Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
WO 92/06172PCl'/US91/06984
POLYHYDROXY FATTY ACID AMIDES IN BRIGHTENER-CONTAINING
._
LIQUID DETERGENT COMPOSITIONS
~092S6D
TECHNICAL FIELD
5Polyhydroxy fatty acid amides are used in the formulation of
liquid detergent compositions containing optical brighteners.
BACKGROUND OF THE INVENTION
Numerous optical brightener materials are used in detergent
compositions. Such materials are designed to deposit onto fibers
and fabrics and to alter the chromaticity of items to yield a more
preferred white. Optical brighteners work by converting invisible,
ultraviolet radiation to a visible blue frequency which shifts the
chromaticity of a surface away from a yellow cast to a preferred
clean bluish cast.
In general, such optical brightener molecules have at least one
relatively large chromophoric group and one or more substituent
groups. For use in laundry detergents, the molecules must not only
exhibit the correct optical properties, but also must be capable of
being deposited onto fabrics from an aqueous wash liquor containing
various surfactants, detergency builders and other detersive
adjuncts.
Detergent compositions containing optical brighteners may be
formulated in a number of ways. One formulation method involves
adding the brightener to the detergent composition as a free powder.
However, this preparation method causes problems such as dusting,
which can be particularly troublesome at a detergent composition
manufacturing site. Another problem with this formulation method is
that optical brighteners can require long dispersing times when
added as powders to liquid detergent compositions.
One method of avoiding such dusting and dispersion problems is
to add the brighteners to the liquid detergent compositions via a
premix which contains the optical brighteners and an additional
compound.
However, other problems arise when optical brighteners are
added to liquid detergent compositions as a premix, especially when
W o 92/06172 ~ ~ 9'~ ~ 6 ~ - 2 - pcT/ussl/o6984
added to highly built liquid detergent compositions. For example,
when the optical brightener is combined with nonionic surfactants
such as Neodol~ in the premix, the addition of the premix to highly
built liquid detergent compositions causes haziness and phase
separation. When the optical brightener is combined with alkyl
polyglycoside in the premix, the addition of the premix to highly
built liquid detergent compositions results in a milky, one-phase
product.
Therefore, it would be desirable to develop a premix by which
brighteners can be added to highly built liquid detergent
compositions which avoid such problems. It has now been discovered
that if brighteners are added to such detergent compositions via a
premix containing the brighteners and certain polyhydroxy fatty acid
amides, the aforementioned dusting and dispersing problems can be
avoided. Furthermore, adding brighteners via such a premix allows
for the formulation of clear, isotropic, highly built liquid
detergent compositions. Additionally, the use of such a premix, in
certain cases, allows for formulation and performance flexibility by
enabling facile addition of optical brighteners which are otherwise
difficult to incorporate into liquid detergent compositions.
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-methylglùcamide," 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 dissocittion 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,
WO 92/06172 ' PCI'/US91/06984
~()92560
_ - 3 -
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
surfacttnts, which can include N-methyl gluc~m,de, added ~; 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 con-
stituents to impart desirable properties to the composition can also
be included in the compositions, such as fluorescent dyes, bleaching
agents, perfumes, etc.
U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz,
relates to aqueous detergent compositions containing the condensa-
tion reaction product of N-alkyl glucamine and an aliphatic ester of
a fatty acid. The product of this reaction is said to be useable in
aqueous detergent compositions without further purification. It is
also known to prepare a sulfuric ester of acylated glucamine as
disclosed in U.S. Patent 2,717,894, issued September 13, 1955, to A.
M- Schwartz.
PCT International Application WO 83/04412, published December
22, 1983, by J. Hildreth, relates to amphiphilic compounds contain-
ing polyhydroxyl aliphatic groups said to be useful for a variety of
purposes including use as surfactants in cosmetics, drugs, shampoos,
lotions, and eye ointments, as emulsifiers and dispensing agents for
medicines, and in biochemistry for solubilizing membranes, whole
cells, or other tissue samples, and for preparing liposomes.
Included in this disclosure are compounds of the formula
R'C0N(R)CH2R" and RnCON(R)R' wherein R is hydrogen or an organic
grouping, R' is an aliphatic hydrocarbon group of at least three
carbon atoms, and R" is the residue of an aldose.
-European Patent 0 285 768, published October 12, 1988, H.
Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty
acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a
C1-C17 (preferably C7-C17) alkyl, R2 is hydrogen, a C1-C1g
(preferably C1-C6) alkyl, or an alkylene oxide, and X is a
polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl,
w o 92/06172 2 0 9 '~ 5 6 0 PCT/US91/06984
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 surfact-
ant systems can contain other anionic surfactants, such as alkylaryl
sulfonates, olefin sulfQnate, sulfosuccinic acid half ester salts,
and fatty alcohol ether sulfonates, and nonionic surfactants such as
fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty
acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed
polymers, etc. Paraffin sulfonate/N-methyl coconut fatty acid
glucamide/nonionic surfactant shampoo formulations are exemplified.
In addition to thickening attributes, the N-polyhydroxy alkyl fatty
acid amides are said to have superior skin tolerance attributes.
U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al.,
relates to detergent bars containing urea, sodium lauryl sulfate
anionic surfactant, and an N-alkylglucamide nonionic surfactant
which is selected from N-methyl,N-sorbityl lauramide and N-methyl,
N-sorbityl myristamide.
Other glucamide surfactants are disclosed, for example, in DT
2,226,872, published December 20, 1973, H. W. Eckert, et al., which
relates to washing compositions comprising one or more surfactants
and builder salts selected from polymeric phosphates, sequestering
agents, and washing alkalis, improved by the addition of an
N-acylpolyhydroxyalkyl-amine of the formula R1C(O)N(R2)CH2(CHOH)n-
CH20H, wherein R1 is a C1-C3 alkyl, R2 is a C1o-C22 alkyl, and n is
3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a soil
suspending agent.
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert,
et al., relates to detergent compositions comprising at least one
surfactant selected from the group of anionic, zwitterionic, and
nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl
polyhydroxylalkyl compound of the formula R1N(Z)C(O)R2 wherein R1 is
a C10-c22 alkyl, R2 is a C7-C21 alkyl, R1 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
R1N(R)CH(CHOH)mR2 wherein R1 is H, lower alkyl, hydroxy-lower alkyl,
WO 92/06172 . PCT/US91/06984
_ 5 2092a 60
or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as
Rl but both cannot be H, and R2 is CH20H or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial
Solvents Corporation, relates to solutions of formaldehyde
stabilized against polymerization with the addition of amides of the
formula RC(O)N(Rl)G wherein R is a carboxylic acid functionality
having at least seven carbon atoms, Rl is hydrogen or a lower alkyl
group, and G is a glycitol radical with at least 5 carbon atoms.
German Patent 1,261,861, February 29, 1968, A. Heins, relates
to glucamine derivatives useful as wetting and dispersing agents of
the formula N(R)(Rl)(R2) wherein R is a sugar residue of glucamine,
Rl is a Clo-C20 alkyl radical, and R2 is a Cl-Cs acyl radical.
G.B. Patent 745,036, published February 15, 1956, assigned to
Atlas Powder Company, relates to heterocyclic amides and carboxylic
esters thereof that are said to be useful as chemical intermediates,
emulsifiers, wetting and dispersing agents, detergents, textile
softeners, etc. The compounds are expressed by the formula
N(Rj(Rl)C(o)R2 wherein R is the residue of an anhydrized hexane
pentol or a carboxylic acid ester thereof, Rl is a monovalent
hydrocarbon radical, and -C(O)R2 is the acyl radical of a carboxylic
acid having from 2 to 25 carbon atoms.
U.S. Patent 3,312,627, issued April 4, 1967 to D. T. Hooker,
discloses solid toilet bars that are substantially free of anionic
detergents and alkaline builder materials, and which contain lithium
soap of certain fatty acids, a nonionic surfactant selected from
certain propylene oxide-ethylenediamine-ethylene oxide condensates,
propylene oxide-propylene glycol-ethylene oxide condensates, and
polymerized ethylene glycol, and also contain a nonionic lathering
component which can include polyhydroxyamide of the formula
RC(O)NRl(R2) wherein RC(O) contains from about 10 to about 14 carbon
atoms, and Rl and R2 each are H or Cl-C6 alkyl groups, said alkyl
groups containing a total number of carbon atoms of from 2 to about
7 and a total number of substituent hydroxyl groups of from 2 to
about 6. A substantially similar disclosure is found in U.S. Patent
3,312,626, also issued April 4, 1967 to D. T. Hooker.
However, none of these references disclose clear, isotropic,
highly built liquid detergent compositions prepared by adding one or
more optical brighteners in admixture with one or more polyhydroxy
w o 92/06172 PCT/US91/06984
2 0 ~ 2 S 6 U - 6 -
fatty acid amides. Nor do these references disclose preparing a
premix containing one or more optical brighteners and one or more
polyhydroxy fatty acid amides, or a method of preparing brightener-
containing liquid detergent compositions by adding the optica
brighteners to the detergent compositions via said premix.
It is therefore an object of the present invention to provide
such clear, isotropic brightener-containing, highly built liquid
detergent compositions.
It is another object of the present invention to provide an
optical brightener-containing premix which can be used as a vehicle
for adding brighteners to liquid detergent compositions.
It is still another obiect of the present invention to provide
a process for preparing optical brightener-containing liquid
detergent compositions, wherein said optical brightener is added in
conjunction with one or more polyhydroxy fatty acid amides in a
premix.
These objects will be realized by the present invention.
SUMMARY OF THE INVENTION
The present invention is directed toward highly-built,
liquid detergent compositions comprising:
(a) one or more conventional anionic, nonionic or
cationic detersive surfactants;
(b) one or more optical brighteners;
(c) one or more polyhydroxy fatty acid amides of the
general formula
O R1
R2 - C - N - Z
wherein Rl is H, a Cl-C4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl, or mixtures thereof, R2 is a
Cs-C31 hydrocarbyl group, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain with at least 3 hydroxyl groups directly
connected to the chain, or an alkoxylated derivative
thereof;
(d) one or more detergent builders; and
(e) a liquid carrier;
W O 92/06172 PC~r/US91/06984
_ - 7 - 2~2~6~
wherein the optical brightener is added to the detergent composition
in admixture with the polyhydroxy fatty acid amide.
The present invention is also directed toward a premix for use
in the formulation of liquid detergent compositions, said premix
comprising one or more optical brighieners, one or more polyhydroxy
fatty acid amides and a liquid carrier.
The present invention is also directed toward a method for
preparing optical brightener-containing liquid detergent
compositions wherein said brightener is added to said detergent
compositions via the above-described premix.
DETAILED DESCRIPTION OF THE INVENTION
DETERGENT COMPOSITIONS
The highly built liquid detergent compositions of the present
invention comprise one or more conventional anionic, nonionic or
cationic detersive surfactants, one or more optical brighteners, one
or more polyhydroxy fatty acid amides, one or more detergent
builders, and a liquid carrier. By ~highly built" it is meant that
the liquid detergent compositions comprise at least about 10% by
weight of one or more detergent builders.
The detergent compositions of the present invention preferably
comprise from about lX to about 30~h, more preferably from about 8Yo
to about 18%~ most preferably from about 10% to about 15X by weight
of the detersive surfactants; from about 0.01% to about 3%, more
preferably from about 0.01% to about 2.5%, most preferably from
about 0.01% to about 2% by weight of the optical brighteners; from
about 0.5% to about 30Z, more preferably from about 0.5% to about
20%, most preferably from about 0.5% to about 15% by weight of the
polyhydroxy fatty acid amides; from about 10% to about 50%, more
preferably from about 15X to about 35%, most preferably from about
15% to about 30% by weight of the detergent builders; and from about
20% to about 90%, more preferably from about 30% to about 77%, most
preferably from about 40% to about 75% by weight of the liquid
~ carrier.
Anionic Surfactants
One type of anionic surfactant which can be utilized encom-
passes alkyl ester sulfonates. Alkyl ester sulfonate surfactants
hereof include linear esters of Cg-C20 carboxylic acids (i.e., fatty
acids) which are sulfonated with gaseous SO3 according to "The
WO 92/06172 6 o - 8 - PCI'/US91/06984
Journal of the American Oil Chemists Society,~ 52 (1975), pp.
323-329. Suitable starting materials would include natural fatty
substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for
laundry applications, comprise alkyl ester sulfonate surfactants of
the structural formula:
O
R3 - CH - C - oR4
S03M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a Cl-C6 hydrocarbyl, preferably an alkyl,
or combination thereof, and M is a cation which forms a water
soluble salt with the alkyl ester sulfonate. Suitable salt-forming
cations include metals such as sodium, potassium, and lithium, and
substituted or unsubstituted ammonium cations, such as monoethanol-
amine, diethanolamine, and triethanolamine. Preferably, R3 is
Clo-C16 alkyl, and R4 is methyl? ethyl or isopropyl. Especially
preferred are the methyl ester sulfonates wherein R3 is Clo-C16
alkyl.
Alkvl Sulfate Surfactant
Alkyl sulfate surfactants hereof are water soluble salts or
acids of the formula ROS03M wherein R preferably is a Clo-C24
hydrocarbyl, preferably an alkyl or 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), or ammonium or substituted ammonium (e.g.,
methyl-, dimethyl-, and trimethyl ammonium cations and quaternary
ammonium cations such as tetramethylammonium and dimethyl
piperdinium cations and quaternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine, triethylamine, and
mixtures thereof, and the like). Typically, alkyl chains of C12 16
are preferred for lower wash temperatures (e.g., below about 50-C)
and C16 18 alkyl chains are preferred for higher wash temperatures
(e.g., above about 50-C).
Alkvl Alkoxvlated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M wherein R is an
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' ,~
unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C24
alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-Clg alkyl or hydroxyalkyl, A is an ethoxy or propoxy
unit, m is greater than zero, typically between about 0.5 and about
6, more preferably between about 0.5 and about 3, and M is H or a
cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperdinium cations and those
derived from alkylamines such as ethylamine, diethylamine, triethyl-
amine, mixtures thereof, and the like. Exemplary surfactants are
C12-Clg alkyl polyethoxylate (1.0) sulfate (C12-c18E(l-O)M)~ ~12-C18
alkyl polyethoxylate (2.25) sulfate (cl2-cl8E(2.2s)M)~ C12-C18 alkyl
polyethoxylate (3.0) sulfate (C12-C1gE(3.0)M), and C12-Clg alkyl
polyethoxylate (4.0) sulfate (C12-ClgE(4.0)M), wherein M is conven-
iently selected from sodium and potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive purposes can
also be included in the compositions hereof. These can include
salts (including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and triethanolamine
salts) of soap, Cg-C20 linear alkylbenzenesulfonates, Cg-C22 primary
or secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed
product of alkaline earth metal citrates, e.g., as described in
British patent specification No. 1,082,179, Cg-C24 alkylpolyglycol-
ethersulfates (containing up to 10 moles of ethylene oxide); alkylglycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin sulfonates, alkyl phosphates, isethionates such as the acyl
isethionates, acyl taurates, fatty acid amides of methyl tauride,
3s alkyl succinamates and sulfosuccinates, monoesters of sulfosuccin-
ates (especially saturated and unsaturated C12-C18 monoesters) and
diesters of sulfosuccinates (especially saturated and unsaturated
_ ~ ~ Q
C6-C1z diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such
as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds
being described below), branched primary alkyl sulfates, and fatty acids
esterified with isethionic acid and neutralized with sodium hydroxide.
Resin acids and hydrogenated resin acids are also suitable, such as rosin,
hydrogenated rosin, and resin acids and hydrogenated resin acids present
in or derived from tall oil. Further examples are described in "Surface
Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and
Berch). A variety of such surfactants are also generally disclosed in
U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al., at
Column 23, line 58 through Column 29, line 23.
Nonionic Deterqent Surfactants
Suitable nonionic detergent surfactants are generally disclosed in
15 U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, at
column 13, line 14 through column 16, line 6. Exemplary, non-limiting
classes of useful nonionic surfactants are listed below. The nonionic
polyhydroxy fatty acid amide contained in the composition of the present
invention is not considered to be a member of these conventional, nonionic
20 detersive surfactants for purposes of this invention.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
condensates are preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from about 6 to
2 5 about 12 carbon atoms in either a straight chain or branched chain
configuration with the alkylene oxide. In a preferred embodiment, the
ethylene oxide is present in an amount equal to from about 5 to about 25
moles of ethylene oxide per mole of alkyl phenyl. Commercially available
nonionic surfactants of this type include IgepalTM C0-630, marketed by the
GAF Corporation; and TritonTM X-45, X-114, X-100, and X-102, all marketed
by the Rohm & Haas Company.
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary or
3 5 secondary, and generally contains from about 8 to about 22 carbon
~ i
WO 92/06172 PCI/US91/06984
20~2S6~
- 11 -
atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from about 10 to about 20
carbon atoms with from about 2 to about 10 moles of ethylene oxide
~ per mule of alcohol. Examples of commercially avaiiable nonionic
surfactants of this type include TergitolTM 15-S-9 (the condensation
product of Cll-Cls linear alcohol with 9 moles ethylene oxide),
TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary
alcohol with 6 moles ethylene oxide with a narrow molecular weight
distribution), both marketed by Union Carbide Corporation; NeodolTM
45-9 (the condensation product of C14-Cls linear alcohol with 9
moles of ethylene oxide), NeodolTM 23-6.5 (the condensation product
of C12-C13 linear alcohol with 6.5 moles of ethylene oxide),
NeodolTM 45-7 (the condensation product of C14-Cls linear alcohol
with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation
product of C14-Cls linear alcohol with 4 moles of ethylene oxide),
marketed by Shell Chemical Company, and KyroTM EOB (the condensation
product of C13-Cls alcohol with 9 moles ethylene oxide), marketed by
The Procter & Gamble Company.
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide with
propylene glycol. The hydrophobic portion of these compounds
preferably has a molecular weight of from about 1500 to about 1800
and exhibits water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the water
solubility of the molecule as a whole, and the liquid character of
the product is retained up to the point where the polyoxyethylene
content is about 50X 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
oxide, and generally has a molecular weight of from about 2500 to
about 3000. ~nis hydrophobic moiety is condensed with ethylene
oxide to the extent that the condensation product contains from
W o 92/06172 2 0 9 2 5 6 0 PCT/USgl/06984
- 12 -
about 40% to about 80% by weight of polyoxyethylene and has a
molecular weight of from about 5,000 to about 11,000. Examples of
this type of nonionic surfactant include certain of the commercially
available TetronicTM compounds, marketed by BASF.
5. Semi-polar nonionic surfactanis are a specia7 caiegory of
nonionic surfactants which include water-soluble amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon
atoms and 2 moieties selected from the group consisting of alkyl
groups and hydroxyalkyl groups containing from about 1 to about 3
carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and hydroxyalkyl
groups containing from about 1 to about 3 carbon atoms; and
water-soluble sulfoxides containing one alkyl moiety of from about
10 to about 18 carbon atoms and a moiety selected from the group
consisting of alkyl and hydroxyalkyl moieties of from about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
0
R3(oR4)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
1 to about 3 carbon atoms or a polyethylene oxide group containing
from about 1 to about 3 ethylene oxide groups. The R5 groups can be
attached to each other, e.g., through an oxygen or nitrogen atom, to
form a ring structure.
These amine oxide surfactants in particular include Clo-Clg
alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl
amine oxides.
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group
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 contiining from about 1.3 to about
w o 92/06172 2 0 9 2 a 6 ~ PcT/usg1/O6984
10, preferably from about 1.3 to about 3, most preferably from about
1.3 to about 2.7 saccharide units. Any reducing saccharide contain-
ing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and
galactosyl moieties can be substituted for the glucosyl moieties.
- 5 (Optionally the hydrophobic group is attached at the 2-, 3-, 4-,
etc. positions thus giving a glucose or galactose as opposed to a
glucoside or galactoside.) The intersaccharide bonds can be, e.g.,
between the one position of the additional saccharide units and the
2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
Optionally, and less desirably, there can be a polyalkylene-
oxide chain joining the hydrophobic moiety and the polysaccharide
moiety. The preferred alkyleneoxide is ethylene oxide. Typical
hydrophobic groups include alkyl groups, either saturated or
unsaturated, branched or unbranched containing from about 8 to about
18, preferably from about 10 to about 16, carbon atoms. Preferably,
the alkyl group is a straight chain saturated alkyl group. The
alkyl group can contain up to about 3 hydroxy groups and/or the
polyalkyleneoxide chain can contain up to about 10, preferably less
than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are
octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecy~, and octadecyl, di-, tri-, tetra-, penta-, and
hexaglucosides, galactosides, lactosides, glucoses, fructosides,
fructoses and/or galactoses. Suitable mixtures include coconut
alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl
tetra-, penta-, and hexaglucosides.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(91YC~syl )x
wherein R2 is selected from the group consisting of alkyl, alkyl-
phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in
which the alkyl groups contain from about 10 to about 18, preferably
from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2;
t is from O to about 10, preferably 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
~ n ~ ~ 5 6~
- 14 -
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:
o
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, ~onoethanolamides,
diethanolamides, and isopropanolamides.
Cationic Surfactants
Cationic detersive surfactants can also be included in deter-
gent 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(CH20H)-,
-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-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
polymer having a molecular weight less-than about 1000, and hydrogen
when y is not O; R5 is the same as R4 or is an alkyl chain wherein
the total number of carbon atoms of R2 plus R5 is not more than
about 18; each y is from 0 to about 10 and the sum of the y values
is from 0 to about 15; and X is any compatible anion.
Other cationic surfactants useful herein are also described in
U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
Other Surfactants
Ampholytic surfactants can be incorporated into the detergent
compositions hereof. These surfactants can be broadly described as
~5 aliphat;c 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
B
J
~ - 15 - ~ 5 B ~
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
5 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.
Optical Bri~htener Component
The optical brighteners of the present invention are substantive to
textiles being washed and sometimes are of comparatively low solubilities.
Accordingly, it is important that they be maintained in solution in the
liquid detergent composition and, even more important, they must be
immediately dispersed in the washed water so as to avoid producing a wash
containing noticeable brightened spots, rather than a uniformly bright
appearance.
The choice of optical brighteners 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
temperature of the wash water, the degree of agitation, and the ratio of
the material washed to the tub size.
The brightener selection is also dependent upon the type of material
to be cleaned, e.g., cottons, synthetics, etc. Since most laundry
detergent products are used to clean a variety of fabrics, the detergency
compositions should contain a mixture of brighteners which are effective
for a variety of fabrics. It is of course necessary that the individual
35 components of such a brightener mixture be compatible.
B~
5 ~ ~
~_ - 16 -
Optical brighteners useful in the present invention are
commercially available and will be appreciated by those skilled in
the art. Commercial optical brighteners which may be useful in the
present invention czn ~e classified into subgroups which include,
but are not necessarily limited to, derivatives of stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines, diben~othio-
phene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles and
other miscellaneous agents. 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 inven-
tion include, but are not necessarily limited to, derivatives of
bis(triazinyl)amino-stilbenei bisacylamino derivatives o~ stilbene;
triazole derivatives of stilbene; oxadiazole derivatives of stil-
bene; oxazole derivatives of stilbene; and styryl derivatives of
stilbene.
Certain derivatives of bis(triazinyl)aminostilbene which may be
useful in the present invention may be prepared from 4,4'-diamine-
stilbene-2,2'-disulfonic acid. Examples of such derivatives
include, but are not limited to, those compounds disclosed at pages
39-42 of the Zahradnik reference which have the general formula
Rl N NH ~ CH~CH ~ HN N R
25 \C/ \C/ ~ ~ \C// \C/
l 11 1 11
N N S03Na S03Na N N
\\/ \\/
C C
R2 R2
30 wherein Rl and R2 are each selected from, respectively, Cl and
N(CH2CH20H)2; NH2 and NHCH2CH20H; N(CH3)CH2CH2S03H and N(CH2CH20H)2;
NH2 and NHC6Hs; NHCH2CH20H and NHC6Hs; N(CH2CH20H)2 and NHC6Hs;
N(CH2CH20H)2 and NHC6H4S03H (1,3); N(CH2CH20H)2 and NHC6H3(S03H)2
(1,2,4); N(CH3)CH2CH2S03H and NHC6H4S03H (1,3); NHC6Hs and NHC6Hs;
NHC6H4S~3H (1,4) and NHC6H4S03H (1,4); NHC6Hs and ~orpholino;
NHC6H3(S03H)2 (1,2,4) and morpholino; NHcH2cH2so3H and NHC6H3(S~3H)2
(1,2,4); OCH3 and N(CH2CH2~H)2; OCH3 and N(CH3)CH2CH2S03H; OH and
1D '
D i
- 17 - ~ n ~ ~ 5 ~ ~
'_
NHC6Hs; OCH3 and NHC6Hs; HHC6Hs and NHC6H4SO3H (1,3); and OCH3 and
~ NHCH3. Rl and R2 may also be individually selected from chloro,
bromo, hydroxy, Cl-C4 alkoxy, phenoxy, methyl-phenoxy, hydroxy-
oxaalkylamino, piperidino, pyrrolidino, analino, substituted
anilino, amino, aliphatic amine, heterocyclic amine, and thio
groups.
Examples of other stilbene derivatives which may be useful as
optical brighteners in the present invention can be found under the
heading ~8righteners, Optical~, in The Kirk-Othmer EncYcloDedia of
Chemical Technol w Y, Volume 3, pp. 737-750 (1962). '
Examples of pyrazoline derivatives which may be useful in the
present invention include, but are not necessarily limited to, those
disclosed on pages 59~62 of the Zahradnik reference.
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 both the-3-
and. 7-positions. Examples of coumarin derivatives substituted in
the 3-position include, but are not necessarily limited to, those
disclosed on pages 63-64 of the Zahradnik reference. Examples of
coumarin derivatives substituted in the 7-pos~tion include, but are
not necessarily limited to, those disclosed on pages 64-66 of the
Zahradnik reference. Examples of coumarin derivatives substituted
in both the 3- and 7-positions include, but are not necessarily
limited to, those disclosed on pages 66-~1 of the Zahradnik
reference. Other examples of coumarin derivatives which may be
useful in the present invention are disclosed at pages 744-745 of
the Kirk-Othmer reference.
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.
Examples of fumaric acid derivatives which may be useful in the
present invention include, but are not necessarily limited to, those
disclosed at pages 72-74 of the Zahradnik reference. Examples of
benzoic acid derivatives which may be useful in the present
~B-I
WO 92/06172 PCI/US91/06984
2 ~ g 2 ~ 6 0 - 18 -
invention include, but are not necessarily limited to, those
disclosed on pages 75-77 of the Zahradnik reference. Examples of
p-phenylene-bis-acrylic acid derivatives, naphthalenedicarboxylic
acid derivatives, and heterocyclic acid derivatives which may be
useful in the present invention include, but are not necessarily
limited to, those disclosed on pages 84-91 of the Zahradnik
reference.
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,
styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles,
and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik
reference. Styrylazoles can be further subclassified into styryl-
benzoxazoles, styrylimidazoles and styrylthiazoles, as disclosed on
page 78 of the Zahradnik reference. It will be understood that
these three identified subclasses may not necessarily reflect an
exhaustive list of the subgroups into which styrylazoles may be
subclassified.
Examples of cinnamic acid derivatives which may be useful in
the present invention include, but are not necessarily limited to,
those disclosed on pages 77-78 of the Zahradnik reference.
Examples of styrylbenzoxazole derivatives, 2-styrylbenzimidaz-
ole derivatives, styrylbenzofuran derivatives, styryloxadiazole
derivatives, and styrylpolyphenyl derivatives which may be useful in
the present invention include, but are not necessarily limited to,
those disclosed on pages 78-83 of the Zahradnik reference.
Methinecyanine derivatives which may be useful as optical
brighteners in the present invention include, but are not neces-
sarily limited to, those disclosed at pages 91-93 of the Zahradnik
reference. Examples of these types of brighteners include oxameth-
inecyanines and thiamethinecyanines.
Another class of brighteners which may be useful in the present
invention are the derivatives of dibenzothiophene-5,5-dioxide
disclosed on pages 741-749 of the Kirk-Othmer reference. Examples
of such brighteners include, but are not necessarily limited to,
3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.
Still another class of brighteners which may be useful in the
present invention include azoles, which are derivatives of
-19~ 5 ~ ~
5-membered ring heterocycles. These can be further subcategorized into
monoazoles and bisazoles. Examples of monoazoles are disclosed at pages
741-743 of the Kirk-Othmer reference. Examples of bisazoles which may be
5 useful in the present invention are disclosed at pages 743-744 of the
Kirk-Othmer reference.
An additional class of brighteners which may be useful in the
present invention are the derivatives of 6-membered-ring heterocycles
disclosed on page 745 of the Kirk-Othmer reference. Examples of such
compounds include brighteners derived from pyrazine and brighteners
derived from 4-aminonaphthalamide.
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
15 reference, and include 1-hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-
dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-di-phenylimidazolone-disulfonic
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 following
Phorwhites from Verona: BHC, BKL, BUP, BBH solution, BRN solution, DCR
liquid, DCBVF, EV liquid, DBS liquid and ANR. Other brighteners disclosed
in this reference include, Tinopal UNPA, Tinopal CBS and Tinopal 5BM,
available from Ciba-Geigy, located in Switzerland; Arctic White CC and
25 Arctic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-
styryl-phenyl)-2H-naphthol-[1,2-d]triazoles; 4,4'-bis(1,2,3-triazol-2-yl)-
stilbenes; 4,4'-bis-(styryl)bisphenyls; and the y-aminocoumarins.
Specific examples of these brighteners include 4-methyl-7-diethyl-amino
coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene: 1,3-diphenylphrazolines;
30 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[1,2-d]oxazole; and 2-
(stilbene-4-yl)2H-naphtho[1,2-d]triazole.
Other optical brighteners which may be useful in the present
invention include those disclosed in U.S. Patent 3,646,015, issued
February 29, 1972 to Hamilton, and those disclosed in U.S. Patent
3 5 4,483,780, issued November 20, 1984 to Llenado.
..
~.
w o 92/06172 P ~ /US91/06984
2092S~0 - 20 - _f
Anionic optical brighteners are preferred in the present
invention. More preferred are the brighteners having the following
structures:
Rl RI
C ~ N N - C
N C - N ~ CH=CH ~ N - C N (I)
C - N N... C
NaO3S S03Na
R~ R2
C ~ N N - CH
¦N ~ CH-CH ~ N ¦ (IIJ
HC - N ~ r N = C
NaO3S S03Na
CH-CH ~ CH=CH ~ (III)
S03Na S03Na
~ C - CH-CH - C ~ (IV)
H3C N ~ CH3
~ ~ C ~ C ~ ~ (V)
CH=CH ~ N _ ~ (VI)
S03Na l~ ~J
and mixtures thereof, wherein Rl is -NHC6Hs ~ R2 is selected from
-N(CH2CH20H)2, -N(CH3)CH2CH20H, -NHC6Hs and a morpholino group.
Most preferred are the compounds having the structures I, III,
and YI.
Polvhvdroxv Fattv Acid Amide
The polyhydroxy fatty acid amide surfactant component of the
present invention comprises compounds of the structural formula:
O Rl
I) R2 C - N - Z
W O 92/06172 PC~r/US91/06984
- 21 -2'0 g 2 ~ 6 0
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
other suitable raw materials. Z preferably will be selected from
the group consisting of -CH2-(CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n 1-
-CH2OH, -CH2-(CHOH)2(CHOR')(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 are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
In Formula (I), Rl can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy
propyl.
R2-CO-N< can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,
1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl, 1-deoxymalto-
triotityl, etc.
The most preferred polyhydroxy fatty acid amide has the general
formula
0 CH3
u
R2 - C - N - CH2 - (CHOH)4CH2OH
wherein R2 is a C11-C17 straight-chain alkyl or alkenyl group.
Methods for making polyhydroxy fatty acid amides are known in
the art. In general, they can be made by reacting an alkyl amine
- 22 - ~ 5 ~ ~ -
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 compositionscontaining polyhydroxy fatty acid amides are disclosed, for example,
in G.B. Patent Specification 809,060, published February 18, 1959,
by Thomas Hedley ~ Co., Ltd., U.S. Patent 2,965,576, issued December
20, 1960 to E. R. Wilson, and U.S. Patent 2,703,798, Anthony M.
Schwartz, issued March 8, 1955, and U.S. Patent 1,985,424, issued
December 25, 1934 to Piggott.
In one process for producing N-alkyl or H-hydroxyalkyl,
N-deoxyglycityl fatty acid amides wherein the glycityl component is
derived from glucose and the N-alkyl or N-hydroxyalkyl functionality
is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or
N-hydroxypropyl, the product is made by reacting N-alkyl- or
N-hydroxyalkyl-glucamine with a fatty ester selected from fatty
methyl esters, fatty ethyl esters, and fatty triglycerides in the
presence of a catalyst selected from the group consisting of tri-
lithium phosphate, trisodium phosphate, tripotassium phosphate,tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium
hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide,
lithium carbonate, sodium carbonate, potassium carbonate, disodium
tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium
citrate, tripotassium citrate, sodium basic silicates, potassium
basic silicates, sodium basic aluminosilicates, and potassium basic
aluminosilicates, and mixtures thereof. The amount of catalyst is
preferably from about 0.5 mole X to about 50 mole %, more preferably
from about 2.0 mole % to about 10 mole %, on an N-alkyl or
N-hydroxyalkyl-glucamine molar basis. The reaction is preferably
carried out at from about 138-C to about 170-C for typically from
about 20 to about 90 minutes. When triglycerides are utilized in
the reaction mixture as the fatty ester source, the reaction is also
preferably carried out using from about 1 to about 10 weight % of a
phase transfer agent, calculated on a weight percent basis of total
w o 92/06172 ~ a 9 2 ~ ~ O PCT/USg1/06984
- 23 -
reaction mixture, selected from saturated fatty alcohol polyethoxyl-
ates, alkylpolyglycosides, linear glycamide surfactant, and mixtures
thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138-C to about 170-C;
(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the
heated fatty acid ester and mixing to the extent needed to
form a two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and
(d) stirring for the specified reaction time.
Also preferably, from about 2% to ibout 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-
petrochemical feedstocks and are degradable. They also exhibit low
toxicity to aquatic life.
It should be recognized that along with the polyhydroxy fatty
acid amides of Formula (~), 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 pr~ferred processes described above are
advantageous in that they can yield rather low levels of
by-products, including such cyclic amide by-product.
Builders
The detergent compositions of the present invention comprise
inorganic or organic detergent builders to assist in mineral
hardness control.
,
- 24 -
~~ Inorganic detergent builders include, but are not limited to,
the alkali metal, ammonium and alkanolammonium sa1ts of polyphos-
phates (exemplified by the tripolyphosphates, pyrophosphates, and
glassy polymeric meta-phosphates), phosphonates, silicates, carbon-
ates (including bicarbonates and sesquicarbonates)~ sultates, and
aluminosilicates. Borate builders, as well as builders containing
borate-forming materials that can produce borate under detergent
storage or wash conditions, can be used but preferably are not used
in the compositions of the invention.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiO2:Na20 ratio in the range 1.6:1 t~
3.2:1. However, other silicates may also be useful such as for
example magnesium silicate, which can serve as a crispening agent in
granular formulations, as a stabilizing agent for oxygen bleaches,
and as a component of suds control systems.
Examples of carbonate builders are the alkaline earth and
alkali metal carbonates, including sodium carbonate and sesquicar-
bonate and mixtures thereof with ultra-fine calcium carbonate as
disclosed in German Patent Application No. 2,321,001 published on
November 15, 1973.
Aluminosilicate builders are es?ecially useful in the present
invention. Aluminosilicate builders are of great importance in most
currently marketed heaYy duty granular detergent compositions, and
can also be a significant builder ingredient in liquid detergent
formulations. Aluminosilicate builders include those having the
formula:
Naz[(Alo2)z(sio2)y] xH2o
wherein z and y are integers of at least 6, the molar ratio of z to
y is in the range from 1.0 to about 0.5, and x is an integer from
about 15 to about 264. Preferred amorphous hydrated aluminosilicate
materials have the empirical formula:
MZ(zAlo2-ysio2)
wherein M is sodium, potassium, ammonium or substituted ammonium, z
is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
E~
-25- .2 ~
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be crystalline or amorphous in
structure and can be naturally-occurring aluminosilicates or synthetically
5 derived. A method for producing aluminosilicate ion exchange materials is
disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12,
1976. Preferred synthetic crystalline aluminosilicate ion exchange
materials useful herein are available under the designations Zeolite A,
Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the
crystalline aluminosilicate ion exchange material has the formula:
Nal2[(Aloz)l2(sioz)lz] xHzO
wherein x is from about 20 to about 30, especially about 27.
Specific examples of polyphosphates are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium
15 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. Particularly preferred
are the alkali metal tripoly- and pyro- phosphates.
Examples of phosphonate builder salts are the water-soluble salts
of ethane 1-hydroxy-1,1-diphosphonate particularly the sodium and
potassium salts, the water-soluble salts of methylene diphosphonic acid
e.g. the trisodium and tripotassium salts and the water-soluble salts of
substituted methylene diphosphonic acids, such as the trisodium and
tripotassium ethylidene, isopyropylidene benzylmethylidene and halo
25 methylidene phosphonates. Phosphonate builder salts of the aforementioned
types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 issued
December 1, 1964 and October 19, 1965, to Diehl: U.S. Patent No. 3,422,021
issued January 14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and
3,422,137 issued September 3, 1968, and January 14, 1969 to Quimby.
Organic detergent builders 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.
,p ~
'i~" ~S
5 ~; ~
- 26 -
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of polycar-
boxylate builders encompasses the ether polycarboxylates. A number
of ether polycarboxylates have been disclosed for use as d~tergent
builders. Examples of useful ether polycarboxylates include oxydi-
succinate, 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 ~ 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 (T~S) and its water-soluble salts. If A
is H and B is -O-CH(COOX)-CH2(COOX), then the compound is tartrat-e
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 ~DS in a weight ratio of TMSto 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.
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:
HO-[C(R)(COOM)-C(R)(COOM)-o]n-~
wherein M is hydrogen or a cation wherein the resultant salt is
water-soluble, preferably an alkali metal, ammonium or substituted
ammonium cation, n is from about 2 to about 15 (preferably n is from
about 2 to about 10, more preferably n averages from about 2 to
about 4) and each R is the same or different and selected from
3~ hydrogen, C1 4 alkyl or C1 4 substituted alkyl (preferably R is
hydrogen).
~5 'I
-27-
Still other ether polycarboxylates include copolymers of maleic
anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-
2,4,6-trisulfonic acid, and carboxy-methyloxysuccinic acid.
Organic polycarboxylate builders also include the various alkali
metal, ammonium and substituted ammonium polyacetatess. Examples of
polyacetate builders are the sodium, potassium, lithium, ammonium and
substituted ammonium salts of ethylenediamine tetraacetic acid,
nitrilotriacetic acid, and mellitic acid.
Also included are polycarboxylates such as mellitic acid, tartaric
acid, itaconic acid, succinic acid, oxydisuccinic acid, maleic acid,
polymaleic acid. benzene 1,3,5-tricarboxylic acid, and
carboxymethyloxysuccinic acid.
Citric builders, e.g., citric acid, polycarboxylate builder of
particular importance for heavy duty liquid detergent formulations, but
can also be used in granular compositions.
Other carboxylate builders include the carboxylated carbohydrates
disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973.
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 or alkanolammonium salts are
preferred.
Also suitable in the detergent compositions of the present invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent 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 dodecenyl-
succinic acid. Alkyl succinic acids typically are of the general formula
R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid, wherein R is
hydrocarbon, e.g., C1o-C20 alkyl or alkenyl, preferably C12-C16 or wherein R
may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents,
all as described in the above-mentioned patents.
The succinate builders are preferably used in the form of their
water-soluble salts, including the sodium, potassium, ammonium and
alkanolammonium salts.
..
28 - ~ ~
Specific examples of succinate builders include: lauryl succinate,
myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred)
2-pentadecenyl succinate, and the like.
Examples of useful builders also include sodium and potassium
carboxy-methyloxmalonate, carboxmethyloxysuccinate, cis-cyclohexane-
hexacarboxylate, cis-cyclopentane-tetracarboxylate phloroglucinol tri-
sulfonate, water-soluble polyacrylate (these polyacrylates having
molecular weights to above about 2,000 can also be effectively utilized as
dispersants), and the copolymers of maleic anhydride with vinyl methyl
ether or ethylene.
Other suitable polycarboxylates are the polyacetyl carboxylates
disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13,
1979. These polyacetyl 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.
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.
Liquid Carrier
The detergent compositions of the present invention comprise a
liquid carrier, e.g., water, preferably a mixture of water and a C1- C4
monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol, and
mixtures thereof), with ethanol being the preferred alcohol.
Optional Inqredients
Bleachinq Compounds - Bleachinq Aqents and Bleach Activators
The detergent compositions hereof may contain bleaching agents
or bleaching compositions containing bleaching agent and one or more
bleach activators. When present bleaching compounds will typically
be present at levels of from about 1% to about 20%, more typically
from about 1% to about 10%, of the detergent composition. In
5 ~ ~
_ - 29 -
general, bleaching compounds are optional components in non-liquid
formulations, e.g., granular detergents. If present, the amount of bleach
activators will typically be from about 0.1% to about 60%, more typically
from about 0.5% to about 40% of the bleaching composition.
The bleaching agents used herein can be any of the bleaching agents
useful for detergent compositions in textile cleaning, hard surface
cleaning, or other cleaning purposes that are now known or become known.
These include oxygen bleaches as well as other bleaching agents. For wash
conditions below about 50~C, especially below about 40~C, it is preferred
0 that the compositions hereof not contain borate or material which can form
borate in situ (i.e. borate-forming material) under detergent storage or
wash conditions. Thus it is preferred under these conditions that a non-
borate, non-borate-forming bleaching agent is used. Preferably,
detergents to be used at these temperatures are substantially free of
borate and borate-forming material. As used herein, "substantially free of
borate and borate-forming material" shall mean that the composition
contains not more than about 2% by weight of borate-containing and
borate-forming material of any type, preferably, no more than lX, more
preferably 0%.
2 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 monoperoxyphthalate hexahydrate,
the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoper-
oxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are
2 5 disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984,
Burns et al., Canadian Patent Application Serial No. 1,245,222, 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-nonyl-amino-6-oxoperoxycaproic
acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to
Burns, et al.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of hypohalite
bleaching agents, for example, include trichloro isocyanuric acid
C
. ~
~ Q ~
- 30 -
and the sodium and potassium dichloroisocyanurates and N-chloro and N-
bromo alkane sulfonamides. Such materials are normally added at 0.5-10%
by weight of the finished product, preferably 1-5% by weight.
Peroxygen bleaching agents can also be used. Suitable peroxygen
bleaching compounds include sodium carbonate peroxyhydrate, sodium
pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
Peroxygen bleaching agents are preferably combined with bleach
activators, which lead to the in situ production in aqueous solution
(i.e., during the washing process) of the peroxy acid corresponding to the
bleach activator.
Preferred bleach activators incorporated into compositions of the
present invention have the general formula:
o
R - ~ - L
wherein R is an alkyl group containing from about 1 to about 18 carbon
atoms wherein the longest linear alkyl chain extending from and including
the carbonyl carbon contains from about 6 to about 10 carbon atoms and L,
20 is a leaving group, the conjugate acid of which has a PKa in the range of
from about 4 to about 13. These bleach activators are described in U.S.
Patent 4,915,854, issued April 10, 1990 to Mao, et al, and U.S. Patent
4,412,934.
Bleaching agents other than oxygen bleaching agents are also known
2 5 in the art and can be utilized herein. One type of non-oxygen bleaching
agent of particular interest include photo-activated bleaching agents such
as the sulfonated zinc and/or aluminum phthalocyanines. These materials
can be deposited upon the substrate during the washing process. Upon
irradiation with light, in the presence of oxygen, such as by hanging
clothes out to dry in the daylight, the sulfonated zinc phthalocyanine is
activated and, consequently, the substrate is bleached. Preferred zinc
phthalocyanine and the 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.
B~i
- 3 1
'_
- PolYmeric Soil Release Aqent
Any polymeric soil release agents kno~n to those skilled in the
art can be employed in the practice of this invention. Polymeric
soil release agents are characterized by having both hydrophilic
5 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.
Polymeric soil release agents useful in the present invention
include cellulosic derivatives such as hydroxyether cellulosic
polymers, copolymeric blocks of ethylene terephthalate or propylene
15 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
ce~lulose 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 hydroxybutyl methylcellulose. A
variety of cellulose derivatives useful as soil release polymers are
disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to
Nicol, et al.
Soil release agents characterized by poly(vinyl ester)
hydrophobe segments include graft copolymers of poly(vinyl ester),
e.g., Cl-C6 vinyl esters, preferably poly(vinyl acetate) grafted
30 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., SckalanTM
35 HP-22, available from BASF (West Germany).
B 1
_ - 32 ~
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephthalate and polyethylene oxide (PEO)
terephthalate. More specifically, these polymers are comprised of
5 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
5 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
2 5 product of a substantially linear ester oligomer comprised of an
oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units
and terminal moieties covalently attached to the backbone, said soil
release agent being derived from allyl alcohol ethoxylate, dimethyltere-
phthalate, and 1,2 propylene diol, wherein the terminal moieties of each
oligomer have, on average, a total of from about 1 to about 4 sulfonate
groups. These soil release agents are described fully in U.S. Patent
4,968,451, issued November 6, 1990, to J.J. Scheibel and E.P. Gosselink.
Other suitable polymeric soil release agents include the ethyl- or
methyl-capped 1,2-propylene terephthalate-polyoxyethylene terephthalate
B -~
~_ - 33 -
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
5 comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG),
the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued
October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula
X-(OCH2CH2)n- wherein n is from 12 to about 43 and X is a Cl-C4 alkyl, or
preferably methyl.
Additional soil release polymers include the soil release polymers
of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al.,
which discloses anionic, especially sulfoaroyl, end-capped terephthalate
esters. The terephthalate esters contain unsymmetrically substituted oxy-
1,2-alkyleneoxy units. Included among the soil release polymers of U.S.
15 Patent 4,877,896 are materials with polyoxyethylene hydrophile components
or C3 oxyalkylene terephthalate (propylene terephthalate) repeat units
within the scope of the hydrophobe components of (b)(i) above. It is the
soil release polymers 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%, preferably from about 0.1% to about 5.0%, more
preferably from about 0.2% to about 3.0% by weight of the detergent
compositions herein.
2 5 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, poly-functionally-substituted aromatic
30 chelating agents and mixtures thereof, all as hereinafter defined.
Without intending to be bound by theory, it is believed that the benefit
of these materials is due in part to their exceptional ability to remove
iron and manganese ions from washing solutions by formation of soluble
chelates.
D i
W O 92/06172 PC~r/US91/06984
2092~60 34
Amino ca~boxylates 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-hydroxyethyl-
ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine
tetraproprionates, triethylenetetraaminehexaacetates, diethylenetri-
aminepentaacetates, and ethanoldiglycines, alkali metal, ammonium,and substituted ammonium salts thereof and mixtures thereof.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low levels
of total phosphorus are permitted in detergent compositions.
Compounds with one or more, preferably at least two, units of the
substructure
- CH2
\
N - (cH2)x - 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
(methylenephosphonates) and diethylenetriaminepentakis (methylene-
phosphonates). Preferably, these amino phosphonates do not containalkyl 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
~~ - 35 -
OH
R ~ OH
10 1
R ~ R
R
wherein at least one R is -SO3H or -COOH or soluble salts thereof and
mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974-to Connor et
al, discloses polyfunctionally-substituted aromatic chelating and
5 sequestering agents. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
Alkaline detergent compositions can contain these materials in the form of
alkali metal, ammonium or substituted ammonium (e.g. mono- or triethanol-
amine) salts.
If utilized, these chelating agents will generally comprise from
about 0.1% to about 10% by weight of the detergent compositions herein.
More preferably chelating agents will comprise from about 0.1% to about
3.0% by weight of such compositions.
Clay Soil Removal/Anti-redeposition Aqents
The compositions of the present invention can also optionally
contain water-soluble ethoxylated amines having clay soil removal and
anti-redeposition properties. Examples of such agents include
polyethylene glycols and water-soluble ethoxylated amines having clay soil
removal and anti-redeposition properties.
Polyethylene glycol compounds useful in the compositions of the
present invention typically have a molecular weight in the range of from
about 400 to about 100,000, preferably from about 1,000 to about 20,000,
more preferably from about 2,000 to about 12,000,~most preferably from
about 4,000 to about 8,000. Such compounds are commercially available and
25 are sold as Carbowax~, which is available from Union Carbide, located in
Danbury, Conn.
The water-soluble ethoxylated amines are preferably selected from
the group consisting of:
(1) ethoxylated monoamines having the formula:
(X-L-)-N-(R2)2
~. .
w o 92/06172 2 ~ 9 2 5 6 0 36 - PCT/ussl/06984
(2) ethoxylated diamines having the formula: -
R2-N-Rl N R2 (R2)2-N-,Rl-N-(R2)2
L L
X X X
5or
(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) ethoxylatd amine polymers having the general formula:
R2
[(R2)2-N3WERl-N3XE~l-N3yERl~N~L~X)z
and
(5) mixtures thereof; wherein Al is
O O O O O
"
-NC-, -NCO-, -NCN-, -CN-, -OCN-,
R R R lR R R~0
O O 0 00
Il 11 U 1! 11
-CO-, -OCO-, -OC-, -CNC-,
or -0-; R is H or Cl-C4 alkyl or hydroxyalkyl; Rl is C2-C12 alkyl-
ene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C2-C3
oxyalkylene moiety having from 2 to about 20 oxyalkylene units
provided that no O-N bonds are formed; each R2 is Cl-C4 or hydroxy-
alkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r,
-A2-(CH2)S-, wherein A2 is -O- or -CH2-, r is 1 or 2, s is 1 or 2,
and r + s is 3 or 4; X is a nonionic group, an anionic group or
mixture thereof; R3 is a substituted C3-C12 alkyl, hydroxyalkyl,
alkenyl, aryl, or alkaryl group having substitution sites; R4 is
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 0-0 or O-N bonds are formed; L is a hydro-
philic chain which contains the polyoxyalkylene moiety -[(R50)m~
(CH2CH20)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m
and n are numbers such that the moiety -(CH2CH~O)n- comprises at
_ 37 =~ ~ ~ 6~
least about 50% by weight of said polyoxyalkylene moiety; for said
monoamines, m is from 0 to about 4, and n is at least about 12: for said
diamines, m is from 0 to about 3, and n is at least about 6 when R1 is C2-C3
alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when 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 tetraethylene-pentamine. 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 thé
amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October
22, 1985.
Granular detergent compositions which contain such compounds
typically contain from about 0.01% to about 10.0% by weight of the clay-
removal agent, liquid detergent compositions typically contain from about
0.01% to about 5% by weight.
Polymeric Dispersinq Aqents
Polymeric polycarboxylate dispersing agents can advantageously
be utilized in the compositions hereof. These materials can aid
in calcium and magnesium hardness control. In addition to acting
as a builder adjunct analogously to the polycarboxylate described
above in the Builder description, it is believed, though it is
not intended to be limited by theory, that these higher molecular
weight dispersing agents can further enhance overall detergent
builder performance by inhibiting crystal growth of inorganics, by
particulate soil peptization, and by antiredepositions, when used in
~r
~ 1
w o 92/06172 P ~ /US91/06984
2 ~ 9 ~ 5 6 ~ - 38 -
combination with other builders including lower molecular weight
polycarboxylates.
The polycarboxylate materials which can be employed as the
polymeric polycarboxylate dispersing agent component herein are
ihese pulymers Gr copolymers which contain at least about 60~'- by
weight of seçments with the general formula
X Z
l l
-- 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 hydroxy-
methyl; a salt-forming cation and n is from about 30 to about 400.
Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is
hydrogen and M is hydrogen, alkali metal, ammonia or substituted
ammonium.
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 poly-
carboxylates include acrylic acid, maleic acid (or maleic
anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic
acid, citraconic acid and methylenemalonic acid. The presence in
the polymeric polycarboxylates herein of monomeric segments,
containing no carboxylate radicals such as vinylmethyl ether,
styrene, ethylene, etc. is suitable provided that such segments do
not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived
from acrylic acid. Such acrylic acid-based polymers which are
useful herein are the water-soluble salts of polymerized acrylic
acid. The average molecular weight of such polymers in the acid
form ranges from about 2,000 to 10,000, more preferably from about
4,000 to 7,000 and most preferably from about 4,000 to 5,000.
Water-soluble salts of such acrylic acid polymers can-include, for
example, the alkali metal, ammonium and substituted ammonium salts.
Soluble polymers of this type are known materials. Use of
- 39 -
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 agent. Such materials include the
water-soluble salts of copolymers of acrylic acid and maleic acid.
The average molecular weight of such copolymers in the acid form
ranges from about 5,000 to 100,000, preferably from about 6,0Q0 to
60,000, more preferably from about 7,000 to 60,000. The ratio of
acrylate to maleate segments in such copolymers will generally range
from about 30:1 to about 1:1, more preferably from about 10:1 to
2:1. Water-soluble 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.
If utilized, the polymeric dispersing agents will generally
comprise from about 0.2% to about 10X, preferably from about 1% to
about 5% by weight of the detergent compositions herein.
Suds SuDPressors
Compounds known, or which become known, for reducing or
suppressing the formation of suds can be incorporated into the
compositions of the present invention. The incorporation of such
materials, hereinafter ~suds suppressors," 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 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 c~ suds
suppressors can also be of particular importance under hot water
40 ~
washing conditions and under high surfactant concentration conditions.
A wide variety of materials may be used as suds suppressors in the
compositions hereof. Suds suppressors are well known to those skilled in
5 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
15 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, high molecular weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty aci d
20 triglycerides), fatty acid esters of monovalent alcohols, aliphatic Cl8-C40
ketones (e.g. stearone), etc. Other suds inhibitors include N-alkylated
amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-
alkyldiamine chlortriazines formed as products of cyanuric chloride with
two or three moles of a primary or secondary amine containing 1 to 24
2 5 carbon atoms, propylene oxide, and monostearyl phosphates such as
monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.,
sodium, potassium, lithium) phosphates and phosphate esters. The
hydrocarbons, such as paraffin and haloparaffin, can be utilized in
liquid form. The liquid hydrocarbons will be liquid at room
30 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
35 suppressor for detergent compositions. Hydrocarbon suds suppressors are
~ - 41 -
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
5 from about 12 to about 70 carbon atoms. The term "paraffinic," 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 of polyorganosiloxane
with silica particles wherein the polyorganosiloxane is chemisorbed or
fused onto the silica. Silicone suds suppressors are well known in the
art and are, for example, disclosed in U.S. Patent 4,265,779, issued May
15 5, 1981 to Gandolfo et al. and European Patent Application No. 89307851.9,
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
20 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 U.S. Patent
25 4,652,392, Baginski et al., issued March 24, 1987.
An exemplary silicone based suds suppressor for use herein is a suds
suppressing amount of a suds controlling agent consisting essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from about
20 cs. to about 1500 cs. at 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 about (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 1O0 parts by weight of (i)
of a solid silica gel;
Bl
.,
WO 92/06172 PCI/US9t/06984
20~2~60 - 42 -
Suds suppressors, when utilized, are present in a "suds sup-
pressing amount." By "suds suppressing amount" is meant that the
formulator of the composition can select an amount of this suds
controlling agent that will control the suds to the extent desired.
The amount of suds control will vary with the detergent surfactant
selected. For example, with high sudsing surfactants, relatively
more of the suds controlling agent is used to achieve the desired
suds control than with low foaming surfactants.
The compositions hereof will generally comprise from 0% to
about SX of suds suppressor. When utilized as suds suppressors,
monocarboxylic fatty acids, and salts thereof, will be present
typically in amounts up to about 5%, by weight, of the detergent
composition. Preferably, from about 0.5% to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to about 2.0%, by
weight, of the detergent composition, although higher amounts may be
used. This upper limit is practical in nature, due primarily to
concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from about
0.01% to about lX of silicone suds suppressor is used, more
preferably from about 0.25X 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 O.OlX to about 5.0%, although higher levels can
be used.
Enzvmes
Detersive enzymes can be included in the detergent formulations
for a variety of reasons including removal of protein-based,
carbohydrate-based, or triglyceride-based stains, for example, and
prevention of refugee dye transfer. The enzymes to be incorporated
include proteases, amylases, lipases, cellulases, and peroxidases,
as well as mixtures thereof. ~hey 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 Esperase2. 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
2 o described in European Patent Application 130,756, published January 9,
1985. Protease B is a proteolytic enzyme which differs from Protease A in
that it has a leucine substituted for tyrosine in position 217 in its
amino acid sequence. Protease B is described in European Patent
Application EP 251446, published January 7, 1988. Methods for preparation
2 5 of Protease B are also disclosed in European Patent Application 130,756,
Bott et al., published January 9, 1985.
Amylases include, for example, ~-amylases obtained from a special
strain of B.licheniforms, described in more detail in British patent
specification No. 1,296,839 (Novo). Amylolytic proteins include, for
example, RAPIDASETM, International Bio-Synthetics, Inc. and TERMAMYLTM, Novo
Industries.
The cellulases usable in the present invention include both
bacterial or fungal cellulase. Preferably, they will have a pH optimum of
between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent
4,435,307, Barbesgoard et al., issued March-6, 1984, which discloses
fungal cellulase produced from Humicola insolens. Suitable cellulases are
also disclosed in GB-A-2.075.028; GB-A-2.095,275 and DE-OS-2.247.832.
B~
- 44 ~
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
5 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 lipase, 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
15 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, using a standard and well-known immunodiffusior
2 o 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
25 trade name Amano-B), lipase ex Pseudomonas nitroreducens var. 1ipo1yticum
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 vi scosum 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.
B~'
~~ - 45 -
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,
5 and include, for example, horseradish peroxidase, ligninase, and
haloperoxidase 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
15 materials useful for liquid detergent formulations, and their
incorporation into such formulations, are disclosed in U.S. Patent
4,261,868, Hora et al., issued April 14, 1981.
Enzymes are normally incorporated at levels sufficient to provide
up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of
active enzyme per gram of the composition.
For granular detergents, the enzymes are preferably coated or
prilled with additives inert toward the enzymes to minimize dust formation
and improve storage stability. Techniques for accomplishing this are well
known in the art. In liquid formulations, an enzyme stabilization system
25 iS preferably utilized. Enzyme stabilization techniques for aqueous
detergent compositions are well known in the art. For example, one
technique for enzyme stabilization in aqueous solutions involves the use
of free calcium ions from sources such as calcium acetate, calcium
formate, and calcium propionate. Calcium ions can be used in combination
with short chain carboxylic acid salts, preferably formates. See, for
example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1982. It
has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-
alcohols, dialkylglycoethers, mixtures of polyvalent alcohols with
polyfunctional aliphatic amines (e.g., alkanolamines such diethanolamine,
3 5 triethanolamine, diisopropanolamine, etc.), and boric acid or alkali metal
B~
,
- 46 ~
borate. Enzyme stabilization techniques are additionally disclosed and
exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et
al., U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al., and
European Patent Application Publication No. 0 199 405, Application No.
86200586.5, published October 29, 1986, Venegas. Non-boric acid and
borate stabilizers are preferred. Enzyme stabilization systems are also
described, for example, in U.S. Patents 4,261,868, 3,600,319, and
3,519,570.
0 Other Inqredients
A wide variety of other ingredients useful in detergent compositions
can be included in the compositions hereof, including other active
ingredients, carriers, processing aids, dyes or pigments, perfumes,
solvents for liquid formulations, hydrotropes (as described below) etc.
Liquid detergent compositions can contain water and other solvents.
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 about 2 to about 6 carbon atoms and from about 2 to'
20 about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol,
glycerine, and 1,2-propanediol) can also be used.
The detergent compositions hereof will preferably be formulated such
that during use in aqueous cleaning operations that 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 (10% dilution)
pH between about 7.5 and about 10.0, more preferably between about 7.5 and
about 9Ø Techniques for controlling pH at recommended usage levels
include the use of buffers, alkali, acids, etc., and are well known to
those skilled in the art.
3 0 PREMIX
The premix of the present invention comprises one or more
optical brighteners, one or more polyhydroxy fatty acid amides
and a liquid carrier. The optical brighteners, polyhydroxy fatty acid
amines and liquid carrier are as already described herein for the
B~
_ - 47 -
detergent compositions of the present invention. Preferably the
premix comprises from about 1% to about 20%~ more preferably from
about 1% to about 10% by weight of the optical brighteners; from
about 10% to about 60%? more preferably from about 30~~ to about 50%
by weight of the polyhydroxy fatty acid amides; and from about 20%
to about 89%, more preferably from about 40% to about 69% by weight
of the liquid carrier.
It is important to note that the premix of the present
invention has a gelling temperature in the range of from about 40~C
to about 48~C, depending upon the product purity. However, this
gelling temperature can be lowered by the addition of one or more
select additional components. Thus, if the premix is to be used
when preparing optical brightener-containing liquid detergent
compositions, it must either be kept above about 40~C to about 48~C
or it must contain the select additional component.
Select additional components useful for lowering the gelling
temperature of the premix include, but are not limited to, anionic
surfactants (as already described herein), solvents, ethanolamine,
preferably mono- and triethanolamines, and hydrotropes. Examples of
solvents useful for lowering the gelling temperature of the premix
include, but are not limited to, C1-C6 alcohols, preferably C2-C4
alcohols, and C1-C6 glycols, preferably C2-C4 glycols. Examples of
hydrotropes useful for lowering the gelling temperature of the
premix include, but are not necessarily limited to, alcohol (as
already described herein), sodium and potassium toluene sulfonate,
sodium and potassium xylene sulfonate, sodium and potassium cumene
sulfonate, trisodium and tripotassium sulfosuccinate, and related
compounds (as disclosed in U.S. Patent 3 915 903). When included in the
premix of the present invention such select additional components will
typically be present at a concentration in the range of from about 1% to
about 40% preferably from about 5% to about 30%, more preferably from
about 5% to about 20% by weight.
The premix of the present invention may be prepared by methods
which will be apparent those skilled in the art. One such
preparation method is as follows: the liquid carrier preferably
water and the polyhydroxy fatty acid amide are combined in a mixing
vessel to form an initial binary composition. The polyhydroxy amide
B
WO 92/06172 - PCI'/US91/06984
2~92560 - 48-
will typically comprise from about 30% to about 70%, preferably from
about 45% to about 55% by weight of the initial binary composition.
This initial binary composition must be maintained at a temperature
aboYE about 50~C to allow for a free-flowing composition. The
initial binary composition is then mixed until the ingredients are
sufficiently interspersed, typically for a period of from about 5 to
about 60 minutes, more typically for a period of from about 10 to
about 20 minutes.
The desired amount of optical brightener is then added to the
initial binary composition to form the premix. The brightener is
added to the initial binary composition as a powder and may be in
the form of a salt or an acid. If added as an acid, a neutralizing
agent is then added to the premix, typically in quantities
sufficient to effectively neutralize substantially all the added
brightener.
Any solvents or hydrotropes desired for viscosity adjustments
are next added, optionally followed by any additional components for
lowering the gelling temperature of the premix to the desired
temperature. Other optional ingredients may also be added at this
point.
The premix is then mixed until a uniform or single phase is
formed, typically for a period of from about 5 to about 60 minutes,
more typically from about 10 to about 30 minutes. The additional,
optional ingredients may also be added to the premix after this
mixing step, although it is preferred that any ingredients added to
lower the gelling temperature be added prior to this final mixing
step.
ODtional Ingredients
The premix of the present invention may also contain optional
ingredients which include, but are not necessarily limited to,
buffering agents, solvents and hydrotropes of the type already
described herein. The hydrotropes are especially preferred for
lowering the gel temperature of the premix and for the viscosity
properties they impart to the premix.
Buffering agents which may be included in such premix include,
but are not necessarily limited to, glycine, N,N-bis(2-hydroxy-
ethyl)glycine, tris(hydroxymethyl)aminoethane, triethanolamine,
2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol,
W o 92/06172 ~ n 9 2 ~ 6 ~ PCT/USgl/06984
- 49 -
N-methyl diethanolamine, 1,3-diamino-2-hydroxypropane, and mixtures
thereof. When present in the premix of the present invention, such
buffering agents typically comprise from about 1% to about 40%,
preferably from about 3% to about 20%, more preferably from about 5%
to about 20Yo by weight of the premix.
Process for PreDarinq Detergent ComDosition Containinq ODtical
Briqhteners
The present invention is also directed toward a process for
preparing liquid detergent compositions containing one or more
conventional anionic, nonionic or cationic detersive surfactants,
optional detersive adjuncts, optical brighteners, and a polyhydroxy
fatty acid amide. This process is especially suited for preparing
clear, isotropic highly built liquid detergent compositions. By
"highly builtn, it is meant a detergent composition having a high
builder content, typically comprising from about 10% to about 50%,
preferably from about 15% to about 40%, most preferably from about
15% to about 30~h by weight.
In the process of the present invention, the detergent
compositions may be prepared in any manner known to one skilled in
20 the art, with the exception of the critical step of adding the
brightener as a brightener/polyhydroxy fatty acid amide premix as
already described herein.
In a typical detergent composition preparation process, a
detersive surfactant, which is typically selected from a linear
25 alkylate sulfonate, a sulfonic acid, ether sulfate, olefin
sulfonate, ether sulfonate, or amine oxide, is charged into a mixing
vessel. Any necessary solvents are then added to the mixing vessel.
Examples of such solvents include, but are not necessarily limited
to, propane diol, methyl and ethyl alcohol, monoethanolamine and a
hydrotrope of the type already described herein. The optical
brightener is next added to the mixing vessel via the premix already
described herein. It is not critical that the optical brightener be
added at this point in the process, although it is critical that it
be added via the premix. The optical brightener may also be added,
35 via the premix, after the builders have been added. There are
different advantages associated with each preparation method. For
example, adding the brightener premix following the solvent addition
allows for longer mixing time, whereas adding the brightener premix
w O 92/06172 PcT/ussl/o6984
2 0 ~ 2 j 6 1)
following the builder addition allows for greater formulation
flexibility.
Following the addition of the optical brightener, any acidic
surfactants and builders will typically be added. A neutralizing
step will then follow to adjust the pH of the composition to the
desired range, which is typically from about 5 to about 11,
preferably from about 6 to about 10, most preferably from about 7 to
about 10. After these ingredients have been added to the mixing
vessel, they are stirred until thoroughly mixed. The detergent
mixture is then allowed to cool. The cooling step is typically
accompanied by further mixing. At this point pre-neutralized
builders and other performance boosters, such as dispersants, soil
release polymers, perfumes, and enzymes may be added.
EXPERIMENTAL
This exemplifies a process for making a N-methyl, l-deoxy-
glucityl lauramide surfactant for use herein. Although a skilled
chemist can vary apparatus configuration, one suitable apparatus for
use herein comprises a three-liter four-necked flask fitted with a
motor-driven paddle stirrer and a thermometer of length sufficient
to contact the reaction medium. The other two necks of the flask
are fitted with a nitrogen sweep and a wide-bore side- arm lcaution:
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 g., 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 solidlliquid mixture is heated with stirring
under a nitrogen sweep to form a melt (approximately 25 minutes).
When the melt temperature reaches 145- C, catalyst (anhydrous
powdered sodium carbonate, 10.5 9., 0.1 mole, J. T. Baker) is added.
The nitrogen sweep is shut off and the aspirator and nitrogen bleed
are adjusted to give 5 inches (5/31 atm.) Hg. vacuum. From this
W O 92/06172 - 51 -~ ~ 9 2 3 6 ~
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.
Methanul is distilled over until its rate subsides. The vacuum is
adjusted to give about 10 inches ~9. (10/31 atm.) vacuum. The
vacuum is increased approximately as follows (in inches Hg. at
minutes): 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of
methanol evolution, heating and stirring are discontinued
co-incident with some foaming. The product is cooled and
solidifies.
The following examples are meant to exemplify compositions of
the present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention, said scope being
determined according to claims which follow.
EXAMPLES
The following examples are meant to exemplify compositions of
the present invention, including premix compositions, and methods
for preparing detergent compositions by use of an optical
brightener/polyhydroxy fatty acid amide premix. These examples are
not meant to limit or otherwise define the scope of the invention,
said scope being determined according to claims which follow.
EXAMPLE I
The following premix is prepared by adding the components to a
mixing tank with continuous mixing.
Component Wt. % of ComDosition
N-coconut, N-methyl glucamide 40.0
Monoethanolamine 15.0
Brightener 4.5
Water balance to 100%
This premix is formed by adding 400 grams of purified
N-coconut, N-methyl glucamide to 405 grams of water (heated to 50~C)
in a stainless steel mixing vessel to form an initial binary
composition. This initial binary composition is maintained at a
temperature of about 50~C while being stirred for a period of 20
minutes. 150 grams of monoethanolamine is then added to the initial
binary composition, followed by the addition of 45 grams of
brightener, thereby forming a premix. The temperature of the premix
W O 92/06172 PC~r/US91/06984 2092~ 52 -
is maintained at 50~C while being stirred for a period of 20
minutes. This yields 1000 grams of a single phase product.
EXAMPLE II
The following premix is prepared:
Component Wt.% of ComDosition
N-coconut, N-methyl glucamide 50.0
Sodium cumene sulfonate 2.0
Brightener 5.0
Water balance to 100%
This premix is formed in the same manner as the premix of
Example I, except the sodium cumene sulfonate is substituted for the
monoethanolamine.
EXAMPLE III
A highly built, brightener-containing liquid detergent
composition is prepared as follows:
A surfactant paste prepared with ethanol, caustic, propylene
glycol and sodium C14 15 alkyl ethoxy sulfonate is introduced into a
glass or metal beaker with mixing by an IKA or equivalent mixer
equipped with an appropriately sized propeller shaft. The following
ingredients are then sequentially weighted and added to the beaker
under agitation (all ingredients are added at room temperature
unless otherwise specified): a 45 wt.X sodium cumene sulfonate
solution; propylene glycol; the brightener premix of Example I;
additional monoethanolamine; ethanol; potassium hydroxide; sodium
hydroxide; C11-C13 linear alkylbenzene sulfonate; the acid form of
methyl ester sulfonate (if needed); fatty acid (warmed to 120~F);
aqueous citric acid; aqueous mixtures of sodium oxydisuccinate and
tartrate disuccinate; aqueous calcium formate; aqueous sodium
formate; aqueous tallow trimethyl ammonium chloride; aqueous
ethoxylated tetraethylenepentaamine; boric acid and remaining water.
The pH is adjusted with either citric acid solution or sodium
hydroxide solution to the desired target of 9.5 + 1Ø
The following ingredients are added after pH adjustment: soil
release agents; enzyme stock solution; color mix and perfume.
Within 5 minutes, depending upon batch size, the mixture becomes a
single phase, isoptropic fluid having a viscosity of about 90 cps,
measured with a Brookfield RVT viscometer at 70~F using a #2 spindle
@ 50 rpm.
W O 92/06172 2 0 9 2 ~ 6 0 P~/us9l/o6984
- 53 -
A typical composition prepared in this manner is comprised as
follows:
ComDonent Wt. ~ of ComDosition
C14 ;5 ethcxyl2ted c-ulfate paste* 12.41
Sodium cumene sulfonate solution (45%) 11.11
Additional propylene glycol 3.7
Brightener premix of Example I 2.45
Monoethanolamine 1.0
NaOH 0.65
C11-C13 linear alkylbenzene sulfonate (95%) 6.32
C12-C14 fatty acid (warmed to 120~F) 1.0
Tetrasodium oxydisuccinate 20.0
Soil release agents 1.0
Enzyme stock solution (40g/l) 0.25
*The C14 15 ethoxylated sulfate paste is comprised as follows (all
percentages are weight percent): 11% ethanol; 7.7% caustic; 17.6%
propylene glycol; and 63.7% sodium C14 15 alkyl ethoxy sulfate.
Boric acid 1.0
Water & misc. balance
(p~fumes, dyes
o~acifiers, dispersing agents, etc.)
EXAMPLE IV
The following liquid detergent compositions are prepared in the
25 same manner as the composition of Example III. All percentages are
weight percentages.
COMPONENTS A B ~ D ~ E G H
SURFACTANTS:
C12 14 alkyl N-methyl
glucamide 3.1 5.0 5.0 6.0 1.0 5.0 8.0 7.0
C16-l8 olefin sulfonate -- -- -- -- 5.0 -- -- --
Dodecyl benzene sulfonate -- 3.0 -- -- 5.0 15.0 -- --
C14 16 alkyl ethoxy
(2.25 ave.) sulfate 6.2 5.0 5.0 8.0 -- 5.0 5.0 --
C14-18 paraffin sulfonate -- -- -- -- -- -- -- 8.0
C12-l6 polyglycoside
(1.5 ave.) - 5.0 5.0
C14 16 alkyl sulfate 3.1 -- 3.0 2.0 -- -- 1.0 2.0
2 0 9 2 ~ 6 ~ - 54 - PCT/US91/06984
C12 18 alkyl ethoxy
(1-3 ave.) carboxylate -- -- -- -- 3.0 -- -- --
BUILDERS:
Sodium oxydisuccinate -- -- 19.0 8.0 -- -- -- --
Sodium diethyl trinitrilo
pentaacetate -- 2.0 -- -- -- -- -- --
Sodium citrate 7.5 11.0 -- -- -- -- -- 7.0
Sodium tartrate
monosuccinate 7.0 4.0 -- -- -- -- 7.0 --
10 Sodium tartrate disuccinate 3.0 2.0 -- -- -- --
Sodium carboxymethyl
Tetrasodium oxysuccinate -- -- -- -- -- 6.0 -- --
Sodium oxydiacetate -- -- -- -- -- -- 1.0 --
Sodium carboxymethyl
tartronate -- -- -- -- -- -- -- 1.0
Sodium carboxymethyl-
aspartate -- -- -- -- -- 2.0 -- --
Sodium N-methyl carboxy-
methyl aspartate -- -- -- -- -- -- 2.0 --
Sodium iminodisuccinate -- -- -- -- -- -- -- 2.0
Sodium maleate -- -- -- -- -- 2.0 -- --
Sodium tartrate -- -- -- -- 3.0 -- -- --
Sodium glutarate -- -- -- 3.0 -- -- -- --
Sodium glycine -- 2.0 -- -- -- -- -- --
Sodium sarcosine -- 3.0 -- -- --
Myristic acid (C14
saturated) -- -- -- -- -- 3.0 -- --
Polyacrylic acid
(3,000 M-W-) -- 1.0 -- -- --
HYDROTROPES/SOLVENTS:
Monoethanolamine 1.0 3.0 3.0 -- -- 2.0 2.0 2.0
Sodium cumene sulfonate/
potassium cumene sulfonate 5.0 5.0 5.0 -- 5.0 -- -- --
Sodium xylene sulfonate/
potassium xylene sulfonate -- -- -- 3.0 -- 5.0 -- 5.0
Sodium toluene sulfonate/
potassium toluene
sulfonate -- 1. 5 -- 2.0 -- -- 5.0 --
W O 92/06]72 55 2 ~ 9 2 5 6 ~ P~US91/06984
. ..~
Propanediol 5.5 6.0 5.0 5.0 1.0 3.0 2.5 1.0
Ethanol 0.87 0.60 0.60 1.0 -- 0.60 0.60 0.50
Isopropanol 1.0 -- -- -- 3.0 2.0 2.5 4.0
ADDITIVES:
Brightener premix of
Example I 2.4 -- -- -- 3.0 2.0 4.0 5.0
Brightener premix
of Example I1 -- 3.0 3.0 2.5 3.0 -- -- --
NaOH o.5 0.5 0 4 O 3
KOH -- 0.5 -- 0.4 -- 0.2 -- 0.2
Polyethylene glycol -- -- -- 2.0 -- 3.0 -- --
Water & misc. -- balance to 100% --
(enzymes, perfumes, dyes,
dispersants and other
minor additives)
EXAMPLE V
The following liquid detergent compositions are prepared in the
s~me manner as the composition of Example III. All percentages are
weight percentages.
COMPONENTS A B C ~ ~ E G
SURFACTANTS:
C12 14 alkyl N-methyl
glucamide 12.0 20.0 5.0 10.~ 7.0 5.0 10.0
C16 18 olefin sulfonate -- -- -- -- 5.0
Dodecyl benzene sulfonate -- -- -- -- 5.0 -- --
C14 16 alkyl ethoxy
(1.0 ave.) sulfate -- 6.0 .-- -- -- -- --C14 16 alkyl ethoxy
(2.25 ave.) sulfate -- -- -- -- -- 12.0 --
gO C14-l8 methylester
sulfonate -- -- 10.0 -- -- -- --C12 16 polyglycolside -- -- -- ~.0 -- -- 5.0
(1.3 ave.)
C14 16 alkyl sulfate 2.0 -- -- -- -- -- --
C12 16 ~lycerol sulfonate -- -- -- 4~0 -- -- --
C12 18 sarcosinates 5.0 -- -- -- ~ .0
Sucrose monoalkylate -- -- 4.0 -- -- -- --
C12 18 taurinate -- -- - 2.0 -- -- --
w o 92/06172 2 ~ 9 2 ~ ~ U - 56 - P ~ /US91/06984
BUILDERS:
Sodium ditartronate 10.0 -- -- -- -- -- -
TKPP -- 13.0 -- -- -- -- --
Sodium ethylene diamine
disuccinate -- -- 12.0 -- -- -- --
Sodium nitrilotriacetate -- -- -- 12.0 -- -- --
Sodium pyridine-2,6-di-
carboxylate -- -- -- -- 5.0 -- --
Sodium iminodisuccinate -- -- -- -- - 5.0 --
Sodium N-2-hydroxyethyl
iminodiacetate -- -- -- -- -- -- 5.0
Sodium N-(2-(2-hydroxy-
ethoxy)ethyl)
iminodiacetate -- -- -- -- -- 5.0 --
Sodium N-(2,3-dihydroxy-
propyl) iminodiacetate -- -- -- -- 5.0 -- --
Sodium malate 2.0 -- -- -- -- -- --
Sodium fumarate -- -- 2.0 -- -- -- --
Sodium succinate -- -- -- 2.0 -- -- --
Sodium hydroxyacetate -- -- -- -- 4.0 --
Sodium adipate -- -- -- -- -- -- 2.0
Oleic acid -- -- -- 2.0 -- -- --
Dodecenyl succinate -- -- -- -- 2.0 -- 2.0
Tetradocenyl succinate -- -- -- -- -- 2.0 2.0
HYDROTROPES/SOLVENTS:
Monoethanolamine 2.0 3.0 4.0 2.0 1.0 4.0 3.0
Sodium cumene sulfonate/
potassium cumene
sulfonate 1.0 -- -- 5.0 5.0 -- --
Sodium xylene sulfonate/
potassium xylene
sulfonate 3.0 3.0 5.0 -- -- 4.0 --
Sodium toluene sulfonate/
potassium toluene
sulfonate -- 4.0 -- 2.0 -- -- 5.0
Propanediol 5.0 4.0 4.0 3.0 -- 4.0 4.0
Ethanol -- 0.5 1.0 O.S -- 2.0 1.0
Isopropanol -- 2.0 -- 3.0 6.0 4.0 --
WO 92/06172 ~ 0 9 2 S 6 0 PCI /US91/06984
- 57 -
",_
Sodium sulfosuccinate 2.0 -- -- -- -- -- 3.0
ADDITrVES:
Brightener premix of
Example I 2.0 1.5 3.0 3.0 2.5 -- --
Brightener premix of
Example II -- -- -- _ 3.0 3.0
NaOH -- -- -- -- -- -- 1.0
KOH 1.5 1.5 1.8 1.8 1.0 1.0 --
Polyethylene glycol -- -- -- -- -- -- -
~ater & misc. -- balance to 100% --
(enzymes, perfumes, dyes,
dispersants and other
minor additives)
EXAMPLE VI
An alternate method for preparing the polyhydroxy fatty acid
amides used herein is as follows. A reaction mixture consisting of
84.87g. fatty acid methyl ester (source: Procter & Gamble methyl
ester CE1270), 75g. 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 samp~ing 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.
w o 92/06172 ~ 5 ~ o - ~8 - PCT/US91/06984
The following is not intended to limit the invention herein,
but is simply to further illustrate additional aspects of the
technology which may be considered by the formulator in the
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. lX) 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 Cl2-C~4) are more soluble than their
tallow alkyl (predominantly C16-C18) counterparts. Accordingiy,
the Cl2-Cl~ 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 C16-C~8 materials may be better detersive surfactants than
their Cl2-Cl~ counterparts. Accordingly, the formulator may wish
to balance ease-of-manufacture vs. performance when selecting a
w o 92/06172 ~ 0 9 2 S 6 0 PCT/USg1/06984
- 59 -
particular polyhydroxy fatty acid amide for use in a given
formulation.
It will also be appreciated that the solubility of the polyhy-
droxy fatty acid amides can be increased by having points of unsat-
uration and/or chain branching in the fatty acid moiety. Thus,materials such as the polyhydroxy fatty acid amides derived from
oleic acid and iso-stearic acid are more soluble than their n-alkyl
counterparts.
Likewise, the solubility of polyhydroxy fatty acid amides
prepared from disaccharides, trisaccharides, etc., will ordinarily
be greater than the solubility of their monosaccharide-derived
counterpart materials. This higher solubility can be of particular
assistance when formulating liquid compositions. Moreover, the
polyhydroxy fatty acid amides wherein the polyhydroxy group is
derived from maltose appear to function especially well as deter-
gents when used in combination with conventional alkylbenzene
sulfonate ("LASn~ surfactants. While not intending to be limited by
theory, it appears that the combination of LAS with the polyhydroxy
fatty acid amides derived from the higher saccharides such as
maltose causes a substantial and unexpected lowering of interfacial
tension in aqueous media, thereby enhancing net detergency perform-
ance. (The manufacture of a polyhydroxy fatty acid amide derived
from maltose is described hereinafter.)
The polyhydroxy fatty acid amides can be manufactured not only
from the purified sugars, but also from hydrolyzed starches, e.g.,
corn starch, potato starch, or any other convenient plant-derived
starch which contains the mono-, di-, etc. saccharide desired by the
formulator. This is of particular importance from the economic
standpoint. Thus, ~high glucose" corn syrup, "high maltose" corn
syrup, etc. can conveniently and economically be used.
De-lignified, hydrolyzed cellulose pulp can also provide a raw
material source for the polyhydroxy fatty acid amides.
As noted above, polyhydroxy fatty acid amides derived from the
higher saccharides, such as maltose, lactose, etc., are more soluble
than their glucose counterparts. Moreover, it appears that the more
soluble polyhydroxy fatty acid amides can help solubilize their less
soluble counterparts, to varying degrees. Accordingly, the formu-
lator may elect to use a raw material comprising a high glucose corn
WO 92/06172 PCI'/US91/06984
2092r~6o - 60 -
-
syrup, for example, but to select a syrup which contains a modicum
of maltose (e.g., 1% or more). The resulting mixture of polyhydroxy
fatty acids will, in general, exhibit more preferred solubility
properties over a broader range of temperatures and concentrations
5 than would a "pure" glucose-derived polyhydroxy fatty aciu amiue.
Thus, in addition to any economic advantages for using sugar mix-
tures rather than pure sugar reactants, the polyhydroxy fatty acid
amides prepared from mixed sugars can offer very substantial advant-
ages 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 maltamide levels above
about 25% and some loss in sudsing above about 33% (said percentages
being the percentage of maltamide-derived polyhydroxy fatty acid
amide vs. glucose-derived polyhydroxy fatty acid amide in the
mixture). This can vary somewhat, depending on the chain length of
the fatty acid moiety. Typically, then, the formulator electing to
use such mixtures may find it advantageous to select polyhydroxy
fatty acid amide mixtures which contain ratios of monosaccharides
(e.g., glucose) to di- and higher saccharides (e.g., maltose) from
about 4:1 to about 99:1.
The manufacture of preferred uncyclized polyhydroxy fatty acid
amides from fatty esters and N-alkyl polyols can be carried out in
alcohol solvents at temperatures from about 30-C-90-C, preferably
about 50-C to 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. Like-
wise, the formulator of, for example, solid, typically granular,
detergent compositions may find it convenient to run the process at
30-C-90-C in solvents which comprise ethoxylated alcohols, such as
the ethoxylated (EO 3-8) C12-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. (nT" designation.)
W O 92/06172 PcT/ussl/o6984
~ - 61 ~ 20~2~6~
While methods for making polyhydroxy fatty acid amides per se
form no part of the invention herein, the formu1ator can also note
other syntheses of polyhydroxy fatty acid amides as described
hereinafter.
Typically, the industrial scale reaction sequence for
preparing the preferred acyclic polyhydroxy fatty acid amides will
comprise: SteD 1 - preparing the N-alkyl polyhydroxy amine
derivative from the desired sugar or sugar mixture by formation of
an adduct of the N-alkyl amine and the sugar, followed by reaction
with hydrogen in the presence of a catalyst; followed by SteD 2 -
reacting the aforesaid polyhydroxy amine with, preferably, a fatty
ester to form an amide bond. While a variety of N-alkyl
polyhydroxy amines useful in Step 2 of the reaction sequence can
be prepared by various art-disclosed processes, the following
process is convenient and makes use of economical sugar syrup as
the raw material. It is to be understood that, for best results
when using such syrup raw materials, the manufacturer should
select syrups that are quite light in color or~ preferably, nearly
colorless ("water-white n ) .
Preparation of N-Alkyl Polyhydroxy Amine
From Plant-Derived Sugar Syrup
I. Adduct Formation - The following is a standard process in
which about 420 g of about 55% glucose solution (corn syrup
about 231 9 glucose - about 1.28 moles) having a Gardner Color of
less than 1 is reacted with about 119 9 of about 50% aqueous
methylamine (59.5 9 of methylamine - 1.92 moles) solution. The
methylamine (MMA) solution is purged and shielded with N2 and
cooled to about 10-C, or less. The corn syrup is purged and
shielded with N2 at a temperature of about 10--20-C. The corn
syrup is added slowly to the MMA solution at the indicated
reaction temperature as shown. The Gardner Color is measured at
the indicated approximate times in minutes.
3~
WO 92/06172 PCI'/US91/06984
~ o ~ 2 5 6 0 TABLE 1
Time in Minutes: 10 30 60 120 180 240
Reaction TemD. ~C Gardner Color (ADDroximate~
0
s 20
1 1 2 2 4 5
4 6 10 - - -
As can be seen from the above data, the Gardner Color for the
adduct is much worse as the temperature is raised above about 30-C
and at about 50-C, the time that the adduct has a Gardner Color
below 7 is only about 30 minutes. For longer reaction, and/or
holding times, the temperature should be less than about 20-C.
The Gardner Color should be less than about 7, and preferably less
than about 4 for good color glucamine.
When one uses lower temperatures for forming the adduct, the
time to reach substantial equilibrium concentration of the adduct
is shortened by the use of higher ratios of amine to sugar. With
the 1.5:1 mole ratio of amine to sugar noted, equilibrium is
reached in about two hours at a reaction temperature of about
30-C. At a 1.2:1 mole ratio, under the same conditions, the time
is at least about three -hours. For good color, the combination of
amine:sugar ratio; reaction temperature; and reaction time is
selected to achieve substantially equilibrium conversion, e.g.,
more than about 90%, preferably more than about 95%, even more
preferably more than about 99%, based upon the sugar, and a color
that is less than about 7, preferably less than about 4, more
preferably less than about 1, for the adduct.
Using the above process at a reaction temperature of less
than about 20-C and corn syrups with different Gardner Colors as
indicated, the MMA adduct color (after substantial equilibrium is
reached in at least about two hours) is as indicated.
TABLE 2
Gardner Color (ADDroximate)
Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2
As can be seen from the above, the starting sugar material
must be very near colorless in order to consistently have adduct
that is acceptable. When the sugar has a 6ardner Color of about
~O 92/06172 PCr/US91/06984
- 63 - 2~D92~6D
1, the adduct is sometimes acceptable and sometimes not accept-
able. ~hen the Gardner Color is above 1 the resulting adduct is
unacceptable. The better the initial color of the sugar, the
better is the color of the adduct.
iI. HYdroqen Reaction - Adduct from the above having a
Gardner Color of 1 or less is hydrogenated according to the
following procedure.
About 539 9 of adduct in water and about 23.1 9 of United
Catalyst G49B Ni catalyst are added to a one liter autoclave and
purged two times with 200 psig H2 at about 20-C. The H2 pressure
is raised to about 1400 psi and the temperature is raised to about
50-C. The pressure is then raised to about 1600 psig and the
temperature is held at about 50-55'C for about three hours. The
product is about 95% hydrogenated at this point. The temperature
is then raised to about 85-C for about 30 minutes and the reaction
mixture is decanted and the catalyst is filtered out. The
product, after removal of water and MMA by evaporation, is about
95% N-methyl glucamine, a white powder.
The above procedure is repeated with about 23.1 9 of Raney Ni
catalyst with the following changes. The catalyst is washed three
times and the reactor, with the catalyst in the reactor, is purged
twice with 200 psig H2 and the reactor is pressurized with H2 at
1600 psig for two hours, the pressure is released at one hour and
the reactor is repressurized to 1600 psig. The adduct is then
pumped into the reactor which is at 200 psig and 20-C, and the
reactor i-s 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 9 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
w o 92/06172 2 0 9 2 ~ 6 0 - 64 - P ~ /US91/06984
added slowly to the methylamine solution at a temperature of less
than about 20-C. The solution is mixed for about 30 minutes to
give about 95% adduct that is a very light yellow solution.
About 190 9 of adduct in water and about 9 9 of United
Catalyst G49B Ni catalyst are added to a 200 ml autoclave and
purged three times with H2 at about 20-C. The H2 pressure is
raised to about 200 psi and the temperature is raised to about
50-C. The pressure is raised to 250 psi and the temperature is
held at about 50-55-C for about three hours. The product, which
is about 95% hydrogenated at this point, is then raised to a
temperature of about 85-C for about 30 minutes and the product,
after removal of water and evaporation, is about 95% N-methyl
glucamine, a white powder.
It is also important to minimize contact between adduct and
catalyst when the H2 pressure is less than about 1000 psig to
minimize Ni content in the glucamine. The nickel content in the
N-methyl glucamine in this reaction is about 100 ppm as compared
to the less than 10 ppm in the previous reaction.
The following reactions with H2 are run for direct comparison
of reaction temperature effects.
A 200 ml autoclave reactor is used following typical
procedures similar to those set forth above to make adduct and to
run the hydrogen reaction at various temperatures.
Adduct for use in making glucamine is prepared by combining
about 420 9 of about 55% glucose (corn syrup) solution (231 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.
WO 92/06172 PCT/US91/06984
- - 65 -2092560
4. Once all corn syrup solution is added in, agitate for about
1-2 hours.
The adduct is used for the hydrogen reaction right after
making, or is stored at low temperature to prevent further
degradation.
The glucamine adduct hydrogen reactions are as follows:
1. Add about 134 9 adduct (color less than about Gardner 1) and
about 5.8 9 G49B Ni to a 200 ml autoclave.
2. Purge the reaction mix with about 200 psi H2 twice at about
20-30-C.
3. Pressure with H2 to about 400 psi and raise the temperature
to about 50-C.
4. Raise pressure to about 500 psi, react for about 3 hours.
Keep temperature at about 50-55-C. Take Sample 1.
5. Raise temperature to about 85-C for about 30 minutes.
6. Decant and filter out the Ni catalyst. Take Sample 2.
Conditions for constant temperature reactions:
1. Add about 134 9 adduct and about 5.8 9 G49~ 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.
25 5. Decant and filter out the Ni catalyst. Sample 3 is for about
50-55-C; Sample 4 iS for about 75-C; and Sample 5 iS for about
85-C. (The reaction time for about 85-C is about 45 minutes.)
All runs give similar purity of N-methyl glucamine (about
94%); the Gardner Colors of the runs are similar right after
30 reaction, but only the two-stage heat treatment gives good color
stability; and the 85-C run gives marginal color immediately after
reaction.
EXAMPLE VII
The preparation of the tallow (hardened) fatty acid amide of
35 N-methyl maltamine for use in detergent compositions according to
this invention is as follows.
WO 92/06172 66 PCJ/US91/06984
2S~eD ~ - Reactants: Maltose monohydrate ~Aldrich, Tot
01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, S0% slurry (UAD 52-73D, Aldrich, lot 12921LW).
The reactants are added to glass liner (250 9 maltose, 428 9
me~hylamine solution, 100 9 catalyst slurry - 50 9 Raney Ni) and
placed in 3 L rocking autoclave, which is purged with nitrogen
(3X500 psig) and hydrogen (2X500 psig) and rocked under H2 at room
temperature over a weekend at temperatures ranging from 28-C to
50-C. The crude reaction mixture is vacuum filtered 2X through a
glass microfiber filter with a silica gel plug. The filtrate is
concentrated to a viscous material. The final traces of water are
azetroped off by dissolving the material in methanol and then
removing the methanol/water on a rotary evaporator. Final drying
is done under high vacuum. The crude product is dissolved in
refluxing methanol, filtered, cooled to recrystallize, filtered
and the filter cake is dried under vacuum at 35-C. This is cut
#1. The filtrate is concentrated until a precipitate begins to
form and is stored in a refrigerator overnight. The solid is
filtered and dried under vacuum. This is cut #2. The filtrate is
again concentrated to half its volume and a recrystallization is
performed. Very little precipitate forms. A small quantity of
ethanol is added and the solution is left in the freezer over a
weekend. The solid material is filtered and dried under vacuum.
The combined solids comprise N-methyl maltamine which is used in
Step 2 of the overall synthesis.
SteD 2 - Reactants: N-methyl maltamine (from Step 1); hardened
tallow methyl esters; sodium methoxide (25% in methanol); absolute
methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst
level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level
50% (wt.).
In a sealed bottle, 20.36 9 of the tallow methyl ester is
heated to its melting point (water bath) and loaded into a 250 ml
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 9
of methanol, and the resulting slurry is added to the tallow ester
with good mixing. 1.51 9 of 25% sodium methoxide in methanol is
added. After four hours the reaction mixture has not clarified,
so an additional 10 mole % of catalyst (to a total of 20 mole %)
w o 92/06172 - 67 - ~ O 9 ~ ~ /US91/06984
.,_
is added and the reaction is allowed to continue overnight (c~.
68-C) after which time the mixture is clear. The reaction flask
is then modified for distillation. The temperature is increased
to llO-C. Distillation at atmospheric pressure is continued for
60 minutes. High vacuum distillation is then benun and continued
for 14 minutes, at which time the product is very thick. The
product is allowed to remain in the reaction flask at llO'C
(external temperature) for 60 minutes. The product is scraped
from the flask and triturated in ethyl ether over a weekend.
Ether is removed on a rotary evaporator and the product is stored
in an oven overnight, and ground to a powder. Any remaining
N-methyl maltamine is removed from the product using silica gel.
A silica gel slurry in 100% methanol is loaded into a funnel and
washed several times with 100% methanol. A concentrated sample of
the product (20 9 in 100 ml of 100% methanol) is loaded onto the
silica gel and eluted several times using vacuum and several
methanol washes. The collected eluant is evaporated to dryness
(rotary evaporator). Any remaining tallow ester is removed by
trituration in ethyl acetate overnight, followed by filtration. The
filter cake is vacuum dried overnight. The product is the
tallowalkyl N-methyl maltamide.
In an alternate mode, Step 1 of the foregoing reaction
sequence can be conducted using commercial corn syrup- comprising
glucose or mixtures of glucose and, typically, 5%, or higher,
maltose. The resulting polyhydroxy fatty acid amides and mixtures
can be used in any of the detergent compositions herein.
In still another mode, Step 2 of the foregoing reaction
sequence can be carried out in 1,2-propylene glycol or NEODOL. At
the discretion of the formulator, the propylene glycol or NEODOL
need not be removed from the reaction product prior to its use to
formulate detergent compositions. Again, according to the desires
of the formulator, the methoxide catalyst can be neutralized by
citric acid to provide sodium citrate, which can remain in the
polyhydroxy fatty acid amide.
Depending on the desires of the formulator, the compositions
herein can contain more or less of various suds control agents.
Typically, for dishwashing high sudsing is desirable so no suds
control agent will be used. For fabric laundering in top-loading
W o 92/06172 P ~ /ussl/06984
2092560 - 68 -
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
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[0CH2CH2]160H), a source of tere-
phthaloyl units (e.g., dimethyl terephthalate); a source of
poly(oxyethylene)oxy units (e.g., polyethylene glycol 1500); a
source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol);
and a source of oxyethyleneoxy units (e.g., ethylene glycol)
especially wherein the mole ratio of oxyethyleneoxy units:oxyiso-
propyleneoxy units is at least about 0.5:1. Such nonionic soil
release agents are of the general formula
0 0 0 0
RlO-(CH2CH20)x C ~ CO-CH-CH20 - C ~ CO(CH2CH20)y
_ R2 _ m _ _ n
O ~ O
C~C - O (CH2CH20)x-Rl
wherein R1 is lower (e.g., C1-C4) alkyl, especially methyl; x and
y are each integers from about 6 to about 100; m is an integer of
from about 0.75 to about 30; n is an integer from about 0.25 to
about 20; and R2 is a mixture of both H and CH3 to provide a mole
W o 92/06172 ~ O 9 2 ~ ~ O P ~ /US91/06984
~_ - 69 -
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 following relates to the preparation of a preferred liquid
heavy duty laundry detergent according to this invention. It will
be appreciated that the stability of enzymes in such compositions is
considerably less than in granular detergents. However, by using
typical enzyme stabilizers such as formate and boric acid, lipase
and cellulase enzymes can be protected from degradation by protease
enzymes. However, lipase stability is still relatively poor in the
presence of alkylbenzene sulfonate (nLASn) surfactants. Apparently,
LAS partially denatures lipase, and, further, it seems that
denatured lipase is more vulnerable to attack by protease.
In view of the foregoing considerations, which, as noted, can
be particularly troublesome in liquid compositions, it is a
challenge to provide liquid detergent compositions containing
lipase, protease and cellulase enzymes, together. It is particu-
larly challenging to provide such tertiary enzyme systems in
stable liquid detergents together with an effective blend of
detersive surfactants. Additionally, it is difficult to
incorporate peroxidase and/or amylase enzymes stably in such
compositions.
It has now been determined that various mixtures of lipases,
proteases, cellulases, amylases and peroxidases are adequately
stable in the presence of certain non-alkylbenzene sulfonate
surfactant systems, such that effective, heavy-duty solid and even
liquid detergents can be formulated. Indeed, the formulation of
WO 92/06172 PCI/US91/06984
20~25~0 70-
stable, liquid, enzyme-containing detergent compositions consti-
tutes a highly advantageous and preferred embodiment afforded by
the technology of the present invention.
In particular, prior art liquid detergent compositions
typically contain LAS or mixtures of LAS with surfactants of the
RO(A)mS03M type (~AESn) noted hereinabove, i.e., LAS/AES mixtures.
By contrast, the liquid detergents herein preferably comprise
binary mixtures of the AES and polyhydroxy fatty acid amides of
the type disclosed herein. While minimal amounts of LAS can be
present, it will be appreciated that the stability of the enzymes
will be lessened thereby. Accordingly, it is preferred that the
liquid compositions be substantially free (i.e., contain less than
about 10%, preferably less than about 5%, more preferably less
than about 1%, most preferably 0%) of LAS.
The present invention provides a liquid detergent composition
comprislng:
(a) from about 1% to about 50%, preferably from about 4% to
about 40%, of anionic surfactant;
(b) from about 0.0001% to about 2X of active detersive
enzyme;
(c) an enzyme performance-enhancing amount (preferably from
about 0.5X to about 12~) of a polyhydroxy fatty acid
amide material of the formula
O R
u
R2 C - N - Z
wherein R1 is H1, C1-C~ hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl, or a mixture thereof, R2 is C5-C31
hydrocarbyl, and Z is a polyhydroxylhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls
directly connected to said chaini or an alkoxylated
derivative thereof;
and wherein the composition is substantially free of alkylbenzene
sulfonate.
The water-soluble anionic surfactant herein preferably
comprises ( nAESn ):
RO(A)m S03 M
wherein R is an unsubstituted C~0-C2~ alkyl or hydroxyalkyl
(C10-C2~) group, A is an ethoxy or propoxy unit, m is an integer
WO 92/06172 ~ 2 ~ 6 ~ PCI~/US91/06984
'~_
greater than 0 and M is hydrogen or a cation. Preferably, R is an
unsubstituted C12-C18 alkyl group, A is an ethoxy unit, m is from
about 0.5 to about 6, and M is a cation. The cation is preferably
a metal cation (e.g., sodium-preferred, potassium, lithium,
calcium, magnesium, eLc.) or afi ar~onium or substitùted ammonium
cation.
It is preferred that the ratio of the above surfactant
(nAES") to the polyhydroxy fatty acid amide herein be from about
1:2 to about 8:1, preferably about 1:1 to about 5:1, most preferably
about 1:1 to about 4:1.
The liquid compositions herein may alternatively comprise
polyhydroxy fatty acid amide, AES, and from about 0.5% to about 5%
of the condensation product of C8-C22 (preferably C1o-C20) linear
alcohol with between about 1 and about 25, preferably between
about 2 and about 18, moles of ethylene oxide per mole of alcohol.
As described above, the liquid compositions herein preferably
have a pH in a 10% solution in water at 20-C of from about 6.5 to
about 11.0, preferably from about 7.0 to about 8.5.
The instant compositions preferably further comprise from
about 0.1% to about 5~/O of detergency builder. These compositions
preferably comprise from about 0.1% to about 2~h of citric acid,
or water-soluble salt thereof, and from about 0.1% to about 20% of
a water-soluble succinate tartrate, especially the sodium salt
thereof, and mixtures thereof, or from about 0.1X to about 20% by
weight of oxydisuccinate or mixtures thereof with the aforesaid
builders. 0.1%-50% alkenyl succinate can also be used.
The preferred liquid compositions herein comprise from about
0.0001% to about 2%, preferably about 0.0001% to about 1%, most
preferably about 0.001% to about 0.5%, on an active basis, of
detersive enzyme. These enzymes are preferably selected from the
group consisting of protease (preferred), lipase (preferred),
amylase, cellulase, peroxidase, and mixtures thereof. Preferred
are compositions with two or more classes of enzymes, most
preferably where one is a protease.
While various descriptions of detergent proteases, cellulases,
etc., are available in the literature, detergent lipases may be
somewhat less familiar. Accordingly, to assist the formulator,
lipases of interest include Amano AKG and Bacillis Sp lipase (e.g.,
~_ - 72 -
Solvay enzymes). Also, see the lipases described in EP A 0 399 681,
published November 28, 1990, EP A 0 218 272, published April 15, 1987 and
PCT/DK 88/00177. published May 18, 1989.
Suitable fungal lipases include those producible by Humico1a
1dnuginos~ and Thermomyces 1anuginosus. Most preferred is the lipase
obtained by cloning the gene from Humico1d 1anuginosd and expressing the
gene in Aspergi11us oryzae, as described in European Patent-Application
0 258 068, commercially available under the trade name LIPOLASE.
From about 2 to about 20,000, preferably about lO to about
6,000, lipase units of lipase per gram (LU/g) of product can be used
in these compositions. A lipase unit is that amount of lipase which
produces 1 ~mol of titratable butyric acid per minute in a pH stat,
where p~ is 7.0, temperature is 30-C, and substrate is an emulsion
15 tributyrin and gum arabic, in the presence of Ca++ and NaCl in
phosphate buffer.
The following Example illustrates a preferred heavy duty liquid
detergent composition.
EXAMPLE VIII
Ingredients Wt.Yo
Cl4-15 alkyl polyethoxylate (2.25) sulfonic acid 21.00
C12-14 fatty acid N-methyl glucamide1 7.00
Sodium tartrate mono- and di-succinate (80:20 mix) 4.00
Citric acid 3.80
C12-14 fatty acid 3 0O
Tetraethylene pentaamine ethoxylate(l5-18) l.50
Ethoxylated copolymer of polyethylene 0.20
- polypropylene terephthalate polysulfonic acid
Protease B (34g/l) 2 0 . 68
30 Lipase (lOOKLU/g)3 0.47
Cellulase (5000 cevu/g)4 0.14
Brightener 365 0.15
Ethanol 5.20
Monoethanolamine 2.00
35 Sodium formate 0.32
1,2 propane diol 8.00
Sodium hydroxide 3.10
~i B~
- 73 -
Silicon suds suppressor 0.0375
Boric acid 2.00
Water/misc. Balance to 100
lPrepared as disclosed above
2Protease B is a modified bacterial serine protease described in EP
2 514 466, published January 7 1988.
3Lipase used herein is the lipase obtained by cloning the
gene from Humico1z 1anuginosa and expressing the gene in
10 Aspergi77us oryzae, as described in European Patent Application
0 258 068, commercially available under the trade name LIPOLASE
(ex Novo Nordisk A/S, Copenhagen Denmark).
4Cellulase used herein is sold under the trademark CAREZY~E
(Novo Nordisk, A/S, Copenhagen Denmark).
sBrightener 36 is commercially available as TINOPAL TAS 36.
EXAMPLE IX
A liquid laundry detergent composition suitable for use at
the relatively high concentrations common to front-loadlng
automatic washing machines, especially in Europe, and over a wide
20 range of temperatures is as follows.
Inqredient ~It. Yo
Coconutalkyl (Cl2) N-methyl glucamide 14
Cl4 l5EO(2.25) sulfate, Na salt 10.0
Cl4 lsEO(7) 4.0
Cl2-l4 alkenylsuccinic anhydride1 4.0
C12 14 fatty acid* 3-0
Citric acid (anhydrous) 4.6
Protease (enzyme) 2 0.37
Termamyl (enzyme) 3 0.12
Lipolase (enzyme)4 0.36
Carezyme (enzyme) 5 0.12
Dequest 2060S 6 1 . 0
NaOH (pH to 7.6) 5.5
1,2 propanediol 4.7
Ethanol 4.0
Sodium metaborate 4.0
CaCl 2 0.0l4
Ethoxylated tetraethylene pentamine7 0.4
B-
WO 92/06172 PCI/US91/06984
'~ o 3 ~ 5 6 ~ - 74 -
Brightener8 0.13
Silane9 0-04
Soil release polymerl~ 0.2
Silicone (suds control)1l 0.4
Silicone dispersantl2 0.2
Water and minors Balance
lAs SYNPRAX 3 from ICI or DTSA from Monsanto.
2As Protease B as described in EPO 0342177 November 15, 1989,
percentage at 40 g/l.
3Amylase, from NOVO; percentage at 300 KNU/g.
4Lipase, from NOVO; percentage at 100 KLU/g.
5Cellulase from NOVO; percentage at 5000 CEVU/l.
6Available from Monsanto.
'From BASF as LUTENSOL P6105.
8BLANKOPHOR CPG766, Bayer.
9Silane corrosion inhibitor, available as A1130 from Union
Carbide or DYNASYLAN TRIAMINO from Huls.
0Polyester, per U.S. Patent 4,711,730.
11Silicone suds control agent available as Q2-3302 from Dow
Cornjng.
12Dispersant for silicone suds control agent available as
DC-3225C from Dow Corning.
*Preferred fatty acid is topped palm kernel, comprising 12%
oleic and 2% each of stearic and linoleic.
EXAMPLE X
In any of the foregoing examples, the fatty acid glucamide
surfactant can be replaced by an equivalent amount of the malt-
amide surfactant, or mixtures of glucamide/maltamide surfactants
derived from plant sugar sources. In the compositions the use of
ethanolamides appears to help cold temperature stability of the
finished formulations. Moreover, the use of sulfobetaine (aka
"sultainen) surfactants provides superior sudsing.
In the event that especially high sudsing compositions are
desired (e.g., dishwashing), it is preferred that less than about
5%, more preferably less than about 2%, most preferably substan-
tially no C1~ or higher fatty acids be present, since these can
suppress sudsing. Accordingly, the formulator of high sudsing
w o 92/06172 75 2 0 9 2 5 6 0 P~/USg1/06984
compositions will desirably avoid the introduction of suds-
suppressing amounts of such fatty acids into high sudsing composi-
tions with the polyhydroxy fatty acid amides, and/or avoid the
formation of C14 and higher fatty acids on storage of the finished
compositions. One simple means is to use C12 ester reactants to
prepare the polyhydroxy fatty acid amides herein. ~ortunately, the
use of amine oxide or sulfobetaine surfactants can overcome some of
the negative sudsing effects caused by the fatty acids. Conversely,
if low sudsing is desired, AE or DC-544 (Dow Corning) are additional
examples of useful suds-suppressing 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- tnd 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.
