Note: Descriptions are shown in the official language in which they were submitted.
~lt ~3~a~
GRANULAR DETERGENT COMPOSITION CONTAINING
POLYHYDROXY FATTY ACID AMIDE SURFACTANTS TO
ENHANCE ENZYME PERFORMANCE
FIELD OF THE INVENTION
5This invention pertains to detergent compositions containing enzymes.
More importantly, this invention pertains to detergent compositions containing
enzyme and polyhyd~ y fatty acid amide surfactant. This is a division of
(~n~ n Patent Application Serial No. 2,092,556.
BACKGROUND OF THE INVENTION
10It is common commercial practice to include various enzymes in liquid
and granular laundry detergents to enhance cleaning performance. Proteolytic
enzymes are well-known for this use, but other enzymes such as the amylases,
the cellulases, the lipases, the peroxidases, combinations thereof, have also
been suggested for such use. The literature and standard formularies are
15replete with references to the use of enzymes in fabric laundering
compositions.
Since enzymes are biological materials they are subject to denaturation
and deactivation, especially after prolonged contact with other ingredients
present in fully formulated detergent compositions. Thus, a freshly formulated
20detergent composition containing enzymes will often exhibit substantially
higher cleaning performance than will older product which has been
warehoused or stored on the shelf. Shelf-stability of enzyme-containing
detergent compositions, especially liquid detergents, has been of considerable
concern to formulators, and a variety of enzymes stabilizers have been devised.
25For example, various boron compounds, formate salts, ethanolamines, and/or
various short chain fatty acids are commonly added to detergent compositions
to provide enzyme stability. Such stabilizers are often used in liquid detergentcompositions containing enzymes.
W O 92/06154 21 Q 13 1~ P ~ ~US91/07028
- 2 -
-- Moreover, enzymes are relatively expensive, and their
inclusion in detergent compositions represents an added cost to
the formulator and, ultimately, to the user. Accordingly, it
would be advantageous if enzyme performance were improved by less
5expensive additives.
It is theoretically possible not only to stabilize enzymes
against degradation, but also to enhance their performance with
various boosters. However, whether stabilized or enhanced, the
net objective in a market situation where long-term enzyme
lOactivity must be considered is the same - the provision of better
performance of the detergent composition for the user.
There is a continuing search for materials to stabilize or
otherwise enhance the performance of enzymes in fully-formulated
detergent compositions, inasmuch as nearly all enzymes are costly,
15and nearly all enzymes will lose at least some of their activity
on storage.
While not intending to be limited by theory, it appears that
polyhydroxy fatty acid amide surfactants of the type disclosed
hereinafter provide a stabilizing and/or performance boosting
20function for enzymes. Quite possibly, the polyhydroxy fatty acid
amides function by removing molecular "fragments" produced as the
enzymes attack soils and stains, thereby allowing the enzymes to
perform more efficiently. Whatever the mechanism of action, the
invention herein achieves the ultimate goal of delivering enhanced
25removal of enzyme-labile soils and stains and, thus, improves
overall performance, in fully-formulated enzyme-containing
detergent compositions.
I~ addition to boosting enzyme performance, the polyhydroxy
fatty acid amide itself is an excellent detersive surfactant.
30~oreover, this type of surfactant can be obtained largely or
entirely from natural, renewable raw materials, and can be
substituted in whole or part for petroleum-based surfactants
without loss of detergency.
BACKGROUND A~T
5A variety of polyhydroxy fatty acid amides have been
described in the art. N-acyl, N-methyl glucamides, for example.
are disclosed by J. ~. 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,
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2 ~ 0~ 3 -
Yolume 3, No. 11, pp 156~ 81, and by A. Muller-Fahrnow, V.
Zabel, M. Steifa, and R. Hilgenfeld in "Molecular and Crystal
Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J.
Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl
- 5 polyhydroxyamide surfactants has been of substantial interest
recently for use in biochemistry, for example in the dissociation
of biological membranes. See, for example, the journal article
"N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic
Detergents For Membrane Biochemistry,~' Biochem. J. (1982), Yol.
207, pp 363-366, by J. E. K. Hildreth.
The use of N-alkyl glucamides in detergent compositions has
also been discussed. U.S. Patent 2,965,576, issued December 20,
1960 to E. R. Wilson, and G.B. Patent 809,060, published February
18, 195g, assigned to Thomas Hedley ~ Co., Ltd. relate to
detergent compositions containing anionic sur~actants and certain
amide surfactants, which can include N-methyl glucamide, added as
a low temperature suds enhancing agent. These compounds include
an N-acyl radical of a higher straight chain fatty acid having
10-14 carbon atoms. These compositions may also contain auxiliary
materials such as alkali metal phosphates, alkali metal silicates,
sulfates, and carbonates. It is also generally indicated that
additional constituents to impart desirable properties to the
composition can also be included in the compositions, such as
fluorescent dyes, bleaching agents, perfumes, etc.
U.S. Patent 2,703,798, issued March 8, 1955 to A. M.
Schwartz, relates to aqueous detergent compositions containing the
condensation reaction product of N-alkyl glucamine and an
aliphatic ester of a fatty acid. The product of this reaction is
said to be useable in aqueous detergent compositions without
further purification. It is also known to prepare a sulfuric
ester of acylated glucamine as disclosed in U.S. Patent 2,717,894,
issued September 13, 1gSS, to A. M. Schwartz.
PCT International Application WO 83/04412, published December
2~, 1983, by J. Hildreth, relates to amphiphilic compounds con-
taining 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 solubil-
izing membranes, whole cells, or other tissue samples, and for
~ v ~ u~ / u~y l / u / v~7
2~Q~49 - 4 -
preparing liposomes. Included in this disclosure are compounds of
the formula R'CON(R)CH2R" and R~CON(R)R' wherein R is hydrogen or
- an organic 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, 1g88, 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 RlC(O)N(X)R2 wherein R1 is a
C~-C1~ (preferably C7-C1~) alkyl, R2 is hydrogen, a C1-C1~
(preferably C1-C6) alkyl, or an alkylene oxide, and X is a poly-
hydroxy alkyl having four to seven carbon atoms, e.g., N-methyl,
coconut fatty acid glucamide. The thickening properties of the
amides are indicated as being of particular use in liquid surfact-
ant systems containing paraffin sulfonate, although the aqueous
surfactant systems can contain other anionic surfactants, such as
alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half
ester salts, and fatty alcohol ether sulfonates, and nonionic
surfactants such as fatty alcohol polyglycol ether, alkylphenol
polyglycol ether, fatty acid polyglycol ester, polypropylene
oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfon-
ate/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 ~ecember 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-acylpolyhydroxy-alkyl-amine of the formula R1C(0)N(R2)CH2-
(CHOH)nCH2OH, wherein R1 is a Cl-C3 alkyl, R2 is a Cl0-C2~ alkyl,
and n is 3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a
soil suspending agent.
W ~ 92/06154 PCT/US91/07028
~ , 2la'~ 49-S-
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 R~ is a C10-C22 alkyl, R2 is a C~-C21 alkyl, Rl and R2
total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl
which can be -CH2(CHOH)mCH20H where m is 3 or 4.
U.S. Patent 4,021,53g, 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, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the
same as R1 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 formalde-
hyde stabilized against polymerization with the addition of amides
of the formula RC(O)N(R1)G wherein R is a carboxylic acid func-
tionality haYing at least seven carbon atoms, Rl is hydro~en or a
lower alkyl group, and ~ 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 C1o-C20 alkyl radical, and R2 is a C1-C5 acyl
radical.
G.B. Patent 745,036, published February 15, lg5~, assigned to
Atlas Powder Company, relates to heterocyclic amides and
carboxylic esters thereof that are said to be useful as chemical
intermediates, emulsifiers, wetting and dispersing agents,
detergents, textile softeners, etc. The compounds are expressed
by the formula N(R)(Rl)C(O)R2 wherein R is the residue of an
anhydrized hexane pentol or a carboxylic acid ester thereof, Rl is
a monovalent hydrocarbon radical, and -C(O)R2 is the acyl radical
of a carboxylic acid haYing from 2 to 25 carbon atoms.
U.S. Patent 3,312,627, issued ~pril ~, 1967 to D. T. Hooker,
disclcses solid toilet bars that are substantially free of anionic
detergents and alkaline builder materials, and which contain
CA 02104349 1998-07-24
lithium soap of certain fatty acids, a nonionic surfactant
selected from certain propylene oxide-ethylenediamine-etnylene
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 R1 and RZ each are H or C1-C6 alkyl
groups, said alkyl groups containing a total number of carbon
atoms of from 2 to about 7 and a total number of substituent
hydroxyl groups of from 2 to about 6. A substantially similar
disclosure is found in U.S. Patent 3,312,6Z6, also issued April 4,
1~67 to D. T. Hooker.
SUMMARY OF THE INVENTTON
The present invention is directed to a granular detergent
composition having improved enzyme cleaning performance comprising from
lX to 50X by weight of anionic surfactant and from 0.0001% to 2% by
weight of active detersive enzyme, characterized in that said
composition contains at least 3~ by weight of a polyhydroxy fatty acid
amide material of the formula
o R1
R2 . Il IN - Z
wherein Rl is Hl, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl.
or a mixture thereof R2 is C5-C3l hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least
3 hydroxyls directly connected to said chain. or an alkoxylated
derivative thereof.
The present invention further provides a method for improving
the cleaning performance of detergent compositions containing
detersive surfactant, such as anionic, nonionic, or cationic
surfactants, especially anionic sur~actants, in the presence of an
aque~us media, by adding to said detergent composition an enzyme
enhancing amount of the above-described polyhydroxy fatty acid
amide.
The present invention further provides a method for cleaning
substrates, such as fibers, fabrics, hard surfaces, skin, etc., by
contacting said substrat~ with a detergent compo;it;on comprising
one or more anionic, nonionic, or cationic surfactants, and a
detersive enzyme, wherein said composition comprises an enzyme
~ W O 92/U6154 PCT/US91/07028
2~3~3~ 7
-- performance enhancing amount of the polyhydroxy fatty acid amide surfactant.
DETAILED DESCRIPTION OF THE INVENTION
Polyhydrox~ FattY Acid Amide Surfactant
The detergent compositions hereof contain an ~enzyme
performance-enhancing amount" of polyhydroxy fatty acid amide. By
"enzyme-enhancing" is meant that the formulator of the composition
can select an amount of polyhydroxy fatty acid amide to be
incorporated into the compositions that will improve enzyme
cleaning performance of the detergent composition. In general,
for detergent containing conventional levels of enzyme, the
incorporation of about lX, by weight, polyhydroxy fatty acid amide
will enhance enzyme performance.
The detergent compositions hereof will typically comprise at
I5 least about 1%, weight basis, polyhydroxy fatty acid amide
surfactant, preferably at least about 3Y., even more preferably
will comprise from about 3% to about 50%, most preferably from
about 3% to about 30%, of the polyhydroxy fatty acid amide.
The polyhydroxy fatty acid amide surfactant component of the
present inven~ion comprises compounds of the structural formula:
O R
u
(I) R2 C - N - Z
wherein: R1 is H, C1-C~ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy
propyl, or a mixture thereof, preferably Cl-C~ alkyl, more
preferably C1 or C2 alkyl, most preferably C1 alkyl (i.e.,
methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain
C~-C19 alkyl or alkenyl, more preferably straight chain Cg-Cl,
alkyl or alkenyl, most preferably straight chain C~1-C1s alkyl or
alkenyl, or mixtures 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 will be a glycityl. Suitable reducing
3~ 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
- 8 - 2~34~
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 form the group consisting
of -CH2-(CHOH)n-CH2OH, -CH(CH2OH)-(CHOH)n1-CH2OH, -CH2-
(CHOH)2(CHOR')(CHOH)-CH2OH, and alkoxylated derivatives thereof, where
n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or
aliphatic monosaccharide. Most preferred are glycityls wherein n is
4, particularly -CH2(CHOH )4 - CH20H .
In Formula (I), R' 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-
deoxymaltotriotityl, etc.
Methods for making polyhydroxy fatty acid amides are known in the
art. In general, they can be made by reacting an alkyl amine with a
reducing sugar in a reductive amination reaction to form a
corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl
polyhydroxyamine with a fatty aliphatic ester or triglyceride in a
condensation/amidation step to form the N-alkyl, N-polyhydroxy fatty
acid amide product. Processes for making compositions containing
polyhydroxy fatty acid amides are disclosed, for example, in G.B.
Patent Specification 809,060, published February 18, 1959, by Thomas
Hedley & Co., Ltd., U.S. Patent No. 2,965,576, issued December 20, 1960
to E.R. Wilson, and U.S. Patent No. 2,703,798, Anthony M. Schwartz,
issued March 8, 1955, and U.S. Patent No. 1,985,424, issued December
25, 1934 to Piggott.
In one process for producing N-alkyl or N-hydroxyalkyl, N-
deoxyglycityl fatty acid amides wherein the glycityl component is
derived from glucose and the N-alkyl or N-hydroxyalkyl functionality
is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxy-
propyl, the product is made by reacting N-alkyl- or N-
hydroxyalkyl-glucamine with a fatty ester selected from fatty
A
W O 92/06154 PCT/US91/07028
~ L O 4 ~ 9
methyl esters, fatty ethyl esters, and fatty triglycerides in the
presence of a catalyst selected from the group consisting of
trilithium phosphate, trisodium phosphate, tripotassium phosphate,
tetrasodium pyrophosphate, pentapotassium tripolyphosphate,
lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium
hydroxide, lithium carbonate, sodium carbonate, potassium carbon-
ate, disodium tartrate, dipotassium tartrate, sodium potassium
tartrate, trisodium citrate, tripotassium citrate, sodium basic
silicates, potassium basic silicates, sodium basic aluminosili-
cates, and potassium basic aluminosilicates, and mixtures thereof.
The amount of catalyst is preferably from about 0.5 mole % to
about 50 mole %, more preferably from about 2.0 mole % to about ~0
mole X, 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 used as the fatty ester source, the reaction is
also preferably carried out using from about 1 to about 10 weight
% of a phase transfer agent, calculated on a weight percent basis
of total reaction mixture, selected from saturated fatty alcohol
polyethoxylates, alkylpolyglycosides, linear glycamide surfactant,
and mixtures thereof.
Preferably, this process is carried out as follows:
(a) preheating the fatty ester to about 138-C to about
170-C;
(b) adding the N-alkyl or. N-hydroxyalkyl glucamine to the
heated fatty acid ester and mixing to the extent needed
- to form a two-phase liquid/liquid mixture;
(c) mixing the catalyst into the reaction mixture; and
(d) stirring for the specified reaction time.
Also preferably, from about 2% to about 20% of preformed
linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide
product is added to the reaction mixture, by weight of the
reactants, as the phase transfer agent if the fatty ester is
triglyceride. This seeds the reaction, thereby increasing
reaction rate. A detailed experimental procedure is provided
below.
W O 92/06l54 PCT/USs1/07028
21~3-l9 lo-
-- The polyhydroxy "fatty acid" amide materials used herein also
offer the advantages to the detergent formulator that they can b~
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 (I), the processes used to produce them
will also typically produce quantities of nonvolatile by-product
such as esteramides and cyclic polyhydroxy fatty acid amide. The
level of these by-products will vary depending upon the particular
reactants and process conditions. Preferably, the polyhydroxy
fatty acid amide incorporated into the detergent compositions
hereof will be provided in a form such that the polyhydroxy fatty
acid amide-containing composition added to the detergent contains
less than about 10~., preferably less than about 4%, of cyclic
polyhydroxy fatty acid amide. The preferred processes described
above are advantageous in that they can yield rather low levels of
by-products.
