Note: Descriptions are shown in the official language in which they were submitted.
W O 92/06153~,~PCTJ/~ /07022
DETERGENT COMPOSITIONS WI~H POLY~YDROXY FAT~Y ACID
AMIDE SURFACTANT AND POLYMERIC DISPERSING AGENT
FIELD OF INVENTION
5This invention relates to detergent compositions con~aining
detersive surfactant and polymeric dispersing agent. In oarticular
this invention relates to detergent compositions con~aini..g ~
sive surfactant systems including a polyhydroxy fatty acid amide
surfactant.
~A~ U~D 0~
De~ergent compositions useful fol clPani"s pur pO525~ SUO" a.
1~ laundering of f~brics~ have commonly utilized a vlrie ~; o,
surfactants, adjunct cleaning ingredients specifically tailore~ tO
the type of cleaning that is needed, as well as other ingredients
added for processing and/or aesthetic purposes.
One of the types of adJunct cleaning ingredients that is
commonly added to detergent compositions to be used for laundry and
other textile-cleaning application is polymeric dispersing agent
such as polycarboxylate dispersing agents and polyethylene glycol
dispersing agents, to assist in removal of particulate soil from
fabrics, textiles, etc. These polymeric dispersing agents are used
in combination with detersive surfactants and other ootional
detergent adjuncts known in the art.
Many of the most commonly used surfactants in recent years have
been derived from petroleum-based feedstocks. These include, most
prominently, surfactants such as the linear alkyl benzene
sulphonates, which can provide excellent overall cleaning
performance over a wide variety of conditions. Significantly, the
linear alkyl benzene sulfonates provide excellent grease and oil
cleaning without necessitating either high wash temperatures or high
concentration, unlike the conven~ional nonionic surfactants which
can alternately be utilized for grease and oil cleaning but which
require high wash temperature and/or high wash concentration.
Whereas these surfactants have provided admirable results, it would
be desirable to reduce the level of surfactant material in tne
compositions based upon petroleum feedstocks while retaining
comparable overall cleaning perrormance.
W O 92/061~i3 PCT/US91/07022
~ 9 ni2 ~ 2 -
Additionally, detergent formulators are traditionally forced
with the problem of providing detergent composition which provides
both good crease and oil cleaning ability with good particulate soil
removal~ sinc-? oo,lY?n-tional '.echni~ues for improving grease and oil
cle~.n ~9 ~ n ? ~ ~ee ~ col ~t? soii removal, and vice
versa. O~i7er surrac.ancs which can interfere with particulate soil
removal ~ .?, fO~m;lnC~ inciude al~l ethoxylates and alkyl phenol
etho~yla~?s.
l nO~ e:~ ~ ol~ln~t h7~. car ~in pol yhyd,oxy fatty acid amide
0 SUr'~~aC~.ai~lbS Cai~ Vitia e~.~cei laial~ ovQrall cleaninai performance,
i nc~ ? 1 '~ ? ~ ~ .? ~'~n~ ? ~ n i n(~ ?'';'~ tn~ r ~7 ~lide
rans2 of ~ia~l -o-l~ on~m ?soC?c~a7ly '.i~i7en combined Witi7 other
~~nl~ r~ ?rm~r~? ~ ~et~?r9~?!1t
cOmpOiSi~ivi7 Cv~ lejc? oo;;liyd'l~o~ a~.y acid amides in
combination Wit;7 one or more polymeric dispersing agents can
additionally provide excellent particulate clay soil removal.
By the practice of this invention, detergent ~ompositions are
provided which contain certain polyhydroxy fatty acid amides,
optional anionic or other nonionic surfactants, and a polymeric
polycarboxylate dispersing agent.
BACKGROUND ART
A variety of polyhydroxy fatty acid amides have been described
in the art. N-acyl, N-methyl ~lucamides, for example, are disclosed
by J. W Goodby, M~ A. Marcus, E. Chin, and P. L. Finn in 'IThe
Thermotropic Liquid-Crystalline Properties of Some Straight Chain
Carbohydrate Amphiphiles." Liquid Crvstals, 1988, Volume 3, No~ 11,
pp 1563-1i81, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R.
~ilgenfeld in "Molecular and Crystal Structure of a Nonionic
Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun.,
1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants
has been of substantial interest recently for use in biochemistry,
for example in the dissociation of biological membranes. See, ;or
example, the journal article "N-D-Gluco-N-methyl-alkanamide
Compounds, a New Class of Non-Ionic Detergents For Membrane
Biochemistry," 3iochem. J. (1982), 'io~. 207, pp 363-366, by J. E. K.
Hildreth.
The use of N-alkyl glucamides in detergent compositions has
also been discussed. U.S. Patent 2,965,576, issued December 20,
.
WO 92/06153 i~ ~ P~ ? g91/07022
- 3 -
1960 to E. R. Wilson, and G.B. Patent 809,060, published February
18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent
compos,tions cont?.lning anicnic surfactants and certain amide
surfactants, ~hich can include N-methyl glucamide, added as a low
temperature suds ~nhancing aaent. These com~ounds include an N-acyl
radical or a nigher s~raigh~ chain fatty acid having 10-14 carbon
atoms. Th?s~ c~.oosltir.ns -~! ?.lso centain ~uxiliary materials such
as al.(aii me~al ~nos~na~.?s, aika7i ,~etal silicates, sulfates, and
carbon~'~s. .. -.s ~l '3 ~''nerll '. '' i nv icatQd that additional
0 COni~ el:à ! 'n.~.~u~'~ d.'~ii'.'bl~ ~ro~ ~ies :o the composition can
also oe m~ciud2~l ln ~,~e cdmodiltivns. such as fluorescent dyes,
U.~. ~aten~ 2,7nv3,/38, issued March 8, 1955 to A. M. Schwartz,
rel at.?s '.O a!''le~''!5 'i''t?'~-~'''. c~pcs;t.iA"s containing the
con~ens~t.on reac' o ~rvvuc' o.~ N-al'iyl ~lu a",ine and an aliphatic
ester of a fatty acid. The product of this reaction is said to be
useable in aqueous detergent compositions without further
purification. It is also known to prepare a sulfuric ester of
acylated glucamine as disclosed in U S. Patent 2,717,894, issued
September 13, 1955, to A. M. Schwartz.
PCT International Application WO 83t04412, published December
22, 1983, by ~. Hildreth, relates to amphiphilic compounds
containing polyhydroxyl aliphatic groups said to be useful for a
variety cf purposes including use as surfactants in cosmetics,
drugs, shampoos, lotions, and eye ointments, as emulsifiers and
dispensing agents for medicines, and in biochemistry for
solubilizing membranes, whole cells, or other tissue samples, and
for pr2parir.s of liposomes. lncluded tn this disclosure are
compounds of the formula R'CON(R)CH2R" and RnCON(R)R' wherein R is
hydrogen or an organic grouping, R' is an aliphatic hydrocarbon
group of at least three carbon atoms, and R" is the residue of an
aldose.
'uropear, ~at~rt 0 285 768, published Cctober 12, 1988, H.
Kelkenberg, et al., relates to the use of ~-polyhydroxy alkyl fatty
acid amides as thickening agents in aqueous detergent systems.
Included are amides of the formula R1C(O)N(X)R2 wherein R1 is a
C1-C17 ~prefer3bl~ C7-C17) alk~l. R2 is hydrogen, a C1-C1g
(preferably C1-C6) alkyl, or an alkylene oxide, and X is a
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~h~ ~ ~ alkyl having four too seven carbon atoms, e.g., N-methyl,
coconut fatty acid glucamide. The thickening properties o, th~
amides are indicated as being of particular use in liquid surfactan~
systems containing paraffin sulfonate, although the aqueous surfac-
tant systems can contain other anionic surfactant~, such as al~yl-
aryl sulfonates, olefin sulfonate, sultosuccinic aci~ h~ e('
salts, and fatty alcohol ether sulfonates, and nonionic surfactants
such as fatty alcohol polyglycol ether, alkyl?,he"ol ~olJ~ljcv,
ether, fatty acid polyglycol ester, polypro~ylene oxide-pol~eth~le!le
oxide mixed polymers, etc. Paraffin sulfonate,~N-m~ c~c~nl:
fatty acid gluoamide/nonionic su;~~ac~an~ sha",poo ~oi~,l.u,~',vn
exempliried. In aàdition to tnickening ~ u~
N-polyhydroxy alkyl fatty acid a~ides are said ~o have s~rerio, s:; "
tolerance attributes.
U.S. Patent 2,982,737, issued May 2, 1961, to Boettner~ et al'!
relates to detergent bars containing urea, sodium lauryl sulfate
anionic surfactant, and an N~alkylglucamide nonionic surfactant
which is selected from N-methyl,N-sorbityl lauramide and N-methyl,
N-sorbityl myristamide.
Other glucamide surfactants are disclosed, for example, in DT
2,226,872, published December 20, 1973, H. W. Eckert, et al., which
relates to washing compositions comprising one or more surfactants
and builder salts selected from polymeric phosphates, sequestering
agents, and washing alkalis, impro~ed by the addition of an
N-acylpolyhydroxyalkyl-amine of the formula R1C(O)N(R2)CH2(CHOH)n-
CH20H, wherein Rl is a C1-C3 alkyl, R2 is a C10-c22 alkyl, and n is
3 or 4. ~he N-acylpolyhydroxyalkyl-amine is added as a soil sus-
pending agent~
U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert,
et al., relates to detergent compositions comprising at least one
surfactant selected from the group of anionic, zwitterionic, and
nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl
polyhydroxylalkyl compound of the formula R1N(Z)C(O)R2 wherein R1 is
a C10-c22 alkyl, R2 is a C7-C21 alkyl, R1 and R2 total from 23 to 39
carbon atoms, and Z is a polyhydroxyalkyl which can be
-CH2(CHOH)mCH20H where m is 3 or 4.
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U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, et
al., relates to skin treating cosmetic compositions containins
N-polyhydroxylalkyl-amines which include compounds of the formula
RlN(R)CH(CHOH)mR2 wherein Rl is H, lower alkyl, hydroxy-lower al~yl,
or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as
Rl but both cannot be H, and R2 is CH20H or COOH.
French Patent 1,360,018, April 26, 1963, assigned to Commercial
Sol~ents Corporation, relates ~ solutions of fo;~,.,aldehJd~
stab;lized against polymerization with the addition of amides of th~
formula RC(O)N(Rl)G wherein R is a carboxylic acid IU~C~'.Onal~''J'
having at least s~o~en carbon at~",s, Rl ii hydroy;~ll or d ~0':1~,' al'~
group, and ~ is a glycitol radical wi;h a; leas~ i carDon a~oms.
German Patent 1,261,861, February 9, i9cq, A. ~eir,s, r~la;ci
to glucamine derivatives useful as wetling and dispersing agents of
the formula N(R)(Rl)(R2) wherein R is a sugar residue of glucamine,
Rl is a Clo-C20 alkyl radical, and R2 is a Cl-Cs acyl radical.
G.B. Patent 745,036, published February 15, 1956, assigned to
Atlas Powder Company, relates to heterocyclic amides and carboxylic
esters thereof that are said to be useful as chemical intermediates,
emulsifiers, wetting and dispersing agents, detergents, textile
softeners, etc. The compounds are expressed by the formula
N(R)(Rl)C(O)R2 wherein R is the residue of an anhydrized hexane
pentol or a carboxylic acid ester thereof, R~ is a monovalent
hydrocarbon radical, and -C(O)R2 is the acyl radical of a carboxylic
acid ha~ing from 2 to 25 carbon atoms.
U.S. Patent 3,312,627, issued April 4, 1967 to D. T. Hooker,
discloses solid toilet bars that are substantially free of anionic
deter~ents and alkaline builder materia'is, and hhich contain lithium
soap of certain fatty acids, a nonionic surfactant selected from
certain propylene oxide-ethylenediamine-ethylene oxide condensates,
propylene oxide-propylene glycol-ethylene oxide condensates, and
polymer ked ethylene glycol, and also contain a nonionic lathering
component which can include polyhydroxyamide of the formula
RC(O)NRl(R2) wherein RC(O) contains from about 10 to about 14 carbon
atoms, and Rl and R2 each are H or Cl-C6 alkyl groups, said alkyl
groups containing a total number of carbon atoms of from 2 to about
7 and a total number of substituent hydroxyl groups of from 2 to
w 0 92/06153 2 ~ 9 2 1~ 7 PCT/US91~0702
- 6 -
about 6. A substantiallyy similar disclosure is found in U.S. Patent
3,312,o20, allso issued April ~, lg67 to D. T. Hooker.
SU~lMARY OF THE INVENTION
The p,~sen~ inYention provides a detergent composition
comprisin3:
~ , a~ ~aa,~ a~c~; .., ~y ~ ..t, or a polyhydroxy fatty acid
amide (oreferablv from about 3% to about 50~') of the formula
~1
~2 r 11 ~
0 ~,lhqr'a~,a ',i ',; N1 ~ \,'tr~S_~b~ -h~drox~ ethyl, 2-hydroxy
pl'Op~ ù.'_ ~h_.'_~l', R~ i~ a Cj-~31 hyurocdrbyl, and Z is a
pol~h'.'~.'r',~'.'' ::',_.~.'', .':.'i'.'~'. ~ .~n~ar .~y~rocarbyl chain with at
leas; ~ ~y~1v~;is, ~r a" aj.~O~1a~~-G deriva;,Ye ;hereof;
(b) from lJ~ ~0 a~out ~iv o, a detersiYe surfactant, other than
said pnlvhvdrnxv attv acid a,ide, selected from anionic and
nonionic deLersive surfactants;
(c) at least about 0.5~' of a polymeric dispersing agent,
wherein the weight~ ratio of said dispersing agent tr said
polyhydroxy fatty acid amide should be from about 10:1 to about
1:10.
The polymeric dispersing agents hereof include polycarboxylate
and polyethylene glycol polymers.
This invention further provides a method for improving the
performance of detergents containing polymeric dispersing agent and
detersive surfactant by additionally incorporating into such
composition at least about 1%~ by weight, of the polyhydroxy fatty
acid amide surfactant described abo~e.
This i~Yention further provides a method for cleaning
substrates, such as fibers, fabrics, hard surfaces, skin, etc., by
contacting said substrate, with a detergent composition comprising
one or more anionic, nonionic, or cationic surfactants, at least
about 0.5YO, ~y weight, polymeric dispersing agent, and at least 1%
of the polyhvdroxy fatty acid amide.
DETAILED DESCRIPTION OF THE INVENTION
Polvhvdroxv Fattv Acid Amide Surfa~tant
The compositions hereof wi 1 comprise at least about 1%,
typically from about 3% to abou; ~û'~, preferably from about 3% to
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7 ~ ~321~7
about 30%, of the polyhydroxy fatty acid amide surfactant described
below.
T,~ ol~;h~droxy fatty acid a~ide surfactant component of the
present invPnticn comprises compounds of the structural formula:
( T ) ~ - !\1 - 7
.~her~~ Rl s '~ C~ 'ny',oc~,byl, 2-hydroxy ethyl, 2-hydroxy
propyl, ~ l ~ xt~rQ thvQrQof, preferably Cl-C4 alkyl, more
pre,~ar~~bl~ ,'x~ os~ ~r~l~rably ~l alkyl (i.e., methyl);
and ~ ; ~ 2 ~9~ a'3;,;'~C'.I ~yi ~ ~r ~ rably straight chain C7-Clg
~l~yl 0'.~ ~1~;?~ '1 ~ ~m~r~ ere. ~r~.hl~.y straisht chain Cg-Cl7 alkyl or
al~ny~ ona,anaù,~ raig,~; c;1din Cll-C17 alkyl or alkenyl, or
mixture thereof: and Z is a pol~hvdroxyhvdrocarbyl having a linear
~ydr~ ~ a'~" '1 ::1' ', ' :1 ' !'. ' ~. ~ ' ' ~~ -,_ t ~ ~yd~rs.Vyl S d ' rcctly connected to
the ch31n, or ~n ~ xylaLed der ya~jyv (pref~rably ethoxylated or
propoxylated) thereof. Z preferably will be derived from a reducing
sugar in a reductive amination reaction; more preferably Z is a
glycityl. Suitable reducing sugars include glucose, fructose,
maltose, lactose, galactose, mannose, and xylose. As raw materials,
high dextrose corn syrup, high fructose corn syrup, and high maltose
corn syrup can be utilized as well as the individual sugars listed
abo~e. These corn syrups may yield a mix of sugar components for Z.
It should be understood that it is by no means intended to exclude
other suitable raw materials. Z preferably will be selected from
the group consisting of -CH2-(CHOH)n-CH20H, -CH(CH20H)-(CHOH)n 1-
CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH20H, where n is an integer from 3
to 5, inclusive, and R' is H or a cyclic or aliphatic monosacchar-
ide, and alkoxylated deri~atives thereof. Most preferred are
glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH20H.
In Formula (I), Rl can be, for example, N-methyl, N-ethyl,
N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy
propyl.
R2-C0-N~ can be, for example, cocamide, stearamide, oleamide,
lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
7 can be l-deoxyglucityl, 2-deoxyfructityl, l-deoxymaltityl,
l-deoxylactityl, l-deoxygalactityl~ l-deoxymannityl, l-deoxymalto-
triotityl, e~c.
WO 92/06153 PCT/US91/07022
2~2187
Methods for making polyhydroxy fatty acid amides are known in
the art. In general, they can be made by reacting an alky~ amine
with a reducing sugar in a reductive amination r actiar, ~o ~ a
corresponding N-alkyl polyhydroxyamine, and then rQacting tne
S N-alkyl polyhydroxyamine with a fattv ali?hatic ?~?~ o~
triglyceride in a condensation/amidation step to form the
N-polyhydroxy fatty acid amide produc'. Pr~c ~es ~~ n~
composit;ons containing polyhydroxy fatty acid amidQs i~~? dico~oced~
for example, in G.B. Patont Specificatiar, ~.~3,0
February 18, 19~9, by Ihomas H~odley ~ C~
2,965,576, issued December 20, 1960 to ~~ R. '~ilson~ ln~iJ ~ n-
2,703,798, Anthony M. Schwartz, issued ;larch ~ ;i, .ni~ ~0~
Patent 1.985,424, issued December 25, 1934 to Piaaott~ eacn ot ~Ynich
is incorporat~d herein by reforenco~
In one process for producing N-al'~yl 'Jr ~ ydi-3,~yat~;;'1,
N-deoxyglycityl fatty acid amides wherein the glycityl component is
derived from glucose and the N-alkyl or N-hydroxyalkyl functionality
is N-methyl, ~-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or
N-hydroxypropyl, the product is made by reacting N-alkyl- or
N-hydroxyalkyl-glucamine with a fatty ester selected from fatty
methyl esters, fatty ethyl esters, and fatty triglycerides in the
presence of a catalyst selected from the group consisting of tri-
lithium phosphate, trisodium phosphate, tripotassium phosphate,
tetrasodium pyrophosphate, pentapotassium tripolyphosphate, l,th,um
hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide,
lithium carbonate, sodium carbonate, potassium carbonate, disodium
tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium
citrate, tripotassium citrate, sodium basic silicates, potassium
basic silicates, sodium basic aluminosilicates, and potassium basic
aluminosilicates, and mixtures thereof. The amount of catalyst is
preferably from about 0.5 mole ~O to about 50 mole %, more preferably
from about 2.0 mole % to about 10 mole %, on an N-alkyl or
N-hydroxyalkyl-glucamine molar basis. The rioaction is pre,~~rably
carried out at from about 138'C to about 170-C for typically from
about 20 to about 90 minutes. hhen triglycerides are utilized in
the reaction mixture as the fatty ester source, the reaction is also
preferably carried out using fro~ about 1 to abcut 10 ~.leight ~,' of a
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~ 7
g
phase transfer agent, calculated on a weight percent basis o~ total
reaction mixture, selected from saturated fatty alcohol
polyethoxylates, alkylpolyglycosides, linear glycamide sur~ac~an.,
and mixtures thereof.
Preferably, this process is carried out as follo~Ys:
(a) preheating the fatty ester to abou~ 138~C to about 17~C;
(b) adding the N-alkyl or N-hydroxyal~yl glucamine 'o thq
heated fatty acid ester and mixing to the extent needQ~ to
form a t~o-phase liquid/liquid mixtur~;
(c) mixing the ca~alyst into ~he reactidn mix~ture: a,
(d) stirring for the specitied reaction time.
Also preferably, from about 2~' to abou~ ~0~0 of p,e,or~"ed l~,l an
N-alkyl/N-hydroxyalkyl, N-linear giucosyl fatty acid amide product
is added to the reaction mixturQ~ by woight Or the rq-~ n'~ ?~5 'he
phase transfer agent if the fatty ester is a ~riglJcanlde. Th'.i
seeds the reaction, thereby increasing reaction rate. A detailed
experimental procedure is provided below in the Experimental.
The polyhydroxy "fatty acid" amide materials used herein also
offer .the advantages to the detergent formulator that they can be
prepared wholly or primarily from natural, renewable, non-petro-
chemical feedstocks and are degradable. They also exhibit low
toxicity to aquatic life.
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, including such cyclic amide by-product.
Additional Detersive Surfactants
In addition to the polyhydroxy fatty acid amide, the com~osi-
tions can contain other detersive surfactants. Typically, the
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- 10 -
compositions will comprise from 1% to about 45% of such other
surfactants, preferably from about 5~~0 to about 40~~0, more typically
from abQut ~' to about 25~~, of such other surfactants. These addi-
tional surfactants can include any surfactants useful for detersive
puroos~s. The~ include anionic and nonionic surfactants, as well as
other sur,~dc.an.s iuch as cationic? zwitterionic, and ampholytic
surfactan~.s .
~ ,12 ?r~s~n~ invention is particularly beneficial when the
det'~'~~'9'qnL ~ JoSi titni ~ncluua anionic surfactants which are
iO r ela', ~ ? .~ a;':' hardn~ss, such as alkyl ben~ena
suirond~ ui,a~ s~ ai~fl ester sul~onates, and alkyl
alko~ s ~'; n ~s. ~h~ riac~an-~s, ~specially commonly used
ones SUCil as alkyl ethvxy7ates~ alkyl polyglycos;des, and paraffin
sul,~nnir~.s cal al~o be in lun~d~ In genaral~ '.he util haticn of the
polyhyd-~vv -alty ac ~ amidq oln ~ssist in the formulation of
detergent compositions containing such surfactants.
Alk~l Ester Sulfonate Surfactant
Alkyl ester sulfonate anionic surfactants hereof include linear
esters of C8-C20 carboxylic acids (i.e., fatty acids) which are
sulfonated with gaseous S03 according to ~The Journal of the
American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable
starting materials would include natural fatty substances as derived
from tallow, palm, and coconut oils, etc.
~he prefer~ed alkyl es~er sulfonate surfactant, especially for
laundry applications, comprise alkyl ester sulfonate surfactants of
the structural formula:
o
R3 - CY~ - C - ~4
S03M
wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a Cl-c6 hydrocarbyl, preferably an alkyl,
or combination thereof, and M is a cation which forms a water
soluble ,~lt with the alkyl estar sulfonate. Suitable salt-forming
cations include metals such as sodium, potassium, and lithium, and
substituted or unsubstituted am onium cations, such as methyl-,
dimethyl~ -trimethyl, and quaternary ammonium cations, e.g.
tet.ameth;l-am".onium and dimethyl p perdinium, and cations derived
from alkanolamines, e.g. monoethanolamine, diethanolamine, and
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- 11 -
triethanolamine. Preferably, R3 is Clo-C16 alkyl, and R4 is methyl,
ethyl or isopropyl. Especially preferred are the methyl ester
sulfonâtas :.he,ain ~3 is Cl~-C16 alkyl.
Alk~/1 Sul-'2te Surfactant
~ ~a'~ surf~c'an's h~ ~of are ~ater soluble salts or
acids o~ ,a f~.mula ROS03H .~herein R preferably is a Clo-C~4
ilydnvca~y,~ na~ly an alkyl or hydroxyalkyl having a Clo-C20
alkyl oomlvonaa~ mor~ oref2ra~1y a C12-Clg alkyl or hydroxyalkyl,
and .~i ;â . ';' i Oà~iOil~ e.5.~ ~n al~ali metal cation (e.g., sodium,
!0 potasi'u~um~ su~s,i~u~ed or unsubstituted ammonium cations
suc~ ~s ~a~ , and trimethyl ammonium and quaternary
ammooi~c-~,ioos, e.a., .etramethyl-~mmonium and dimethyl
piperd;n;~n~ r.~t.ir~nC ~Qrive~ from ~l~anolamines such as
~'ha ~ .h.. ,;'i",l , '~ h_nolam~ioe~ and m; xturPs thereof,
and ~he " ;e. ~ypicaily, alkyl cilains of C12-C16 are preferred for
lower ~.~ash temperatures (e.g., below about 50-C) and C16 18 alkyl
chains are preferred for higher wash temperatures (e.g., above about
50-C).
AlkYl Alkoxvlated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M wherein R is an
unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a Clo-C24
alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
prererably C12-Clg aikyl or hydroxyalkyl, A is an ethoxy or propoxy
unit, m is greater than zero, typically between about 0.5 and about
6, more preferably ~etween about 0.5 and about 3, and M is H or a
cation ~hich can be, for example, a metal cation ~e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or
;ubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as
alkyl propoxylated sulfates are contemplated hèrein. Specific
examples of substituted ammonium cations include methyl-, dimethyl-,
trimethyl-ammonium cations and quaternary ammonium cations such as
tetrameihyl-ammonium, dimethyl piperdinium and cations derived from
alkanolamines, e.g. monoethanolamine, diethanolamine, and
tri~thanolamine, and mixtures thereof. Exemplary surfactants are
C12-C13 alkyl ~olyethoxylate (1.0) sulfate, C12-C18 alkyl
polyetnoxylate (2.25) sui;ate, C12-Clg alkyl polyethoxylate (3.0)
w o 92/06153 PCT/~Sl)l/07022
'~0921~7 - 12 -
sulfate, and C12-C18 alkyl polyethoxylate (4.0) sulfate, wherein M
is conveniently selected from sodium and potassium.
Other Anionic Surfactants
Other anionic surfactants useful for detersive ~uroos~s caa
5 also be included in the compositions hereof~ T~e~? c~
salts (including, for example, sodium, potassium, a~oniu-, ~nd
substituted ammonium salts such as mono-, ~ r' 'r' -'ha.a ~;"~n
salts) of soap, Cg-C20 linear alkylben~ene~u!p~~na~e~, C~3-C~
primary or secondary al~anesulphonat~s, C~.-C~ "~
sulphona-ed polycarboxylic acids pr~oa ~ n;,l : ni
pyrolyzed product of al~aline earth me~al C'~ratas!
described in 3ritish paten~ speci,ic~-~io,l ~o. .~ ; "
glycerol sulfonates, fatty acyl glvcerol sul,ona..es~ ~at~
glycerol sulfat~s~ al~yl ohenol aa~yl~-n~ s;
paraffin sulfonates, alkyl phosphates, ise~hlonl~ s su h a, ~h~ iCyl
isethionates, N-acyl taurates, fatty acid amides of methyl tauride,
alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate
(especially saturated and unsaturated C12-Clg monoesters), diesters
of sulfosuccinate (especially saturated and unsaturated C6-C14
diesters), N-acyl sarcosinates, sulfates of alkylpolysacchariqes
such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated
compounds being described below), branched primary alkyl sulfates,
alkyl polyethoxy carboxylates such as those of the formula
RO(CH2CH20)kCH2COO-M+ wherein R is a Cg-C22 al'~yl, k is an integer
from O to 10, and M is a soluble salt-forming cation, and fatty
acids esterified with isethionic acid and neutralized with sodium
hydroxide. Resin acids and hydrogenated resin acids are also
suitable, such as rosin, hydrogenated rostn, and resin acids and
hydrogenated resin acids present in or derived from tall oil~
Further examples are described in "Surface Active Agents ~nd
Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety
of such surfactants are also generally disclosed in U.S. Patent
3,929,678, issued December 30, 1975 to Laughlin, et al. at Column
23, line 58 through Column 29, line 23 (herein incorporated by
reference).
Nonionic Deterqent Surfactants
Suitable nonionic detergent surfactants are g2nerally disclo,ed
in U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975,
W O 92/06153 ~ 13 - ~ Pr~C~r/US91/07022
at column l3~ line 14 through column 16, line 6, incorporated herein
by reference. Exemplary, non-limiting classes of useful nonionic
surfactants are listed below.
1. The polyethylene, polypropylene, and polybutylene oxide
condensates of alkyl phenols. In general, the polyethylene oxide
condensates are preferred. These compounds incl~ade tho condensa~.on
products of alkyl phenols ha~ing an alkyl ~roup containing from
about 6 to about 12 carbon atoms in ~,~her a st.a,~;,. cilaliî o.
branched chain configuration with the alkvl~n2 oxid~. In
preferred embodiment, the ethylene oxide is p.~sen~ n a.~ ~
equal to ,rom about S to about 25 m,ol~s o, e~'ly, 1,2 ù.~id_ pe,~ ~"0~_
of alkyl phenol. Commercially ava~laDl~ nonimllc iu;~,':c~ai~
this type include Igepal~M C0-630, mar~etod by ~ne ~AF Corporz~lon;
and TritonT~l X-45, X-114, X-100, and X-102, all mar~et~d bv ~he .~ohm
& Haas Company. These surfactants are commonlv referred '.o ~s
alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
2. The condensation products of aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide. The alkyl chain of the
aliphatic alcohol can either be strai'ght or branched, primary or
secondary, and generally contains from about 8 to about 22 carbon
atoms. Particularly preferred are the condensation products of
alcohols having an alkyl group containing from about 10 to about 20
carbon atoms with from about 2 to about 18 moles of ethylene oxide
per mole of alcohol. Examples of commercially available nonionic
surfactants of this type include TergitolTM 15-S-9 (the condensation
product of C11-C1s linear secondary alcohol with 9 moles ethylene
oxide), TergitolTM 24-L-6 NMW (the condensation product of C12-C14
primary alcohol with 6 moles ethylene oxide with a narrow molecular
weight distribution), both marketed b'. Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol
with 9 moles of ethylene oxide), NeodolTM 23-6.5 (the condensation
product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide),
NeodolTM 45-7 (the condensation product of C14-C1s linear alcohol
with 7 moles of ethylene oxide), NeodolTM 45-4 (the condensation
product of C14-C1~ linear alcohol with 4 moles of ethylene oxide)~
marketed by Shell Chemical Company, and KyroTM EOB (the condensation
product of CI3-Cls alcohol with 9 moles ethylene oxide), marketed by
h ~ 7 14 PCT/US91/07022
The Procter & Gamble Company. These surfactants are commonly
referred -~o as alkyl ethoxylates.
3. The condensation products of ethylene oxide with a
hydropnobic uas~ formed by the condensation of propylene oxide with
propyl~ne glycol. Tne hydrophobic portion of these compounds
prer~ra~y hl~ ~ mo ~cul-~r .Yeiyhr or from about lS00 to about 1800
and exhibits ~.~ater insolubility. The addition of polyoxyethylene
moi~ s ~ ':is h~,o~vhoaic po.tion tends to increase the water
solubilitv of th~ mol~cul~ lS a ~hole, and the liquid character of
the pr~.~us~ t~;n~d ~ ;n~ ooint wh~re the polyoxyethylene
cun~ari'' i~ ~v~U'~ 3''~ vr' 'ha ~ota, ~ie,gh~ or ~he cond~nsation
Ot"ad!;O'~ '''O.' '' ~':'r'i,'"na_ ~O ~onc~nsation .~ith up to about ~0 moiPs
of a~hJme,e ~v~ide ~amples v~' co",pounds o, this type include
cer~ain or C~ commerci~iiy-available Pluronic~i~ surfactants,
15 marketod bv 8ASF.
~ . The condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products consists
of the reaction product of ethylenediamine and excess propylene
oxide, and generally has a molecular weight of from about 2500 to
about 3000. This hydrophobic moiety is condensed with ethylene
oxide to the extent that the condensation product contains from
about 40% to about 80% by weight of polyoxyethylene and has a
molecular weight OT from about 5~000 to about 11,000. Examples of
this type of nonionic surfactant include certain of the commercially
available TetronicTM compounds, marketed by BASF.
5. Semi-polar nonionic surfactants are a special category of
noni~nic 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 phosDhine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties
selected from the group consisting of alkyl groups and hydroxyalkyl
groups containing from about 1 to about 3 carbon atoms; and
water-soluble sulfoxides containir,g one alkyl moiety of from about
10 to about 18 carbon atoms anà a moiety selected from the group
w o 92/06153 PCT/US9l/07022
- 15 - ~ i 3 ~
consisting of alkyl and hydroxyalkyl moieties of from about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine
oxide su,,'lctants ~aving the formula
0
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or
mixtur?s tne~~eof containing fro~ about 8 to about 22 carbon atoms;
R~ is an ~ l n~ or hydroxyalkylene group containing from about 2
to abcut ' ~e~b3n s~~m~ 0'.~ mi';''':'es thereo~; x is from O to about 3;
and each ~ s In a~k~l or h~dr~x~/al~ l aroup containing from about
~ t~ d~ sro~ con~l~,ninS
from ;bo~ bou: , ethyl~ile o~lde groups. The R5 groups can be
a~'a~ U''! ~'e"! e'9'~ .''n.'~u~''n ~n ~xygen or nitrogen atom, to
,-orm a r m~ .cuci~ure.
These amine oxide surfactants in particular include Clo-C18
alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl
amine oxides.
6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued ~anuary 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 trom about 1.3 to about 3, most preferably from about
1.3 to about 2.7 saccharide units. Any reducing saccharide
containing S 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 giYing a glucose or galactose as opposed
to a glucoside or galactoside.) The intersaccharide bonds can be,
e.g., between the one position of the additional saccharide units
and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide
units.
Optionally, and less desirably, there can be a polyalkylene-
oxide chain joining the hydrophobic moiety and the polysaccharide
moiety. The preferred alkylene3xide is ethylene oxide. Typical
hydropnobic groups include aik~l groups, either saturated or
unsaturated, branched or unbrancned containing from about 8 to about
W O 92/06153 ~ ~ 9 ~ PCT/US91/07022
- 16 -
18, preferably from about 10 to about 16, carbon atoms. Preferably,
the alkyl group is a straight chain saturated alkyl Srcup. The
alkyl group can contain up to about 3 hydroxy groups and/or th~
polyalkyleneoxide chain can contain up to ~bout 1~ r~~,~ rsul~J ,es;
than 5, alkyleneoxide moieties. Suitable al'~yl ?ol ~SarC~ rr~
octyl, nonyldecyl, undecyldodecyl, triu~c~ r~ ~-CJ ,
hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-, and
hexaglucosides, galactosides, lactosides, ~lu~se~. ~~~ c~ ~~ e~.
fructoses and/or galactoses. Suitable mixtur~s include coconu~
alkyl, di-, tr;-, tetr~-, and pent glu;es,.'es ii,d
tetra-, penta-, and hexaglucosides.
The prnferred ~lkylpolygl~cQsidQs h~n!e the ~~
R20(Cnll2nC)t(glyco~
wherein ~2 is selected ~rom ~hrA ~ro ~ c~ns~ in~ ~' ~ ;, , A;;,
lS phenyl, hydroxyalkyl, hydroxyalkylpnenyl, and ~ix;u,es ;;~~reû, in
which the alkyl groups contain from about 10 to about 13, pre;~rably
from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2;
t is from 0 to about 10, preferably 0; and x is from about l.3 to
about 10, preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived from
glucose. To prepare these compounds, the alcohol or alkylpolyethoxy
alcohol is formed first and then reacted with glucose, or a source
of glucose, to form the giucoside (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(R7)2
wherein R~ is an alkyl group containing from about 7 to about 21
(prefera~ly from about 9 to about 17) carbon atoms and each R7 is
selected from the group consisting of hydrogen, Cl-C4 alkyl, Cl-C4
hydroxyalkyl, and -(C2H40)XH where x varies from about 1 to about 3.
Preferred amides are Cg-C20 ammonia amides, monoethanolamides,
diethanolamides, and isopropanolamides.
