Note: Descriptions are shown in the official language in which they were submitted.
CM6 1 0M/AA
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STABLE AQUEOUS NONIONIC SURFACTANT COMPOSITIONS CONTAlNING
PERSULFATE SALTS.
Technical field
The present invention relates to cleaning and bleaching compositions, more particularly
to highly acidic aqueous CC~ Gs;t;on~ CG~ B nonionic surfactants and pc. "' e
salts being in the form of an emulsion. In its broadest aspect, the present invention
relates to a process of treating hard surfaces, especially toilet bowls, wherein an highly
acidic aqueous; ' -- of at least two nonionic surfactants and further COll.pl _ a
persulfate salts is used in its diluted form.
Back~round
A great variety oftles ' ~g and cleaning C~ ~?~r'~ n~ have been dcsclibcd in the art. It
is also well known that it is ~: b!e to use pc.~..lr~te salts as a ~le~ ' ~ B agent. For
pl~, Eul~ Patent ~p~"~ - EP-A-0 373 613 d;~ &stQ the prcp... - - of a
specific lllonop~ lr~ie d-~}i~ " i.e. ~l " a-3-percarboxylic acid ,llonopc. "'
useful as ~' ~ ' 'C agent in detergent formulations.
IIowc~cr, p~ ... lrdte salts have the d ~.~.ba-' that they deGc.--~l-clse in aqueous d~.tc~ t . - -
cc,--~pc~ n~ due to the prcsence of metal impurities which catalyze the ~ ~ c - . -~
of said pc~ lr - salts and i,.~ present in the c ~ that can be oxidizedby p ~ e Thus persulfate salts in aqueous detergent c- pr - tend to be
c~ ~e It is i' ~efu~i an object of the present .~.. --- to provide -
comp O -' - - - - CC , ' ' lg p~ salts which are chemically stable. . -
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It is another object of the present i.. ~r to provide aqueous cleaning ~ , ~ Y ~ ~ ~ ~ ~
~'Oll~/l' ' 6 P~,~ "' salts which are efficient on various surfaces to clean various soils :~:
and stains.
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The present i... ~_.,t;orl meets the above objects in proposing highly acidic aqueous
- - of nonionic surfactants, which further comprise a persulfate salt. Indeed, it
has been found that the storage stability of p~ lfdte salts in the cs ~por ~;r ~ of the
present i l~ ion is i, o.~,d compared to co-~ cs;';o~ without any nonionic
surfactant
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Aqueous emulsions of nonionic surfactants have been disclosed in the art for instance in
European Patent EP-B-0 092 932. Said patent di~closes nonionic çm~ ;om cci"")( ~ g
hydrogen peroxide and an erm~l~ified organic phase Co.,.~).isi,lg a specific enol ester
bleach activaton Such emlllQ;onC allow to keep the hydrogen pe.~voAydc. separate from the
bleach activator. Persulfate salts are not d C!,lGSc~A~
EP-A-598170 also discloses nonionic emulsions comprising h~d~o,, peroxide, or a
source thereof, and an c .~ r.cd l.~.l..phot:~ liquid i g .' such as a bleach
r~ t,c ~ said enn~ have a pH of from 0.5 to 6. More particularly, said e ' - --
plcf.,._'ly col..~;se hydrogen peroxide. No a, ~" - - are vd in EP-A-598
170 for said . ' - - s, let alone toilet bowls cleaning.
As a further advantage it has ..~ .cvlcAl~ been found that acidic aqueous ~ - of
nonionic s~f- which further ccir..plise a p~ .lrale salt, find a prcfe..~.d 1, ~' - -
in the cleaning of toilet bowls. Indeed, once such an agueous co- ~po ~;on having a pH
of from 0 to 4 has been applied onto the top of the inclined surface of a toilet bowl, said
~ pC9-'-' - slowly reaches the water, is diluted and thereby becomes less acidic, e.g.
from about pH 1 to about pH 2. Such acidic aqueous c-mrDs - in the form of an
~ ' ~ - r of nonionic surfactants, which further cc - -~l" ;Ce a persulfate salt, have . '- - e d
cleaning pe ~ '' - - ~e in their dilute form, c . ed to their neat form. Thus it has been
u--- -l-ev~ found that this "pH jump" effect allows to r~" ' C_. rr' ~r- which
are stable upon storage (acidic pH) and effective in cleaning (pH jumped). ~ ' ~ ~ - lly,
these ~~ A---'- when used to treat hard surfaces, espe~cially toilet bowls, exhibit
-- ~ e soil s-~ )r and soil di~c~lc -- p,~,pc.lies when used diluted
P li~ularly on soil Id -cc'- --- the pv.ru- -" of these co ~.o.,i~;o-~ is better than
similar co~pc :~;ons ~- . ~ ~ ~ only h~b.o peroxide.
S ~; ~ ofthe ;n.e..t;on
The present L.~- '- - e ~ ~- pr - a stable aqueous con ~ : in the form of an
~~ CC;~ lg at least two nonionic surfactants, said aqueous composidon further
comprising a p~ ICd1e salt or mixtures thereof and said cc ~pC! 1 ;o'' having a pH below
0.5.
The present i...~ ;on also encompasses a process of treating surfaces wherein a s~able
aqueous co ~l-osi~;on in the form of an emulsion comprising at least two nonionic
surfactants, said aqueous composition further comprising a persulfate salt or mixtures
thereof and said c " . - - r having a pH of from 0 to 4, is used in its diluted form.
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Detailed description of the invention
The cc..l-pos;lions a~ ding to the present invention are highly acidic aqueous em~lrion.s
of nonionic s~ which further co.. ~ e a persulfate salt or mixtures thereof.
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The Cc!~ )o~;l;ollc h~C3.'d g to the present i~ ealion are stable. By "stable" it is meant
herein that a co-.pc,r~t;on cc...lp~- e a persulfate salt or mixtures thereof does not
undergo more than 20 % persulfate loss, in one month at 25~C. Pt,~Jlrdte
concenll_f ~-- can be measured by titration wi~h ~i.,l pc. n,E,~ ~ after r~Jucl;oa
with a solution ~ ~ e al~ ! - ferrous sulphate. Said stability test method is well
known in the an and is reponed, for example, on the i ' - ' information sheet ofCuroxR cc,.lu..~.rcially available from Interox. Alle. - ~ persulfate conc~ t-ation can
also be ...ca ..l-,d using a cluc ~c~aphy method d~ 5~ - il,ed in the l _ b for peracids
(F. Di Furia et al., Ga~ Ch.. ~ ~graphy Method for Determination of ~e._ ~ '
Analyst, Vol 113, May 1988, p 793-795).
The cs ~ - Pr d g to the present i..._.ltion are aqueous. Accc..~ , the
CO--~I~Or ~;- ''5 A~"D.'d- 3 to the present invention cc....y.;~ from 10% to 95% by weight
of the total co--~l c, ~;o~ of water, p.~f~,. W~ from 30% to 90%, most preferably from
60% to 85%. De-ionized water is p.-,f~,. ''~, used.
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The a ,l-osi';o~ according to the present ;.._.dion comprise as an essential element a --
p~,. "' ~ saltormixturesthereo~ P~,f~ thecom~s ~ tothepresent - -
invention cc, ~p-;ce from 0.1% to 30% by weight of the total ~ , s - of said - . ~
pasulfate salt or mixtures thereof, more ~.~.f.,. ~ from 1% to 20%, most preferably : -
from 2% to 10%. P~f~ ,d persulfate salt to be used herein is the ~..onopc.~ "' ~ salt.
One example of ~n~ r : ~'' ~ 2 salts CO--u--~ available are those ~ ' ~ by
Interox under the trade name CuroxR. Other ~,, " salts such as 'i, '~ ~ salts
comrnacially availaWe from Peroxide Chemie GMBH can be used in the co ~l,c .;~ cacco..- g to the presen~ invention.
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The c ,---; --- according to the present invention are in the form of an ~ r
comprising at least two nonionic surfactants. Said two nonionic surfactants must have
different HLB values (hydrophilic 'i, ~p~ "- balance) in order to form ~ which
are stable, and prefaably the d;Ir~,rence in value of the ~Bs of said two surfactants is of
at least 1, preferably at least 3, more p~fe.~ of at least 6.5. By _,, op. 1~ -
combining at least two of said nonionic surfactants with different HLBs, emulsions ' ~
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as~o~rdil~g to the present invention will be formed One of said nonionic sl-.r~ nl~ used
herein is a nonionic surfactant with an HLB above 11 (herein referred to as h~Jr~pr ' -
nonionic surfactant), whereas the other one is a nonionic surfactant with an HLB below
10 (herein referred to BS h~,d~oprob ~ nonionic surfactant)
P~,f~ tly the CQ po~;l;one P~,C - g to the present i..~_.ltion co..",-i~ from 1% to
50% by weight of the total cc ~po~;l;on of said h,.lro~' ' . and h~J,.phob:~ nonionic
su.'' :~ more pl~f~,. 'ly from 4% to 30%, most p.ef~i. ' ly from 6% to 20%.
Acco.. '~, said c ~ ~nr c1 s ~c - - a: ~ c ~' g to the present i..~_..lion comprise at least 0 1%
by weight of the total CQ..~pO~ ~io.~ of said h,Jl .phot ~ surfactant, p~ef~,. rl~ at least 1%
and more preferably at least 2% and at least 0 1% by weight of the total c o ---r ~ S-' ~ :~r of
said L~Jlupr ' ~ ..Jl~ t, p.~,fe. ~"~, at least 1% and more p.~fe. ' 1,~ at least 2%.
Pl~,f~ ,d to be used herein are h~Jr~r'r~b ~ nonionic surfactants having an HLB below 9
and preferably below 8 and p..,f~,.l.d h,Jlu~ nonionic surfactant to be used herein
have an HLB above 12 and preferably above 13
Suitable nonionic s.ll '' to be used herein are r~ 2 d alcohol nonionic
~.u~ ~ which can be readily made by c. ~ po ces~s which are well known
in the art. IIo. _._., a great variety of such alkoxylated alcohols, especiaUy ethoxylated
and/or p.u~,u~' ~d alcohols is also conveniently co....~ dv -' ''e Surfactant
catalogs are available which list a number of surfactants, including ~ ~ ~, together
with their .~ _ HLB values. The HLB values of such -" ~' d nonionic
s~,.'' : depend essentially on the chain length of the fatty alcohol, the nature of the
alLu~' -- and the degree of -" ~ Jl.p~-'-- nonionic " tend to
have a high degree of ~" ~' ~ and a short chain fatty alcohol, while 1.,.' .~h~b-r
surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
Accordingly, p.~.,.,d alkoxylated alcohols for use herein are nonionic surfactants
acco..' ~p to the formula RO(E)e(P)pH wherein R is a hydrocarbon chain of from 6 to
22 carbon atoms, E is ethylene oxide and P is p.op,'~ ~ oxide, and e and p which,r~-- the average degree of respectively cll.v~la~ -r and propu~' - 1, are of from
O to 60.
In a p~cfe.-~ bcl- -nt said h~JI~phsbic and h~d(,."~ "- nonionic S.J.'' ~ are
~" ~' ~ d alcohols ?r: J ~g to the present invention where the R group is a
h,.h~ l,on chain with ody from 8 to 13 carbon atoms, p.~ ly from 8 to 11. A
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particularly suitable system cGlllpl;ses n hydrophot s nonionic surfactant for instance a
DobanolR 91-2~5 (R=C9-C11, e=2~5, p=0) and a h,.l,~,ph;lic nonionic surfactant for
instance a DobanolR 91-10 (R=C9-CII, e=10, p=0)~ These DobanolR s.l.'a ' ~ are
co,.ul.e..,;ally available from Shell~
The col~pos;l;onc according to the present i;~.. may further cGl~ ;3e other
nonionic surfactants which should however not ~ Iy alter the u. ",h~e d average
HLB value of the overall CQ..\pGSi~ ;o~
Another essential feature of the CD. I~. C~ - according to the present i...~ ion is their
acidity. In order to obtain a~ F op stability of the pc.: "a~e salts in the s~ ~ros;~ione
e ~c- ~' lgtothepresenti..~ iOll,said.,c 1,- ~ needtobe~ p.~,fe~ at
a pH below 0.5, more p.~,f~ at a pH of from 0 to 0.4 and most ~ ,f,. bl~ from 0 to
0~3. The pH of said compGi,itions can be trimmed by a~ ,~ op~ organic or/and
ino.g - acids which physically stabilize the con ~cs;~innc and may build up viscosity.
Said acids can be added typicaUy from 1% to 20% by weight of the total cc r~ - -Examples of organic acids to be used alone or in combination with other organic or/and
h~o-L - acids are citric acid, succinic acid, maleic acid, tartaric acid and the Uke. An
example of i..o.~, ~ - acids to be used herein is sulfuric acid.
In one embodiment, the C~ r~S"'~ of the present i"~ are free of hydrogen
p~.UAi~e~ Said c~ . c ~ ne are particularly stable. In another embodiment, the
c - . - - - - of the present ~ . - further c . ~ - from 0.5% to 20% by weight ofthetotalcc-upo ~ ofh,.'.~ pleiOAi~de/, p.~,f~ from 2% to15~/0,mostp.~,f~"_L1
from 3% to 10%. Said comr~ 9 - -- exhibit 1 ~ " lp cleaning p. f ~ 9
n~F- " L on the end use e... ---d, the com~,oaition3 a~c d g to the present
tion may further comprise a variety of other i..gr~ "~ ~ ~ ' ' B other
of all types, organic or i -, - alkalis, p~ '' -s, dyes, optical b. ' ~ ~, builders,
chelants, p;," -t~, enzymes, dye transfer - ' ' - ~, solvents, b. T ~ e agents, ~ ' ' s
and the like.
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The present invention further e~ c . ~"r ~ a process of treating hard-surfaces wherein a
stable aqueous co...p c -; - r in the form of an: ' ~n comprising at least t vo nonionic
9 '' -t ' ~, said aqueous c r c : ~ - further comprising a pc. " - salt or mixtures
thereof and said composition having a pH of from 0 to 4, is used in its diluted form. By
"in its diluted form" it is meant herein that said comp Dsit - - - may be diluted with water
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up to a pH of 6. Said dilution may occur either before, after or while said co..-pos;lion is
applied to a hard-surface.
Stable aqueous cor..p~silions in the form of ernll' '- Col..~ ,. at least two nonionic
s~,lr , said aqueous cc--~cs' '~ - further co.l.p.i ' e a persulfate salt or mixtures
thereof and said comrcr :~ic.l~c having a pH of from O to 4, find a prefe.l~,d lrF" -.- in
the cleaning of hard-surfaces, particularly toilet bowls and bath tubs. In this field it is
p~ef.,.-~,d to use a process of treating a hard-surface wherein such a ~ is
diluted after or while it is applied to said surface. For ~ , ' o, said c o ., - - - -- may be
~; ~p~ d from a c ~ ~ - onto said hard ju.r - e, then diluted in water and le~ to act
onto said surfaces, then removed by rinsing or flushing.
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IIo.._.~.., stable aqueous co~ -o-:~;ons in the form of emulsions comprising at least two
nonionic s~ t~Q,~ said agueous co"~pG~:~;o~c further comprising a persulfate salt or
mixtures thereof and said coml~os:' ;,,.~c having a pH of from O to 4, are also particularly
suitable to be used for denture ap~"~ ' - - In this field it is suitable to use a process of
treating a hard-surface wherein such a composition is either diluted before, after or
while said c~ ~o-' ~r is applied to said surface. For example said cc ~pos;'io~ may be
first diluted in water before it is applied to said denture or may be diluted in water which
is already in contact with a denture.
As used in the rOI.~ g paragraphs, the eA~ne --- 't,. ,," includes washing as the
~s l~os~ - used in the process according to the present i.~ tiO1l co--",.;;,e surfactants
and ~ g as said C~ Q also comprise persulfate salts.
The present i..._.Lo.~ further encompasses a process for the r ~; of the
~ ~ ' ~~ de _-il.ed herein. The process acco-.' g to the present ~ tion comprises at
least three steps:
, ~ --.
In the first step, a hJJ..phc~ r mixture is prepared which c- . ~ said h~J~uph~'r
nonionic surfactant together with other h,J .Fhcb'r ' ~g ~" which are to be
rOI ' ~ i in the c - ~"c~ n~ such as metal chelants, perfumes, solvents, enymes.
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In the second step, a hydrophilic mixture is prepared which ~ ~pliQs~Q at least said water,
said h~Jr~p~"'- nonionic s~ur ~ ~ and said persulfate salts. Said h~J~op~ mixture
optionally furtha ~- . i~s other h,l~ " ~ which are to be r ~ ~.d in
the ~ .--''--- such as dyes, optical ~ , builders, '"' ~, chelants, an
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organic acid or mixtures thereof, hydrogen peroxide and buffering agents. In this second
step hydrogen peroxide if present is p.~ !y added last, a~er said buffering agent has
been added. The pH of said hyJ.op~"ic phase is adjusted to the desired value before the
third step.
Naturally, said first and said second steps can be p~.rol,..ed in any order, i.e. second ~tep
first is also suitable. - -:
In the third step of the process a:cc ~d' ~ to the present invention, said h,d-.ph~b ~ '
mixture and said h~d~p~ mixture are mixed together and stirred.
The present i..~ t;on is further illu~truted by the f 1' ~- . ;ng ~ . ' - - . -
Examples --
compGsi~ions are made which co.r,)lise the listed ingredients in the listed p~po.~;ans
(weight %).
C~ ~;t;Qns #1 #2 ..
DobanolR 91-2.5 4.8% 4.2%
DobanolR 91-10 (R=C9-CI 1, e=10, p=0) 1.2% 1.8%
CuroxR * 2.0% 6.0%
Citric acid 6.0% --- -~
Perfume 0.5% 0.5% , -~
Water and mirors - up to 100%-- ' ~
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Sulfuric acid up to pH 1 0.2 -~- ' ,- '.'
* CuroxR is one of the co.~ .. ' -' names of ll.onope.: ~ - salts ~ . ~
Compo~ #2 is ~p~ of the cc~ po~ of the present invention.~'
C; , - ~' ' # 2 is an aqueous emulsion of at least two nonionic surfactants comprising
a mono p~,, . ' ~ ~ salt and being ~ e ~ at a pH below 0.5.
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It has surpr~singly been found that the compositions according to the present invention
exhibit good stability. Indeed, cor..~Gs;lion #2 had virtually no persulfate loss after 3
weeks at 20~C
Co..~l os;~;on #l is r~ r~ e of the co...~osidons suitable to be used in the process
of treating hard s~ s, especially toilet bowls, ~ d e to the present i..;_.,t;on.
Co...pos;lion #l is an emulsion of nonionic surfactants and further CO..1~-i~3 al.lonop~ .Jlfate salt.
l~.fc ~--~ data
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C~ .o~ c are made which c~ ,rise the listed in~ "- in the listed },rol,o.~ions
(weight ~/0).
Co~ ;t;Gl~c: #1 #2 - - -
DobanolR 91-2;5 4.8% 4.8%
DobanolR 91-lO~R=C9-Cll,e=lO,p=0) 1.2% 1.2% -
CuroxR ~ 6.00% ---
Hydl~g pe.~,~ide 6.00% 6.00%
citric acid 6.00% 6.00%
Water and minors up to 100% 100%
pH=l
~CuroxRisoneoftheco..".._.. 1'namesof~ c~ ~..lrdtesalts
Composition #l which is .~ ._ of the c~ suitable to be used in the
process of treating hard-surfaces of the present i..._.ldon was evaluated for its cleaning
performance on artificial toilet soils, i.e. soil solubilization efficiency and soil
d ~c~lc ~ion elI'~,;.,n~,~. In this study C9--~1~G~ ';0-' #2 which is an; ' ~ P
h,J~.ger ~cr(,~idc, is taken as .~,~.ence. The evaluation (psu) used was a visual
evaluation on a four points scale wherein "O" is attributed to the tested composidon
when no difference versus the ..,f~ nce is observed and wherein "4" is attributed when
the tested r ~ , _ "' is much better than the f~ rcnce.
Artificial toilet soil ~ r (psu):
Neat form of #l
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Diluted forrn of # I : 2
:
Artificial toilet soil ~ c!caration (psu):
Neat forrn of#l : 3
Dilutedformof#1 : 3 :
The use of cc ~pCIQ;tiol #l for treating hard surface soiled by toilet soils allow
c -- ~ e cleaning pc~roll...u~ce by e, '- e the pH jump that takes place upon
product u~ 3~ l '- Indeed, the cleaning p .rul -e of the c-, ~ #l is .
' ~ e d when increasing the pH from I (neat product) to 2 (diluted product). :.. .
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Indeed above results sul~ show that the use of highly acidic aqueous
c~ pQr ~;ol~c being in the form of an e ' ~-r of nC - ~~: and further comprising i~
-onûp~ te provides significant benefits in toilet soils cleaning compared to the use
of h.~ ge i p~,.u.ude ~ ' - , both when used neat or diluted. ~ ;~
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