CA2191571A1 - Bleaching compositions - Google Patents
Bleaching compositionsInfo
- Publication number
- CA2191571A1 CA2191571A1 CA002191571A CA2191571A CA2191571A1 CA 2191571 A1 CA2191571 A1 CA 2191571A1 CA 002191571 A CA002191571 A CA 002191571A CA 2191571 A CA2191571 A CA 2191571A CA 2191571 A1 CA2191571 A1 CA 2191571A1
- Authority
- CA
- Canada
- Prior art keywords
- composition according
- hydrophilic
- hydrogen peroxide
- peroxide
- hydrophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/825—Mixtures of compounds all of which are non-ionic
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3945—Organic 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3947—Liquid compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/146—Sulfuric acid esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Abstract
Compositions are described which are fomulated as emulsions of a hydrophilic nonionic surfactant and a hydrophobic nonionic surfactant, and which further comprise an effective amount of benzoyl peroxide. Preferred compositions further comprise hydrogen peroxide. The compositions herein are particularly useful for the bleaching of fabrics.
Description
~WO 95135255 P~~
r -- ~ c~ ~;,,r Technical Field The present invention relates to bleaching co",r ,~. The CulllpoaiLiulla 1S of the present invention are particularly useful for laundry bleaching.
Backaround Cu,,,~.ositiù,)s for the bleaching of laundry have been e,~tar,~;,/aly describedin the art. Bleaching cu..,~-osit;ons can be classified into peroxide bleaching Cullll~u~itiulla and hy~o~,lllul bleaching ~ u~ a. Peroxide bleaching cu",r- ,:. have the advantage over l.~poullluli bleaching Co~ usitiùl)s 2s that they are generally con ,ida,ed as being somewhat safer to fabrics, -r~' ~ ~Iy to colored fabrics. Peroxide c~ ns however have the inconveniency that they are often ul, 'Iy unstable, which makes it difficult to formulate peroxide bleaching Culll,~u~itiw~S which are sufficiently stable tobe COIlllllel~ ' ' A possible solution to this problem consists in 30 formulating cu" I,uOaitiOl)S with a high level of peroxide, to extend the "effective" period of the cu,,,, ~. A possible drawback of this solution is that cc"",osiliu"s may reach the user which still comprise a high amount of peroxide, whereby possible skin itching may occur if the user's skin comes in contact with the peroxide ~~ osilion. This itching phe,,u,,,el)ol) is quite 3s moderate and fully reversible, but is does constitute potential di;,~,o~rult for tha user.
WO95135255 r~"-J~ s 21 ~1571 Also, peroxide species are poorly effective in bleaching at lower temperatures, so that it is required to formulate activated peroxide bleaching cu~ uosiliulls for use auoss a wider range of temperatures. Activated bleaching cu~ ositiùns comprise a bleach activator, typically a peracid s precursor, which will react in an aqueous medium with hydrogen peroxide to form the coll~a~ùlldi~lg peracid. This peracid is more effective at lower temperatures.
It is thus an object of the present invention to formulate a peroxide bleaching 10 ~ ' ol, which is stable, without having to resort to usins higher amounts of peroxide, and which can be activated in a stable manner.
It is also an object of the present invention to formulate a bleaching co,,,,uosiliul~ with superior bleaching pt:rru""c-"ce.
In response we have now found that this objed can be met by formulating an aqueous emulsion of nonionic surfactants, in which benzoyl peroxide is in~ u~ ,uul ~t 'J 8enzoyl peroxide may constitute the bleaching peroxide specie alone, as it hydrolyzes in aqueous medium in ne~ ~' ,JIJ. " '~ ,e pH so 20 as to generate a peracid. But in a preferred u..~uudi..,t,,,l of the present invention, a ~" ,~u ,itiùn is formulated which comprises hydrogen peroxide in one phase of the emulsion and benzoyl peroxide in the other phase of the emulsion.
25 Bleaching .,u,,,~..u ,itiùns formulated as emulsions have been disclosed in EP
598 170. The cullr "' )s in ~170 are emulsions cul~ ill9 hydrogen peroxide in one phase and a hJdlulJhuLi~. liquid ingredient in the other phase. This hyd~u,ullùbic liquid ingredient can be a peracid precursor.
Summarv of the invention The present invention is an aqueous bleaching UU~,Uo~itiUIl in the form of an 35 emulsion cu~ ill9 a hydrophilic nonionic surfactant and a hydlu,ullouic nonionic surfactant, said emulsion further colll~JIiaill9 an effective amount ofbenzoyl peroxide.
W0 95/35255 I ~ . .'C
219ls7~
Detailed des4, iL~lion of the invention The cu~ o~iliolls according to the present invention are stable aqueous s emulsions of nonionic surfactants. By stable emulsion it is meant an emulsion w'nich does not ",au~s :p;- 'Iy separate into distinct layers, upon standing for at least two weeks at 20 ~C, more preferably at least six months.
As used herein, the term emulsion refers to emulsions which are obtained when smaller amounts of benzoyl peroxide are used, so that it is ~",~ .t~,ly 10 soluble in the h~dlu~ huLic nonionic surfactant, as well as suspen:lions which are obtained when the level of Benzoyl peroxide is inueased to the point where part of it is not dissolved in the hydlu~ uLic nonionic surfactant, and agyl . _ ' s of Benzoyl Peroxide are formed in the aqueous phase.
The colll~Juailiùlla according to the present invention are aqueous.
Ac~u~di~ly'y, the COIll~uai~iuil5 according to the present invention comprise from 10~h to 95~h by weight of the total co,,,~,u~itiun of water, preferably from 30~h to 90~h, most ~ f~dLly from 60~h to 85~h. Deionized water is 2n preferably used.
