Note: Descriptions are shown in the official language in which they were submitted.
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PC9602
CONCENTRATED ALK~INE ISOTROPIC
DETERGENT LIQUID WITH BLEACH
5 This invention relates to conce~ Led aLkaline isotropic fabric washing Liquid detergents with
hydrogen peroxide bleach
Conc~ ed alkaline isotropic fabric washing liquid d~l~d~ usually contain a hy~o~upe to allow
10 a high surfactant level to be used without the viscosity becoming too great Typical hydrotropes are
sodium xylene sulphonate, ethanol, and propylene glycol. International application WO 96/30483
contains such compositions comprising a rr~ixture of nonionic surfactant and anionic surfactant
together ~Mth a hydrotrope and hydrogen peroxide characterised in that the composition comprises
greater than 40% total surfactant when nonionic rich or greater than 20% total surfactant when
15 anionic rich. A concentrated peroxide liquid is desirable because of the reduced transport and
storage costs A solution to the problem of how to formulate stable concentrated alkaline isotropic
fabric washing liquid detergents with peroxide has eluded those skilled in the art for many years
20 Although there are many pllblir~tions of concentrated alkaLine isotropic fabric washing Liquid
d~d form~ ions collL~ii,1g a hyd~ollupe, there are very few indeed that disclose hydrotrope-
free f~rnallations. The closest prior art is probably the 15% anionic (secondary alkane sulphonate)
and 3.75% nonionic (prirnary alcohol ethoxylate (7EO)) composition disclosed in WO96/01311.
- This form~ tion had a total surfactant level below 20%. Furthermore, this composition did not
25 contain additional ingredients such as optical brightener, anti-redeposition or anti-dye transfer agent
which renders the composition uns ~itable for use as a practical concentrated alkaline isotropic fabric
washing liquid detergent with hydrogen peroxide bleach.
30 Thickened peroxide compositions are also known. These contain a thickening system to boost
viscosity when only low levels of surfactant are present. GB 2255507 is typical and discloses a
AMENDED SHEEI
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PC9602
thickened peroxide-containing composition with less than 10% surfactant. These composirions are
not suitable for use as laundry detergents. They are thickened in order to give the desired result of
a squeezable composition that does not run when put on to a vertical su~face. Such compositions
do not contain a hydrotrope and always contain less than 10% total surfactant. A skiUed person
- 5 would not use these thickened hydrotrope-free compositions as a starting point for the formulation
of a new concentrated fabric washing detergent.
We have now found that the presence of a hydrotrope has a large and very undesirable negative
10 effect on the storage stability of concentrated aU~line isotropic fabric washing liquid d~e~ s,
particularly we have found that this is a problem for compositions cull~ing high levels of
surfactant. This is a problem for the formulation of concellLI~ed liquid detergents because
conventionally such detergents contain hydrotropes. In this specification concel~ ed means that
the liquid in its undiluted state contains more than 15% and ~ r~l~bly at least 20% and most
15 ,I"~r~ y at least 23% total surfactant. Unless stated otherwise aU percentages are on a w/w basis.
According to the present invention there is provided a conc~ Led aU~aline isotropic fabric washing
liquid detergent composition comprising a total surfactant level which includes at least 15%
20 surfactants and further complises at least 0.2% hydrogen peroxide bleach and an optical brightener,
cha~cterised in that the composition is substantiaUy free from hydrotropes. It is preferred that the
colll~ ition has no added hydrotrope whatsoever. A smaU presence of up to 2.5% preferably less
than 1.5%, and most preferably less than 0.5% of a material which may function as a hydrotrope
may be present perhaps as a result of one of the ingredients of the composition colllail~i lg this
25 material as a minor constituent or impurity. Such ingredients are advantageously avoided as they
probably compromise the shelf life of the composition, however, for an otherwise very stable
composition the loss in pe-rullllance due to a very smaU amount of material which may function as
a hy ;11 oLI upe may still leave an acceptable shelf life. SubstantiaUy free from h~ 1~ U~l opes is in this
specification defined to mean that materials which may function as hydrotropes are present at a
concentration of less than 2.5%"~ r~l~bly less than 1.5%, and most preferably less than 0.5%.
AMENDED SHEET
... , .. . , . .. ..... , . _ . .. .
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W 097/45518 PCT/GB97/01449
-3-
The tûtal ~fi~-~ level is pl~ably at least 20%, more ~l~f~d)ly at least 23 %. ~ y the
q~Q A;~ C~lq~ ; aoionicandno~ ~ic~ ~ A~;
S Al~y a~l 1~ at is compadble u~th peroxide may be used An opical b~tener that has
good c~ y ~l~y with p~c bleach is Tmopal CBS-X a disl~yl biphenyl de~a~ve ex Ciba
Geigy. St~bene based ~uu.~ may also be used as the ophcal 1" ~A~ ." .
10 Accol~;.,g to a second aspect of the mvention there is provided a conce~ted alkaline isotropic
f~cic wa~g liquid d~ A cr~ q~ a tvtal ~... r ~ A level which mchldes at least
23% of.q--r-~ i selectedf~mthe g~up c~ g anionic and noniv~ic surfactallts, and further
cv~q~;~c at least 0.2% hydrogen p~v~ide bleach, ~ ;~ in that the co~o~iu~ isY ~ 1y free from h~hvLIope~ The C~ q~O~ :';f n may also C~q~;Y~ an vptical ~ r as
15 definedabvve.
When present, the nvnionic ~ r-- ~ r C~ q~ s more than 5% by weight of ~e tvtal
Cc~q)O-i;~ andad~ A ~.r""~ly the C~ q~Q--~ inch~cnomorethan5%ofsurfiactantswhich20 do not satisFy the pH cn~eria when tested accordmg to Test A ac ~ il.ed h~aa~. Most
adva~ r~ y it ~--y--;-,3 no more than 5% of su~actants which do not satis~y the resi~al
p -~ le cr~ia when tested accv.~g to Test A as ~",-.il.~A her~ er.
25 The y~Tr--~- ~I sy~mis ~ a m~ure of anivnic and nv~ionic ~iàc~ms, although en~ly
nnn~ r. or anionic ~-.r--~ ys~ems may be used Ch~.q~O~ may co~ain an ~ lu~te
builder or be Im~
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Among the ~ ;d anionic ~ are:
a) Second~y alkane ~ f"t~, such as Hostapur SAS 93 a 93% actnre flake ex. Hoechst or
Ma~on PS65 a so&m n-alkane (Cl3 ~ h~e with low sodmm su}phate content ex. E~ls;
b) Linear alkyl (Cl0.l3) benz~e sulphonic acids such as M~on AS3 ex Huls;
c) Alkyl ether sulphates such as Neopon LOS70, a 70% ac~nfe sodil~m salt ex Wltco; and
10 d) Olefn ~Iphonates such as l~.~ OS supplied as 40~~O actn~es ex ~l~e~'h~
Among the ~ l nanioDic .~ are:
e) Pnmary alcohol (Cl3 l~) ethoxylates, ethoxylated with ~om 5 to 9 moles of ethylene oxide,
~ bly 7 moles, ~ch as S~o~ A7 ex ICI / Cargo Fleet
The pH ofthe C~ q~O A;"~ may }ie in the range 7 to 12, and is ~f~d~ly around 9.5.
The pc~u~ide is pr~ably present as disso~ed hydrogen p~u dide in an amount by weight in the
ra~ge 0.2 to 15% preferably l to 8% and most preferably around 5%.
Ihe cc ~~ may also ~ ; rn~nor C-~ t~ comelltiona~y found in a heavy duty liquid
d~t~, ~,~ C~ q~~ A;~ These in~de p~, s~tab~ t~t,d er~ymes, ~ -r--~ A
25 preser~es, t~ickeners, colorants, builders an~ )Q~ entS anli dye tra~fer agents -
polyvinylpyrro}idone (PVP) which acts both as an an~l~A~ 1,o A;,~ ag~t and an a~dye transfer
poh,fmer is ~l~f~,d - and other co~ -' ad~ves
30 The CUII~IO:~LIU~1 ~lefe~ y C~ S~ . A~ F~ed Sh~ A~ are so~m diethylene
tn~ne p A ~-~h~/lene ~ h.... A~ sold as Dequest 2066 by ~ fOn~07 either alone or used with
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2,2' dipyridyla~e (DPA) or 1,2' dia~ocyclohexyl tetrakis methylene phocrh~ acid Other
a~ents for 1, . ~ A ;~ metal ione may he used instead of, or m addition to, these yl~cllcd
In a pl~f~l~ embodiment the ~""1'~ A;-)- e acco~ to the inven~ion are activated by use of a
blead~ a~vator ~ as TAED ~ may h~e br~t into contact wih the c~ o A;. n at the time
of use by means of a two c~ A ~ system.
Acca~g to a third a~ect ofthe i~vention the CQ"~ ~ alka~e isotropic fahric wa~g li~d
~o~nn may be used to pr~treat sta~ed or other specific fabric l~ iPe before the
fabric ie waehe~ ln th~e process t_e stain removal is superior to that w_ich can be obt~inP~l from
the kno~ acid ~v.~ile c~ .e and the overall performance is f.~t~ '4l by the high level of
15 e~ t~t which is possible in CQ~q~O- A;~ according to the present inventiv~L The use of a
concenhated forn~lation aLeo conf~rs the adva~age of lower tran~ort and p~ ~.L~, g cost, wb,ich
is en~ ~lly desrable. The pre-l.~ method con~e of admi~eter~ng the co..~po A;n-
~accor>o any one of claims 1 to 11 to a selected area ofthe item, leaving it in contact wi~hthe
or a shoIt 1l~ period and then washing the item. The 1l~ period u~l typically be20 1 to 5 minutes, ~ ly about 2 minutes.
Cn~ of ~n r~ w~hr~
25 The fo~owillg pluc~h~, refeIIed to as Test A is used for id~j~ smtable $ - ~ At~ on the
ba~s of pH and p~u~ stab~y data. A trial formul~vn Le prepared us~g 20% wh~ (except
Ma~at CM20 w}~ch wae tested at l5% w/w) ofthe ~ctant to be su~ A~er ~ ;o~.
w~h Dequest 2066, hydrogell p~u~ide y-~: 1 to gr~re a S% wh~ rA-~ on of pel~df
added alldthe pHLe ad.~usted to 9.5 by the add~tivn of prc s~ ,d caus~ic soh~v~ DetaiLe of
30 the surfac~e te~eted are gn/en ill Table 1.
.
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Table 1- Surfactants tested
Code Surfactant Source Type Ac~ves
wt%
Anionic
Al M~on AS3 Huls linear anyl (C,~u) benzene sulphonic acid 97
A2 MaIlon Huls Iinear a~yl (Cl~3) benzene sulphonate, 50
AS350 ~dbml salt
A3 Ma~on Huls secondary an~ane (C,3 ,7) sulphonate, so&lm 65
PS65 sa~t
A4 TT.~ Hoech~ secondary alkane (Cu,d sulphonate 93
SAS93
A5 Empicol Alb~ a~yl sulphate 95
0045 sod~ lauryl sulph~te
A6 Neopon ~co allcyl ether sulphate 70
LOS 70 lauryl e~er ~Iphate? sod~ salt
A7 M~inat Huls a~yl ether carboylic acid 90
CM20 Cl2/CI4filtlyalooholpo~1ycoledler(2EO)
caT~oxylic acid
A8 Crodasil~ic Croda sarcosinate - RCONC~(C~)COOH? 30
LS30 R=alkyl so& lauroyl saroosille
A9 Adinol CT95 Croda taurate - RCON(CH3)(~ 03Na? 95
R=alkyl sod~m methyl cocoyl ta~ate
A10 TTt ~ ~.. t OS Hoe hst Olefill sulphonate 40
Nonionic
N1 Sy~,~ ICI primary alcohol ethoylate 90
A7 CIJCI5 p~y aloohol ethoxylate (7EO)
N2 Ge~ ox Hoe~hst amiIIe o~ide 30
LA }~yl ~methylami~le oxide
Amphoteric
P1 Dehyton H~nkel betaine - RN(C~)2CE~COO, R= alkyl 30
AB30 coco-betaile
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From ~ e we have dern~ed the following pH and Peroxide Stab~y Ta~ Residual
pero~ade is deter~mned by pPlmQ-~Qte titration. A suIfactant should pass both the pH and the
peroxide ta~ It is possible to use small (<5% pr~ of ~ ; which does notpass a~thet~ but this is on~ hrQ~ en the m~gori~ ofthe ~ t~ exceed the ta~ets
5 by a good ma~L As w~l be s~n from the test results in Table 2 it is possible to have A ;.~r 1U~
room r~ A~ / even if the elevated 1~ stability is poor. Suc~ -1 A-~ would
not be suitable for use in c~o~iuns destined to be stored at tempe~es in excess of 30~C,
wt ich is o~en the case in walmer climate~
pH targets:
PH~512 2 9.0 a~er 12 weeks at 25~C
pH~ 12 2 7.5 a~er 12 weeks at 3 .7~C
p~54 2 8.0 a~er 4 weeks at 45~C
Resi~al P~uAide targets:
per25l2 2 85% after 12 weeks at 25~C
Per3',2 2 50% after 12 weeks at 37~C
Per~5~, 2 55% after 4 weeks at 45~C
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Table 2 - Results of Test A
Surfac~nt P~2 PE~7,2 PEI454 Per25~2 Per37,2 PerJSJ
Target 29.0 27.S 28.0 285.0 250.0 255.0
A1 9.7 9.4 9.5 85.0 53.8 56.4
A2 9.3 6.9 6.7 69.2 34.8 43.2
A3 9.9 10.0 9.9 99.2 58.0 55.6
A4 9.9* 10.1* 9.6 84.8* 51.8* 64.0
A5 9.7** 9.2** 8.4 70.4** 25.6** 22.2
A6 9.4 7.5 8.2 85.4 56.8 62.2
A7 9.4** 7.7** 7.3 97.6** 82.4** 83.8
A8 7.7 7.2 7.0 75.2 37.4 52.5
A9 6.9 5.7 6.1 84.7 70.2 71.1
AlO 9.6*** 9.5*** 9.5 96.5*** 88.2*** 76.5
N1 9.1 8.2 8.8 90.0 79.6 82.2
N2 8.2 7.5 7.5 90.0 59.0 64.6
P1 9.3** 8.1** 7.5 84.2** 0** 0.2
* 16 we~k data
** 8 wee~ data
*** 4 week data
Ihe ~su~ichpassboth~e pH and p~u,.id~ stab~,r tests are listed belûw (this e~es
~e ,~r ~S ~;fûr~ good ~u,ude stabil~r is due predominan~ly to a d~l~e in composition
pH~ A3 a~A4 are inf :rior intenns of pH stability because the pHhas d~ed u~ ls forthem.
25 In prachce an upward d~ may not be a problem because the benef~s of an a~alme cr~ o A;,~-.
are retained.
ln dP~P-~L~ order of pH stab~ A1 > A41A3 > Nl/A6
In r3P~n~ order of p~u,~ide stabil~: N1 > A6 > A3 > A4 > A1
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C~. ~L ;.~bothpHandpero~e~abil~,the~ . r~ 1careIh~r~ t_oselistedabove.
Fq~ql1y pl~ for t_eir combination of pH stability and pero~de stab~ are the s~ yalkane sulrhnndPs A3 and A4.
In add~on to pH and pG.o~ide stab~ity, phase behaviour must also be sl~itable. We ~l~ed the
q-.r~ hpassed the pH and per.,~ stability cntena and obta~ed the follo~ resu~s in
a ~ h is referred to in th~c ~ ;A;o-- as Test B. Test B ~s of ...~ the
vi~os¢y of a selies of ~ A SOh~ S vnth c~ .c ~ ~g by ~ ~ of 5%. The
10 cnnc-.l~.A;.... above which the viscosity exceeds a vah~e of 1200 cps is refeIIed to in this
A;~ as the ~, ' ~ A;n~ The test uses 1200 cps as being an a~plu~te upper
limit in ~ms of C~ n-~ acc~. The level at which a p&Li~ ~- r.-~ is used in a liquid
d~,.cl~,~t should be below the t reshold c~ ,A;nl~, pl~ bly by at least 5%, and more
h~f by at least 9~/O. T_is is to allow for; ~ . e dosing in the COl.J~ C~;a1 ... r- ~ ; Of
15 a }iquid ~ ~,. .1 and/or evaporanon on storage. The results ofthe detemm~hon ofthe 1~ 1 ~~
conr~ntrations for the ~lcr~lcd ~Qnfi~t~tc iS given in Table 3. The ~....ni~ in brackets are the
viscos~y in c~ ~ at 25~C, 21s-' of the aqueous soh~ion of ~...r- ~ --,. at the .~ifi~
C~ ., A,, jA ;~1"
Table 3 - Results of Test B
Surfactant Co.. ~ a~on (wt.%) bdow w~ich viscosity
is ~1200 cp at 2S~C, 21 s-
Anionic
Al 25 (1165)
A3 35 (g25)
A4 40 (7SS)
A6 25 (15)
Nonionic
Nl 25 (675)
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-10-
The nn~on w~l now be fuIther ~ .. il .ul wh~ ltrcil~ce to the fo~owing non-limit ng ~ples:
Table 4 gives deta~s ofthe example r.. l ~;.. e All cu~y~o ~;o~ data is on a 100% w~w basis
Table 4
mple: 1 2 3 4 5
h~
Nl 14.0 17.5 7.5 7.5 15.4
Al 6.0 - - - 5.6
A3 - 7.5 17.5 - 7.0
A4 - - 17.5
NaO~ 0.77 - - - 0.71
Dequest 2066 0.5
DPA 0.06
PVP 0.5
Tmopal CBS-X 0.2
r~uAide 5.0
Water to 100
Tnil;~l pH 9.50 9.489.S0 9.S1 9.45
V-lscosity (21 s ', 25~C) 840 280 1 15 70 370
*fi~er NaOH is added to make ~e final pH adjustment
ru. . ""~ e mch~ded PVP (poly~pyno~done) as a~l a~~ and a~e t~er agent
25 and IINOPAL CB~X, an ~cal b. ;~ -- ex Ciba Geigy. Storage Data for the r~ ; nLs at
a rallge of ;~u~h ~ storage conditiûns is gnren in Tables 5 to 9. Bodl pH and ~al ~u~
data is give~ O~en, because p~u~e is more stable under more acid cond~ions, a ~su~ld~le
peroxide stabili~r is obtained ~there is a deaease in C4~q~0 ~ p~ A pH drop is !1--~ , ble
because it reduces the d~ y and it makee it harder to ac~vate the p~u~ e v~th a bleac~
30 ac~vator such as TAED.
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Tab1e 5 - EXa~le 1
Time (WeekS) PH Re5idUal Pe~O~nde (%)
5OC 25~C 37OC 45OC 5OC 25~C 37OC 45OC
0 9.50 9.SO 9.50 9.50 100 100 100 100
1 9.39 9.25 9.22 9.16 - - -
2 9.63 9.37 9.37 9.24 10~ 99.59 96.69 96.48
4 9.34 9.22 9.19 8.98
8 9 37 9.07 8.92 7.21 100 97.52 88.61 82.61
12 9.43 9.13 8.73 7.0 100 94.21 84.89 77.64
16 9.30 9.13 7.77 6.50 100 94.20 84.88 81.98
24 9.47 9.03 7.47 6.05 100 92.55 78.70 75.80
Table 6 - EY~n~PIe 2
Time(WeekS) pH Re~ O~de(%)
5~C 25~C 37~C 45~C 5~C 25~C 37~C 45~C
0 9.48 9.48 9.48 9.48 100 100 100 100
9.36 9.44 9.32 9.42 100 100 99.60 98.60
2 9.54 9.16 9.14 9.14 100 100 97.60 95.19
4 9.44 9.08 9.03 7.35 100 100 95.79 89.38
8 9.35 8.87 8.14 6.86 91 100 92.86 88.17
12 9.52 9.03 7.52 6 50 100 100 90.60 92.60
, . . ..
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-12-
Table7-F.Y~ple3
Time~weeks)pH Resi~ualPero~nde(%)
5~C25~C37~C45~C5~C25~C37~C45~C
o 9.50 9.50 9.50 9.50 100 100 100 100
9.40 9.65 9.32 9.30 98.80 99.60 98.60 100
2 9.61 9.47 9.51 9.38 100 98.00 96.60 91.38
4 9.46 9.37 9.38 8.88 100 99.00 87.20 79.36
8 9.31 9.15 9.0S6.99 100 95 82.17 70.94
12 9.55 9.35 9.15 6.85 100 96.2 80.6 71.70
Table8-~xan~le4
rlme(wee~s)pH Resid~lr~u~e(%)
5~C25~C37~C45~C5~C25~C37~C45~C
0 9.51 9.51 9.51 9.51 100 100 100 100
9.57 9.55 9.56 9.62 100 100 98.97 92.61
2 9.86 9.67 9.74 9.78 100 100 96.72 85.42
4 9.61 9.55 9.47 9.35 100 98.56 78.03 73.10
8 9.68 9.57 9.44 7.80 98.15 96.72 75.16 59.10
12 9.88 9.59 9.37 7.00 100 98.15 73.70 55.10
Table9- F.Y~~Q~
rlme(weeks)pH Resi~ u~(%)
5~C25~C37~C45~CS~C25~C37~C45~C
0 9.45 9.45 9.45 9.45 100 100 100 100
9.53 9.49 9.42 9.39 100 100 95.42 92.03
2 9.58 9.50 9.40 9.31 99.4 98.41 95.62 91.44
4 9.62 9.46 9.32 8.16 100 99.0 90.24 81.08
8 9.80 9.63 9.05 6.99 100 100 86.70 78.50