Cationic Surfactants
Cationic detersive surfactants can also be included in
detergent compositions of the present invention. Cationic
W o 92/06153 PCT/US91/07022
surfactants include the ammonium surfactants 2suc~ ~as ~al~yldimethyl-
ammonium halogenides, and those surfactants having the formula:
[R2(oR3)y] [R4(0R3)y]2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group h2ving ,rom abou~ 8 ~o
about 18 carbon atoms in the alkyl chain, each R3 is selected from
the group consisting of -CH~CH2-, -CH?C~'CH~-, -CH2CU(~u ~~u~ ~
-CH2CH2CH2-, and mixtures thereof; each R~ is select~d from the
group consisting of Cl-C4 alkyl, Cl-C~ h~dro~ja1!~J~l, ben.jl, n
structures formed by joining the t~.~o ~ sroups,
-CH2CHOH-CHOHCOR6CHOHC~20H ~.~herein R6 is any h~ ;oie OiA he,~ose
polymer having a molecular weight less than abc~ )00~ and n~alvgen
when y is not O; RS is the same as R~ or is an ll~yl ch~in ~he~A? ~
the total number Ot carbon atoms o, R2 plus ~- is n~t more indil
about 18; each y is from O to about 10 and the sum of the v ~alues
is from O to ~bout 15; and ~ is ~y -~m~-A. ble - i~~.
Other cationic surfactants use,ul herein ~re al,o described in
U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated
herein by reference.
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
2S aliphatic substituents contains at least about 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at least one
contains an anionic water-solubilizing group, e.g., carboxy,
sulfonate, sulfate. See U.S. Patent l~o. 3,929,678 to Laughlin et
al., issued December 30, 1975 at column 19, lines 18-3S (herein
incorporated by reference) for examples of ampholytic surfactants.
~witterionic 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
w o s2/06t53 PcT~uss1/07022
~ 18 -
through column 22, line 48 (herein incorporated by reference) for
examples of zwitterionic surfactants.
Ampholytic and zwitterionic surfactants are generally used in
combination with on~ or more anionic and/or nonionic surfactants.
Polv~a~lc nisoersina Aqents
~ ~ o d-s ersi"g ag-nts c2n adYantageously be utilized in
the compositions hereof. These materials can aid in calcium and
magnesium hardnas~ control. Suit~ble polymeric dispersing agents
includ~ polymeric polycarboxylates and polyethylene glycols,
althcus~, o~ln2.~s ~"o:Yn in ~e art can also be used. It is believed,
thouch i~ is not intended to be limited by theory, that the
nt, ~h~ncq o~ l d~t~3nt cl ~ni~,3
per,~o~ n~ by crys~ ro~ith inhibition, aiding in p~rticul~te soil
p ~ p ' ~ ' '! il t '' ~ ~ n ~ '' O :~ .
li ii~ oo,nposi~,ons nereor ~.~ill contain at least about 0.5~~o~
prefer~bly from about l~ to about 1O0~D~ more preferably from about 2%
to about 5,', of the polymeric dispersing agent.
Polycarboxylate materials which can be employed as the
polymeric dispersing agent component herein are these polymers or
copolymers which contain at least about 60% by weight of monomer
units with the general formula
X Z
l l
C - C
Y COOM
wherein X, Y, and 2 are each selected from the group consisting of
hydrogen, methylt carboxy, carboxymethyl, hydroxy and hydroxymethyl;
M a salt-forming cation and n is from about 30 to about 400.
Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is
hydrogen and M is hydrogen, alkali metal, ammonia or substituted
ammonium.
Polymeric polycarboxylate materials of this type can be
prepared by polymerizing or copolymerizing suitable unsaturated
carboxylate monomers, preferably in their acid form. Suitable
monomer starting materials include acrylates, maleates, fumarates,
W O 9t/06153 - 19 - 2 ~ ~ ~i 8CT'US9l/07022
itaconates, aconitates, mesaconates, citraconates, and methylene-
malonaLes. Corresponding unsaturated monomeric acids that can be
polymPrized to form suitable polymeric polycarboxylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid,
itaconic acid, aconitic acid, mesaconic acid, citraconic acid and
metilyl~l~m~ ~nlo ~e-~ he pr~s~nce in the polymeric polycarboxyl-
ates herein of monomeric segments, containing non-carboxylate
.adic21~ su~. as ~Ji~Jl.,Qth,l ~thor, styrene, ethylene, etc. is
suitable pro~/ided ~hat such segments do not constitute more than
!0 ~bo~
,io;..;~ly ~ ab'l e ~ îe;~lc polycarboxylates are the
~0~ ''"~'-U_i',~ WlliCIl~ ~re,erably, are derived from acry1ic
acid. âuc n :~cn,~, ic acid-based ~olymers which are useful herein
inciude chD waLDr-soiuoie sa~ts o,~ polymeri~ed acrylic acid. The
average mol~cular weight of such polyacrylate polymers will
preferably be at least about 1,000, and will preferably range 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, said molecular weights
being based upon the acid form. Water-soluble salts of such acrylic
acid polymers can include, for example, the alkali metal, ammonium
and substituted ammonium salts. Soluble polymers of this type are
known materials. Use of polyacrylates of this type in detergent
compositions has been disclosed, for example, in Diehl, U.S. Patent
No. ~,308~06~, issued ~arch ~, 1967. This patent is incorporated
herein by reference.
Acrylic/maleic-based copolymers may also be used as a preferred
component of the polymeric dispersing agent. Such materials include
the water-soluble salts of copolym~rs of acrylic acid and maleic
acid. The average molecular weight of such copolymers in the acid
form ranges from about 2,000 to 100,000, more preferably from about
S,00~ to about 75,000, most preferably from about 7,000 to 65,000.
The ratio of acrylate to maleate segments in such copolymers will
generally ran~e 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
3S 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
w O 92/06153 ~'~921~ ~ PCT/US91/07022
- 20 -
Patent Application No. 66915, published December 15, 1982, which
publication is incorporated herein by reference
Another polymeric material ~hich can be incl~ed ls ~ol~,~e~
ene glycol (PEG). PEG can exhibit dispersiTlg agent perFor~ailce a
well as act as a clay soil removal!anti-re~aDositic~ ace~ al
molecular weight ranges for these purpojes ,"ai7ue ~nG~ iuoU~ 0
about 100,000, preferably from about l~0~0 ~~ 71'~!'t S
preferably from about 1,500 ~o abou~ iu.ùuù.
Builders
Detergent compositions o~, ~he ,~ '.n'' ~ !S'.. '
inorganic or organic detergent buiiders ~o as~ls; In l~ i a~r~-
ness control.
The level of builder can vary widely depending u~on ~ne end use
of the composition and its desirsd ohys~ u'a~
lS tions typically comprise at l~ast abcut .~v~, ~nvra '.~,i;a'',; -i~~",
about 5X to about 50%, preferably about S~O to about 30%, by weight
of detergent builder~ Granular formulations typically comprise at
least about lY., more typically from about 10% to about 80%, prefer-
ably 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 polyphos-
phates texemplified by the tripolyphos?hates, pyrophosphates, and
glassy polymeric meta-phosphates), phosphonates, phytic acid,
silicates, carbonates (including bicarbonates and sesquicarbonates),
sulphates, and aluminosilicates. 3Orate bu;ld~rs, as well as
builders containing borate-forming materials that can produce borate
under detergent storage or wash conditions (hereinafter collectively
"borate buildersn), can also be used. Preferably, non-borate
builders are used in 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 SiO2:Na20 ratio in the range 1.6:1 to
3.2:1 and layered silicates, such as the layered sodium silicates
described in U.S. Patent 4,664,839, issued ~ay 17, 1987 to H. P.
Rieck, incorporated herein by reference. However, other silicates
W O 92/06153 PC~r/US91/07022
- 21 ~ 7
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 ~l',caline earth and
alkali metal carbonates, including sodi~u" carbona~e al,a
sesquicarbonate and mixtures thereof with ultra-fine calcium
carbonate as disclosed in German Paten~ ~pplica~ion ,~o~ 2,321,~
published on NoYember 15, 1973, the disclo~urQ of ~Yhich is
incorporatPd herein by refer~nc~.
Aluminosilicat~ buiiders are es~ecia "~ ~jc u, ,;t .h~ p,~ iell~
invention. Aluminosilicato buil d~rs are o,~;~; ",~p~ ;"ca "~ ~,os;
currently marketed heavy duty granular d2~ers~-n~ compos,~ions, and
can also be a significant builder ingrQdient ~n li~uid ~etercent
formulations. Aluminosilicate builders include ,hos~ having the
empirical formula:
Mz(zAlO2 YSio2)
wherein M is sodium, potassium, ammonium or substituted ammonium, z
is from about 0.5 to about 2; and y is 1; this material having a
magnesium ion exchange capacity of at least about 50 milligram
equivalents of CaC03 hardness per gram of anhydrous aluminosilicate.
Preferred aluminosilicates are zeolite builders which have the
formula:
Naz[(A102)~ (sio2)y~'xH2o
wherein z and y are integers of at least 6, the molar ratio of z to
y is in the range from 1.0 to about 0.5, and x is an integer from
about 15 to about 264.
Useful aluminosilicate ion exchan~e materials are commercially
available. These aluminosilicates can be crystalline or amorphous
in structure and can be naturally-occurring aluminosilicates or
synthetically deri~ed. A method for producing aluminosilicate ion
exchange materials is disclosed in U.S. Patent 3,985,669, Krummel,
et al., issued October 12, 1976, incorporated herein by reference.
Preferred synthetic crystalline aluminosilicate ion exchange
materials useful herein are available under the designations Zeolite
A, Zeolite P (8), and Zeolite X. In an especially preferred
embodiment, the crystalline aluminosilicate ion exchange material
has the formula:
w o 92/06153 PC~/US91/07022
2 a ~ 22 -
Nal2[tAlo2)l2(sio2)l2] X~20
wherein x is from about 20 to about 30, especially about 27. ~his
material is ~nown as Zeolite A. Preferably, the aluminosilicate has
a particl e Sj~~ of about 0.1-10 microns in diameter.
SDe~jFjC xamples of polyphosphates are the alkali metal
~ni~m.',~ ;n tL~ A~;;m~ poLassium and ammonium pyrophosphate,
sodium and potassium and ammonium pyrophosphate, sodium and
potas,ilim ~'h~r'~ns~ te, sodium polymeta phosphate in which the
degree Ot oolymerieation ranges from about 6 to about 21, and salts
1 0 0, o ,~
'-x~mp~ f ~h~ on~e huild~-r salts are the water-soluble
dn~ i, l-di~;lo~ohona~ particularly the sodium
and po..a~ u,~ ~~,'~s, ~he water-soluble salts o; methylene
diphos~"o,l,c acid e.g. .he ~riiodium anci tripotassium salts and the
water-j~luble salts of substituted methylene diphosphonic acids,
such as the triscdium and tripotassium ethylidene, isopyropylidene
benzylmethylidene and halo methylidene phosphonates. Phosphonate
builder salts of the aforementioned types are di~closed 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, said
disclosures being incorporated herein by reference.
Polycarboxylate builder can generally be added to the
composition in acid form, but can also be added in the form of a
neutralized salt. When utilized in salt form, alkali metals, such
as sodium, potassium, and lithium salts, especially sodium salts, or
ammonium and substituted ammonium (e.g., alkanolammonium) salts are
prefer~ed.
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
includ~ oxydisuccinate, as disclosed in ~erg, U.S. Patent 3,128,287,
issued April 7, 196~, and Lamberti et al., U.S. Patent 3,635,830,
issued January 18, 1972, both of which are incorporated herein by
reference.
WO 92/06153 PCI'/US91/07022
2 ~ 3 7
- 23 -
A specific type of ether polycarboxylates useful as builders in
the present invention also include those having the general formula:
C (~)(COOX)-CH(COOX)-O-C~(COOX)-C~COOX)(B)
wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); and X is H or
a sllt-;nr~inn clt~on For example, if in the above general formula
A and 3 ~re '~oth H, then the compound is oxydissuccinic acid and its
:~ata, s~lub,e sal',. Ic ~ is 0~ and ~ is H, then the compound is
tartra~ morosuccinic acid (TMS) and its water-soluble salts. If A
is l anu ~ COA~-C~I2(COOX)~ then the compound is tartrate
disuccm~ rD~) ~înd l~s ~a. r-soluble salts. Mixtures of
thes~ ~ni d~ns ar~ ~sperially pr~ferred for use herein.
Par L icùi~ i\J ar~ rrad are mix-urPs o~ T~S and TDS in a weight ratio
of T~lS to IDS of from about 97:3 to about 20:80. ~hese builders are
d~ ?~ .~?', ~ss~'~d L~ ~sh ~t al., on ~ay 5,
19&,.
Suitable ether polycarboxylates also include cyclic compounds,
particularly alicyclic compounds, such as those described in U.S.
Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903,
all of which are incorporated herein by reference.
Other useful detergency builders include the ether hydroxypoly-
carboxylates represented by the structure:
HO-IC(R)(COOM)-C(R)(COOM)-O~n-H
wherein M is hydrogen or a cation wherein the resultant salt is
water-soluble, preferably an al~ali 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 ~) and each R is the same or different and selected from
hydrogen, C1 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 carboxymethyloxysuccinic
acid.
Organic polycarboxylate builders also include the various
3j alkali metal, ammonium and substituted ammonium salts of polyacetic
acids. Fxamples of polyacetic acid builder salts are the sodium,
potassium, lithium, ammonium and substituted ammonium salts of
ethylenediamine tetraacetic acid and nitrilotriacetic acid.
WO 92/06153 PCr/US91/07022
r~ 24
Also included are polycarboxylates such as mellitic acid,
succinic acid, polymaleic acid, benzene 1,3,;-tricarboxylic acid,
benezene pentacarboxylic acid, and carboxymQth~lcx"s:os~nic ~c
and soluble salts thereof.
Citric builders, e.g., citric acid and soluble sa~ eneo~
is a polycarboxylate builder of particular impor~ance ,~on neavy du~y
li~uid detergent formulations, but can ~lSQ ~e Use~ ir. s~
compositions. Suitable salts incluàe ~he me~al s~l~s such lS
sodium, lithium, and potassium salts, as e~ ~m,ni j ~n~,
substituted ammonium salts.
Other carboxylate builaers inciuae ~ne c;lnooxY,~~èl;
carbohydrates disclosed in U.S. P~t~n~
March 28, 1973, incorporated herein by rêference.
Also suitable in the deteng2nt com~o~ ~ on~ O~ e ?~?s~n~.
lS invention are the 3,3-dicarboxy-4-oxa-1,5-hex~ned ~ s ~n~ ~hQ
related compounds disclosed in U.S. Patent ~,56O,g8~, ~usnh, issued
January 28, 1986, incorporated herein by reference. Useful succinic
acid builders include the Cs-C20 alkyl succinic acids and salts
thereQf. A particularly preferred compound of this type is
dodecenylsuccinic acid. Alkyl succinic acids typically are of the
general formula R-CH(COOH)CH2(COOH) i.e., derivatives of succinic
acid, wherein R is hydrocarbon, e.g., Clo-C20 alkyl or alkenyl,
preferably C12-C16 or wherein R may be substituted with hydroxyl,
sulfo, sulfoxy or sulfone substituents, all as described in the
above-mentioned patents.
The succinate builders are preferably used in the form of their
water-soluble salts, including the sodium, potassium, ammonium and
alkanolammonium salts.
Specific examples of succinate builders include: laurylsuccin-
ate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate
(preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin-
ates are the preferred builders of this group, and are described in
European Patent Application 86200590.5/0,200,263, published November
5, 1986.
Examples of userul builders aiso include sodium and potassium
carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohex-
anehexacarboxylate, cis-cyclopentan~-tetracarboxylate, water-solubFe
polyacrylates (these polyacrylates having molecular weights to above
WO 92/06153 PCI'/US9]/07022
- 25- ,~ nC~ '3r~7
about 2,000 can also be effectively utilized as dispersants), and
the copolymers of maleic anhydride with vinyl methyl ethQr or
ethylene.
Other suitable polycarboxylates are the polyace'al carboxylates
disclosed in U.S. Patent 4,14~,226, Crutchfield et al... issued ,'~arcn
13, 1979, incorporated herein by rP,~erence. In i~ ,'O~j~iCeCd~
carboxylates can be prepared by bringing together, under polymeriza~
tion conditions, an ester of glyoxylic ac~d and 1 poly,e~~ ~a ion
initiator. The resulting polyacetal carboxylate estQr is then
attached to chemically stable end groups ~o i'abili_~ ~he ~'O~ C~C21
carboxylate against rapid depolymerizatio~ in all~al'~? '.~ i?r.
convertQd to ~he corr~spondins salt, and ~ddad 'o a ,u ~sc~sn~.
Polycarbox~late builders are ~lso ~ls losQd iu .,'.~~. ,'a~an~
3,303,067, Diehl, issued ,'~arch ~, '9i7, ~ncur~ura. ~ "e;~c~
reference. 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, citra-
conic 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.
EnzYmes
Detersive enzymes can be included in the detergent formulations
for a variety of reasons including removal of protein-based,
carbohydrate-based, or triglyceride-based stains, for example, and
prevention of refugee dye transfer. Tne enzymes to be incorporated
include proteases, amylases, lipases, cellulases, and peroxidases,
as well as mixtures thereof. They may be of any suitable origin,
such as vegetable, animal, bacterial, fungal and yeast origin.
However, their choice is governed by several factors such as
pH-activity and/or stability optima, thermostability, stability
versus active detergents, builders and so on. In this respect
bacterial or fungal enzymes are preferred, such as bacterial
amylases and proteases, and fungal cellulases.
W 0 92/06153 ~ 7 - 26 - PCT/US91/07022
Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B.subtilis and B.licheniforms.
Another suitable protease is obtained from a strain of Bacillus,
having ,na~i"ui~ activity througnout the pH range of 8-12, developed
and sold ~y ~ovo Industries A/S under the registered trade name
Espe~ hq ~~a~a~at ~n a-f 'hls en~me and analogous enzymes is
described n 3rltish patent speci'ication No. 1,243,784 of Novo.
Proteoiy~.,c all.,-m2s iui~able ,or removing protein-based stains that
are co,~,~rc.ally availab1e include those sold under the tradenames
ALC~L~S '' ~' S:i~.ir!i~S ~ y ,~ovo Inàustries A/S (Denmark) and
PlA'tA~;S~-;' ay ;n~at~ lonal 3io-~ynthQtics, Inc. (The Netherlands).
