Note: Descriptions are shown in the official language in which they were submitted.
W092/0352:` 2a~327~j PCr/US91/05533
- ! -
DE.ERGENT C0!:?3S'-- 0~5This invention relates to laundry detergent _ompositionsand more especially to laundry detergent compositions hat
incorporate little or no phosphorus containing materials.
~aundry detergen. compositions of this type have become
widely available as a result of public concern over,
and~or iegislative action to cont ol, the environmentai
impac~ ~ a~ueous effluent from untreated or partially
~r2àt~d dvi~es~ic s2wa52 contain~ng d~ssolvQA ?hospha'es~
~he co-l~nercial introduction of zero-phospha~e detergen.
products, whilst meeting the primary objective of reducing
the phosphate load on the environment arising from
detergent products, has added to formulation complexity
and has also increased the load on the environment of
organic materials. Zero phosphate compositions employ a
combination of materials to replace the phosphate builder,
the principal component usually being a water insoluble
sodium aluminosilicate zeolite supplemented by a mixture
of water soluble inorganic and polymeric organic salts.
Much effort has been e2pended by those working in the
field in developing such multi-component builder systems,
the need for which arises from the difficulty of finding a
single material that will carry out all of the functions
previously performed by the phosphate builder. Although
not completely characterised, these functions include
chelation of both Ca++ and Mg++ ion hardness together with
peptisation and suspension of the soils removed from
fabrics during the washing process.
It has now been found that the use of crystalline or
so-called layered silicates (known ~ se) in particular
combinations of detergent builder components provides
enhanced performance and permits certain other materials
W092/03525 PCT/US91/05533
2 ~3 ~ ,'3 .~ 7 j 2
to be reduced in le~el or omitted altogether from the
resultant particulato det~rgent pr~d~cts. Tn preferred
embodiments of the invention, cleaning perfor~ance
equivalent to ~ha. o 2~ J ?~ ts _~n _~ ob~ained at
a significantly ;o~,ve 1~ 1 o_ uias~ o~ e detergent
builder compo~se;~ s~ e~ .;e ;~ s.. ~-12
environment. Other advantages i~clude e:~;qanced dispensing
characteristics, .e. ~ i s `~7 ' n~ J ~ ' O n ~ .e
particulate product at the s~ar~ of the wash _ycle i~ an
automatic domos~ic w~hlnc ~ a~ a ia
insolubl~ pr~c~ ? ~ C ~ P~t~
in fabric v~
~ccording ~o '~2 `~ 2~a~ d
particula;a ~e~rg~na ~ SL~''v~p'_S~
a) from 5~ to 50~ by weig`nt of one or ~ore a~ionic,
nonionic, ampholytic, z~i~tsrionic o- cationic
surfactants or a misture of any thereof;
(b) from 10~ to g5~ of a detergent builder system
comprising a misture of
i) from 20% to 60% by weight of the misture of a
sodium aluminosilicate zeolite;
ii) from 10% to 30S by weight of the misture of a
water soluble monomeric or oligomeric organic
carbosyla~e chela~ing agen~; and
iii) from 10% to 65% by weight of the mi~ture of a
crystalline layered sodium silicate having the
composition ~aMSi~O2s+l.yH2O, wherein M is
sodium or .hydroqen, ~ is ~ number from 1.9 to 4
and y is a number from 0 to 20; and
(c) from 0 to 40~ of non-surfactant, non-builder deterqent
ingredients.
Preferably component (b)(iii) of the buildsr systsm is ~,
, ~, or ~-Na2Si2o5 and component (b)(i) is a
W092/03s2~ PCr/US91/0~33
- 3 - 2 ~ ~ 3 2, ~
synthetic hydrated zeolite of unit cell formula
Naz[(AlO~)_(SiO2)v]. x~O
wherein ~ and ~- a~e ~ s_ ~" .he ~a~io ^- z to y is
from 1.0 '3 ' . ~ ` a ~ ly ---om
to 276.
Preferably also the monomeric or oiigomeric organic
carbo~ylat~ s ~ yl
logarith~ic ~ .?. ~ c '~ ?- S ~ 9,
preferab~y o~ a
The present ~nve-l~io-l COn_~ la a ~ iCU` a~e ~e.ergen~
composition incorporating one or more sur~ac~ants and a
detergent builder system composed of th ee principal
components viz. a sodium aluminosilicate zeolite, a water
solùble monomeric or oligomeric organic carbo~ylate
chelating agent and a crystalline layered sodium
silicate. Preferred compositions in accordance with the
invention, also contain other, non surfactant, non-builder
detergent ingredients.
A wide range of surfactants can ~e us2d in the detergent
compositions. A typical listing of anionic, nonionic,
ampholytic and zwitterionic classes, and species of these
surfactants, is given in U.S.P. 3,66~,961 issued to Norris
on May 23, 1972.
Mistures of anionic surfactants are particularly suitable
herein, especially mi~tures of sulphonate and sulphate
surfactants in a weight ratio of f om 5:1 to 1:2,
preferably from 3:1 to 2:3, more ?-ef~orably from 3:1 to
1:1. Preferred sulphonates include alkyl benzene
W092/03S2~ PCT/~S9l/0~533
2 7 ~
sulphonates having from 9 to 15, especially 11 to 13
carbon atoms in the alkyl radical, and alpha-sulphonated
methyl fatty acid esters in which the fatty acid is
derived from a C12-C18 fatty source, preferably ~rom a
C16-C18 fatty source. In each instance the cation is
an alkali metal, preferably sodium. Preferred sulpha~e
surfactants are alkyl sulphates having from 12 to 22,
preferably 14 to 18 carbon atoms in the alkyl radical,
optionally in admi2ture with ethosy sulphates havinq ~om
10 to 20, preferably 10 to 16 carbon atoms i~ the alkyi
radical and an average degree of etho~ylat~on of l .o 6.
~he cat on ~a ~ch. ~nstanco is ~gain an al`ia!~ ,~e~l
cation, pr~forably sodium.
One class of nonionic suractants useful in the present
invention are condensates of ethylene oside with a
hydrophobic moiety to provide a surfactant having an
average hydrophilic-lipophilic balance (HLB) in the range
from 8 to 17, preferably from 9.5 to 13.5, more preferably
from 10 to 12.5. The hydrophobic (lipophilic) moiety may
be aliphatic or aromatic in nature and the length of the
polyosyethylene group which is condensed with any
particular hydrophobic group can be eadily adjusted to
yield a water-soluble compound having the desired degree
of balance between hydrophilic and hydrophobic elements.
Especially preferred nonionic surfactants of this type are
the Cg-Cl5 primary alcohol ethosylates containi~g 3-8
moles of ethylene oside per mole of alcohol, particularly
the C14-C15 primary alcohols containing 6-8 moles of
ethylene oside per mole of alcohol and the C12-C14
primary alcohols containing 3-5 moles of ethylene oside
per mole of alcohol.
W092/03525 ~ PCT/US91/0~533
Another class of nonionic surfactants comprises alkyl
polyglucoside compounds of general formula
~o (CnH~nO)tzx
wherein Z is a moiety derived from glucose; ~ is a
saturated hydrophobic alkyl group that contains from 12 to
18 carbon atoms; t is from 0 to 10 and n is 2 or 3; ~ is
from 1.3 to 4, the compounds including less than 10~
uareacted atty alcohol and less than 50% sho-t chain
alkyl polyglucosides. Compounds of this type and their
~ase in d~ on~ camQositions are disclosed in ~P-B
0070074, 007007 " 0075996 and 0094113.
A further class o~ surfactants are the semi-polar
surfactants such as amine o~ides. Suitable amine o~ides
are selected from mono C8-C20, preferably C10-Cl4
N-alkyl or alkenyl amine osides and propylene-1,3-diamine
diosides wherein the remaining N positions are substituted
by methyl, hydrosyethyl or hydrosypropyl groups.
Cationic surfactants can also be used in the detergent
compositions herein and suitable ~uaternary ammonium
surfactants are selected from mono C8-C16, preferably
C10-Cl4 N-alkyl or alkenyl ammonium surfactants
wherein remaining N positions are substituted by methyl,
hydrosyethyl or hydrosypropyl groups.