The cu~ uùsi~iùns according to the present invention are emulsions of nonionic surfactants. Said emulsions of nonionic surfactants comprise at least two nonionic surfactants. In order to form emulsions which are stable, 2s said two nonionic surfac~ants must have different HLB values (hydluiJh"
lipophilic balance), and preferably the difference in value of the HLBs of said two surfactants is at least 1, more preferably at least 3. By d~J~Iupri ' 'y co"lL,i"i,ly at least two of said nonionic surfactants with different HLBs in water, emulsions according to the present invention will be formed.
One of said nonionic surfactants used herein is a nonionic surfactant with an ,,~ HLB above 11 (herein referred to as hydrophilic nonionic surfactant), whereas the other one is a nonionic surfactant with an HLB below 10 (herein referred to as hyd~ ulJhoLic nonionic surfactant). Preferably, the 3s cun~lll~dtion ratio between hydrophilic and h~ldluplluLi~, surfactants shouldbe chosen in such a way that the weighted average of their HLB is of from 9 to 11. The weighted average HLB is defined as:
woss/3s2ss 2 1 9 1 57 1 P ~
(C/o of hydrophilic x HLB of hydrophilic) + (~/0 of hyd,ul,hubic x HLB of hydl u,uhuLicj where:
~fOofhydlu~ = [hydrophilic]/total[hydrophilic-I I Iy~lU~ Ul;~iC], ~fO of hydlu,uhubic = [hydlu~hubic] / total [hydrophilic + hydlu,uhùbic], and % of hydrophilic + ~fO hydlu~J hdbiC = 1.
10 By [hylluui,' ~ and [I;ydlu~llûbi~,] we mean the weight ~/0 con~,,t,d~iunl based on the total formula, of the hJdlu~ and hydlupl)ùbic surfactants, ~ ,.euli~oly. In addition to the above two surfactants, the cù~ usilions according to the present invention may comprise any other nonionic surfactants, but preferably the weighted average HLB, calculated with the lS additional surfactants, still falls in the specified range.
Suitable nonionic surfactants for use herein include ~" yldtud fatty alcohols. Indeed, a great variety of such alkoxylated fatty alcohols are w"""e" "y available which have very different HLB values (hydrophilic 20 lipophilic balance). The HLB values of such lh .,' ' ' nonionic surfactants depend esse "~ "y on the nature of the " ,1~';JI I and the degree of .yldtiu, ,. Hydrophilic nonionic surfactants tend to have a higher degree of alkoxylation, while h~dlu~Jhobic surfactants tend to have a lower degree of 'h .yl~lion and a long chain fatty alcohol. Surfactants c~~'ogu~s are 25 available v,/hich list a number ûf surfactants including noniûniCS, tûgether with their rt::",ec~hro HLB values.
The wlll~Josi~iùna according to the present invention comprise from 2~~6 to 70~h by weight of the total cu",,uosiliu" of said hydrophilic and h~dlu~hoL~k, 30 nonionic surfactants, preferably from 3% to 4û~h, most preferably from 4~,6 to 3û%
As an essential ingredient, the co,,,,uosilions according to the present invention further comprise an effective amount of benzoyl peroxide in the 3s hyd~u,uhubi~, phase. By effective amount, it is meant herein an amount sufflcient for the bleaching of fabrics. According to the present invention, benzoyl peroxide can be used with or without hydrogen peroxide. When it is _ _ _ _ _ .. _ . . . .. . . _ _ . . _ ..
WO 95135_55 r~ 7~7 5 5 ~ 1 used without hydrogen peroxide, it simply hydrolyzes in neutral/alkaline medium, i.e. in the bleaching liquor fommed by diluting the w~ uaiLion, of the present invention in water, so as to form peroxybenzoate which is the bleaching specie. Ar,w,di,,yly, when benzoyl peroxide is used alone, the s w",po:,itions herein comprise from 1 ~h to 20 ~h by weight of the total w~uo~ iun, preferably from 2 ~h to 10 ~h by weight.
As an " , lali ~c, benzoyl peroxide can be used herein together with hydrogen peroxide. Both i"yl.' ~t~ are prevented from reacting in the 10 wlll,uu:~;tiùn, as hydrogen peroxide is i~lW~U~ ' ' in the hydrophilic phase,while benzoyl peroxide is i,,w,~ u, ' ' in the hydlu~lluL.ic phase. Thus both illylt~di~,"t~ are kept separate until the w",~,osi~iùn is diluted in an aqueousmedium for use. Upon dilution, the emulsion stnucture is nuptured, and benzoyl peroxide is perhydrolyzed by hydrogen peroxide so as to fomm 15 peroxybenzoate. In this scenario, two moles of p~luAyb~ ' are fommed per mole of benzoyl peroxide, whereas in the previously described scenario, only one mole of pel u,~"L~I ,_ ' was fommed per mole of benzoyl peroxide.
20 Acwldi,l5~1y, when the ~ oc~ ns herein are formulated with hydrogen peroxide, they should comprise from 1 ~h to 10 ~h by weight of the total w"",ositiu" of hydrogen peroxide, preferably from 2 ~h to 4 ~h, and from 1~h to 20~h by weight of the total w,,,~u,itiu,, of benzoyl paroxide, preferably from 1 ~h to 10~h. Of course, instead of hydrogen peroxide itself, one may 25 use sources of hydrogen peroxide. Suitable sources of hydrogen peroxide for use herein include pel w, bùrld~t s, pt:, L,u, s, persulfates and the like.
We have observed that the pH of the ~f ".,l ~o~ ,s herein plays a role in the 30 chemical stability of the cu",~,o~itiùn. Acculdi.l~ly, the w",,uo~itiù,)s herein are ,ul~i".,dLly formulated at a pH of from 1 to 6, preferably 2 to 5. A varietyof suitable means can be used for adjusting the pH of the WlllpO ,itions, including organic or inorganic acids, " wld",i.,es and the like. It may be advantageous to use -lh ,old".;.,es, in particular ,,.unot,ll,a,)ola,..;.,e, 3s inasmuch as they have an additional effect of regulating the viscosity of the emulsion, without .,o..,~,u,..;~.. ,9 on its physical stability.
wo ss/3s2ss 2 1 9 1 5 7 1 ~ 'C' 7??