0~ a ca''ao3rv of pro~eolvtic enz~vmes, especially
for liqui-i de~r~Qn' compositions, ~re en7ymos referred to herein as
protoaSa 4 an~ Dro~e~s~ Q, 9_ol ~ase ,~ ~nd m~thods for its prepar2-
',an ~ s '- _ H~ n~ n ~ en' ~ppiication 130,7~o, published
January 9, 1~ , incorpora-ced herein by reference. Protease B is a
proteolytic ~nzyme 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 descri~bed in European Patent Application
Serial No. 87303761.8, filed April 28, 1987, incorporated herein by
reference. Methods for preparation of Protease B are also disclosed
in European Patent Application 130,756, Bott et al., published
January 9, 1985, incorporated herein by reference.
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), previously
incorporated herein by reference. Amylolytic proteins include, for
example, R~PTDAS~TM, International Bio-Synthetics, ~nc. and
TERMAMYLTM, Novo Industries.
The callulases 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. Datent 4,435,307, Barbesgoard et al., issued March 6, 1984,
incorporated herein by reference, which discloses fungal cellulase
produced from Humicola insolens. Suitable cellulases are also
disclosed in G3-A-2.075.02~; G3-A-2.095.27~ and DE-OS-2.247.832.
EV mP1eS ~f such cellulases ar~ cellulases produced by a strain
Ot Humicola insolens (Humicola grisea var. thermoidea), particularly
w o 92/061~3 PCT/USg1/07022
- 27 - ~a;~ 7
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 marin~ mollusc (Dolabella Auricula Solander)
Sui~ lipase enzymes for detergent usage include those
?rcd~ :'d '- :l.O.~O~ ?.nisms 0l i.he Pseudomonas group, such as
Pseudomon-~s itut.Pri ATCC 19.15~, as disclosed in British Patent No.
1,3ï2~31~ ~ncorporat.ed herein by reference. Suitable lipases
include ~hos;~ ~hich show a positive immunoligical cross-reaction
wi~h 'il~ an.l~~d~ or tne lir~as~ roduc~d by the microorganism
Pse,~',Jiila,7~s , MiD~escen~ ,/. T'nis lipase and a method for its
pllrii''.i'.~ ;la~lQ, !~en ~e~crihi~d in ~jlpanese Patent Application No
53-~C'~7~ la ~ -ape" 'o ?Ub1 C iilsv~ction on February 24, 1978. This
li?~ s '-.bl~ m Mlla~o Pha,maceutical Co. !td., Nagoya,
1~ Japan, ùnù-n ;ne ~ e ilame Lipase P 'Amano," hereinafter referred
to as ilAmano-P." Such lipases of the present invention should show
a positive immunological cross rPaction with the Amano-P antibody,
using the standard and well-known immunod;ffusion procedure accord-
ing to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)).
These lipases, and a method for their immunological cross-reaction
with Amano-P, are also described in U.S. Patent 4,707,291, Thom et
al., issued November 17, 1987, incorporated herein by reference.
Typical examples thereof are the Amano-P lipase, the lipase ex
Pseudomonas frag7 FERM P 1339 (available under the trade name
2j Amano-B), lipase ex Psuedomonas nitroreducens var. 1ipo1yticum FERM
P 1338 (available under the trade name Amano-CES), lipases ex
Chromobacter viscosum, e.g. Chromobacter viscosum var. 7ipo1yticum
NRRLB 3673, commercially available ;rom Toyo Jozo Co., Tagata,
Japan; and further Chromo~acter viscosum lipases from U.S.
Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and
lipases ex Pseudo-~nas g1adio1i.
Peroxidase enzymes are used in combination with oxygen sources,
e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc.
They are used for "solution bleaching," i.e. to prevent transfer of
dyes or pigments removed from substrates during wash operations to
other substrates in the ~ash solution. Peroxidase enzymes are known
in the art, and include, For example, horseradish peroxidase,
ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
w o 92/06153 pcT/us91/n7o22
2~ 1 8 l 28 -
Peroxidase-containing detergent compositions are disclosed, for
example, in PC~ International Application WO ~9/099~13, publishe
October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
incorporated herein by reference.
A wide range of enzyme materials and m~an~ for ~"~i,~
incorporation into synthetic detPngent gr~nules i~ i ;o;~:
U.S. Patent 3,553,139, issued January 5, 1971 to McCarty ~t al.
(incorporated herein by reference). ~nzym s ar~ '~'3~ . ~ .J '. "
in U.S. Patent No. 4,101,~57, Place et al.~ issued Jul~/ 18
and in U.S. Patent ~,507,219, Hughes, issued .'arcn 'i~
incorporated herein by referencP. En ~/me m~ r; l~
liquid deters~nt fo,"ul~ions, a;,d ~ha" es,~o~
formulations, are disclos~d in U.S. ,'aten~ $1,0~-)0~, "on
issued Ap'~~il 14~ 1981~ aljo i,lco1pora~ed her~in oy ne,~n nc~
Enzymes are normally incorporated at levels sufficien~ ;o
provide up to about 5 mg by weight, more typica71y ~bout 3.05 ",9 to
about 3 mg, of active enzyme per gram of the composition.
For granular detergents, the enzymes are preferably coated or
prilled with additives inert toward the enzymes to minimize dust
formation and improve storage stability. Techniques for accomplish-
ing this are well known in the art. ln liquid formulations, an
enzyme stabilization system is preferably utilized. Enzyme stabili-
zation techniques for aqueous dètergent 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, perferably formates. See, for example, U.S. Patent
4,318,818, Letton, et al., issued March 9, 1982, incorporated herein
by reference. It has also been proposed to use polyols like gly-
cerol and sorbitol. Alkoxy-alcohols, dialkyl91ycoethers, mixtures
of polyvalent alcohols with polyfunctional aliphatic amines (e.g.,
alkanolamines such as diethanolamine, triethanolamine, di-isopropan-
olamine, etc.), and boric acid or al~ali metal borate. Enzyme
stabilization techniques are additionally disclosed and exemplified
in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al.,
U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al., both
incorporated herein by reference, and European Patent Application
W O 92/06153 PCT/~S91/07022
2i '~2~ 3'7
- 29 -
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 descri~od, for
example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
8leachinq ComPounds - Bleachinq Aqents and Sleach 4ctivato,s
The detergent compositions hereof may contain bleaching agen.s
or bleaching compositions containing bleaching agent and one or more
bleach activators. When present bleaching compounds wi~l typically
be present at l~vels of from about 1~' to about 2~ ore ~yp call~
from about 1% to about 10%, of th~ det?r~ent col,~pcsl~ ~n. i~l
general, Sleaching compounàs are optional CO;nDollencs in non- i iqula
formulations, e.g., granular detergents. I, pr~,an~, n~ mQun; ~,~
bleach activators will typically be from abou~ 0.i/o ~o abou~ 6û~o~
more typically from about 0.5% to about lO~o Ot t~he ble~c~lna
composition
The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other cleaning purposes that are now known or
become known. These include oxygen bleaches as well as other
bleaching agents~ For wash conditions below about 50-C, especially
below about 40-C, it is preferred that the compositions hereof not
contain borate or material which can form borate in situ (i.e.
borate-forming material) under detergent storage or wash conditions.
Thus it is preferred under these conditions that a non-borate,
non-borate-forming bleaching agent is used. Preferably, detergents
to be used at these temperatures are substantially free of borate
and borate-forming material. As used herein, "substantially free of
borate and borate-forming material'' shall mean that the composition
contains not more than about 2% by weiyht of borate-containing and
borate-forming material of any type, ~referably, no more than 1%,
more preferably 0%.
One category of bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable
examples of this class of agents include magnesium
monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro
perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and
diperoxydodecanedioic acid. Such bleaching agents are disclosed in
U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S.
WO 92/061S3 PCT/US91/07022
2 ~ 30 -
Patent Application 740,446, Burns et al., filed June 3, 1985,
European Patent Application 0,133,354, Banks et al., published
February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued
Novembe, 1, 1983, all of which are incorporated by reference herein.
Hishl~/ pre ~rred bleaching agonts also include 6-nonylamino-6-
oxo~e;''''''.!e'~''''~'' lC'G ?.5 ~esc i~d in U.S~ Patent 4,634,SSl, issued
January ~, 1''~7 to 3urns, et al., incorporated herein by reference.
.~no~e~ calQgor~ of bleaching agents that can be used encom-
passes ~ nalog~on bleaching ag~onts. ~xamples of hypohalite bleach-
ing ~ n~ . ?X~pl~, includo trichloro isocyanuric acid and the
sodium and ~or?.sslun dichloroisoc~/anurates and N-chloro and N-bromo
n~ l s ''~ d~d lt 0 . 5~1~~o
by ~ei~;h' ~~ ~h~ , nisll?d i),o('uct, ~refor~bly l-~C~o by ~.~eight~
~ ;~e; .~ e~ ;an:~ :a~ so bo us~d. Suitabl~ peroxy-
1~ gen ~i~ cni~y c~atpounos inciude sodium carsonate peroxvhydrate,
sodium ?yrophosphate ~eroxyhydrate, urea peroxyhydrate, and sodium
peroxide.
Peroxygen bleaching agents are preferably combined with bleach
activators, which lead to the in situ production in aqueous solution
(i.e., during the washing process) of the peroxy acid corresponding
to the bleach activator.
Preferred bleach activators incorporated into compositions of
the present invention have the general formula:
o
R - C - L
wherein R is an alkyl group containing from about 1 to about 18
carbon atoms wherein the longest linear alkyl cha;n extending from
and including the carbonyl carbon contains from about 6 to about 10
carbon atoms and L is a leaving group, the conjugate acid of which
has a pKa in the range of from about 4 to about 13. These bleach
activators are described in U.S. Patent 4,915,854, issued April 10,
1990 to Mao, et al., incorporated herein by reference, and U.S.
Patent 4,412,934, which was previously incorporated herein by
reference.
3~ Bleaching agents other than oxygen bleaching agents are also
~nown in the ~rt and c~n be utili7ed herein. One type of non-oxygen
bleaching agont of particular in erest includes photoactivated
bleaching agents such as the sulfonated zinc and/or aluminum
W O 92/06153 P~r/US91/07022
2~3'~7
- 31 -
phthalocyanines. These materials can be deposited upon the sub-
strate during .he washing process. Upon irradiation with light, in
the presenco of ox~g3n, such as by hanging clothes out to dry in the
daylight, ~he .ulfonated zinc phthalocyanine is activated and,
conseouen'lv. tha substrate is bleached. Preferred zinc phthalocya-
nine ana a o;loL~ac~ivated Dleaching process are described in U.S.
Patent ~ 3 ?~ i,sued July 5, !977 to ~olcombe et al., incorpor-
ated nerein ~y rererence. Iypically, detergent compositions will
COn~ a"cl.Z'. l.u~~5''~ 'o ~.bo!lt l~A~;A~ y weight, of sulfonated zinc
} U p i~
Polv~er~ ? ~ S ~ i~q ~
~ ''i''' r~ e~_ -;'-'; n'ia:lS' asan~s '.~nown to those skilled in the
art can be employed in tne practice of this invention. Polymeric
soil re~ r.'.s aYo charlctr.r~.-ed bv having both hydrophilic
S3smQntS, to ~vdr~?hil~,~a 'he .urflc~ of hydrophobic fibers, such as
polyester and nylon, and hydrophobic segments, to deposit upon
hydrophobic fibers and remain adhered thereto through completion of
washing and rinsing cycles and, thus, serve as an anchor for the
hydrophilic segments. This can enable stains occurring subsequent
to treatment with the soil release agent to be more easily cleaned
in later washing procedures.
Whereas it can be beneficial to util ke polymeric soil release
agents in any of the datergent compositions hereof, especially those
compositions utilized for laundry or other applications wherein
removal of grease and oil from hydrophobic surfaces is needed, the
presence of polyhydroxy fatty acid amide in detergent compositions
also containing anionic surfactants can enhance performance of many
of the more commonly util ked 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-interlctive.
The compositions hereof for which improved polymeric soil
release agent performance can b3 obtained through the use of
polyhydroxy fatty acid amide are those which contain an anionic
surfact nt system, an anionic surfactant-interactive soil release
agent and a soil release agent-enhancing amount of the polyhydroxy
w o 92/061~3 ~ Q ~ 2 ~ 8 7 PCT/USg1/07022
- 32 -
fatty acid amide (PFA), wherein: (I) anionic surfactant-
interaction between the soil releas2 ~gent and th~ ~nionic
surfactant system of the detergent composition can be sho~Yn by a
comparison of the level of soil release ~gon~ ~S~A~ ~ioposltio~ on
hydrophobic fibers (e.g., polyester) in aqueous solu~io,~ ~e~!aan (')
a "Control" run wherein deposition oi~ n- ~ o ~,.a d ;a:~g ~.;
composition ;n aqueous solution, in the absence o; the othor
detergent ingredients, is measur~d, a..d ~, a" '~;~A,~i;',.iilic
surfactant'' test run where;n the same ty?e lnd amQI'nt e~- ''ao ln',OniC
surfactant system utiliz~d in detergen~ p~s ~ ~n ~ ns~ ~
aqueous soluticn w th th~ S~A, at ~h a~ ;;a s, ~; ,J
the anlonic surîac~an~ sys'~m o; tile ie~ p~s:: n~
reduced depositton in (D) relati~é c~ ~-i, i,àlca~s ~,.io,";-
surfactant in~eraction; and ~ hether -~no ~a~rc~n. c.~m~oii~lon
contains a soil release agent-enhancing amount o' polyhvdro~y ~at~v
acid amide can be determined by a comparison o,' the SRA deposi~ion
of the SRA/Anionic surfactant test run of (B) with soil release
agent deposition in (C). an "SRA/Anionic surfacta~t/PFA test run"
wherein the same type and level of polyhydroxy fatty acid amide of
the detergent composition is combined with the soil release agent
and anionic surfactant system corresponding to said SRA/Anionic
surfactant test run, whereby improved deposition of the soil release
agent in test run (C) relative to test run (B) indicates that a soil
release agent-enhancing amount of polyhydroxy fatty acid amide is
present. For purposes hereof, the tests hereof should be conducted
at anionic surfactant concentrations in the aqueous solution that
are above the critical micelle concentration (C~1C) 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 solu-
tions for the respective test runs for a period of 12 minutes, then
removed, and analy~ed. 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
W O 92/06153 PC~r/US91/07022 2n~l37
- 33 -
determined in the above test runs (i.e., test runs A, B, and C) by
determination of ultraviolet light (UV) absorbance of the test
solutions, according to techniques well known in the art. Dec,Aeased
UV absorbance in the test solution after removal of the hydrophobic
fiber material corresponds to increased SRA d~30sition. ~s ~ e
understood by those s~illed in the art, UV analysis should not be
utilized for test solutions containing types and l-~!els Oe matA-rials
which cause excessive UV absorbance inLer~'erence, such as high
levels of surfactants wiLh aromatic ~roups ~e.~,., al'v~l be,-ene
sulfonates, etc.).
Thus by "soil release agent-ennancing imoiln~" or ~olyhy.ro~
fatty acid amide is meant an alnoun' o,~ sue,l s r,~actai,; ~na; will
enhance deposition Ot the soil release agent upon hvdroDhobic
fibers, as described ~bo~ r ~n ~m o~ 1. ~
grease/oil cleaning performance can be obtainc~A 'or 'abric, waiiled
in the detergent composition hereof in the next subsequent cleaning
operation.
The amount of polyhydroxy fatty acid amide needed to enhance
deposition will vary with the anionic surfactant selected, the
amount of anionic surfactant, the particular soil release agent
chosen, as well as the particular polyhydroxy fatty acid amide
chosen. Generally, compositions will comprise from about 0.01% to
about 10%, by weight, of the polymeric soil release agent, typically
from about 0.1% to about 5XO~ and from about 4~O to about SO,O, more
typically from about 5~ to about 307a of anionic surfactant. Such
compositions should generally contain at least about 1%, preferably
at least about 3X, by weight, of the polyhydroxy fatty acid amide,
though it is not intended to necessarily be limited thereto.
The polymeric soil release agen:s for which performance ;s
enhanced by polyhydroxy fatty acid amide in the presence of anionic
surfactant include those soil release agents having: (a) one or
more nonionic hydrophile components consisting essentially of (i)
polyoxyethylene segments with a degree of polymerization of at least
2, or (ii) oxypropylene or polyoxypropylene segments with a degree
of polymerization of from 2 to 10, wherein said hydrophile segment
does not encompass any oxypropylene unit unless it is bonded to
adjacent moieties at each end by etner linkages, or (iii) a mixture
of oxyalkylene units comprising oxyethylene and from 1 to about 30
W o 92/06153 c~ 34 PCT/~S91/07022
oxypropylene units wherein said mixture contains a sufficient amount
of oxyethylene units such that the hydrophile component has hydro-
philicity great enough to increase the hydrophilicity of conven-
tional polyester synthetic fiber surfaces upon deposit of the soil
S rele~se ~9e?.t on such surface, said hydrophile segments preferably
co~r ~-~3 ~ t ~bout 25~' oxyethylenQ units and more preferably,
especially ~Cor such components having about 20 to 30 oxypropylene
units, ~t !e~st ~bout 50~~ oxyethylene units; or (b) one or more
hydrophobe components comprising (i) C3 oxyalkylene terephthalate
s2s"e~ e~ sa;d hydrophobe components also comprise
oxvetlYiene tene~h+h~late, th~ ratio of oxvethylene terephthalate-C3
oV~ q ~ ?-?~ hC'~ 0~ r, ~ii) C~-CO
alk~lene or o~o 6~-6~ lk~lenQ sesnents, or mixtures thereof, (iii)
pol~ yi ~ .j sqgmerts, pre.~~rioly poly~vinyl ac~tate), having
a dpsr~e o, pol~mori~ation of at least 2, or ~iv) Cl-C4 alkyl ether
or C~ hydroxyal~yl ether substituents, or mixtures thereof, wherein
said substituents are present in the form of Cl-C4 alkyl ether or C4
hydroxyalkyl ether cellulose derivatives, or mixtures thereof, and
such cellulose derivatiYes 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 sur-
faces and retain a sufficient level of hydroxyls, once adhered to
such conventional synthetic fiber surface, to increase fiber surface
hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segments of (a)(i) will have a
degree of polymerization of from 2 to about 200, although higher
levels can be used, preferably from 3 to about 150, more preferably
from 6 to about 100. Suitable oxy G4-C6 alkylene hydrophobe seg-
ments include, but are not limited to, end-caps of polymeric soil
release agents such as M03S(CH2)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, incorporated herein by
reference.
Polymeric soil release agents useful in the present invention
include cellulosic derivatives such as hydroxyether cellulosic
polymers, copolymeric blocks of ethylene terephthalate or propylene
terephthalate ~ith polyethylene oxide or polypropylene oxide
terephthalate, and the like.
W O 92/06153 PC~r/US91/07022~ '~ " 2 ~ ~ ~
- 35 -
Cellulosic derivatives that are functional as soil release
agents are commercially available and include hydroxyethers of
cellulose such as ~ethocelR (Dow).
C~llulosic soil release agents for use herein also include
those selectQd from the group consisting of Cl-C4 alkyl and C4
hydroxyal~yl ce71ulose such as methylcellulose, ethylcellulose,
hydroxynropv1 mQthvlcellulose, and hydroxybutyl methylcellulose. A
variety or~ cellulose derivatives useful as soil release polymers are
disclo~~d 'n IJ.S. ~ateRt 4,000,093, issued December 28, 1976 to
1~ ,licol, ~ ,., "~oorpo,a~ her in by reference.
Oi i ~e'leaSa agen~s characterized by poly(vinyl ester)
~y~re/~o;! ,a-,meil~s '"lclu~e gra,t copolymers of poly(vinyl ester),
e.g., Cl-O~ vinyl esters, preferably poly(vinyl acetate) grafted
onto oQ~ 'c~lene oxide bac~bones~ such as polyethylene oxide
lS bac~bcnes. S~ch m,at rials a,e '~nown in the art and are described in
European Patent Application 0 219 048, published April 22, 1987 by
Kud, et al. Suitable commercially availa~le soil release agents o~
this kind include the SokalanTM type of material, e.g., SokalanTM
HP-22, available from BASF (West Germany).
One type of preferred soil release agent is a copolymer having
random blocks of ethylene terephthalate and polyethylene oxide (PEO)
terephthalate. More specifically, these polymers are comprised of
repeating units of ethylene terephthalate and PEO terephthalate in a
mole ratio of ethylene terephthalate units to PEO terephthalate
units of from about 25:75 to about 35:65, said PEO terephthalate
units containing polyethylene oxide having molecular weights of from
about 300 to about 2000. The molecular weight of this polymeric
soil release asent is in the range of from about 25,000 to about
5i,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976,
which is incorpc~ated by reference. See also U.S. Patent 3,893,929
to Basadur issued July 8, 19?5 (incorporated by reference) which
discloses similar copolymers.
Anoth~r pr~f~rred polymeric soil r~lease agent is a polyester
with repeat units of ethylene terephthalate units containing 10-15%
by weight of ethylene ter~phthalate units together with 90-80% by
weight of polyoxyethylene terephthalate units, derived from a
polyovyethylene glycol of average molecular weight 300-5,000, and
the mole ratio of ethylene terephthalate units to polyoxyethylene
W o 92/06153 PCT/US91/07022
2 ~ 9 ~ 36 -
terephthalate units in the polymeric compound is between 2:1 and
6:1. Examples of this polymer include the commerciall~ a'/ailabl2
material ZelconR 5126 (from Dupont) and MileaseR T (from IGI). These
polymers and methods of their preparation are ~oro l'U~ / describe~
in U.S. Patent 4,702,857, issued October ~ 7 o ~csselin~
which is incorporated herein by reference.
Another preferred polymeric soil release aaent is a sulfonated
product of a substantially lin~r ~st~~ o;,ga,-,~er Cv~ o, .n
oligomeric ester backbone of terephthalovl a1-d ox~al k'!l ?nee'O~ reee?~t
units and terminal moieties coYalently l a
said soil r~l~as~ ag~nt ~i"s ler,~; d f;~ IvvkJI vnU~'la~e~
dimethyl ~erephthala~, and î, f ,~j~Qe '!, n~ .. !' ~ ,' !,' ,' i, .'.'
sulfonation, the ter~inal moieties o; e1c o,,g~",~r na~ie~ o"
average, a total of ;rom about i to aDou~ ,ui,-ona e ~r~u;~s. ~he~e
soil release agents are described fully in U.S. Patent ~!958,~
issued November 6, 1990 to J. J~ ScheibPl and ~. P. Goss~link, ~.S.
Serial No. 07/474,709, filed January 29t 1990, incorporated herein
by reference.
Other suitable polymeric soil release agents include the ethyl-
or methyl-capped 1,2-propylene terephthalate-polyoxyethylene
terephthalate polyesters of U.S. Patent 4,711,730, issued December
8, 1987 to Gosselink et al., the anionic end-capped oligomeric
esters of U.S. Patent 4,721,580, issued January 26, 1988 to
Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy
groups derived ~rom polyethylene glycol (PEG), the block polyester
oligomeric compounds of U.S. Patent 4,702,857, issued October 27,
1987 to Gosselink, haYing 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, all of these patents being incorporated
herein by reference.
Additional polymeric soil release agents include the soil
release agents of U.S. Patent 4,877,896, issued October 31, 1989 to
Maldonado et al., which discloses anionic, especially sulfoaroyl,
end-capped terephthalate esters, said patent being incorporated
herein by reference. The terephthalate esters contain
unsymmetrically substituted oxy-1,2-alkyleneoxy units. Included
among the soil release polymers of U.S. Patent 4,877 896 are
materials with polyoxyethylene hydrophile components or C3
W o 92/06153 2 ~ g ~ /US91/07022
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 ;rom the inclusion
of the polyhydroxy fatty acid amides hereof in the presence of
anionic surfactants.
If ut;lized, soil release agents will generally co~priae from
about 0.01% to about 10.0%~ by weight, of che de~ergent comoositions
herein, typically from about 0.1~o to abou. 5~', prererably from about
0.2% to about 3.0~'0.
Chelatinq Acents
The detergent composi~ions herein ,nav al~ "~
one or more iron and manganese chelating ager. s as a ~Ul~dQ- ~J'U
material. Such chel~ting agonts ean be selq~'~d rr~ .he 9'~~
consisting o,~ amino carbox~,a~ à~ a,'";~lv phOâvhvna;ei,
polyfunctionally~substituted aromatic chelating agents and mixtures
thereof, all as hereinafter defined. Without intending to be bound
by theory, it is belieYed that the benefit of these materials is due
in part to their exceptional ability to remove iron and manganese
ions from washing solutions by formation of soluble chelates.
Amino carboxylates useful as optional chelating agents in
compositions of the invention can have one or more, preferably at
least two, units of the substructure
CH2 ~
N - (CH2)X - COOM,
wherein M is hydrogen, alkali metal, ammonium or substituted
ammonium (e.g. ethanolamine) and x is from l to about 3, preferably
l. Preferably, these amino carboxylat~s do not contain alkyl or
alkenyl groups with more than about 6 carbon atoms. Operable amine
carboxylates include ethylenediaminetetraacetates, N-hydroxyethyl-
ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine
tetrapropriQnates, triethylenetetraaminehexaacetates, diethylenetri-
aminepentaacetates, and ethanoldiglycines, al~ali 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 lo~ level
of total phosphorus are permitted in detergent compositions.
w o 92/n6t53 PCT/US91/07022
~ 38 -
Compounds with one or more, preferably at least two, units of the
substructure
CH
(CH2) X - P~3M2 .
~herein ~ is hydrogen, alkali metal, ammonium or substituted
a!nmon-.~ n ~ om ~o ~bout 3, pre;er~bly 1, are useful and
include ethylenediaminetetrakis ~methylenephosphonates), nitrilotris
(metn~lenephosphonates) and diethylenetriaminepentakis (methylene-
phosphonates). ~refQr~bly, these amino phosphonates do not contain
al!~ enJ~l ~roups ~Yith more than about 6 carbon atoms.
Alky~an~ ~3ro~ can be sildred by substructures
~7l\/-5~ ituted ~romatic chelating ~gQnts are also
use~ t~i~ comDosi~ions herein. These materials can comprise
C ;)~ 5 ~ ~1 ? ~; _ il ? 'l~ a ~ u l a
v11
R~"~ ,OH
101
R ~ R
R
wherein at least one R is -S03H or -COOH or soluble salts thereof
and mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974,
to Connor et al., incorporated herein by reference, discloses
polyfunctionally-substituted aromatic chelating and sequestering
agents. Preferred compounds of this type in acid form are dihy-
droxydisulfobenzenes such as 1~2-dihydroxy -3,5-disulfobenzene.
Alkaline detergent compositions can contain these materials in the
form of alkali metal, ammonium or substituted ammonium (e.g. mono-
or tr;ethanol-amine) salts.
If utilized, these chelating agents will generally comprise
from about 0.1% to about 10% by weight of the detergent compositions
herein. More preferably chelating agents w;ll comprise from about
0.1% to about 3.0% by weight of such compositions.
Clav Soil Removal/Anti-redeDosition Aqents
The compositions of the present invention can also optionally
contain water-soluble ethoxylated amines having clay soil removal
and anti-rQdeposition properties. Granular detergent compositions
which contain these compounds typioally contain from about 0.01% to
about 10.0% by weight of the ~;ater-soluble ethoxylated amines;
w o 92/06153 PCT/US91/07022
~ 39 ~ '~09218~
liquid detergent compositions, typically about 0.01% to about 5%.
These compounds are selected preferably from the group consisting
of:
(l) e~hoxylated monoamines having the formula:
S ('~-L-)-N-(R2)2
.h~yl~'~d di-min s havin3 the Sormula:
2 (R2)2-N-,Rl-N-(R2)2
L L L
'~ X X
cr
;; L ' ~ - N - ~ ~2 ) 2
;o~ d ~ amilles ~aving the formula:
~2
~3 rl~ql~ 4~ ]i~
;;) ~ .n~ ,~o'.Jiimars having the general formula:
R2
~(R2)2-N~ Rl~N3xERl~N3yERl-N-L-x)z
L
X
and
(5) mixtures thereof; wherein Al is
O O O O O
11 u I ~
~NC-, -NCO-, -NCN-, -CN-, -OCN-,
R R R R R R
O O 0 00
-CO-, -OCO-, -OC-, -CNC-,
or -0-; R is H or Cl-C4 alkyl or hydroxyalkyl; Rl is C2-Cl2
alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a
C2-C3 oxyàlkylene moiety having from 2 to about 20 oxyalkylene units
pro~ided that no O-N bonds are formed; each R2 is Cl-C4 or
hydroxyal,byl, the moiety -L-X, or two R2 together form the moiety
-(CH2)r, -A2-(CH2)S-, wherein A2 is -O- or -CH2-, r is l or 2, s is
l or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group
or mixtu,e ther~of; ~3 is a substituted C3-C12 alkyl, hydroxyalkyl,
al~enyl, aryl, or alk~ryl group ha~ing substitution sites; R4 is
Cl-Cl2 alkyl~ne, hydroxyalkylene, alkenylene, arylene or alkarylene,
W O 92/06153 PCT/US91/07022
2~2~7 - 40 -
or a C2-C3 oxyalkylene mo;ety having from 2 to about 20 oxyalkylene
units provided that no 0-0 or O-N bonds are ,or,,,ed; L ii 1 hydro-
philic chain which contains the polyoxyalkylene moiet~ -~(RSO)m-
(CH2CH20)n]-, wherein R5 is C3-C4 alkyl-ne or hydro~yal~yl~,lo ~nd m
and n are numbers such that the mole~y -(C'I2C;i~jn- ~,r s~s a~
least about 50% by weight of s~id ~ e~ e,e ;~ ; ,o~
monoamines, m is from O to about 4, and n is at least about 12; for
said d;amines! m is from O to aboll~ 3, an~ be~
when Rl is C2-C3 alkylene, hydroxyalkyleno~ or ai'<en~l na~ and at
least about 3 when Rl is other ~han ~ ?il ' . '' ' ' ''"~ ?
or alkenylene; for said ~oly~mi~-s
to about 1~ and n is a~ l ast abou' ~;
O; t is 1 or 0, pro~ided th~t t is 1 ~.en 9 ,~ ~ on
+ z is ~t 12as~ 2i a~à y ~ ; a~ "~
15 release and anti-redeposition agent is echoxyla~d -tecr~e~h~lene-
pentamine. Exemplary ethoxylated amines ar further dasoribed in
U.S. Patent 4,597,898, VanderMeer, issued ?ul y 1, 1986, incorporated
herein by reference. Another group of preferred clay soil removil/
anti~redeposition agents are the cationic compounds disclosed in
European Patent ApplicatiQn 111,965, Oh and Gosselink, published
June 27, 1984, incorporated herein by reference. Other clay soil
removal/anti-redeposition agents which can be used include the
ethoxylated amine polymers disclosed in European Patent Application
111,984, Gosselink, published June 27, 1984; the .witt2rionic
polymers disclosed in European Patent Application 112,532,
Gosselink, published July 4, 1984; and the amine oxides disclosed in
U.S. Patent 4,54B,744, Connor, issued Octob~r 22, 1985~ all of ~hich
are incorporated herein by reference.
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 tCMC) materials. These mater;als are well known in
the art.
Brightener
Any optical brighteners or other brightening or whitening
agents known in the art can be incorporat d into the detergent
compositions hereof.
W O 92/06153 PC~r/US91/0702' - 41 - ~ ~ ~2~ ~
The choice of brightener for use in detergent compositions will
depend upon a number of factors, such as the type of detergen~, the
nature of other components present in the detergent composition~ ~he
temperatures of wash water, the degree of agitation, and the ra.io
of the material washed to tub size.
The brightener selection is also dependen~ upon t~ ~ype o,~
material to be cleaned, e.g., cottons, synthetics, etc. Since most
laundry detergent products are used to cle2n a va ,Pty c,A ,~a~r c,,
the detergent compositions should contain a mi~ture of brighteners
which will be effective for a variety of fabrics. It is ~- c~u-~~
necessary that the individual ccm?onents~ o~ ,u;h a '~r,~ ee
mixtu,2 be cor"pat;ble.
Commercial optical brighteners which ,n~y ;e useru~, ln ~"e
present invention can be classified into subgroups whicn inc~uae,
but are not necessarily limited to, derivatives of stilhene,
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 Agentsn, M. Zahradnik, Published by John
Wiley & Sons, New York (1982), the disclosure of which is
incorporated herein by reference.
Stilbene derivatives which may be useful in the present
invention include, but are not necessarily limited to, derivatives
of bis(tria~inyl)amino-stilbene; bisacylamino derivatives of
stilbene; triazole derivatives of stilbene; oxadiazole derivatives
of stilbene; oxazole derivatives of sti'lbene; and styryl derivatives
of stilbene.
Certain derivatives of bis(triazinyl)aminostilbene which may be
useful in the present invèntion 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
WO 92/06i~ 7 PCT/US91/07022
~ 42 ~
derivativesi naphthalenedicarboxylic acid derivatives; heterocyclic
acid deriYatives; and cinnamic acid derivatives.
Cinnamic acid deri~atives which may be useful in the present
invention can be further subclassified into groups which include,
5but ~re not necessarilV limited to! cinnamic acid derivatiYes,
styrylaaolas~ styrylbenzo;urans~ styryloxadiazoles, styryltriazoles,
and 5t~r~lpol~!phenvls, ~s disclosod on pago 7; of the Zahradnik
referenc~.
~'.1? ;~ ol ~s can 'ae ~ur'her subclassified into styrylbenz-
10oxa o~ ;mi ii"o~S ~nd i~r~lthi~xolDs, as disclosed on page
78 or ~na aln~l~ni;~ ,e~?rence. ït will be understood that these
L~re_ _a:n~.i'ia'_ ~ bo ' ass ~S nay not nec~ssarily reflect an exhaus-
tive lis'~ o-f subgroups into which styrylazoles may be subclassified.
~n~'.hor ela~ ~~ oe';nal br:nhteno-s ~hich -,ay be usoful in the
15presQnt in~.~nt on a a th~ der,vati~es of dibenzothiophene-5,5-
dioxide disclosed at page 741-749 of The Kirk-Othmer EncYcloDedia of
Chemical Technologv~ Yolume 3, pages 737-750 (John Wiley & Son,
Inc., 1962), the discl~sure of which is incorporated herein by
reference, and include 3,7-diaminodibenzothiophene-2,8-disulfonic
20acid 5,5 dioxide.
Another class of optical brighteners which may be useful in the
present invention include azoles, which are derivatives of
5-membered ring heterocycles. These can be further subcategorized
into moncazoles and bisa~oles. ~xamples of monoazoles and bisazoles
25are 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 K.rk-Othmer reference. Examples of such compounds
include brighteners derived from pyrazine and brighteners derived
30from 4-aminonaphthalamide.
In addition to the brighteners already described, miscellaneous
agents may also be useful as briahteners. Examples of such miscel-
laneous agents are disclosed at pages 93-95 of the Zahradnik refer-
ence, and include 1-hydroxy-3,6,8-pyrenetri- sulphonic acid; 2,4-
35dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolone-
disulphonic acid; and derivatives of pyrazoline- quinoline.
0th r specific examples of optical brighteners which may be
useful in the present invention are those identified in U.5. Patent
WO 92/06153 PCr/US91/07022
- 43 -
2~92137
4,790,856, issued to Wixon on December 13, 1988, the disclosure of
which is incorporated herein by reference. These brighteners
include the PhorwhiteTM series of brighteners from Verona. Other
brightln2rs ' s losed in this reference include: Tinopal UNPA,
5 Tinopal g~n~5 a~d Tlnopal S~'l; available from Ciba-Geigy; Arctic White
CC a.~ u ~ ;a,' b,e ,~,c~ ~ilton-Davis, located in
Italy; ~he 2-(~-styryl-phenyl)-2H- naphtholt1,2-d]triazoles;
4,~'-bis~ 3~'rll~ol~2-yl!~st,l- benes; 4,4'-bis(styryl)bis-
phenyls: and ~he y-aminocoumarins. Specific examples of these
bri~3nt.. l~.r. .lc~d~ eth~il-7-di2-'~/l- amino coumarin; 1,2-bis-
(-ben~lmie~azo!-'-~l?ethylnne l,~ dip~enyl~hrazolines; 2,5-bis-
~ ;t ~ 1 a~~h'"~~ ~d]oxazol~; and
2 - ( s ~ r ~ - à ~ o 1
''.h~ a bn ~;.t no;~; w;ic;, maj be useFul in the present
in~en~ion inciuà2 those 1lsclosed in U.S. Patent 3,646,015, issued
February 29, 1972 to Hamilton, the disclosure of which is incorpor-
ated herein by reference.
