Note: Descriptions are shown in the official language in which they were submitted.
W092/07927 ~r,r/US~-1/07~
a~ 2~5~
- ~` FABRIC TREATMENT COMPOSITION
Technical Field
The present invention relates to fabxic treatment
compositions. In particular it relates to fabric treatme~t
compositions comprising 50~tening clays and softsning
polysiloxanés and floccula~ing agents.
, . . " . ~
Backuround_of the_Inven~ion
-- The use of ~oftening clays in ~abric trea~ment
compositions is well known in the art and has found wide
commercial application. Clays have been us~d in particular
because their application and the so~tening they i~par~ on
fabrics is different ~rom that of cationic soEteners,
Examples and description of clay appli~ation~ can be found
in a large number o~ publicati4ns, fQr example U.S.
3,966,629 or U.~. 1,400,89~ describe different ~inds o~
clays and modes of application of ~hem in fabric treatment
compositions.
,,
W0 92t07927 PCT/IJS91~(379l9
-- 2 --
Co~binatioll o~F clay with so:etening am~ne:; ha5 also b2en
disc:lo~;ed to provide so~tening enhance~t. Further
DE-3 833 648 dess~ proved aggl~meration o~ tergQnts
conta~ soft~ing clay. Further a huD~ctant is p:rovicl~l
~n EP-~ 313 146 facilitating impro~red wetalbility o~ t:he
slay.
Other agents which have been known for fabric treatment
benefit:s are substituted polysiloxanes. They are disclosed
for use at law levels for example in E~A-150 867 or
EP-~-150 872. Relatively high concentrations of
substitu~ polysiloxanes are not uncommon to the textile
~ndustry and have been disc:losed :~or example ir
EP-A~58 ~93 or U.S. 4,247,592.
In EP A-354 856 the comb:Lnation of siloxanes and
cationi :: quaternary almnonium is disclosed.
EP-A-381 487 disc:loses liquid dete2~ent compositions
corltaining a clay component which is pretreated with
siloxane to supply phase ar~d viscosi~r stability while not
deteriora~:ing the cle~ing performance.
It has now been found that the fabric treatment
performance of substikuted polysiloxanes, soft~.ing c:lay
and a clay flocculating agent is substantially hi~7her than
was to be e:~pected by simple adltlitiYe perfor~mce.
Part~cularly when praviding ~ntimate mixh~es of soft2lling
clay ~d substikuted ps:~lysiloxanes in ~e presence o~ clay
flocculating agents the so~t~irlg ~rfonnance ris2s beyond
the expectable acldlitive softening perfonnance of the
com~ounds pro~ided.
., .~W092/07927 P~T/~X~ 7919
2~9 52~-
It is an objective of the in~ention to provide fabric
treatment co~positions containing substituted
polysiloxanes, so~tening clay and a clay floc~ul~ting
agent, pr~ferably as an intimate mix*ure. Further it is an
objective to provide softening-through~the-wash deterg~nt
compositions comprising such fabric treat~ent composition~
preferably granular datergent compositions.
It is another aspec~ of ~he invention to have very good
environmen~al compatibility o~ ~he softening composition in
all modes of application or use.
Summary__~ the Inventlon
The present inven~ion rela~es to fabric treatment
compositions cQmprising a sof~ening clay, a clay
flocculating agent, and a subs~ituted polysiloxaneO The
substituted polysiloxane is present in said composltions at
0.1% to 50% of said softening clay and the clay
flocculaking agent is presen~ at 0.005% to 20% of said
softening clay.
The fabric treatment composition can be applied in
liguid or granular products and used as such in th~ w~sh or
in the rin~e cycle of the laundry. In a pre~erred
t embodi~ent of the present invention said fa.bric treatmant
compositions are co~prised in softening through-the-~ash
(STW~ detergent compositions~ According to the in~ention
STW detergent ompositions contain at least one surfactant
and ~rom 1% to 50~, pre~erably ~rom l-~ to 20%, mor~
preferably ~rom 5~ to 15%, o~ said ~abric tr2atment
compositions.
,
.
WO 92/07927 PCr/US91/07919
2~5.~Zk,4 ~,,,,,~,;,
.-Even more preferred æe particles comprising
coaggl~merated ~oftening clay and substituted
polysiloxanes.. Together wi~h clay flocculating agents
~hese particles can b~ used in granular softenlng
c~mpositions or preferably in granular STW detergent
. composi~ions.
Defin~tions
Unless stated otherwise, the following definitions will
be used hereinafter :
- percentages are ~ _
- softening refers to a range of f~bric treatments
o~her ~han cleaning; in particular it includes
softening, anti-wrinkling, anti-~tatic and ease
o~ ironing treatm~nts.
- clays are softening claYs as described in more
detail below
siloxanes are subs~ituted polysiloxanes for
fabric trea~m~nt as descr~bed in more detail below.
Detailed D2scriptic~ ~' r ention
The so_teninq clay
one essential component of ~he present compo.sitions
consis~s of a clay.
~ ! W092/0792? Pcr/uss 1~07~19
2~9~2~ 1
-- 5 ~ , .
Any clay used in the art or mix~ures thereo~ can be used in
~he present invention.
Included among such clays are various h~at-tre~ed
kaolins and various multi-layer s~ecti~es. As kno~ ~ro~
the art, preferred smectite clays exhibit a cation-exchange
capacity o~ at least 50 meq per loo grams of clay.
Further pre~erred are clays which have a particle size
in the 5-50 micromeker range.
Additionally pre~erred smec~ite clays are hectorite
clays of the general foxmula
~(Mg3_xLix) Si4_yMeIIIyOlO(OH2_z~z)] (x Y~X~
n
wherein y-o: or, i~ ~$o, MeIII is Al, Fe, or B,
is a monovalent (n=l) or divalent (n=2~ metal ion, for
example selected fro~ Na, K, Mg, ca, sr. The value o~
(x~y) is the layer charge of the hectorite clay. The
hectorite clays suitable ~or the detergent compositions of
th~ present invention have a Layer charge distributiDn such
that at least 50% i~ in the range of ~rom 0.23 to 0.31.
Pre~erred are hectorite clays o~ natural oriyin having
a layer charge distribution such that at least 65% is in
the range o~ from 0.23 to 0.31.
, ~ . ...
~
WO 92/07927 ~ItUS~1)7919
eic non-limi~ng examples of fabric so~ten~ng
smectite clay mineral~ are: ¦
Sodi~ lt~on~orilloni~e
Volclay BC R
Gelwhite GP R
Thixo~Jel R
Ben~A-Gel R
Sodium Hectorite
Vee~ F R
Laponite SP R
Sosli~ Sapo~ite
-Barasym N~S 100 R
Caic um Montmorillonite
Sot Clark R
C~elwhite L ~'s
Imvite K ~
Lithlum }le e
Barasym hI~ 200 R
~W~ 92/07927 P~/VS~ 7919
J ~
The clay floçcu~ a~LA~ent
Clay flo ~ ating agents are not commonly used in
fabric treat~e~t compositions~ on the contrary, one is
inclined to usz clay dispersants, which aid in removing
clay stains fro~ fabrics. Clay flocculating agents are,
however, vexy well Xnown in othPr industr.ies like oil well
drilling, and for ore flotation in metallurgy. Most of
th~se materials ~re fairly long chain polymers and
copolymers derived from such monomers as ethylene oxide,
acrylamide, acrylic acid, dime~hylam mo e~hyl me~hacrylate,
vinyl alcohol, vinyl pyrrolidone, ethylene imine. 5ums,
like guar gum, are suitable as well.
Preferred are polymers of ethylene oxida, acryl amide~
or acrylic acid. It has been found that ~hese polymers
dramatically enhance the deposition o~ a d ay if their
molecular weights (weight average) are in the range of from
lOO,OOO^to 10 million. Preferred are -~uch polymers having
a (weight average) ~olecular weight of from 150.000 to 5
million, more preferably ~rom 150,000 to 800,000.
The most preferred polymer is poly-(e~hylene-oxide).
Molec~lar wei~ht distributions can be read.ily dPtermln~d
usLng gel perm~ation chromat~graphy, ayainst standards of
poly-(e~hylene-oxide) o~ narrow molecular weight
distrihutions.
m e amount of clay flocculating agent, expr2ss~d as
percent of ~he clay, ranges ~rom 0.005~ to 20%. For clay
flocculating age~ts having a (w~lght average) molec~llar
wPight of less ~han 800~000, the pref2rred amount is ~rom
WO 92~07927 l ( . . P'C~/US91~7919
2~244 ~.
-- 8
2% to 2~% of the clay. For (weight average) molecular
weight abov~ 800, 000 the prefPrred amount is f:rom 0. 00596 to
2% of th~ lay.
The amour~t of siloxane ranges from 0.1% to 50% by
weigh-t of the clay~ preferably from 0.1% ~o 20%, most
pre:Eerably from 1. 0% to 10% .
The siloxanes useful in the present inven~ion can be
described as softening, stxaight or branched,
organo-functional polydi-C~ alkyl siloxane having the
gen~3ral formula:
R'--si--O-- i~ O~ o- i R'
wher~in R is Cl_4~alkyl,
R~ is R or a polyether of (C2-3~oxides) 1-50~ w ith
a capping group c~f H or R;
R" is branched or straight C~ alkyl;
q1 and q2 are integers;
m and ~ql ~ q2) ~r~ integer5 :erom ~ ~o 1700;
n i$ an integer from 0 to 6;
Y is a poly~ther o~ (C2~3-ox.ides) 1~ whe:re :k has an
average value ~rom 7 ~o 100, with a capping group of ~I or
Cl_4 -alkyl;
W~ 92/~7927 P~r/VS~l/V7919
~ 2 b g"5'2'~ 4
_ g _
- or y is . -
N whereby X and V are selPcted from -EI;
-Cl_3 ~-alkyl, -C-aryl;
C5-6-CYClOa~ Cl_6-M~2;
X V -COR; with the proviso that the
nitrogen can be quaterniz~d such as
to represerlt:
N ~ W
X V
whereby W can be selected from X and
V.
or Y is
H ~ C--T whereby T and P axe selected from ~,
-COOH, -CO-O-C1_2-alkyl, or
H- --C--H epoxy-C~j_6~cycloalkyl
P
Pre~erred silox~anes of said general formula arP
charact~rized by
ql + q2 being an integer ~rom 50 to 1500 ancl
m being an integer from 4 to 1.00~
W0~ 92/0~927 P~r/lJ~;9 I/079l~J
`2~52~ ~
, I . i ~ ~.
