more typically
W o 92/06150 2 0 9 2 5 5 7 PCT/US9l/07026
- 23 -
from about 5% to about 50%, preferably about 5% to about 30Z, by
weight of detergent builder. Granular formulations typically
comprise at least about 1X, more typically from about 10X to about
80X, preferably from about 15X to about 50~/. by weight of the
detergent bu;lder. Lower or higher levels of builder, however, are
not meant to be excluded.
Inorganic detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium salts of polyphos-
phates (exemplified by the tripolyphosphates, pyrophosphates, and
glassy polymeric meta-phosphates), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na20 ratio in the range 1.6:1 to
3.2:1 and layered silicates, such as the layered sodium sili~ates
described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P.
Rieck. However, other silicates may also be useful such as for example
magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a
component of suds control s~ystems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and sesquicar-
bonate and mixtures thereof with ultra-fine calcium carbonate as
disclosed in German Patent Application No. 2,321,001 published on
NoYember 15, 1973.
Aluminosilicate builders are especially useful in the present
invention. Aluminosilicate builders are of great importance in most
currently marketed heavy duty granular detergent compositions, and
can also be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate builders include those having the
empirical formula:
MZ(zAlo2-ysio2)
wherein M is sodium, potassium, ammonium or substituted ammonium, z
is from aoout 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
~L~
- - 24 - ~0~2557
Preferred aluminosilicates are zeolite builders which have the
formula:
Naz[(Alo2)z (Sio2)y]-xH2o
wherein z and y are integers of at least 6, the molar ratio of z to
y is in the range from 1.0 to about 0.5, and x is an integer from
about 1~ to about 264.
Useful aluminosi1icate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous
in structure and can be naturally-occurring aluminosilicates or
synthetically derived. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 3,985,66g, Krummel,
et al., issued October 12, 1976. Preferred synthetic crystalline
aluminosilicate ion exchange materials useful herein are available under
the designations Zeolite A. Zeolite P (B), and Zeolite X. In an
especially preferred embodiment, the crystalline aluminosilicate ion
exchange material has formula:
Nal2[(A102)l2(SiO2)l23 ~XH20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Preferably, the aluminosilicate has
a particle size of about 0.1-10 microns in diameter.
Specific examples of polyphosphates are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta phosphate in which the
degree of polymerization ranges from about 6 to about 21, and salts
of phytic acid.
Examples of phosphonate builder salts are the water-soluble
salts of ethane 1-hydroxy-1, 1-diphosphonate particularly the sodium
and potassium salts, the water-soluble salts of methylene diphos-
phonic acid e.g. the trisodium and tripotassium salts and the
water-soluble salts of substituted methylene diphosphonic acids,
such as the trisodium and tripotassium ethylidene, isopyropylidene
benzylmethylidene and halo methylidene phosphonates. Phosphonate
builder salts of the aforementioned types are disclosed in U.S.
Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and
October 19, 1965, to Diehl; U.S. Patent No. 3,422,021 issued January
14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137
f~
- 25 - 20 9 25 57
issued September 3 1968, and January 14, 1969 to Quimby.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide variety
of polycarboxylate compounds. As used herein, ~polycarboxylate"
refers to compounds having a plurality of carboxylate groups,
preferably at least 3 carboxylates.
Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such
- as sodium, potassium, and lithium salts, especially sodium salts, or
ammonium and substituted ammonium (e.g., alkanolammonium) salts are
preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates. A
number of ether polycarboxylates have been disclosed for use as
detergent builders. Examples of useful ether polycarboxylates
include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287,
issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830,
issued January 18, 1972.
A specific type of ether polycarboxylates useful as builders in
the present invention also include those having the general formula:
CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or
a salt-forming cation. For example, if in the above general formula
A and B are both H, then the compound is oxydissuccinic acid and its
water-soluble salts. If A is OH and B is H, then the compound is
tartrate monosuccinic acid (TMS) and its water-soluble salts. If A
is H and B is -O-CH(COOX)-CH2(COOX), then the compound is tartrate
disuccinic acid (TDS) and its water-soluble salts. Mixtures of
these builders are especially preferred for use herein. Particu-
larly preferred are mixtures of TMS and TDS in a weight ratio of TMS
to TDS of from about 97:3 to about 20:80. These builders are
disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5,
1987.
- 26 - 20 ~ 25 57
-
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypoly-
carboxylates represented by the structure:
H0-[C(R)(COOM)-C(R)(C00M)-0]n-H
wherein M is hydrogen or a cation wherein the resultant salt is
water-soluble, preferably an alkali metal, ammo~ium or substituted
ammonium cation, n is from about 2 to about 15 (preferably n is from
about 2 to about 10, more preferably n averages from about 2 to
about 4) and each R is the same or different and selected from
hydrogen, Cl 4 alkyl or Cl 4 substituted alkyl (preferably R is
hydrogen).
Still other ether polycarboxylates include copolymers of maleic
anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy
benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic
acid.
Organic polycarboxylate builders also include the various
alkali metal, ammonium and substituted ammonium salts of polyacetic
acids. Examples of polyacetic acid builder salts are the sodium,
potassium, lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,
benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid,
and soluble salts thereof.
Citric builders, e.g., citric acid and soluble salts thereof,
is a polycarboxylate builder of particular importance for heavy duty
liquid detergent formulations, but can also be used in granular
compositions. Suitable salts include the metal salts such as
sodium, lithium, and potassium salts, as well as ammonium and
substituted ammonium salts.
Other carboxylate builders include the carboxylated carbohy-
drates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28,
1973.
Also suitable in the detergent compositions of the present
invention are the 3,3-dicarboxy-~-oxa-1,6-hexanedioates and the
- 27 - 2092557
related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January
28, 1986. Useful succinic acid builders include the Cs-C20 alkyl succinic
acids and salts thereof. A particularly preferred compound of this type
is dodecenylsuccinic acid. Alkyl succinic acids typically are of the
general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid,
where R is hydrocarbon, e.g., C1o-C20 alkyl or alkenyl, preferably C12-Cl6
or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone
substituents, all as described in the above-mentioned patents.
The succinate builders are preferably used in the form of their
water-soluble salts, including the sodium, potassium, ammonium and
alkanolammonium salts.
Specific examples of succinate builders include: laurylsuccinate,
myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),
2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred
builders of this group, and are described in European Patent Application
86200690.5/0,200,263, published November 5, 1986.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-
cyclohexanehexacarboxylate, cis-cyclopentane-tetracarboxylate, water-
soluble polyacrylates (these polyacrylates having molecular weights toabove about 2,000 can also be effectively utilized as dispersants), and
the copolymers of maleic anhydride with vinyl methyl ether or ethylene.
Other suitable polycarboxylates are the polyacetal carboxylates
disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13,
1979. These polyacetal carboxylates can be prepared by bringing together,
under polymerization conditions, an ester of glyoxylic acid and a
polymerization initiator. The resulting polyacetal carboxylate ester is
then attached to chemically stable end groups to stabilize the polyacetal
carboxylate against rapid depolymerization in alkaline solution, converted
to the corresponding salt, and added to a surfactant.
A
- 28 - 20~2557
Polycarboxylate builders are also disclosed in U.S. Patent
3,308,067, Diehl, issued March 7, 1967. Such materials include the water-
soluble salts of homo- and copolymers of aliphatic carboxylic acids such
as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic
acid, citraconic acid and methylenemalonic acid.
EnzYmes
Detersive enzymes can be included in the detergent formulations for
a variety of purposes including, for example, removal of protein-based,
carbohydrate-based, or triglyceride-based stains, or other soils or
stains, and for prevention of refugee dye. The enzymes to be incorporated
include, but are not limited to, proteases, amylases, lipases,
peroxidases, and cellulases, as well as mixtures thereof. They may be of
any suitable origin, such as vegetable, animal, bacterial, fungal and
yeast origin. However, their choice is governed by several factors such
as pH-activity and/or stability optima, thermostability, stability versus
active detergents, builders and so on. In this respect bacterial or
fungal enzymes are preferred, such as bacterial amylases and proteases,
and fungal cellulases.
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and B.licheniforms.
Another suitable protease is obtained from a strain of Bacillus, having
maximum activity throughout the pH range of 8-12, developed and sold by
Novo Industries A/S under the registered trade name Esperase3. The
preparation of this enzyme and analogous enzymes is described in British
patent specification No. 1,243,784 of Novo. Proteolytic enzymes suitable
for removing protein-based stains that are commercially available include
those sold under the trade names ALCALASETM and SAVINASETM by Novo
Industries A/S (Denmark) and MAXATASETM by International Bio-Synthetics,
Inc. (The Netherlands).
Of interest in the category of proteolytic enzymes, especially for
liquid detergent compositions, are enzymes referred to herein as Protease
A and Protease B. Protease A and methods for its preparation are
described in European Patent Application 130,756, published January 9,
1985. Protease B is a proteolytic enzyme which differs from Protease A
in that it has a leucine substituted for tyrosine in position 217 in
.~
-
- 29 - 2092557
its amino acid sequence. Methods for preparation of Protease B are also
disclosed in Bott et al., U.S. Patent 5,264,366.
Amylases include, for example, ~-amylases obtained from a special
strain of B.licheniforms, described in more detail in British patent
specification No. 1,296,839 (Novo). Amylolytic proteins include, for
example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTMTM,
Novo, Industries.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH optimum
of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent
4,435,307, Barbesgoard et al., issued March 6, 1984, which discloses
fungal cellulase produced from Humicola insolens. Suitable cellulases are
also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of
Humicola insolens (Humicola grisea var. thermoidea), particularly the
Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus
N or a cellulase 212-producing fungus belonging to the genus Aeromonas,
and cellulase extracted from the hepatopancreas of a marine mollusc
(Dolabella Auricula Solander).
Suitable lipase enzymes for detergent usage include those produced
by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri
ATCC 19.154, as disclosed in British Patent No. 1,372,034. Suitable
lipases include those which show a positive immunological cross-reaction
with the antibody of the 1ipase, produced by the microorganism Pseudomonas
f1uorescens IAM 1057. This lipase and a method for its purification have
been described in Japanese Patent Application No. 53-20487, laid open to
public inspection on February 24, 1978. This lipase is available from
Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase
P "Amano," hereinafter referred to as "Amano-P". Such lipases of the
present invention should show a positive immunological cross-reaction with
the Amano-P antibody,
1~
- 2092557
using the standard and well-known immunodiffusion procedure according to
Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These lipases,
and a method for their immunological cross-reaction with Amano-P, are also
described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987.
Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas
fragi FERM P 1339 (available under the trade name Amano-B), lipase ex
Psuedomonas nitroreducens var. 7ipo1yticum FERM P 1338 (available under
the trade name Amano-CES), lipases ex Chromobacter viscosum, e.g.
Chromobacter viscosum var. 1ipo1yticum NRRLB 3673, commercially available
from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum
lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas g1adio1i.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They
are used for "solution bleaching", i.e. to prevent transfer of dyes or
pigments removed from substrates during wash operations to other
substrates in the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase, ligninase, and
haloperoxidases such as chloro- and bromo-peroxidase. Peroxidase-
containing detergent compositions are disclosed, for example, in PCT
International Application WO 89/099813, published October 19, 1989, by O.
Kirk, assigned to Novo Industries A/S.
A wide range of enzyme materials and means for their incorporation
into synthetic detergent granules is also disclosed in U.S. Patent
3,553,139, issued January 5, 1971 to McCarty et al. Enzymes are further
disclosed in U.S. Patent No. 4,101. 457, Place et al., issued July 18,
1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985. Enzyme
materials useful for liquid detergent forumations, and their incorporation
into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et
al., issued April 14, 1981.
Enzymes are normally incorporated at levels sufficient to provide
up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg,
of active enzyme per gram of the composition.
- 31 - 20 9255 7
For granular detergents, the enzymes are preferably coated or
prilled with additives inert toward the enzymes to minimize dust formation
and improve storage stability. Techniques for accomplishing this are well
known in the art. In liquid formulations, an enzyme stabilization system
is preferably utilized. Enzyme stabilization techniques for aqueous
detergent compositions are well known in the art. For example, one
technique for enzyme stabilization in aqueous solutions involves the use
of free calcium ions from sources such as calcium acetate, calcium
formate, and calcium propionate. Calcium ions can be used in combination
with short chain carboxylic acid salts, preferably formates. See, for
example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1982. It
has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-
alcohols, dialkylglycolethers, mixtures of polyvalent alcohols with
polyfunctional aliphatic amines (such as diethanolamine, triethanolamine,
di-isopropanolamine, etc.), and boric acid or alkali metal borate. Enzyme
stabilization techniques are additionally disclosed and exemplified in
U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al, U.S. Patent
3,600,319, issued August 17, 1971 to Gedge, et al., and European Patent
Application Publication No. 0 199 405, Application No. 86200586.5,
20published October 29, 1986, Venegas. Non-boric acid and borate
stabilizers are preferred. Enzyme stabilization systems are also
described, for example, in U.S. Patents 4,261,868, 3,600,319 and
3,519,570.
Bleachinq Compounds - Bleachinq Aqents and Bleach Activators
25The detergent compositions hereof may contain bleaching agents or
bleaching compositions containing bleaching agent and one or more bleach
activators. When present bleaching compounds will typically be present
at levels of from about 1% to about 20%, more typically from about 1% to
about 10%, of the detergent composition. In general, bleaching compounds
are optional components in non-liquid formulations, e.g., granular
detergents. If present, the amount of bleach activators will typically
be from about 0.1% to about 60%, more typically from about 0.5% to about
40% of the bleaching composition.
A
- 32 - 2 0 q 2 5 57
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other cleaning purposes that are now known.
These include oxygen bleaches as well as other bleaching agents.
For wash conditions below about 50-C, especially below about 40 C,
it is preferred that the compositions hereof not contain borate or
material which can form borate in situ (i.e., borate-forming
material) under detergent storage or wash conditions. Thus it is
preferred under these conditions that a non-borate, non-borate-
forming bleaching agent is used. Preferably, detergents to be used
at these temperatures are substantially free of borate and borate-
forming material. As used herein, "substantially free of borate and
borate-forming material" shall mean that the composition contains
not more than about 2%, by weight, of borate-containing and borate-
forming material of any type, preferably no more than 1%, more
preferably O%.
One category of bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium monoperoxyphthal-
ate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid,
4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
Such bleaching agents are disclosed in U.S. Patent 4,4~3,781,
Hartman, issued November 20, 1984, U.S. Patent Application 740,446,
Burns et al., filed June 3, 1985, European Patent Application
0,133,354, Banks et al., published February 20, 1985, and U.S.
Patent 4 412 934 Chung et al. issued November 1 1983. Highly preferred
bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as
described in U.S. Patent 4 634 551 issued January 6 1987 to Burns et
al.
Another category of bleaching agents that can be used encom-
passes the halogen bleaching agents. Examples of hypohalite bleach-
ing agents, for example, include trichloro isocyanuric acid and the
sodium and potassium dichloroisocyanurates and N-chloro and N-bromo
alkane sulphonamides. Such materials are normally added at 0.5-10%
by weight of the finished product, preferably 1-5% by weight.
- 33 - 20~ 2 5 5 7
-
Peroxygen bleaching agents can also be used. Suitable peroxy-
gen bleaching compounds include sodium carbonate peroxyhydrate,
sodium per borate, sodium pyrophosphate peroxyhydrate, urea peroxy-
hydrate, and sodium peroxide.
Peroxygen bleaching agents are preferably combined with bleach
activators, which lead to the in situ production in aqueous solution
(i.e., during the washing process) of the peroxy acid corresponding
to the bleach activator.
Preferred bleach activators incorporated into compositions of
the present invention have the general formula:
o
R - C - L
wherein R is an alkyl group containing from about l to about 18
carbon atoms wherein the longest linear alkyl chain extending from
and including the carbonyl carbon contains from about 6 to about 10
carbon atoms and L is a leaving group, the conjugate acid of which
has a pKa in the range of from about 4 to about 13. These bleach
activators are described in U.S. Patent 4,915,854, issued Aprii l0,
1990 to Mao et al. and U.S. Patent 4 412 934.
ZO Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated
bleaching agents such as sulfonated zinc and aluminum phthalocya-
nines. These materials can be deposited upon the substrate during
the washing process. Upon irradiation with light, in the presence
of oxygen, such as by hanging clothes out to dry in the daylight,
the sulfonated zinc phthalocyanine is activated and, consequently,
the substrate is bleached. Preferred sulfonated zinc phthalocya-
nines and a photoactivated bleaching process are described in U.S.
Patent 4 033 718 issued July 5 1977 to Holcombe et al. Typically
detergent compositions will contain about 0.025% to about 1.25% by
weight of sulfonated zinc phthalocyanine.
PolYmer;c Soil Release Aqent
Any polymeric soil release agents known to those skilled in the
art can be employed in the practice of this invention. Polymeric
WO 92/06150 PCI/US91/07026
2~ soil release agents are characterized by having both hydrophilic
segments, to hydrophilize the surface of hydrophobic fibers, such as
polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the
hydrophilic segments. This can enable stains occurring subsequent
to treatment with the soil release agent to be more easily cleaned
in later washing procedures.
Whereas it can be beneficial to utilize polymeric soil release
agents in any of the detergent compositions hereof, especially those
compositions utilized for laundry or other applications wherein
removal of grease and oil from hydrophobic surfaces is needed, the
presence of polyhydroxy fatty acid amide in detergent compositions
also containing anionic surfactants can enhance performance of many
of the more commonly utilized types of polymeric soil release
agents. Anionic surfactants interfere with the ability of certain
soil release agents to deposit upon and adhere to hydrophobic
surfaces. These polymeric soil release agents have nonionic
hydrophile segments or hydrophobe segments which are anionic
surfactant-interactive.