The uo,,,~,o~iGù,-s herein may comprise a variety of optional illylt:dit:llLa A
preferred optional feature of the cu,,,~,o,iliu,,s herein is the presence of radical scavengers, which are beneficial to the stability of the uU~l~,vosii;u~sherein. Suitable radical scavengers for use herein include the well-known s s~ ~h5tit~ mono and di hydroxy benzenes and their analogs, alkyl and aryl Udll/UAy' ' , and mixtures thereof. Preferred radical scavengers for use herein include butyl hydroxy toluene, mono-tert-butyl hydroquinone, benzoic acid, toluic acid, t-butyl catechol, be" yl_."i"e, 1,1,3-tris(2-methyl4-hydroxy-5-t-butylphenyl) butane, CO~ vl ~ 'Iy available under the trade name c Topanol CA ~3 ex ICI, as well as n-propylyallate. Radical s.~.le.-ye,a, when used, are typically present herein in amounts ranging from 0.01 ~/0 to 2 % by weight of the total COlllpG_ ~;on, preferably 0.01 ~/0 to 0.2 ~h.
It may also be useful to formulate chelants herein, which may further improve 15 the chemical stability of the co,.~pv~iliuns herein. Typical chelants useful herein include ~ho~,uhûn ' , ethylene diamine dissuccinic acid, dipicolinic acid and diethylene triamine penta acetate and the like. Suitable levels for chelants herein are ~ liaed between 0.01~~6 and 5~~0 by weight of the total CUlll,UUaitiUll. An increase in chemical stability could ba observed by a 20 synergistic action of both the previous illylud;e~l~a~ radical scavengers and chelants, combined together.
The wll,,uoai~ions herein may further comprise other optionals, including anionic and cationic surfactants, to be formulated in the hydrophilic phase 25 herein, other bleach activators to be used in mixture with benzoyl peroxide, such as acetyl triethyl citrate, builders and chelants, as well as aesthetics, including dyes and perfumes and the like.
The culllyoaitiùns according to the present invention are particularly useful 30 as laundry bleaches, including as ~ t~vdlc:la, i.e colllpua;;iuns which are dispensed and lefl to act onto fabrics before they are washed. Cu~lluuSiliOIla herein can be formulated as laundry additives to be used before or together with ~ .yell~a in an aqueous medium to boost their p~lrulllldllce, or as detergent cu""~osiliu"s per se. Culllpoa;liùn-s herein can also be used as 3s automatic or hand di~l, . ',;.,9 uu~ Joailiul~s, as hard surface cleaners, as denture cleansers, or as carpet cleaners.
~WO95~35255 21 91 571 r~ c~
The present invention further enco",l)asses a process for the manufacture of the uo",posilions described herein. The process according to the present invention uulllprises at least three steps:
s In the first step, a l,jlluphobic mixture is prepared which cu"")rises said hy~llupllulJic nonionic surfactant, said benzoyl peroxide, together with other, optional, hydl upllobic i"yl Jd;e ula which are to be formulated in the cu,,,~osiliu,,, such as perfumes, solvents, enzymes, bleach activators and polymers.
In the second step, a hydlu,ull' mixture is prepared which cu"~ ises at least said water, and said hydrophilic nonionic surfactant. Said hydrophilic mixture ,ulufu.dbly further culll~uli~es other hyl~u,ull "~ i"y~u.';_.~k, which are to be fommulated in the ~_ullllJosition such as dyes, optical u(i~u,hlane~a, 15 builders, chelants, hydrogen peroxide or sources thereof and buffering agents.
Naturally, said first and said second steps can be perro""ed in any order, i.e second step first is also suitable.
In the third step of the process according to the present invention, said hydl u,uhuLi~, mixture and said hydrophilic mixture are mixed together.
Examoles - ExL~ l lldl data CollllJOaitiull 1:
Benzoyl Peroxide 2%
H202 4%
Sodium Coconut Alkyl Sulfate 5~~0 Dobanol @)23-3 5%
Dobanol ~ 91-8 3~~0 Coconut trimethyl ammonium chloride 1~~0 3s Water and minors to balance pH 4 wo gs/3s255 r~ 77~ ~
~ 21918571 Col, ,,)o~i~iul, 2 8enzoyl Peroxide 3.5%
H202 4%
5 Sodium CoconutAlkyl Sulfate 2%
Lutensol ~ TO3 7%
Dobanol 3 45-7 8%
Water and minors to balance pH 4 C~l"u~siLiu" 3 E~enzoyl Peroxide 3.5%
Sodium Coconut Alkyl Sulfate 0.5%
Dobanol 45-7 11%
Lutensol TO3 4%
Water and minors to balance pH 4 The technical data he,t i"drle, illustrates the benefits obtained from benzoyl peroxide, according to the present invention.
The tests are ,cerru,,,,ed on rotton fabrics stained as indicated below. 0.2g Of2s tested bleaching ~Ill~Jo~iliull is applied on each stain. The fabrics (6 replicates each) are then washed in a Launder-o-meter, using 5 9 of Dash ultra Powder in 50û ml water. There is no waiting period between -rr'' " I
of tested bleaching c~" ~,uO~itiOI ~ and washing. A reference bleaching culll~uGait;on is used which is an activated bleaching c,um,uo~iliu,, ~Illpliaing 30 hydrogen peroxide and acetyl triethyl citrate, as disclosed in WO 93/12067.
Specifically, the reference culllpOailiul) ~,w,,lJrised 6% H202, 3.5% Acetyl triethyl citrate, 7~/O Lutensol ~T03, 8% Dobanol ~ 45-7, 2% Sodium Alkyl Sulfate, water to balance, pH=4. A cc)lll,udliaon is made, in a single variable test, between benzoyl peroxide (the prototype) and acetyl triethyl citrate (the 3s reference) at the same level (3.5%).
~WO95/3525S 2 1 9 1 571 F~,l/u~ o The results are e~ ":~sed as panel score units, as evaluated by expert panel judges.
PrototvDe vs. reference 40~ C 60~ C
Tomato 4.0s 3.5s Tea 1.2s 1.7s Cocoa 0.3 1.2s Grass 0.2s 0.1 Wine 0.7s 1.1s Vegetal Oil 3.2s 2.8s Blood 1.2s 0.8 The results above indicate a strong benefit on all stains, using benzoyl peroxide instead of acetyl triethyl citrate, at a given level of hydrogen peroxide, and the same level of activator.
10 Using the same test c."ditions as above, a similar cc"",arison was made between a prototype with 4~~O H202 and 2% benzoyl peroxide, vs a reference cu",~"isi"~3 7~/O of H202 .
prototvpe vs. reference 40~ C 60~ C
Tomato 2.2s 2.2s Tea 1.2s 0.4 Cocoa 0 4 0 7s Grass 1.0s 0 4 Wine 0.8s 0.2 Vegetal Oil 2.2s 1.7s Make up 1.8s 0.9s r The results above show that superior results are still obtained, even though the level of hydrogen peroxide was reduced from 7~~6 in reference, to 4~~0 in prototype.
r -- ~ c~ ~;,,r Technical Field The present invention relates to bleaching co",r ,~. The CulllpoaiLiulla 1S of the present invention are particularly useful for laundry bleaching.
Backaround Cu,,,~.ositiù,)s for the bleaching of laundry have been e,~tar,~;,/aly describedin the art. Bleaching cu..,~-osit;ons can be classified into peroxide bleaching Cullll~u~itiulla and hy~o~,lllul bleaching ~ u~ a. Peroxide bleaching cu",r- ,:. have the advantage over l.~poullluli bleaching Co~ usitiùl)s 2s that they are generally con ,ida,ed as being somewhat safer to fabrics, -r~' ~ ~Iy to colored fabrics. Peroxide c~ ns however have the inconveniency that they are often ul, 'Iy unstable, which makes it difficult to formulate peroxide bleaching Culll,~u~itiw~S which are sufficiently stable tobe COIlllllel~ ' ' A possible solution to this problem consists in 30 formulating cu" I,uOaitiOl)S with a high level of peroxide, to extend the "effective" period of the cu,,,, ~. A possible drawback of this solution is that cc"",osiliu"s may reach the user which still comprise a high amount of peroxide, whereby possible skin itching may occur if the user's skin comes in contact with the peroxide ~~ osilion. This itching phe,,u,,,el)ol) is quite 3s moderate and fully reversible, but is does constitute potential di;,~,o~rult for tha user.
WO95135255 r~"-J~ s 21 ~1571 Also, peroxide species are poorly effective in bleaching at lower temperatures, so that it is required to formulate activated peroxide bleaching cu~ uosiliulls for use auoss a wider range of temperatures. Activated bleaching cu~ ositiùns comprise a bleach activator, typically a peracid s precursor, which will react in an aqueous medium with hydrogen peroxide to form the coll~a~ùlldi~lg peracid. This peracid is more effective at lower temperatures.
It is thus an object of the present invention to formulate a peroxide bleaching 10 ~ ' ol, which is stable, without having to resort to usins higher amounts of peroxide, and which can be activated in a stable manner.
It is also an object of the present invention to formulate a bleaching co,,,,uosiliul~ with superior bleaching pt:rru""c-"ce.
In response we have now found that this objed can be met by formulating an aqueous emulsion of nonionic surfactants, in which benzoyl peroxide is in~ u~ ,uul ~t 'J 8enzoyl peroxide may constitute the bleaching peroxide specie alone, as it hydrolyzes in aqueous medium in ne~ ~' ,JIJ. " '~ ,e pH so 20 as to generate a peracid. But in a preferred u..~uudi..,t,,,l of the present invention, a ~" ,~u ,itiùn is formulated which comprises hydrogen peroxide in one phase of the emulsion and benzoyl peroxide in the other phase of the emulsion.
25 Bleaching .,u,,,~..u ,itiùns formulated as emulsions have been disclosed in EP
598 170. The cullr "' )s in ~170 are emulsions cul~ ill9 hydrogen peroxide in one phase and a hJdlulJhuLi~. liquid ingredient in the other phase. This hyd~u,ullùbic liquid ingredient can be a peracid precursor.
Summarv of the invention The present invention is an aqueous bleaching UU~,Uo~itiUIl in the form of an 35 emulsion cu~ ill9 a hydrophilic nonionic surfactant and a hydlu,ullouic nonionic surfactant, said emulsion further colll~JIiaill9 an effective amount ofbenzoyl peroxide.
W0 95/35255 I ~ . .'C
219ls7~
Detailed des4, iL~lion of the invention The cu~ o~iliolls according to the present invention are stable aqueous s emulsions of nonionic surfactants. By stable emulsion it is meant an emulsion w'nich does not ",au~s :p;- 'Iy separate into distinct layers, upon standing for at least two weeks at 20 ~C, more preferably at least six months.
As used herein, the term emulsion refers to emulsions which are obtained when smaller amounts of benzoyl peroxide are used, so that it is ~",~ .t~,ly 10 soluble in the h~dlu~ huLic nonionic surfactant, as well as suspen:lions which are obtained when the level of Benzoyl peroxide is inueased to the point where part of it is not dissolved in the hydlu~ uLic nonionic surfactant, and agyl . _ ' s of Benzoyl Peroxide are formed in the aqueous phase.
The colll~Juailiùlla according to the present invention are aqueous.
Ac~u~di~ly'y, the COIll~uai~iuil5 according to the present invention comprise from 10~h to 95~h by weight of the total co,,,~,u~itiun of water, preferably from 30~h to 90~h, most ~ f~dLly from 60~h to 85~h. Deionized water is 2n preferably used.
The cu~ uùsi~iùns according to the present invention are emulsions of nonionic surfactants. Said emulsions of nonionic surfactants comprise at least two nonionic surfactants. In order to form emulsions which are stable, 2s said two nonionic surfac~ants must have different HLB values (hydluiJh"
lipophilic balance), and preferably the difference in value of the HLBs of said two surfactants is at least 1, more preferably at least 3. By d~J~Iupri ' 'y co"lL,i"i,ly at least two of said nonionic surfactants with different HLBs in water, emulsions according to the present invention will be formed.
One of said nonionic surfactants used herein is a nonionic surfactant with an ,,~ HLB above 11 (herein referred to as hydrophilic nonionic surfactant), whereas the other one is a nonionic surfactant with an HLB below 10 (herein referred to as hyd~ ulJhoLic nonionic surfactant). Preferably, the 3s cun~lll~dtion ratio between hydrophilic and h~ldluplluLi~, surfactants shouldbe chosen in such a way that the weighted average of their HLB is of from 9 to 11. The weighted average HLB is defined as:
woss/3s2ss 2 1 9 1 57 1 P ~
(C/o of hydrophilic x HLB of hydrophilic) + (~/0 of hyd,ul,hubic x HLB of hydl u,uhuLicj where:
~fOofhydlu~ = [hydrophilic]/total[hydrophilic-I I Iy~lU~ Ul;~iC], ~fO of hydlu,uhubic = [hydlu~hubic] / total [hydrophilic + hydlu,uhùbic], and % of hydrophilic + ~fO hydlu~J hdbiC = 1.
10 By [hylluui,' ~ and [I;ydlu~llûbi~,] we mean the weight ~/0 con~,,t,d~iunl based on the total formula, of the hJdlu~ and hydlupl)ùbic surfactants, ~ ,.euli~oly. In addition to the above two surfactants, the cù~ usilions according to the present invention may comprise any other nonionic surfactants, but preferably the weighted average HLB, calculated with the lS additional surfactants, still falls in the specified range.
Suitable nonionic surfactants for use herein include ~" yldtud fatty alcohols. Indeed, a great variety of such alkoxylated fatty alcohols are w"""e" "y available which have very different HLB values (hydrophilic 20 lipophilic balance). The HLB values of such lh .,' ' ' nonionic surfactants depend esse "~ "y on the nature of the " ,1~';JI I and the degree of .yldtiu, ,. Hydrophilic nonionic surfactants tend to have a higher degree of alkoxylation, while h~dlu~Jhobic surfactants tend to have a lower degree of 'h .yl~lion and a long chain fatty alcohol. Surfactants c~~'ogu~s are 25 available v,/hich list a number ûf surfactants including noniûniCS, tûgether with their rt::",ec~hro HLB values.
The wlll~Josi~iùna according to the present invention comprise from 2~~6 to 70~h by weight of the total cu",,uosiliu" of said hydrophilic and h~dlu~hoL~k, 30 nonionic surfactants, preferably from 3% to 4û~h, most preferably from 4~,6 to 3û%
As an essential ingredient, the co,,,,uosilions according to the present invention further comprise an effective amount of benzoyl peroxide in the 3s hyd~u,uhubi~, phase. By effective amount, it is meant herein an amount sufflcient for the bleaching of fabrics. According to the present invention, benzoyl peroxide can be used with or without hydrogen peroxide. When it is _ _ _ _ _ .. _ . . . .. . . _ _ . . _ ..
WO 95135_55 r~ 7~7 5 5 ~ 1 used without hydrogen peroxide, it simply hydrolyzes in neutral/alkaline medium, i.e. in the bleaching liquor fommed by diluting the w~ uaiLion, of the present invention in water, so as to form peroxybenzoate which is the bleaching specie. Ar,w,di,,yly, when benzoyl peroxide is used alone, the s w",po:,itions herein comprise from 1 ~h to 20 ~h by weight of the total w~uo~ iun, preferably from 2 ~h to 10 ~h by weight.
As an " , lali ~c, benzoyl peroxide can be used herein together with hydrogen peroxide. Both i"yl.' ~t~ are prevented from reacting in the 10 wlll,uu:~;tiùn, as hydrogen peroxide is i~lW~U~ ' ' in the hydrophilic phase,while benzoyl peroxide is i,,w,~ u, ' ' in the hydlu~lluL.ic phase. Thus both illylt~di~,"t~ are kept separate until the w",~,osi~iùn is diluted in an aqueousmedium for use. Upon dilution, the emulsion stnucture is nuptured, and benzoyl peroxide is perhydrolyzed by hydrogen peroxide so as to fomm 15 peroxybenzoate. In this scenario, two moles of p~luAyb~ ' are fommed per mole of benzoyl peroxide, whereas in the previously described scenario, only one mole of pel u,~"L~I ,_ ' was fommed per mole of benzoyl peroxide.
20 Acwldi,l5~1y, when the ~ oc~ ns herein are formulated with hydrogen peroxide, they should comprise from 1 ~h to 10 ~h by weight of the total w"",ositiu" of hydrogen peroxide, preferably from 2 ~h to 4 ~h, and from 1~h to 20~h by weight of the total w,,,~u,itiu,, of benzoyl paroxide, preferably from 1 ~h to 10~h. Of course, instead of hydrogen peroxide itself, one may 25 use sources of hydrogen peroxide. Suitable sources of hydrogen peroxide for use herein include pel w, bùrld~t s, pt:, L,u, s, persulfates and the like.
We have observed that the pH of the ~f ".,l ~o~ ,s herein plays a role in the 30 chemical stability of the cu",~,o~itiùn. Acculdi.l~ly, the w",,uo~itiù,)s herein are ,ul~i".,dLly formulated at a pH of from 1 to 6, preferably 2 to 5. A varietyof suitable means can be used for adjusting the pH of the WlllpO ,itions, including organic or inorganic acids, " wld",i.,es and the like. It may be advantageous to use -lh ,old".;.,es, in particular ,,.unot,ll,a,)ola,..;.,e, 3s inasmuch as they have an additional effect of regulating the viscosity of the emulsion, without .,o..,~,u,..;~.. ,9 on its physical stability.
wo ss/3s2ss 2 1 9 1 5 7 1 ~ 'C' 7??
The uo,,,~,o~iGù,-s herein may comprise a variety of optional illylt:dit:llLa A
preferred optional feature of the cu,,,~,o,iliu,,s herein is the presence of radical scavengers, which are beneficial to the stability of the uU~l~,vosii;u~sherein. Suitable radical scavengers for use herein include the well-known s s~ ~h5tit~ mono and di hydroxy benzenes and their analogs, alkyl and aryl Udll/UAy' ' , and mixtures thereof. Preferred radical scavengers for use herein include butyl hydroxy toluene, mono-tert-butyl hydroquinone, benzoic acid, toluic acid, t-butyl catechol, be" yl_."i"e, 1,1,3-tris(2-methyl4-hydroxy-5-t-butylphenyl) butane, CO~ vl ~ 'Iy available under the trade name c Topanol CA ~3 ex ICI, as well as n-propylyallate. Radical s.~.le.-ye,a, when used, are typically present herein in amounts ranging from 0.01 ~/0 to 2 % by weight of the total COlllpG_ ~;on, preferably 0.01 ~/0 to 0.2 ~h.
It may also be useful to formulate chelants herein, which may further improve 15 the chemical stability of the co,.~pv~iliuns herein. Typical chelants useful herein include ~ho~,uhûn ' , ethylene diamine dissuccinic acid, dipicolinic acid and diethylene triamine penta acetate and the like. Suitable levels for chelants herein are ~ liaed between 0.01~~6 and 5~~0 by weight of the total CUlll,UUaitiUll. An increase in chemical stability could ba observed by a 20 synergistic action of both the previous illylud;e~l~a~ radical scavengers and chelants, combined together.
The wll,,uoai~ions herein may further comprise other optionals, including anionic and cationic surfactants, to be formulated in the hydrophilic phase 25 herein, other bleach activators to be used in mixture with benzoyl peroxide, such as acetyl triethyl citrate, builders and chelants, as well as aesthetics, including dyes and perfumes and the like.
The culllyoaitiùns according to the present invention are particularly useful 30 as laundry bleaches, including as ~ t~vdlc:la, i.e colllpua;;iuns which are dispensed and lefl to act onto fabrics before they are washed. Cu~lluuSiliOIla herein can be formulated as laundry additives to be used before or together with ~ .yell~a in an aqueous medium to boost their p~lrulllldllce, or as detergent cu""~osiliu"s per se. Culllpoa;liùn-s herein can also be used as 3s automatic or hand di~l, . ',;.,9 uu~ Joailiul~s, as hard surface cleaners, as denture cleansers, or as carpet cleaners.
~WO95~35255 21 91 571 r~ c~
The present invention further enco",l)asses a process for the manufacture of the uo",posilions described herein. The process according to the present invention uulllprises at least three steps:
s In the first step, a l,jlluphobic mixture is prepared which cu"")rises said hy~llupllulJic nonionic surfactant, said benzoyl peroxide, together with other, optional, hydl upllobic i"yl Jd;e ula which are to be formulated in the cu,,,~osiliu,,, such as perfumes, solvents, enzymes, bleach activators and polymers.
In the second step, a hydlu,ull' mixture is prepared which cu"~ ises at least said water, and said hydrophilic nonionic surfactant. Said hydrophilic mixture ,ulufu.dbly further culll~uli~es other hyl~u,ull "~ i"y~u.';_.~k, which are to be fommulated in the ~_ullllJosition such as dyes, optical u(i~u,hlane~a, 15 builders, chelants, hydrogen peroxide or sources thereof and buffering agents.
Naturally, said first and said second steps can be perro""ed in any order, i.e second step first is also suitable.
In the third step of the process according to the present invention, said hydl u,uhuLi~, mixture and said hydrophilic mixture are mixed together.
Examoles - ExL~ l lldl data CollllJOaitiull 1:
Benzoyl Peroxide 2%
H202 4%
Sodium Coconut Alkyl Sulfate 5~~0 Dobanol @)23-3 5%
Dobanol ~ 91-8 3~~0 Coconut trimethyl ammonium chloride 1~~0 3s Water and minors to balance pH 4 wo gs/3s255 r~ 77~ ~
~ 21918571 Col, ,,)o~i~iul, 2 8enzoyl Peroxide 3.5%
H202 4%
5 Sodium CoconutAlkyl Sulfate 2%
Lutensol ~ TO3 7%
Dobanol 3 45-7 8%
Water and minors to balance pH 4 C~l"u~siLiu" 3 E~enzoyl Peroxide 3.5%
Sodium Coconut Alkyl Sulfate 0.5%
Dobanol 45-7 11%
Lutensol TO3 4%
Water and minors to balance pH 4 The technical data he,t i"drle, illustrates the benefits obtained from benzoyl peroxide, according to the present invention.
The tests are ,cerru,,,,ed on rotton fabrics stained as indicated below. 0.2g Of2s tested bleaching ~Ill~Jo~iliull is applied on each stain. The fabrics (6 replicates each) are then washed in a Launder-o-meter, using 5 9 of Dash ultra Powder in 50û ml water. There is no waiting period between -rr'' " I
of tested bleaching c~" ~,uO~itiOI ~ and washing. A reference bleaching culll~uGait;on is used which is an activated bleaching c,um,uo~iliu,, ~Illpliaing 30 hydrogen peroxide and acetyl triethyl citrate, as disclosed in WO 93/12067.
Specifically, the reference culllpOailiul) ~,w,,lJrised 6% H202, 3.5% Acetyl triethyl citrate, 7~/O Lutensol ~T03, 8% Dobanol ~ 45-7, 2% Sodium Alkyl Sulfate, water to balance, pH=4. A cc)lll,udliaon is made, in a single variable test, between benzoyl peroxide (the prototype) and acetyl triethyl citrate (the 3s reference) at the same level (3.5%).
~WO95/3525S 2 1 9 1 571 F~,l/u~ o The results are e~ ":~sed as panel score units, as evaluated by expert panel judges.
PrototvDe vs. reference 40~ C 60~ C
Tomato 4.0s 3.5s Tea 1.2s 1.7s Cocoa 0.3 1.2s Grass 0.2s 0.1 Wine 0.7s 1.1s Vegetal Oil 3.2s 2.8s Blood 1.2s 0.8 The results above indicate a strong benefit on all stains, using benzoyl peroxide instead of acetyl triethyl citrate, at a given level of hydrogen peroxide, and the same level of activator.
10 Using the same test c."ditions as above, a similar cc"",arison was made between a prototype with 4~~O H202 and 2% benzoyl peroxide, vs a reference cu",~"isi"~3 7~/O of H202 .
prototvpe vs. reference 40~ C 60~ C
Tomato 2.2s 2.2s Tea 1.2s 0.4 Cocoa 0 4 0 7s Grass 1.0s 0 4 Wine 0.8s 0.2 Vegetal Oil 2.2s 1.7s Make up 1.8s 0.9s r The results above show that superior results are still obtained, even though the level of hydrogen peroxide was reduced from 7~~6 in reference, to 4~~0 in prototype.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
What is claimed is:
1. An aqueous bleaching composition in the form of an emulsion comprising at least two nonionic surfactants with different HLBs, characterized in that said emulsion further comprises an effective amount of benzoyl peroxide.
2. A composition according to claim 1 which comprises from about 1% to about 20% by weight of the total composition of benzoyl peroxide.
3. A composition according to claim 1 which further comprises an effective amount of a source of hydrogen peroxide.
4. A composition according to claim 3 wherein said source of hydrogen peroxide is hydrogen peroxide.
5. A composition according to claim 4 which comprises from about 1% to about 8% by weight of the total composition of hydrogen peroxide
6. A composition according to claim 5 which comprises from about 2% to about 4% by weight of the total composition of hydrogen peroxide
7. A composition according to claim 6 which comprises from about 2% to about 10% by weight of the total composition of benzoyl peroxide.
8. A composition according to claim 1, having a pH of from about 1 to about 6.
9. A composition according to claim 1 wherein said hydrophilic nonionic surfactant has an HLB above 11.
10. A composition according to claim 1 wherein said hydrophobic surfactant has an HLB below 10.
11. A process for the manufacture of a composition according to claim 1 which comprises the steps of:
- Preparing a hydrophobic mixture comprising said hydrophobic nonionic surfactant and said benzoyl peroxide, together with other, optional, hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers;
- Preparing a hydrophilic mixture comprising at least said water, and said hydrophilic nonionic surfactant and possibly other, optional, hydrophilic ingredients which are to be formulated in the composition such as dyes, optical brighteners, builders, chelants, hydrogen peroxide or sources thereof and buffering agents.
- Wherein benzoyl peroxide is added in either said hydrophobic or said hydrophilic mixtures, or said derivatives thereof are added in said hydrophobic phase;
- Subsequently mixing said hydrophobic mixture and said hydrophilic mixture together.
- Preparing a hydrophobic mixture comprising said hydrophobic nonionic surfactant and said benzoyl peroxide, together with other, optional, hydrophobic ingredients which are to be formulated in the composition, such as perfumes, solvents, enzymes, bleach activators and polymers;
- Preparing a hydrophilic mixture comprising at least said water, and said hydrophilic nonionic surfactant and possibly other, optional, hydrophilic ingredients which are to be formulated in the composition such as dyes, optical brighteners, builders, chelants, hydrogen peroxide or sources thereof and buffering agents.
- Wherein benzoyl peroxide is added in either said hydrophobic or said hydrophilic mixtures, or said derivatives thereof are added in said hydrophobic phase;
- Subsequently mixing said hydrophobic mixture and said hydrophilic mixture together.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP94870097A EP0687726B1 (en) | 1994-06-17 | 1994-06-17 | Bleaching compositions |
| EP94870097.6 | 1994-06-17 | ||
| PCT/US1995/006222 WO1995035255A1 (en) | 1994-06-17 | 1995-05-18 | Bleaching compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2191571A1 true CA2191571A1 (en) | 1995-12-28 |
Family
ID=8218648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002191571A Abandoned CA2191571A1 (en) | 1994-06-17 | 1995-05-18 | Bleaching compositions |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0687726B1 (en) |
| JP (1) | JPH10504584A (en) |
| CN (1) | CN1049402C (en) |
| AT (1) | ATE191002T1 (en) |
| AU (1) | AU706186B2 (en) |
| CA (1) | CA2191571A1 (en) |
| DE (1) | DE69423613T2 (en) |
| DK (1) | DK0687726T3 (en) |
| ES (1) | ES2143538T3 (en) |
| GR (1) | GR3032831T3 (en) |
| MX (1) | MX9606565A (en) |
| PT (1) | PT687726E (en) |
| WO (1) | WO1995035255A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE318298T1 (en) * | 1995-03-27 | 2006-03-15 | Procter & Gamble | LIQUID ACTIVATED BLEACH COMPOSITIONS |
| GB9600159D0 (en) * | 1996-01-05 | 1996-03-06 | Warwick Int Group | Process for bleaching or disinfecting a substrate |
| DE19750455C1 (en) * | 1997-11-14 | 1999-04-29 | Henkel Kgaa | Aqueous hydrogen peroxide formulation used as bleach for pretreating soiled textile, especially laundry |
| AU6255098A (en) * | 1998-01-29 | 1999-08-16 | Procter & Gamble Company, The | Method for cleaning dentures |
| ES2256927T3 (en) * | 1998-11-10 | 2006-07-16 | THE PROCTER & GAMBLE COMPANY | WHITENING COMPOSITIONS. |
| GB9917885D0 (en) * | 1999-07-29 | 1999-09-29 | Procter & Gamble | Method of removing plaque from a denture |
| TWI400330B (en) | 2005-12-28 | 2013-07-01 | Kao Corp | Liquid detergent |
| CA2910953C (en) * | 2013-05-24 | 2018-06-26 | The Procter & Gamble Company | Low ph detergent composition comprising nonionic surfactants |
| DE102014204389A1 (en) * | 2014-03-11 | 2015-09-17 | Henkel Ag & Co. Kgaa | Improved surfactant blend with optimized degree of ethoxylation |
| US10376901B2 (en) | 2014-09-18 | 2019-08-13 | Akzo Nobel Chemicals International B.V. | Use of branched alcohols and alkoxylates thereof as secondary collectors |
| WO2017162563A2 (en) * | 2016-03-22 | 2017-09-28 | Akzo Nobel Chemicals International B.V. | Use of emulsifier in collector composition |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3825509A (en) * | 1972-11-13 | 1974-07-23 | Goodrich Co B F | Initiator emulsion for olefinic polymerization reactions |
| AR208425A1 (en) * | 1975-03-14 | 1976-12-27 | Akzo Nv | PROCEDURE FOR THE PREPARATION OF AN AQUEOUS SUSPENSION CONTAINING A SOLID ORGANIC PEROXIDE AT A TEMPERATURE OF APPROXIMATELY 20 C |
| US4440885A (en) * | 1980-04-02 | 1984-04-03 | Ppg Industries, Inc. | Peroxide emulsions and sizing composition containing same |
| US4401835A (en) * | 1981-09-17 | 1983-08-30 | Warner-Lambert Company | Method for preparing small sized benzoyl peroxide crystals |
| US4552682A (en) * | 1982-09-30 | 1985-11-12 | Ppg Industries, Inc. | Peroxide composition containing phenolic antioxidant |
| JPS6251666A (en) * | 1985-08-29 | 1987-03-06 | Nippon Oil & Fats Co Ltd | Dibenzoyl peroxide-containing composition |
| JPH01190666A (en) * | 1988-01-25 | 1989-07-31 | Nippon Oil & Fats Co Ltd | Aqueous suspension of dibenzoyl peroxide |
| TW291496B (en) * | 1991-02-01 | 1996-11-21 | Hoechst Ag | |
| GB2272450A (en) * | 1992-11-13 | 1994-05-18 | Albright & Wilson | Aqueous surfactant VI phase compositions |
| DE69224389T2 (en) * | 1992-11-16 | 1998-08-13 | Procter & Gamble | Detergent and bleach compositions |
| EP0598692A1 (en) * | 1992-11-16 | 1994-05-25 | The Procter & Gamble Company | Pseudoplastic and thixotropic cleaning compositions |
| US5409632A (en) * | 1992-11-16 | 1995-04-25 | The Procter & Gamble Company | Cleaning and bleaching composition with amidoperoxyacid |
| EP0598973A1 (en) * | 1992-11-26 | 1994-06-01 | The Procter & Gamble Company | Multi-purpose liquid cleaning composition |
-
1994
- 1994-06-17 AT AT94870097T patent/ATE191002T1/en not_active IP Right Cessation
- 1994-06-17 DK DK94870097T patent/DK0687726T3/en active
- 1994-06-17 ES ES94870097T patent/ES2143538T3/en not_active Expired - Lifetime
- 1994-06-17 DE DE69423613T patent/DE69423613T2/en not_active Expired - Fee Related
- 1994-06-17 EP EP94870097A patent/EP0687726B1/en not_active Expired - Lifetime
- 1994-06-17 PT PT94870097T patent/PT687726E/en unknown
-
1995
- 1995-05-18 CA CA002191571A patent/CA2191571A1/en not_active Abandoned
- 1995-05-18 AU AU25933/95A patent/AU706186B2/en not_active Ceased
- 1995-05-18 MX MX9606565A patent/MX9606565A/en unknown
- 1995-05-18 CN CN95193652A patent/CN1049402C/en not_active Expired - Fee Related
- 1995-05-18 JP JP8502165A patent/JPH10504584A/en active Pending
- 1995-05-18 WO PCT/US1995/006222 patent/WO1995035255A1/en active Application Filing
-
2000
- 2000-03-23 GR GR20000400511T patent/GR3032831T3/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| ATE191002T1 (en) | 2000-04-15 |
| ES2143538T3 (en) | 2000-05-16 |
| DE69423613T2 (en) | 2000-11-02 |
| EP0687726A1 (en) | 1995-12-20 |
| CN1151149A (en) | 1997-06-04 |
| AU706186B2 (en) | 1999-06-10 |
| DE69423613D1 (en) | 2000-04-27 |
| CN1049402C (en) | 2000-02-16 |
| WO1995035255A1 (en) | 1995-12-28 |
| GR3032831T3 (en) | 2000-06-30 |
| EP0687726B1 (en) | 2000-03-22 |
| JPH10504584A (en) | 1998-05-06 |
| AU2593395A (en) | 1996-01-15 |
| MX9606565A (en) | 1997-03-29 |
| PT687726E (en) | 2000-09-29 |
| DK0687726T3 (en) | 2000-07-03 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |