Note: Descriptions are shown in the official language in which they were submitted.
WO 95/25160 ~ SU3
21 ~55~5
Granular'~'~~ ' ' ,g co.,~l o~
.
Technical field
The present invention relates to the cleaning of fabrics under soaking
15 conditions. More s~,euiri~:~y~ granular c~"",osilio,ls for soaking fabrics are
described which giYe optimum p~,ru""d"ce in cleaning andlor ~ re~ g
fabrics upon long soaking periods.
Backqround of the invention
It is desirable that a c~",~:,ilio,~ which is typically formulated to be used insoaking conditions retains its capacity to bleach after a long period of time.
2s This is even more desirable in ~ a such as the ui_,.lreuLiull and/or
cleaning of highly soiled fabrics, such as baby napkins.
It is known in the art to use peroxy hydrate compounds in such d~)~liCd~iUI 15
Said peroxy hydrate compounds release hydrogen peroxide which is an
30 oxidizing agent, in solution.
However, the use of such peroxy hydrate compounds in ,.~",~.o~ilio,~s designed
to be used upon long soaking periods has been restricted by the relative
instability of said bleaches in wash solutions. Indeed, due to the reiative
35 instability of such a bleach in a wash solution, said wash solution does not
retain its bleaching activity over extended periods required for cleaning and/ordi ,illrè~,li"g highly soiled fabrics. In fact, the hydrogen peroxide produced by
WO 95125160
2 ~ 5
such peroxy hydrate compounds is rapidly dec~ Josed by the presence of
ions of heavy metals such as iron, copper and Illdlludll~se often found in tap
water as well as by the presence in the wash solution of bacteria or organic
materials provided by the soiled napkins, e.g. soils like feces and urine.
Indeed, the presence of such heavy metal ions is unavoidable in the usage
conditions of granuiar soaking .,ulll,uu ,it,ùna~ To overcome this problem US - 4
4û5 482 discloses the use of stabilizers like chelants, i.e. diethylene triaminop~ dC~, acid and magnesium sulfate, in granular c~lll,uuailiulls. Magnesium
~o sulfate allows to stabilize the hydrogen peroxide and to harden the water in the
wash solution obtained with said granular culllpOailio~l and diethylenl:l,idl"i"e
pdl~ldu~, acid neutralizes metal ions which are not ~dcu",uu~ed themselves
by the oxidizing action of hydrogen peroxide.
However, there is a constant strive for the development of granular
culll,uo:~iliul~5 to be used in soaking conditions, which provide a longer period of
effective bleaching.
Accordingly, it is an object of the present invention to provide a granular
20 colll,uu~iliol~ Co~,ulisill9 a source of available oxygen whereby the
decu,,,~,uailio,, with time of the available oxygen produced upon dissolution ofsaid COIll,u~aSiliùr~ in wa`ter is reduced.
It has now been found that the addition of an alkali metal salt of silicate, or
25 mixtures thereof, to a granular soaking cu"")osilio,- uo~ u~ g a source of
available oxygen, allows to reduce the decu,,,uoai~;o,~ of available oxygen
which occurs in the wash solution obtained therewith. More sueuiri~':y, it has
been found that granular c~" ,posili~lls cu" ~uriail ,9 a source of available oxygen
and stabilizers like chelants together with an alkali metal salt of silicate, sucn
30 as sodium silicate, allow to produce wash solutions wherein the bleaching
capacity is retained upon longer periods of time as compared to the same
co",posi~iù,~s but without sodium silicate. In other words, the use of an alkalimetal salt of silicate on top of other stabilizers like chelants in granular
uoll~,uùsiliùns provides wash solutions which remain more active for over 245 hours and provide long term S~ dliùll andlor cleaning and/or bleaching
;P5 which are less affected by variable water supply quality or by soils
~ss~ d with highly soiled fabrics, as for example, baby napkins.
. . . _
WO95125160 2 1 8 5 5 '1~
3 2 l~5~5
A further advanSage is that the available oxygen decu,,,uoai~iù,l reduction effect
of an alkali metal salt of silicate has also been observed in CullllJùs~ s
comprising a source of available oxygen together with a bleach activator.
s
Summarv of the invention
Co~uosiliùl~s according to the present invention are granular ~u,,,posiliù,ls
cu,,,urisill~ a source of available oxygen and diethylene triamino pe"lact:lic
acid. Said ù,,luosiliu,~s further comprise an alkali metal salt of silicate or
mixtures thereof.
The present invention also encol"passes the use of an alkali metal salt of
silicate, or mixtures thereof in a granular laundry CulllpOait;OIl Culll~risi,lg a
source of available oxygen whereby the dec~",uo~ " with time of the
available oxygen produced upon dissolution of said c~ Juailiùll in water is
20 reduced.
The present invention also el~co,,,udaaes a process of treating fabrics with a
source of available oxygen wherein a granular ~ul~luùailiull culllp~iaillg said
source of available oxygen and an alkali metal salt of silicate or mixtures
2s thereof is dissolved in water and said fabrics are left to soak in said diluted
c~ ûsiliul 1 then either washed and left to dry or rinsed and left to dry.
Cetailed cl~su, iuliul~ of the invention
The CCIll,ùOai~iùl-a according to the present invention comprises as a first
essential ingredient a source of available oxygen. By source of available
35 oxygen it is meant herein an active oxygen-releasing peroxy compound or
mixtures thereof. The peroxy compound may be hydrogen peroxide or any of
the addition compounds of hydrogen peroxide or organic peroxyacid or
wo 95/25160 2 1 8 5 5 ~ 5r~
mixtures thereof. By addition compounds of hydrogen peroxide it is meant
compounds which are formed by the addition of hydrogen peroxide to a second
chemical compound, which may be for example an inorganic salt, urea or
organic carboxylate, to provide the addition compound. Examples of the
s addition compounds of hydrogen peroxide include inorganic perhydrate salts,
the compounds hydrogen peroxide fomms with organic carboxylates, urea, and
compounds in which hydrogen peroxide is clathrated.
Examples of inorganic perhydrate salts include perborate, pe,w,bù,,dL~l10 pel;Jl~apl~dl~ and p~, ' ' salts. The inorganic perhydrate salts are
normally the alkali metal salts.
The alkali metal salt of pe,w,L,u"ale, perborate or mixtures thereof, are the
preferred inorganic perhydrate salts for inclusion in the w,np~ailiuns in
accu, dd,~-,e with the present inYention. Preferred alkali metal salt of
pe(~;d,u.",dla to be used herein is sodium p~w~vnale. Sodium pelwlb~l~dl~
is available cu"""e,~ -'ly as a crystalline solid. Most cu"""e~ !y available
materials include low levels of heavy metal sequestrats such as EDTA, 1-
hydroxyethylidene 1, 1 d~ ua~Jllorlic acid (HEDP) or an amino-pl)ospl~ù~ e,
20 which are illC~ uldl~d during manufacturing process Preferred alkali metal
salt of perborate to be used herein is sodium perborate. For the purposes of
the present invention, the pe,w,L.u,lc,l~ or perborate can be ill~,~l,uo,dlt:d into
detergent cu, ~,uuSi~iO~ la without additional protection.
2s Whilst heavy metals present in the sodium carbonate used to manufacture the
pe,w,Lul,c,L~ can be controlled by the inclusion of sequestrats in the reaction
mixture, it is preferred that the pel~,dl~Ulld~t: be protected from heavy metalspresent as impurities in other i"u~ ic. Il:- of the product. It has been found that
the total level of Iron, Copper and Al ,ga"ese ions in the product should not0 exceed 25 ppm and preferably should be less than 2û ppm in order to avoid an
Jl~ adverse effect on p~lwlLor~ , stability during its storage.
The Cûll,pOsiliul,S according to the present invention comprise from 10% to
80% by weight of the total Culll~uosiliu" of a source of available oxygen,
3s preferably from 15% to 50% and more preferably from 20% to 45%. When a
co",posi~iu" of the present invention is used under normal conditions to
produce the wash solu~ion, i.e. 15-7û9 of a c~ ailiul~ according to the
~ WO 95/25160 2 1 8 5 5 ~ 5 r~
present invention are dissolved in about 7 liters of water, said wash solution
comprises from 0.3% to 11% by weight of the total wash solution of available
oxygen, preferably of from 0.45% to 7% and more preFerably of from 0.6% to
6.2%. By "available oxygen" it is meant herein the active oxygen released by
5 hydro3en peroxide in the wash upon its reduction. Said hydrogen peroxide
beins itself released by the active oxygen-releasing peroxy compounds, more
generally defined herein under the name of source of available oxygen.
As a second essential Gompound the cu",,uo~ilio,~s of the present invention
10 Gomprise diethylene triamino pélltace~ acid as a stabilizer like chelant. Said
Gheiating agent helps to control the ievel of free heavy metal ions in the wash
solution, thus avoiding rapid dec~",~osi~i~n of the hydrogen peroxide released
by said source of available oxygen of the ~u",posi~io,~s of the present invention.
Other suitable amino calL ox~l..'~, chelating agents may be used in the
15 G~lllpûai~iOIla of the present invention such as ethylelledid"~i"e lètldace~dLes
(EDTA), N-hydroxyethylethyle,~e.Jia",i"e l~iac~t.,t~,3, Il ilu;,iace~ 3,
ethy~ e~id",i"e léLla,ulu,uliOII_~ ., triethyl~ t~,;,dd")i"e h~ æ~ ;, and
t:LI Idl "~Idiy,ycines, alkali metal ammonium and sl Ihstit~ It~d ammonium saltsthereof or mixtures thereof. Further suitable chelating agents include
20 ethylc~edialllille-N~N~- disuccinic acids (EDDS) or alkali metal, alkaline earth
metal, ammonium, or sllhsti~t~d ammonium salts thereof, or mixtures thereof.
Particularly suitable EDDS compounds are the free acid form and the sodium or
magnesium salt or complex thereof. Also others suitable chelating agents may
be the organic ,ul luaiJI lurldleSl including amino alkylene poly(alkylene
2s ~ OalJl lùl 1_`~.), alkali metal ethane 1 -hydroxy di~l~o~,l lOndlèS, nitrilotrimethylene pllOapl~Orl-~3l ethylene diamine tetra methylene pl~ûa,ullOIldlès
and diethylene triamine penta methylene l~llùsullulld~es. The ,ullosullo~ld~e
compounds may be present either in their acid form or in the form of their metalalkali salt. Preferably the organic ,ul)osul~r~_`u compounds where present are
30 in the form of their magnesium salt.
The cOIll~oaiLiol~s according to the present invention comprise from 0.01% to
5% by weight of the total Culll~Oailiul ,s of said chelating agents, preferably from
û.û5% to 2%, more preferably from 0.1% to 1%.
3s
As a third essential compound the c~",,uosiliuns of the present invention further
comprise an alkali metal salts of silicate or mixtures thereof. Preferred alkali
wo ssnsl60 ;~ 1 8 5 5 ~, 5P~
metal salt of silicate to be used herein is sodium silicate. It has been found that
the decu",posilio,1 of available oxygen produced in the wash solution upon
dissolution of a culll,uuailiull of the present invention is reduced by the
presence of at least 4û parts per million of sodium silicate in said wash
s solution. Accordingly, the present cc",~oai~iùns comprise from û.5% to 15% by
weight of the total l,u~,uOailion of an alkali metal salt of silicate, or mixtures
thereof, preferably from 1% to 10% and more preferably from 2% to 7%.
Any type of alkali metal salt of silicats can be used in the colll,uo5iliol~s of the
present invention including the crystalline forms as well as the amorphous
forms of said alkali metal salt of silicate or mixtures thereof. Preferred herein is
to use the crystalline forms as well as the amorphous forms of sodium silicate
or mixtures thereof.
Suitable cr,vstalline forms of sodium silicate to be used according to the present
invention are the crystalline layered silicates of the granular formuia
NaMSixO2xt1 yH2o
wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a
number from û to 20, or mixtures thereof. Crystalline layered sodium silicates of
this type are disclosed in EP-A-164 514 and methods for their ul~dldliùl~ are
2s disclosed in DE-A-34 17 649 and DE-A-37 42 043. For the purposes of the
present invention, x 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 examples
of this formula comprise the a, b, g and d forms of Na2Si2Os These
materials are available from Hoechst AG FRG as respectively NaSKS-5,
NaSKS-7, NaSKS-11 and NaSKS~. The most preferred material is d -
Na2Si2Os NaSKS~. Crystalline layered silicates are i~-,UI,UUI~ either as
dry mixed solids, or as solid Culll~ol1~llLa of au~lullle:ldlc:s with other
cc,,,~û, ,e, ILa.
3s
Suitable amorphous forms of sodium silicate to be used herein have the
following generai formula:
WO 95125160 2 1 8 5 5 4 5 . ."J~ s ~ ~
7
NaMSixo2x+1
wherein M is sodium or hydrogen and x is a number from 1.9 to 4 or mixtures
s thereof. PreFerred to be used herein are the amorphous fomms of Si20s Na20.
Other suitable alkali metal salt of silicate to be used herein are al~",i, IOail;~Lt:s
including those having the empirical formula:
Mz(zAI02.ySiO2)
wherein M is sodium potassium ammonium or s~hstit~'?~ ammonium z is
from about 0.5 to about 2; and y is 1; this material having a magnesium ion
exchange capacity of at ieast about 50 milligram equivalents of CaC03
hardness per gram of anhydrous alulllill~a;i~ . Preferred alu",i"c
are zeolites which have the formula:
Nazi(AI02)z (SiO2)yù.xH20
20 wherein z and y are integers of at least 6 the molar ratio of z to y is in the
range from 1.0 to about 0.5 and x is an integer from about 15 to about 264.
Useful alu",i,-os;l,. d~ ion exchange materials are ~u~ kA~'y available.
These al~",i,~: c can be crystalline or amorphous in structure and can be
25 naturally-occurring alullli~losil;~ a or s~"~ ic~l'y derived. A method for
producing alL""i"osili~ e ion exchange materials is disclosed in U.S. Patent
3 985 669 Krummel et al issued October 12 1976. Preferred synthetic
crystalline aiL",i" :~ ion exchange materials useful herein are available
under the desi~"d~i-,ns Zeolite A Zeolite P (B) and Zeolite X. In an especially
30 preferred ~ bodi~llell~ the crystalline alullli,l ion exchange material
has the formula:
Na12i(AI02)12(SiO2)12u.xH20
3s wherein x is from 2û to 30 especially about 27. This material is known as
Zeolite A. Preferably the al~",i,: - has a particle âize of about û.1-10
microns in diameter.
wo ssns l 60 r ~ ~ r. ~
8 2l 855~5 ~
Other suitable silicates to be used herein are for instance magnesium silicates
such as Mg3(0H)4Si20s.
s
The Cul~l,ùOa;liùlla according to the present invention may comprise a
magnesium compound 1,vhich acts to partially stabilize the hydrogen peroxide
and hardens the water in the wash solution in which the Culll,uOaitiullS are used.
The CullIpOai~iul~S of the present invention preferably comprise from 0.1% to 5%10 by weight of the total ,u~,uosiliol~ of magnesium compounds, e.g. magnesium
sulfate, and preferably from 0.5% to 3%.
The ~,ullluOaiLiulls according to the present invention may naturally comprise
inorganic filler salts such as alkali metal cdluol,~,L~s, bi~dluull. ~,~ and
15 sulphates. Such fillers for instance sodium bicdlL,u,,dL~, may also act as
acidifyin3 agent as described herein after. Accordingly, sodium ~iCdlLJUlldLe
and sodium sulphate are the preferred filler materials for use herein.
20 The present invention makes possible the production of a cu,,,~siLiu,, which
provides stain removal, cleaning, deûr~ dliol~, whitening, bleaching and/or
d,ai"r~ iul, d~e"u'~"g on the i"y,c~dirl,~a included therein. Co,ll,uuailiOI~S in
accu,dd"ce with the invention can thus comprise optional i, Iyl~,iie:l ,Ls such as
optical b,iyl,lel~e,a, anti dusting agents such as olefines and waxes, enzymes,
2s other chelarlts, ~iSp~ladllla, surfactants, soil release agents, soil suspenders,
builders, photoactivated bleaches such as Zn phthalocyanine sulphonate,
dyes, dye transfer inhibitors, pigments and perfumes. Said optional i"yl t:~ie, lls
can be added in varying amounts as desired.
30 Indeed, particularly preferred herein are uulll,uOailiul15 which beside theirprolonged bleaching properties, i.e. Ionger period of effective bleaching
provided upon dissolution of said cu~uùsilion in water, further provide good
cleaning pe,ru,,,,d,,ce on fabrics soiled with mud/clay containing soils, such as
socks. Accordingly the cull"~ailions herein may further comprise a soil
3s suspender. Suitable soil suspenders, also dch"o.~'~iyed in the art under the
name of "anti-,ed~ agents", to be used in the ,u,,,pùsilio~s of the
present invention include cellulose derivatives such as methylcellulose,
wo 95/25160 2 1 8 ~, r~ 4 5PC~
carboxymethylcellulose and hydroxyethycellulose, homo-or co-polymeric
polycarboxylic acids or their salts and polyamino compounds. Polymers of this
type include the polyacrylates and copol~" ,~, ~ of maleic anhydride with
ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic
s anhydride constituting at least 20 mole percent of the copolymer disclosed in
detail in EP-A-137 669. Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight of from 1 0û0 to 10000 and more
preferably of from 2û00 to 8û00.
10 Accordingly the ,,o"",~sili~ns of the present invention comprise up to 20% byweight of the total c~ ,u~i~io,, of a soil suspender, or mixtures thereof,
preferably from 3% to 15% by weight and more preferably from 5% to 14% and
most preferably from 7 to 14%.
15 As an optimal but highly preferred cu,~,,uull~ the c~",~.osiliù,~s according to
the present invention further comprise an acidifying system. The purpose of
said acidifying system is to control the alkalinity generated by the source of
available oxygen and any alkaline compûunds present in the wash solution.
Said system comprises anhydrous acidifying agent, or mixtures thereof, which
20 needs to be i"~,u~,uul ' i in the product in an anhydrous form, and to have agood stability in oxidizing environment. Suitable anhydrous acidifying agents
for use herein are carboxylic acids such as citric acid, succinic acid, adipic
acid, glutaric acid, 3 chetoglutaric acid, citramalic acid, tartaric acid and maleic
acid or their salts or mixtures thereof. Other suitable acidifying agents include
2s sodium bicdl ~u"ale, sodium sesquicd, ~u"dle and silicic acid. Preferred
acidifying system to be used herein comprise citric acid and/or sodium citrate
and optionally bicdl ~ondl~. Highly preferred as the acidifying system is
citricacid. Indeed, citric acid is uu,,,,,,t:,-,ially available in anhydrous form, it
a~di~io~ y acts as a builder and a chelant, and it is bi~dey,~dable. The
30 cu,,,,uûsiliulls according to the present invention comprise from up to 20% by
weight of the total cu",,uosiliu,~ of anhydrous citric acid, preferably from 5% to
15%, most preferably about 10%.
It has been found that by formulating the uu~,uosiliol)s of the present invention,
35 especially the ones which further comprise a soil suspender, to control pH inthe wash solution and keep it below 9.5, said cu,,,,oosiliù~)s are able of boosting
the cleaning pe,ru""d-,ce on mud/clay c~"lai"i,~g soil. Accordingly preferred
WO95/25160 2 ~ T~
uo~,poailions to be used according to the present invention comprise an
acidifying system, the weight ratio of the source of available oxygen, alkali
metal salt of silicate together with carbonate, if present, to said acidifying
system being inferior to 4, preferably inferior to 3.5.
s
Optional but highly preferred ill~ ta are peroxy carboxylic acids bleach or
precursors thereof, commonly referred to as bleach activators, which are
preferably added in a prilled or a~ ",e,d~d form. Examples of suitable
10 compounds of this type are disclosed in British Patent GB 1 586 769 and GB 2
143 23~ and a method for their formation into a prilled form is described in
European Published Patent Application EP-A-62 523. Preferred examples of
such compounds are tetracetyl ethylene diamine, (TAED), sodium 3, 5, 5
trimethyl hexanoyloxybenzene sulphonate, diperoxy dudeLdl ,oi-, acid as
15 described for instance in US 4 818 425 and nonylamide of peroxyadipic acid asdescribed for instance in US 4 259 201 and n-nonanoylox~b~"~t~,~esulphonate
(NOBS), and acetyl triethyl citrate (ATC) such as described in European patent
91870207.7. Also particularly preferred are N-acyl ,d,UIUId~,
selected from the group consisting of sllhstitlJt~d or uns~hstit~lt~d benzoyl
20 Cd~)l Uldl,ldl 11, octanyl Cd~.ll uld~,lal 11, nonanoyl Cd,Ul uld~.lal 11, hexanoyl
Cd~)l Uldl,ldl 11, decanoyl Cd,ul Uld-,ldl 11, undecenoyl Capl ulal~ld~ formyl
Ud,UI UldUIdl 11, acetyl Cd,Ul UldUIdl 11, propanoyl Cdul UldUIdl 11, butanoyl W,UI ula~.Ldl 11
pentanoyl Cd,ulUlal,lalll. The Culll~uailiullS of the present invention may
comprise one of the above " le:l ,liù,~ed bleach activators or mixtures thereof
2s
Preferred mixtures of bleach activators to be used in the ,u~,uosiliùns of the
present invention comprise n-nonanoylox~lu~ esulphonate (NOBS~ together
with a second bleach activator having a low tendency to generâte diacyl
peroxide but which delivers in the wash mainly peracid. Said second bleach
30 activators include tetracetyl ethylene diamine (TAED), acetyl triethyl citrate
(ATC), acetyl ud,ululd~,ldll~, benzoyl ca~lulduLdl~l and the like, or mixtures
thereof. Said mixtures of bleach activators are preferably used in the
~Illbudi~ l of the present invention where the C~lll,uOailiûl~s of the present
invention, especially the ones which further comprise a soil suspender, are
3s formulated to allow the control of the pH in the wash solution below 9.5.
Indeed, it has been found that the above ",~"lioned c~lll,u~ailiul~s of the
present invention which further comprise a mixture of bleach activators
WO 95/25160 11 I ~ U~ O2SO3
,u, ",urisi"~ n-nûnanoyloxyb~ en~sulphûnate and said second bleach
activatûr, allow tû boûst particulate sûil (clay) cleaning pa~ru""a~ue while
exhibiting at the same time gûûd p~lrUlllldll-~e on diacyl perûxide sensitive soil
(e.g. beta-carotene) and ûn peracid sensitive sûil (e.g. bûdy soils).
Accordingly in an ~"ILoui",a"l of the present inventiûn the c~,,,pûsiliu,,:, maycomprise mûre than 3% by weight of the total ~,u,,,pûsiliu,, of n-
nonanûylûx~e, ~ e:,ulphonate, préferably frûm 4% to 1 û% and more
preferably from 5% to 7% and mûre than û.5% by weight of the tûtal
cr.,,,,uo:~iliùl~ of said second bleach activatûr, or mixtures thereof, preferably
from 2% to 8% and more preferably from 5% to 7% .
The c~l~l,uOailiûl~ according to the present invention can be made by a variety
5 of methods well knûwn in the art, including dry-mixing, spray drying,
a~!Jlu" ,~ .,lion and granulation and ~,~" IL;, ICII;OI ~5 thereof.
The cu,,,,uosili~,~s according to the present invention can be prepared with
20 different bulk densities, frûm conventional granular products to so-called
"uul~c~l ,t, ~l~d" products (i.e. with a bulk density above 600911).
The present invention also e,~c~",,uasses the use of an alkali metal salt of
25 silicate, or mixture thereof, in a granular r~r.",,uùsiliu" uu"~p~isi"9 a source of
available oxygen, whereby the decu,,,,uo~ilio,~ with time of the available oxygen
produced upon dissolution of said co"".osi~io,~ in water is reduced.
30 By ''d~,,,,.,osiliû,~ of available oxygen is reduced" it is meant herein that the
amount of available oxygen in the wash solution is higher when said wash
solution is produced with the c~"~ û~itions of the present invention as
compared to the same cu,,,i,osiliùns but without an alkali metal salt of silicate,
- even if measured after 24 hours. The available oxygen clecu",posiLioll
3s reduction effect of an alkali metal salt of silicate, i.e. the higher available
oxygen retention phel,u,na"u" through the wash, may be measured using a
standard indirect redox titration with iodide and thiosulfate as titratin3 agents
WO 95/25160 P~
~ ~ 8 ~ 12
and starch as indicator. This method is reported in the literature, see for
instance "Analisi Chimica Quantitativa, Emilio Bottari, Arnaldo Liberti, 1983,
page 308".
s The present invention aiso e,~ ""~asses the use of an acidifying system in a
laundry cu",posiliu~ u~p~isi"~ a source of available oxygen, an alkali metal
salt of silicate and optionally carbonate, v~herein the weight ratio of the source
of available oxygen, alkali metal salt of silicate together with carbonate, if
present, to said acidifying system is inferio! to 4, whereby the pH in the dilution
10 Culll,uuailiull (wash solution) obtained upon diâsolution of said cu",pùsili,o,l in
water is kept below 9.5, whereby the cleaning pe,ru""d"ce on mudlclay
Cullld;llillg soil is improved. In a preferred ~",uodi",~"l said cu",uosiliu"
further comprise a soil suspender and/or a chelating agent, andlor a bleach
activator. In a further preferred ~",bodi",t",l said culll~Joai~iul) comprises a15 mixture of bleach activators, said mixture cu",~,risi"g n-
nonanoyloxybt"l~l1es.llphonate and a second bleach activator, said second
bleach activator being selected from the group of tetracetyl ethylene diamine,
acetyl triethyl citrate, acetyl Cd,ulUId~,ldlll, benzoyl cau,ula~,ld,,, or mixtures
thereof, preferably said cu",~osi~iù,) comprises more than 3% by weight of the
20 total Culll,uOailiull of n-nonanoyloxy~e"~nesulphonate and more than û.5% by
weight of the total COIll,uua;~iull of said second bleach activator.
The present invention also 3nco",~asses a process of treating fabrics with a
source of available oxygen wherein a granular C~ uai~iull wlll,u,isi"g said
2s source of available oxygen and an alkali metal salt of silicate, or mixture
thereof, is diluted in water and said fabrics are left to soak in said diluted
cu",,uùsi~;on (wash solution), then either rinsed and left to dry or washed and
left to dry.
30 By "washed" it is meant herein that the soaking step carried out according tothe process of treating fabrics of the present invention may be followed by a
washing step, said washing step includes washing with an automatic washing
machine andlor washing by hand.
The culll~Josiliùl)s of the present invention are particularly suitab~e to be used
for treating baby napkins, linen and clothing co"ld",i"dl~d by body exudates.
WO95/25160 r_l,l,.. ..
13 2 1 ~
Depending on their lesl,euli;e formulation said c~"~uosili~",s are alsoparticularly suitable to be used for treating socks and linen and clothing
co, lldll ,i, . by mud/clay soils. The cu,,,~osiliu,ls of the present inventions are
also particularly suitable to be used upon long soaking periods in both hot and
s cold water.
Ex~el il l lel ILdl data
1 ) Part A
The following cu,,,p~ iù,~s are made with the listed illyre~ie"La in the listed
~, u~u, liù~ ,s.
Co"",usilions (% by wêight)
2 3 4
15 ll lul ediél ,~
Sodium perw,l,~" 3û 30 30 30
TAED 2 2 2 2
Sodium carbonate 30 30 30 3û
Citric acid 5 5 5 5
20 Polyacrylate 2 2 2 2
Sodium Li~ dl L,oll 25 25 25 25
LAS~ 5 5 5 5
Sodium silicate / 5 / 5
Magnesiumsulphate / 1 1.2 1.2
25 DETMPA~ / l û.3 0.3
Minors and water up to 1 oo%
30 LAS ~ is linear sodium alkyl benzene sulfonate.
DETMPA~ is diethylen triamino péllldCeli. acid.
~ .
WO 95/25160 r~,l"
14
2)PartB 21 85545
The c~,,,,uosiliù~s above were evaluated in terms of the amount of available
oxygen present in the wash solutions produced by using respectively said
S Culll~Oai liu~s.
The eApe~i"~ l was conducted to replicate the realistic soaking conditions.
For this purpose we used hard water (17gr/us gallon) and stains standards on
cotton of blood, wine, coffee, grass and sebum From the EMPA institute.
The wash solutions were prepared by dissolving 3û grams of each of the
c~ uaiLiùl~â 1, 2, 3 and 4 in 7 liters of water. These wash solutions were
prepared at 60C and held for 24 hours at an ambient temperature of about
25C. The available oxygen content remaining in each of the wash solutions
was measured at time 1 hour, 6 hours, 16 hours and 24 hours.
The method used for measuring the available oxygen content remainin3 in the
wash solutions was a standard indirect redox titration with iodide and
thiosulfate as titrating agents and starch as indicator.
The table below lists the results obtained for the above mentioned
culll~ailiO~Is with and without sodium silicate, in terms of % of available
oxygen (AvO2) retained in the wash solutions at different times following the
pdld~iUI) of said wash solutions with said c~""~osili~ns.
Co" ,!,osi~iùl ,s 1 2 3 4
(% of AvO2 retained)
1 hour 1ûO 10û 100 100
6 hours 1 78 87 96
30 16 hours / 58 73 89
24 hours 31 55 66 88
The results show that a c~",posilio,~ co",~.,isi"g pe,ud,uol,d~e and sodium
silicate (c~",~o:,iliù,~ 2) as compared to the same cu",~ailion but without
35 sodium silicate (c~,,,,uùsiliùll 1), allows to produce a wash solution wherein the
amount oF available oxygen is higher, even after a long soaking period, e.g. 24
hours. This clearly shows that the use of sodium silicate allows to reduce the
w095/25160 2 1 8 5 5 ~ 5
decomposition of available oxygen produced in the wash solution and thereby
allows to retain the bleaching capacity of said wash solution upon longer
periods of time. The results obtained with c~,,,pc,siliu,,s 2 and 3 are
equivalents. Indeed, sodium silicate allows to obtain the same benefits as
compared to others known stabilizers like chelants. However, when adding
sodium silicate on top of said other stabilizers like chelants such as diethylene
triamino p~ dC~IiC acid and magnesium sulphate in a ~",l~u~ designed to
prepare a washlsûaking solution, the available oxygen in said wash solution is
i~ll~ill~d to up to 88% of the initial available oxygen after 24 hours. This
0 translates in an overall improved pe~rulllldll~e ~so~ with the use of the
cu~,uusil;ol la of the present invention, e.g. better Uiiil II~I..liOl~ and/or cleaning.
ExamPles
15 Further examples of cull~,u~ailiOlla according to the present invention are the
following. The following ctj",~,osiliol1s are made with the listed illyl~ llla in
the listed ~lu~ ulliu"s.
Cu"luosiliol)a (% by weight)
1 2 3 4 5 6
"t~
Sodium pe,w,bù,~dl~ 34 26 26 30 30
Sodium perborate
monohydrate I I I I 1 27
2s TAED 2 1 2 / 6
NOBS I I 1 12 6 12
Sodium sulfate 30 30 30 25 25
Citric acid 5 5 5 10 10 10
Sodium tjiCdl uu, Idl~ ~ 9 25 19
30 LAS~ 7 5 7 6 6 5
Nonionic / I 1 1 1 2
Sodium silicate 4 3.5 4 5.9 5.9
Zeolites I I I I 1 10
Magnesium sulphate 1.2 1.2 1.2
3s DETMPA~ û.3 0.3 û.3 0.2 0.2 0.3
Polyacrylate / I 1 1û 10 10
Minors and water up to 100%
WO 95/25160 1 ~,I/~J.,.
16 21 ~5~5
LAS ~ is linear sodium alkyl benzene sulfonate.
DETMPA~ is diethylen triamino ,u~"lacelic acid.
s
The co",uosiLiù,~s above when used to produc~ a soak solution show an overall
improved pe, ru""c"~3 compared to the product cu~ "y available. These
c~,,,,uosiliù,~s are efficient in terms of cleaning, cle~du,i~i,,g, bleaching,
~ ;. Irt ~ u and/or stain removal. For example c~,,,,uosiliu,, 5 when used upon
10 soaking conditions for treating fabrics (e.g. Iinen and/or clothing) delivers at the
same time optimized pe,ru""anc~ on particulate soil (clay), on diacyl peroxide
sensitive soil (e.g. beta-carotene) and on peracid sensitive soil (e.g. shirts
collars, body soil).