Suds SuDDressors
Compounds known, or which become known, for reducing or sup-
pressing the formation of suds can be incorporated into the composi-
tions 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 polyhy-
droxy fatty acid amide surfactant. Suds suppression is particularly
desirable for compositions intended for use in front loading auto-
matic washing machines. These machines are typically characterized
by having drums, for containing the laundry and wash water, which
ha~e 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 ~/ariet~ o, ,aterials may be used as suds suppressors in
the cor.,positions hereof. Suds suppr~ssors are well ~nown to those
skilled in the art. ~hey are generally described, for example, in
w o 92/06153 PCT/US91/07022
;~ ~S't 2 ~ ~ 7 - 44 -
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 encomDasses
monocarboxylic fatty acids and soluble jalts tha,8o,~~ i.tase
- 5 materials are discussed in U.S. Patent 2,9i~,347, issueG 6ep;a?~l~er27, 1960 to ~ayne St. John, said ~atent be,ng inconpoi~a~ed ilonain a;
reference. ~he monocarboxylic fatty acids, and salts thereof~ for
use as suds suppressor typ;cally have hydrocarb~1 ha~;s o~ ~' ;o
about 24 carbon atoms, preferably 12 to 18 carbon atom~. Suitlbl?
salts include the alkali metal salts such as sodiu,~ tn~m :~
llthium salts, ~nd ammonium ~nd ~lkanol?~mm~n.um ss : ~ T,~
materials are a p,~fer, ed cat240ry o, uds SUi'?,'i-i~.' i',' ' ~ ;
compositions.
The de~ergent compositions may also collcain non~,ur,~lc~an; Sl!~S
suppressors. These include, for example, list: nigh molecular
weight hydrocarbons such as paraffin, fatty acid estars ,e.g., ,~atty
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.,
sodium, potassium, lithium) phosphates and phosphate esters. The
hydrocarbons, such as paraffin and haloparaffin, can be utilized in
liquid form. The liquid hydrocarbons will be liquid at room
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 llO-C (atmospheric pressure). It is also known
to utilize waxy hydrocarbons, preferrably having a melting point
below about lOO-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., incorporated herein by
reference. The hydrocarbons, thus, include aliphatic, alicyclic,
aromatic, and heterocyclic saturated or unsaturaied hydrocarbons
having from about 12 to about 70 carbon atoms. The term "paraffin,"
WO 92/06153 PCl'lUS91/07022
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 co~?ris~s
silicone suds suppressors. This category includes thQ use of
polyorganosiloxane oils, such as polydimethylsiloxane~ dlsoersions
or emulsions of polyorganosiloxane oils or resins, and comvioa~ions
of polyorganosiloxane with silica particlQs whe~?in the
polyorganosiloxane is chemisorbed of fused on~o .ne silica.
Silicone suds supprPssors are well kncwn in the a,t ~ d a~e, ~o~
example, disclosed in U.S. Patent ~,255,77g, ,ssued ;la~ o
Gandolfo et al. and European ~aten~ App~ication No. ~~OiB~
published February 7, 1990, by Sta,ch, ~1. S., '~o~h ~ncan~v~a~
herein by reference.
Other silicone suds suppressors are disclosed ;~ a~.ent
3,455,839 which relates to compositions and processQs ~~r da~oa"1ns
aqueous solut;ons by incorporating therein small amounts of
polydimethylsiloxane fluids.
Mixtures of silicone and silanated silica are described, for
instance, in German Patent Application ~OS 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 ~eight 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
W O 92/06153 PCT/US91/07022
~ rl - 46 -
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
detersent for use in automatic laundry washing machines. The amount
of suds control ~Yill vary with the detergent surfactants selected.
For e~ ;?le~ ''n hi$n sudsiRg surfactants, relatiYely more of the
suds controiling agent is used to achieve the desired suds control
than with lessar foaming surfactants. In general, a sufficient
amount Ot suds supprPssor should be incorporated in low sudsing
detergent oo~positions so .hat the suds that form during the wash
cycle OT ~ne ~utomatic washing machine (i~e~, upon agitation of the
datQ~.'?n' ;~ eC'!~ ~olution ur~r th~ intend d wash te",pera~ul~e
and co,lcen'r1t,on conditions) do not exceed about 75~' of the void
~ J ~ ih~.?~'s r~nt~l"~nt ~r~ ra~ly ~e iuds do
not eV~o~d aoau~ ;ù~fO or said void volume, wherein the void volume is
determinPd as the difference between total volume of the containment
drum and the volume of the water plus the laundry.
The compositions hereof will generally comprise from 0% to
about 5Y. of suds suppressor. When utilized as suds suppressors,
monocarboxylic fatty acids, and salts thereof, will be present
typically in amounts up to about SY., by weight, of the detergent
composition. Preferably, from about 0.5% to about 3% of fatty
monocarboxylate suds suppressor is utilized. Silicone suds
suppressors are typically utilized in amounts up to about 2.0%, by
weight, of the detergent composition, although higher amounts may be
used. This upper limit is practical in nature, due primarly to
concern with keeping costs minimized and effectiveness of lower
amounts for effectively controlling sudsing. Preferably from about
.Ol~. to about lX of silicone suds suppressor is used, more
preferably from about 0.25% to about 0.5%. As used herein, these
weight percentage values include any silica that may be utilized in
combination with polyorganosiloxane, as well as any adjunct
materials that may be utilized. Monostearyl phosphates are
typically used in amounts of from about 0.1% to about 2%, by weight,
of the composition.
Hydrocarbon suds suppressors are typically utilized in amounts
ranging ;rom about .Oi~o to about 5.0%, although higher levels can
be used.
WO 92/06t53 PCI'/US91/07022
47 h~v32~37
Other Inaredients
A wide variety of other ingredients useful in detergent
compositions can be included in the compositions hereof, including
other active ingredients, carriers, hydrotropes, processing aids,
dyes or pigments, solvents for liquid formulations, etc.
Li~ ergent compositions can contain water and other
water-miscible solvents as carriers. Low molecular weight primary
or secondary alcohols exemplified by methanol, ethanol, propanol,
and isopropanol are suitable. Monohydric alcohols are preferred for
solubil, ing su,,~~c'ant, but polyols such as those containing from 2
to abo~ can~on atoms and from 2 to about 6 hydroxy groups (e.g.,
nr~"'/î'?!''? '''''~ t!~ylene glycol, gl~/cerine, ~nd 1,2-propanediol~
can al~o be us~d~
;'? '..''-'.';? '. ;omposit',ons hereor ~Yill ~referably be formulated
sucn ~i~d; ouriog use i,~ aqueous cleaning operations, the wash water
will have a pH of between about 6.5 and about 11, preferably between
about 7.~ and about 10.5. L;quid 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
recc--?nded usage levels include the use of buffers, alkalis, acids,
etc., and are well known in the art.
This invention further provides a method for improving the
performance of detergents containing polymeric dispersing agent and
detersive surfactant by add;tionally incorporating into such
2~ composition at least about lX, by weight, of the polyhydroxy fatty
acid amide surfactant described above.
Th;s ;n~ent;on further prov;des a method for cleaning
substrates, such as f;bers, fabrics, hard surfaces, skin, etc., by
contact;ng said substrate, with a detergent composition comprising
one or more anionic, nonionic, or cationic surfactants, at least
about O.5X, by weight, polymeric d;spersing agent, and at least 1%
of the polyhydroxy fatty acid amide.
The preferred surfactants, polymeric dispersing agents,
add;tional ;ngredients, and levels of such mater;als preferred from
the compos;tions hereof are also preferred in the above methods.
EXPERI~ENTdL
Ihis exempli~ies a process for making a N-methyl~
l-deoxyglucityl lauramide surfactant for use herein. Although a
w o 92/06ls3 pCl/US~l/07022
7 - 48 -
skilled chemist can vary apparatus configuration, one suitable
apparatus for use herein comprises a three-liter four-necked flask
fitted with a motor-driven paddle stirrer and a thermometer of
length sufficient to contact tne redciion me1ilJ,n. lne other two
5 necks of the flask are fitted with 2 nitroC'?~ S'Y'.?S~ id'?-~o~A?
side-arm (caution: ~ wide-hor~ n~
very rapid methanol evolution) to .whioh ,i connecied an ~,,icien~
collecting condenser and vacuu,~ ou~ie~. ',he ia~~~en is oonn ec ~ed tO
a n;trogen bleed and vacuum gaugt~ tilei ~.o ~n ijpiri,or and I ~rt~.
A 500 watt heating ma~tl~ v,~
controller ("Yariac") us~d j~O !nea~ '~,'' s~'~o '~vn '~ S _u ~ Aca~i Oil
lab-jac~ that it may be rsadily ;A~ 's~ ?,'
temperature of the reaction.
N-methylglucamine (I~S g~ n ~ q~
methyl laur~ta (~rcct n 1 ~a,"'~ ,-c
placed in a flas~. The solid/liquid i~iX~UrQ is hQa~ea ~.Yitn stirring
under a nitrogen sweep to form a melt (appr oxim,ately 25 ~inutes).
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.) Hg. vacuum. From this
point on, the reaction temperature is held at 150- C by adjusting
the Variac and/or by raising or lowering the mantle.
Within 7 minutes, first methanol bubbles are si3hted at the
meniscus of the reaction mixture. A vigorous reaction soon follow;.
Methanol is distilled over until its rate subsides. The vacuum is
adjusted to give about 10 inches Hg. (10/31 atm.) vacuum. The
vacuum is increased approximately as follcws ~in inches Hg. at
minutes): 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of
methanol evolution, heating and stirring are discontinued
co-incident with some foaming. The product is cooled and
solidifies.
The following examples are meant to exempli,~y compositions of
the present invention, but are not necessarily meant to limit or
otherwise define the scope of the invention, said scope being
determined according to claims whleh -ollow.
WO 92/06153 PCT/US91/07022
- 49 - 2 ~ 8 ~
EXAMPLES
The following examples are meant to exemplify compositions of
the present invention, but are not necessarily meant to limit or
otherwise define the scope of the inveilLion, said scope being
determined according to claims which tollo~
~XA,~lPI.~S l--
These examples show heavy duty granular detergent compositionsconta;n;ng polyhydroxy fatty ac;d ~m,.de ~nd rolJ~meric dispe.stns
agent.
Base Gra~nule t
C14-13 .~ yl Sul,~t~ '; ~ '; ~
C14 15 dlkyl ~thoxy(2.25~ SulCa~e
C12-18 Al~yl Sulea~
N-Methyl N-l-Deoxyglucityl
Cocoamide S.S5.5 i.5 7.3
Zeolite A 15.030.1 30.1 18.0
Sodium Citrate 7.5
Sodium Carbonate 18.518.5 18.5 18.5
Sodium Silicate 5.02.5 2.5 2.5
Sodium Sulfate 12.012.0 12.0 17.1
Sodium Polyacrylate (4500 MW) 1.54.5 3.0 2.0
Polyethylene Glycol (8000 MW) 1.11.0 3.0
Ethoxylated
Tetraethylenepentamine 2.0 3.0
~m~
Citric acid 8.0
Miscellaneous . 8.4 2.4 1.9 2.9
Residual Water 7.0 ~.0 7 0 __~ Q
100.0 100.0 100.0 100.0
Examples 1-4 are formulations for preferred use of about 1400
ppm, wash water weight basis, for temperatures below about 50-C~
The above examples are made by combining the base granule
ingredients as a slurry, and spray drying to about 4-8% residual
moisture. The remaining dry ingredients are admixed in granular or
powder form with the spray dryed granule in a rotary mixing drum,
and the liquid ingredients (nonionic surfactant and perfume) sprayed
on.
w o 92/06153 PCT/US9l/07022
~ 7 50 -
EXAMPLES 5-10
The examples below demonstrate heavy duty liquid compositions
containing polyhydroxy fatty acid amides and polymeric dispersing
agent.
Inaredients 5 6 1 8
N-~et~20~jslucityl
Cocoamide 4~2 3.1 3.1 8.S
C~ o~y (2.~)
Sulf~t~ 12.6 9.3 8.5
C 1 C. ~ J ~ _ ~ 5 ) ~ U 1 f ;It'~ 6.2Ci2 ~,J ~ JU I ~ 3.1
~12- ~ 3.~ 2.
Dodecyl Tri,..~.,y, ;'mm~m3niUm
Chloride 0.5 0.2
Dodecenvl Suc~inate 5.0
Citrate 3.4 15.0 5.0
TMStTDS (80/20) * 3,4
C12 14 Fatty Acid 3.0 3.0
Oxydisuccinate 20.0
Exthoxylated Tetraethylene
Pentamine 2.0 0.5 2.0
Polyacrylate (4500 MW) 2.5 2.5
Silicone Oil (suds suppressor) 0.9 0,9
Miscellaneous (enzymes,
brighteners, release agents,
stabilizers, etc) 15.3 14.0 12.5 16.3
Water 52~2 50.2 ~1.2 54.0
100.0 100.0 100.0 100.0
* TMS/TDS is tartrate monosuccinate/tartrate disuccinate
In~redients Q 10
N-Methyl N-1-Deoxyglucityl Cocoamide 5.5 5,5
C12 13 Alkyl Ethoxylate (6.5 mole) 2.5 2.5
C14 15 Alkyl Exthoxylate (2.25) Sulfate 17.0 17.0
C12 14 Fatty Acid 3 0 3
Dodecyl Trim~thyl Ammonium Chloride 0.2 0.2
Citric Acid 1.0 1.0
Monoethanolamine 2.5 2.5
Ethoxylated Tetraethylenepentamine 1.5 3.0
W O 92/06153 2 ~ v ~ ~ ~
- 51 -
Polyethylene Glycol (8000 MW) 3.0 3.5
Miscellaneous and solvents balance balance
100.0 100.0
E~amples 3-10 are preferably used at about 2000 ppm, wash water
weight basis, for wash tPmperatures below about 50'C. These are
prepar2~ ~j combiRiRg non-aqueous solvents, aqueous surfactant
pastes or solut;ons~ melted fatty acids, aqueous solutions of
polycarbox~a~e ~uilders and other salts, aqueous ethoxylated
tetraethvlenoentamine, ~uffering agents, caustic, and the remaining
.C Wa~em The V~i i; adJusted using either an aqueous citric acid
soiu~.~n Ol~ iOdlUI~ hydroxide solution to about pH 8.5. After pH
adj~ n~:, ; e lnal lngr~diants, such as soil release agents,
en.Jrl~cs~ ;ololan~s, and perfume, are added and the mixture stirred
until ~ single ~hase is achieYed.
EXAMP~E 11
An alternate method for preparing the polyhydroxy fatty acid
amides used herein is as follows. A reaction mixture consisting of
84.879. fatty acid methyl ester (source: Procter ~ Gamble methyl
ester CE1270), 759. N-methyl-D-glucamine (source: Aldrich Chemical
Company M4700-0), 1.049. sodium methoxide (source: Aldrich Chemical
Company 16,499-2), and 68.51g. methyl alcohol is used. The reaction
vessel comprises a standard reflux set-up fitted with a drying tube,
condenser and stir bar. In this procedure, the N-methyl glucamine
is combined with methanol with stirring under argon and heating is
begun with good mixing ~stir bar; reflux). After 15-20 minutes,
when the solution has reached the desired temperature, the ester and
sodium methoxide catalyst are added. Samples are taken periodically
to monito. the course of the reaction, but it is noted that the
solution is completely clear by 63.5 minutes. It is judged that the
reaction is, in fact, nearly complete at that point. The reaction
mixture is maintained at reflux for 4 hours. After removal of the
methanol, the recovered crude product weighs 156.16 grams. After
vacuum drying and purification, an overall yield of 106.92 grams
purified product is recovered. However, percentage yields are not
33 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%
W O 92/061~3 PCT/US91/07022
~92187 ~2 -
reactant concentrations for periods up to 6 hours to yield products
with extremely small by-product formation.
The following is not intended to limit the invention herein,
but is simply to further illustrate additiona~ ~s~c~s o~ th~
technology which may be considPred bJ~ th~e -~o,mulata,- n ~e
manufacture of a wide variety Ot ae ~'n-~ a ..' '~~.-.'p,~' m '~
polyhydroxy fatty acid amides.
It will be readily appreciated tha~ '~e ool~'n~ fa~J~ ~ci'
amides are, by ~irtue of their ami~e bond~ SU~JeO~ .0 ,o~e
instability under highly basic or niS~ly ~a '~ S e~;'n ' ',',',"', '~
some decomposltion can be tolerated~ ie ls 'rea'e~''"! an'?. t'~.e~e
materials not be subj~cted to p~'s ai~ e ~~ ? ~~
nor belo~Y about 3 ~or unduly a~ nded r~r~di~ ~~n~ ,r~ uo: ~Y
(liquids) is typtc~lly .~.0~9Ø
During the manufacture of the poiynyàroxJ~ fa~c~ ac a amiavs i~
will typically be necessary to at least p~rtially neutralize the
base catalyst used to form the amide bond. While any acid can be
used for this purpose, the detergent formulator will recognize that
it is a simple and convenient matter to use an acid which provides
an anion that is otherwise useful and desirable in the finished
detergent composition. For example, citric acid can be used for
purposes of neutralization and the resulting citrate ion (ca. 1%) be
allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry
and be pumped into the later manufacturing stages of the o~erall
detergent-manufacturing process. The acid forms o~ materials such
as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate,
tartrate/succinate, and the like, can be used similarly
The polyhydroxy fatty acid amides derived from coconut alkyl
fatty acids (predominantly C12-C1,) are more soluble than their
tallow alkyl (predominantly C16-C18) counterparts. Accordingly, the
C,2-C~, materials are somewhat easier to formulate in liquid
compositions, and are more soluble in cool-water laundering baths.
However, the C16-C,a materials are also quite useful, especially
under circumstances where warm-to-hot wash water is used. Indeed,
the C~6-C1a materials may be better detersive surfactants than their
C12-C1, counterparts~ Accordingly, the formu7ator may ~ish to
balance ease-of-manufacture vs. per;ormance ~nen selecting a
W O 92/06t53 PC~r/US91/07022
53 ~V2i,~7
particular polyhydroxy fatty acid amide for use in a given
formulation.
It will also be appreciated that the solubility o,~ the
polyhydroxy fatty acid amides can be increased by having points of
unsaturation and/or chain branching in the ,atty acid moiety. Thus~
materials such as the polyhydroxy fatty aci~ amides derived rrom
oleic acid and iso-stearic acid are more soluble than their n-al~vl
counterparts.
Likewise, the solubility of polyhydroxv fl~ty lC'.~ es
prepared from disaccharides, trisacchl,id~s~ ~e.~ l m di~
be greater than the solubillty or ~h~ir mo,loiaocil~ri~e-ueri~e~
counterpart materials. This higher soiubiii~/ o~" o~ o, ;~ ;~ ou, ~;A
assistance when formulating liquid compos-,~ions. ,loreo~er, tne
polyhydroxy fatty ~cid amides wherein the ~,ol~h~rox~ crou~ is
derived from maltose appear to function esp~cially well a~
detergents when used in combination with conventional alkylbenzene
sulfonate ("LAS") surfactants. While not intending to be limited by
theory, it appears that the combination of LAS with the polyhydroxy
fatty acid amides derived from the higher saccharides such as
maltose causes a substantial and unexpected lowering of interfacial
tension in aqueous media, thereby enhancing net detergency
performance. (The manufacture of a polyhydroxy fatty acid amide
derived from maltose is described hereinafter.)
The polyhydroxy fatty acid amides can be manufactured not only
from the purified sugars, but also from hydrolyzed starches, e.g.,
corn starch, potato starch, or any other convenient plant-derived
starch which contains the mono-, di-, et~. 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-ligni-
fied, 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
3S than their glucose counterparts. Moreover, it appears that the more
soluble polyhydroxy fatty acid amides can help solubilize their less
soluble counterparts, to varying degrees. Accordingly, the formu-
lator may elect to use a raw material comprising a high glucose corn
WO 92/061~3 PCT/US91/07022
8 ~
- 54 -
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 ~Yill, in general, exhibit more preferred solubility
properties over a broader range of temperatures and concentrations
than ~io~lld a "oure'' glucose-derived polyhvdroxy fatty acid amide.
Thus, in addition ~o any economic advantages for using sugar
mixturQs ra+hqr than purQ sugar reactants, the polyhydroxy fatty
acid amides pre~ared from mixed sugars can offer very substantial
advant~g~s ~ith ,~~s?~~c~ ~o performance and/or ease-of-formulation.
0 ~n S~'' Nl~ Cai, hO'~ieYei', iome loss of gr4ase removal performance
(dis~ a~iling3 ,~ay oe no;~d at fatty acid maltamide levels abo~e
~bou; ' :~ ~n~ s~ma ioss ml sudsing above about 33% (said percentagPs
being tne percentage o; maltamiàe-derived polyhydroxy fatty acid
a~;de ~s~ glucos~~derived polvhvdroxy fattv acid amide in the
mixtu ~. Th s -an v~rv scm~what, 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 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 r.ow been detormined that lt ~ay 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
fintshed deter~ent formulation. Likewise, the formulator of, for
example, solid', typically granular, detergent compositions may find
it convenient to run the process at 30-C-90-C in solvents which
comprise ethoxylated alcohols, such as the ethoxylated (EO 3-8)
C12-C1l alcohols, such as those available as NEODOL 23 E06.5
(Shell). '.lhen such ethoxylates are used, it is preferred that they
not contain substantial amounts of unethoxylated alcohol and, most
preferably, not contain substantial amounts of mono-ethoxylated
alcohol. ("T" designation.)
~Ihile methods for making polyhydroxy fatty acid amides per se
form no part of the invention herein, the formulator can also note
W o 92/06153 PCT/US91/07022
- 55 - ~2~7
other syntheses of polyhydroxy fatty acid amides as described
hereinafter.
Typically. ,.he industrial scale reaction sequence for preparing
the pre,~errDd ~cyclic polyhydroxy fatty acid amides will comprise:
SteP I - preparing the N-al~yl polyhydroxy amine derivative from the
desi, ~G ;uyal ûr ,ugar mixtui~e by formation of an adduct of the
N-alkyl amino an~i the sugar! followed by reaction with hydrogen in
the pi'riei7C- Oi' a cata1yst; ,'ollowed by SteD 2 - reacting the
aforesai~ ~ol~h~drcvJ~ am~~e w~,th~ oreferably, a fatty ester to form
~n ~-..ca smw~. '..;.,1e a va;~~e'; o,~ ,I-al'~yl polyhydroxy amines useful
in S~ a, ~1e i~ c~ion iequ~ ce oan ~e prepared by various
ar~-d~c ~à~ ;~ce:;ses, ~he ~'al10~,ii"g proc~ss is convenient and
ma~es uia a,' ~canu,,,-,cal sugan syrup as the raw material. It is to
be unc2rs~0ûd 'nat~ ,or best results when using such syrup raw
materials, tho ~anufacturer should select syrups that are quite
light in color or, pre;erably, nearly colorless (''water-white").
Preparation of N-Alkyl Polyhydroxy Amine
From Plant-Derived Sugar Syrup
I. Adduct Formation - The following is a standard process in
which about 420 9 of about 55% glucose solution (corn syrup - about
231 9 glucose - about 1.28 moles) haYing a Gardner Color of less
than 1 is reacted with about 119 9 of about 50Y. aqueous methylamine
(5g.5 9 of methylamine - 1.92 moles) solution. The methylamine
(MMA) solution is ~ur~ed and shielded with N2 and cooled to about
lO-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 Gardnar Color is measured at the indicated approximate times in
minutes.
TA8LE 1
Time in Minutes: L~ 30 60 120 180 240
Reaction TemP~ 'C Gardner Color (APProximate)
0
3530 1 1 2 2 4 5
~ 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
W O 92/06153 PC~r/US91/07022
r~ - 56 -
and at about 50-C, the time that the adduct has a Gardner Color
below 7 is only about 30 minutes. For longer reaction, and~or
holding times, the temperature should be less than about 20'C. The
Gardner Color should be less than about 7, and prQrerably iess than
about 4 for good colcr glucamine.
When one uses lo~iler temperatures ;or ,o,,n~ y ;n- ~ui l ne
time to reach substantial equilibrium concPntration of the adduct is
shortened by the use of hlgher ratios o, amdne su,an. ~h ~;~e
1.5:1 mole ratio of amine to sugar notQd, eouilihriu~ is reached ~'n
about two hours at a reaction ~empera~ura o,' a'o;'ln~ ''n'~
mole ratio, under the sa~e conditio~s, ~'ne ~ ~ a~ as;~
thr~e hou, s. ~or good colo" .h 03ja'J ', " ~'; n ~' ~" ,' ; ~i;,. ', '~ ~ O
reaction te~per~turQ; and r2actisn ~i",e ~., ,e,ec i o ~h~ve
substar,tially eguil,brium ;onvers.on, a.~., "~on~ " ~ u~ j~""
preferably more than about 95~,', even more prerera'oly more thsn .oout
99%, based upon the sugar, and a color that is less than -~bout 7,
preferably less than about 4, more preferably less than about 1, for
the adduct.
Using the above process at a reaction temperature of less than
about 20-C and corn syrups with different Gardner Colors as
indicated, the MMA adduct color (after substantial equilibrium is
reached in at least about two hours) is as indicated.
TABLE 2
Gardner Color (A~Drox,mate)
Corn syrup 1 1 1 1+ 0 0 0+
Adduct 3 4/5 7/8 7/8 1 2
As can be seen from the above, the starting sugar material must
be very near colorless in order to consistently have adduct that is
acceptable. When the sugar has a Gardner Color of about 1, the
adduct is sometimes acceptable and sometimes not acceptable. When
the Gardner Color is above 1 the resulting adduct is unacceptable.
The better the initial color of the sugar, the better is the color
of the adduct.
II. HYdroqen Reaction - Adduct from the above having a Gardner
Color of 1 or less is hydrogenated according to the following
procedure.
About j39 9 of adduct in water and about 23.1 9 of United
Catalyst G49B Ni catalyst are added to a one liter autoclave and
WO 92/06153 PCI~US91/07022
h ~ i 3 r~
purged two times with 200 psig H2 at about 20 C. The H2 pressure is
raised to about 1400 psi and the temperature is raised to about
50 C. The pressure is then raised to about 1600 psig and the
temperature is held at about 50-55~C for about three hours. The
S product is about 95% hydrogenated at this point. The t~,p-~raL~re is
then raised to about ~5~C ,or abo~ as and ;~ s~ a~
mixture is decanted and the catalyst is filtered out. The product,
after removal of water and MMA by ev2~0ra~ion~ is abcut 95~', N-~eth3~l
glucamine, a white powder.
The above procedure is repeatPd wit~ avou~ 23.1 9 ~' ~anev 'li
catalyst with the following chan~es. The oa~.al~!st is washea three
times and the reactor, with the c~talyC~ ~n ~a~ -e~ s ~-s~-
twice with 200 psig H2 and the reaotor i~ ssuri7~d 'Y"h ,~ at
1600 psig r~r t:lC hours, ~h~ pressure ~s na~a s~ ~s ~ h "~ ~n~
the reactor is repressurized to i~00 psig. Ine aaàucl is tnen
pumped into the reactor which is at 200 psig and 20~C, and the
reactor is purged with 200 psig H2, etc., as above.
The resulting product in each ca$e is greater than about 95~JO
H-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 l~o) 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 pre~ared starting with about 159
g of about 50X methylamine in water, which is purged and shielded
with N2 at about 10-20-C. About 330 9 of about 700ZD corn syrup (near
water-white) is degassed with N2 at about 50-C and is added slowly
to the methylamine solution at a temperature of less than about
20-C. The solution is mixed for about 30 minutes to give about 95%
adduct that is a very light yellow solution.
About 190 9 of adduct in water and about 9 9 of United Catalyst
G49B Ni catalyst are added to a 200 ml autoclave and purged three
times with H2 at about 20~C. The H2 pressure is raised to about 200
psi and the temperature is raised to about 50~C. The pressure is
raised to 250 psi and the temperature is held at about 50-55~C for
abcut three hours. The product, which is about 95% hydrogenated at
W O 92/06t~3 PCT/US91/07022
~ 58 -
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 minimi~e contact between adduct and
catal~/st when the H2 pressure is less than about 1000 psig to
'b ~a the ~lucamir,e~ The nickel content in the
N-methyl glucai~ine in this reaction is about 100 ppm as compared to
che l~ c;)~n 10 oom in the previous reaction.
T,le ,-ollowing reactions with H2 are run for direct comparison
of ;?a~ o,~ at' ~. ~ll;~? ~ ~ I acts .
' 'O',i" autocl~v~ reac~o~,A is us~d ,ollowing typical procedures
sli"i,;,~ os~ r~l abo~e to Inake adduct and to run the
hyt!~OS~ ?~C'~O~ lt '!a~ ious t~mp~r~tur~s.
~d!'~~ ~~r '.'S~ in ...ak~ng gluca"ine is p,epa,~d by combining
1~ aD~ '2i j a, ~vu~ ~,0 ~,uc~sP ~conn syrup) jolution (231 9
glucose; 1.28 moles) (the solution is made using 99DE corn syrup
from CarGill, the solution having a color less than Gardner 1) and
about 119 9 of 50% methylamine (59.5 9 MMA; 1.92 moles) (from Air
Products).
The reaction procedure is as follows:
1. Add about 119 9 of the 50% methylamine solution to a N2 purged
reactor, shield with N2 and cool down to less than about 10-C.
2. Degas and/or purge the 55% corn syrup solution at 10-20-C with
N2 to remove oxygen in the solution.
3. Slowly add the corn syrup solution to the methylamine solution
and keep the temperature less than about 20-C.
4. Once all corn syrup solution is added in, agitate for about 1-2
hours.
The adduct is used for the hydrogen reaction right after
making, or is stored at low 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 ~.8 9 G49B Ni to a 200 ml autoclave.
2. Purge the reaction mix with about 200 psi H2 twice at about
2~-3C-C.
3. Pressure with H~ to about 400 ;,i and raise the temperature to
about 50~C.
WO 92/061~3 PCl'/US9l/07022
- 59 - ''7 ~ r~
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. ~ec~nt and ,~il.er out ~he Ni catalyst. Take Sample 2.
Conditions for constant temperature reactions:
1~ 'd~ a~~ut 1~ ~ ad~uct and about 5~ 9 G49B Ni to a 200 ml
~utccla~!e.
2. ?ur~a .;i~~~ a~out 2CC psi H2 t~iC~ at low temperature.
3. ~ressure ~.~i+h ~2 to about ~00 psi and raise temperature to
1 O ~ U ~. ' j J ~, .
4. ~~"~e ~siui~ ~a ibout iC0 psi, react for about 3.5 hours.
~e~ t~m?~ratUI e ~At indicated t~mperaturQ.
S. ~e.:~n,. anu ,il~er out ~.he Ni catalyst. Sample 3 is for about
5~-SS~f: Sample ~ is for abollt 75~C; and Sample 5 is for about
'!m. ' me ,~r about ~ is about ~S minutes.)
~11 runs ~ e simiiar pu,i~y or N-methyl glucamine (about 94%);
the Gardner Colors of the runs are similar right after reaction, but
only the two-stage heat treatment gi'ves good color stability; and.
the 85-C run gi~es marginal color immediately after reaction~
EXAMPLE 12
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~
Steo 1 - Reactants: Maltose monohydrate (Aldrich, lot
2S 01318KW3; methylamine (~0 wt% in water) (Aldrich, lot 03325TM);
Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).
The reactants are added to glass liner (250 9 maltose, 428 9
methylamine solution, 100 S catalyst slurry - 50 9 Raney Ni) and
placed in 3 L rocking autoclave, which is purged with nitrogen
(3X500 psig) and hydrogen (2X500 psig) and rocked under H2 at room
temperature over a weekend at temperatures ranging from 28~C to
50-C. The crude reaction mixture is vacuum filtered 2X through a
glass microfiber filter with a silica gel plug. The filtrate is
concentrated to a viscous material. The ~inal traces of water are
3S azetroped Off by dissolving the material in methanol and then
remoYinS the mQthanol/water on a rotarV evaporator. Final drying is
done under high vacuum. The crude product is dissolved in refluxing
methanol, fil-tered, cooled to recrystallize, filtered and the filter
WO 92/06153 PCI'/US9~/07022
2~2~ 60 -
cake is dried under vacuum at 35'C. This is cut #1. The filtrate
is concentrated until a precipitate begins to form and is stor~d in
a refrigerator overnight. The solid is filtered and dried ~nd~r
vacuum. This is cut ~2. The ;iltrate is again concentra~ed ~o hal
its volume and a recrystallization is oerform~d~ Yery l-~le
precipitate forms. A small quantity or e~ha,lo, i; ~ddcu an.l ~he
solution is left in the freezer over a weekend~ The solid m~torial
is filtered and dried ùnder vacuum. The co~mùlilcd ioiidi o~ e
N-methyl maltamine which is used in Steo 2 of 'he o~eral '.,','!'~'ne;',S.
Ste~ 2 - Reactants: N-methyl mal~ami;e (m~om ' s~ :~ s~
tallow methyl eat~rs; sod;lim ii~,e~hoxid~ Nl m,_~ n~ iOS~îù~e
methanol (solvent); mole ra~io 1:i al,lin-~:a;~ n'~ a~ i
level 10 mole % ~w/r maltamine), raiseG ;o '0 m,ole ~O; iolveil~ le~iel
50% ~wt.).
In a sealed bottle, 20.36 9 of the tallo~ me'hvl ~ster is
heated to its melting point (water bath) and loaded into a 2;0 ,nl
3-neck round-bottom flask with mechanical stirring. The flask is
heated to ca. 70'C to prevent the ester from solidifying.
Separately, 25.0 9 of N-methyl maltamine is combined with 45.36 9 of
methanol, and the resulting slurry is added to the tallow ester with
good mixing. 1.51 9 of 25X sodium methoxide in methanol is added.
After four hours the reaction mixture has not clarified, so an
additional I0 mole % of catalyst (to a total of 20 mole ~JO) 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 pro~duct 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
3~ product using silica gel. A silica gel slurry in 100% methanol is
loaded into a funnel and washed several times with 100% methanol. A
concentrated sample of the product (20 9 in 100 ml of 100% methanoll
is loaded onto the silica gel and eluted several times using vacuum
and several methanol washes. The collected eluant is evaporated to
w o 92/06153 ,~~ eT ~ ~91/07022
- 61 -
dryness (rotary evaporator). Any remaining tallow ester is removed
by trituration in ethyl acetate overnight, followed by filtration.
The filter cake is dried overnight. The product is the ~allo~al'~yl
N-methyl maltamide.
In an alternate ~ode, Step 1 of the forecoing reac~ion ser~e~co
can be conducted using commercial corn syrup comorising glucose or
mixtures of glucose and, typically, 5~', or higher, ~ tosa The
resulting polyhydroxy fatty acid amides and mixtures can be used in
any of the detergent compositions heroin.
In still another mode, Step 2 of thQ ,~oregoiog r~ao~lo~
sequence can be carried out in 1,2-propylene glycol or NEODO!. ~t
the discretion of the formulator, the propylene glycoi on ;~O~OL
need not be removed from the reaction Droduct orior to its use to
formulate det~rcent compositions~ ~gain. a~-~rding ta ~h~ a- n?s
of the formulator, the methoxide catalyst can be neu~i~ali~eu '~y
citric acid to provide sodium citrate, which can remain in the
polyhydroxy fatty acid amide.
Depending on the desires of the formulator, the compositions
herein can contain more or less of various suds control agents.
Typically, for dishwashing high sudsing is desirable so no suds
control agent will be used. For fabric laundering in top-loading
washing machines some control of suds may be desirable, and for
front-loaders some considerable degree of suds control may be
preferred. A wide variety of suds control agents are kno~n 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 controi agents of various types are more
eff;cient (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.
3S The formulator of fabric laundering compositions which can
advantageously contain soil release agent has a wide variety of
known materials to choose from (see, for example, U.S. Patents
3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and
W O 92/06t53 PC~r/US91/07022
2 g (~ 7 62 -
4,877,896). Additional soil release materials useful herein include
the nonionic oligomeric esterification product of a reaction mixture
comprising a source of Cl-C4 alkoxy-terminated polyethoxy units
(e.g., C13[0CH2CH,]l60H), a source of terephthaloyl units (e.g.,
dimetinyl ~repntha7ate); a source of poly(oxyethylene)oxy units
(e.9 , pi..~ ne giycol ;~0); a source of oxyiso-propyleneoxy
units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy
units ;~.9.. r~ Ynvl ~n e 91 ycol) es~ecially wherein the mole ratio of
oxyethyl~neoxy units:oxyiso-propvleneoxy units is at least about
0 0,~ nl,''. ';~'.1 r~l~ase ~g nts_are of the g~neral formula
" ~= ~
C~ C;~.~ - C ~ /~-CO(CH2CH20)y
_ - ~2 _ m - - n
C~ ,~C - () (CH~CH~O!x-Rl
wherein ~; is lower (e.g., Cl-C~) al~yl, especially methyl; x and y
are each integers from about 6 to about 100; m is an integer of from
about 0.75 to about 30; n is an integer from about 0.25 to about 20;
and R2 is a mixture of both H and CH3 to provide a mole ratio of
oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.
Another preferred type of soil release agent useful herein is
of the general anionic type described in U.S. Patent 4,877,896, but
with the condition that such agents be substantially free of
monomers of ~he HOROH type wherein R i propylene or higher alkyl.
Thus, the soil release agents of U.S. Patent 4,877,896 can comprise,
for example, the reaction product of dimethyl terephthalate,
ethylene glycol, 1,2-propylene glycoi and 3-sodiosulfobenzoic acid,
where~s these additional soil release agents can comprise, for
example, the reaction product of dimethyl terephthalate, ethylene
glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid. Such
agents are preferred for use in granular laundry detergents
The formulator may also determine that it is advantageous to
include a non-perborate bleach, especially in heavy-duty granular
laundry detergents. A variety of peroxygen bleaches are available,
commercially~ and can be used herein, but, of these, percarbonate is
convenient and economical. Thus, ~he compositions herein can
contain a solid percarbonate bleach~ normally in the form of the
sodium salt, incorporated at a level of from 3% to 20% by weight,
W O 92/061~3 PCTtUS91/07022
- 63 - ~3921g7
more preferably from 5% to 18% by weight and most preferably from 8%
to 15% by ~.~eight of the composition.
Sodium percarbonate is an addition compound having a formula
corr~sronding to 2Na2C03. 3H20~, and is available commercially as a
crystalli"~ ~vlld. ~ost commorcially available material includes a
lOi ~ ' ~~ 'l?-U'''' ".~tal s~qu strant such as EDTA, 1-hydroxy-
ethylidene l,1-diphosphonic acid (HEDP) or an amino-phosphonate,
tha~ oratod durin~ th~ manufacturing process. For use
herein, ~h~ varcarbonate can be incorporated into detergent composi-
tiOïl~ ii ''~i :' add,tional ~rot~ction, but preferred embodiments of
the i~ ti~n ~til~ a stable form o~ the material (FMC). Although
a ~ar ~ a~a~ ~~~ ~an ~ u~s~d, th,~ ~st oconomic~l is sodium
silica~ ' z~ 'io s~,oln 1.5:1 to 2.8:1, preferably 2.0:1,
~Pr ~_~ '; n a~'a~'_s ,OIU~ ~n an~ c i~d t3 ~ive a l~ovel or from 2~o
iS to 1~ (nor",ally ,rom 3~ to j~'), of silicate solids by weight of the
percar'~ona-te. Magnesium silicat~ can also be used and a chelant
such as one of those mentioned above can also be included in the
coating.
The particle size range of the crystalline percarbonate is from
350 micrometers to 450 micrometers with a mean of approximately 400
micrometers. When coated, the crystals have a size in the range
from 400 to 600 micrometers.
While heavy metals present in the sodium carbonate used to
manufacture the percarbonate can be controlled by the inclusion of
sequestrants in the reaction mixture, the percarbonate still
requires protection from heavy metals present as impurities in other
ingredients of the product. It has been found that the total level
of iron, copper and manganese ions in the product should not exceed
25 ppm and preferably should be less than 20 ppm in order to avoid
an unacceptably adYerse effect on percarbonate stability.
A modern, condensed laundry detergent granule is as follows.
EXAMPLE 13
Inqredient Wt.%
Cl, 1s alkyl alcohol sulfonic acid 13
C1~ 1s alkyl polyethoxy (2.25) sulfonic acid 5.60
C12 l3 alkyl polyethoxylat~ (6.5) 1.45
C 12 -1~ ~ ~Ity acid N-methyl glucamid~ 2.50
Sodium aluminosilicate (as hydrated Zeolite A) 25.2
W O 92/06153 PC~r/US91/07022
r~ - 64 -
Crystalline layered silicate builder~ 23.3
Citric acid 10~0
Sodium carbonate To get wash o~ = 9.90
Sodium polyacrylate (m.w. 2000-4500) 3.2
Diethylenetriamine pentaacetic acid 0~45
Savinase2 )~o
6-Nonanoylamino-6-oxo-peroxycaproic acid 7 ~0
Sodium perborate monohydrate ' '0
Nonanoyloxyben~ene sulfonic acid ~.oo
Brightener i~ o
~ Layered s licat- bu;tders ar2 k .~.Jn ' ~:~ ar- ?;~~'. r~d ~
the layered iodium silic~tes. See, ,or ~va~?l~ r,~ Oill
silicate builders of U.S. Patent ',ôo~,O~3, is~ued i~ c
~. P. Rieck, incorporated herein by re;erenco. i ~ui~2~ie ia~-r~d
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 0.00017. to about 2~o 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.
EXAMP~E 14
The following illustrates a perborate bleach-plus-bleach
activator detergent composition of the present invention which is
prepared by admixing the listed ingredients in a mixing drum.
In the example, Zeolite A refers to hydrated crystalline
Zeolite A containing about 20~ water and having an average particle
size of 1 to 10, preferably 3 to 5 microns; LAS refers to sodium
C12 3 l;near alkylbenzene sulfonate; AS refers to sodium C,~-C1s
alkyl sulfate; nonionic refers to coconut alcohol condensed with
about 6.5 moles of ethylene oxide per mole of alcohol and stripped
of unethoxylated and monoethoxylated alcohol, also abbreviated as
CnAE6.5T.; and DTPA refers to sodium diethylenetriamine
pentaacetate.
Parts by Weight of
Final ComDosition % of Granulos
Base Granules1 51.97 100.00
AS 9.44 18.16
LAS 2.92 5.62
W O 92/06t53 PCT/US91/07022
- 65 - 2 ~ ~ 2 ' '.
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 ~6 ~ ~9
Sodium carbonate 13.29 25.57
Brightener 0.20 0.38
Sodium aluminosilicate 9.11 17.~3
DTPA 0.~7 0.~2
Perfume C.~O 0 ~8
NAPAA Granules 2 6.09 lOO.;~1
NAPAA 2.~6 '5.96
LAS 0.30 S.,3
Sulfate and ,1isc. ~.93 i8.ii
NOBS Granules3 3.88 100.00
NOBS 3.15 81.19
LAS 0.12 3.09
PEG 8000 0.19 4,90
Misc. 0.42 10.82
Zeolite Cranules~ 12.00 100.00
Zeolite A (includes bound water) 7.39 61.58
PEG 8000 1.50 12.47
Nonionic 1.16 9.70
Moisture 1.66 13.83
Misc. 0.29 2.42
Admix
Sodium SKS-6
layered silicate 15.84
Protease
(0.078 mg/g activity) 0.52
Sodium perborate
monohydrate 1.33
Citric acid 6.79
Cl2-Cl~ N-methyl glucamide 1.58
Total of final composition 100.00
lThe base granules are produced by spray drying an aqueous
crutcher mix of the listed ingredients.
W O 92/06153 (' PCT/US91/07022
66 -
2A freshly-prepared sample of NAPM wet cake, which typically
consists of about 60% water, about 2% peroxyacid available oxygen
(AvC) (oor.es?onding to about 36% NAPAA), and the rest (about 4%)
unre~ct~d st~rting m terial, is obtained. This wet cake is the
crude ,eacti3n ?r~duct of N MA (monononyl amide of adipic acid),
sulfuric acid~ and hyd oaen oeroxide ~hich is subsequently quenched
by addi~ion ~o .ia~r ,~ollowed ~y r~iltration, washing with distilled
water~ phosohate bllffer washinQ and final suction filtration to
recover ch~ ~et ca,;e. A portion or the wet cake is air-dried at
room ~m-,~r~u~~~ 'o ob,ain a d,~~- ;am~l2 wh'ch typically consists of
abou~ J ~OV!';' ~spond ~ 3 ~.o ;~out 90~0 ~APM) and about 10%
Utlr~o~ S~ln ;Ing ma~eri~ ih~n dry, the sample pH is about 4.5.
~ ~nu; , n~ o~a~ar~ by -,lixing ~bout 51.7 parts of the
dried ,~ cake (conta;ning about iO~o unreacted), about 11.1
~arti o, sodi~lm O ~ ~ linear ~ Vl hen2ene sulfonate (LAS~ caste
(45~' act ~o'~ ab~ut ~?,3 p~rts 0,~ sodlum sulfate, and about 30 parts
of water in a CUISINART mixer. After drying, the granules (which
contain about 47% NAPM ) are sized by passing through a No. 14 Tyler
mesh sieve and retaining all parttcles not passing through a No. 65
Tyler mesh. The average amtde peroxyacid particle (agglomerate)
size is about 5-40 microns and the median particle size is about
10-20 microns, as determined by Malvern particle size analysis.
3The NOBS (nonanoyloxybenzene sulfonate) granules are prepared
according to U.S. Patent 4,997,596, ~owling et al, issued March 5,
1991, incorpcrated herein by reference.
~ 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 bY Wetqht
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 .~ater 10.80 0.80
The PEG 8000 is in an aqueous form containing 50% water and is
at a temDerature of approximately 55'F (12.3~C). The CnAE6.5T is in
a liquid state and is held at approximately 90~F (32.2'C). The two
liquids ~re ocmbined by pumping through a 12 element static mixer.
W O 92/06153 PC~r/US91/07022 - 67 - 2 ~ ~ 2 ~ ~ 7
~he resulting binder material has an outlet temperature of
approximately 75'F (23.9'C) and a viscosity of approximately 5000
cps. The ratio of PEG 8000 and CnAE6.5~ through the static mixer is
72:2a respectively.
Th~ Fi,~ich ~08 energy intensive mi~er is operated in a batch
~yp~q 'ilC'~'~. ''i''~'~ ~''~..1 ';'~ 0~' OO~.'idQ'r'e'1 _~olitQ ,A iS weighed into the
pan o-f ~he ;ni~r. The mixer is started by first rotating the pan in
a coun~qrcl~c~ ise direction at a~proximately 75 rotations per
minute ~rpin), 1nd then rotating the rotor blade in a clockwise
direc~io~ '\) n~m. M~e binder ~t~riîl is then pumped from the
stat,c ",~"i~r ùi.ac~ M~o ~he Eirich ~08 energy intensive mixer
~hlc,~ ~oi"~ ? ~. Mle ''~e(i -~a~e ~; the binder material is
abc!~t ' ~i u qs. M~~ "i~; r continu~s to ~ix for an additional
minu~q ~r ~ a~o~ ~jr", 0s -,v?,a~;i,,,a.ely 3 minutes. The batch
ls ~ ,)ù ~ 2r ~ru~;
The ~acch st p is r~peated until approximately 225 kg of ~et
product has ba2n collected. This discharged product is then dried
in a fluid bed at 240-2?0-F (116-132'C). The drying step removes
most of the free water and changes the composition as described
above. The total energy input by the mixer to the product in a
batch mode is approximately 1.31X10l2 erg/kg. at a rate of
approximately 2.18X109 erg/kg-s.
The resulting free flowing agglomerates have a mean particle
size of about 450-500 microns.
EXAMP!E 1i
A granular laundry detergent composition suitable for use at
the relatively high concentrations common to front-loading automatic
washing machines, eS?ecially in Europe, and over a wide range of
temperatures is as follows.
Inqredient Wt. %
SOKALAN CP5 (lOOX acti~e as Na salt)1 3.52
DEQUEST 2066 (100% as acid)2 0 45
TINOPAL DMS3 0.28
MgSO, 0-49
Zeolite A (anhydrous 2-5 ~) 17.92
CMC (lOC% ac~ive)~ 0 47
Na2CO3 9 44
Citric acid 3.5
W o 92/06153 PCT/US91/07022
'~92~7 - 68 -
Layered Silicate SKS-6 12.9
Tallow alkyl sulfate (100% active; Na salt) 2.82
C,~-C1s alkyl sulfate (100% active; Na salt) 3.5
C12-C1s alkyl EO~3) sulfate 1.7
C16-Cl8 N-methyl glucamide 4 l
DOBANOL C12-C,s EO(3)
LIPOLASE (100,000 LU/g)s o t
SAVINASE (4.0 KNPU) 6
Perfume 0 -~3
X2-34197
Starch ; ~;~
Stearyl alcohol
Sodium percarbonate (coated) ~.~
Tetraacetylathylenediamine (TAED) 5.~3
Zinc phthalocyanin ~ ~
Water (ex zeolite) ~,a,lce
1SOKALAN is sodium poly-acrylate/maleate available from
Hoechst.
2Monsanto brand of pentaphosphonomethyl diethylenetriamine.
30ptical brightener available from Ciba Geigy.
~Trade name FINNFIX ava;lable from Metasaliton.
5LIPOLASE lipolytic enzyme from NOVO.
65AVINASE protease enzyme from NOVO.
7X2-3419 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 CP5 3.52%
DEQUEST 206C 0.45%
TINOPAL DMS 0.28Yo
Magnesium sulfate 0.49%
ZEOLITE A as anhydrous 7.1%
CMC O 47%
WO 92/06153 PCrlUS91/07022
B. Surfactant Aqqlomerates
Bl. Aqqlomeration of Sodium Salt of Tallow Alkvl Sulfate and
Sodium Salt of C17 1 S EOt3) Sulfate Pastes - A 50~0 active paste of
tallow alkyl sulfate and a 70~/0 paste of Cl2-Cls ~0(3) sul'a. ar~
agglomerated with Zeolite A and sodium carbonate according to the
following formula (contribution to the deter~ent formulation aft~r
the drying of the agglomerate).
Tallow alkyl sulfate
C,2 ls EO(3) sulfate 1.18%
Zeolite A i.3~'
Sodium carbonate I.
B2. Aaqlomerate of the C~.-CI~ Alkyl S~llf~te~ o.~
Ethoxv Sulfate~ ~OBANOl C,,-Cl5 EO(3) and Cl~-C~q N-,~e.~yl ~luc~;-
amide - The B~6-Cl~ glucose amide nonionic material is synthesi~ed
with DO~ANO~ Cl~ ~sEO(3) prQsent durins the ,e~,o~lon o- m -hyl ~ r
and N-methyl glucamine. The C~2 ,5EO(3) acts as a ~elting pOi~lt
depressor which allows the reaction to be run without forming cyclic
glucose amides which are undesirable.
A surfactant mixture of 20X DOBANOL Cl2 l5 EO(3) and 80%
Cl6-Cl8 N-methyl glucose amide is obtained and coagglomerated with
lOY. sodium carbonate.
Second, the above particle is then coagglomerated with a high
active paste (70YO) of a sodium salt of Cl,-Cls alkyl sulfate and
C,2 ls EO(3) sulfate and Zeolite A and extra sodium carbonate. This
particle evidences a good dispersibility in cold water of the
Cl6-C~8 N-methyl glucose amide.
The overall formulation of this particle (contribution to the
detergent formulation after the drying of the agglomerate) is:
Cl6-Cl8 N-methyl glucose amide 4.1%
DOBANOL Cl2 ls EO(3) 0.94%
Sodium carbonate 4.94X
Zeolite A 5,3%
Na Cl~-Cl5 alkyl sulfate 3.5%
Na Cl2 l5 EO(3) sulfate O.S9%
C. Dr~ Additives
The following ingredients are added.
Percarbonate 22.3%
TAED (tetraacetylethylenediamine) 5.9%
WO 92/06153 PCT/US91/07022
~23 ~ ~ 70 - ~'
~ Layered silicate SKS 6 from Hoechst 12.90~X
Citric acid 3.5%
Lipolase 0.42%
100,000 LU/g
SAYINASE ~.0 ~PU 1.65%
~inc ~hth~loc~anin (photobleach) 0.02%
. ~or~v on
~03~ ! C~ '0(3) 2.60%
Perfume 0.~3%
1 0 ~ s ~ ~,
~ a ,i ana sllds supp,~esso, ~2-3419 (95%-97% high molecular
eight line~n silicon?; ~-5~' hydrophob;c silica) ex Dow Corning is
coagg,o~ na;ed .ii~ oltt~ ~ (2-~ u size), starch and stearyl
alcohol binder~ This particle has the following formulation:
0 . ~"
S~ 1.08%
X2-3419 0.22%
Stearyl alcohol 0.35yO
The detergent preparation' exhibits excellent solubility,
superior performance and excellent suds control when used in
European washing machine, e.g., using 85 9 detergent in a AEG-brand
washing machine in 30-C, 40-C, 60-C and 90-C cycles.
EXAMPLE 16
In any o; the foregoing examples, the fatty acid glucamide
surfactant can be replaced by an equ;valent amount of the maltamide
surfactant, or mixtures of glucamide/maltamide surfactants derived
from plant sugar sources. In the compositions the use of ethanol-
amides appears to help cold temperature stability of the finished
formulations. MoreoYer, the use of sulfobetaine (aka "sultaine")
surfactants provides superior sudsing.
In the event that especially high sudsing compositions are
desired (e.g., dishwashing), it is preferred that less than about
~%, more preferably less than about 2%, most preferably substan-
tially no C1~ or higher fatty acids be present, since these can
3~ 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 composi-
tions w,th the polyhydroxy fatt~ acld amides, and/or avoid the
WO 92/061~3 ;~ ~ ~) 2 ~ ~ ~ PCI'/US91/07022
formation of C,~ 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 negati~3~ sudsing effQcts caused by the fatty acids.
The formulator wishing to add anionic optical brighteners to
liquid deter~e~ts containing relatively high concentrations (e.g.~
10% and greater; o; anionic or polyanionic substituents such as the
polyc?lhQx~ bl~;ldPrs may find it useful to pre-mix the bright-
ener with wa~ar and t,he ~oiyhydroxy fatty acid amide, and then toadd ~ Z~ ; '3 ~ Q C~ilal ~olllQ~sition.
-ol~;;;.~Z~l~ icid )r polyaspartic acid dispersants can be
useru,i~ e!n~iove~ ~ith -~oiit~-~uilt detergents. AE fluid or flake
and ~ a:i 'oin~i"g) aie 3Lh r examplPs of useful suds control
lS agents herein.
~ t wi~ e aQprQci~ed bv those s~illed in the chemical arts
that the ?-~paration Or the polyhydroxy f~tty 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.