The compositions hereof for which improved polymeric soil
release agent performance can be obtained through the use of
polyhydroxy fatty acid amide are those which contain an anionic
surfactant system, an anionic surfactant-interactive soil release
agent and a soil release agent-enhancing amount of the polyhydroxy
fatty acid amide (PFA), wherein: (I) anionic surfactant-
interaction between the soil release agent and the anionic
surfactant system of the detergent composition can be shown by a
comparison of the level of soil release agent (SRA) deposition on
hydrophobic fibers (e.g., polyester) in aqueous solution between (A)
a "Control" run wherein deposition of the SRA of the detergent
composition in aqueous solution, in the absence of the other
detergent ingredients, is measured, and (B) an "SRA/Anionic
surfactant" test run wherein the same type and amount of the anionic
surfactant system utilized in detergent composition is combined in
aqueous solution with the SRA, at the same weight ratio of S M to
the anionic surfactant system of the detergent composition, whereby
W O 92/06150 2 0 ~ 2 5 5 7 PC~r/US91/07026
- 35 -
reduced deposition in (B) relative to (A) indicates anionic-
surfactant interaction; and (II) whether the detergent composition
contains a soil release agent-enhancing amount of polyhydroxy fatty
acid amide can be determined by a comparison of the SRA deposition
of the SRA/Anionic surfactant test run of (B) with soil release
agent deposition in (C) an ~SRA/Anionic surfactant/PFA test run"
wherein the same type and level of polyhydroxy fatty acid amide of
the detergent composition is combined with the soil release agent
and anionic surfactant system corresponding to said SRA/Anionic
surfactant test run, whereby improved deposition of the soil release
agent in test run (C) relative to test run (B) indicates that a soil
release agent-enhancing amount of polyhydroxy fatty acid amide is
present. For purposes hereof, the tests hereof should be conducted
at anionic surfactant concentrations in the aqueous solution that
are above the critical micelle concentration (CMC) of the anionic
surfactant in the aqueous solution of test run (A), and preferably
above about 100 ppm. The polymeric soil release agent concentration
should be at least 15 ppm. A swatch of polyester fabric should be
used for the hydrophobic fiber source. Identical swatches are
immersed and agitated in the 35-C aqueous solutions of the respec-
tive test runs for a period of 12 minutes, then removed, and
analyzed. Polymeric soil release agent deposition level can be
determined by radiotagging the soil release agent prior to treatment
and subsequently conducting radiochemical analysis, according to
techniques known in the art.
As an alternative to the radiochemical analytical methodology
discussed above, soil release agent deposition can alternately be
determined in the above tests runs (i.e., test runs A, B, and C) by
determination of ultraviolet light (UV) absorbance of the test
solutions, according to techniques well known in the art. Decreased
UV absorbance in the test solution after removal of the hydrophobic
fiber material corresponds to increased SRA deposition. As will be
understood by those skilled in the art, UV analysis should not be
utilized for test solutions containing types and levels of materials
which cause excessive UV absorbance interference, such as high
levels of surfactants with aromatic groups (e.g., alkyl benzene
sulfonates, etc.).
WO 92/p6~,50 PCl/US91/07026
?,Og?,~) ' 36 -
Thus by ~soil release agent-enhancing amount" of polyhydroxy
fatty acid amide is meant an amount of such surfactant that will
enhance deposition of the soil release agent upon hydrophobic
fibers, as described above, or an amount for which enhanced
grease/oil cleaning performance can be obtained for fabrics washed
in the detergent composition hereof in the next subsequent cleaning
operation.
The amount of polyhydroxy fatty acid amide needed to enhance
deposition will vary with the anionic surfactant selected, the
amount of anionic surfactant, the particular soil release agent
chosen, as well as the particular polyhydroxy fatty acid amide
chosen. Generally, compositions will comprise from about 0.01% to
about lOYo~ by weight, of the polymeric soil release agent, typically
from about O.lX to about 5%, and from about 1% to about 50%, more
typically from about 4% to about 30% of anionic surfactant. Such
compositions should generally contain at least about 1%, preferably
at least about 3Z, by weight, of the polyhydroxy fatty acid amide,
though it is not intended to necessarily be limited thereto.
The polymeric soil release agents for which performance is
enhanced by polyhydroxy fatty acid amide in the presence of anionic
surfactant include those soil release agents having: (a) one or
more nonionic hydrophile components consisting essentially of (i)
polyoxyethylene segments with a degree of polymerization of at least
2, or (ii) oxypropylene or polyoxypropylene segments with a degree
of polymerization of from 2 to 10, wherein said hydrophile segment
does not encompass any oxypropylene unit unless it is bonded to
adjacent moieties at each end by ether linkages, or (iii) a mixture
of oxyalkylene units comprising oxyethylene and from 1 to about 30
oxypropylene units wherein said mixture contains a sufficient amount
of oxyethylene units such that the hydrophile component has
hydrophilicity great enough to increase the hydrophilicity of
conventional polyester synthetic fiber surfaces upon deposit of the
soil release agent on such surface, said hydrophile segments
preferably comprising at least about 25% oxyethylene units and more
preferably, especially for such components having about 20 to 30
oxypropylene units, at least about 50% oxyethylene units; or (b) one
or more hydrophobe components comprising (i) C3 oxyalkylene
terephthalate segments, wherein, if said hydrophobe components also
_ - 37 - 2 0 9 2 S 5 7
comprise oxyethylene terephthalate, the ratio of oxyethylene
terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or
lower, (ii) C4-C6 alkylene or oxy C4-C6 alkyler,e segments, or
mixtures thereof, (iii) poly (vinyl ester) segments, preferably
poly(vinyl acetate), having a degree of polymerization of at least
2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents,
or mixtures thereof, wherein said substituents are present in the
form of Cl-C4 alkyl ether or C4 hydroxyalkyl ether cellulose
derivatives, or mixtures thereof, and such cellulose derivatives are
amphiphilic, whereby they have a sufficient level of C1-C4 alkyl
ether and/or C4 hydroxyalkyl ether units to deposit upon
conventional polyester synthetic fiber surfaces and retain a
sufficient level of hydroxyls, once adhered to such conventional
synthetic fiber surface, to increase fiber surface hydrophilicity,
or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a
degree of polymerization of from 2 to about 200, although higher
levels can be used, preferably from 3 to about 150, more preferably
from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe
segments include, but are not limited to, end-caps of polymeric soil
release agents such as M03S(C~2)nOCH2CH20-, where M is sodium and n
is an integer from 4-6, as disclosed in U.S. Patent 4,721,580,
issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present invention
include cellulosic derivatives such as hydroxyether cellulosic
po1ymers, copolymeric blocks of ethylene terephthalate or propylene
terephthalate with polyethylene oxide or polypropylene oxide
terephthalate, and the like.
Cellulosic derivatives that are functional as soil release
agents are commercially available and include hydroxyethers of
cellulose such as MethocelR (Dow).
Cellulosic soil release agents for use herein also include
those selected from the group consisting of Cl-C4 alkyl and C4
hydroxyalkyl cellulose such as methylcellulose, ethylcellulose,
hydroxypropyl methylcellulose, and ~ydroxy~utyl methylcellulose. A
variety of cellulose derivatives useful as soil release polymers are
A
- 38 - 20 92 5 5 7
disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to
Hicol, et al.
Soil release agents characterized by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl ester),
e.g., Cl-C6 vinyl esters, preferably poly(vinyl acetate) grafted
onto polyalkylene oxide backbones, such as polyethylene oxide
backbones. Such materials are known in the art and are described in
European Patent Application 0 219 048, published April 22, 1987 by
Kud, et al. Suitable commercially available soil release agents of
this kind include the SokalanTM type of material, e.g., SokalanTM
HP-22, available from BASF (West Germany).
One type of preferrèd soil release agent is a copolymer having
random blocks of ethylene terephthalate and polyethylene oxide (PEO)
terephthalate. More specifically, these polymers are comprised of
repeating units of ethylene terephthalate and PEO terephthalate in a
mole ratio of ethylene terephthalate units to PEO terephthalate
units of from about 25:75 to about 35:65, said PEO terephthalate
units containing polyethylene oxide having molecular weights of from
about 300 to about 2000. The molecular weight of this polymeric
soil release agent is in the range of from about 25,000 to about
55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976,
See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 which
discloses similar copolymers.
Another preferred polymeric soil release agent is a polyester
with repeat units of ethylene terephthalate units containing 10-15%
by weight of ethylene terephthalate units together with 90-80% by
weight of polyoxyethylene terephthalate units, derived from a
polyoxyethylene glycol of average molecular weight 300-5,000, and
the mole ratio of ethylene terephthalate units to polyoxyethylene
terephthalate units in the polymeric compound is between 2:1 and
6:1. Examples of this polymer include the commercially available
material ZelconR 5126 (from Dupont) and MileaseR T (from ICI). These
polymers and methods of their preparation are more fully described
in U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated
product of a substantially linear ester oligomer comprised of an
39 20~2557
- oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat
units and terminal moieties covalently attached to the backbone,
said soil release agent being deriYed from allyl alcohol ethoxylate,
dimethyl terephthalate, and 1,2 propylene diol, wherein after
sulfonation, the terminal moieties of each oligomer have, on
average, a total of from about 1 to about 4 sulfonate groups. These
soil release agents are described fully in U.S. Patent 4,968,451,
issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink, Canadian
Patent No. 1 332,953.
-10 Other suitable polymeric soil release agents include the ethyl-
or methyl-capped 1,2-propylene terephthalate-polyoxyethylene
terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al., the anionic end-capped oligomeric
esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy
groups derived from polyethylene glycol (PEG), the block polyester
oligomeric compounds of U.S. Patent 4,702,857, issued October 27,
1987 to Gosselink, having polyethoxy end-caps of the formula
X-(OCH2CH2)n- wherein n is from 12 to about 43 and X is a C1-C4
alkyl, or preferably methyl.
Additional polymeric soil release agents include the soil
release agents of U.S. Patent 4,877,896, issued October 31, 1989 to
Maldonado et al., which discloses anionic, especially sulfoaroyl,
end-capped terephthalate esters, said patent being incorporated
herein by reference. The terephthalate esters contain unsymmetric-
ally substituted oxy-1,2-alkyleneoxy units. Included among the soil
release polymers of U.S. Patent 4,877,896 are materials with poly-
oxyethylene hydrophile components or C3 oxyalkylene terephthalate
(propylene terephthalate) repeat units within the scope of the
hydrophobe components of (b)(i) above. It is the polymeric soil
release agents characterized by either, or both, of these criteria
that particularly benefit from the inclusion of the polyhydroxy
fatty acid amides hereof, in the presence of anionic surfactants.
If utilized, soil release agents will generally comprise from
about 0.01% to about 10.0%, by weight, of the detergent compositions
WO 92/061~0 PCI/US91/07026
- 40 - 20~25 57
herein, typically from about 0.1~ to about 5%, preferably from about
0.2% to about 3.0YO.
Chelatinq Aqents
~ The detergent compositions herein may also optionally contain
one or more iron and manganese chelating agents as a builder adjunct
material. Such chelating agents can be selected from the group
consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures
thereof, all as hereinafter defined. Without intending to be bound
by theory, it is believed that the benefit of these materials is due
in part to their exceptional ability to remdve iron and manganese
ions from washing solutions by formation of s61uble chelates.
Amino c~rboxylates useful as optional chelating agents in
compositions of the invention can have one or more, preferably at
least two, units of the substructure
CH2 ~
N - (CH2)X - COOM,
wherein M is hydrogen, alkali metal, ammonium or substituted ammon-
ium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1.
Preferably, these amino carboxylates do not contain alkyl or alkenyl
groups with more than about 6 carbon atoms. Operable amine car-
boxylates include ethylenediaminetetraacetates, N-hydroxyethylethyl-
enediaminetriacetates, nitrilotriacetates, ethylenediamine tetrapro-
prionates, triethylenetetraaminehexaacetates, diethylen$triamine-
pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and
substituted ammonium salts thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelatingagents in the compositions of the invention when at least low levels
of total phosphorus are permitted in detergent compositions.
Compounds with one or more, preferably at least two, units of the
substructure
CH2 ~
_ N - (cH2)x - P~3M2,
wherein M is hydrogen, alkali metal, ammonium or substituted
ammonium and x is from 1 to about 3, preferably 1, are useful and
include ethylenediaminetetrakis (methylenephosphonates), nitrilotris
- 41 - 209~ 5 5 7
-
(methylenephosphonates) and diethylenetriaminepentakis (methylene-
phosphonates). Preferably, these amino phosphonates do not contain
alkyl or alkenyl groups with more than about 6 carbon atoms.
Alkylene groups can be shared by substructures.
Polyfunctionally - substituted aromatic chelating agents are
also useful in the compositions herein. These materials can
comprise compounds having the general formula
OH
~ OH
wherein at least one R is -SO3H or -COOH or soluble salts thereof and
mixtures thereof. U.S. Patent 3 812 044 issued May 21 1974 to Connor et
al. discloses polyfunctionally-substituted aromatic chelating and
sequestering agents. Preferred compounds of this type in acid form are dihy-
droxydisulfobenzenes such as l,2-dihydroxy -3,5-disulfoben~ene.
Alkaline detergent compositions can contain these materials in the
form of alkali metal, ammonium or substituted ammonium (e.g. mono-or
triethanol-amine) salts.
If utilized, these chelating agents will generally comprise
from about 0.lX to about lO~o by weight of the detergent compositions
herein. More preferably chelating agents w;ll comprise from about
0.1% to about 3.0X by weight of such compositions.
ClaY Soil Removal/Anti-redePosition Aqents
The compositions of the present invention can also optionally
contain water-soluble ethoxylated amines having clay soil removal
and anti-redeposition properties. Granular detergent compositions
which contain these compounds typically contain from about 0.01% to
about lO.O~o by weight of the water-soluble ethoxylated amines;
liquid detergent compositions, typically about 0.01% to about 5%.
These compounds are selected preferably from the group consisting
of:
(l) ethoxylated mo~oamines having the formula:
(X-L-)-N-(R2)2
(2) ethoxylated diamines having the formula:
W O 92/061~0 PCT/US91/07026
~ ~ ~5S~ R2-~-Rl-r-R2 - 42 -
L L
X X
or
(X-L-)2-N-Rl-N-(R2)2
(3) ethoxylated polyamines having the formula:
R2
R3-[(Al)q-(R4)t-N-L-X]p
(4) ethoxylated amine polymers having the general formula:
R2
[ (R2)2-N~WERl-N3xERl -N3yERl-N-L-X)z
and
(5) mixtures thereof; wherein Al is
O O O O O
-NC-, -NCO-, -NCN-, -CNj-, -OCN-,
R R R R R R
O O 0 00
Il 1~ 1l n 1~
-CO-, -OCO-, -OC-, -CNC-,
R
or -O-; R is H or Cl-C4 alkyl or hydroxyalkyl; Rl is C2-C12
alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a
C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units
provided that no O-N bonds are formed; each R2 is Cl-C4 or hydroxy-
alkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r,
-A2-(CH2)S-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2,
and r + s is 3 or 4; X is a nonionic group, an anionic group or
mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl,
alkenyl, aryl, or alkaryl group having substitution sites; R4 is
Cl-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene,
or a C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene
units provided that no O-O or O-N bonds are formed; L is a hydro-
philic chain which contains the polyoxyalkylene moiety -[(R50)m(CH2-
CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and
n are numbers such that the moiety -(CH2CH20)n- comprises at least
about 50% by weight of said polyoxyalkylene moiety; for said mono-
amines, m is from O to about 4, and n is at least about 12; for said
209~557
- 43 -
diamines, m is from 0 to about 3, and n is at least about 6 when R1 is Cz-
C3 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 where
R1 is other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said
polyamines and amine polymers, m is from 0 to about 10 and n is at least
about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is
1 when q is 1; w is 1 or 0; x ~ y + z is at least 2; and y + z is at least
2. The most preferred soil release and anti-redeposition agent is
ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are
further described in U.S. Patent 4,597,898, VanderMeer, issued July 1,
1986. Another group of preferred clay soil removal/anti-redeposition
agents are the cationic compounds disclosed in European Patent Application
111,965, Oh and Gosselink, published June 27, 1984. Other clay soil
removal/anti-redeposition agents which can be used include the ethoxylated
amine polymers disclosed in European Patent Application 111, 984,
Gosselink, published June 27, 1984; the zwitterionic polymers disclosed
in European Patent Application 112,592, Gosselink, published July 4, 1984;
and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued
October 22, 1985.
Other clay soil removal and/or anti-redeposition agents known in
the art can also be utilized in the compositions hereof. Another type of
preferred anti-redeposition agent includes the carboxy methyl cellulose
(CMC) materials. These materials are well known in the art.
Polymeric Dispersinq Aqents
Polymeric dispersing agents can advantageously be utilized in the
compositions hereof. These materials can aid in calcium and magnesium
hardness control. Suitable polymeric dispersing agents include polymeric
polycarboxylates and polyethylene glycols, although others known in the
art can also be used.
The polycarboxylate materials which can be employed as the
polymeric polycarboxylate dispersing agent component herein are these
polymers or copolymers which contain at least about 60% by weight of
segments with the general formula
2092557
_ C C
l l
Y COOM
- n
wherein X, Y, and Z are each selected from the group consisting of
hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl;
a salt-forming cation and n is from about 30 to about 400. Prefer-
ably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is
hydrogen and M is hydrogen, alkali metal, ammonia or substituted
ammonlum.
Polymeric polycarboxylate materials of this type can be
prepared by polymerizing or copolymerizing suitable unsaturated
monomers, preferably in their acid form. Unsaturated monomeric
acids that can be polymerized to form suitable polymeric polycar-
boxylates include acrylic acid, maleic acid (or maleic anhydride),
fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citra-
conic acid and methylenemalonic acid. The presence in the polymeric
polycarboxylates herein of monomeric segments, containing no car-
boxylate radicals such as vinylmethyl ether, styrene, ethylene, etc.
is suitable provided that such segments do not constitute more than
about 40% by weight.
Particularly suitable polymeric polycarboxylates can be deriYed
from acrylic acid. Such acrylic acid-based polymers which are
useful herein are the water-soluble salts of polymerized acrylic
acid. The average molecular weight of such polymers in the acid
form preferably ranges fro~ about 2,000 to 10,000, more preferably
from about 4,000 to 7,000 and most prefereably from about 4,000 to
5,000. Water-soluble salts of such acrylic acid polymers can
include, for example, the alkali metal, ammonium and substituted
ammonium salts. Soluble polymers of this type are known materials.
Use of polyacrylates of this type in detergent compositions has been
disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued
March 7, 1967.
Acrylic/maleic-based copolymers may also be used as a preferred
component of the dispersing/anti-redeposition agent. ~uch materials
include the water-soluble salts of copolymers of acrylic acid and
A
- 45 - 209 2 5 5 7
-
maleic acid. ~he average molecular weight of such copolymers in the
acid form preferably ranges from about 2,000 to 100,000, more
preferably from about 5,000 to 75,000, most preferably from about
7,000 to 65,000. The ~atio of acrylate to maleate segments in such
copolymers will generally range from about 30:1 to about 1:1, more
preferably from about 10:1 to 2:1. Water-soluble salts of such
acrylic acid/maleic acid copolymers can include, for example, the
alkali metal, ammonium and substituted ammonium salts. Soluble
acrylate/maleate copolymers of this type are known materials which
are described in European Patent Application No. 66915, published
December 15, 1982.
Another polymeric material which can be included is polyethyl-
ene glycol (PEG). PEG can exhibit dispersing agent performance as
well as act as a clay soil removal/anti-redeposition agent. Typical
molecular weight ranges for these purposes range from about 500 to
about 100,000, preferably from about 1,000 to about 50,000, more
preferably from about 1,500 to about 10,000.
Briqhtener
Any optical brighteners or other brightening or whitening
agents known in the art can be incorporated into the detergent
compositons hereof.
The choice of brightener for use in detergent compositions will
depend upon a number of factors, such as the type of detergent, the
nature of other components present in the detergent composition, the
temperatures of wash water, the degree of agitation, and the ratio
of the material washed to tub size.
The type of brightener is also dependent upon the type of
material to be cleaned, e.g., cottons, synthetics, etc. Since most
laundry detergent products are used to clean a variety of fabrics,
the detergent compositions should contain a mixture of brighteners
which wili be effective for fabric mixtures comprising a variety of
fabrics. It is of course necessary that the individual components
of such a brightener mixture be compatible.
A variety of optical brighteners useful in the present
invention are commercially available and ~ill be appreciated by
those skilled in the art. Commercial optical brighteners which may
be useful in the present invention include those, but are not
A
- 46 - 2 0 9 2 5 57
necessarily limited, derivatives of stilbene, pyrazoline, coumarin,
carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide,
azoles, 6-membered-ring heterocycles and other miscellaneous agents.
Some examples of these types of brighteners are disclosed in ~The
Production and Application of Fluorescent Brightening Agents~, M.
Zahradnik, Published by John Wiley & Sons, New York (1982).
Stilbene derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
of bis(triazinyl)amino-stilbene; bisacylamino derivatives of
stilbene; triazole derivatives of stilbene; oxadiazole derivatives
of stilbene; oxazole derivatives of stilbene; and styryl derivatives
of stilbene.
Some derivatives of bis(triazinyl)aminostilbene which may be
useful in the present invention may be prepared from 4,4'-diamine-
stilbene-2,2'-di- sulfonic acid.
Coumarin derivatives which may be useful in the present inven-
tion include, but are not necessarily limited to, derivatives
substituted in the 3-position, in the 7-position, and in the 3- and
7-positions.
Carboxylic acid derivatives which may be useful as optical
brighteners in the present invention include, but are not
necessarily limited to, fumaric acid derivatives; benzoic acid
derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalene-
dicarboxylic acid derivatives; heterocyclic acid derivativesi and
cinnamic acid derivatives.
Cinnamic acid derivatives which may be useful as optical
brighteners in the present invention can be further subclassified
into groups which include, but are not necessarily limited to,
cinnamic acid derivatives, styrylazoles, styrylbenzofurans,
styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as
disclosed on page 77 of the Zahradnik reference.
The styrylazoles can be further subclassified into styrylben-
zoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on
page 78 of the Zahradnik reference. It will be understood that
these three identified subc7asses may not necessarily reflect an
exhaustive list of the subgroups into which styrylazoles may be
subclassified.
47 2092557
Another class of optical brighteners reference which may be useful
in the present invention are the derivatives of dibenzothiophen-5,5-
dioxide disclosed at pages 741-749 of The Kirk-Othmer Encyclopedia of
Chemical TechnoloqY, Volume 3, pages 737-750 (John Wiley & Son, Inc.,
1962), and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5
dioxide.
In addition to the brighteners already described, miscellaneous
agents may also be useful as brighteners. Examples of some of these
miscellaneous agents are disclosed at pages 93-95 of the Zahradnik
reference, and include 1-hydroxy-3,6,8-pyrenetri-sulphonic acid; 2,4-
dimethyoxy-1,3,5-triazin-6-yl-pyrene; 4,5-di-phenylimidazolone-disulphonic
acid; and derivatives of pyrazoline-quinoline.
Other examples of optical brighteners which may be useful in the
present invention are those disclosed in U.S. Patent 4,790,856, issued to
Wixon on December 13, 1988. These brighteners include the PhorwhiteTM
series of brighteners from Verona. Other brighteners disclosed in this
reference include, Tinopal UNPA, Tinopal CBS and Tinopal 5BM, produced by
Geigy; Arctic White CC and Arctic White CWD, produced by Hilton-Davis,
located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[1,2-d]triazoles;
4,4'-bis(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and
the y-aminocoumarins. Specific examples of these brighteners include 4-
methyl-7-diethyl-aminocoumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-
diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-
[1,2-d]oxazole; and 2-(stilbene-4-yl)2H-naptho[1,2-d]triazole.
Other optical brighteners which may be useful in the present
invention include those disclosed in U.S. Patent 3,646,015, issued
February 29, 1972 to Hamilton.
Another group of optical brighteners which may be useful in the
present invention include azoles, which are derivatives of 5-membered ring
heteroxycles. These can be further subcategorized into monozoles and
bisazoles. Examples of monoazles are disclosed in the Kirk-Othmer
reference.
Examples of bisazoles which may be useful in the present invention
are disclosed in the Kirk-Othmer reference.
WO 92/06150 PCI/US91/07026
- 48 - 20~2557
20~ Another group of brighteners which may be useful in the present
invention are the derivatives of 6-membered-ring heterocycles
disclosed in the Kirk-Othmer reference. Examples of such compounds
include brighteners derived from pyrazine and brighteners derived
S from 4-aminonaphthalamide.
Other Inqredients
A wide variety of other ingredients useful in detergent
compositions can be included in the compositions hereof, including
other active ingredients, carriers, hydrotropes, processing aids,
dyes or pigments, solvents for liquid formulations, etc.
Liquid detergent compositions can contain water and other
solvents as carriers. Low molecular weight primary or secondary
alcohols exemplified by methanol, ethanol, propanol, and isopropanol
are suitable. Monohydric alcohols are preferred for solubilizing
surfactant, but polyols such as those containing from 2 to about 6
carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene
glycol, ethylene glycol, glycerine, and 1,2-propanediol) can also be
used.
The detergent compos~itions hereof will preferably be formulated
such that during use in aqueous cleaning operations, the wash water
will have a pH of between about 6.5 and about 11, preferably between
about 7.5 and about 10.5. Liquid product formulations preferably
have a pH between about 7.5 and about 9.5, more preferably between
about 7.5 and 9Ø Techniques for controlling pH at recommended
usage levels include the use of buffers, alkalis, acids, etc., and
are well known to those skilled in the art.
This invention further provides a method for cleaning
substrates, such as fibers, fabrics, hard surfaces, etc., by
contacting said substrate, with a detergent composition comprising
alkyl benzene sulfonate surfactant and the polyhydroxy fatty acid
amides hereof, wherein the weight ratio of alkyl benzene sulfonate
to polyhydroxy fatty acid amide is from about 1:10 to about 10:1, in
the presence of water or water-miscible solvent (e.g., primary and
secondary alcohols). Agitation is preferably provided for enhancing
cleaning. Suitable means for providing agitation include rubbing by
hand preferably with the aid of a brush, or other cleaning device,
automatic laundry washing machines, automatic dishwashers, etc.
20~2~S7
w o 92/06150 PCT/US91/07026
- 49 -
In the above method, the more preferred surfactant weight
ratios, as discussed herein, as well as the utilization of suds
suppressors, the preferred or other auxiliary surfactant, and other
detergent adjuncts, can be utilized.
EXPERIMENTAL
This exemplifies a process for making a N-methyl,
1-deoxyglucityl 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
under a nitrogen sweep to form a melt (approximately 25 minutes).
When the melt temperature reaches 145- C, catalyst (anhydrous
powdered sodium carbonate, 10.5 9., 0.1 mole, ~. 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.
WO 92/06150 PCr/US91/07026
2 ~ ~ 2 5 5 The following examples ar; meant to exemplify compositions of
the present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention, said scope being
determined according to claims which follow.
EXAMPLES 1-6
These examples below show compositions containing alkylbenzene
sulfonates and polyhydroxy fatty acid amides, for wash temperatures
above about 50-C.
Base Granule 1 2 3
Linear C12 Alkylbenzene Sulfonate S.9 3.0 4.5
N-Methyl N-l-Deoxyglucityl Lauramide 7.0
C16 18 Alkyl Sulfate 2.5 2.5 2.5
Zeolite 20.9 20.0 20.5
Polyacrylate (4500 MW) 3.9 3.9 3.9
Sodium Carbonate 12.7 16.0 12.7
Water and Miscellaneous 8.1 8.2 8.7
Admix and SDraY-on
N-Methyl N-l-Deoxyglucityl Cocoamide 5.6
N-Methyl N-l-Deoxyglucityl
Tallow Fatty Amide 4.0
Miscellaneous (filler salts, brightener,
enzyme, buffer, zeolite or other
builder, etc) 40.4 39.4 43.2
100.0 100.0 100.0
Examples 1-3 show standard density heavy duty granular
detergent compositions for wash temperatures preferably between
about SO-C to 95-C, at concentrations of about 8000 ppm, wash water
weight basis. The compositions are prepared by spray drying a
slurry of the base granule ingredients to about 10-13% moisture,
adding additional dry powdered ingredients, such as bleach,
activators, and other adjuncts, and spraying on liquids such as
perfume, nonionics, or suds suppressor fluids.
Base Granule 4 5 6
C16 18 Alkyl Sulfate 2.4 2.4 2.4
Linear C12 Alkylbenzene Sulfonate 4.6 4.6 7.6
C16 18 Alkyl Ethoxylate (1I mole) 1.1 1.1 1.1
Zeolite 22.0 24.0 21.3
Acrylate/maleate copolymer (60000 MW) 4.3 5.6 4.3
2~92~7
W O 92/06150 - 51 - PCT/US91/07026
Water and Miscellaneous 9.4 9.2 10.1
Admix
N-Methyl N-l-Deoxyglucityl Cocoamide 7.0
N-Methyl N-l-Deoxyglucityl
Tallow Fatty Amide 7.0 4.0
Sodium Citrate 8.0 8.0
Sodium Carbonate 17.5 17.3 17.5
Sodium Silicate (1.6r) 3.5 3.0 3.5
Miscellaneous (filler salts, brightener,
enzyme, buffer, zeolite or other
builder, etc) 19.3 24.8 19.4
SPraY-on
Perfume 0.4 0.4 0.4
Silicone Fluid 0.5 0.5 0.5
100.0 100.0 100.0
The compositions of Examples 4-6 are preferably utilized at
concentrations of about 6000 ppm, wash water weight basis, at
temperature of from about 50-C to 95-C. These compositions are made
by slurrying the base granule ingredients and spray drying to about
9% moisture content. Remaining dry ingredients are added admixed
followed by spray-on addition of the liquid ingredients.
EXAMPLES 7-9
The examples show heavy duty liquid detergent compositions
containing polyhydroxy fatty acid amide and alkylbenzene sulfonates.
Base Granule 1 8 9
Linear C12 Alkylbenzene Sulfonate 12.8 12.8 10.0
C12 14 Alkyl Sulfate 1.8 1.8
C12 14 Alkyl Ethoxylate (7 moleJ 1.6
N-Methyl N-l-Deoxyglucityl Cocoamide 8.4 6.5
N-Methyl N-l-Dexoyglucityl Oleamide 8.4
Oleic acid 1.8 1.8 4.0
Citric acid 4.1 4.1 9.0
Dodecenyl succinic acid 11.1 11.1 5.0
Silicone Oil 0.5 0.5 0.3
W O 92/06150 P(~r/US91/07026
0 3 ~ Miscellaneous (solvents, enzymes,
brighteners, stabilizers, buffer, etc) 14.6 14.6 15.8
~ater 45.0 45.0 .47.8
100.0100.0 100.0
Examples 7-9 are prepared by combining non-aqueous solvents,
aqueous surfactant pastes or solutions, melted fatty acids, aqueous
solutions of polycarboxylate builders and other salts, aqueous
ethoxylated tetraethylenpentamine, buffering agents, caustic, and
the remaining water. The pH is adjusted using either an aqueous
citric acid solution sodium hydroxide solution to about pH 8.5.
After pH adjustment, the final ingredients, such as soil release
agents, enzymes, colorants, and perfume, are added and the mixture
stirred until a single phase is achieved.
EXAMPLE 10
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
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 reaction can be carried out at 80% and 90%
reactant concentrations for periods up to 6 hours to yield products
with extremely small by-product formation.
2Q~557
W O 92/06150 PC~r/US91/07026 - 53 -
The following is not intended to limit the invention herein,
but His simply to further illustrate additional aspects of the
technology which may be cons;dered by the formulator in the
manufacture of a wide variety of detergent compositions using the
polyhydroxy fatty acid amides.
It will be readily appreciated that the polyhydroxy fatty acid
amides are, by virtue of their amide bond, subject to some
instability under highly basic or highly acidic conditions. While
some decomposition can be tolerated, it is preferred that these
materials not be subjected to pH's above about 11, preferably 10,
nor below about 3 for unduly extended periods. Final product pH
(liquids) is typically 7.0-9Ø
During the manufacture of the polyhydroxy fatty acid amides it
will typically be necessary to at least partially neutralize the
base catalyst used to form the amide bond. While any acid can be
used for this purpose, the detergent formulator will recognize that
it is a simple and convenient matter to use an acid which provides
an anion that is otherwise useful and desirable in the finished
detergent composition. For example, citric acid can be used for
purposes of neutralization and the resulting citrate ion (ca. 1%) be
allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry
and be pumped into the later manufacturing stages of the overall
detergent-manufacturing process. The acid forms of materials such
as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate,
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
tallow alkyl (predominantly Cl6-Cl8) counterparts. Accordingly, the
Cl2-Cl4 materials are somewhat easier to formulate in liquid
compositions, and are more soluble in cool-water laundering baths.
However, the Cl6-Cl8 materials are also quite useful, especially
under circumstances where warm-to-hot wash water is used. Indeed,
the Cl6-Cl8 materials may be better detersive surfactants than their
C12-Cl4 counterparts. Accordingly, the formulator may wish to
balance ease-of-manufacture vs. performance when selecting a
particular polyhydroxy fatty acid amide for use in a given
formulation.
WO 92/06150 PCI/US91/07026
- 54 -
2 0 9 ? S ~ It will also be appreciated that the solubility of the
polyhydroxy 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
detergents when used in combination with conventional alkylbenzene
sulfonate ("LAS") 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
performance. (The manufacture of a polyhydroxy fatty acid amide
derived from maltose is described hereinafter.)
The polyhydroxy fatty acid amides can be manufactured not only
from the purified sugars, but also from hydrolyzed starches, e.g.,
corn starch, potato starch, or any other convenient plant-derived
starch which contains the mono-, di-, etc. saccharide desired by the
formulator. This is of particular importance from the economic
standpoint. Thus, "high glucose" corn syrup, "high maltose" corn
syrup, etc. can conveniently and economically be used.
De-lignified, hydrolyzed cellulose pulp can also provide a raw
material source for the polyhydroxy fatty acid amides.
As noted above, polyhydroxy fatty acid amides derived from the
higher saccharides, such as maltose, lactose, etc., are more soluble
than their glucose counterparts. Moreover, it appears that the more
soluble polyhydroxy fatty acid amides can help solubilize their less
soluble counterparts, to varying degrees. Accordingly, the
formulator may elect to use a raw material comprising a high glucose
corn syrup, for example, but to select a syrup which contains a
modicum of maltose (e.g., 1% or more). The resulting mixture of
2~25~7
w o 92/06150 PCT/USsl/07026
- 55 -
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 about33% (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-90-C, preferably
about 50-C-80-C. It has now been determined that it may be
convenient for the formulator of, for example, liquid detergents to
conduct such processes in 1,2-propylene glycol solvent, since the
glycol solvent need not be completely removed from the reaction
product prior to use in the finished detergent formulation.
Likewise, 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-C14 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.
WO 92/p~150 PCI'/US91/07026
2~3~5 ' - 56 -
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 Step 2 - reacting the
aforesaid polyhydroxy amine with, preferably, a fatty ester to form
an amide bond. While a variety of N-alkyl polyhydroxy amines useful
in Step 2 of the reaction sequence can be prepared by various
art-disclosed processes, the following process is convenient and
makes use of economical sugar syrup as the raw material. It is to
be understood 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 (nwater-whiten).
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 reiction temperature as shown.
The Gardner Color is measured at the indicated approximate times in
minutes.
TABLE 1
Time in Minutes: 10 30 60 120 180 240
30Reaction Temp. ~C Gardner Color (ADDroximate)
0
1 1 2 2 4 5
4 6 10
35As 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
2~ 31255~
WO 92/06150 PCI/US91/07026
- 57 -
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 90YO,
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
indicated, the MMA adduct color (after substantial equilibrium is
reached in at least about two hoursJ is as indicated.
TABLE 2
Gardner Color (ADDroximate)
Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2
As can be seen from the above, the starting sugar material must
be very near colorless in order to consistently have adduct that is
acceptable. When the sugar has a Gardner Color of about 1, the
adduct is sometimes acceptable and sometimes not acceptable. When
the Gardner Color is above 1 the resulting adduct is unacceptable.
The better the initial color of the sugar, the better is the color
of the adduct.
II. HYdr w en Reaction - Adduct from the above having a Gardner
Color of 1 or less is hydrogenated according to the following
procedure.
About 539 9 of adduct in water and about 23.1 9 of United
Catalyst G49B Ni catalyst are added to a one liter autoclave and
purged two times with 200 psig H2 at about 20 C. The H2 pressure is
raised to about 1400 psi and the temperature is raised to about
W O 92/061~0 P ~ /US91/07026
- 58 -
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 140-C for
a short exposure time.
It is important to have good adduct that has low sugar content
(less than about 5%, preferably less than about 1%) and a good color
(less than about 7, preferably less than about 4 Gardner, more
preferably less than about 1).
In another reaction, adduct is prepared starting with about 159
g of about 50% methylamine in water, which is purged and shielded
with N2 at about 10-20-C. About 330 9 of about 70% corn syrup (near
water-white) is degassed with N2 at about 50-C and is added slowly
to the methylamine solution at a temperature of less than about
20-C. The solution is mixed for about 30 minutes to give about 95%
adduct that is a very light yellow solution.
About 190 9 of adduct in water and about 9 9 of United Catalyst
G49B Ni catalyst are added to a 200 ml autoclave and purged three
times with H2 at about 20-C. The H2 pressure is raised to about 200
psi and the temperature is raised to about 50-C. The pressure is
raised to 250 psi and the temperature is held at about 50-55-C for
about three hours. The product, which is about 95% hydrogenated at
this point, is then raised to a temperature of about 85-C for about
2~2~57
W O 92/06150 PCT/USsl/07026
_ - 59 -
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 lO0 ppm as compared to
the less than 10 ppm in the previous reaction.
The following reactions with H2 are run for direct comparison
of reaction temperature effects.
A 200 ml autoclave reactor is used following typical procedures
similar to those set forth above to make adduct and to run the
hydrogen reaction at various temperatures.
Adduct for use in making glucamine is prepared by combining
about 420 9 of about 55% glucose (corn syrup) solution (231 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.
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 temF)erature to prevent further
degradation.
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.
W O 92/06150 60 - PC~r/US91/07026
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.
5. Decant and filter out the Ni catalyst. Sample 3 is for about
50-55-C; Sample 4 is for about 75-C; tnd 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 11
The preparation of the tallow (hardened) fatty acid amide of
N-methyl maltamine for use in detergent compositions according to
this invention is as follows.
SteD 1 - Reactants: Maltose monohydrate (Aldrich, lot
01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 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
50-C. The crude reaction mixture is vacuum filtered 2X through a
glass microfiber filter with a silica gel plug. The filtrate is
concentrated to a viscous material. The final traces of water are
azetroped off by dissolving the material in methanol and then
removing the methanol/water on a rotary evaporator. Final drying is
done under high vacuum. The crude product is dissolved in refluxing
methanol, filtered, cooled to recrystallize, filtered and the filter
WO 92/06150 2 Q ~6~ ~ ~; 7 PCr/US91/07026
cake is dried under vacuum at 35-C. This is cut #1. The filtrate
is concentrated until a precipitate begins to form and is stored in
a refrigerator overnight. The solid is filtered and dried under
vacuum. This is cut #2. The filtrate is again concentrated to half
its volume and a recrystallization is performed. Very little
precipitate forms. A small quantity of ethanol is added and the
solution is left in the freezer over a weekend. The solid material
is filtered and dried under vacuum. The combined solids comprise
N-methyl maltamine which is used in Step 2 of the overall synthesis.
SteD 2 - Reactants: N-methyl maltamine (from Step 1); hardened
tallow methyl esters; sodium methoxide (25% in methanol); absolute
methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst
level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level
50% (wt.).
In a sealed bottle, 20.36 9 of the tallow methyl ester is
heated to its melting point (water bath) and loaded into a 250 ml
3-neck round-bottom flask with mechanical stirring. The flask is
heated to ca. 70-C to prevent the ester from solidifying.
Separately, 25.0 9 of N-methyl maltamine is combined with 45.36 g of
methanol, and the resulting slurry is added to the tallow ester with
good mixing. 1.51 9 of 25% sodium methoxide in methanol is added.
After four hours the reaction mixture has not clarified, so an
additional 10 mole % of catalyst (to a total of 20 mole %) is added
and the reaction is allowed to continue overnight (ca. 68-C) after
which time the mixture is clear. The reaction flask is then
modified for distillation. The temperature is increased to 110 ~ 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
W O 92/06~50 - 62 - PC~r/US91/07026
~9~ dryness (rotary evaporator). Any remaining tallow ester is removea
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 optionally contain more or less of various suds control
agents. Typically, for dishwashing high sudsing is desirable so no
suds control agent will be used. For fabric laundering in
top-loading washing machines some control of suds may be desirable,
and for front-loaders some considerable degree of suds control may
be preferred. A wide variety of suds control agents are known in
the art and can be routinely selected for use herein. Indeed, the
selection of suds control agent, or mixtures of suds control agents,
for any specific detergent composition will depend not only on the
presence and amount of polyhydroxy fatty acid amide used therein,
but also on the other surfactants present in the formulation.
However, it appears that, for use with polyhydroxy fatty acid
amides, silicone-based suds control agents of various types are more
efficient (i.e., lower levels can be used) than various other types
of suds control agents. The silicone suds control agents available
as X2-3419 and Q2-3302 (Dow Corning) are particularly useful herein.
The formulator of fabric laundering compositions which can
advantageously contain soil release agent has a wide variety of
known materials to choose from (see, for example, U.S. Patents
3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and
2~92~5~
WO 92/06150 PCr/US91/07026
- 63 -
4,877,896). Additional soil release materials useful herein include
the nonionic oligomeric esterification product of a reaction mixture
comprising a source of C1-C4 alkoxy-terminated polyethoxy units
(e.g., CH3[OCH2CH2]l6OH), a source of terephthaloyl units (e.g.,
dimethyl terephthalate); a source of poly(oxyethylene)oxy units
(e.g., polyethylene glycol 1500); a source of oxyiso-propyleneoxy
units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy
units (e.g., ethylene glycol) especially wherein the mole ratio of
oxyethyleneoxy units:oxyiso-propyleneoxy units is at least about
10 0.5:1. Such nonionic soil release agents are of the general formula
O O O O
Il /~\ 11 11 /=\ 1~
R10-(CHzCH20)x C ~ CO-CH-CH20 - C ~ CO(CH2CH20)y
O ~=~ O
C ~ C - O (CH2CH2O)x-R1
wherein R1 is lower (e.g., Cl-C4) alkyl, especially methyl; x and y
are each integers from about 6 to about lOO; m is an integer of from
about 0.75 to about 30; n is an integer from about 0.25 to about 20;
and R2 is a mixture of both H and CH3 to provide a mole ratio of
oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
Another preferred type of soil release agent useful herein is
of the general anionic type described in U.S. Patent 4,877,896, but
with the condition that such agents be substantially free of
monomers of the HOROH type wherein R is propylene or higher alkyl.
Thus, the soil release agents of U.S. Patent 4,877,896 can comprise,
for example, the reaction product of dimethyl terephthalate,
ethylene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid,
whereas these additional soil release agents can comprise, for
example, the reaction product of dimethyl terephthalate, ethylene
glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid. Such
agents are preferred for use in granular laundry detergents.
The formulator may also determine that it is advantageous to
include a non-perborate bleach, especially in heavy-duty granular
laundry detergents. A variety of peroxygen bleaches are available,
commercially, and can be used herein, but, of these, percarbonate is
convenient and economical. Thus, the compositions herein can
contain a solid percarbonate bleach, normally in the form of the
sodium salt, incorporated at a level of from 3% to 20% by weight,
WO 92/06150 PCr/US91/07026
more preferably from 5% to 18% by e;ght and most preferably from 8%
to 15% by weight of the composition.
Sodium percarbonate is an addition compound having a formula
corresponding to 2Na2C03. 3H202, and is available commercially as a
crystalline solid. Most commercially available material includes a
low level of a heavy metal sequestrant such as EDTA, 1-hydroxy-
ethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate,
that is incorporated during the manufacturing process. For use
herein, the percarbonate can be incorporated into detergent composi-
tions without additional protection, but preferred embodiments ofthe invention utilize a stable form of the material (FMC). Although
a variety of coatings can be used, the most economical is sodium
silicate of SiO2:Na20 ratio from 1.6:1 to 2.8:1, preferably 2.0:1,
applied as an aqueous solution and dried to give a level of from 2%
to 10% (normally from 3% to 5%), of silicate solids by weight of the
percarbonate. Magnesium silicate can also be used and a chelant
such as one of those mentioned above can also be included in the
coating.
The particle size range of the crystalline percarbonate is from
350 micrometers to 450 micrometers with a mean of approximately 400
micrometers. When coated, the crystals have a size in the range
from 400 to 600 micrometers.
While heavy metals present in the sodium carbonate used to
manufacture the percarbonate can be controlled by the inclusion of
sequestrants in the reaction mixture, the percarbonate still
requires protection from heavy metals present as impurities in other
ingredients of the product. It has been found that the total level
of iron, copper and manganese ions in the product should not exceed
25 ppm and preferably should be less than 20 ppm in order to avoid
an unacceptably adverse effect on percarbonate stability.
A modern, condensed laundry detergent granule is as follows.
EXAMPLE 1?
The foll owi ng illustrates a perborate bleach-plus-bleach
activator detergent composition of the present invention which is
prepared by admixing the listed ingredients in a mixing drum.
In the example, Zeolite A refers to hydrated crystalline
Zeolite A containing about 20% water and having an average particle
size of 1 to 10, preferably 3 to 5, microns; LAS refers to sodium
~0~ 5 7
~ O 92/06150 PC~r/US91/07026 - 65 -
Cl2.3 linear alkylbenzene sulfonate; AS refers to sodium C,4-Cls
alkyl sulfate; nonionic refers to coconut alcohol condensed with
about 6.5 moles of ethylene oxide per mole of alcohol and stripped
of unethoxylated and monoethoxylated alcohol, also abbreviated as
CnAE6.5T.; and DTPA refers to sodium diethylenetriamine
pentaacetate.
Parts by Weight of
Final ComPosition % of Granules
Base Granulesl 51.97 lOO.OO
AS 9.44 18.16
LAS 2.92 5.62
Moisture 4.47 8.60
Sodium silicate (1.6 ratio) 1.35 2.60
Sodium sulfate 6.47 12.45
Sodium polyacrylate (4500 MW) 2.61 5.02
PEG 8000 1.18 2.27
Nonionic 0.46 0.89
Sodium carbonate 13.29 25.57
Brightener 0.20 0.38
Sodium aluminosilicate 9.11 17.53
DTPA 0.27 0.52
Perfume 0.20 0.38
NAPAA Granules2 6.09 100.00
NAPM 2.86 46.96
LAS 0.30 4-93
Sulfate and Misc. 2.93 48.11
NOBS Granules 3 3.88 100.00
NOBS 3.15 81.19
LAS 0.12 3.09
PEG 8000 0.19 4.90
Misc. 0.42 10.82
Zeolite Granules4 12.00 100.00
Sodium aluminosilicate 7.39 61.58
PEG 8000 1.50 12.47
Nonionic 1.16 9.70
Moisture 1.66 13.83
Misc. 0.29 2.42
- 2092557
Admix
Sodium SKS-6
layered silicate 15.84
Protease
(0.078 mg/g activity) 0.52
Sodium perborate
monohydrate 1.33
Citric acid 6.79
C~2-Cl4 N-methyl glucamide 1.58
Total of final composition 100.00
lThe base granules are produced by spray drying an aqueous
crutcher mix of the listed ingredients.
2A freshly-prepared sample of NAPM wet cake, which typically
consists of about 60% water, about 2% peroxyacid available oxygen
(AvO) (corresponding to about 36% NAPM), and the rest (about 4%)
unreacted starting material, is obtained. This wet cake is the
crude reaction product of NAAA (monononyl amide of adipic acid),
sulfuric acid, and hydrogen peroxide which is subsequently quenched
by addition to water followed by filtration, washing with distilled
water, phosphate buffer washing and final suction filtration to
recover the wet cake. A portion of the wet cake is air-dried at
room temperature to obtain a dry sample which typically consists of
about 5% AvO (corresponding to about 90% NAPM) and about 10%
unreacted starting material. When dry, the sample pH is about 4.5.
NAPM granules are prepared by mixing about 51.7 parts of the
dried NAPM wet cake (containing about 10% unreacted), about 11.1
parts of sodium Cl2.3 linear alkyl benzene sulfonate (LAS) paste
(45~/. active), about 43.3 parts of sodium sulfate, and about 30 parts
of water in a CUISINART mixer. After drying, the granules (which
contain about 47% NAPM) are sized by passing through a No. 14 Tyler
mesh sieve and retaining all particles not passing through a No. 65
Tyler mesh. The average amide peroxyacid particle (agglomerate)
size is about 5-40 microns and the median particle size is about
10-20 microns, as determined by Malvern particle size analysis.
3The NOBS (nonanoyloxybenzene sulfonate) granules are prepared
according to U.S. Patent 4,997,596, Bowling et al, issued March 5,
1991 .
~2~s7
W O 92/06150 PC~r/US91/07026
- 67 -
~ Zeolite granules having the following composition are made by
mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich R08 energy
intensive mixer.
Parts bv Weight
Before Drving After Drvinq
Zeolite A (includes bound water)70.00 76.99
PEG 8000 10.80 12.49
CnAE6.ST* 8.40 9.72
Free water 10.80 0.80
The PEG 8000 is in an aqueous form containing 50% water and is
at a temperature of approximately 55-F (12.8-C). The CnAE6.5T is in
a liquid state and is held at approximately 90-F (32.2-C). The two
liquids are combined by pumping through a 12 element static mixer.
The resulting binder material has an outlet temperature of
approximately 75-F (23.9-C) and a viscosity of approximately 5000
cps. The ratio of PEG 8000 and CnAE6.5T through the static mixer is
72:28 respectively.
The Eirich R08 energy intensive mixer is operated in a batch
type mode. First, 34.1 kg of powdered Zeolite A is weighed into the
pan of the mixer. The mixer is started by first rotating the pan in
a counterclockwise direction at approximately 75 rotations per
minute (rpm), and then rotating the rotor blade in a clockwise
direction at 1800 rpm. The binder material is then pumped from the
static mixer directly into the Eirich R08 energy intensive mixer
which contains Zeolite A. The feed rate of the binder material is
about 2 minutes. The mixer continues to mix for an additional
minute for a total batch time of approximately 3 minutes. The batch
is then discharged and collected in a fiber drum.
The batch step is repeated until approximately 225 kg of wet
product has been collected. This discharged product is then dried
in a fluid bed at 240-270-F (116-132-C). The drying step removes
most of the free water and changes the composition as described
above. The total energy input by the mixer to the product in a
batch mode is approximately 1.31Xl0l2 erg/kg. at a rate of
approximately 2.18X109 erg/kg-s.
The resulting free flowing agglomerates have a mean particle
size of about 450-500 microns.
W O 92/06150 P~r/US91/07026
~9?,5~ - 68 -
EXAMPLE 13
In any of the foregoing examples, the fatty acid glucamide
surfactant can be replaced by an equivalent amount of the maltamide
surfactant, or mixtures of glucamide/maltamide surfactants derived
from plant sugar sources. In the compositions the use of ethanol-
amides appears to help cold temperature stability of the finished
formulations. Moreover, the use of sulfobetaine (aka "sultaine")
surfactants provides superior sudsing.
In the event that especially high sudsing compositions are
desired it is preferred that less than about 5%, more preferably
less than about 2%, most preferably substantially no C1~ or higher
fatty acids be present, since these can suppress sudsing. Accord-
ingly, the formulator of high sudsing compositions will desirably
avoid the introduction of suds-suppressing amounts of such fatty
acids into high sudsing compositions with the polyhydroxy fatty acid
amides, and/or avoid the formation of C14 and higher fatty acids on
storage of the finished compositlons. One simple means is to use
Cl2 ester reactants to prepare the polyhydroxy fatty acid amides
herein. Fortunately, the use of amine oxide or sulfobetaine sur-
factants can overcome some of the negative sudsing effects caused bythe 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.
Polyglutamic acid or polyaspartic acid dispersants can be
usefully employed with zeolite-built detergents. AE fluid or flake
and DC-544 (Dow Corning) are other examples of useful suds control
agents herein.
It will be appreciated by those skilled in the chemical arts
that the preparation of the polyhydroxy fatty acid amides herein
using the di- and higher saccharides such as maltose will result in
the formation of polyhydroxy fatty acid amides wherein linear
substituent Z is "capped" by a polyhydroxy ring structure. Such
materials are fully contemplated for use herein and do not depart
from the spirit and scope of the invention as disclosed and claimed.
