Note: Descriptions are shown in the official language in which they were submitted.
W094/14939 2 i 5 ~ ~ ~ Q PCT~S93/12090
DTSPF~T~G AGFNT
Field of the Tnvent;on
The present invention relates to the U8Q of poly(amino
acids) and derivatives thereof as di~persing agent~,
espQeially in cl~Aning eompositions, for example in laundry
detergent eompositions.
Backaround to the Invention
Polyaerylates and aerylate/maleate eopolymers are
widely used a~ dispersing agents, speeifieally a~ soil-
suspending and/or anti-reA~rQ~ition agents, in detergent
eompositions and eonfer important eleaning benefits thereon.
However, the~e polymers and eopolymer~ are not readily
biodegradable, thereby po~ing potential environmental
probl~m~. Ca.Lox~methyl eellulose i~ biodegradable at a
de~aaof substitution (DS) of 1-88 than 0.7 but, al~h~7h
it eonfers ~ome whitenes~-main~enAnce benefit to-detergent
eompositions, it is defieient with regard to soil-~uspension
properties.
In EP-A-0,454,126, it i~ diselo~ed that eertain
poly(amino aeids) and derivatives thereof ean be used as
2S builder~ or eo-builders in the formulation of detergent
eompo~itions. The ~aid polymer~, e~peeially tho~e derived
from aspartie aeid, glutamie aeid and mi~ e3 thereof, are
de~eribed a~ effeetive agents for the eomplexing of ealeium
and for ~L~el.~ing the formation of ealeium earbonate
erystals. The said polymers are ~tated to have further
advantages, in that they are re~ifitant to heat, stable to
pH, non-toxie, non-irritant and entirely biodegradable.
However, ~ ch by the ~ ent Applieant has
revealed that polya~partate or other salt~ of poly(amino
aeids) ineorporated in a granular detergent eomposition will
degrade over a period of time, espeeially under eonditions
of elevated temperature and/or high humidity (e.g.
eonditions of 90F (32.2C) and 80% relative humidity), sueh
WO94/14939 PCT~S93/12090
~S~ 6~ 2
as are typical of Southern European and other Mediterranean
countries (and which may obtain even in warehouses
elsewhere). Such degradation, which i8 irrever~ible, may
give rise to a significant 108s in dispQrsant activity
within the storage periods (typically up to 8 weeks) that
may occur in practice. Thi~ degradation was unexpected in
view of the relative ~trength of the amide linkages pre~ent
in poly(amino acids).
10 ~marv of the Invent~on
The present invention provides a cleaning composition
containing a poly(amino acid) com~oul~d or a ~rc_~L~or
thereof and a detersive surfactant, characteri~ed in that
the poly(amino acid) compound or ~Le~ or thereof is
protected from contact with a level of alkalinity a8 would
cau~Q degradation thereof.
The ~L~ 7Qnt invention al~o provides a poly(amino acid)
com~oul.d or a ~Le_u.~or thereof, characterised in that it is
provided with a coating, is encAp~ ated or is mixed, in the
form of an agglomerate or granulate, with at lea~t one other
material.
The ~L~7ent invention also provides a poly(amino acid)
compound or a ~Le~ or thereof, characterised in that it is
in the for~ of an agglomerate with an alkaline or alkaline-
reacting ~aterial.
The ~rc~ent invention further provides a ~oce~s for
producing a poly(amino acid) com~o~.~ in the form of an
agglomerate suitable for incoL ~GL ation into a cleaning
composition, which comprise~ agglomerating the alkaline or
alkaline-reacting material with a compound that is converted
into the poly(amino acid) com~-o,-,-l in alkaline conditions,
the agglomeration being effected in the ~L~-~n~e of
sufficient moisture for the conversion into the poly(amino
acid) com~ou~-d to proceed.
DescriDtion of ~YemDlary Embodiments
W094/14939 2 1 5 2 6 2 0 PCT~S93/12090
The exprQssion "poly(amino acid)~ compound includes
herein not only a poly(amino acid) as ~uch but also a
derivative thereof, such as an amide, an ester or a salt.
The poly(amino acid) may be a homopolymer or may be
copolymer of two or more amino acids. The a~ino acid may be
a D-amino acid, an L-amino acid or a mixture, e.g. a racemic
mixture, thereof. The amino acids include, for instancQ,
alanine, glycine, tyrosine, serine and lysine, although
glutamic, carboxyglutamic and aspartic acida are preferred.
Of these, aspartic acid is particularly preferred.
Normally, for the ~ Q~ of formulating a cleaning
composition, in particular a laundry detergent compo~ition,
the poly(amino acid) will be u~ed in the for~ of a salt
thereof, preferably an alkali metal salt and more preferably
lS the sodium salt.
It will b~ under~tood that the poly(amino acid)
compound ~ay be constituted by a ~ixture of two or more
com~o~ of the a~ iate description.
Al~o contemplated herein i~ the uae of a ~C~rsor of
a poly(amino acid) compound, suitable y~ G~ being
com~o~.~s that will undergo convQrsion into a poly(amino
acid) or derivative thereof when exposed to alkaline
conditions. Thus, a preferred ~e~ or herein is
polysuccinimide, which hydrolysQs to polyaspartic acid at
a pH greater than 9, the hydroly~i~ being particularly rapid
at pH value~ Or lO or higher. Thia opens up the possibility
of for~ing the poly(amino acid) or derivative thereof in
situ in the wash liquor formed by the addition of the
1 A~ detQrgent or other cleaning compo~ition to water;
such wash liquors typically have a pH value of lO.S or
ther~h~t~.
The molecular weight of the poly(amino acid) compound
or its ~L e_Ul aor may be varied within wide limits.