-- 10 --
The most preferred siloxanes of said gener~l formula
are characterized by either of the ~Eollowing
- R, R t iS methyJL and Rl' is propyl and
(ql ~ q2) is 329 and m is 21 and n is 1 and
y i5 a polyether consisting of 12 e thyl oxides ancl an
acetic acid capping qroup or
- R, R ' is methyl and R" i5 propyl and
(ql ~ ~2~ is 485 and m is 15 and n is 1 a~d
y i5 a polyether consisting of 12 ethyl oxides and
acetic acid capping group or
- R, R' is methyl and R'l i5 methyl-2-propyl
(~1 ~ q2) is 1470 and m is 30 and n is 1 and
y is an - ( ami~o ethyl ) amine
Optional,s ~ ina~edients
The fabric treatment compositions herein can ::omprise
in addition to the ess~ntial compountls other use:eul
compounds known in the arlt. These compounds can be
present, deperlding on applica~ion and preparation needs or
other esires, irl an added amount of up to 85% o:E the
fabric treatment compositiorlO
Suiltable ~xamples amons~ thase other sof teniTIg compo~ ds
include the followirlg softening amines OI the fsrmula
RlR2R3N~ wherein Rl is C6 t~ C;20 hydroca y,
R2 is C L ~ C2 0 hydrocar}:3yl ~ and R3 i~ Cl to
Clo hydrocarbyl or hydrogerl~ P. pre~e:rred amine of ttl LS
type is ditallowme thylal~ine .
WO 9~/07927 ' ' 2 0 ~.5 2 A ~ P~T/~S~ 7~1~
-- 11 --
Preerably, the soften mg amine is present as a complex
with a fatty acid of the formula ~COO~, wherein R is a C~
to C20 alkyl or alkenyl. It is desirable that the
softening amine/fat~y acid complex be present in the ~o~m
of microfine particles, haYi~g a particle size in the ra~ge
~rom 0.1 to 20 micrometers. These softening amine/fatty
acid complexes are disclosed more fully in EP-A-133 804.
Preferred are fabric trea~nent compositions that contain
from 1% to 10% of the arnine.
Suitable are also complexes of the above described
softenLng amine and phosphate esters of the formula
O O
Il 11
R80 -p OH and HO ~ I ~ OH
O~g 0~9
wherein R8 2nd Rg ar~ C1-C20 alkyl, or eth~xyla~ed
alkyl gr~ups of the general formula alkyl-(OC~2CH2)y,
wherein the alkyl substitue~t is Cl-C20, preferably
C8-C16, and y is an mteger of 1 to 15, preferably
2-10, most preferably 2-5. Softeniny amine/phosphate es~er
complexes of this t:ype are more fully disclosed in EP-A lS8
889 q
"
Suitable optional softening inqrediPnts are also the
softening am~nes disclose~ in GB 2 173 827, in particular
the substi~ted cyclic amines. Suitable arP imidazolines
of the gelleral formula
-(C12-22 ~ amide-(C~ al}cyl)-2-(C12_22 alkyl
i~nidazoline .
: ~ WO 92/~7927 r ~ 1 PC~/~S~It~79
-- 12 --
A p.r~ yclic am~ne is
ï~tallawa~id~t~yl-2-tallow~idalzol~ne. Pneferred falbric
~reabsle~t c~osi~ions co~itain ~ro~ 1% ~o 109~ ~f t~
s~stitu~d cyclic am~ne.
~ er examE~les of taptional ingredients include the
softening ami~aes of the fonnula R~ NC(:)R12~ ~erein
Rlo and Rll are ~ndependently select~d f:rom cl-c22
alkyl, alkenyl, hydroxy-alkyl, aryl, and al~yl-aryl yroups~
R12 is hydrogen, or a C1-C22 alkyl or alkenyl~ ~n
aryl or alkyl-aryl ~roup. Preferred exa3~1es of these
soften ~ g ~ das are ditallow-acetamide and
ditallow-benzamide. Good results ~re obtaLn~d when ~he
softening amides are present in the c~mposition in the form
of a co~posite wi~h a ~a~y acid or wi~h a phosphate est~r,
as described hereinbefore for ~he so~teniny amines.
m e soft~nLng a~ides are pre~erably present in ~he
fabric treatment softenl~g c~mFosition at 1%-10%.
~ oreover, the fabric trea~ment compositio~s herein can
con~ain, in addition to ingredients already men~ioned,
various o~her optional i~gredien~s typically used in
commercial products to provide aesthetic or additional
product performance b~ne~its. Typical ingredien~s include
p~ r~gulants, humectants/ which are more fully dis~losed in
EP~313 146~ silicones~ perfumes, dyes, hydro~ropes and
gel-con~rol agents, freeze-~haw stabiliz ~s, bactericides
or pr~serva~ives. Preferred ~abric ~reat~en~ ~omposi~ions
contain fr~m 0.05% ~o 30% o~ ~hese in~redients~
W09~/079~7~ P~ S~I/079~1~
. .
Industr al~A.~plicati.ons
The fabric treatment compositions of the present
invention can be provided in liquid or granular fo~m. Lt
can be applied in the rinse cycle or, together with a
detergent co~position, in ~he wash. In a preferred
embodiment said fabric treatm~nt compvsi~ions are compris~d
in soft2ning-through-the-wash (STW) detergent compositions.
Further in a preferred embodimen~ said fabric treatm~nt
compositions are particula~e agglomerates, and in a more
preferred e~bodiment said agglomera~es are integrated in
particulate detergent compositions to form granular STW
detergents.
Liquid and Granular A~plicatiQn
.. . . ..
- The fabric treatment compositions of th~ ~resent
invention can be provided in liquid form as an agueou~
dispersion. If provided a~ an aqueous dispersion, the
fabric treatment composition preferably further compri~es
an antisettling agent~ ~ccording to the invention, the
aqueous di~persion com~rises clay of thP fabric treatment
composition ~ro~ 005~ to 30% of the aqueous di~persion and
siloxane and clay ~locculating agent in according amountsO
.,
A suitable antisettling ag~nt must provide a fully
activated suppor~ matrix ~o suspend par~ioles ~ithin ~he
liquid compositionsO
WO 92/07927 ~ P~ 7gl9
2 ~ r;
14 -
Particles in this sense are granul~s or droplets of
suspendable size for the desired properties of the liquid
composition. Usually said particle size will be less th~n
200 micr~meters. The individual par~icles can c~mpris2 one
or more of the essential or optional c~mpounds o~ the
fabric treatment compositions.
Finally, an acceptable antisettling agent must not
adversely effect the viscosi~y, elas~icity or aes~hetics of
the product~
These antise~tling agents, or mixtures thereo~, are
used in the compositions of the present invention at le~els
of from 0.25% to 5%.
Organophillic quaternized ammonium-clay compounds for
example of the Bentone R family of clays ~nd also f~uned
silicas are examples of an~ise~tling agen~s suita~le for
use in ~he present invention. Bentone R rheological
additi~es axe described as the products of a clay which
contains a negative layer-la~ice and an organic compound
which con~ains a cation and at least one alkyl group
containing at leas~ 10 car~on atoms. Bentones R have ~he
propert~ of swelling in certain organic liquids.
Organophillic: quaternized alm~onium-clay cor[~ounds are
preferred antisettling agents as described in UOS. pat~nt
4,287,08~.
Fumed 5ilicas also provide excellent antisettling
characteristics to the compositions of ~he present
invention~ Fumed silicas are generally defined as a
colloidal fonm of silica made by combustion o:~ silicon
tetrachloride in a hydroyen oxygen ~urnace. F~ed silicas
are normally used as ~hickener, thixotrop.lc and reinEoxcing
W092/07~27 ', ; ~CrlUS91l~7
- 15
agents in inks, resins, rubber, paints and cosmetics.
O-SIL~ ~umed silica~ are sui~abl~ antlsettling agent~
for use in th~s invent1on~
.. . . , ~
Other antisettling agents are cellulosic ~uspending
agents. For example carboxy-alkyl~celluloses, pre~erably
carboxy-methyl-cellulose, are excellent suspending ag~nts.
Furthermore other suspending agents known in the art can be
applied.
Mixtures of Bentone R clays, fumed silicas or
cellulosic suspending agents are also suitable antisettling
agents.
The rheological characteristics o~ the resulting liquld
compositions are very importa~t to 2 co~mercially
acoeptable product. A liquid which oan be described as
stringy ( i . e ., elastie), ~hick or lumpy is undesirable.
The antisettling agents described above avoid these
unde~irable rheological properties while maintaining a
pourable, homogeneous produc~ with good consumex appeal~ A
viscosity in the range of ~rom about 100 to about 1000
kg/(ms) is desirable.
It is also desirable ~or th liquid oompo~ition to
exhibit plastic rheology. Materials th~t exhi~it plastic
flow characteristics will flow only ~t~r an ~pplied
shearing stress e~ceeds a critical minimum val ue .
Fabric treatment compositions of the present invention
can also be provided in granular form as particulate
W~92/07927 2 ~ 9 ~ 2 ~ ~ . P~l~U~9~/~79~ l
'' ` ~
- 16 - .
-compositions~ ~ccording ~o ~he in~ention p~rticula-~e
composition~ co~prise clay of the fabric treatment
composition from a~ least 15~, preferably a~ove 50~ 9 of the
partic~late compositions and siloxane and clay flocculating
agent in according amoun~s.
To provide particulate compositions, th~ compounds o~
said fabric trea~men~ composition are preferably
agglomerated. The typical agglomera~e siz~ useful in the
present invention is from 0.2 to 1.2 millime~er on average,
with in~ividual agglomerates ranging from 0.05 mm ~o
2.5 mm.
According to ~ preferred execution of the inv~ntion the
clays, siloxanes and clay flocculating agents ar~
agglomerated together from a slurryO
In a ~urther preferred embodiment the agglomerakes
containing clay and siloxane are made separa~ely ~rom the
agglomerates containing the clay flocculating agent and
both kinds of agglomerates are mixed aocording to the
invention.
-Agglomeration methads and equipme~t suitable for use
herein include those methods known in ~he art.
Agglomeration methods includP usage o~ agglomeration aids
including for example sodium carbona~e, sodi~2m sulfa~e 7
potassium carbona~e, potassium sul~at~, magnesi~m sul~atR,
lithium ~ul~ate, lithium carbonat~, sodi~tm citrate~ so~lium
sesquicarbonate and water. Non limiting ~xamples of the
equipment suitablQ for a~glomeration of clay from smaller
W092/07927 2 0 9 ~ 2 ~ ~ PC~/US~/07~
- 17 -
particles include a DravoR pan agglomerator, Loedi~e~
agglomeration XG/Schugi Beldne ~-Granulator~ whirling
knife continuous vertical fluidized bed agglomerator.
NiroR Fluidized Bed ag~lomerator, O~rianR
Mixer/~gglomerator, and a Li~tlefordR mixPr (Little~ord 1.
Brothers, Inc., Florence, Kentucky, USA, eg. Model FM130D).
Qther methods and equipment which use larger amounts of
water, inclu~ing th~ manufacture o~ agglomerates directly
from a slurry, include a spray drying tow~r, and a prilling
tower.
On a laboratory scale, food processors which are widely
available to the general public can be used ~o agglomerate
smaller clay particles into agglomerates in the disclosed
size ranges.
Deterqent Compositions
.
If applied together with detergent compositions,
preferably;as in~egral part o~ S~W-deterg nt compositions
the fabric treatment compo~i~ion is present ~rom 1% to 50%~
preferably from 1~ to 20% and most preferably ~rom 5% to
15% of the total composition.
STW detergent co:npositions o:E the pres~nt invention can
be provided in liquid or granular ~orm. To provide liquid
or granular STW deterg~nt compositions the detergent
compounds can be eith~r prepared and then mixed with the
aqueous suspension or thQ granular agglolaerates of thP
fabric treatment composition or the detergent compound and
the fabric treatment composition compound can be prepared
together in an inteyr~l process.
WO 92/!~79~7 2~ 5 2 ~ ~ P~/~ 7~
STW~ekergent compositis:ns a~ pref~rably ~ranular
SWT~dete~en~ ~posil;ions o:~ ~e presen~ inYen~ion are
characterized l~y camprising ak least one s~Lrfac~t in
addition to said :Eabric: treatmen~ ccm~sikions. ~Chey can
~er contain other usual clekerg~t c~pour~3~ in
quantities c~mmon ~n the art.
Detersive surfactants particularly use~ul herein
mclude well-kno~n synthetic ~nionic, nonionic, amphoteric
and æwitterionic surfatants. Typical of th~se are the
alkyl benzene sulfonates, alkyl- and alkyle~her sulfates,
paraffin sulfona~2s, olefin sulfonates, alkoxylated
(especially ethoxylated) alcohols and alkyl phenols, amine
oxid~s, alpha sulfonates of ~a~y acid~ ~nd of fatty acid
estexs9 and ~he like, which are well-known f~om ~he
detergency art. In gene~al, such detersi~e sur~ac~ants
contain an alkyl group in the Cg-Cl8 r~nge; the anionic
detersive s~rfactants can b~ used ~ the fonm of their
sadium, potassium or triethanolammonium salts; the
. .
nonionics generally contain from c~ut 5 to about 17
ethylene oxide groups. U.S. patent 3 995 669 cont~ins
dekailed listl~gs of such typical detersive surfactantsO
Cll-C16 alkyl benzene sulfonates, C12-Cl~ paraffin
sulfonates and alkyl phenols are especially pre~erred in
~he co~positions o~ ~he presen~ ~ype.
Also useful h re m as ~he sur~actant are ~he
watar:soluble soaps, e.g. ~he common sodium ~nd potassium
c~conu~ or ~allow soaps well~mown in ~he art.
The de~rgent composition can Gomprise a~ little as 1%
surfactan~ composition~ but pref~rab.Ly it will contain S~
to 50%~ more prefe~ably 10% to 30% surf~ctants. Mixture~
WO 92/07927~ 2 0 9 ~2,,~ 4, Pcr/ussl/o7~
-- 19 --
of the ethoxylatec3 nonionics with aniDnics such as ~he
allyl benzene sulfo~tes, al~yl sul~ates and para:ff~n
sulfona~es ar~ preferxed :~or ~hrough-the wash cl~nsing of
a broad spectn~ of soils and stains from fabrics.
D~tersiye Ad~unç~;
me dete~ent composition useful in the present
invention can contain o~cher ingredients which aid in their
cleanin~ performance. For example, it is highly preferred
that detergent compositions contain a detergent build2r
and/or metal ion sequestrant or chelant. Compou~ds
classifiable a~d well~known .Ln ~he art as detergent
builders include ~he nitrilokriace~ates, polycarboxylates,
citrates, carbona~es, zeolites, water-sol~ble ~hosphat~s
such as tri-polyphosphate and sodium ortho- and
pyro-phosphates, silicat~s, and mlxt~res thereof. ~etal
ion seques~rants include all o~ the ~bove, plus materials
like ethylenediaminetetraace~ate, the
amino-polyphosphona~s (DE ~ T ~ ~nd a wide variety of
G~her poly-fun~tional organic acids and sal~s ~oo numerous
to mention in detail here. U.S. pa~enk 3 579 454 discloses
typical examples o~ the use of such materials în various
cl~aning compo~itions. In general, ~he builder/seguestrant
will comprise about 0.~% to 45~ of ~he total c~mposition.
The 1-10 mic~on size zeoli~e (e.g. zeolite A) builders7
disclosed in German paten~ 2 422 ~5j, are especially
pre~exred for use in low-phospha~e composi~ions.
Particularly sui~able phosphate-free build2rs are ether
carboxylate mixtur~s compris mg
WC~ 92/07~27 ~ ; 2 ~ ~ ~ P~r/U~ 7~1
-- 20 --
a) from 1% to 99% of the builder o~ a tartrate
monosuccinat~ cong?onent o~ the structure
HOCE~ o CH --~
,12
coo~ coox cooX ~o~
wherein X is H or salt-forming cation; and
b) from 1% to 99% of the builder by weight of a tartrate
discussinate component of the structure :
CH2-- CH--O--CH--CH--O -CH CH2
COOX ~OOX COOX COOX CC~OX COO~
wh~rein X .is H or a salt-forming cation.
Builder systems o~ this type are more fully disclosed
in U.S. patent 4,663,0710
Typical detergent compositions useful in the present
invention contain from 5% to 35~ of this ~uilder syst~mO
m e detergent compositions herein also preferably
contain enzymes or enzyme mlxtures to e~hance their
cleaning performance on a variety of soils and stains.
Hydrolases and isomerases like amylase, lipase, cell~lase,
and protease enzymes suitable for use in de~tergen~s ar~
well-kno~n in ~he art and in 5~mmerr~ially availabl2 li~ui~
2nd granular
WO 92/07927 2 1~ 9 ~ 2 ~ 4 ~/U~ 7~
de~ents. Ca~xial ~etersive enzymes (pr~era~ly a
mixtu:re of a~ylase, lipase, celllll~;e and protease~ z~e
typically used. at levels of 0~ 001% to 5% o:E said dete:rgent
cu~positions. I:~ter~ent cellulase enzymes~ w~ich pr~ide
~oth cleaning and softening }~efits, particulæly tQ
~ ton ~abrics, are highly desir~le in the ~positions of
thi5 irlvention.
Further said detergent ccmpositions can contain other
ingredients which aid in their cleaning performance. For
example, the compositions hereln can a*vantageously contain
a bleachiny agent, especially a peroxyacid bleaching agent.
In ~he context of the present invention, the term
peroxyacid bleaching agent enc~mpasses ~oth peroxyacids per
se and systems which are able to yield peroxyaci~s in situO
Peroxyacids per se are meant to include ~he alkaline
and alkaline-earth metal salts ~hereof. Peroxyacids and
diperoxyacids are commonly used; examples are
diperoxydodecanoic acid.(DPDA3 or peroxyph~halic acid~
Systems capable of deliveriny peracids in situ çonsist
of a pero~g~n bleaching agent and an activator thereofO
Ihe pero~ygell bleaching agerl~ are those capa;bla of
yield~ing h~drogerl ~n an aqueous 501ution; these ~ompounds
are well-kna~ in ~e a~, and include ~ydrogen perox:~de,
al~l~mel:al peroxides, orgarl~c pero~fida bleaching agents
such as urea peroxid~ in~rganic psrsalt bleadling agents
such as alkali metal perbora~es, percarborlates,
pe~phosph2ltes and persilicates~
W092/07927 2;D ~ 4 ~T/VS~1/07
- 22 -
The libexated hydrogen peroxide reacts with a bleach
activator to form the peroxyacid bleach. Class~s of blPach
activators include es~ers, imides, imidazoles, oximes, and
.carbona~es. In ~hese cla~ses, pre~erred materials includs
methyl o-acetoxy benzoates; sodium-p-acetoxy benzene
sulfonates such as sodium-4-nonanoxyloxybenez~ne sulfonat~.p
and sodium-4-decanoyloxybenzenesulfonate : biophenol A
diacetate; te~ra acetyl ethylene diamine; ~e~ra acetyl
hexamethylene diamine; tetra acetyl methylene diamine.
Other highly preferred peroxygen bleach activators
which are disclosed in UuS. pa-tents ~ 3.778 and
4.539.130, are alpha-subs~i~uted alkyl or alkenyl esters,
such as sodium-4~2-chlorooactanoyloxy)benzene sulfonate,
sodium 4-(3,5,5-~rimethyl hexanoyloxy)benzene sulfonateO
Suitable peroxyacids are also peroxygen bleach activators
such as described in EP-A--116 571, i.e~, compounds of the
general type RX~OO~I and ~X~L, wherein R is a hydroxcarbyl
group, X is a hetero-akom, ~ is a carbonyl bri~ging group
and L is~a:leaving-group, especially oxybenzenesulfon~te,
Also polymeric soil release agents are us~ul in th~
detergent compositions of the present inventionO Thsy
include cellulosic derivatives such as hydroxyether
cellulosic polymers, copolymeric blocks of sthyle~e
~erp~thalate and polyethylene oxide or p~lypropylene oxide
terephthalate, cationic guar gums, and the like.
WO9~/079~7 1~:2,'~ J~ P~T/~5~ 791~
~ ~ .. .
- 23 -
The cellulosic derivatives that ar~ functional as soil
release agents are commercially available ~nd includa
hydroxyethers of cellulose ~uch as MethocelR (Dow~ and
c~tionic cellulose ether derivative~ such as Poly~er
JR-124R, JR-400R, and JR-30MR (Union Carbide).
Othar e~fective ~oil rel~ase agen-ts ar~ cationic guar
gums ~uch as Jaguar PlauR (Stein Hall) and Gendrive
458R (General Mills~.
Pxeferred cellulo~ic soil release agents for use herein
have a viscosity in aqueous solution at 20~C of 15 to
75,000 kg/(ms) and are selected ~rDm the group consisting
of methyl cellulose; hydroxypropyl methylcellulos~,
hydroxybutyl methylcallulose, or mixtures thereof.
A more prsferred soil release agent is a copolymer
having random blocks o~ ethylene terphthalate and
polyethylene oxide ~PEO) ~erephthala~2. Mor~ speci~ica~ ly9
these pol~ers are ccmprised o~ repeating units of ethylene
terephthalte and PEO tereph~halate in a mol2 ratio of
ethylene ~erephthalate unit5 0~ ~rom about 25:75 to about
35 65~ said PEO ter~phthalate units containing polyethylene
oxide having molecular weights o~ ~rom 300 to 2000. Tha
molecular weight o~ this polymeric soil release agen~ .is in
the range of from 25,000 ~o ~59000. U.S. paten*s 3,9~230
and 3,893,929 disclose similar copolymers in a large
variety~ It has been ~ound previously that these polymeric
soil release agent~ provide a more uniform distribution
over a range o~ fabrics and can there~ore yiield :improved
~abric care ~ualities.
W092/07927 2` Q 9 ~ ~ 4 ~ P~r/vs~ 79
,~
- 24 -
Another preferred poly~eric soil releasQ agent is a
crystallizable polyes~er wi~h repeat units of et~ylenQ
terephthalate units containing about 10-15% by weight of
ethylene terep~thalate uni~s togeth~r with about ~0% to
about 90% by weight of polyo~yethylene terephthal~te units,
derived from a polyoxyethylene glycol of average molscular
weight 300-5,000, and the mole ratlo of ethylene
terephthalate units to polyoxyethylene terephthalate units
in the crystallizable polymeric compound is between ~:1 and
6:1. Examples of this ~ype o~ polymer include the
commercially available material ZelconR 5126 (from
Dupont) and MileaseR T ~from ICI~.
Preferred soil release polymers and methods for their
preparation are described in EP-A-1~5,417.
If utilized, these soil release agents will generally
comprise from 0.05~ to 5% of the ~etergent compositions~
. ~ . . ,. ~
` wo 92~07927 2 ~ `~ 5 2 4 4 PCT/US91/07919
~,, .1~,. ,
- 25 -
EXAMPLES
The following examples illustrate preferred ex~cutions
of this inv2ntion, an~ facilitate i~s under~tanding.
Abbreviations for individual ingredien~s in the
examples have the ~ollowing meaning :
LA5 : Sodium salt o~ linear dodecyl benzene
sulfonate
TAS : Sodium sal~ of tallow alcohol sul~ate
AOS ~ Sodium salt o~ alpha-olefin (C12-18
sulfonate
TAE 11 : Tallow alcohol ethoxylate~ with about 11
moles of et~ylene oxide
FA25E7 : Fatty alcohol (C12-15) ethoxylated with 7
moles o~ ethylene oxide
DTMA : Ditallow methyl amine
~FA : Coconut fatty acid .
HFA . Hrdrogenated C16-~2 ~atty acid
Zeolite A :-- Sodium salt of fully hydrated zeollte 4A
(average p rticle size be-tw~en 2-~ microns~
NTA : Sodium salt of nitrilotriacetate
Copolymer O AA30/M~7~ = copolymer o~ acryli acid 30
mole~% and malsic acid 70 mole-~-50-70 ~mole
weight
CMC : Sodium ~alt o~ carbox~methylcellulose
EDTA o SOdium salt of ethylen~ diamine
tetra-ace.tate
W092/07~27 2 ~ 9~-2~ PCT/~S91/~7
- 26
Example I
For compositions A,B,A',B' the following was preparPd
500g of ~mectite clay having a cation exchange capacity of '.
70-80meg/lOOg was mixed with 50g polysiloxane (10% of
clay). The polysiloxane was of th~ general ~ormula with R
being methyl, R' being a strait propyl, q being 329, m
being 21, n being 1 and y being a polyether of 12 ethyl
oxides capped with acetic acid. Both compounds were
intimately mixed and agglomerated by using a BraunR
multipractic-electronic-de-luxe mixer. The agylom~ration
aid was water and ~h2 agglomerates were sie~ed to a
particle size from 0.15 ~o 0.85 mm. A reference without
the siloxane was also prepaxed in the same manner.
Composition A was prepared by dry mixing of the
clayJsiloxane granules with the deterg~nt granules of
composition I, according to Table I, such that the
resulting softening through~the wash detergent contained
1005~ of-the s~ectite clay. ~s a reference compDsition B
wa~ prepared by dry mixing the clay granules wi~h the same
detergent granules of composition I, Table I, such that the
resulting STW detergen~ also contained 10.5% of th~
sm~ctite clay. Further composikions A',B' were prepared in
the same way as compositions ~,B respectively bu~ uslng
detergent-compo~ition II of Table I which contain~ clay
flocculating agent.
To facilitate a softness comparison of A,~,A',B1 the
following test procedure was used :
3.5 kg of clean fabric laundry loads ar~ wa~hed in an
automatic drum washing machine ~ieleR ~23 at 60~C for 1.
: W~92/07927 . PCT~VS91/~7~19
2 ~3 9 S ~
27 - .
hoursn The hardness of the water was 3~0 mmol o~ Ca2t
and Mg2~ per liter and -the composition concPntration was
1% in the wash liguid. For softness evaluation swa~ches of
terry towel softness ~racers were added. The o~-tness
tracers were line dried prior to assessment of sc~tness.
~omparative softness a~ e~sment was done by expert judg~s
using a scale of O to 4 panel-score-units (PSU). In this
scale 0 is given for no difference and 4 is given for
maximum difference. Softness was assessed after one and
after four wash cycles.
Softness evaluation results of composi~ions A,B,A',B7
Result
comparison of one wash cycle four wash cycl s
composition
1.A to B- 0.1 PSU O . O PSU
2 u- A~ ~to B ' o . 6 3?SU O . 9 PSU
Taking result 1 there is no additive so~tening ef ~ect
realized by adding siloxane to a clay-containing STW
detergent. ~he effect of the invention is demons~rated in
result 2 where the combinatiorl of clay, flocclalatirlg agent
and siloxane shows surprislngly clear softening super:Lority
over prior art co~aposi1:ion c:ontainirlg clay and fl3cculatlng
agent .
_xample II
~ he same compositions a,b,~',b' respectively as in
example I were prepared except ~or using 5g o~
polysiloxane, i.e. l~ of the we.ight of the clay. The
W~g2/079~7 ~r/-US~ 7919
2~9~
-- 28 -
polysiloxane used in this example II was Silwet L720 ~rom
Union Carbide~
Result
comparison of one wash cycle four wash cycles
composition
3. a to b - 0.2 O.l
4. a' to b' 0.3 0.6
Examples III - XII
Accordins to the inven~ion other detergent compositions
can be used together with the clay siloxane agglomerates
and flocculating agent. Alternative granular detergent
compositions are listed in Table IIo
Similar compositions in which the clay/siloxane
granules are initially dry mixed with granules containing
the flocculating agent have be~n found to be equally
effective when a~ded to granular detergent compositions.
Exam~le_XIII
Exe~plifying u~age of the fabric treatment composition
as aqueous dispersion ~he following composi~ion showe~
excellent 50ftening per~ormanc~ when ad~ed in an
appropriate amount to the last rinse of th~ wash o
80g o~ sm~ctite clay are dispersed in l kg of water. 8g of
siloxane as described in example I or II are added under
strong agitation. The flocculating agent and thi~ mixture
are added together to the last rinse of the wash.
~ W092/07~27. 2 ~ 9 5 ~ ~ ~ PCT/US~I/07~
- 29 -
Exam~le XV
A stabilized aqueous dispersion o~ the ~abric treat~entcomposition is prepared by using a propeller mixer at
rotation of 100 to ~OOD per second and combininy liquid
carrier, sof~ening clay, siloxane and an an~isettling agent
in said propeller mixer ~or abou~ 30 minutes. The
resulting mixture is the~ passed 4 to lO ~imes through a
colloid mill (e.g~ model SD-40, distribut~d by Tekmo ~
Corporation) providing a shear of 10 40x103 per second at
a temperature o~ 20-40~C. Then the flocculating agent is
added slowly using said propeller mixer for an ad~itional 5
minutes.
The resulting mixture is stable, iOe. shows ~OW phase
separation or set~ling of the clay, for several wePks at
amblent conditions~
, . .
WC~ 92/07927 % ~ 9 5 2 4 4 ! p~r/us~3/o7~19
''' ~
30 -
Table I
Composition of ~ranular detergents. All values in wei~ht
percent. - ¦
. Composltion
I II
LAS 8 8
TAS 2 2
C12-C14 Dimsthyl(hydrDxyethyl)ammonium chloride 2 2
FA25E7
Zeolite A 23 23
Copoly~er 5 5
Diethylene tri-amine penta (me~hylene phosphonic acid) 0.5 0.5
Sodium perborate (1 aq.) 12 12
Tetra~cetylethylene diamine 4
~n phtalocyanine sulphonate 20ppm 20ppm
Perfume O.4 0.4
En2yme (protPase) 2 2
Montmorrillonite clay ll 11
Glycerol 0 5 0.5
Polyethylene oxide (MW 300.000) - O.25
Sodium carbonate 11 ll
Sodium silicate 5 5
Silicone/silica suds suppressor
CMC 0.4 0.4
Optical brightener 0.2 0.2
moisture and minor balance t~ 100
~ ` ` Wl) 92/07927. 2 0 9 5 2 ~! 4 P~V~g 1/D7~ 19
- 31 -
INGREDIE~ a~OSI~12~S
(% by w~i~;ht
III IV V VI VII VIII~ ~ IX X XI X:[I
IAS 7.0 5.0 4.01.0 6.520.16.77.0 8.0
'rAS ~ 2.0 - - 1.0 - - - 2.02.0
C14 15alkyl sulfate ~Na) - 6.7
AOS - - 2.0 - - - - - - -
Tallow~a~no Cl 4-alkyl - - - 8.0
gl~Y:ose amide
TAE-ll 1.0 2.0 2.0 - 0.8 - - 1.0
FA25E7 - - - 6.0 - - 1.0 - 1.01.0
HFA 2.5 1.0 - 1.0 1.0 - - 2.5
CFA - - 1.5
~12'C14 D~ethYl thydroxy 1.5 - 1.5 - 2.0 2.0
ethyl) Anium cloride
Sodium tripolyphosphate 24.018.022.0 32.0 - 36.9 26.3 24
Zeoli~e.A - - - - 20.0 - - - .23.0 23.0
Polye~ylene oxide 5~ le wt0.05 - - - 0.05 0.10.1
Polyethylene oxide 0.3M~ mole wc - - - 0.2 - - - 0.2 0.25
Polyacrylate - O.2
Polyacrylamide - - 1.5
~A - - - - 5.0
Sodium sulfate 12.6.17.715.0 21.312.728.3 13.012.4
Sodium ca~bonate - 8.0 - 5.0 - - 15.05.0 11.011.0
~WQ\ 92/07~327 ~2 ~ J591/l~l79l~
i; ,.;:
- 32 -
Table II - Cont-inued
a~POS,~EI, O S
- !
(9~ by wei~ht)
III IV V VI VII VIII IX X XI XII
~ ..
Sodium silicate 6.0 7.0 4.0 6.0 2.0 5.75.6 6.0 5.0 5.0
Sodium pexborate t4aq.) 20.015.0 18.010.0 18.0 - 5.0 15.0
Sodium perbora~e ~laq.) - - - - - - - - 12.0 12.0
~IC 0.3 0.3 0.5 0.8 0.4 - - 0.3 0.4 0.4
Polyacrylate (~1000 20000) - 1.S - - - - O.80
Polyac~ylate (MW4000-5000) - - - - 3.0
Copolymer 2.0 - 1.5 2.5 - - - 2.0 4.0 5.0
Enymes (protease, amylase,
lipase, cellul3se) 0.6 0.2 0.5 0.5 0.3 - 0.6 0.6 2.0 2.0
Optical brightener 0.2 0.2 0.3 0.30.25 - 0.8 0.2 0.4 0.4
Zn phthalocyarune sulphonate 30ppm - -25ppm 25ppm - - 30ppm 20ppm 20ppm
D~ 0.2 0.2 0.3 0.15 0.2 - 0.1 0.2
Ethylenediarnine te cra~ethylene
phosphonic acid 0.2 0.1 - 0.1 0.1 - - 0.2
Diëthylenetriamine penta - - - - - - - - 0.2 0.5
(~ethylene phosponic acid)
Tetrsace~yl et~ylenediamine1.5 - - - 1.5 - - 2.0 4.0 4.O
Iso-non~sloyloxy-benzene
sulfonate (Na) - 2.0 - 2.0
Silicone/silica suds suppressor0.2 0.150.15 0.250.2 - 0.30 0.2 1.0 1.0
Per~ume 0.25 0.250.30 0.20.25 0.20.250.25 0.4 0.4
Mont morillonite clay10.0 7.015.0 5.010.0 - 5.6 9.5 11.011.0
Hectorite clay - - - - - 8.9
Moisture ar~d minors bal~nce to 100_ _
'
,:
