CA2252634A1 - Concentrated alkaline isotropic detergent liquid with bleach - Google Patents
Concentrated alkaline isotropic detergent liquid with bleach Download PDFInfo
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- CA2252634A1 CA2252634A1 CA002252634A CA2252634A CA2252634A1 CA 2252634 A1 CA2252634 A1 CA 2252634A1 CA 002252634 A CA002252634 A CA 002252634A CA 2252634 A CA2252634 A CA 2252634A CA 2252634 A1 CA2252634 A1 CA 2252634A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/40—Dyes ; Pigments
- C11D3/42—Brightening agents ; Blueing agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
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- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
A concentrated alkaline isotropic fabric washing liquid detergent composition comprising at least 23 % of surfactants and further comprising at least 0.2 %
hydrogen peroxide bleach, the composition is substantially free from hydrotropes which cause the pH to reduce and impair the effectiveness of the composition. Also a concentrated alkaline isotropic fabric washing liquid detergent composition comprising at least 15 % by weight of surfactant further comprises at least 0.2 % by weight hydrogen peroxide bleach and an optical brightener and is also substantially free from hydrotropes. The compositions may be used as a main wash bleaching liquid or a pretreatment liquid and may be activated with a bleach activator.
hydrogen peroxide bleach, the composition is substantially free from hydrotropes which cause the pH to reduce and impair the effectiveness of the composition. Also a concentrated alkaline isotropic fabric washing liquid detergent composition comprising at least 15 % by weight of surfactant further comprises at least 0.2 % by weight hydrogen peroxide bleach and an optical brightener and is also substantially free from hydrotropes. The compositions may be used as a main wash bleaching liquid or a pretreatment liquid and may be activated with a bleach activator.
Description
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
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
... , .. . , . .. ..... , . _ . .. .
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~
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 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.
.
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 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 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
CA 022s2634 1998-10-20 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 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) W O 97/45~18 PCT/GB97/01449 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.
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 , . . ..
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
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
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
... , .. . , . .. ..... , . _ . .. .
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~
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 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.
.
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 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 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
CA 022s2634 1998-10-20 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 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) W O 97/45~18 PCT/GB97/01449 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.
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 , . . ..
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
Claims (13)
1. A concentrated alkaline isotropic fabric washing liquid detergent composition comprising at least 15% by weight of surfactant and further comprises at least 0.2% by weight hydrogen peroxide bleach and an optical brightener, characterised in that the composition is substantially free from hydrotropes as hereinbefore defined.
2. A composition according to claim 1 in which the composition comprises at least 20% by weight of surfactant.
3. A concentrated alkaline isotropic fabric washing liquid detergent composition comprising at least 23% of surfactants and further comprising at least 0.2% hydrogen peroxide bleach, characterised in that the composition is substantially free from hydrotropes as hereinbeforedefined.
4. A composition according to any preceding claim in which the surfactant comprises anionic and nonionic surfactant.
5. A composition according to any preceding claim which further comprises an anti-redeposition agent.
6. A composition according to any preceding claim which further comprises an anti-dye transfer agent.
7. A composition according to any one of claims 4 to 6 in which the nonionic surfactant comprises more than 5% by weight of the total composition.
8. A composition according to claim 7 which comprises at most 5% of a surfactant which does not satisfy the pH targets when tested according to Test A as described herein.
9. A composition according to claim 8 comprising at most 5% of a surfactant which does not satisfy the residual peroxide targets when tested according to Test A as described herein.
10. A composition according to claim 6 wherein at least 95% of the surfactant comprises surfactants which are being used at a level below their threshold concentration as determined by Test B described herein.
11. A composition according to claim 3 in which all of the surfactants used satisfy the pH
targets and preferably also the peroxide stability targets of Test A and are used at a level below their threshold concentration as determined by Test B.
targets and preferably also the peroxide stability targets of Test A and are used at a level below their threshold concentration as determined by Test B.
12. A method of washing laundry with a wash liquor comprising adding to the wash liquor a composition according to any preceding claim together with a bleach activator, preferably TAED.