EnzYmes
Detersive enzymes can be included in the detergent formula-
tions for a wide variety of purposes including removal of protein-
based, carbohydrate-based, or triglyceride-based stains, for
example, and preYention of refugee dye transfer. The enzymes to
be incorporated include proteases, amylases, lipases, cellulases,
and peroxidases, as well as mixtures thereof. Other types of
enzymes may also be included. They ~ay 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-act~vity 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.
Enzymes are normally incorporated at levels sufficient to
provide up to about 5 mg by weight, more typically about 0.05 mg
to about ~ mg, of active enzyme per gram of the composition.
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,
3 ~ 9
having maximum activity throughout the pH range of 8-12, developed and
sold by Novo Industries A/S under the registered trade name ESPERASE.
The preparation of this enzyme and analogous enzymes is described in
British Patent Specification No. 1,243,784 of Novo. Proteolytic
enzymes suitable for removing protein-based stains that are
commercially available include those sold under the tradenames ALCALASE
and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by
International Bio-Synthetics, Inc. (The Netherlands).
Of interest in the category of proteolytic enzymes, especially
for liquid detergent compositions, are enzymes referred to herein as
Protease A and Protease B. Protease A and methods for its preparation
are described in European Patent Application No. 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 Serial No. 87303761.8, filed April 28,
1987. Methods for preparation of Protease B are also disclosed in
European Patent Application No. 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, RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL,
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
No. 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.
- 12 - ~ P ~ 43~ ~
Examples of such cellulases are cellulases produced by a strain
of Humicola insolens (Humicola grisea var. thermoidea), particularly
the Humicola strain DSM 1800, and cellulases produced by a fungus of
Bacillus N or a cellulase 212-producing fungus belonging to the genus
Aeromonas, and cellulase extracted from the hepatopancreas of a marine
mollusc (Dolabella Auricula Solander).
Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent No.
1,372,034. Suitable lipases include those which show a positive
immunological cross-reaction with the antibody of the lipase, produced
by the microorganism Pseudomonas f7uorescens IAM 1057. This lipase and
a method for its purification have been described in Japanese Patent
Application No. 53-20487, laid open to public inspection on February
24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd.,
Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter
referred to as "Amano-P." Such lipases of the present invention should
show a positive immunological cross-reaction with the Amano-P antibody,
using the standard and well-known immunodiffusion procedure according
to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These
lipases, and a method for their immunological cross-reaction with
Amano-P, are also described in U.S. Patent No. 4.707,291, Thom et al.,
issued November 17, 1987. Typical examples thereof are the Amano-P
lipase, the lipase ex Pseudomonas fragi FERM P 1339 (Available under
the trade name Amano-B), lipase ex Pseudomonas nitroreducens var.
7ipo7yticum FERM P 1338 (available under the trade name Amano-CES),
lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
7ipo7yticum NRRLB 3673, commercially available from Toyo Jozo Co.,
Tagata, Japan; and further Chromobacter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and
lipases ex Pseudomonas g7adio1i.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc.
They are used for "solution bleaching", i.e. to prevent transfer of
dyes or pigments removed from substrates during wash operations to
other substrates in the solution. Peroxidase enzymes are known in the
A
- 13 ~ 3 ~ ~
art, 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 No. 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 No. 4,507,219, Hughes,
issued March 26, 1985. Enzyme materials useful for liquid detergent
formulations, and their incorporation into such formulations, are
disclosed in U.S. Patent No. 4,261,868, Hora et al., issued April 14,
1981.
For granular detergents, the enzymes are preferably coated or
prilled with additives inert toward the enzymes to minimize dust
formation and improve storage stability. Techniques for accomplishing
this are well known in the art. In liquid formulations, an enzyme
stabilization system is preferably utilized. Enzyme stabilization
techniques for aqueous detergent compositions are well known in the
art. For example, one technique for enzyme stabilization in aqueous
solutions involves the use of free calcium ions from sources such as
calcium acetate, calcium formate, and calcium propionate. Calcium ions
can be used in combination with short chain carboxylic acid salts,
preferably formates. See, for example, U.S. Patent No. 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., such as diethanolamine, triethanolamine, di-
isopropanolamine, etc.), and boric acid or alkali metal borate. Enzyme
stabilization techniques are additionally disclosed and exemplified in
U.S. Patent No. 4,261,868, issued April 14, 1981 to Horn, et al.,
U.S. Patent No. 3,600,319, issued August 17, 1971 to
Gedge, et al., and European Patent Application
W o 92/061~4 2 1 ~ ~ 3 !-1 9 14 - PCT/US91/07028
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, 3,6~0,31~, and 3,519,570.
In addition to the polyhydroxy fatty acid amide, the
compositions hereof can contain other detersive surfactants to aid
in cleaning performance. The particular surfactants utilized can
vary widely utilizing any detersive surfactants useful for the
particular end-use envisioned. Enzyme-containing detergents will
most commonly be used for cleaning of laundry, fabrics, textiles,
fibers, hard surfaces, etc. Suitable surfactants include anionic,
nonionic, cationic, and other surfactants, and are exemplified
below. Preferably, the compositions will include one or more
anionic surfactants, one of more other nonionic surfactants, or a
combination thereof. The benefits of the present invention are
especially pronounced in compositions containing surfactants or
other ingredients that are harsh to the enzymes. These, in
oeneral, include (but are not limited to) anionic surfactants such
as alkyl ester sulfonates, linear alkyl benzene sulfonates, alkyl
sulfates, etc. Typically, the amount of additional detersive
surfactant present is from about 3Y. to about 407., by weight, of
the detergent composition, preferably from about 5% to about 30X.
Suitable surfactants are described below.
Anionic Surfactants
One type of anionic surfactant which can be utilized
encompass alkyl ester sulfonates. These are desirable because
they can be made with renewable, non-petroleum resources. Prepar-
ation of the alkyl ester sulfonate surfactant component can be
effected according to known methods disclosed in the technical
literature. For instance, linear esters of C~-C20 carboxylic
acids can be sulfonated with gaseous 503 according to "The Journal
of the American Oil Chemists Society," 52 (1975), pp. 323-329.
Suitable starting materials would include natural fatty substances
as deriYed from tallow, palm, and coconut oils, etc.
The preferred alkyl ester sulfonate surfactant, especially
for laundry applications, comprise alkyl ester sulfonate
surfactants of the structural formul~:
W o 92/06154 2~ il9 1S - PCT/US91/07028
O
R3 - CH - C - OR~
SO3M
wherein R3 is a C~-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R~ is a C1-C6 hydrocarbyl, preferably an
alkyl, or combination thereof, and M is a soluble salt-forming
cation. Suitable salts include metal salts such as sodium,
potassium, and lithium salts, and substituted or unsubstituted
ammonium salts, such as methyl-, dimethyl, -trimethyl, and
quaternary ammonium cations, e.g., tetramethyl-ammonium and
dimethyl piperdinium, and cations derived from alkanolamines,
e.g., monoethanolamine, diethanolamine, and triethanolamine.
Preferably, R3 is C10-Cl6 alkyl, and R~ is methyl, ethyl or
isopropyl. Especially preferred are the methyl ester sulfonates
wh-erein R3 is C~-CI6 alkyl.
Alkyl sulfate surfactants are another type of anionic
surfactant of importance for use herein. In addition to providing
excellent overall cleaning ability when used in combination with
polyhydroxy fatty acid amides, including good grease/oil cleaning
over a wide range of temperatures, wash concentrations, and wash
times, dissolution of alkyl sulfates can be obtained, as well as
improved formulability in liquid detergent formulations are water
soluble salts or acids of the formula ROSO3M wherein R preferably
is a C10-C2~ hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a C1o-C20 alkyl component, more preferably a C12-C1~ alkyl
or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
cation (e.g., sodium, potassium, lithium), substituted or
unsubstituted ammonium cations such as methyl-, dimethyl-, and
trimethyl ammonium and quaternary ammonium cations, e.g.,
tetramethyl-ammoniu~ and dimethyl piperdinium, and cations derived
from alkanolamines such as ethanolamine, diethanolamine, trietha-
nolamine, 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).
r~ UJ711VI-JLO
2la~ 4~-l6
Alkyl alkoxylated sulfate surfactants are another category of
- useful anionic surfactant. These surfactants are water soluble
salts or acids typcially of the formula Ro(A)mso3~ wherein R is an
unsubstituted C10-C2~ alkyl or hydroxyalkyl group haYing a C10-C2~
alkyl component, prefera~ly a C~2-C20 alkyl or hydroxyalkyl, more
preferably Cl2-Cl8 alkyl or hydroxyalkyl, A is an ethoxy or
propoxy unit, m is great~r than zero, typically between about C.5
and about 6, more preferably between about O.S and about 3, and M
is H or a cation which can be, for example, a metal cation (e.g.,
sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulfates as well
as alkyl propoxylated sulfates are contemplated herein. Specific
examples of substituted ammonium cations include methyl-,
dimethyl-, trimethyl-ammonium and quaternary ammonium cations,
such as tetramethyl-ammonium, dimethyl piperdinium and cations
derived from alkanolamines, e.g. monoethanolamine, diethanolamine,
and triethanolamine, and mixtures thereof. Exemplary surfactants
are Cl2-Cl8 alkyl polyethoxylate (l.OJ sulfate, Cl2-Cl8 alkyl
polyethoxylate (2.25) sulfate, Cl2-C~8 alkyl polyethoxylate (3.0)
sulfate, and Cl2-Cl8 alkyl polyethoxylate (4.0) sulfate wherein M
is conveniently 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 alkylbenzenesulphonates, C8-C22
pri~ry or secondary alkanesulphonates, C~-C2~ olefinsulphonates,
sulphonated polycarboxylic acids prepared by sulphonation of the
pyrolyzed product of atkaline earth metal citrates, e.g., as
described in British Patent Specification No. 1,082,179, alkyl
glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin sulfonates, alkyl phosphates, isethionates such as the
acyl isethionates, N-acyl taurates, fatty acid amides of methyl
tauride, alkyl succinamates and sulfosuccinates, monoesters of
sulfosuccinate (especially saturated and unsaturated Cl2-Cl8
monoesters) diesters of sulfosuccinate (especially saturated and
- 17 ~
unsaturated C6-Cl4 diesters), N-acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the
nonionic nonsulfated compounds being described below), branched primary
alkyl sulfates, alkyl polyethoxy carboxylates such as those of the
formula RO(CH2CH2O)kCH2COO Mf wherein R is a C8-C22 alkyl, k is an integer
from 0 to 10, and M is a soluble salt-forming cation, and fatty acids
esterified with isethionic acid and neutralized with sodium hydroxide.
Resin acids and hydrogenated resin acids are also suitable, such as
rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids
present in or derived from tall oil. Further examples are described
in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz,
Perry and Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent No. 3,929,678, issued December 30, 1975 to
Laughlin et al., at Column 23, line 58 through Column 29, line 23.
Nonionic Deterqent Surfactants
Suitable nonionic detergent surfactants are generally disclosed
in U.S. Patent No. 3,929,678, Laughlin et al., issued December 30,
1975, at Column 13, line 14 through Column 16, line 6. Exemplary, non-
limiting classes of useful nonionic surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
condensates are preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group containing from about
6 to about 12 carbon atoms in either a straight chain or branched chain
configuration with the alkylene oxide. In a preferred embodiment, the
ethylene oxide is present in an amount equal to from about 5 to about
25 moles of ethylene oxide per mole of alkyl phenol. Commercially
available nonionic surfactants of this type include IGEPAL C0-630,
marketed by the GAF Corporation; and TRITON X-45, X-114, X-100, and X-
102, all marketed by the Rohm & Haas Company. These compounds are
commonly referred to as alkyl phenol alkoxylates, (e.g., alkyl phenol
ethoxylates).
2. The condensation products of aliphatic alcohols with from
about to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be straight or branched, primary
'.~
W 0 92/06154 P ~ /US91/07028 2~ ~?49 18 -
or secondary, and generally contains from about 8 to about 22
- carbon atoms. Particularly preferred are the condensation
products of alcohols having an alkyl group containing from about
10 to about 20 carbon atoms with from about 2 to about 18 mo1es of
S ethylene oxide per mole of alcohol. Examples of commercially
available nonionic surfactants of this type include TER~IT~L
15-S-9 (the condensation product of C~l-C15 linear secondary
a1cohol with 9 moles ethylene oxide), TERGITOL 24-L-6 N~W (the
condensation product of C~2-CI~ primary alcohol with 6 moles
ethylene oxide with a narrow molecular weight distribution), both
marketed by Union Carbide Corporation; NEODOL 45-9 (the condensa-
tion product of C1~-C~5 linear alcohol with 9 moles of ethylene
oxide), NEODOL 23-6.5 (the condensation product of C12-C13 linear
alcohol with 6.5 moles of ethylene oxide), NEODOL 45-7 (the con-
densation product of Cl~-C~5 linear alcohol with 7 moles of ethy-
lene oxide), NEODOL 45-4 (the condensation product of CI~-Cl5
linear alcohol with 4 moles of ethylene oxide), marketed by Shell
Chemical Company, and KYRO EOB (the condensation product of
Cl3-C~5 alcohol with 9 moles ethylene oxide), marketed by The
Procter & 6amble Company. This category of nonionic surfactant is
referred to generally as ~alkyl ethoxylates.~
3. The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene oxide
with propylene glycol. The hydrophobic portion of these compounds
preferably has a molecular weight of from about 1500 to about 1800
and exhibits water insolubility. The addition of polyoxyethylene
moieties to this hydrophobic portion tends to increase the water
solubility of the molecule as a whole, and the liquid character of
the product is retained up to the paint where the polyoxyethylene
content is about 5070 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-aYailable PLURONIC
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
W 0 92/06154 P ~ /US91/07028
propylene oxide, and generally has a molecular weight of from
about 2500 to about 3000. This hydrophobic moiety is condensed
with ethylene oxide to the extent that the condensation product
contains from about 407. 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 TETRONIC compounds, marketed by BASF.
5. Semi-polar nonionic surfactants are a special category
of nonionic surfactants which include water-soluble amine oxides
containing one alkyl moiety of from about 10 to about 18 carbon
atoms and 2 moieties selected from the group consisting of alkyl
groups and hydroxyalkyl groups containing from about 1 to about 3
carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and hydroxy-
alkyl groups containing from about 1 to about 3 carbon atoms; and
water-soluble sulfoxides containing one alkyl moiety of from a60ut
10 to about 18 carbon atoms and a moiety selected from the group
consisting of alkyl and hydroxyalkyl moieties of from about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide surfactants having the formula
O
R3(0R~)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;
R~ is an alkylene or hydroxyalkylene group containing from about 2
to about 3 carbon atoms or mixtures thereof; x is from O 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 R~
groups can be attached to each other, e.g., through an oxygen or
nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include ClO-Cl8
alkyl dimethyl amine oxides and C8-Cl2 alkoxy ethyl dikydroxy
ethyl amine oxides.
W o 92/061~4 PCT/US91/07~28
21~ l9 20 -
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from
about 10 to about 16 carbon atoms and a polysaccharide, e.g., a
polyglycoside, hydrophilic group containing from about 1.3 to
about 10, preferably from about 1.3 to about 3, most preferably
from about 1.3 to about 2.7 saccharide units. Any reducing
saccharide containing 5 or 6 carbon atoms can be used, e.g.,
glucose, galactose and galactosyl moieties can be substituted for
the glucosyl moieties. (Optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a glucose
or ga1actose 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 polysacchar-ide
moiety. The preferred alkyleneoxide is ethylene oxide. Typical
hydrophobic groups include alkyl groups, either saturated or
unsaturated, branched or unbranched containing from about 8 to
about 18, preferably from about 10 to about 16, carbon atoms.
Preferably, the alkyl group is a straight chain saturated alkyl
group. The alkyl group can contain up to about 3 hydroxy groups
and/or the polyalkyleneoxide chain can contain up to about 10,
preferably less than 5, alkyleneoxide moieties. Suitable alkyl
polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-,
tri-, tetra-, penta-, and hexaglucosides, galactosides,
lactosides, glucoses, fructosides, fructoses and/or galactoses.
Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and
pentaglucosides and tallow alkyl tetra-, penta-, and hexa-
glucosides.
The preferred alkylpolyglycosides have the formula
R2o(cnH2no)t(glycosyl )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,
- W ~ 92/061~4 2 1 0 3 !1 9 P ~ /US91/07028
- 21 -
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 pre-
ferably derived from glucose. To prepare these compounds, the
alcohol or alkylpolyethoxy alcohol is formed first and then
reacted with glucose, or a source of glucose, to form the
glucoside (attachment at the l-position). The additional glycosyl
units can then be attached between their l-position and the
preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably
predominately the 2-position.
7. Fatty acid amide surfactants having the formula:
O
R6 C - N(R')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, C1-C4 alkyl, Cl-C4
hydroxyalkyl, and -(C2H~O)xH where x varies from about 1 to about
3.
Preferred amides are C8-C20 ammonia amides, monoethanol-
amides, diethanolamides, and isopropanolamides.
Cationic Surfactants
Cationic detersive surfactants can also be included in
detergent compositions of the present invention. Cationic sur-
factants include the ammonium surfactants such as alkyldimethyl-
ammonium 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 R~ is
selected from the group consisting of Cl-C~ alkyl, C1-C~
hydroxyalkyl, benzyl, ring structures formed by joining the two R~
groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or
hexose polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; Rs is the same as R~ or is an alkyl
chain wherein the total number of carbon atoms of R2 plus R~ is
not more than about 18; each y is from O to about 10 and the sum
of the y values is from O to about 15; and X is any compatible
anion.
~ ~ - 22 ~
Other cationic surfactants useful herein are also described in
U.S. Patent No. 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
aliphatic derivatives of secondary or tertiary amines, or aliphatic
derivatives of heterocyclic secondary and tertiary amines in which the
aliphatic radical can be straight chain or branched. One of the
aliphatic substitutents contains at least about 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at least one
contains an anionic water-solubilizing group, e.g., carboxy, sulfonate,
sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at Column 19, lines 18-35 for examples of ampholytic
surfactants.
Zwitterionic surfactants can also be incorporated into the
detergent compositions hereof. These surfactants can be broadly
described as derivatives of secondary and tertiary amines, derivatives
of heterocyclic secondary and tertiary amines, or derivatives of
quaternary ammonium, quaternary phosphonium or tertiary sulfonium
compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at Column 19, line 38 through Column 22, line 48 for
examples of zwitterionic surfactants.
Ampholytic and zwitterionic surfactants are generally used in
combination with one or more anionic and/or nonionic surfactants.
In addition to enzymes, the polyhydroxy fatty acid amide, and any
optional detersive surfactants, the detergents hereof can include one
or more other detergent adjunct materials or other materials for
assisting in or enhancing cleaning performance, treatment of the
substrate to be cleaned, or modify the aesthetics of the detergent
composite or modify the (e.g., perfumes, colorants, dyes, etc.).
Builders
Detergent builders can optionally be included in the compositions
hereof to assist in controlling mineral hardness. Inorganic as well
as organic builders can be used.
A
- - 23 ~ 3 ~ ~ ~
The level of builder can vary widely depending upon the end use
of the composition and its desired physical form. When present, the
compositions will typically comprise at least about 1% builder. Liquid
formulations typically comprise from about 5% to about 50%, more
typically about 5% to about 30%, by weight, of detergent builder.
Granular formations typically comprise from about 10% to about 80%,
more typically from about 15% to about 50% by weight, of the detergent
builder. Lower or higher levels of builder, however, are not meant to
be excluded.
Inorganic detergent builders include, but are not limited to, the
alkali metal, ammonium and alkanolammonium salts of polyphosphates
(exemplified by the tripolyphosphates, pyrophosphates, and glassy
polymeric meta-phosphates), phosphonates, phytic acid, silicates,
carbonates (including bicarbonates and sesquicarbonates), sulphates,
and aluminosilicates. Borate builders, as well as builders containing
borate-forming materials that can produce borate underdetergent storage
or wash conditions (hereinafter, collectively "borate builders"), can
also be used. Preferably, non-borate builders are used in the
compositions of the invention intended for use at wash conditions less
than about 50~C, especially less than about 40~C.
Examples of silicate builders are the alkali metal silicates,
particularly those having a SiOz:Na2O ratio in the range 1.6:1 to 3.2:1
and layered silicates, such as the layered sodium silicates described
in U.S. Patent No. 4,664,839, issued May 12, 1987 to H.P. Rieck.
However, other silicates may also be useful such as for example
magnesium silicate, which can serve as a crispening agent in granular
formulations, as a stabilizing agent for oxygen bleaches, and as a
component of suds control systems.
Examples of carbonate builders are the alkaline earth and alkali
metal carbonates, including sodium carbonate and sesquicarbonate and
mixtures thereof with ultra-fine calcium carbonate as disclosed in
German Patent Application No. 2,321,001 published on November 15, 1973.
. . " ~
- 24 - ~ 3 ~ 9
Aluminosilicate builders are especially useful in the present
- - invention. Aluminosilicate builders are of great importance in
most currently marketed heavy duty granular detergent composi-
tions, and can also be a significant builder ingredient in liquid
detergent formulations. Aluminosilicate builders include those
having the empirical formula:
MZ(zAl02-ysio2)
wherein M is sodium, pot~ssium, 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 aluminosili-
cate. Preferred aluminosilicates are zeolite builders which have
the formula:
Naz[(AlO2)z (SiO2)y]-xH20
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.
Useful aluminosilicate ion exchange materials are commer-
cially available. These aluminosilicates can be crystalline or
amorphous in structure and can be naturally-occurring aluminos-ili-
cates or synthetically derived. A method for producing alumino-
silicate 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[(Al02)l2(SiO2)l2] ~X~20
wherein x is from about 20 to about 30, especially about 27. This
material is known as Zeolite A. Preferably, the aluminosilicate
has a particle size of about 0.1-lO microns in diameter.
Specific examples of polyphosphates are the alkali metal
tripolyphosphates, sodium, potassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potassium orthophosphate, sodium polymeta phosphate in which the
degree of polymerization ranges from about 6 to about 21, and
salts of phytic acid.
~' ',f.
~'
~ ~ ~ 4 3 4 9
- 25 -
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 disphosphonic acids, such as the trisodium and
tripotassium ethylidene, isopyropylidene benzylmenthylidene and halo
methylidene phosphonates. Phosphonate builder salts of the
aforementioned types are disclosed in U.S. Patent Nos. 3,159,581 and
3,213,030 issued December 1, 1964 and October 19, 1965, to Diehl; U.S.
Patent No. 3,422,021 issued January 14, 1969, to Roy; and U.S. Patent
Nos. 3,400,148 and 3,422,137 issued September 3, 1968, and January 14,
1969 to Quimby.
Organic detergent builders suitable for the purposes of the
present invention include, but are not restricted to, a wide variety
of polycarboxylate compounds. As used herein, "polycarboxylate" refers
to compounds having a plurality of carboxylate groups, preferably at
least 3 carboxylates.
Polycarboxylate builder can generally be added to the composition
in acid form, but can also be added in the form of a neutralized salt.
When utilized in salt form, alkali metals, such as sodium, potassium
and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of
categories of useful materials. One important category of
polycarboxylate builders encompasses the ether polycarboxylates. A
number of ether polycarboxylates have been disclosed for use as
detergent builders. Examples of useful ether polycarboxylates include
oxydisuccinate, as disclosed in Berg, U.S. Patent No. 3, 128,287,
issued April 7, 1964, and Lamberti et al., U.S. Patent No. 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)
~ ,,~
A
- 26 - ~ 3 ~ ~
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H
or a salt-forming cation. For examp)e, if in the above general
formula A and B are both H, then the compound is oxydissuccinic
acid and its water-soluble salts. If A is OH and B is H, then the
compound is tartrate monosuccinic acid (TMS) and its water-soluble
salts. If A is H and B is -O-CH(COOX)-CH2(COOX), then the com-
pound is tartrate disuccinic acid (TDS) and its water-soluble
salts. Mixtures of these builders are especially preferred for
use herein. Particularly preferred are mixtures of TMS and TDS in
a weight ratio of TMS to TDS of from about 97:3 to about 20:80;
These builders are disclosed in U.S. Patent 4,663,071, issued to
Bush et al, on May ~, 1987.
Suitable ether polycarboxylates also include cyclic com-
pounds, 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 hydroxy-
polycarboxylates represented by the structure:
Ho-[c(R)(cooM)-c(R)(~ooM)-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 d;fferent and selected from
hydrogen, Cl 4 alkyl or C1 4 substituted alkyl (preferably R is
hydrogen).
Still other ether polycarboxylates include copolymers of
maleic anhydride with ethylene or vinyl methyl ether, 1, 3,
5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyl-
oxysuccinic acid.
Organic polycarboxylate builders also include the various
alkali metal, ammonium and substituted ammonium salts of poly-
acetic acids. Examples include the sodium, potassium, lithium,
ammonium and substituted ammonium salts of ethylenediamine tetra-
acetic acid, and nitrilotriacetic acid.
Also included are polycarboxylates such as mellitic acid,
succinic acid, oxydisuccinic acid, polymaleic acid, benzene
1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and
soluble salts thereof.
A
Citrate builders, e.g., citric acid and soluble salts thereof
(particularly sodium salt), are polycarboxylate builders 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 No. 3,723,322, Diehl, issued March 28, 1973.
Also suitable in the detergent compositions of the present invention
are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds
disclosed in U.S. Patent No. 4,566,984, Bush, issued January 28, 1986.
Useful succinic acid builders include the C5 - C20 alkyl succinic acids and
salts thereof. A particularly preferred compound of this type is
dodecenyl succinic acid. Alkyl succinic acids typically are of the
generally formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic acid,
wherein R is hydrocarbon, e.g., Cl0-C20 alkyl or alkenyl, preferably C12-Cl6
or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone
substitutents, all as described in the above-mentioned patents.
The succinate builders are preferably used in the form of their
water-soluble salts, including the sodium, potassium, ammonium and
alkanolammonium salts.
Specific examples of succinate builders include: laurylsuccinate,
myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate(preferred), 2-
pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred
builders of this group, and are described in European Patent Application
No. 86200690.5/0,200,263, published November 5, 1986.
Examples of useful builders also include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane-
hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble
polyacrylates (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 polyacetal carboxylates
disclosed in U.S. Patent No. 4,144,226, Crutchfield et al., issued March
13, 1979. These polyacetal carboxylates can be prepared by bringing
- 28 ~ 3 ~ ~
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 No.
3,308,067, Diehl, issued March 7, 1967. Such materials include the
water-soluble salts of homo- and copolymers of aliphatic carboxylic
acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid,
aconitic acid, citraconic acid and methylenemalonic acid.
Other organic builders known in the art can also be used. For
example, monocarboxylic acids, and soluble salts thereof, having long
chain hydrocarbyls can be utilized. These would include materials
generally referred to as "soaps". Chain lengths of C1o-C20 are typically
utilized. The hydrocarbyls can be saturated or unsaturated.
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 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 cleansing, or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other bleaching
agents. For wash conditions below about 50~C, especially below about
40~C, it is preferred that the compositions hereof not contain
borate or material which can form borate in situ (i.e.
borate-forming material) under detergent storage or
~A''~"-
- 29 -
wash conditions. Thus it is preferred under these conditions that
a non-borate, non-borate-forming bleaching agent-is used. Prefer-
ably, detergents to be used at these temperatures are substan-
tially free of borate and borate-forming material. As used
herein, ~substantially free of borate and borate-forming material~
shall mean that the composition contains not more than about 2~ by
weight of borate-containing and borate-forming material of any
type, preferably, no more than 1%, more preferably 0X.
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 monoperoxy-
phthalate hexahydratet the magnesium salt of meta-chloro perben-
zoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydo-
decanedioic acid. Such bleaching agents are disclosed in U.S.
Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent
Application 740,446, Burns et al, filed June 3, 1985, European
Patent Application 0,133,354, Banks et al, published February 20,
lg85, and U.S. Patent 4,412,934, Chung et al, issued November 1,
1983. Highly preferred bleaching agents also include 6-nonylamino-6-
oxoperoxycaproic acid as described in U.S. Patent No. 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
and the sodium and potassium dichloroisocyanurates and N-chloro
and N-bromo alkane sulphonamides. Such materials are normally
added at 0.5-10~. by weight of the finished product, preferably
- 1-5% by weight.
Peroxygen bleaching agents can also be used. Suitable
peroxygen bleaching compounds include sodium carbonate peroxy-
hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate,
and sodium peroxide.
Peroxygen bleaching agents are preferably combined with
bleach activators, which lead to the in s;tu production in aqueous
solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator.
. . ...
'A
_ - 30 ~
Preferred bleach activators incorporated into compositions of the
present invention have the general formula:
o
Il
R - C - L
wherein R is an alkyl group containing from about 1 to about 18 carbon
atoms wherein the longest linear alkyl chain extending from and
including the carbonyl carbon contains from about 6 to about 10 carbon
atoms and L is a leaving group, the conjugate acid of which has a PKa
in the range of from about 4 to about 13. These bleach activators are
described in U.S. Patent No. 4,915,854, issued April 10, 1990 to Mao,
et al., and U.S. Patent No. 4,412,934.
Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated
bleaching agents such as 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
phthalocyanines and a photoactivated bleaching process are described
in U.S. Patent No. 4,033,718, issued July 5, 1977 to Holcombe et al.
Typically, detergent compositions will contain about 0.025% to about
1.25%, by weight, of sulfonated zinc phthalocyanine.
Polymeric Soil Release Aqent
Any polymeric soil release agents known to those skilled in the
art can be employed in the practice of this invention. Polymeric soil
release agents are characterized by having both hydrophilic segments,
to hydrophilize the surface of hydrophobic fibers, such as polyester
and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers
and remain adhered thereto through completion of washing and rinsing
cycles and, thus, serve as an anchor for the hydrophilic segments.
This can enable stains occurring subsequent to treatment with the soil
release agent to be more easily cleaned in later washing procedures.
~ - r~
A
W O 92/06154 P ~ /US91/07028. 210~5 31 -
Whereas it can be beneficial to utilize polymeric soil
- release agents in any of the detergent compositions hereof,
especially those compositions utilized for laundry or other
applications wherein removal of grease and oil from hydrophobic
surfaces is needed, the presence of polyhydroxy fatty acid amide
in detergent compositions also containin~ anionic surfactants can
enhance performance of many of the more commonly utili~ed types of
polymeric soil release agents. Anionic surfactants interfere with
the ability of certain soil release agents to deposit upon and
adhere to hydrophobic surfaces. These polymeric soil release
agents have nonionic hydrophile segments or hydrophobe segments
which are anionic surfactant-interactive.
The compositions hereof for which improved polymeric soil
release agent per~ormance can be obtained through the use of
polyhydroxy fatty acid amide are those which contain an anionic
surfactant system, an anionic surfactant-interactive soil release
agent and a soil release agent-enhancing amount of the polyhydroxy
fatty acid amide (PFAJ, wherein: (I) anionic surfactant-
interaction between the soil release agent and the anionic
surfactant system of the detergent composition can be shown by a
comparison of the level of soil release agent (SRA) deposition on
hydrophobic fibers (e.g., polyester) in aqueous solution between
(A) a "Control~ run wherein deposition of the SRA of the detergent
composition in aqueous solution, in the absence of the other
detergent ingredients, is measured, and (B) an "SRA/Anionic
surfactant~ test run wherein the same type and amount of the
anionic surfactant system utilized in detergent composition is
combined in aqueous solution with the SRA, at the same weight
ratio of SRA to the anionic surfactant system of the detergent
3~ composition, whereby reduced deposition in (B) relative to (A)
indicates anionic-surfactant interaction; and (II) whether the
detergent composition contains a soil release agent-enhancing
amount of polyhydroxy fatty acid amide can be determined by a
comparison of the SRA deposition of the SRA/Anionic surfactant
test run of (B) with soil release agent deposition in (C) an
"SRA/Anionic surfactant/PFA test run" wherein the same type and
level of polyhydroxy fatty acid a~ide of the detergent composition
is combined with the soil release agent and anionic surfactant
w o 92/06154 P ~ tUS91/07~2~ 21~ ~3 ~ 32 -
system corresponding to said S M /Anionic surfactant test run,
whereby improYed deposition of the soil release agent in test run
(C) relative to test run (B) indicates that a soil release
agent-enhancing amount of polyhydroxy fatty acid amide is present.
For purposes hereof, the tests hereof should be conducted at
anionic surfactant concentrations in the aqueous solution that are
above the critical micelle concentration (CMC) of the anionic
surfactant and preferably above about 100 ppm. The polymeric soil
release agent concentration should be at least 15 ppm. A swatch
of polyester fabric should be used for the hydrophobic fiber
source. Identical swatches are immersed and agitated in 35 C
aqueous solutions for the respective test runs for a period of 12
minutes, then removed, and analyzed. Polymeric soil release agent
deposition level can be determined by radiotagging the soil
release agent prior to treatment- and subsequently conducting
radiochemical analysis, according to techniques known in the art.
As an alternative to the radiochemical analytical methodology
discussed above, soil release agent deposition can alternately be
determined in the above test runs (i.e., test runs A, B, and C) by
determination of ultraviolet light (UY) absorbance of the test
solutions, according to techniques well known in the art.
Decreased UV absorbance in the test solution after removal of the
hydrophobic fiber material corresponds to increased SRA deposi-
tion. As will be understood by those skilled in the art, UV
analysis should not be utilized for test solutions containing
types and leYels of materials which cause excessive UV absorbance
interference, such as high levels of surfactants with aromatic
groups (e.g., alkyl benzene sulfonates, etc.).
Thus by "soil release agent-enhancing amount" of polyhydroxy
fatty acid amide is meant an amount of such surfactant that will
enhance deposit;on of the soil release agent upon hydrophobic
fibers, as described above, or an amount for which enhanced
grease/oil cleaning performance can be obtained for fabrics washed
in the detergent composition hereof in the next subsequent
c~eaning operation.
The amount of polyhydroxy fatty acid amide needed to enhance
deposition will vary with the anionic surfactant selected, the
amount of anionic surfactant, the particular soil release agent
W ~ 92~06154 P ~ /US91/07028 2~Q4~ 33 ~
chosen, as well as the particular polyhydroxy fatty acid amide
_ chosen. Generally, compositions will comprise from about 0.01% toabout 107., by weight, of the polymeric soil release agent,
typical'ly from about 0.1% to about 5Ya~ and from about 4% to about
50X, more typically from about 5~ to about 30X of anionic
surfactant. Such compositions should generally contain at least
about 1%, preferably at least about 3%, by ~eight, of the
polyhydroxy fatty acid amide, though it is not intended to
necessarily be limited thereto.
The polymeric soil release agents for which performance is
enhanced by polyhydroxy fatty acid amide in the presence of
anionic surfactant include those soil release agents having: (a)
one or more nonionic hydrophile components consisting essentially
of (i) polyoxyethylene segments with a degree of polymerization of
at least 2, or (ii) oxypropylene or polyoxypropylene segments with
a degree of polymerization of from 2 to 10, wherein said hydro-
phile segment does not encompass any oxypropylene unit unless it
is bonded to adjacent moieties at each end by ether linkages,~ or
(iii) a mixture of oxyalkylene units comprising oxyethylene and
from 1 to about 30 oxypropylene units wherein said mixture con-
tains a sufficient amount of oxyethylene units such that the
hydrophile component has hydrophilicity great enough to increase
the hydrophilicity of conventional polyester synthetic fiber
surfaces upon deposit of the soil release agent on such surface,
said hydrophile segments preferably comprising at least about 25~/.
oxyethylene uni~s and more preferably, especially for such compon-
ents having about 20 to 30 oxypropylene units, at least about 50%
oxyethylene units; or (b) one or more hydrophobe components
comprising (i) C3 oxyalkylene terephthalate segments, wherein, if
said hydrophobe components also comprise oxyethylene terephthal-
ate, the ratio of oxyethylene terephthalate:C3 oxyalkylene tere-
phthalate units is about 2:1 or lower, (ii) C~-C6 alkylene or oxy
C~-C6 alkylene segments, or mixtures thereof, (iii) poly (vinyl
ester) segments, preferably poly(vinyl acetate), having a degree
~5 of polymerization of at least 2, or (iv) C1-C~ alkyl ether or C~
hydroxyalkyl ether substituents, or mixtures thereof, wherein said
substituents are present in the form of Cl-CI alkyl eiher cr C~
hydroxyalkyl ether cellulose derivatives, or mixtures thereof, and
- 34 - ~ 4 ~
such cellulose derivatives are amphiphilic, whereby they have a
- sufficient level of Cl-C4 alkyl ether and/or C4 hydroxyalkyl ether
units to deposit upon conventional polyester synthetic fiber
surfaces and retain a sufficient level of hydroxyls, once adhered
to such conventional synthetic fiber surface, to increase fiber
surface hydrophilicity, or a combination of (a) and (b).
Typically, the po~yoxyethylene segments of (a)(i) will have a
degree of polymerization of from 2 to about 200, although higher
levels can be used, preferably from 3 to about 150, more prefer-
ably from ~ to about 100. Suitable oxy C~-C6 alkylene hydrophobe
segments include, but are not limited to, end-caps of polymeric
soil release agents such as MO3S(CH~)nOCH2CH20-, where M is sodium
and n is an integer from 4-6, as disclosed in U.S. Patent
4,721,580, issued January 26, 1988 to Gosselink.
lS Polymeric soil release agents useful in the present invention
include cellulosic derivatives such as hydroxyether cellulosic
polymers, copolymeric blocks of ethylene terephthalate or propyl-
ene terephthalate with polyethylene oxide or polypropylene oxide
terephthalate, and the like.
Cellulosic derivatives that are functional as soil release
agents are commercially available and include hydroxyethers of
cellulose such as MethocelR (Dow).
Cellulosic soil release agents for use herein also include
those selected from the group consisting of Cl-C, alkyl and C~
2 5 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose,
hydroxypropyl methylcellulose, and hydroxybutyl methylcellulose.
A variety of cellulose derivatives u~eful 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
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 SOKALAN type of material, e.g.,
SOKALAN HP-22, available from BASF (West Germany).
'"A~"
- 35 -
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephthalate and polyethylene oxide (PEO)
terephthalate. More specifically, these polymers are comprised of
repeating units of ethylene terephthalate and PEO terephthalate in a
mole ratio of ethylene terephthalate units to PEO terephthalate units
of from about 25:75 to about 35:65, said PEO terephthalate units
containing polyethylene oxide having molecular weights of from about
300 to about 2000. The molecular weight of this polymeric soil release
agent is in the range of from about 25,000 to about 55,000. See U.S.
Patent No. 3,959,230 to Hays, issued May 25, 1976. See also U.S.
Patent No. 3,893,929 to Basadur issued July 8, 1975 which discloses
similar copolymers.
Another preferred polymeric soil release agent is a polyester
with repeat units of ethylene terephthalate units containing 10-15% by
weight of ethylene terephthalate units together with 90-80% by weight
of polyoxyethylene terephthalate units, derived from a polyoxyethylene
glycol of average molecular weight 300-5,000, and the mole ratio of
ethylene terephthalate units to polyoxyethylene terephthalate units in
the polymeric compound is between 2:1 and 6:1. Examples of this
polymer include the commercially available material ZELCON 5126 (from
Dupont) and MILEASE T (from ICI). These polymers and methods of their
preparation are more fully described in U.S. Patent No. 4,702.857.
issued October 27, 1987 to Gosselink.
Another preferred polymeric soil release agent is a sulfonated
product of a substantially linear ester oligomer comprised of an
oligomeric ester backbone of terephthaloyl and oxylakyleneoxy repeat
units and terminal moieties covalently attached to the backbone. said
soil release agent being derived from allyl alcohol etholoxylate,
dimethyl terephthalate, and 1,2-propylene diol, wherein after
sulfonation, the terminal moieties of each oligomer have, on average,
a total of from about 1 to about 4 sulfonate groups. These soil
release agents are described fully in U.S. Patent No. 4,968,451, issued
November 6, 1990 to J.J. Scheibel and E.P. Gosselink, U.S. Serial No.
07/474,709, filed January 29, 1990.
A
- 36 ~
Other suitable polymeric soil release agents include the ethyl-
or methyl-capped 1,2-propylene terephthalate-polyoxyethylene
terephthalate polyesters of U.S. Patent No. 4,711,730, issued December
8, 1987 to Gosselink et al., the anionic end-capped oligomeric esters
of U.S. Patent No. 4,721,580, issued January 26, 1988 to Gosselink,
wherein the anionic end-caps comprise sulfo-polyethoxy groups derived
from polyethylene glycol (PEG), the block polyester oligomeric
compounds of U.S. Patent No. 4,702,857, issued October 27, 1987 to
Gosselink, having polyethoxy end-caps of the formula X-(OCH2CH2)n-
wherein n is from 12 to about 43 and X is a C1-C4 alkyl, or preferably
methyl.
Additional polymeric soil release agents include the soil release
agents of U.S. Patent No. 4,877,896, issued October 31, 1989 to
Maldonado et al., which discloses anionic, especially sulfoaroyl, end-
capped terephthalate esters. The terephthalate esters contain
unsymmetrically substituted oxy-1,2-alkyleneoxy units. Included among
the soil release polymers of U.S. Patent No. 4,877,896 are materials
with polyoxyethylene hydrophile components or C3 oxyalkylene
terephthalate (propylene terephthalate) repeat units within the scope
of the hydrophobe components of (b)(i) above. It is the polymeric soil
release agents characterized by either, or both, of these criteria that
particularly benefit from the inclusion of the polyhydroxy fatty acid
amides hereof, in the presence of anionic surfactants.
If utilized, soil release agents will generally comprise from
about 0.01% to about 10.0%, by weight, of the detergent compositions
herein, typically from about 0.1% to about 5%, preferably from about
0.2% to about 3.0%.
Chelatinq Aqents
The detergents 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, amiro phosphonates. polyfunctionally-
substituted aromatic chelating agents and mixtures thereof, all as
hereinafter defined. Without intending to be bound by
theory, it is believed that the benefit of these
.,,, ~ ''. IL
W 0 92/06154 ~ 1 0 4 ~ 4 3 P ~ /US91/07028
- 37 -
materials is due in part to their exceptional ability to remove
iron and manganese ions from washing solutions by formation of
soluble chelates.
Amino carboxylates useful as optional chelating agents in
compositions of the invention can have one or more, preferably at
least two, units of the substructure
CH2 -
N - (CH2)% - COOM,
wherein M is hydrogen, alkali metal, ammonium or substituted
ammonium (e.g. ethanolamine) and x is from 1 to about 3, pref-
erably 1. Preferably, these amino carboxylates do not contain
alkyl or alkenyl groups with more than about 6 carbon atoms.
Operable amine carboxylates include ethylenediaminetetraacetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates, triethylenetetraaminehexa-
acetates, diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts thereof and
mixtures thereof.
Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at least low
levels of total phosphorus are permitted in detergent composi-
tions. Compounds with one or more, preferably at least two, units
of the substructure
CH2
2~ N (cH2)x PO3M2,
wherein M is hydro~en, alkali metal, a~monium or substituted
ammonium and x is from 1 to about 3, preferably 1, are useful and
include ethylenediaminetetrakis (methylenephosphonates), nitrilo-
tris (methylenephosphonates) and diethylenetriaminepentakis
(methylenephosphonates). Preferably, these amino phosphonates do
not contain alkyl or alkenyl groups with more than about 6 carbon
atoms. Alkylene groups can be shared by substructures.
Polyfunctionally - substituted aromatic chelating agents are
also useful in the compositions herein. These materials can
comprise compounds having the general formula
- 38 -
- OH
R ~ OH ~ 3 ~ ~
~0~
. ~ R
R
wherein at least one R is - SO3H or - COOH or soluble salts
thereof and mixtures thereof. U.S. Patent No. 3,812,044,
issued May 21, 19i4, to Connor et al.. discloses
polyfunctionally - substituted aromatic chelating and sequestering
agents. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-
disulfobenzene. Alkaline detergent compositions can contain these
materials in the form of alkali metal, ammonium or substituted
ammonium (e.g. mono-or triethanol-amine) salts.
If utilized, these chelating agents will generally comprise
from about 0.1% to about 10% by weight of the detergent composi-
tions 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. Granular detergent compositions
which contain these compounds typically contain from about 0.01%
to about 10.0% by weight of the water-soluble ethoxylated amines;
liquid detergent compositions, typically about 0.01% to about 5~
These compounds are selected preferably from the group consisting
of:
(l) ethoxylated monoamines haviny the formula:
- (X-L-)-N-(R2) 2
(2) ethoxylated diamines having the formula:
R2 -N_Rl _ ~ R2 (R2 ) 2 -N-IRl-N-(R2) 2
LL
X ~ ' X
or
(X-L-) 2 -N-Rl-N- (R2 ) 2
(3) ethoxylated polyamines having the formula:
,R2
R3-[(A1)q-(R~)t-N-L-X]p
~ff ~ -
W ~ 92/06154PCT/US91/0702~
2 1 0 ~ 1 9 89
(4) ethoxylated amine polymers having the general formula:
R2
[ (R2 ) 2-N~W~Rl-N~XERl- ~l3y~Rl-N-L-X)z
and
(5) mixtures thereof; wherein Al is
O O O O O
n 1l o 1l 1l
-NC-, -NCO-, -NCN-, -CN-, -OCN-,
10 R R R R R R
O O 0 00
n ~1
-CO-, -OCO-, -OC -, -CNC -,
R
or -0-; R is H or Cl-C, alkyl or hydroxyalkyl; Rl is C2-Cl2
alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a
C2-C3 oxyalkylene moiety having from 2 to about 20 oxyalkylene
units provided that no 0-N bonds are formed; each R2 is Cl-Cl or
hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety
-(CH2)r, -A2-(CH2)S-, wherein A2 is -0- 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-Cl2 alkyl,
hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution
sites; R~ 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 0-N bonds are
formed; L is a hydrophilic chain which contains the polyoxyalkyl-
ene moiety -[(R50~m(CH2CH20)n~-, wherein Rs is C3-C~ alkylene or
hydroxyalkylene and m and n are numbers such that the moiety
-~CH2CHz~)~- comprises at least about 50~ by weight of said
polyoxyalkylene moiety; for said monoamines, m is from 0 to about
4, and n is at least about 12; for said diamines, m is from 0 to
about 3, and n is at least about 6 when Rl is C2-C3 alkylene,
hydroxyalkylene, or alkenylene, and at least about 3 when Rl is
other than C2-C3 alkylene, hydroxyalkylene or alkenylene; for said
polyamines and amine polymers, m is from 0 to about 10 and n is at
least about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0,
provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at
least 2i and y + ~ is at least 2. The most preferred soil release
_ 40 ~ 3 ~ 9
and anti-redeposition agent is ethoxylated tetraethylenepentamine.
Exemplary ethoxylated amines are further described in U.S. Patent No.
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 No. 111, 984, Gosselink,
published June 27, 1984; the zwitterionic polymers disclosed in
European Patent Application No. 112,592, Gosselink, published July 4,
1984; and the amine oxides disclosed in U.S. Patent No. 4,548,744,
Connor, issued October 22, 1985.
Other clay soil removal and/or anti-redeposition agents known in
the art can also be utilized in the compositions hereof. Another type
of preferred anti-redeposition agent includes the carboxy methyl
cellulose (CMC) materials. These materials are well known in the art.
PolYmeric Dispersinq Aqents
Polymeric dispersing agents can advantageously be utilized in the
compositions hereof. These materials can aid in calcium and magnesium
hardness control. Suitable polymeric dispersing agents include
polymeric polycarboxylates and polyethylene glycols, although others
known in the art can also be used. It is believed, though it is not
intended to be limited by theory, that polymeric dispersing agents
enhance overall detergent builder performance, when used in combination
with other builders (including lower molecular weight polycarboxylates)
by crystal growth inhibition, particulate soil release peptization, and
anti-redeposition.
Polycarboxylate materials which can be employed as the polymeric
dispersing agent herein are those polymers or copolymers which contain
at least about 60% by weight of segments with the general formula
,A~
- 41 -
- X Z
-- C - C
l l
Y COOM
n
wherei~n 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 substi-
tuted 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 polycar-
boxylates 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, contain-
ing 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 preferably ranges from about 2,000 to 10,000, more
preferably from about 4,000 to 7,000 and most preferably from
about 4,000 to 5,000. Water-soluble salts of such acrylic acid
polymers can include, for example, the alkali metal, ammonium and
substituted ammonium salts. Soluble polymers of this type are
known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example,~ in Diehl, U.S.
Patent 3,308,067, issued March 7, 1967.
-~A
,
- 42 -
Acrylic/maleic-based copolymers may also be used as a preferred
component of the dispersing/anti-redeposition agent. Such materials
include the water-soluble salts of copolymers of acrylic acid and
maleic acid. The average molecular weight of such copolymers in the
acid form preferably ranges from about 2,000 to 100,000, more
preferably from abut 5,000 to 75,000, most preferably from about 7,000
to 65,000. The ratio of acrylate to maleate segments in such
copolymers will generally range from about 30:1 to about 1:1, more
preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic
acid/maleic acid copolymers can include, for example, the alkali metal,
ammonium and substituted ammonium salts. Soluble acrylate/maleate
copolymers of this type are known materials which are described in
European Patent Application No. 66915, published December 15, 1982.
Another polymeric material which can be included is polyethylene
glycol (PEG). PEG can exhibit dispersing agent performance as well as
act as a clay soil removal/anti-redeposition agent. Typical molecular
weight ranges for these purposes range from about 500 to about 100,000,
preferably about 1,000 to about 50,000, more preferably from about
1,500 to about 10,000.
Bri~htener
Any optical brighteners or other brightening or whitening agents
known in the art can be incorporated into the detergent compositions
hereof.
The choice of brightener for use in detergent compositions will
depend upon a number of factors, such as the type of detergent, the
~ nature of other components present in the detergent composition, the
temperatures of wash water, the degree of agitation, the temperatures
of wash water, the degree of agitation, and the ratio of the material
washed to tub size.
The brightener selection is also dependent upon the type of
material to be cleaned, e.g., cottons, synthetics, etc. Since most
laundry detergent products are used to clean a variety of fabrics, the
detergent compositions should contain a mixture of brighteners which
will be effective for a variety of fabrics. It is of course necessary
that the individual components of such a brightener mixture be
compatible.
s
- ~ - 43 -
Commercial optical brighteners which may be useful in the
present invention can be classified into subgroups which include,
but are not necessarily limited to, derivatives of stilbene,
pyrazoline, coumarin, carboxylic acid, methinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in ~The Production and Application of
Fluorescent Brightening Agents~, M. Zahradnik, Published by John
~iley ~ Sons, Hew York (1982).
Stilbene derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
of bis(triazinyl)amino-stilbene; bisacylamino derivatives of
stilbene; triazole derivatives of stilbene; oxadiazole derivatives
of stilbene; oxazole derivatives of stilbene; and styryl deriva-
tives of stilbene.
Certain derivatives of bis(triazinyl)aminostilbene which may
be useful in the present invention may be prepared from 4,4'-
diamine-stilbene-2,2'-disulfonic acid.
Coumarin derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
substituted in the 3-position, in the 7-position, and in the 3-
and 7-positions.
Carboxylic acid derivatives which may be useful in the
present invention include, but are not necessarily limited to,
fumaric acid derivatives;- benzoic acid derivatives; p-phenylene-
bis-acrylic acid derivatives; naphthalenedicarboxylic acid deriva-
tives; heterocyclic acid derivatives; and cinnamic acid
derivatives.
Cinnamic acid derivatives which may be useful in the present
invention can be further subclassified into groups which include,
but are not necessarily limited to, cinnamic acid derivatives,
styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltria-
zoles, and styrylpolyphenyls, as disclosed on page 77 of the
Zahradnik reference.
The 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
~ ~
- 44 -
these three identified subclasses may not necessarily reflect an
exhaustive list of subgroups into which styrylazoles may be
subclassified.
Another class of optical brighteners which may be useful in the
present invention are the derivatives of dibenzothiophene-5,5-dioxide
disclosed at pages 741-749 of The Kirk-Othmer EncYclopedia of Chemical
TechnoloqY, Volume 3, pages 737-750 (John Wiley & Son, Inc., 1962), and
include 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.
Another class of optical brighteners which may be useful in the
present invention include azoles, which are derivatives of 5-membered
ring heterocycles. These can be further subcatergorized into
monoazoles and bisazoles. Examples of monoazoles and bisazoles are
disclosed in the Kirk-Othmer reference.
Another class of brighteners which may be useful in the present
invention are the derivatives of 6-membered-ring heterocycles disclosed
in the Kirk-Othmer reference. Examples of such compounds include
brighteners derived from pyrazine and brighteners derived from 4-
aminonaphthalamide.
In addition to the brighteners already described, miscellaneous
agents may also be useful as brighteners. Examples of such
miscellaneous agents are disclosed at pages 93-95 of the Zahradnik
reference, and include 1-hydroxy-3,6,8-pyrenetrisulphonic acid; 2,4-
dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-diphenylimidazolonedisulphonic
acid; and derivatives of pyrazoline-quinoline.
Other specific examples of optical brighteners which may be
useful in the present invention are those identified in U.S. Patent
4,790,856, issued to Wixon on December 13, 1988. These brighteners
include the PHORWHITE series of brighteners from Verona. Other
brighteners disclosed in this reference include: Tinopal UNPA, Tinopal
CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and
Arctic White CWD, available from Hilton-Davis, located in Italy; the
2-(4-styrul-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.
.,.~ i~
A
- - 45 -
Specif;c examples of these brighteners include 4-methyl-7-diethyl-
amino coumarin; 1,2-bis(-benzimidazol-2-Yl)ethylene; 1,3-diphenyl-
phrazolines; 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.
s 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.
Suds SuDDressors
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 of suds suppressors can also be of
particular importance under hot water washing conditions and under
high surfactant concentration conditions.
A wide variety of materials may be used as suds suppressors
in the- compositions hereof. Suds suppressors are well known to
those skilled in the art. They are generally described, for
example, in Kirk Othmer Encyclopedia of Chemical Technology, Third
Edition, Volume 7, pages 430-447 (John Wiley ~ Sons, Inc., 1979).
One category of suds suppressor of particular interest encompasses
monocarboxylic fatty acids and soluble salts thereof. These
materials are discussed in U.S. Patent 2,954,347, issued September
3s 27 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts
thereof for use as suds suppressor typically have hydrocarbyl chains
- 46 ~
of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
Suitable salts include the alkali metal salts such as sodium,
potassium, and lithium salts, and ammonium and alkanolammonium salts.
These materials are a preferred category of suds suppressor for
detergent compositions.
The detergent compositions may also contain non-surfactant suds
suppressors. These include, for example, list: high molecular weight
hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid
triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-
C40 ketones (e.g. stearone), etc. Other suds inhibitors include N-
alkylated amino triazines such as tri- to hexa-alkylmelamines or di-
to tetra-alkyldiamine chlortriazines formed as products of cyanuric
chloride with two or three moles of a primary or secondary amine
containing 1 to 24 carbon atoms, propylene oxide, and monostearyl
phosphates such as monostearyl alcohol phosphate ester and monostearyl
di-alkali metal (e.g. K, Na, and Li) phosphates and phosphate esters.
The hydrocarbons such as paraffin and haloparaffin can be utilized in
liquid form. The liquid hydrocarbons will be liquid at room
temperature and atmospheric pressure, and will have a pour point in the
range of about -40~C and about 5~C, and a minimum boiling point not
less than about 110~C (atmospheric pressure). It is also known to
utilize waxy hydrocarbons, preferably having a melting point below
about 100~C. The hydrocarbons constitute a preferred category of suds
suppressor for detergent compositions. Hydrocarbon suds suppressors
are described, for example, in U.S. Patent 4,265,779, issued May 5,
1981 to Gandolfo, et al. The hydrocarbons, thus, include aliphatic,
alicyclic, aromatic, and heterocyclic saturated or unsaturated
hydrocarbons having from about 12 to about 70 carbon atoms. The term
"paraffin," as used in this suds suppressor discussion, is intended to
include mixtures of true paraffins and cyclic hydrocarbons.
Another preferred category of non-surfactant suds comprises
silicone suds suppressors. This category includes the use of
polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or
emulsions of polyorganosiloxane oils or resins, and combinations of
polyorganosiloxane with silica particles wherein the
- _ - 47 -
polyorganosiloxane is chemisorbed of fused onto the silica.
Silicone suds suppressors are well known in the art and are, for
example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to
Gandolfo et al and European Patent Application No. 89307851.9,
published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent
3,45~,839 which relates to compositions and processes for
defoaming aqueous solutions by incorporating therein small amounts
of polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for
instance, in German Patent Application DOS 2,124,526. Silicone
defoamers and suds controlling agents in granular detergent
compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et
al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24,
1987.
An exemplary silicone based suds suppressor for use herein is
a suds suppressing amount of a suds controlling agent consisting
essentially of:
(i) polydimethylsiloxane fluid having a viscosity of from
about 20 cs. to about 1500 cs. at 25-C;
(ii) from about 5 to about 50 parts per 100 parts by weight
of (i) of siloxane resin composed of (CH3)3 Siol/2 units
of SiO2 units in a ratio of from (CH3)3 Siol/2 units and
to SiO2 units of from about 0.6:1 to about 1.2:1; and
(iii) from about 1 to about 20 parts per 100 parts by weight
of (i~ of a solid silica gel;
For any detergent compositions to be used in automatic
laundry washing machines, suds should not form to the extent that
they overflow the washing machine. Suds suppressors, when
utilized, are preferably present in a "suds suppressing amount."
By "suds suppressing amount" is meant that the formulator of the
composition can select an amount of this suds controlling agent
that will sufficiently control the suds to result in a low-sudsing
laundry detergent for use in automatic laundry washing machines.
. ,
A
--
W O 92/06154 P ~ /US91~07028 ~ 1 9 - 48 -
The amount of suds control will vary with the detergent surfact
ants selected. For example, with high sudsing surfactants,
relatively more of the suds controlling agent is used to achie~e
the desired suds control than with lesser foaming surfactants. In
general, a sufficient amount of suds suppressor should be
incorporated in low sudsing detergent compositions so that the
suds that form during the wash cycle of the automatic washing
machine (i.e., upon agitation of the detergent in aqueous solution
under the intended wash temperature and concentration conditions)
do not exceed about 75% of the Yoid volume of washing machine's
containment drum, preferably the suds do not exceed about 50~ of
said void volume, wherein the void volume is determined as the
difference between total volume of the containment drum and the
volume of the water plus the laundry.
-15 The co~positions hereof will generally comprise from C% to
about 57. 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
composttion. Preferably, from about 0.5Y. to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to about 2.0Y., by
weight, of the detergent composition, although higher amounts may
be used. This upper limit is practical in nature, due primarly to
concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from
about 0.01% to about 17~ of silicone suds suppressor is used, more
preferably from about 0.25Z 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 0.17, to about 270,
by weight, of the composition.
Hydrocarbon suds suppressors are typically utilized in
amounts ranging from about .017. to about 5.0%, although higher
leYels can be used.
W 0 92/06154 ~ 3 ~ ~ PCT/US91/07028
- 49 -
_ Other Inqredients
A wide variety of other ingredients useful in detergent
compositions can be inc~uded in the compositions hereof, including
other active ingredients, carriers, hydrotropes, processing aids,
dyes or pigmentst solYents for liquid formulations, etc.
Liquid detergent compositions can contain water and other
solvents as carriers. Low molecular weight primary or secondary
alcohols exemplified by methanol, ethanol, propanol, and
isopropanol are suitable. Monohydric alcohols are preferred for
solubilizing surfactant, but polyols such as those containing from
2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups
(e.g., propylene glycol, ethylene glycol, glycerine, and
1,2-propanediol) can also be used.
The detergent compositions hereof will preferably be
formulated such that during use in aqueous cleaning operations,
the wash water will have a pH of between about 6.5 and about 11,
preferably between about 7.5 and about 10.5. Liquid product
formulations preferably have a pH between about 7.5 and about 9.5,
more preferably between about 7.5 and about 9Ø Techniques for
controlling pH at recommended usage levels include the use of
buffers, alkalis, acids, etc., and are well known to those s~illed
in the art.
This invention- further provides a method for improving the
performance of detergents containing anionic, nonionic, and/or
cationic surfactant, and detersive enzyme, by utilizing therein an
enzyme performance-enhancing amount of the polyhydroxy fatty acid
amide surfactant described above, typically at least about 1% of
such surfactant.
This invention further provides a method for cleaning
~~ substrates, such as fibers, fabrics, hard surfaces, skin, etc., by
contacting said substrate, with a detergent composition comprising
detersive enzyme and one or more anionic, nonionic, or cationic
surfactants, wherein said detergent composition contains an enzyme
performance-enhancing amount of polyhydroxy fatty acid amide,
typically at least about lX, by weight, of the composition, in the
presence of a solvent such as water or water-misc,ole solvent
(e.g., primary and secondary alcohols). Agitation is preferably
provided for enhancing cleaning. Suitable means for providing
W o 92/06154 PCT/US91/07~28
21~3~ 50 -
agitation include rubbing by hand or preferably with use of a
brush, sponge, cloth, mop, or other cleaning device, automatic
laundry washing machines, automatic dishwashers, etc.
EXP~RIMENTAL
This exemplifies a process for making a N-methyl,
1-deoxyglucityl lauramide surfactant for use herein. Although a
skilled chemist can vary apparatus configuration, one suitable
apparatus for use herein comprises a three-liter four-nec~ed flask
fitted with a motor-driven paddle stirrer and a thermometer of
length sufficient to contact the reaction medium. The other two
necks of the flask are fitted with a nitrogen sweep and a
wide-bore side-arm (caution: a wide-bore side-arm is important in
case of very rapid methanol evolution) to which is connected an
efficient collecting condenser and vacuum outlet. The latter is
connected to a nitrogen bleed and vacuum gauge, then to an
aspirator and a trap. A 500 watt heating mantle with a variable
transformer temperature controller (nVariacn) 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 solid/liquid mixture is heated with
stirring under a nitrogen sweep to form a melt (approximately 2~
minutes). When the melt temperature reaches 145- C, catalyst
(anhydrous powdered sodium carbonate, 10.5 g., 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.) H~.
vacuum. From this point on, the reaction temperature is held at
1~5- C by adjusting the Variac and/or by raising or lowering the
mantle.
~ithin 7 minutes, first methanol bubbles are sighted at the
meniscus of the reaction mixture. A vigorous reaction soon
follows. Methanol is distilled over until its rate subsides. The
vacuum is adjusted to give about 10 inches Hg. (10/31 atm.)
3~ 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 evolui;ion, heating and stirring are
discontinued co-incident with some foaming. The product is cooled
and solidi~ies.
W O 92/06154 2 1 ~ 4 3 ~ 9 PCT/US91/07028
- 51 -
~~ The following examples are meant to exemplify compositions ofthe 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 I-III
These examples show heavy duty granular detergent
compositions containing polyhydroxy fatty acid amide and protease
enzymes.
Base Granule I II III
C~ l5 Alkyl Sulfate 16.9 16.g
Cl4 .S Alkyl Ethoxylate (2.25) Sulfate 16.9
N-Methyl N-1-Deoxyglucityl Cocoamide 5.6 5.6 5.6
Zeolite A - 30.1 1R.8 18.8
Sodium Citrate 11.3 11.3
Sodium Carbonate 16.9 16.9 16.9
Sodium Silicate 5.6 5.6 5.6
Sodium Sulfate 15.1 15.1 15.1
Sodium Polyacrylate (4500 MW) 1.1 1.1 1.1
Polyethyelene Glycol (8000 MW) 1.1 1.1 1.1
~allow Fatty Acid 1.1 1.1 1.1
Brightener 0.2 0.2 0.2
Admix and SDraY-on
Protease (1.4Y. active enzyme) 2.1 0.9 0.9
Perfume 0.3 0.3 0.3
C12_~3 Alkyl Ethoxylate (6.5 mole) 1.1 1.1 1.1
Water and Miscellaneous 3.8 3.8 3.8
100.0 100.0 100.0
Examples I-III are formulations for preferred use of about
1400 ppm, wash water weight basis, for temperatures below about
5C-C. The above examples are made by combining the base granule
ingredients as a slurry, and spray drying to about 4-8~ residual
moisture. The remaining dry ingredients are admixed in granular
or powder form with the spray dryed granule in a rotary mixing
drum, and the liquid ingredients (nonionic surfactant and perfume)
sprayed on.
EXA~PLES IV-IX
The following examples demonstrate heavy duty liquid
compositions containing polyhydroxy fatty acid amides and protease
and amylase enzymes.
WO 92/061~ PCr/US91/07~28
2la~l9 - 52 - ,
Inqredients IV V VI
H-Methyl N-1-Deoxyglucityl Cocoamide 10.0 5.5 5.5
C12 13 Alkyl Ethoxylate (6.5 mole) 15.0 2.5 2.5
Cl4 ls Alkyl Ethoxylate (2.25) Sulfate 17.0 17.0
Cl2 l~ Fatty Acid 3.0 3.0 3.0
Dodecyl Trimethyl Ammonium Chloride 0.2 0.2 0.2
Citric Acid 1.0 1.0 1.0
Monoethanolamine 2.5 2.5 2.5
Ethoxylated Tetraethylenepentamine 1.5 1.5 1.5
Protease (3.1% active) 0.4 0.5 0.4
Amylase (11.5% active) 0.2
Miscellaneous and solvents balance balance balance
100.0 100.0 100.0
Inqredients VII VIII IX
N-Methyl N-1-Deoxyglucityl Cocoamide 4.2 3.1 3.1
C1~ 15 Alkyl Ethoxylate (2.25) Sulfate 12.6 9.3
C12-18 Alkyl Ethoxylate (2.5) Sulfate 6.2
C 12 -1~ Alkyl Sulfate 3.1
C12-1~ Alkyl Ethoxylate 3.4
Dodecyl Trimethyl Ammonium Chloride0.5
Dodecenyl Succinate 5.0
Citrat~ 3.4 15.0
TMS/TDS (80/20) * 3.4
Cl2 1~ Fatty Acid 3.0
Oxydisuccinate 20.0
Ethoxylated Tetraethylene Pentamine1.5
Polyacrylate (4500 MW) 1.5 1.5
Protease (3.1X active) 0.5 0.2 0.2
Amylase (11.5% active) 0.2
~iscellaneous and solvents balancebalance balance
100.0100.0 100.0
TMS/TDS is tartrate monosuccinate/tartrate disuccinate
Examples IV-IX are preferably used about 2000 ppm, wash water
weight basis, for wash temperatures below about 50-C.
Examples IV-IX are prepared by combining non-aqueous
solvents, aqueous surfactant pastes or solutions, melted fatty
acids, aqueous solutions of polycarboxylate builders and other
salts, aqueous ethoxylated tetraethylenpentamine, buffering
W O 92/06154 2 ~ O ~ 53 PCT/US91/0702X
agents, caustic, and the remaining water. The pH is adjusted
_
using either an aqueous citric acid solution sodium hydroxide
solution to about pH 8.5. After pH adjustment, the final
ingredients, such as soil release agents, enzymes, colorants, and
perfume, are added and the mixture stirred until a single phase is
achieved.
EXAMPLE X
An alternate and highly preferred 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
68.51g. methyl alcohol is us2d. 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 reoovered crude product weighs 156.16
grams. After vacuum drying and purification, an overall yield of
106.92 ~rams purified product is recoYered. However, percentage
yields are not calculated on this basis, inasmuch as regular
sampling throughout the course of the reaction makes an overall
percentage yield value meaningless. The reaction can be carried
out at 80% and 90% reactant concentrations for periods up to 6
hours to yield products with extremely small by-product formation.
A modern, condensed laundry detergent granule is as follows.
EXAMPLE XI
Inqredient Wt.%
C1~ 1s alkyl alcohol sulfonic acid 13
C 1 1- 1 5 alkyl polyethoxy (2.25) sulfon-,c acid 5.60
C 1 2 - 1 3 alkyl polyethoxylate (6.5) 1.45
- 54 -
C12 ~ fatty acid N-methyl glucamide 2.50
Sodium aluminosilicate (as hydrated Zeolite A) 25.2
- Crystalline layered silicate builder1 23.3
Citric acid 10.0
Sodium carbonate To get wash pH = 9.90
Sodium polyacrylate (m.w. 2000-4500) 3.2
Diethylenetriamine pentaacetic acid 0.45
Savinase2 - 0.70
6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40
Sodium perborate monohydrate 2.10
Nonanoyloxybenzene sulfonic acid 5.oo
Brightener ~ 0.10
1Layered silicate builders are known in the art. Preferred
are the layered sodium silicates. See, for example, the layered
sodium silicate builders of U.S. Patent 4,664,859, issued May 12,
1987 to H.P. Rieck. A suitable layered silicate builder is available
as SKS-6 from Hoechst.
2Available from Novo Nordisk A/S, Copenhagen.
Highly preferred granules of the foregoing types are those
which comprise from about 0.0001~/. to about 2% by weight of active
enzyme and at least about 1% by weight of said polyhydroxy fatty
acid amide, and, most preferably, wherein the anionic surfactant
is not an alkylbenzene sulfonate surfactant.
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
(~LAS~) 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
~,.
W ~ 92/06154 21~ 4 3 ~ 9 55 PCT/~S91/07028
~ lipase, protease and cellulase enzymes, together. It is particu-
larly challenging to provide such tertiary enzyme systems in
stable li~uid 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
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 disc1Osed herein. ~hile 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 107., preferably less than about 5Z, more preferably less
than about 1%, most preferably OZJ of LAS.
The present invention proYides a liquid detergent composition
comprising:
(a) from about lX to about 507O~ preferably from about 4% to
about 40X, of anionic surfactant;
(b) from about 0.00017. to about 2X of active detersive
enzyme;
(c) an enzyme performance-enhancing amount (preferably from
about 0.5% to about 12X) of a polyhydroxy fatty acid
amide material of the formula
0 R~
R2 C - N - Z
wherein R1 is H1, Cl-C~ hydrocarbyl, 2-hydroxy ethyl,
2-hydroxy propyl, or a mixture thereof, R2 is C5-C3l
W O 92/061~4 P ~ /US91/07~28
2i O~349 56 -
hydrocarbyl, and Z is a polyhydroxylhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls
directly connected to said chain, or an alkoxylated
derivative thereof;
and wherein the composition is substantially free of alkylbenzene
sulfonate.
The water-soluble anionic surfactant herein preferably
comprises (~AES~):
RO(A)m S03 M
wherein R is an unsubstituted C10-C2~ alkyl or hydroxyalkyl
(C10-C2~J group, A is an ethoxy or propoxy unit, m is an integer
greater than 0 and M is hydrogen or a cation. Preferably, R is an
unsubstituted C~2-C~8 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, etc.) or an ammonium or substituted ammonium
cation.
It is preferred that the ratio of the above surfactant
("AES~) 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 0.5Y. to about 5%
of the condensation product of C8-C22 (preferably C~o-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 fro~
about 0.1% to about 50% of detergency builder. These compositions
preferably comprise from about O.lX to about 20X of citric acid,
or water-soluble salt thereof, and from about O.lX to about 20% of
a water-soluble succinate tartrate, especially the sodium salt
thereof, and mixtures thereof, or from about 0.1% to about 20% by
weight of oxydisuccinate or mixtures thereof with the aforesaid
builders. 0~1%-50% alkenyl succinate can also be used.
- 57 -
-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~/O~ on an active basis, of
detersive enzyme. These enzymes are preferably selected from the
5group 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,
10cellulases, 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., Solvay enzymes). Also, see the lipases described in
EP A 0 399 681, published November 28, 1990, EP A 0 218 272,
15published April 15, 1987 and PCT/DK 88/00177, published May 18,
1989.
Suitable fungal lipases include those producible by Humico?a
1anug7nosa and Thermomyces 1anuginosus. Most preferred is the
lipase obtained by cloning the gene from Hvmico1a 1anuginosa and
20expressing 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 10 to about
6,000, lipase units of lipase per gram (LU/g) of product can be
25used in these compositions. A lipase unit is that amount of
lipase which produces 1 ~mol of titratable butyric acid per minute
in a p~ stat, where pH is 7.0, temperature is 30-C, and substrate
is an emulsion tributyrin and gum arabic, in the presence of Ca++
and NaCl in phosphate buffer.
30The following Example illustrates a preferred heavy duty
liquid detergent composition comprising:
(a) an enzyme selected from proteases, cellulases and
lipases, or, preferably, a mixture thereof, typically
comprising from about 0.01% to about 2~o-by weight of the
35total composition, although the amounts used can be
adjusted according to the desires of the formulator to
provide an "effective" amount (i.e., soil-removing
amount) of said enzyme or enzyme mixture;
W o 92/06154 PCT/US91/07Q28
2 i ~ ~ 3 l ~, - 58 -
(b) a polyhydroxy fatty acid amine surfactant of the type
disclosed herein, typically comprising at least about 2%
by weight of the composition, more typically from about
3% to about 15X, preferably from about 7~h to about 14%;
(c) a surfactant of the RO(A)mSO3M type, as disclosed
herein, preferably RO(CH2CH20)mSO3M, wherein R is
C~4-Cls (avg.) and m is 2-3 (avg.), wherein M is H or a
water-solu~le salt-forming cation, e.g., Na+, said
surfactant typically comprising from about 5X to about
25% by weight of the composition;
(d) optionally, a surfactant of the ROSO3M type, as dis-
closed herein, preferably wherein R is Cl2-Cl~ (avg.),
said surfactant preferably comprising from about 1% to
about 10% by weight of the compositions;
(e) a liquid carrier, especially water or water-alcohol
mixtures;
(f) optionally, but most preferably, effective amounts of
enzyme stabilizers, typically about 1% to about 10%, by
weight of the composition;
(g) optionally, but preferably, water-soluble builders,
especially polycarboxylate builders, typically at about
4X to a~out 25% by weight of the composition;
(h) optionally, the various detersive adjuncts, brighteners,
etc., noted hereinabove, typically (if used) at about 1%
to about 10% by weight of the composition; and
(i) the composition is substantially free from LAS.
EXAMPLE XII
Inaredients Wt.%
C14-15 alkyl polyethoxylate (2.25) sulfonic acid 21.0
C12-14 fatty acid N-methyl glucamide1 7.0
Sodium tartrate mono- and di-succinate (80:20 mi%) 4.00
Citric acid 3.80
ClZ-14 fatty acid 3.00
Tetraethylene pentaamine ethoxylate(15-18) 1.50
Ethoxylated copolymer of polyethylene 0.20
- polypropylene terephthalate polysulfonic acid
Protease B (84g/l) 2 0.68
Lipase (100KLU/gJ 3 0.47
~ ~ ~ 4 3 4 5~ ''
59
Cellulase (5000 cevu/g) 4 0.14
Brightener 365 0.15
Ethanol 5.20
Monoethanolamine 2.00
Sodium formate 0.32
1,2 propane diol 8.00
Sodium hydroxide 3.10
Silicone suds suppressor 0.0375
Boric acid 2.00
Water/misc. Balance to 100
Prepared as disclosed above.
2Protease B is a modified bacterial serine protease described in
U.S. Patent 4.810,414.
3Lipase used herein is the lipase obtained by cloning the~
gene from Humico1a 1anug7nosa and expressing the gene in
Aspergi11us oryzae, as described in European Patent Application
0 258 068, commercially available under the trade name LIPOLASE
(ex Novo Nordisk A/S, Copenhagen ~enmark).
~Cellulase used herein is sold under the trademark CAREZYME
(Novo Nordisk, A/S, Copenhagen Denmark).
sBrightener 36 is commercially available as TINOPAL TAS 36.
The brightener is added to the composition as a separately
prepared pre-mix of brightener (4.5%), monoethanolamine (60%) and
water (35.5%).
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
A '
W O 92/06154PCT/US91/07~28
2 1 0 ~ 60 -
_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. ~hile any acid can
be used for this purpose, the detergent formulator will recognize
5that it is a simple and convenient matter to use an acid which
provides an anion that is otherwise useful and desirable in the
finished detergent composition. For example, citric acid can be
used for purposes of neutralization and the resulting citrate ion
(ca. 1%) be allowed to remain with a ca. 40% polyhydroxy fatty
10acid 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.
15The polyhydroxy fatty acid amides derived from coconut alkyl
fatty acids (predominantly C12-C1~) are more soluble than their
tallow alkyl (predominantly C 16 -C ~ ~ ) counterparts. Accordin~ly,
the C12-C14 materials are somewhat easier to formulate in liquid
compositions, and are more soluble in cool-water laundering baths.
20However, the C16-C~8 materials are also quite useful, especially
under circumstances where warm-to-hot wash water is used. Indeed,
the C16-C18 materials may be better detersive surfactants than
their C12-C14 counterparts. Accordingly, the formulator may wish
to balance ease-of-manufacture vs. performance when selecting a
25particular polyhydroxy fatty acid amide for use in a given
formulation.
It will also be appreciated that the solubility of the
polyhydroxy fatty acid amides can be increased by having points of
unsaturation and/or chain branching in the fatty acid moiety.
30Thus, 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
35be greater than the solubility of their monosaccharide-derived
counterpart materials. This higher solubility can be of particu-
lar assistance when formulating liquid compositions. Moreover,
the polyhydroxy fatty acid amides wherein the polyhydroxy group is
'.W ~ 92/061~4 PC~r/US91/07028
~2 i ~ f~ - 61 -
.
derived from maltose appear to function especially well as deter-
gents when used in combination with conventional alkylbenzene
sulfonate (nLASn) surfactants. While not intending to be limited
by theory, it appears that the combination of LAS with the polyhy-
droxy fatty acid amides derived from the higher saccharides such
as maltose causes a substantial and unexpected lowering of inter-
facial tension in aqueous media, thereby enhancing net detergency
performance. (The manufacture of a polyhydroxy fatty acid amide
derived from maltose is described hereinafter.)
The polyhydroxy fatty acid amides can be manufactured not
only from the purified sugars, but also from hydrolyzed starches,
e.g., corn starch, potato starch, or any other convenient plant-
derived starch which contains the mono-, di-, etc. saccharide
desired by the formulator. This is of particular importance from
the economic standpoint. Thus, "high glucose" corn syrup, "high
maltose" corn syrup, etc. can conveniently and economically be
used. De-lignified, hydrolyzed cellulose pulp can also provide-a
raw material source for the polyhydroxy fatty acid amides.
As noted above, polyhydroxy fatty acid amides derived from
the higher saccharides, such as maltose, lactose, etc., are more
soluble than their glucose counterparts. Moreover, it appears
that the more soluble polyhydroxy fatty acid amides can help
solubilize their less soluble counterparts, to varying degrees.
Accordingly, the formulator may elect to use a raw material
comprising a high glucose corn syrup, for example, but to select a
syrup which contains a modicum of maltose (e.g., 1% or more). The
resulting mixture of polyhydroxy fatty acids will, in general,
exhibit more preferred solubility properties over a broader range
of temperatures and concentrations than would a "pure" glucose-
derived polyhydroxy fatty acid amide. Thus, in addition to any
economic advantages for using sugar mixtures rather than pure
sugar reactants, the polyhydroxy fatty acid amides prepared from
mixed sugars can offer very substantial advantages with respect to
performance and~or ease-of-formulation. In some instances,
however, some loss of grease removal performance (dishwashing) may
be noted at fatty acid maltamide levels above about ~5~,' and some
loss in sudsing above about 33% (said percentages being the
percentage of maltamide-derived polyhydroxy fatty acid amide vs.
W O 92/06154 PCT/US91/07Q28
~ 3-19 - 62 -
glucose-derived polyhydroxy fatty acid amide in the mixture).
This can vary somewhat, depending on the chain length of the fatty
acid moiety. Typically, then, the formulator electing to use such
mixtures may find it advantageous to select polyhydroxy fatty acid
amide mixtures which contain ratios of monosaccharides (e.g.,
glucose) to di- and higher saccharides (e.g., maltose) from about
4:1 to about 99:1.
The manufacture of preferred, uncyclized polyhydroxy fatty
acid amides from fatty esters and N-alkyl polyols can be carried
out in alcohol solvents at temperatures from about 30-C-90-C,
preferably about 50-C-80-C. It has now been determined that it
may be convenient for the formulator of, for example, liquid
detergents to conduct such processes in 1,2-propylene glycol
solvent, since the glycol solvent need not be completely removed
from the reaction product prior to use in the finished detergent
formulation. Likewise, the formulator of, for example, solid,
typically granular, detergent compositions may find it convenient
to run the process at 30-C-90-C in solvents which comprise
ethoxylated alcohols, such as the ethoxylated (EO 3-8) Cl2-C,~
alcohols, such as those available as NEODOL 23 EO6.5 (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.)
While methods for making polyhydroxy fatty acid amides per se
form no part of the invention herein, the formulator can also note
other syntheses of polyhydroxy fatty acid amides as described
hereinafter.
Typically, the industrial scale reaction sequence for prepar-
ing the preferred acyclic polyhydroxy fatty acid amides will
comprise: SteD 1 - preparing the N-alkyl polyhydroxy amine
derivative from the desired sugar or sugar mixture by formation of
an adduct of the N-alkyl amine and the sugar, followed by reaction
with hydrogen in the presence of a catalyst; followed by SteP 2 -
reacting the aforesaid polyhydroxy amine with, preferably, a fatty
ester to form an amide bond. While a variety of N-alkyl polyhy-
droxy amines useful in Step 2 of the reaction sequ2nce can be
prepared by various art-disclosed processes, the following process
W O 92/061~4 ~ 1 D 4 3 l~ ~ P ~ /ussl/o7o28
- 63 -
is convenient and makes use of economical sugar syrup as the raw
material. It is to be understood that, for best results when
using such syrup raw materials, the manufacturer should select
syrups that are quite light in color or, preferably, nearly
colorless ("water-white").
Preparation of N-Alkyl Polyhydroxy Amine
From Plant-Derived Sugar Syrup
I. Adduct Formation - The following is a standard process in
which about 420 9 of about 55% glucose solution (corn syrup -
about 231 g glucose - about 1.28 moles) having a Gardner Color of
less than 1 is reacted with about 119 g 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.
TABLE 1
20Time in Minutes: 10 30 60 120 180 240
Reaction TemP. ~C Gardner Color (ADproximate)
0
1 1 2 2 4 5
4 6 10 - - -
As can be seen from the above data, the Gardner Color for the
adduct is much worse as the temperature is raised above about 30 C
and at about 50-C, the time that the adduct has a Gardner Color
below 7 is only about 30 minutes. For longer reaction, and/or
holding tlmes, 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
~5 is shortened by the use of higher ratios of amine to sugar. With
the 1.~: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
W O 92J06154 P ~ /US91/07928
21~-~13 f1 ~ 64 -
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 95X, even more
preferably more than about g9%, based upon the sugar, and a color
5that 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
10reached in at least about two hours) is as indicated.
TABLE 2
Gardner Color (ADDroximate)
Corn syrup 1 l 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2
15As can be seen from the above, the starting sugar material
must be very near colorless in order to consistently have adduct
that is acceptable. When the sugar has a Gardner Color of about
1, the adduct is sometimes acceptable and sometimes not accept-
able. When the Gardner Color is above l the resulting adduct is
20unacceptable. 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.
25About 539 9 of adduct in water and about 23.1 g of United
Catalyst G498 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
SO-C. The pressure is then raised to about 1600 psig and the
30temperature 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
3595% N-methyl glucamine, a white powder.
The above procedure is repeated with about 23.1 g of ~aney Ni
catalyst with the following changes. The catalyst is washed three
times and the reactor, with the catalyst in the reactor, is purged
W ~ 92/06154 PCT/US91/07028
2 1 0 ~ g- 65
- twice with 200 psig H2 and the reactor is pressurized with H2 at
1600 psig for two hours, the pressure is released at one hour and
the reactor is repressurized to 1600 psig. The adduct is then
pumped into the reactor which is at 200 psig and 20-C, and the
reactor is puryed with 200 psig H2, etc., as above.
The resulting product in each case is greater than about 95%
N-methyl glucamine; has less than about 10 ppm Ni based upon the
glucamine; and has a solution color of less than about Gardner 2.
The crude N-methyl glucamine is color stable to about 140-C
for a short exposure time.
It is important to have good adduct that has low sugar
content (less than about 5%, preferably less than about 1%) and a
good color (less than about 7, preferably less than about 4
Gardner, more preferably less than about 1).
In another reaction, adduct is prepared starting with about
159 g of about 50Z methylamine in water, which is purged and
shielded with N2 at about 10-20-C. About 330 g of about 70% corn
syrup (near water-white) is degassed with N2 at about 50-C and is
added slowly to the methylamine solution at a temperature of less
than about 20-C. The solution is mixed for about 30 minutes to
give about 95~/O adduct that is a very light yellow solution.
About 190 g of adduct in water and about 9 g 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 ;s 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 I00 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.
~ W o 92/06154 2 ~ 0~13~ PCT/US91/07~28
- 66 -
~~ A 200 ml autoclave reactor is used followinq typical proce-
dures 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 syrupJ 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 g MMA; 1.92 moles) (from Air
Products).
The reaction procedure is as follows:
1. Add about 119 g of the 50% methylamine solution to a N2
purged reactor, shield with N2 and cool down to less than
about 10-C.
2. Degas and/or purge the 55% corn syrup solution at 10-20-C
with N2 to remove oxygen in the solution.
3. Slowly add the corn syrup solution to the methylamine
solution and keep the temperature less than about 20-C.
4. Once all corn syrup solution is added in, agitate for about
1-2 hours.
The adduct is used for the hydrogen reaction right after
making, or is stored at low temperature to prevent further
degradation.
The glucamine adduct hydrogen reactions are as follows:
1. Add about 134 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 g adduct and about 5.8 9 G498 Ni to a 200 ml
autoclave.
2. Purge with about 200 psi H2 twice at low temperature.
Wl~92/06154 2 ~ O ~ 67 - pcr/us91/o7o2~
3. Pressure with H2 to about 400 psi and raise temperature to
about 50-C.
4. Raise pressure to about 500 psi, react for about 3.5 hours.
Keep temperature at indicated temperature.
S. Decant and filter out the Ni catalyst. Sample 3 is for about
50-55-C; Sample 4 is for about 75-C; and Sample 5 is for
about 8S-C. (The reaction time for about 85-C is about 45
minutes.)
All runs give similar purity of N-methyl glucamine (about
94%); the Gardner Colors of the runs are similar right after
reaction, but only the two-stage heat treatment gives good color
stability; and the 85-C run gives marginal color immediately after
reaction.
EXAMPLE XIII
The preparation of the tallow (hardened) fatty acid amide of
N-methyl maltamine for use in detergent compositions according to
this invention is as follows.
SteD 1 - Reactants: Maltose monohydrate (Aldrich, lot
01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
The reactants are added to glass liner (250 g maltose, 428 9
methylamine solution, 100 g catalyst slurry - 50 g Raney Ni) and
placed in 3 L rocking autoclave, which is purged with nitrogen
(3X500 psig3 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 YiSCous material. The final traces of water are
azetroped off by dissolving the ~aterial 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
W O 92/061~4 PCT/USgl/07~28
2 ~ ~ ~ 3 ~ ~ 68
ethanol is added and the solution is left in the freezer over a
weekend. The solid material is filtered and dried under vacuum.
The comoined 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 g of the tallow methyl ester is
heated to its melting point (water bath) and loaded into a 250 ml
3-nec~ round-bottom flask with mechanical stirring. The flask is
heated to ca. 70-C to prevent the ester from solidifying.
Separately, 25.0 g 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 g 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 ~/O)
is added and the reaction is allowed to continue overnight (ca.
68-C) after which time the mixture is clear. The reaction flask
is then modified for distillation. The temperature is increased
to 110-C. Distillation at atmospheric pressure is continued for
60 minutes. High vacuum distillation is then begun and continued
for 14 minutes, at which time the product is very thick. The
product is allowed to remain in the reaction flask at 110-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 g 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.
W 0 92/06154 2 1 0 ~ 3 1 ~9 PCT/US91/07028
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~/0, 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 s~ds
control agent will be used. For fabric laundering in top-loading
washing machines some control of suds may be desirable, and for
front-loaders some considerable degree of suds control may be
preferred. A wide variety of suds control agents are known in the
art and can be routinely selected for use herein. Indeed, the
selection of suds control agent, or mixtures of suds control
agents, for any specific detergent composition will depend not
only on the presence and amount of polyhydroxy fatty acid amide
used therein, but also on the other surfactants present in the
formulation. However, it appears that, for use with polyhydroxy
fatty acid amides, silicone-based suds control agents of various
types are more efficient (i.e., lower levels can be used) than
various other types of suds control agents. The silicone suds
control agents available as X2-3419 and Q2-3302 (Dow Corning) are
particularly useful herein.
The formulator of fabric laundering compositions which can
advantageously contain soil release agent has a wide variety
of known materials to choose from (see, for example, U.S. Patents
3,962,152; 4,116,885; 4,23~,531; 4,702,8r7; 4,721,580 and
4,877,896). Additional soil release materials useful herein
' WO 92/06154 PCr/US91/07Q'28
2i~ 13 1~ 70
include the nonionic oligomeric esterification product of a
reaction mixture comprising a source of Cl-C, alkoxy-terminated
po1yethoxy units (e.g., CH3[OCH2CH2]~6OH), 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_ _
O O O O
Il ~=~ 1l 1~ /~\ n
R10- (CH2CH20)x C~CO-CH-CH20 - C~CO(CH2CH20)y
_ R2 _ m _ _ n
O ~ O
C~C - O (CH2CH20)x-Rl
wherein Rl is lower (e.g., Cl-C~) alkyl, especially methyl; x and
y are each integers from about 6 to about 100; m is an integer of
from about 0.7S to about 30; n is an integer from about 0.25 to
about 20; and R2 is a mixture of both H and CH3 to provide a mole
ratio of oxyethyleneoxy:oxyisopropyleneoxy of at least about
0.5:1.
Another preferred type of soil release agent useful herein
is of the general anionic type described in U.S. Patent 4,877,896,
but with the condition that such agents be substantially free of
monomers of the HOROH type wherein R is propylene or higher alkyl.
Thust 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 add;tional soil release
agents can comprise, for example, the reaction product of dimethyl
terephthalate, ethylene glycol, 5-sodiosulfoisophthalate and
3-sodiosulfobenzoic acid. Such agents are preferred for use in
granular laundry detergents.
The formulator may also determine that it is advantageous to
include a non-perborate bleach, especially in heavy-duty granular
laundry detergents. A variety of peroxygen bleaches are a~ail-
able, commercially, and can be used herein, but, of these, percar-
bonate is convenient and economical. Thus, the compositions
W O 92/061~4 - PCT/US91/07028
? ~ Q - 71 -
- herein can contain a solid percarbonate bleach, normally in the
form of the sodium salt, incorporated at a level of from 3% to 20
by weight, more preferably from 5% to 18% by weight and most
preferably from 8% to 15% by weight of the composition.
Sodium percarbonate is an addition compound having a formula
corresponding to 2Na2C03. 3H202, and is available commercially as
a crystalline solid. Most commercially available material
includes a low leYel of a heavy metal sequestrant such as EDTA,
l-hydroxyethylidene l,1-diphosphonic acid (HEDP) or an amino-
phosphonate, that is incorporated during the manufacturing
process. For use herein, the percarbonate can be incorporated
into detergent compositions without additional protection, but
preferred embodiments of the invention utilize a stable form of
the material (FMC). Although a variety of coatings can be used,
the most economical is sodium silicate of SiO2:Na20 ratio from
1.6:1 to 2.8:1, preferably 2.0:1, applied as an aqueous solution
and dried to give a level of from 2% to 10% (normally from 3~~O to
5%), of silicate solids by weight of the percarbonate. Magnesium
silicate can also be used and a chelant such as one of those
mentioned above can also be included in the coating.
The particle size range of the crystalline percarbonate is
from ~50 micrometers to 450 micrometers with a mean of approxi-
mately 400 micrometers. When coated, the crystals have a size in
the range from 400 to 600 micrometers.
While heavy metals present in the sodium carbonate used to
manufacture the percarbonate can be controlled by the inclusion of
sequestrants in the reaction mixture, the percarbonate still
requires protection from heavy metals present as impurities in
other ingredients of the product. It has been found that the
total level of iron, copper and manganese ions in the product
should not exceed 25 ppm and preferably should be less than 20 ppm
in order to avoid an unacceptably adverse effect on percarbonate
stability.
EXAMPLE XIV
The following illustrates a perborate bleach-plus-bleach
activator detergent composition of the present invention which is
prepared by admixing the listed ingredients in a mixing drum.
W O 92/06154 2.~ J 1~ 72 - PC~tUS91/07Q28
In the example, Zeolite A refers to hydrated crystalline
Zeolite A containing about 20% water and having an average
particle size of 1 to 10, preferably 2 to S, microns; LAS refers
to sodium C~2.3 linear alkylbenzene sulfonate; AS refers to sodiu~
Cl~-C1s alkyl sulfate; nonionic refers to coconut alcohol con-
densed with about 6.5 moles of ethylene oxide per mole of alcohol
and stripped of unethoxylated and monoethoxylated alcohol, also
abbreviated as CnAE6.5T.; and DTPA refers to sodium diethylenetri-
amine pentaacetate.
Parts by Weight of
Final ComDosition % of Granules
Base Granules1 51.97 100.00
AS 9.44 18.16
LAS 2.92 5.62
Moisture 4.47 8.60
Sodium silicate (1.6 ratio) 1.35 2.60
Sodium sulfate 6.47 12.45
Sodium polyacrylate (4500 MW) 2.61 5.02
PEG 8000 1.18 2.27
Nonionic 0.46 0.89
Sodium carbonate 13.29 25.57
Brightener 0.20 0.38
Sodium aluminosilicate 9.11 17.53
DTPA 0.27 0.52
Perfume 0.20 0.38
NAPAA Granules2 6.09 100.00
NAP M 2.86 46.96
LAS 0.30 4-93
Sulfate and Misc. 2.93 48.11
NOBS Granules 3 3.88 100.00
NOBS 3.15 81.19
LAS 0.12 3.09
PEG 8000 0.19 4.90
Misc. 0.42 10.82
Zeolite Granules~ 12.00 100.00
Sodium aluminosilicate 7.39 61.i8
PEG 8000 1.50 12.47
Nonionic 1.16 9.70
W 9 92/061~4 PCT/US91/07028
2 i a ~ 3 a ~~ 73 -
- Moisture 1.66 13.83
Misc. 0.29 2.42
Admix
Sodium SKS-6
layered silicate 15.84
Protease (0.78 mg/g activity) 0.52
Sodium perborate
monohydrate 1.33
Citric acid 6.79
0 C12 -C 11 N-methyl glucamide 1.58
Total of final composition 100.00
1The base granules are produced by spray drying an aqueous
crutcher mix of the listed ingredients.
2A freshly-prepared sample of NAPM wet cake, which typically
consists of about 60% water, about 2% peroxyacid available oxygen
(AvO) (corresponding to about 36% NAP M), and the rest (about 4%)
unreacted starting material, is obtained. This wet cake is the
crude reaction product of NAAA (monononyl amide of adipic acid),
sulfurie acid, and hydrogen peroxide which is subsequently
quenched by addition to water followed by filtration, washing with
distilled water, phosphate buffer washing and final suction
filtration to recover the wet cake. A portion of the wet cake is
air-dried at room temperature to obtain a dry sample which
typically consists of about 5% AvO (corresponding to about 90%
NAPAA) and about 10% unreacted starting material. When dry, the
sample pH is about 4.5.
NAP M granules are prepared by mixing about 51.7 parts of the
dried NAP M wet cake (containing about 10% unreacted), about 11.1
parts of sodium C12.~ linear alkyl benzene sulfonate (LAS) paste
(45X active), about 43.3 parts of sodium sulfate, and about 30
parts of water in a CUISINART mixer. After drying, the granules
(which contain about 47Z NAPAA) are sized by passing through a No.
14 Tyler mesh sieve and retaining all particles not passing
through a No. 65 Tyler mesh. The average amide peroxyacid particle
(agglomerate) size is about 5-40 microns and the median particle
size is about 10-20 microns, as determined by Malvern particl2
size analysis.
- 74 -
- 3The NOBS (nonanoyloxybenzene sulfonate) granules are
prepared according to U.S. Patent 4,997,596, Bowling et al, issued
~ March 5, 1991.
'Zeolite granules having the following composition are made
by mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich R08
energy intensive mixer.
- Parts b~ Weiqht
Before Drvinq After DrYinq
Zeolite A (includes bound water) 70.00 76.99
PEG 8000 10.80 12.49
CnAE6.5T 8.40 9.72
Free water 10.80 0.80
The PEG 8000 ;s in an aqueous form containing 50% water and
is at a temperature of approximately 55'F (12.8-C). The CnAE6.5T
is in a liquid state and is held at approximately 90 F (32.2-C).
The two liquids are combined by pumping through a 12 element
static mixer. The resulting binder material has an outlet
temperature of approximately 75-F (23.9 C) and a viscosity of
approximately 5000 cps. The ratio of PEG 8000 and CnAE6.5T
through the static mixer is 72:28 respectively.
The Eirich R08 energy intensive mixer is operated in a batch
type mode. First, 34.1 kg of powdered Zeolite A is weighed into
the pan of the mixer. The mixer is started by first rotating the
pan in a counterclockwise direction at approximately 75 rotations
per minute (rpm), and then rotating the rotor blade in a clockwise
direction at 1800 rpm. The binder material is then pumped from
the static mixer directly into the Eirich R08 energy intensive
mixer which contains Zeolite A. The feed rate of the binder
material is about 2 minutes. The mixer continues to mix for an
additional 1 minute for a total batch time of approximately 3
minutes. The batch is then discharged and collected in a fiber
drum.
The batch step is repeated until approximately 225 kg of wet
product has been collected. This discharged product is then dried
in a fluid bed at 240-270-F (116-132-C). The drying step removes
most of the free water and changes the composition as described
above. The tctal energy input by the mixer to the product in a
A
W D 92/06154 PCT/US9l/07028 ~ 3 ~ 9 - 75 -
_ batch mode is approximately 1.31X1012 erg/kg. at a rate of
approximately 2.18X109 erg/kg-s.
The re~ulting free flowing agglomerates have a mean particle
size of about 450-SOO microns.
S EXAMPLE XV
A liquid laundry detergent composition suitable for use at
the relatively high concentrations common to front-loading
automatic washing machines, especially in Europe, and over a wide
range of temperatures is as follows.
Inqredient Wt. %
Coconutalkyl (Cl2) N methyl glucamide 14
C1~ l5EO(2.25) sulfate, Na salt - 10.0
C~ 15EO(7) 4.0
C12 1~ alkenylsuccinic anhydride1 4.0
C12 ~ fatty acid* 3.0
Citric acid (anhydrous) 4.6
Protease (enzyme)2 0.37
Termamyl (enzyme) 3 0.12
Lipolase (enzyme)~ 0.36
Carezyme (enzyme)5 0.12
Dequest 2060S6 1.0
NaOH (pH to 7.6) 5.5
1,2 propanediol 4.7
Ethanol 4.0
Sodium metaborate 4.0
CaCl 2 0.014
Ethoxylated tetraethylene pentamine' 0.4
Brightener8 0.13
Silane9 0-04
Soil release polymerl~ 0.2
Silicone (suds control)11 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 NGVO; percentage at 300 ~NU/g.
~Lipase, from NOVO; percentage at 100 KLU/g.
WO 92/06154 PCl/US91/07~28
21 0~ 3~6 -
- 5Cellulase from NOVO; percentage at SOOO CEYU/l.
6Available from Monsanto.
'From BASF as LUTENSOL P6105.
8 BLANKOPHOR CPG766, Bayer.
9Silane corrosion tnhibitor, 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
Corning.
12Dispersant for silicone suds control agent available as
DC-3225C from Dow Corning.
~ ?referred fatty acid is topped palm kernel, comprising 12%
oleic and 2X each of stearic and linoleic.
EXAMPLE XVI
A granular laundry detergent composition suitable for use at
the relatively hiSh concentrations common to front-loading
automatic washing machines, especially in Europe, and over a wide
range of temperatures is as follows. -
Inqredient Wt. %
SOKALAN CPS (100% active as Na salt)1 3.52
DEQUEST 2066 (100% as acid)2 0.45
TINOPAL DMS3 0.28
MgSO~ O 49
Zeolite A (anhydrous) 17.92
C~C (100% active)l 0.47
Na2CO3 9.44
Citric acid 3.5
Layered Silicate SKS-6 12.9
Tallow a1kyl sulfate (100% active; Na salt) 2.82
C~l-CI5 alkyl sulfate (100% active; Na salt) 3.5
C12-C15 alkyl EO(3) sulfate 1.76
C16-C1~ N-methyl glucamide 4.1
DOBANOL C12-C15 EO(3) 3.54
LIPOLASE (100,000 LU/g) 5 0.42
SAYINASE (4.0 KNPU)5 1.65
Perfume 0-53
X2-3419~ 0.22
Starch 1.08
92/061~4 ~ 1 Q '~ 3 1 ~ - 77 - PC~/US91/07028
Stearyl alcohol o 35
Sodium percarbonate (coated) 22.3
Tetraacetylethylenedicmine (TAED) 5.9
Zinc phthalocyanin 0.02
Water (ex zeolite) Balance
lSOKALAN is sodium poly-acrylate/maleate available from
Hoechst.
2Monsanto brand of pentaphosphonomethyl diethylenetriamine.
30ptical brightener available from Ciba Geigy.
4Trade name FINNFIX available from Metasaliton.
sLIPOLASE lipolytic enzyme from NOVO.
sSAVINASE protease enzyme from NOYO.
'X2-3419 is a silicone suds suppressor available from Dow
Corning.
The procedure for preparing the granules comprises various
tower-drying, agglomerating, dry-additions, etc., as follows. The
percentages are based on the finished composition.
A. Crutched and Blown Throuqh the Tower
Using standard techniques the following components are
crutched and tower-dried.
SOKALAN CPS 3.52%
~EQUEST 2066 0 45~/o
TINOPAL DMS 0.28%
Magnesium sulfate 0.49%
ZEOLITE A as anhydrous 7.1%
CMC 0.47%
B. Surfactant Aqglomerates
B1. Aaqlomeration of Sodium Salt of Tallow Alkyl Sulfate and
Sodium Salt of C~ le EO(3~ Sulfate Pastes - A 50% active paste of
tallow alkyl sulfate and a 70% paste of C12-C1s EO(3) sulfate are
agglomerated with Zeolite A and sodium carbonate according to the
following formula (contribution to the detergent formulation after
the drying of the agglomerate).
Tallow alkyl sulfate 2.82%
C12 1s EO(3) sulfate 1.18%
Zeolite A 5.3%
Sodium carbnnate 4.5%
WO 92/061~4 PCI/US91/07028
2 ~ 3 Q ~ 78 -
B2. Aqqlomerate of the C,l-c 5 Alkyl Sulfate, C~2-C.c Alkvl
cthoxY Sulfate. DOBANOL C~-C~ EO(3) and C~-C,a N-methyl qlucose
amide - The C16-C18 glucose amide nonionic material is synthesized
with DOBANOL C12 15EO(3) present during the reaction of methyl
ester and N-methyl glucamine. The C12 1sEO(3) acts as a melting
point depressor which allows the reaction to be run without
forming cyclic glucose amides which are undesirable.
A surfactant mixture of 20% DOBANOL C12 15 EO(3) and 80%
C16-C1~ N-methyl glucose amide is obtained and coagglomerated with
10% sodium carbonate.
Second, the aboYe particle is then coagglomerated with a high
active paste (70%) of a sodium salt of C1~-C15 alkyl sulfate and
C12 15 EO(3) sulfate and Zeolite A and extra sodium carbonate.
This particle evidences a good dispersibility in cold water of the
C16-C18 N-methyl glucose amide.
The overall formulation of this particle (contribution to the
detergent formulation after the drying of the agglomerate) is: -
C16-C1~ N-methyl glucose amide 4.1%
D08ANOL C 12 - 1 5 EO(3) 0.94%
Sodium carbonate 4.94%
Zeolite A 5.3%
Na C1~-C15 alkyl sulfate 3.s%
Na C12 15 EO(3) sulfate 0.59%
C. DrY Additives
The following ingredients are added.
Percarbonate 22 ~ 3~~0
TAED (tetraacetylethylenediamine) 5.9%
Layered silicate SKS 6 from Hoechst 12.90%
Citric acid 3.5yO
Lipolase 0. 42~o
100,000 LU/g
SAVINASE 4.0 KNPU 1.65Y.
Zinc phthalocyanin (photobleach) O. 02%
O. SDraY on
OOBANOL C12 1s EO(3) 2.60~o
Perfume 0.53%
W ~ 92/061~4 2 i 0 4 ~ I 9 PCT/USg 1/07028
_ - 79 -
E. Suds SuDpressor
The silicone suds suppressor X2-3419 (g5-97Y. high molecular
weight linear silicone, ~Y~-5~/O hydrophobic silica) ex Dow Corning
is coagglomerated with Zeolite A (2-5 ~ size), starch and stearyl
alcohol binder. This particle has the following formulation:
Zeolite A 0.22%
Starch 1.08%
X2-3419 0.22%
Stearyl alcohol 0.35~,
The detergent preparation exhibits excellent solubility,
superior performance and excellent suds control when used in a
European washing machine, e.g., using 85 g detergent in a AEG-
brand washing machine in 30-C, 40-C, 60-C and 90-C cycles.
EXAMPLE XVII
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 and/or
amine oxide surfactants provides superior sudsing.
For compositions where high sudsing is desired it is pre-
ferred that less than about 5%, preferably less than about 2%,
most preferably substantially no Cl~ or higher fatty acids be
present, since these can suppress sudsing. Accordingly, the
formulator of high sudsing compositions will desirably avoid the
introduction of suds-suppressing amounts of such fatty acids into
high sudsing compasitions with the polyhydroxy fatty acid amide
and/or avoid the formation of C1~ and higher fatty acids on
storage of the finished compositions. One simple means is to use
Cl2 ester reactants to prepare the polyhydroxy fatty acid amides
herein. Fortunately, the use of amine oxide or sulfobetaine
surfactants can overcome some of the negative sudsing efrects
caused by the fatty acids.
The formulator wishing to add anionic optical brighteners to
liquid detergents containing relatively high concentrations (e.g.,
10% and greater) of anionic or polyanionic substituents such as
the polycarboxylate builders may find it useful to pre-mix the
- W o 92/06154 2 ~ ~ 1 3 19 PCT/US91/07~28
- 80 -
-- brightener with water and the polyhydroxy fatty acid amide, and
then to add the pre-mix to the final composition.
Polyglutamic acid or polyaspartic acid dispersants can be
usefully employed with zeolite-built detergents. AE fluid or
flake and DC-544 (Dow Corning) are other examples of useful suds
control agents herein.
It will be appreciated by those skilled in the chemical arts
that the preparation of the polyhydroxy fatty acid amides herein
using the di- and higher saccharides such as maltose will result
in the formation of polyhydroxy fatty acid amides wherein linear
substituent Z is "capped" by a polyhydroxy ring structure. Such
materials are fully contemplated for use herein and do not depart
from the spirit and scope of the invention as disclosed and
claimed.