The detergent compositions can comprise from 5~ to 50~ by
weight of surfactant but usually comprises from 5% to 30%,
more preferably from 5% to 15% by weight. Combinations of
surfactant types are preferred, more especially
anionic-nonionic and also anionic-nonionic-cationic
blends. Particularly preferred combinations are described
W092/0352~ PCT/US91/0~33
~l3~ a - 6 -
in GB-A-2040987 and EP-A-0087914. Although the
surfactants can be incorporated into the compositions as
mixtures, it is preferable to control the point of
addition of each sur~actan~ in order to opt.imise the
physical characte.~isaics c:~ he _c~.pvsi '_i5n ~_,A avoi~
processing ?~a:2 e~;. ?~:a -~ ara ~_ S O_
surfactant addition are described hereinafter.
The second essen~ial compone.l~ of cGm?osi.ivas in
accordance wi,h ~he i'a';ea`_.` _a ' S l ~e`i e .'~l'_ `aai!de-
system comDrisin9 a :~i 3~n1r''? Cr so,d~m ~lnmisosil.~c.3te
zeolite, ~ W2~ e ~ S ~ za _ i _
carbo~ylate che~ insJ a';~ n_ -~ __','_-a_`''~e ~-~yQ _~
sodium sil oa;e _.. ~_ _nae ~ s.
Whilst a range of aluminosilica~e ioa e~change materials
can be used, preferred sodium aluminosilicate zeolites
have the unit cell formula
Naz t(AlO2)z (SiO2)y] sH20
wherein z and y are at least 6; the molar ratio of z to y
is from 1.0 to 0.5 and s is at least 5, preferably from
7.5 to 276, more preferably .rom 10 to 25~. The
aluminosilicate materials are in hydrated form and are
preferably crystalline, containing from 10% to 28%, more
preferably from 18~ to .2j water.
The above aluminosilicate ion e~change materials are
further characterised by a particle size diameter of from
0.1 to 10 micrometers, preferably from 0.~ to 4
micrometers~ The term ~particle size diameter~ herein
represents the average particle si7e diameter of a given
W092/0352~ 7 2 ~ 3 ~ ~ 7 ~ PCT/US91/0;533
-
ion e~change material as determined by conventional
analytical techniques such as, for e~ample, ~icroscopic
determination utilizing a scanning elec.ron microscope.
The aluminosilicate ion e:;chan~e m~ ls are further
characterised by their c lcin~. io~. e~c:~an.s~ oapacity,
which is at 'eas ~0~ m^ ~ u ~ ! er
hardness/g of aluminosilicate, calcula.-d on an anhydrous
basis, and which gener~ is ~ ~ae ~ e of ~rom 300 mg
eq./g to 352 mg eq./g. Th~e a`umi-.osi' _ate ion e~change
materials hereia are -~ ised by t~eir
calcium ion e_chanqe ra~e ~ic.~ is ~- le-~s :30 mg
equivalQnt c~ c~c~ 'J-'?.;.'`~S
Ca~/gallon/~inute~;r3m~ s;licate
(anhydrous ~as ), ~n~ .h_ h ,~ `ain ~h~
range of from !30 mg e~uivalent c-
CaCO3/litrè/minute/~gram/litre) [ graias~gallon/minute/
(gram/gallon)~ to 390 mg equivalent
ofCaCO3/litre/minute/ (gram/litre) [6
grains/gallon/minute/(gram/gallon)~, based on calcium ion
hardness. Optimum aluminosilicates for builder purposes
exhibit a calcium ion e~change rate of at least 260 mg
e~uivalent of CaCO3/litre/minute/(gram/litre) ~4
grains/gallon/minute/(gram/gallon)].
Aluminosilicate ion e~change mate. als useful in the
practice of this invention are commercially available and
can be naturally occurring ma~erials, but are preferably
synthetically derived. ~ method for producing
aluminosilicate ion e~change materials is discussed in US
Patent No. 3,985,669. Preferred synthetic crystalline
aluminosilicate ion e~change mater als useful herein are
available under the designations Zeolite A, Zeolite B,
Zeolite X, Zeolite HS and mi~tures thereof. In an
especially preferred embodiment, 'he crystalline
W092/03525 PCT/US91/05533
2 0 ~ X 2 7 ~
aluminosilicate ion e~change material is Zeolite A and has
the formula
Nal2[(~lO2)12 (Si2)12] 2
wherein ~ ;s -rom 20 to 30, especially 27. Zeolite X oL
ormula Na86 [(A12)86(Si2)106] 2
also suitable, as well as Zeolite HS of formula Na6
~(AlO2)6(SiO2)6] 7-5 H2 )
The water-soluble monomeric or oligomeric organic
carbo~,rla~e -be'a'inq agQr.~ can be selQctQd '-om a wid~
range or co~pounds but preferably has a fi st carbo~yl
logarlthm~._ acidi~y~cons~ant (p~Cl) o. les~ ~an 9,
preferably of between 2 and 8.5, more preferably of
between 4 and 7.5.
The logarithmic acidity constant is defined by reference
to the equilibrium
H+ + A ~ H+A
where A is the fully ionized carbo~y;ate anion of the
builder salt.
The ~quilibrium constant is therefore
Kl = (H+ ~)
(H+) (A)
and pKl = loglOK.
For the purposes of this specification, acidity constants
are defined at 25C and at zero ion c strength~ Literature
W092/0352~ PCT/US91/05533
2~"27a - 9 -
values are taken where possible (see Stability Constants
of Metal-Ion Compleses, Special Publication No. 25, The
Chemical Society, London): where doubt arises they are
determined by potentiometric titration using a glass
electrode.
Preferred carbosylates can also be defined in terms of
their calcium ion stability constant (pKCa++) defined,
analogously to pKl, by the equations
pK_~ 910KC~
where ~a = ~Ca~ A)
(Ca++~
Preferably, the polycarbosylate has a pKCa++ in the
range from about 2 to about 7 especially from about 3 to
about 6. Once again literature values of stability
constants are taken where possible. The stability constant
is defined at 25C and at zero ionic strength using a
glass electrode method of measurement as described in
Complesation in Analytical Chemistry by Anders Ringbom
(1963).
The carbosylat2 or polycarbo~ylate builder can be
momomeric or oligomeric in type although monomeric
polycarbosylates are generally preferred for reasons of
cost and performance.
Monomeric and oligomeric builders can be selected from
acyclic, alicyclic, heterocyclic and aromatic carbosylates
having the general formulae
wo 92/0352j ~ t3 (~ ~3 2 7 .`:- lo PCT/US91/0~533
(a)
Rl I X C j R~
_ Z I m
t b ) .. ~
..
_ ~ '
or
( c ) y
u
wherein Rl re-.~sen~s ~,C; ~ù ~
optionally subs~i~u;ed ~i ..id;~ , _a.~o-~-v-, ~u o or
phosphono groups or attached to a ?c ye~hylenc~y moiety
containing up to 20 ethyleneo~y qrou~s; ~ -ep-esents
H,Cl 4 alkyl, alkenyl or hydro~y alkyl, or alkaryl,
sulfo, or phosphono groups;
X represents a single bond; O; S; SO; SO2; or NRl;
Y represents H; carbosy;hydro~y; carbosymethylosy; or
Cl 30 alkyl or alkenyl optionally substituted by hydro~y
or carbosy qroups;
Z represents ~; or carbosy;
m is an integer from 1 to 10;
n is an integer from 3 to 6;
p, q are integers from 0 to 6, p + q being from 1 to 6;
and wherein, X, Y, and Z each have the same or different
representations when repeated in a siven molecular
formula, and wherein at least one Y or Z in a molecule
contain a carbosyl group.
Suitable carbosylates containing on_ carbo~y s-oup include
lactic acid, glycollic acid and ethe- derivatives thereof
W092/03525 ~J~ r~ 7 ~ PCT/US91/0~s3~
as disclosed in Belqian Patent Nos. 831,368, 821, 369 and
821,370. Polycarbo~ylates containing two carbo~y groups
include the water-soluble salts of succinic acid, malonic
acid, (ethylenedio~y) aiacetic ac~d, maieic acid,
diglycollic acid, .artaric ac::d. ta7:' aaic acid ~nd
~umaric acid, as .~e` lS "e ~ e ~ n~ e~ desc~i`~ed
in German Offenlegenschrift 2,~4~,63~, and ~ a, 687 and
U.S. Patent No. 3,935,257 and ~;,e sul~inyl carbo~ylates
described in ael~ian ~ater.. .\1O. ~I0,~_. ?o~,carbo~ylates
containing three carbo~y G ~^U^S in-. ~ U~ articular,
water-soluble citra.as~ aconi;~ e-~ ano ci-:-3conates as
well as st~cc~n~to ~a..~:~
carboxy~ethylo~ysuc-inat.~ ~_a-,~.:`a.aa ~a ~ a ?aten~ ~o~
1,379,2~ c ^~,s~ ?~
No. 1,389,73~, and 3minosuccina ^-s d^-sc ibed in
Netherlands Application 7205873, and .he
oxypolycarbo~ylate materials such as 2-o~a-1,1,3-propane
tricarboxylates described in British Patent No. 1,387,447. `
Polycarbosylates containing four carbosy groups include
osydisuccinates disclosed in British Patent No. 1,261,829,
1,1,2,2-ethane tetracarbosylates, 1,1,3,3-propane
tetracarbosylates and 1,1,2,3-propane tetracarbosylates.
Polycarbosylates containing sulrQ substituents include the
sulfosuccinate derivatives disclosed in British Patent
Nos. 1,398,421 and 1,398,422 and in U.S. Patent No.
3,936,448, and the sulfonated ?yro'ysed cltrates described
in British Patent No. 1,082,179, while polycarbo~ylates
containin~ phosphone substituents are disclosed in British
Patent No. 1,~39,000.
Alicyclic and heterocyclic polycarbo~ylates include
cyclopentane-cis,cis,cis-tetracar~o~yiates,
cyclopentadienide pentacarbo~ylates,
W092/03525 PCT/US91/05533
2 0 ~ ~2 7 ~ 12 -
2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates,
2,5-tetrahydrofuran -cis - dicarboxylates,
2,2,5,5-tetrahydrofuran - tetracarbo~ylates,
1,2,3,4,5,6-he~ane -he~acarboxylates and carbo~ymethyl
derivatives of polyhydric alcohols such as sorbitol,
mannitol a~.d ;;yl~.ol. ~.omatic polycarbo~yla~es include
mellitic acid, pyromellitic acid and the phthalic acid
derivatives disclosed in British Patent No. 1,425,343.
Of ~he a~ove, the preferred polycarbo~ylates are
hydro~yca~o~ylates containing up to three carbosy groups
per molecllle, more ~articularly citrates.
m~.e ~ar~n~ acids of ~he ~,onome~ic or ollgomeric
poiycar~o~yl~ce cn21a~ing agen;s or mis.ures thereof with
their salts, eg. citric acid or citrate/citric acid
mi~tures are also contemplated as components of builder
systems useful in the present invention.
The third element of the builder system is a crystalline
layered sodium silicate having the general formula
NaMSi~c2~+1' YH2
wherein M is sodium or hydrogen, s is a number from 1.9 to
4 and y is a number from 0 to 20. Crystalline layered
sodium silicates of this type are disclosed in
EP-A-0164514 and methods for their preparation are
disclosed in DE-A-3417649 and DE-~-3742043. For the
purposes of the present invention ~, in the general
formula above has a value of 2, 3 or 4 and is preferably
2. More preferably M is sodium and y is 0 and preferred
e~amples of this formula comprise the ~ -,~ - and
-forms of Na2Si205. These materials are available
from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7,
W092/0352~ PCT/US91/05533
2 7~
- 13 -
NaS~S-ll and NaSKS-6. The most preferred material is
~ 2 2 5'
o~ther detersent buiider materials can also form par~ o'
the builder system but are not essential elements
thereof. Such materials can be organic or inorganic in
nature.
Inorganic builder materials that can form optional
el~mon~s ~f ~he ~ui?der system for the purposes of the
~nvention include alkali metal car~onates, bicar~onates
and sil c t~s. S~ bl~ organic materi~ls include ~he
organic phosphonates and amino polyalkylene phosphonates
although these materials are less preferred where the
minimisation of phosphorus compounds in the compositions
is desired
Other suitable water soluble organic salts are the homo-
or co-polymeric polycarbo~ylic acids or their salts in
which the polycarbo~ylic acid comprises at least two
carbo~yl radicals separated from each other by not more
than two carbon atoms. Polymers of the latter type are
disclosed in GB-A-1,596,756. E~amples of such salts are
polyacrylates of MWt 2000-5000 and their copolymers with
maleic anhydride, such copolymers having a molecular
weight of from 20,000 to 70,000, especially about
40,000. These materials are normally used at levels of
from 0.5~ to 10% by weight more preferably from 0.75~ to
8%, most preferably from 1% to 6% by weight of the
composition.
The optional builder materials, if present, will total no
more than 25~ by weight of the composition normally less
than 20~ and most usually less ~han 15% by weight.
W O 92/03525 PC~r/US91/05~33
~ o ~ ~ ~ rl '`
- 14 -
For the purposes of compositions in accordar.ce with the
invention, 'he builder system wili c^-?rise ^rom lO~s to
95% by weight of the compos tior.~s, ~nv ~ ~re a-âblv ~-om
20% to 60~ ? -
~sodium aluminosilicate zeoli~e iviii _or~ r àe '0.~ 20~ to
60~ by weight of the mi~ture. tra ~ n^;~~er:c ar ^ilgo~erlc
carboxylate will comprise ~o~ s `` `~ el~n~ cf ~he
mi~ture and the crystallie~ ap r~ ` a~ c~ ise
from 10~ to 65~ by ~eigil~ c~ e ili;;ur~ .ç~e ~reerabl~,~
the zeolite is oresent ;n ln ~ 9
the monomeric or oligcineric car`as;~ ^m ~^is~x ~^o
to 25~ ~tn~ t~t~ lav-~r~ r~
of the build2r sys~em. ~ a~_~r __s~a ~n~ uiit~ar s~;s~e~
incorporates a combination of au~ ry inorjanic and
organic builders such as sodium carbonate ar.d maleic
anhydride/acrylic acid copolymers in amounts of up to 25~.
Compositions in accordance with the invention can also
contain up to 40~ of non-surfactant non detergent builder
components as optional ingredients. Anti-redeposition
and soil-suspension agents, optical brighteners, soil
release agents, dyes and pigments are e~ampies of such
optional ingredients and can be added in varying amounts
as desired.
Anti-redeposition and soil-suspension agents suitable
herein include cellulose deriva'ives such as
methylcellulose, carbosymethylcellulose and
hydro2yethylcellulose, and homo- or co-polymeric
W092/0352~ - lS _ ? ~ 7 ~CT/US91/0;~33
polycarbosylic acids or their salts. Polymers of this type
include copolymers of maleic anhydride with ethylene,
methylvinyl ether, ~cr~ C ~r me~hacrylic acid, the
maleic anhydriàa consei~lu~ , a~ s_ 20 ~ole percen. of
the copolymer. Th~s~ ma~rials a ~ no ~tally used at
lev81s of ~ .5 ~ ~ r ~ ~ ? ~ ~ , ~ , , _ ~ ~ _ _ _ _ _ _ ~ _ ~ i
from 0.7S~ to 8~, ~os. P~ ~o~ ~ 50 5~ by ~ctight
of the composition.
Other useul pol~ sric ma~ ;h~ poi~sthylan_
glycols, pa;ti~ular iy _.`OS~ h`.;
10 d o--10 o o o, ?~ tO ~ ;~ p ;i ~ C _ .. ~:1 .~ .. ,- .. ~. `, b~ _ _ _ ~.1 ~ O i ~
preferably abou~ ~000. Th~3~ -' " 3?`' `~ als or t rom
0~20~ to 5~ ~,n~ ?~ ? ~t ~ n ~ 5~ ~,t ~ h~.
co-polymeric polycar~o~ylai~ ~di~S ar~ valua~l~ ror
improving whitana~3 maintananc3, ~abrio as~ dsposition,
and cleaning performancs on clay, prot~inac~ous and
o~idiza~le soils in the pre~ence of tran~ition metal
impurities.
However one advantage of compositions in accordance with
the present invention i~ their ability to maintain the
suspension o~ insolu~ld particulat~ solids (a~h) wi~h
rQdUCed 18VQ1~ of polym~ric polycarboxylate builder/anti
redeposition agents or eYen, in preferred compoaitions of
the invention, with no polym~ric polycarboxylats pre3~nt.
Thus a level of polymeric polycar~oxylate o~ 5% in
conventlonal products can ba h~lvad, i.a. to 2.5S with no
increase in fabric ash level in compositions according to
the present invention. If t~e polymeric polycarboxylate
is removed entirely only a alight increase in ra~ric ash
take~ placs in contrast to a vi-tual dou~ling Or the ash
level if the polymer i8 removed fro~ a conventional
formulation.
W092/0352~ PcT/~S91/o~533
275 16 -
Compositions in accordance with the invention also show
robustness in hardness control in under built situatior.s.
i.e. where insufficient detergent builder is available to
control all of the ~ineral hardness present. ~his
benefit is believed to arise because of the ability of
shQ tern~ uildQr syst2m co~pon~nt~ to r~dis~ributP ,~.P
calcium and ~agnesium hardness ions amongst themselves in
underbuil~ sltuations, ta~in~ advanta~e of t~e enhancQd
affinity of t~e crystalline layarad silicate component
'or ~g~iu~ ion.
.~ ~ f~d~d ~ c~ si~ior.................. ~ ~C~ 2
ith ~ho ~~~3ant inventisn is ~ r~duction in da~ag2 t~
f~ric3 a~ q ~a~ 33. ~3 lo~
beLiov~d tO aris~ from the interaction o~ heavy metal
ions depositad on ~abrics during the washing proce~s with
oxygen bleache~. Fabrlcs waehed in composition~ of the
presQnt lnvention show a level o~ dQposition o~ heavy
metal ions and a reduced tQnsilQ strength 108~, rolatlvQ
to compositions in whlch tho crystalline layerQd sllicate
component i~ replaced by a conventional amorp~ou~
silicate
Preferred op~ical brightener~ are anionlc in character,
esamplea of whlch aro di~odiu~
4,4l-bi3-~2-diethanolamino-~-anilino -~- triazin-6-
ylamino)~tilbene-2:21 di~ulphonate, di~odium 4,
41-bia-(2-morpholino-~-anilino-~-triazin-6
-ylamino~tilbene-2:21 - di8ulphonato, di~odium 4, 41 _
bi~-(2,4-dianilino-a-triasin-6-ylamino)atilbeno-2:21 -
disulphonata, mono~odium 41,411 -bi~-(2,4-dianilino-
~-triazin-6-ylamino)~tilbeno-2-~ulphonato, di30dium 4,41
-bis-(2-anilino-~ -mathyl-~-2-hydrosyothylamino)-s-triazin
-6-ylamino~tilbsns-2,21 - di~ul~honat~, disodium 4,41
-bi~-(4-~nonyl-2,1,3-triazol-2-yl)-~tilbeno-2,2
di~ulpho~at 3, disodium 4,41bis(2-anilino-4-(1-methyl-
Wog2/o352s PCT/US91/0~533
2 ~ 7 ~
2-hydrosyethylamino)-s-triazin-6-ylamino)stilbene-
2,21disulphonate and sodium 2(stilbyl-411-
(naphtho-ll, 21:4,5)-1,2,3 - triazole-211-sulphonate.
Soil-release agsnts useful in compositions of the present
..ve~t _- ~r;~ ~o,~v3~tionally copolymers or t~rpclyme~s o~
tPrephthalic acid wi~h ethylene ~lycol and/or p~opylene
glycol units in various arranqements. E~amples of such
polyme~ are ~isclosed in the commonly assigned US Patent
Nos. ~11S335 ~nd ~711730 and Europsan ~ublis~ed Patent
~pplica~ion ~o. 0272333. A particular preferred polymer in
acro;danc3 wi~h ~P-~-0272083 has the ormula
3 ~3 0.~5 ~ o.a6~ )2.8~' ~EG)o,~(oo-~)3 25~tP~G)~3C~3)0
Y~r~ P~ _,pO i~ ~OC3~i60) ~d, ~ pcCCs ~
Cartain pol~fmeric materials suc~ as polyvinyl pyrrolidones
typically of ~Wt 5000-20000, preferably 1000~-15000, also
form usaful agents in pre~entinq the transfer of labile
dye~tuffs between fabric~ during the wa~hing process.
Another optional but hlghly preferred ~ngredient is a
particulate inorganic perhydrate bleach. Any particulate
inorgan~c perhydrate bleach can b~ u~ed, in an amount of
from 3t to 40t by wcisht, more preferably from 8~ to 25~
by weiqht and most preferably from 12~ to 20~ by weight of
the compositlon~. Preferred esamples of such bleaches
are sodium per~orate monohydrato and tetrahydrato and
mi2~uras t~arao~.
Another preferred inqredient is a perosy carbo~ylic acid
bleach precursor, commonly referred to as a bleach
activator, which is preferably added in a prilled or
agglomerated form. Esamples of suitable compounds of this
type are di~clo~d in British Pat~nt ~os, 1586769 and
2143231 and a method for their formation into a prilled
form is described in European Published Patent Application
No. 0062523. ~referred e~amples of such compounds are
tetracst~ hylana diamins and sodium 3, 5, 5 trimethyl
hesanoylosybenzene sulphonate.
W092/03525 PCT/US91/0~533
~ O ~ i 8 -
Bleach activators are normally em~loved at levels of from
0.5% to 10% by weight! more frequently ~rom 1~ to 8~ and
preferably from 2`'s to 6~ by waig~t c ~.a_ co~?osi~ion.
Another optionai i:~g~:edie~ ?~
e2emplified by silicones, and siiica-silicone mi~tures.
Silicones can be generall~ p~asa.n'-~ btr ~. I.';t~?l.?~tod
polysilo ane mat~rials whila si_ios is -..o~ s2d ln
~inely di~id~ ~o~s,
~erogels and hydropnoolc si~.ic~i o` ?~: ~us ~s. ~rh
materials can b~ r~
suds suppras~or is a;l~ `311~ '0~'`:.^. ` :`~?~X ~ en~r,?o~ d
in a wa~r - ~ iub
non-surface-active deterg~n--i.~ ar..i~ car~
Alternatively the suds suppr-ssor can `29 dissolv~d or
dispersed in a liquid car.ier and a~pli2d ~y spraying on to
one or more of the other components.
As mentioned above, useful silicone suds controlling agents
can comprise a misture of an alkylated silosane, of the
type referred to hereinbefore, and solid silica. Such
mistures are prepared by affising the silicone to the
surface of the solid silica. A oreferred silicone suds
controlling asent is represented by a hydropho`oic silanated
(most preferably trimethyl-~ilanated) silica having a
particle size in the range from 10 nanometers to 20
nanometers and a specific surface area aboYe 50 m2/g,
intimately admi~ed with dimethyl si" cone fluid haYing a
molecular weight in the range from about 500 to about
200,000 at a weight ratio of silicone to silanated silica
of from about l:l to about 1:2.
A preferred silicone suds controlli..g agent is disclosed in
8artollota et al. U.S Patent 3,g33, 672. Other
particularly useful suds supprsssor- a 3 ths
self-emulsifying silicons sud~ sup~-essors, d~scri~ed in
W092/03525 PCT/~S91/05;33
German Patent Application DTOS 2,646,126 published April
28, 1977. An example of such a compound is DC-544,
commercially availably from Dow Corning, which is a
silo~ane/glycol copol~mer.
The suds supp~esso s 'esc _a_ b_- :a ~ e~ o~_d
at levels of from 0.001'~ to 0.5~ by weight of the
composition, pr22rably ~rom C.31~j ~.o d.~'i by ~eic~t.
The preferred met:~ods of i~co;n~;a~ a _o~ e ~ her
applicaticn cf ` ``3 ~`!dS ~`.n~ -^.0~ n ~ 9U~ Co~ m b~
spray-on ~o C~le 0- .ilO:.3 ~ `._ C Y ~ O~ ` `a_
composition or al~eL~ el~ ;aa ~o;~maz~ .e suias
suppressors in~o ~e~ara~e g~ a;_a ~ an 'h~n ~a
mi~ed with the other solid componan~3 o~ ~he composition.
The incorporation of the suds modifiar3 as separate
particulate~ also permits the inclusion therein o~ other
suds controlling material~ such as C20-C24 atty acids,
microcrystalline wa~es and high MWt copolymers of ethylene
oside and propylene oside which would otherwise adversely
affect the dispersibility of the matri~. Technigues for
forming such suds modifying particulates are disclosed in
t~e previously mentioned Bartolotta et al U.S. Patent No.
3,933,672.
Another optional ingredient useful in the present invention
is one or more enzymes.
Prefersed enzymatic materials include the commercially
ava~lably amylases, neutral and alkaline proteases,
lipases, esterases and cellulase~ conventionally
incorporated into detergent composition~. Suitable enzymes
are discussad in U.S. Patents 3,519,570 and 3,533,139.
Fabric softening agents can also be incorporated into
detergent compositions in acco: a..o~ ~i.h the pr2sPnt
invention. Thasa agents ~ay be lnc:~an~ organic in
type. Inorganic softening agents a e e~emplified by the
W092/03525 PCT/US9~/0~533
20~27~ ~ -
smectite clays disclosed in GB-A-1,400,898. Organic fabric
softening agents include the water insoluble tertiary
amines as disclosed in ~B-A-lS14276 and Ep-a-ooll34o.
Their combination with mono C12-C14 guaternary ammonium
salts is disclosed in EP-8-0026527 ~ 528. Other useful
organic fabric softening agents are the dilong chain amides
as disclosed in r?-~-0242919. Additional organic
ingredients of fabric softening systems include high
molecular weignt polyethylene oside materials as disclosed
in E-~-0~9~75 and 031~146.
Levels o~ smec~ito clay are normally in the rangs from S%
~o 1~?~, m~ f3rably ~rom 9~ ~o 1?~ by weiqht, with the
material being added a~ a dry mi~ed component to the
remaind~ oe ~.~e eormulation. Org2n~ C fabric so~ni~.a
ag~nts such a~ ~h2 water-insoluble tertiary amines or
dilong chain amide materials are incorporated at levels of
from 0.5~ to S~ by weight, normally from 1~ to ~ by
weight, whilst the high molecular weight polyethylene oside
materials and the water soluble cationic materials are
added at levels of from 0.1% to 2%, normally from 0.15~ to
1.5% by weight. Where a portion of the composition is
spray dried, these materials can be added to the aqueous
slurry fed to the spray drying tower, although in some
instances it may be more convenient to add them as a dry
mised particulate, or spray them as a molten liquid on to
other solid components of the composition.
The compositions of the invention can be made via a ~ariety
of methods including dry misinq, spray dryiny,
agglomeration and granula~ion and preferred methods involve
combinations of these technigue~. A preferred method of
making ths compositions involves a combination of spray
drying, agqlomeration in a high speed mi~er and dry mi~ing.
~seforrQd dQtorgsnt compositions in accordance with the
invention also comprise at least t~o particulate multi-
ingredient components. The first component comprises at
W092/03525 2 ~ g ~ 2 7 ~ PCT/US91/0~533
~; _
least 20%, conventionally from 30~ to 70%, but more
preferably no more than 40% by weight of the composition
and the second component ,rom 1~ to 50~, more preferably
10~ to 40~ by weight of the composition.
The first component comprises a particulate incorporating
an anion__ su~_~c~3nt in a~ ~mount of from 0.75~ to ~5~ by
weight of the powder and one or more inorganic and/or
organic sal~s in an amount of from 99.2S~ to 65~ by weight
of the powder. The particulate can have any suitable form
such as qrai1uta;. flak2s, prills, marumes or noodles but is
pre~r~?~ aular~ The ~nule~ themselYes may be
~;g'~m~ J ~ - ?~ u~um ~g~ 'ion cr ~ ~n-
iine mi~ars ~ut a.2 p;~oferably spray dried particles
produced by atomis~ng an aqueous slurry of the ingredients
in a hot air s~r~am which removes most of the water. In
certain processes, the spray dried granules forming the
first component may themselves be subjected to
densification steps, eg. by high speed cutter mi~ers, to
increase density before being reagglomerated. For
illustrative purposes, the first component is described
hereinafter as a spray dried powder as this constitutes a
preferred embodiment of the invention.
.~n important cha~act_ristic of the principal anionic
surfactant in the first component i~ that it should have a
low rate of solubility in aqueous media at the water
temperatures ~hat pravail during ths fill step of the wash
cycle in an autcmatic washing machine. With respect to
European wash habits the water temperature during the fill
step is predominantly in the range from 5C to 20C, more
usually from 7C to 12-C.
Suitabla anicni_ su factants for the purposes of the first
component have been found to ba linear alkyl sulfate salts
in which tha alkyl group has an average of from 16 to 22
carbon atoms, and linear alkyl carbo~ylate salts in which
tha al~yl srouP ha~ an aYerage of from 16 to 24 carbon atoms.
WO 92/03525 PCr/US91/0:~;33
~ O ~
The alkyl groups for both types o~ s~rfactant are
preferably derived from natural fats such ~s ~llo~.
Shorter chain alkyl sulfates or carbosylates, in which th~
alkyl group is derived from so~ ^es ooi,.?risin. ~ mix~uz~ o~
alkyl moieties more than ~ o- lich coe~in l; or less
carbon atoms, are !ss sui~s~ s -s-p ~ ee ~-~rs..
component to form a sel !ike ~ass du~ing dlssolutlon.
The level o. anionic su.acta..' .~ e s ra ~ ?o~de.
formin~ the first componen~ is ~ b, ~al~-.at,
more usually 2.S~ ~o 5~s ~re~Ia ~b~ _m ~ aa_ ;-o~
pre'erably rom 5~s ~o lS~; b-r :i3ia;~ .s~a:-sa ~
surfactants such as linear a ~ t;l. b~ n~ ss -`s^s~ s c~. ba
included or alt~r~ !Y ?~ o '?~ 5'`~.~?.9"~
the spray dri~d powd~: b~- Sr;~
The other major ingredient o~ the spray dri-d powder is one
or more inorganic or organic salts that provide the
crystalline structure for the granules. The inorganic
and~or organic salts may be water-soluble or water-
insoluble, the latter type being comprised by the, or the
major pàrt of the, water-insoluble builders where these
form part of the builder system. Suitable water soluble
inorganic salts include the alkali metal ca~onatas,
bicarbonates, sulphates and borate~ lkali m2tal silicates
can also be pre~ent in the spray dried granulP provided
that aluminosilicate does not form part of the spray dried
component.
It is preferred that at least part or the alumino~ilicate
builder be incorporated into the spray dried granule and,
as indicated above, where this takes place, any silicate
present should not ~orm part or the spray dried component.
In these circumstances incorporation o~ tha silicats can be
achieved in several ways, e.g. by producing a separate
W092/03525 2 ~ ~) 3 ~ 7 ~; PCT/~S91/0;~3~
-- 3
silicate containing spray dri~d ~ar~i-ulata, by
incorporating the silicate into an agglomerat~ of other
ingredients, or more pr~rarahl~ y a~ g ~.a ~ ate as a
dry mi~ed solid ingrodi~ont.
Any of the previously montlon~d ~?~oaal~ ~uil~e~ salts C?~n
also be incorporated in the spray d~ed ?owc~ ~orming ;he
first component. .he s?ray driad ~ - aa~^ ;'so iaclude
some or even all of tll~ ~iai:ar '0'~ ~S-~:? .~ e ar
oligomeric carbo~ylat2 chelaain~ ag2a~ ~U~. ~m~s iS l~ss
preferred as i~ tends to i~`.s.o ~ aa ~e~l o
ingredient. The osgani~ and~or inoxganic s~ s comprise
from 60~6 to 90~ r ~ 9 ~ t ~ `~ '. '`~ ~? ~ ~ ~ ~ ?~ ~ n~ r c.
preferably from 70~ ~o 90~s an' .os~ -ref~rs~t ~r -sm ~5~S
85~ by weight.
The spray dried powder also normally contains up to 15% by
weight of miscellaneous ingredients.
In preferred compositions where the first component is a
spray dried powder, optional ingredients included in the
first component should be heat stable to the estent
necessary to withstand the temperatu~ encountsred .n the
spray drying process. Where the first component is a spray
dried powder it will normally be dried to a moisture
content of from 7~ to 11~ by weight, mors preferably from
8~ to 10~ by weight of the spray driAd pow~ar. ~oistura
content3 of powder~ produced by other processe~ such a3
agglomeration may ~e lower and can be in the range 1-10~ by
weight.
W092/03525 PCT/US91/05533
~0~ 5 24 -
The particle size of the first component is conventional
and preferably not more than ;s by weight should be above
i.Y mm, wh~ie nc~ more than 10% oy w~Qight should be less
than 0.15 mm in maximum dimension. Preferably at least 60~
and most preferably at least 80% by weight of the powder
lies between 0.~ mm and 0.25 mm in size. For spray dried
powders, ~h~ `oul~ density of the particles should lie in
the range from 350 g/litre to 650g~1itre but is
ccn~entiona'l~ hQ rangQ f~cm ~40 to 6Q0 s~'it~e . ~ulk
densities in the upper part of ~he range rom 600-650
s~litre _~a par~ la-ly use-~ul W~.Q~e produc~ion o~ so
called concentrated products is desired. Bulk densities
above this ranse may be produced if the spray dried powder
is subjected to further processing steps such as size
reduction in a high speed cutter/mi~er followed by
compaction. Alternatively, processes other than spray
drying may be used to form the powder.
A second component of a preferred composition in accordance
with the invention is a particulate containing a water
soluble surfactant.
This may be anionic, nonionic, cationic or semipolar in
type or a mi~ture of any of these. Suitable surfactants
are listed hereinbefore but preferred surfactants are
linear Cll-C15 alkyl benzene sulfonates and fatty
C14-Cl8 methyl ester sulponates.
The second component may have any suitable physical form
i.e. it may take the form of fla~es, prills, marumes,
noodles, ribbons, or granules which may be spray-dried or
non spray-dried agglomerates. Although the second
component could in theory comprise ;he water soluble
surfactant on its own, in practlce at least one organic or
inorganic salt is included to facil tate processing. This
W O 92/03525 2 0 ~ 3 ~ 7 3 P ~ /~S91/05533
- 2S -
provides a degree of crystallinity, and hence acceptable
flow characteristics, to the particulate and may be any one
or more of the organic or inorganic salts present in the
lirs t c0~ .2~.t.
The particle si~e range of the second component is not
critical bu~ should be such as to obviate segregation ~rom
the pa.~iolea of the spray dried firs. component when
blended thQrowi~h. Thus not more than 5% by weight should
a~ m ~hila no~ ~o~e than 10% should be less than
0.15 ~.~ ir. ma-imum dimQnsion.
The bulk densi.y of the second component will oe a function
of its mode of preparation. Thus, in spray dried granular
form the second component may have a density of from 3S0
g/litre to 650 g/litre but more preferably will be in the
range from 500 g/litre to 630 g/litre. The preferred form
of the second component however is a mechanically mised
agglomerate which may be made by adding the ingredients dry
or with an agglomerating agent to a pan agglomerator, Z
blade miser or more preferably an in-line miser such as
those manufactured by Schuqi (Holland) BV, 29 Chroomstraat
8211 AS, L~lystad, Netherlands and Gebruder Lodige
Maschinenban GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9,
Postfach 20S0 F.R.G. By this means the second component
can be given a bulk density in the range from 650 g/litre
to 1190 g/litre more preferably from 750 g/litre to 850
g/litre. This is particularly useful in formulating the
so called 'concentrated' products.
W 0 92/03525 P ~ /US91/Oaa33
2 G ~ 3 ~ ~ v
Preferred compositions include a level of ~lkali metal
carbonate in the seccnd COm?OnQ~. _vr es?on' a.~ .o an
amount of from 3~ to 15~ by wei~ a-. ~`ae ca~ osi~ion, mo~e
?referably from 5"~ to 1~ h~
level of carbonate in the second component o ~rom 20% to
40% by weigh..
A highly preferred ing~edien~ a~ ;U:! ~ie~ aC; ~ aen~- i~-,
also a hvdra~ed wat~r insolu'.l.~ s~ ^ e .
e~changs ma~e~ al af ~ s-.-n~ . n
hereinbeor~Q, pres2nt a~ ~rom ~ o ~J`~ V'~ `e ~ 0
second component. ~he amoun~ o ~ia~ n to ~oi~
aluminosilicate material incorpora~-d in this way is ~ rom
1~ to 10~ by weight of the composition~ more pret2rably
from 2~ to 8~ by weight. If the second component is spray
dried, it is important that it does not contain both
silicate and aluminosilicate ingredients for the reasons
stated hereinbefore. In such circumstances, the silicate
may be incorporated in the first component or, if that also
contains aluminosilicate, may be added as a solid, together
with other dry mi~ed materials, to the first and second
components.
In one process for preparing the second component, the
surfactant salt is formed in situ in an inline mi~er. The
liquid acid form of the surfactant is addad to a mi~ture of
particulate anhydrous sodium carbcnate and hydrated sodium
aluminosilicate in a continuous hish speed blender such as
a Lodige KM mi~er and neutralised to form the surfactant
salt whilst maintaining the partic~late nature of the
mi2ture. The resultant agglomera~ed mi~ture forms the
second component which is then added to other components of
the product. In a variant of this process, the surfactant
salt is pre-neutralised and added as a viscous paste to the
mi~ture of the other ingredients. In this variant, the
mixer serves merely to agglomerate the ingredients to ~orm
the second component.
W092/03525 PCT/US91/0~533
~a~ '~2 ~lv
- 27 -
In a particularly preferred process for making compositions
in accordance with the invention, par~ o- ~he spray ~ried
product comprising the firs. srar.ular c~m~onen~ s div~trted
and subjected to â low level o_ ..oni~n~ s~
on before being reblended with the remainder. The second
granular component is made using ~he -e st--oA process
described above. The first and second components ~ogether
with other dry mi~ ingredien~s such as ~ha _~ bo~f i tt_
chelating ~q~nt, inorganic pero.~ gat. ~'~--h
activator, soil-r~leas~ ?oli,r~e~ si ~ ^a;
then fed to a conveyor belL, ~.o;~n _`~,ic'~ 2'; ~;2
transferred to a horizontaiiy ~OLàL.,IL ~ nic.-
perfume and silicone suds suppressor are sprayed on to ~he
product. In highly preferred composi'ions, a further drum
mi~ing step is employed in which a low ~appro~. 2% by
weight) level of finely divided crystalline aluminosilicate
is introduced to increase density and improve granular flow
characteristics.
Compositions in accordance with the invention can also
benefit from delivery systems that provide transient
localised high concentrations of product in the drum o' an
automatic washing machine at the start of the wash cycle,
thereby also avoiding problems associated with loss of
product in the pipework or sump of the machine.
Delivery to the drum can most easily be achieved by
incorporation of the composition in a bag or container from
which it is rapidly releasable at the start of the wash
cycle in response to agitation, a rlse in temperature or
immersion in the wash water in the drum. Alternatively
the washing machine itself may be aàapted to oermit direct
addition of the compostion to the d~um e.g. by a dispensing
arrangement in the access door.
W092/03525 PCT/US91/0~33
2~ 7~ 28 -
Products comprising a detergent composition enclosed in a
bag or contain~r ar~ usually designed in such a way that
containe. i.._aS -.y is maintained in the dry state to
ena eg aS ~ `'e _^r.~er.~s whQn dry, but are adapted
for release o,~ the container contents on esposure to a
washins env ~~nment, normally on im~ersion in an aqueous
solutio~.
Usuallv ~e -~ in~- ~ilt be Cle~ible, such as a bag or
c~ c 'i`~ v.~ ;uc~_on ~oa~ed wi~.
a wat~- imr~ .e~le F o~eC'iVQ ma~er_al so as 'o retain the
_cn~en~s, suca aa ~a ~.sclos~d ~n ~uropean ?ublished ?atent
Application ~lo. OOlA~78. ~lte;natively it may be formed of
a water-insoluble synthetic polymeric material provided
with an edge seal or closure designed to rupture in aqueous
media as disclosed in European published Patent Application
Nos. 0011500, 0011501, 0011502, and 0011968. A convenient
form of water frangible closure comprises a water soluble
adhesive disposed along and sealing one edqe of a pouch
formed of a water impermeable polymeric film such as
polyethylene or polypropylene.
In a variant of the bag or container product form,
laminated sheet products can be employed in which a central
fle~ible layer is impreqnated and/or coated with a
composition and ~her. one or more outer layers are applied
to produce a fabric-like aesthetic effect. The layers may
be sealed together so as to remain attached during use or
may separate on contact with water to facilitate the
release of the coated or impregnated material.
An alternative laminate form comprises one layer embossed
or deformed to orovide a series of ?ouch-like containers
into each of which the detergent components are deposited
WO 92/03525 PCl`/US91/0~533
~S32~
-- 29 --
in measur_d amounts, with a second layer overlying the
first lay~r and sealed thereto in those areas between the
pouch-lil;~ containers where the two layers are in
-on~act. ~ a~-~on-n-a may be deposi~ed in particulate,
paste or mol~en .orm and the laminaté layers should prevent
egress o. ~he _~n~orA~s o~ ~he pouch-like containers prior
to their addi~.ion to wate~. The layers may separate or
.ay ~ain ^~ac:s~ g~thQr on contact with water, the
only re~ ;_m~ `oe i~g ~A~a~ Ae st ' UC~U_ e should permit
~ap~ld ~ ~a_a a na ^an~enas o tn~ ~ouch-L~ke containers
in~o solu~ia". i~e num~ c- ?ouch-like containers per
unit area of su~s~~ate is a mat~er o~ choice but will
normally varV be~ween 500 and ~5,000 per square metre.
Suitable materials which can be used for the fle~ible
laminate layers in this aspect of the invention include,
among others, sponges, paper and woven and non-woven
fabrics.
However the preferred means of carrying out the process of
the invention is to introduce the composition into the
~iquid su.rour,dins the fabrics that are in the drum via a
reusable dispensing device having walls that are permeable
to liquid but impermeable to the solid composition.
Devices of this ~ind are disclosed in European Patent
Application Publication Nos. 0343069 & 0343070. The latter
Application discloses a device comprising a fle~ible sheath
in the form of a bag eYtending from a support ring defining
an orifice, the orifice being adapted to admit to the bag
sufficient p.oduct for one wash ng cycle in a washing
cycle. A portion of the washing medium flows through the
orifice in~o the bag, dissolves the product, and the
solution then passes outwardly through the orifice into the
W092/03525 rCT/US91/0~533
20~327~
- 30 -
washing medium. The support ring is provideà with a mas'~ing
arrangement to prevent egress of we~~ed, u-.disso!ved,
product, this arrangement typicall~ c3m~r' a' ng ra~_a
e~tending walls e~tending rom c-nsr_` oo__ in ~ s~
wheel configuration, or a similar structure in s~hich tha
walls have a helical ~orm.
WO 92/0352~ PCI/13S91/0~533
20~27 e~
The invention is illustrated in the following non limiting
E~amples, in which all percentages are on a weight ~asis
unless otherwise stated.
In the detergent compositions, the ab~reviated component
identifications have the following ~eanin~s:.
C12 LAS : Sodium !inear Cl~ alkyl ~er.~ene
sulphonate
TAS : Sodium tallow alcohol s;lloaa~n~
C14/li AS : Scdium Cl~-Cls alXyi ~ulpha~o
TAE~ : ~al'ow al_^hol ~t~.~- '.at~ `. z
moles of ethylene o~ide per mole
of alcohol
45E7 : A C4-Cls predominantly linear
primary alcohol condensed with an
average of 7 moles of ethylene
oxide
CnAE~6.5 A C12-C13 primary alcohol
condensed with 5.5 moles of
ethylene oside.
PEG : Polyethylene glycol (MWt normally
follows)
TAED : Tetraacetyl ethylene Diamine
Silicate : Amorphous Sodium silicate
(SiO2:Na20 ratio normally
follows)
NaSKS-6 : Crystalline layered silicate of
formula ~ -Na2si25
Carbonate : Anhydrous sodium carbonate
CMC : Sodium ca_~o~ymethyl cellulose
Zeolite A : Hydrated Sodium Aluminosilicate
of formula
Nal2(AlO~Sio2)l2 27H20
having a primary particle size -
the ranse from 1 to 10 micrometers
Polyacrylate : domopol~.. er of acrylic acid of
MWt 4000
Citrate : Sodium citrate trihydrate
W O 92/03525 P(~r/US91/0~533
` 7-
-32-
Photoactivated : Tetra sulphonated Zinc
Bleach ?h~halocyanine
~L~ C~?c `~ `~'me- or 1: ~ m~ieic/acryi~c
acid, average molecular weight about
80,000~
~5VEk5.~ ielc anhyd ide,'vinyl methyl èther
copol~mer. believed to have an
~? ~e mo~.ecu!ae ~e:-ght o~ 2~10,000.
~`a~s ma~.erial was prehydrolvsed with
.`'..`'_`.i `~^_~^e addl~iQ-..
Perborate : Sod~um perborate tetrahydra~e of
nominal formula
NaB02 3H20 ~ H22
Perborate : Anhydrous sodium perborate bleach
monohydrate empirical formula NaBO2.H2O2
Enzyme : Mi~ed proteolytic and amylolytic
en~yme sold by Novo Industrie AS.
Brightener : Disodium 4,4'-bis(2-morpholino-4-
anilino-s-triazin-6-ylamino)
stilbene-2:2'-disulphonate.
DETPMP : Diethylene triamine penta (methylene
phosphonic acid), marketed by
Monsanto under the Trade name
Dequest 2060
Mised Suds : 25% paraf in wa~ Mpt 50C, 17~
Suppressor hydropho~ c silica, 58~ paraffin oil.
WO 92/03525 2 ~ 2 7 ~f PCI/US91/05533
-- 33 --
EXAMPLE I
The granula~ ~e~arja~. produc~s we~e prepared having
composi~ lo~ :~ r ~ Y ~ 2 i g ~ ~ .
A B
C~ S ~.~ 4.4
TAS ;.0 4.0
t ~; 'B . 3, ? 3 . 7
~ ~,,~ _, _ 1 . 1
1 ` ~ 8 . 0
L~i a - ,,.is- :~ - 11 . O
Citrate 9.25 6.0
MA/~A ~.9 4.9
TAED 5.0 5.0
Perborate 10.0 10.0
Perborate monohydrate 6.0 6.0
DETPMP 0.19 0.19
Enzyme ,1.40 1.40
Silicate (2.0 ratio)4.0
Carbonate lS.5 9.0
Suds suppressor 0.55 0.55
CMC 0.~ 0.8
PhotoactiYated bleach 20 ppm 20 ppm
Perfume 0~43 0-43
Brishtenar 0.24 0.24
Moisture ~ Misc. 10.34 ~ 6.29
Both products were made by a combination of spray dryinq,
agglomeration and dry mi~ing techniques. A spray dried
powder was made incorporating all of the TAS,
approsimately one quarter of the LAS, all of the Maleic
anhydride/acrylic acid copolymer, DETPMP, CMC and
W092/03525 ~CT/US91/05~33
2 ~ ~ ~ 2 7~ 34
brightener and part of the carbonate and zeolite
builders. For Product A appro~ima~ely 82~ of th~ a
and 65% of the carbonate were included in th.Q spra~,- d~
portion, while ~or Product B appro~ ~a~e!y t~
zeolite and 45~ of the carbonate were added in this way.
The spray dried product was passed hro~gh 2 LCdi9Q ~
high speed mi~er/cutter and the 45E, nonionic was sprayed
on to the granules. The treated granules t~er_ ~h_.-
transferred to a conveyor belt. The ~emai~A~e~ o~ ~a
hAS, car~onate and ~eclitQ wQre pr~cess~ n a B~
high speed mi~er to ~orm agglomerated ~rtic'_s ~;`a_C~A;;e~e
fed to the c~r.veyor bel_. Tha o~h~ so'_d
ingredients viz. the citrate, silicate, per~rate and
bleach activator were also added to the belt at the same
time. Finally the mi~ed particulates were subjected to a
low intensity blending step in a mis drum, during which
step the perfume and suds suppressor were sprayed on to
the particulates to form the finished product.
These products were then compared in a split bundle wash
testing programme to enable the assessment of cleaning and
stain removal performance. The test proqram~e was
designed, and contained sufficient replicates, to permit
statistical treatment of the results. Product A was used
in an amount of 95g per load whereas Product 8 was used in
an amount of 79g per load. The di~ference reflected the
higher concentration of ingredients per 100 parts of
Product B and thus the need to use less weight in order to
provide the same levels of non builder ingredients. The
test programme used AEG ~avamat 980 automatic washing
machines set to the No. 2 cycle. The machines were
charged with water of 25 German Hardness having a 8:1
Ca:Mg ratio. Testing was carried ~ut at three
W092/03525 2 ~ 3 ~ 2 7 ~ PCT/USgl/0;533
temperatures, viz. 40C, 60C and 95C, for which
respectively, fabric loads o~ 1.81 kg 2.25 kg, and 2.7~ kg
were employed. Each load comprised a mi~ture of
naturally soiled white cotton ~abric 2r~icles tos~-ha~
with swatches soiled with a variety of stains viz. greasy,
clay soil, en~ymatic and bleachable, to permit the
assessment of whiteness and stain removal performance.
Each swatch comprised half of a pair, the other hal` _ n~
washed in the same machine using the comoarison oroduct.
~f~er washins, th~ fabrics wer~ dr~ed at ambien.t
temperature and were then subjec~ed to panelling ~, a~
judges using a ~-~ Schef.e scale ~ .arac-_ se
differences in whiteness and stain removal performance
between Products A and 3 at the selected temperatures.
The panelling showed significant advantages for Product B
over Product A on greasy and clay stains at 40C and on
clay stains at 95C, the overall stain removal performance
of the products being otherwise statistically
indistinguishable. Useful performance advantages
therefore exist for a composition incorporating a builder
system in accordance with the present invention over a
prior art composition. Moreover, such advantages can be
obtained with a significant reduction (13.0 parts) in the
level of builder ingredients.
WO 92/03525 PCT/US91/05~i33
2 J ~ b~ .~ 7
~o
E~l?Lr T I
A comparison ~_ na c!?~OUn~ O_ deJosi.ed inorsanic material
on ,abr~ s .~,~d~ ~etween
Product B in _-~mplQ and a non-phosphate laundry
detergen~ ~Ui `~ U.`-~ .`.a`~ C u~ad ~r. u.; `~y Procter &
Gamble Limi~s;).
no~ra~ e
0~ 95C. Saca -J~ Ob'~iicl was use~ ~0 w`_ jh d '~oad comprisir.g
.,2 `,~ d~ric 3nd tne
respective wash2à loads were ~her. subjec~ed to a further
14 complete wash cycl~s.
A sample of the fabric from each load was then weighed,
incinerated and the residue weighed to provide a value for
the inorganic material deposited during the wash cycles.
Results were as follows:
Produc. ~osage/wash (g) Ash (wt%)
Ariel Ultra '25g 0.698t
Product 8 102g 0.483%
The results indi_ate that com?ositions in accordance with
the invention produce lower levels of inorganic salt
deposition than those obtained with commercially available
non-phosphate detergent products.
W O 92/03525 PC~r/US91/05533
2 ~ 3 ~3 `~ 7 ''3
EX~MPLE III
T~2 follG.;~ .r~ itn the
invention and is made i~ the same manner as product B of
E~ample ~.
Cl~L.~S j, ~
T~S ~,~o
~201
NaS~S ~
Citrat~ 6.00
MA/~A i.2~
Carbonate 9.00
TAED 5.00
Perborate Monohydrate 12.50
DETPMP 0.19
Enzyme 1.20
CMC 0.48
Photac~iva~Pd Bleach 20 ppm
Brightener 0.2~
Suds Suppressor 0.49
Perfume 0.~3
Moisture & Misc. 8.70
W O 92/03525 PC~r/US91/05~33
2 G ~ ~ 2 7 .j
EXAMPLE IV
Three detergent products C,D & E were preparPd in the manner o.~ and
having compositions identical to, Composition B of Example I other
than the builder system differences shown below (values are in part.s ',~y
weight in the composition)~
C D E
Zeolite A 13.0 13Q !3.~3
Citrate 6.0 6.0 6~0
NaSK36 11.0 11.0
Silica~e (~ .0 Ratio~* - - 13 ., _
M.~/AA ~.''5 ~.u .v
~supplied as (,0~o active, providing 11.0 parts on an annvdrous I~S!S
The products were used to conduct full scale washing machine tests in
which terry towelling cotton swatches were included with 4 Kg of clean
fabric ballast loads and subjected to multiple wash cycles to determine
the levels of heavy metal ions (Fe & Mn) and total ash (inorganic salts)
building up on the fabrics after repeated washing. A heavy metal ion
'spike' of 2.5 ppm Fe as FeCl3 and 0.2 ppm Mn as MnCl2 was added
to the water fed to the machines.
The wash conditions were
Machine Type Miele Hydromatic W698
Machine Cycle 95 C Cotton
Wa~er Hardness Newcastle upon Tyne (UK) City Wate.
adjusted to give 25 German Hardness with
Ca:Mg ratio of 3:1. (This water source
typically contains 0-3ppm Cu).
Artificial Soil 20g/load of a mixture made up of
Palmitic Acid 250g
Stearic Acid 250g
Garden Clay 2C0g
Dirty Motor Oil 150g
Glyceryl trioleate 150g
Iron Oxide (Fe ~ O3) 5 .36g
WO 92/03525 PCl/US9]/05533
2 ~ ~ g 2 ~ ~
-39-
The swatches are subjected to 25 wash cycles and then analysed for
heavy metal ion content (ppm! and total inorganic salt content (ash).
The latter required the burning of a weighed terry towelling ~abric
swatch in a flame for 3 minutes followed by calcination at 3C0C for
2 1/2 hours. The ash was then analysed for che el~m~n.s b~lo~.v
reported as a fraction of the original sample wéight.
Results were as follows:
C D
Fe ppm 8.8 9.9 '7.
Mn ppm 1.9 3.5 ;~
Cuppm 1.4 2.3 ~.0
Ca+Mg% 0.42 0.16 1.05
Si & Al% 0.18 0.27 0.4~
It can be seen that cotton fàbrics washed in Products C + D,
comprising compositions in accordance with the invention, display
similar ash and heavy metal ion contents. However Composition D
contains a level of polymeric pol`ycarboxylate auxiliary builder which is
~50% of that used conventionally, showing that the use of the ternary
builder system of the invention provides enhanced robustness to
detergent compositions.
The results for Products C + D, when compared with those of
Comparative Product E, also show the reduction in the level of
deposited inorganic salts (ash) arising from the use of the ternasy
builder system relative to prior art builder systems. More particularly,
the comparision of Products C + D with Product E shows the
significant reduction in heavy metal ion levels on fabrics resulting from
use of the compositions of the invention. Fabric heavy metal ion
content can be direcsly correlated with Tensile Strength Loss in fabrics
which is believed to arise from catalytic decomposition of inorganic
perhydrate bleaches on the surface of the fabrics.