Preferably, the molecular weight is fro~ 500 to 200,000,
more preferably 2000 to 20,000.
According to the ~ ?nt invention, a poly(amino acid)
com~ou~.d or precursor thereof is atabili~ed -g~in~t
degradation sufficiently to render it acceptably storage-
2 ~5 PCT~S93/12090
stable. This i~ effected, in particular, by protecting thesaid com~ound or precursor from contact with a level of
alkalinity as would cause unacceptable degradation thereof.
The stabilisation or protection should be such that the
amount of degradation of the poly(amino acid) co~u..d or
precursor thereof is less than 50% over an 8 week storage
period under ~ 7e~ conditions (90-F(32.2-C) and 80%
relative humidity), preferably less than 30~ and most
preferably le~s than 5%.
A preferred method for stabllislng the poly(amino
acid) com~o~.d against degradation is to apply a ~tabilising
coating thereon. The coating material, which should be
compatible with other components of the cleaning
composition, may be selected from a wide variety of
biodegradable and non-biodegr~dable comF~nd~. or ~Ou~
the coating may comprise a mixture Or two or more suitable
materials.
In certain preferred embodiments, the coating material
is an organic acid compound, in particular such a com~our.d
that is solid at ambient temperatures; thus, the organic
compounds should in general have a melting point of at least
30C and will preferably have a melting point Or at least
40C and, more preferably, a melting point in ~x_ T - - of
50C. The organic acid com~G~.d ~o~l~ also be highly
~5 soluble in water at ambient t-mperatures, "highly soluble"
being defined for the purposes Or the pre~ent invention as
at -l-a~t 5g Or the acid dissolving in lOOg of distilled
wat-r at 20-C. PrefQrably, th- organic acid compound ha~ a
solubility of at lQast 20g/lOOg of water at 20C and most
pref~rably the organic acid compound will dissolve in its
own weight of water at 20C.
Organic acid com~ suitable as coating agents for
the pu.~_-e~ of the ~ -ent invention include aliphatic or
aromatic, monomeric or oligomeric carboxylic acids,
preferably the monomeric aliphatic carboxylic acids.
Examples of such aliphatic acid COm~O~ln~ are glycolic,
glutamic, succinic, l-lactic, malonic, glutaric, adipic,
maleic, malic, tartaric, diglycolic, carboxymethyl
W094/14939 PCT~S93/~090
21S26'2~
succinic, citric, citraconic, itA~oniC and ~esaconic acids;
and copolymers for~ed from an unsaturated polyca~Lo~ylic
acid (e g maleic, citraconic, it~ro~ic or mesaconic acid)
as one monomer and an unsaturated monocarboxylic acid such
a~ acrylic acid or an alpha-Cl-C4 alkyl acrylic acid ~8 the
r- n~1 ~ono~er, suitable copolymers being available fro~
BASF under the trade na~e- ~c~alAn- CP5 and CP45
The organic acid com~o~ d may be used in ad~ixture
with another material suitable rOr U5~ in the cleAn~ng
composition thus, for example, a coating which will impart
an acid environment around the poly(a~ino acid) co~pound nay
comprise citric acid or the like di-solved in a nonionic
surfactant The use of gelatine a- an ad ixture is also
possiblQ The use Or a coating of a poly(~ino acid) to
protect a poly(amino acid) derivative also com 8 into
consideration
The acid- are applied at levels of, in general, frou
2% to 20% by weight Or th- coated substrate, preferably fro~
2% to 15~, more preferably from 3~ to ~2Yo and most
preferably fro~ 3~0to 10% by weight Or the coated ub~trate
Glycolic acid at a level of a~Loximat-ly 5% by weight of
the coated substrate is a part~ rly preferred coating
agent
The organic acid compound may be sprayed on as a
molten mat-rial or as a solution or di-p~rsion in a olvent/
carrier liquid uhich is subsequently r~oved by ~ tion
The organic acid compound can also be applied as a powder
coating although this is 1~88 preferred as the provi~ion of
a uniforu layer of coating material is le88 easy and
therefore le~ effective
Molten coating i~ a preferred tec~n~que for organic
acid compound~ of melting point less than 80 C, ~uch a~
glycolic and l-lactic acids, but is le88 convenient for
higher melting point acids (e g higher than lOO C) such as
citric acid For organic acid com~o~ of melting point
higher than 80 C spraying-on a~ a ~olution or dispersion is
preferred Organic solvent~ such as ethyl and is~Lo~yl
alcohol can be used to form the solution- or dispersions,
wo 94/l49392~52 62 ~ PCT~S93/12090
although this will r~c--~itate a solvent ~e_ovcry stage in
order to make their uQe economic. However, the use of
organic solvent~ also gives rise to safety problems such as
flammability and operator safety and thus aqueous solution~
or dispersions are preferred.
Aqueous solutions are particularly advantageous where
the organic acid com~ou--d has a high agueous solubility
(e.g. citric acid) and the solution ha~ a sufficiently low
visco~ity to enable it to be ~ d. Preferably a
0 ~Q~ "L.ation of at least 25% by weight of the organic acid
com~o~.d in the solvent i~ used in order to reduce the
drying/evaporation load after coating has taken place. The
coating apparatus can be any of those norm~lly used for this
purpose, such a~ inclined rotary pans, rotary drums and
fluidised beds.
The poly(~mino acid) compound ~ay alternatively be
s~h~ ed by means of a coating for~ed fro~ a water-
soluble film-forming poly~er. Such poly~ers include water-
soluble cellulose ethQr~, for exa~ple ~ethyl cellulose,
ethyl cellulose, hy~Lo~yethyl cellulose, ~ethyll,y~Lo~y-ethyl
cellulose, methyl hydLo~y~LG~yl cellulosQ, carboxymethyl
cellulo~e (in particular a~ -the sodium salt) and
methylearboxy methyl eQllulose (in par~ Ar as the sodium
salt); water-soluble starehes, for example maize stareh or
depolyoerised stareh; stareh ethers, for example
earboxy-ethyl stareh,l.~d~ox~eLhyl stareh and methyl stareh;
an~ mix-u~__ of any two or more of these. Sodium
e~ ~ethyl eellulose (CMC) is preferred.
Suitable film-forming polymers also inelude
homopolymers or eopolymers of carboxylie aeids, such as
polyaerylie aeid, polymethaerylie aeid and polymaleie aeid;
eopolymers of aerylie aeid or methaerylie aeid with maleic
aeid, or a eopolymer of maleie aeid with vinylmethyl ether;
and the salts, in particular the sodium salts, of such
polymeric aeids. Preferred film-forming agents from this
group are sodium polyaerylate and the sodium salts of
aerylie aeid/maleie aeid copolymers with a weight ratio of
aerylie aeid: maleie aeid of 10:1 to 1:1, preferably 7:1 to
W094/14939 PCT~S93/12090
7 21 ~2620
2:1. These compounds may have a molecular weight of 3000 to
150,000, preferably 5000 to 10,000.
A further clas~ of film-forming polymers are the
carbon-chain polymers with nonionic hyd~o~l,ilic ~-u~_ as
well as polyether group~, example~ of which include
polyvinyl alcohol, partially saponified polyvinyl acetate,
polyvinyl pyrrolidone, polyacrylamide and polyethylene
glycol ether.
Suitable mixture~ of film-forming polym rs include,
for example, a mixture of CMC or methyl cellulose with
polyacrylate or with an acrylic/maleic acid copolymer, or a
mixture of polyethylene glycol ether with polyacrylate or an
acrylic acid/maleic acid copolymer.
Another, and particularly preferred, method of
stabilising the poly(amino acid) com~o~.d i8 to formulate it
as an agglomerate with an alkaline or alkaline-reacting
- com~o~ . An alkali as ~uch, e.g. sodium or potassium
hyd~oxide, al~o~gh not precluded, may not be ~uitable for
many cle~ning compositions and it is preferred to U8Q an
alkaline salt, for example a carbonate, bicarbonate or
silicate. Preferred salts are the alkali metal salts,
especially sodium salts. Naturally, a mixture of two or
more alkaline or alkaline-reacting com~o~ may be used.
Moreover, the alkaline or alkaline-reacting com~ou..d may be
used in admixture with one or more other suitable materials,
for example an anionic surfactant such as alkyl ethoxy
sulfonate (AES).
Bearing in mind that polyaspartate or the like is
-urc~ptible to alkaline hydrolysis, it i~ particularly
surpri~ing that poly(amino acid) comlo~ can be rendered
storage-stable by agglomerating them with an alkaline or
alkaline-reacting compound. However, in accordance with one
aspect of this invention, the degradation of the poly(amino
acid) com~ou..d can be inhibited by cG..~lolling the level of
alkaline or alkaline-reactive com~ou..d in the agglomerate:
in certain preferred embodiments, there i~ no more than 1
mole of alkaline or alkaline-reacting compo~nA per mole of
monomeric unit in the poly(amino acid) compound.
W094/14939 PCT~S93/12090
6~ 8
In a preferred emhc~iment of this invention, the
alkaline or alkaline-reacting comro~A is mixed initially
with a precursor of the poly(amino acid) compound, in
particular such a ~.e_~L~or that converts into a poly(amino
acid) com~-d under alkaline condition~. The agglomeration
stage is normally effected in the presence of ~ufficient
water to allow such conversion to take place and, even after
drying, the agglomerate~ will normally contain sufficient
residual moi~ture to permit the conver~ion to ~L~_ eeA to
completion if it has not already done 80 by then. Suitable
precursors are, for example, the imides of those poly(amino
acids) that form such imides. Thus, storAgc _~able
poly(aspartic acid) or a salt thereof, in particular sodium
polyaspartate, can be readily prepared by agglomerating
polysuccinimide with an alkaline or alkali-~lYaacting
com~o~ , the polysuccinimide being co..~LLed into the
polyaspartic acid or polyaspartate in s~tu. This method is
particularly advantageous in that the poly~uccinimide is
markedly cheaper than the commercially available
polyaspartate and yet this method provides the latter
com~ou~.d in a storage-stable form that i~ suitable for
incorporation into a granular~ (which term includes
pulverulent) cle~ninq composition, for example a laundry
detergent composition.
The preferred alkaline or alkaline-reacting material
i~ sodium carbonate, which salt is a worthwhile component in
cl~-n~ng compositions in its own right, since it acts as an
effective dissolution aid. Normally, the carbonate is
included in laundry detergent composition~ in the form of a
micronized powder; however, the use of carbonate having a
larger particle size, or carbonates having different
particle sizes, comes into consideration, since this will
reduce the surface area per unit mass and thereby will
--- reduce the rate of reaction between the poly(amino acid)
com~ou..d and the carbonate.
In certain preferred embodiments there is no more than
1 mole of alkaline or alkaline-reacting compo~n~, e.g.
carbonate, per mole of monomeric unit in the ~e_u~or, e.g.
W094/14939 21 PCT~S93112090
the ~uccinimide moiety in polysuccinimide.
Another preferred embodiment consists in forming
agglomerates from polyaspartic acid (or other poly(amino
acid)) and sufficient carbonate (or other alkaline or
alkaline reacting com~ou..~) to effect neutralisation but not
degradation. The poly(amino acid) may be formed in s~tu
from a suitable PL e~ Or~ e.g. polysuccinimide. Other
components may, of course, be included in ~uch ~gglomerate~.
The agglomeration of the poly(amino acid) compound,
or its precursor, and the alkaline or alkaline-reacting
com~vund may be carried out using any suitable agglomeration
tec~nique and apparatus, if appropriate with compatible
agglomeration auxiliaries. Such technique~, apparatu~ and
auxiliaries are well-known in the detergent-formulating art.
Once the agglomerates are formed, they may be dried, if
required, by conventional mean~.
Agglomeration of the poly(amino acid) compound or
~,e_~or thereof can be conveniently carried out in variou~
type~ of high ~ r mixer~, for exa~ple a Z-blade mixer, an
Eirich mixer or a L~dige mixer.
The agglomerates according to thi~ invention may
contain, for example, the following: 20-40% of anionic
surfactant, 0-30~ of sodium carbonate, 0-50% of zeolite, O-
15% of the poly(amino acid) com~o~-d or ~Le_~.~or thereof,
0-10% of CMC, with the balance being water. In a typical
dure the agglomeration mixer i~ charged with the
inorganic ~aterials and the CMC, together with the
poly(~ino acid) CO~O~ld or precur~or thereof, the
resultant mixture being agglomerated with a high-active
anionic ~urfactant (typically from 50-85% active by weight),
suitable anionic ~urfactant~ being, for ex~mple, C45AS, LAS
or TAS. Typically, the paste addition i~ effected at 50-
80C and the agglomeration time will typically be from 1 to
15 minutes. The agglomeration may be followed by an
optional drying and cooling step. Typical physical
properties of the resultant agglomerates are a density in
the range of 500-9OOg/l, a mean particle size of 200-800 ~m,
a coL~z~ronAing low cake strength and good free-flowing
W094/14935 ~6~ PCTtUS93tl2090
properties.
It is, of course, also possible to agglomerate the
poly(amino acid) compo~n~ with a non-A 1 ~A 1; ne material, e.g.
a nonionic surfactant, zeolite, bicarbonate, or a mixture of
S two or more of thesQ and/or other non-alkaline materials.
A further method according to this invention of
stabilising the poly(amino acid) compound is to spray-
granulate it in admixturs with, for ~xample, a nonionic
~urfactant. Yet another method according to the invention
is to encapsulate the poly(amino acid) compound, for example
using a silicone-based resin.
Yet another method of stabilising the poly(amino acid)
com~o~.d against alkaline hydrolysis and hence degradation
consists in i-- oL~o~ating the said compound as a dispQrsing
lS agent in a cleaninq composition, in particular a laundry
detergent composition, that is 80 formulated as to be
essentially neutral in terms of it~ pH. In this emho~iment,
the detergent matrix itself is acting, a~ it were, as the
stabilising medium and it i~ not therefore neces~ary to
coat, agglomerate, spray-granulate or ~ncap~ulate the
dispersing agent as described above, al~o-~g~ this is not
precluded.
. ~ L L~ ~atment of the poly(a~ino acid) compound or
precur~or thereof may be carried out if a~. O~L iate. For
example, the said com~o~.d or ~LL_~r~lor may bQ premixed with
a surfactant paste prior to agglomeration, coating, spray-
granulating, enr~rsulation or the like, or it may be mixed
in the form of an aqueous ~olution with the surfactant,
followed by drying to remove moisture. The latter ~.o~ ke
permit~ a predetermined moisture le~el to be achieved.
By suitable adjustment of the ~.~L.c~tmQnt, e.g. via
premixing of the poly(amino acid) com~o~.~ or a ~c_u~or
thereof with surfactant pa~te, it is possible to obtain
agglomerates cont~ining an exces~ of carbonate or other
3S alkaline or alkaline-reacting compound.
As demonstrated in Example 2 hereinafter, degradation
of a poly(amino acid) com~oul.d may also be caused by the
~ qnce of a bleach, in particular a source of hyd~G~en
W094/14939 PCT~S93/12090
11 2I52620
peroxide. Accordingly, it is a further aspect of this
invention to provide a eleAni~g eomposition containing a
poly(amino aeid) com~o~.d or a precursor thereof and a
detersive ~urfaetant, characteri~ed in that the poly(amino
acid) compound or precursor thersof is protected from
contact with a level of bleach as would cause degradation
thereof. The poly(amino acid) eompound or its precursor may
be stabili~ed or proteeted against unaeeeptable degradation
(a~ defined above) by eoating, by ene~p~ulation or by
mixing, in the form of an agglomerate or granulate, with at
least one other material, by means analogous to those
de~eribed above. In certain preferred emhoAiments~ the
poly(amino acid) eomro~nA or ~e~ or thereof is included
in a detergent or other eleaning eomposition that eontains
no, or substantially no, bleaeh; in ~ueh a ease, depenAin~
upon the level of alkaline or alkaline-reaeting material, it
may not be ne_-~s?ry to further Qtabili~e the poly(amino
aeid) eompound or it6 ~e~ or by means of eoating,
ene~r~ulation, agglomerating, granulating or the like,
although this i8 not preeluded.
The stabili~ed poly(aspartie aeid) eompound aeeording
to the present invention may be usQd a~ a dispersing agent
(whieh term herein ineludes a elay-~oil-suspenA~ng agent
and/or an anti-re~ero~ition agent) in solid (e.g. grA~ Ar
or other partieulate) eleaning eomposition~ and will
g~nerally be employed therein at a level of from 0.1% to
50%, usually at least 0.4%, preferably 1 to 15%, more
pref~rably 2.5 to 10% and moct preferably 3 to 6%, by
weight. The eleAning eompositions will generally contain
one or more detersive surfaetant~, the total amount of such
~urfaetant being in general up to 70%, typieally 1% to 50%,
preferably 1 to 30%, more preferably 5 to 25% and especially
10 to 20%, by weight of the total eomposition.
Although the poly(amino aeid) eom~o~.d may be included
in a wide variety of eleaning eompositions, for example
ha~ rfaee and other household eleaner~ and dishwashing
compositions, they are particularly suitable for use in
laundry detergent eompositions, e.g. general~ o~? or
2~2~o
W094tl4939 PCT~S93/12090
12
heavy-duty grAnl~lAr laundry detergent compositions. These
will contain not only the stabilised poly(amino acid)
compound dispersing agent and detersive surfactant but al~o,
optionally, one or more further components conventional in
the art; these may be selQcted from, for example, a
detergent builder, a bleach (in pArticular a source of
hyd~Gyen peroxide, Q .g. sodium perborate or sodium
percarbonate), a bleach activator (e.g. TAED), an enzyme, a
polymeric soil-releasQ agent, a chelating agent, a
conventional dispersing agent, a brightener, a suds
su~e_sor, a pH-buffering agent, a dye, a dye transfer
inhibition agent or a pigment. It will be under~tood that
any of the above-mentioned components, whether essential or
optional, may be con tituted, if desired, by a mixture of
two or more com~o~ of the a~Lo~iate dQscription.
A wide range of surfactants can be used in the
clqAn~g compositions. A typical listing of anionic,
nonionic, ampholytic and zwitterionic clas~es, and specie~
of these surfactants, is given in US-A-3,664,961 ~ to
Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly
suitable herein, especially mix~les of sulfonate and
sulfate surfactants in a weight ratio of from 5:1 to 1:2,
preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
Preferred sulfonates include alkyl benzene sulfonates having
from 9 to 15, especially 11 to 13, carbon atoms in the alkyl
radical, and alpha-sulphonated methyl fatty acid e~ters in
which the fatty acid is derived from a C12-C18 fatty source,
preferably from a C16-Cl8 fatty source. In each instance
the cation is, in general, an alkali metal, preferably
sodium. Preferred sulfate surfactants are alkyl sulfates
having from 12 to 18 carbon atoms in the alkyl radical,
optionally in admixture with ethoxy sulfates having from 10
to 20, preferably 10 to 16, carbon atoms in the alkyl
radical and an average degree of ethoxylation of 1 to 6.
Examples of preferred alkyl sulfates are tallow alkyl
sulfate, coconut alkyl sulfate, and Cl4_l5 alkyl sulfates.
The cation in each instance is again, in general, an alkali
WO94/14939 2 I 5 2 6~a PCT~S93/12090
metal cation, preferably sodium.
one class of nonionic surfactants particularly useful
in the ~ ent invention are conA~n~Ates of ethylene oxide,
with a hy~ko~hobic moiety to provide a surfactant having an
average hydrophilic~ op~ilic balance (HLB) in the range
from 5 to 17, preferably from 6 to 14, more preferably from
7 to 12. The hydrophobic (lipophilic) moiety may be
aliphatic or aromatic in nature and the length of the
poly~e~hylene group which is ~o~ with any particular
h~d~G~hobic group can be readily ad~usted to yield a water-
soluble compound having the desired degree of balance
between hydrophilic and hydrophobic elements.
E~pecially preferred nonionic surfactants of this type
are the Cg-Cl5 primary alcohol ethoxylates cont~i ni ng 3-8
moles of ethylene oxide per mole of alcohol, particularly
the C14-C15 primary alcQhols con~ in~ 6-8 mole8 of
ethylene oxide per mole of alcohol, the C12-C15 primary
alcohols containing 3-5 moles of ethylene oxide per mole of
alcohol, and mi~u~ ~3 thereo~.
Another suitable class of nonionic surfactants
comprising alkyl polyglucoside com~o~ Or general formula
RO (CnH2nO)tzs
wherein Z i8 moiety derived from glucose; R is a
saturated ~y~.G~hobic alkyl group that contains from 12 to
18 carbon atoms; t is from O to lO and n i8 2 or 3; x is
from 1.3 to 4, the compounds including less than 10%
unreacted fatty alcohol and less than 50% short chain alkyl
polyglucosides. Compounds of this type and their use in
detergents are disclosed in EP-A-O, 070, 077, EP-A-O, 075, 996
and EP-A-0,094, 118 .
Also suitable as nonionic surfactants are poly hydroxy
fatty acid amide surfactants of the formula
R2 _ C - N - Z, wherein Rl is H,
Il 11 , ,
0 R
or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl
or a mixture thereof, R2 is C5_3l hydrocarbyl, and Z is a
polyhydroxyhydrocarbyl having a linear hydrocarbyl chain
with at least 3 hydroxyls directly ~ol-~.ccted to the chain,
W094/14939 ~S ~6~Q 14 PCT~S93112090
or an alkoxylated derivative thereof. Preferably, Rl is
methyl, R2 is a straight Cl1_15 alkyl or alkenyl chain such
as coconut alkyl or mixtures thereof, and Z iB derived from
a reducing sugar such as glucose, fructo~e, maltose,
lacto~e, in a reductive amination reaction.
A further class of surfactants-are the semi-polar
surfactants such a~ ~mine OY~ . Suitable amine oxide~ are
selectQd from mono C8-C20, preferably C10-Cl4, N-alkyl or
alkenyl amine oxides and propylone-1,3-diaminQ dioxides
wherein the remaining N position~ are substituted by methyl,
hydroxyethyl or hydroxypropyl groups.
Another class of surfactants are amphoteric
surfactants, such as polyamine-based species.
Cationic surfactant~ can also be used in the detergent
compositions herein and suitable guaternary ammonium
surfactants are selected from mono C8-C16, preferably
Clo-C14, N-alkyl or alkenyl ammonium surfactants wherein the
remaining N positions are substituted by methyl,
hydroxyethyl or hyd~o~ v~yl ~.ou~s.
~ixLu~e_ of surfactant types are preferred, more
especially anionic-nonionic and also anionic-nonionic-
cationic mixtures. Particularly preferred mixtures are
described in GB-A-2,040,987 and EP-A-0,087,914.
Builder materials will typically be ~ nt at from
5% to 60% of the elsaning eompositions herein. The
eomposition~ herein preferably are free or substantially
free of phosphate-containing builders (substantially free
being herein defined to constitute less than 1~ of the total
detergent builder system), and the builder system herein
consi~ts of water-soluble builders, water-insoluble
builders, or mi~Lu~e_ thereof.
Water-insoluble builders can be an inorganic ion-
PYchange material, commonly an inorganic hydrated
aluminosilieate material, more partieularly a hydrated
synthetic zeolite such as hydrated Zeolite A, X, B or HS.
Preferred aluminosilicate i~ Y~h~nge materials have
the unit cell formula
Mz [(A102)z (SiO2)y] xH20
W094/14939 PCT~S93/12090
2I 5~620
wherein M is a calcium-exchange cation, z and y are at least
6; the molar ratio of z to y is from 1.0 to 0.5 and x is at
least 5, preferably from 7.5 to 276, more preferably from 10
to 264. The aluminosilicate materials are in hydrated form
and are preferably crystalline, containing from 10% to 28%,
more preferably from 18~ to 22%, water.-
The above aluminosilicate ion eYrhAn~e materials maybe further characterised by a particle size diameter of from
0.1 to 10 micromQtQrs, preferably from 0.2 to 4 micrometers.
The term ~particle size diameter~ herein represents the
average particle size diameter of a given ion ~YchAnge
material as determined by conventional analytical tochniques
such as, for example, mi~ opic determination utilizing a
~cAnning electron mi~-o-cope. The aluminosilicate ion
~YrhAnge materials may be further characterised by their
calcium ion ~Y~h-n~e capacity, which i~ at least 200 mg
equivalent of CaC03 water hardne~s/g of aluminosilicate,
calculated on an anhydrous basis, and which generally is in
the range of from 300 mg eq./g to 352 mg eq./g. The
aluminosilicate ion ~Ychange material~ herein may be still
further characterised by their calcium ion eY~hange rate
which i~ described in detail in GB-A-1,429 143.
Alumino~ilicate ion-exchange materials useful in the
practice of this invention are commercially available and
can be naturally oc~lLing materials, but are preferably
~ynthetically derived. A method for producing
alu~inosilicate ion ex~hAnge material~ is Ai~c~^e~ in US-
A-3,98S,669. Preferred synthetic cry~talline
aluminosilicate ion exchange materials useful herein are
available under the designation Zeolite A, Zeolite B,
Zeolite X, Zeolite HS and mix~e_ thereof. In an
especially preferred embodiment, the crystalline
aluminosilicate ion eYchAnge material is Zeolite A and has
the formula
Nal2[ (A12)12 (sio2)l2] xH20
wherein x is from 20 to 30, especially 27. Zeolite X of
formula Na86 ~(Al2)g6(si2)106]
.276H20 is also suitable, as well as Zeolite HS of formula
W094/14939 ~ 16 PCT~S93/l2090
Na6~(Al02)6(siO2)6~ 7 5 2 )
Another suitable water-soluble, inorganic builder
material is layered silicate, e.g. SKS-6 (H~e~hst). SKS-
6 is a crystalline layered silicate con~isting of sodium
silicate (Na2Si205). The high Ca+'/Mg++ binding capacity is
mainly a cation exchange mech~nism. In hot water, the
material become~ more solublQ.
The water-~oluble builder can be a monomeric or
oligomeric carboxylate chelating agent.
Suitable carboxylates containing one carboxy group
include lactic acid, glycollic acid and ether derivatives
thereof as disclosed in BE-A-831,368, BE-A-821,369 and BE-
A-821,370. Polycarboxylates containing two carboxy ~ uups
include the water-solubl~ salts of succinic acid, malonic
acid, (ethylQnedioxy) diacetic acid, maleic acid,
diglycollic acid, tartartic acid, tartronic acid and fumaric
acid, as well as the ether carboxylates described in DE-A-
2,446,686, DE-A-2,446,687 and US-A-3,935,257, and the
sulfinyl carboxylates dQscribed in BE-A-840,623.
Polycarboxylates containing thr-e carboxy ~rou~s include, in
particular, water-soluble citrates, aconitrates and
citraconate~ as well as succinate derivatives ~uch as the
carboxy~ethyloxysuccinates described in GB-A-1,379,241,
lactoxysuccinates described in NQtherlands Patent
Application 7205873, and the oxypolycarboxylate materials
such as 2-oxa-1,1,3-propane tricarboxylates described in GB-
A-1,387,447.
Polycarboxylates containing four carboxy ~LOU~-
include oxydisuccinates disclosed in GB-A-1,261,829,
1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane
tetracarboxylates and 1,1,2,3,-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the
sulfosuccinate derivatives disclosed in GB-A-1,398,421 and
GB-A-1,398,422 and in US-A-3,936,448, and the sulfonated
pyrolysed citrates described in GB-A-1,082,179, while
polycarboxylates containing phosphone substituents are
disclosed in GB-A-1,439,000.
Alicyclic and heterocyclic polycarboxylates include
WO94/14939 PCT~S93/12090
17 2I~2620
cyclopentane-cis, cis, cis-tetracarboxylates,
cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-
tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-
tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane
hexacarboxylates and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic
polycarboxylates include mellitic acid, pyromellitic acid
and the phthalic acid derivatives disclo~ed in G~-A-
1,425,343.
Of the above, the preferred polycarboxylates arehydroxycarboxylatea containing up to three carboxy groups
per molecule, more particularly citrates.
Preferred builder systems for use in the preferred
granular detergent compositions herein include a mixture of
a water-insoluble aluminosilicate builder such as zeolite A,
and a water-soluble carboxylate chelating agent such as
citric acid.
Other builder materials that can form part of the
builder system include inorganic material~ such a~ alkali
metal carbonates, bicarbonates, silicates and organic
phosphonates, amino polyalkylene pho~rhonate~ and amino
polycarboxylates.
The cleaning compositions or detergent additives
herein may contain a further soil antireAero~ition or soil-
suspension agent, in addition to the poly(amino acid)
comFo~l~A~ herein. Such antire~eFo~ition and soil-suspension
ag~nts suitable herein include cellulose derivatives such as
methylcellulose, carboxymethylcellulo~e and
hydroxycellulose, homo- or co-polymeric polycarboxylic acids
or their salts and polyamino compounds. Polymers of this
type include the polyacrylates and maleic anhydride-acrylic
acid copolymers disclosed in detail in EP-A-0,137,669, as
well as copolymers of maleic anhydride with ethylene,
methyvinyl ether or methacrylic acid, the maleic anhydride
constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.025%
to 5% by weight, of the compositions herein.
WO94/14939 ~0 18 PCT~S93/12090
EP-A-311,342 discloses certain modified polyesters
which act as soil-release agents on polyester fabrics; thQse
modified polyesters also come into consideration herein.
The cleaning compocitions, in particular the detergent
composition~, are preferably in granular form and more
preferably in a "compact" form, i.e. having a density, which
is higher than the density of conventional detergent
compositions. The preferred den~ity of the compositions
herein ranges from 550 to 950g/litre, preferably 650 to
850g/litre of compo~ition, measured at 20-C.
The pre~ent invention is illustrated in and by the
following examples.
E~nle 1
Three formulations containing sodium polyaspartate
were prepared, having the composition.
LAS 9.52 parts by weight
TAS 0.49
25E3 3.26
TAEll 1.11
Zeolite A 19.5
Citrate 6.56
Polyaspartate, sodium 3.19
Silicate (2.0 ratio) 3.5
Carbonate 14.52
TAED 5.0
~L ~ ate 16.0
DETPMP 0.38
MgS04 0.40
Enzyme 1.4
CMC 0.48
Brightener 0.24
Photobleach 0.002
Suds ~ essor 0.54
Perfume 0.43
The first formulation contained the polyaspartate
W094/14939 21 5 ~ 6 2 ~ PCT~S93/12090
added directly by dry addition. The second formulation
contained the polyaspartate added in the form of an
agglomerate with sodium zeolite, sodium carbonate, anionic
surfactant and CMC. The third formulation contained the
s polyaspartate added in the form of an agglomerate with
sodium zeolite, anionic sUrfaCtant and CMC (i.e. with no
carbonate).
The agglomerates added to the sQcond and third
compositions had the following, respective, constituents
Second Thi r~
Anionic surfactant 31 31
Carbonate 21 o
Zeolite 28 40
Polyaspartate 10 10
CMC
Each of the three formulations was placed in a
L~rective, s~nAArd cardboard detergent carton and left
open to the atmc-rh~~e under conditions of stress storage
(90F (32.2-C) and 80% relative humidity) for a period of 8
weeks. Samples of each formulation were removed after given
intervals of time during that storage period and were
analysed by both quantitative and qualitative method~, using
the stan~a~d analytical techn~que of capillary zone
el~_Ll~horesis (CZE) and also by a s~an~ard detergent
for ulation performance test method.
CZ~ traces (ele_LLG~h~.u~ams) were taken on samples
of each of the three formulations removed from the
respQctiYe stored products after intervals of 2, 4, 6 and 8
weeks. A reference sample of polyaspartate that had not
been ~ub~ected to storage was also analy~ed by CZE. The
ele_~ l.eLo~Lams showed degradation of the polyaspartate
over the storage period in the cases of the first
formulation (direct addition of polya~partate) and the
~e~on~ formulation (addition by means of agglomerates
containing carbonate).
From both the qualitative and quantitative analysis
Wo94/14939 PCT~S93/12090
,6~ 20
of the polyaspartate performance over the 8-week storage
period, it could be concluded that the polyaspartate is
degraded when eYpo~e~ to high levels of alkalinity.
~Y~mDle 2
Tests wer~ c~rried out in order to a~certain which of
the detQrgcnt components were rQsponsiblQ for the
degradation of polyaspartate.
A series of open-top, plastics bQakers (500ml
capacity) were prepared, each containing sodium
polyaspartate and one of the following components: (a)
~odium zeolite, (b) sodium percarbonate plus TAED, (c)
sodiu~ perborate tetrahydrate plus TAED, (d) a proteolytic
enzyme and (e) ~odium carbonat~.
The amount~ u~ed in the beaker~ were as follows (% by
weight)
Zeolite 80% 65% 55% 3s%
Carbonate - - 25%
Enzyme - 15%
Powdered
polyaspartate 20% 20% 20% 20%
Bleach/TAED - - - 3~*
All were dry mixes.
The h~Aker~ were subjected, with their tops left open,
to conditions of stress storage (90F (32.2C); 80% relative
hu~idity). The polyaspartatQ content in each ca~e wa~
qu~ntitatively analysed by CZE and the rQsults showed that
there was no significant degradation in the case of the
composition (d) containing the enzyme and only a low level
of degradation in the composition (a) containing the zeolite
(~uch minimal degradation being, it is tho~yht, due to trace
alkalinity in the zeolite material); there was, however,
substantial degradation of the polyaspartate in the
compositions (b) and (c) containing a bleach and a bleach
activator, and substantial degradation also occurred in the
composition (e) containing the carbonate.
WO94/14939 PCT~S93/12090
21 2152620
Example 3
A ~eries of compositions were prepared in the form of
agglomerates, each containing four parts by weight of
poly~uccinimide and, respectively, 0, 1, 2, 3, 4, 5, or 10
part~ by weight of sodium carbonate. The agglomerates were
added to respQctivQ samples of a conventional laundry
detergQnt matrix containing surfactant, builder, bleach,
chelant, enzyme and ~uch minor ingredient~ as perfume and
colouring ~atter. The agglomerates were added at a level
customary for the addition of dispersant to laundry
detergent compositions.
The resultant di~persant-contAining compositions were
maintained over an 8-week storage period under conditions of
~LL~-- storage. During that period samples were analysed
quantitatively using CZE.
The CZE traces indicated that, where the level of
carbonate was less than or equal to equimolar with re~pect
to the monomeric units in the polysuccinimide, the latter
had been CG..~e~ Led partially or wholly into polyaspartate
but that no significant degradation of the latter occurred
over the te~t period. (In the experiment in which carbonate
Wa8 absent there was no ~..v~L.ion of the polysuccinimide
into polyaspartatic acid.) In contrast, where the level of
carbonate was in ~ r ~ of equimolar with respect to the
monomeric units in the polysuccinimide, the latter had been
..~Led into polyaspartate but this had in turn, undergone
signl~icant degradation; inA~-A, in the composition
containing an extremely high level (10 parts) of carbonate,
complete degradation of the polyaspartate had occurred
within two weeks.
E~nle 4
The following laundry detergent products can be
prepared (amounts are in parts by weight) using polyaspartic
acid, its sodium salt or polysuccinimide as the dispersant.
WO94/14939 PCT~S93/12090
~,~5~6~ 22
1~ C
LAS 7.71 7.71 7.71 7.71
TAS 2.43 2.43 2.43 2.43
TAE11 1.10 1.10 1.10 1.10
25E3 3.26 3.26 3.26 3.26
Zeolite A 19.5 19.5 19.5 19.5
Citrate 6.5 6.5 6.5 6.5
Disper~ant 4.25 4.25 4.25 4.25
Carbonate 11.14 11.14 11.14 11.14
10 Perborate 16.0 16.0 16.0 16.0
TAED 5.0 5.0 5.0 5.0
EDTA 0.38 - - -
DETPMP - 0.38
EDDS - - 0.38 0.22
15 CMC 0.48 0.48 0.48 0.48
Sud~ Su~ or 0.5 0.5 0.5 0.5
Brightener 0.24 0.24 0.24 0.24
Photoactivated bleach 0.002 0.002 0.002 0.002
Enzyme 1.4 1.4 1.4 1.4
20 Silicate (2.0 ratio) 4.38 4.38 4.38 4.38
MgS04 0.43 0.43 0.43 0.43
Perfume 0.43 0.43 0.43 0.43
Sulphate 4.10 4.10 4.10 4.10
Water and miscellaneou~ to balance
It will of cour~e be under~tood that the pre~ent
in~ention ha~ been de~cribed above purely by way of example
and that ~odifications of detail can be made within the
scope of the invention.
W094/14939 PCT~S93/12090
23 21526~0
In the detergent compositions, the abbreviated component
identifications have the following mean~n~:
LAS : Sodium liner C12 alkyl benzene
~ulphonate
TAS : Sodium tallow alcohol sulfate
TAEn : Tallow alcohol ethoxylated with n
moles of ethyleno oxide per mole of
alcohol
25E3 : A Cl2_lsprimary alcohol conA-n~^~ with
an average of 3 moles of ethylene
oxide
TAED : Tetraacetyl ethylene diamine
Silieate : Amorphous Sodiu~ Silicate (SiO2:Na20
ratio normally follow~)
Carbonate : AnhydLv~s sodium earbonate
CMC : Sodium ea.~o~Jethyl eellulo~e
Zeolite A : Hydrated Sodium Alumino~ilieate of
formUla Nal2(AlO2sio2)l2 27H20 having
a primary particle ~ize in the range
from l to lO micromQtQrs
Citrate : Tri-sodium citrate dihydrate
Photobleach : Tetra sulfonated Zinc phthalocyanine
MA/AA : Copolymer of 1:4 maleic/acrylic acid,
average moleeular weight about 80,000
Enzyme : Miye~ proteolytie and amylolytic
enzyme sold by Novo Industries AS
Brightener : Disodium 4,4'-bi~(2-morpholino-4-
anilino-s-triazin-6-ylamino)~ ne-
2:2'-disulphonate
DETPMP : Diethylene triamine penta (Methylene
phosp~onieacid), marketed by Moncanto
under the Trade name Dequest 2060
M~Y~ Suds : 25% paraffin wax Mpt 50C, 17%
Suppres~or : hydrophobic silica, 58% paraffin oil