13. A method of pre-treating a laundry item comprising administering the composition according to any one of claims 1 to 11 to a selected area of the item, leaving it in contact with the item for a short treatment period and then washing the item.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9611063.0 | 1996-05-28 | ||
| GBGB9611063.0A GB9611063D0 (en) | 1996-05-28 | 1996-05-28 | Concentrated alkaline isotropic detergent liquid with bleach |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2252634A1 true CA2252634A1 (en) | 1997-12-04 |
Family
ID=10794377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002252634A Abandoned CA2252634A1 (en) | 1996-05-28 | 1997-05-28 | Concentrated alkaline isotropic detergent liquid with bleach |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0912691A1 (en) |
| JP (1) | JP2001501646A (en) |
| KR (1) | KR20000016075A (en) |
| CN (1) | CN1219962A (en) |
| AU (1) | AU2968897A (en) |
| BG (1) | BG102957A (en) |
| BR (1) | BR9709384A (en) |
| CA (1) | CA2252634A1 (en) |
| CZ (1) | CZ385398A3 (en) |
| GB (1) | GB9611063D0 (en) |
| ID (1) | ID17256A (en) |
| IL (1) | IL126559A0 (en) |
| NO (1) | NO985541L (en) |
| PL (1) | PL330118A1 (en) |
| SK (1) | SK160298A3 (en) |
| TR (1) | TR199802461T2 (en) |
| TW (1) | TW381119B (en) |
| WO (1) | WO1997045518A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU733998B2 (en) * | 1997-04-30 | 2001-05-31 | Unilever Plc | A detergent composition |
| US6743763B1 (en) * | 2000-09-05 | 2004-06-01 | Basf Corporation | Stable aqueous laundry detergents containing vinyl pyrrolidone copolymers |
| JP4855140B2 (en) * | 2006-05-18 | 2012-01-18 | 花王株式会社 | Liquid bleach detergent composition |
| JP5197949B2 (en) * | 2006-12-21 | 2013-05-15 | ライオン株式会社 | Bleaching goods |
| JP5342757B2 (en) * | 2007-07-26 | 2013-11-13 | ライオン株式会社 | Liquid bleach composition |
| GB0902917D0 (en) * | 2009-02-20 | 2009-04-08 | Reckitt Benckiser Nv | Composition |
| JP5795956B2 (en) * | 2011-12-21 | 2015-10-14 | 花王株式会社 | Liquid detergent composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4891147A (en) * | 1988-11-25 | 1990-01-02 | The Clorox Company | Stable liquid detergent containing insoluble oxidant |
| CA2073432A1 (en) * | 1990-02-08 | 1991-08-09 | Johannes C. Van De Pas | Liquid bleach composition |
| US5264142A (en) * | 1991-11-25 | 1993-11-23 | Lever Brothers Company, Division Of Conopco, Inc. | Stabilization of peroxygen bleach in enzyme-containing heavy duty liquids |
| MX9207050A (en) * | 1991-12-19 | 1993-06-01 | Ciba Geigy Ag | STABLE BLEACH DISPERSION DURING STORAGE |
| US5244593A (en) * | 1992-01-10 | 1993-09-14 | The Procter & Gamble Company | Colorless detergent compositions with enhanced stability |
| GB9506065D0 (en) * | 1995-03-24 | 1995-05-10 | Warwick Int Group | Alkaline isotropic liquid detergent with peroxide |
-
1996
- 1996-05-28 GB GBGB9611063.0A patent/GB9611063D0/en active Pending
-
1997
- 1997-05-28 CA CA002252634A patent/CA2252634A1/en not_active Abandoned
- 1997-05-28 JP JP09541855A patent/JP2001501646A/en active Pending
- 1997-05-28 IL IL12655997A patent/IL126559A0/en unknown
- 1997-05-28 EP EP97924117A patent/EP0912691A1/en not_active Withdrawn
- 1997-05-28 SK SK1602-98A patent/SK160298A3/en unknown
- 1997-05-28 CZ CZ983853A patent/CZ385398A3/en unknown
- 1997-05-28 ID IDP971773A patent/ID17256A/en unknown
- 1997-05-28 KR KR1019980709642A patent/KR20000016075A/en not_active Application Discontinuation
- 1997-05-28 WO PCT/GB1997/001449 patent/WO1997045518A1/en not_active Application Discontinuation
- 1997-05-28 PL PL97330118A patent/PL330118A1/en unknown
- 1997-05-28 AU AU29688/97A patent/AU2968897A/en not_active Abandoned
- 1997-05-28 TR TR1998/02461T patent/TR199802461T2/en unknown
- 1997-05-28 BR BR9709384A patent/BR9709384A/en not_active Application Discontinuation
- 1997-05-28 CN CN97195017A patent/CN1219962A/en active Pending
- 1997-06-04 TW TW086107677A patent/TW381119B/en active
-
1998
- 1998-11-26 BG BG102957A patent/BG102957A/en unknown
- 1998-11-27 NO NO985541A patent/NO985541L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO985541L (en) | 1998-11-30 |
| CN1219962A (en) | 1999-06-16 |
| PL330118A1 (en) | 1999-04-26 |
| CZ385398A3 (en) | 1999-06-16 |
| SK160298A3 (en) | 1999-04-13 |
| AU2968897A (en) | 1998-01-05 |
| KR20000016075A (en) | 2000-03-25 |
| TR199802461T2 (en) | 1999-02-22 |
| JP2001501646A (en) | 2001-02-06 |
| BG102957A (en) | 1999-09-30 |
| ID17256A (en) | 1997-12-11 |
| EP0912691A1 (en) | 1999-05-06 |
| BR9709384A (en) | 1999-08-10 |
| IL126559A0 (en) | 1999-08-17 |
| WO1997045518A1 (en) | 1997-12-04 |
| NO985541D0 (en) | 1998-11-27 |
| GB9611063D0 (en) | 1996-07-31 |
| TW381119B (en) | 2000-02-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |