CA2149320C - Aqueous cleaning and bleaching composition containing hydrophobic liquid, h2o2 and two nonionic surfactants with different hlbs - Google Patents
Aqueous cleaning and bleaching composition containing hydrophobic liquid, h2o2 and two nonionic surfactants with different hlbsInfo
- Publication number
- CA2149320C CA2149320C CA002149320A CA2149320A CA2149320C CA 2149320 C CA2149320 C CA 2149320C CA 002149320 A CA002149320 A CA 002149320A CA 2149320 A CA2149320 A CA 2149320A CA 2149320 C CA2149320 C CA 2149320C
- Authority
- CA
- Canada
- Prior art keywords
- hlb
- hydrophobic liquid
- hydrophobic
- liquid ingredient
- nonionic surfactant
- 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.)
- Expired - Fee Related
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 87
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 52
- 239000002736 nonionic surfactant Substances 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title claims abstract description 34
- 238000004061 bleaching Methods 0.000 title claims abstract description 12
- 238000004140 cleaning Methods 0.000 title claims abstract description 6
- 239000004615 ingredient Substances 0.000 claims abstract description 40
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012190 activator Substances 0.000 claims abstract description 21
- 239000007844 bleaching agent Substances 0.000 claims abstract description 20
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical group CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 150000002978 peroxides Chemical class 0.000 description 6
- 150000002191 fatty alcohols Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000006172 buffering agent Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000490229 Eucephalus Species 0.000 description 1
- 241000271915 Hydrophis Species 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- SURLGNKAQXKNSP-DBLYXWCISA-N chlorin Chemical compound C\1=C/2\N/C(=C\C3=N/C(=C\C=4NC(/C=C\5/C=CC/1=N/5)=CC=4)/C=C3)/CC\2 SURLGNKAQXKNSP-DBLYXWCISA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- SYOKIDBDQMKNDQ-XWTIBIIYSA-N vildagliptin Chemical compound C1C(O)(C2)CC(C3)CC1CC32NCC(=O)N1CCC[C@H]1C#N SYOKIDBDQMKNDQ-XWTIBIIYSA-N 0.000 description 1
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
- 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
- C11D1/66—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Detergent Compositions (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Cosmetics (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The present invention is an aqueous cleaning and bleaching composition having a pH of from 0.5 to 6, comprising hydrogen peroxide or a source thereof and a hydrophobic liquid ingredient, preferably a bleach activator, wherein said hydrophobic liquid ingredient is emulsified in said composition by a mixture comprising at least one nonionic surfactant with an HLB that is higher than or equal to the HLB of said hydrophobic liquid ingredient and at least one nonionic surfactant with an HLB that is lower than or equal to the HLB of said hydrophobic liquid ingredient, provided that the HLBs of said nonionic surfactants, provided that the HLBs of said nonionic surfactants are not identical.
Description
~ WO ~4Jtl47~ ~ 1 4 9 3 2-~ - PCT/US93/~43~ ' ~
:
AQUEOUS CLEANING AND BLEACHING COMPOSITION~CONTAINING
HYDROPHOBIC LIQUID, H202 AND TWO NONIONIC SURFACTANTS:WITH DIFFERENT HLBS
AAAAAil~AAAAAA
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: ' ;, : ' ;"
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;;' ':
~ ~ .
' , Technical field ~ :
The presen~ invent~ion~ relates to cl~in~ and ble~ching ~
compositions ~hich~;~re:h~F~ on hydrogen peroxide. ~ :
~ i Backqround ~ : .
Bleaching and cleaning compositions: have~ been extensively des~ribed;in the art. ;It; is:~also:~we:ll knuwn ~hat it::i~
des~irable:~ to~ us~e~: hydrogen ~peroxide rather ~han other bleachas su h~as chlorin~ type bleaches. ~ Indeed, ihydrogen peroxidP~is:much~mildèr~and there~ore safer~, both for the 'W094/11475 ~i493~~ PCT/US93/1~432 ~
, item being bleached and for the user. However, hydrogen peroxide based bleaches have the main inconvenient that they perform poorly at~low temperature. In response to ; this object, compositions have been desi~ned which further compri~e a bleach activator.~ The bleach activator reacts with hydroqen peroxide to ~yield a peraci~ which is the bleaching species.
Activate~ bleaching compositions however have the drawback that the activator and the hydrogen~peroxide ters~ to react in the composition~.~ ThUs ,~ such actlvated bleaching compositions tend to be chemically unstable upon storaqe.
It is an object of the present~ invention to provide activated bleaching ~compositions which are chemically stable.
; .
' Another problem~ is that bleach activators which are hydrophobic are problematic to use in aqueous compositions as the product tends to separate into two different layer phases which can be visualized by the consumer. Therefore, physical stability upon storage ig~a further issue.
Th~ present invention meets the above objects in proposing an aqueous cleaning and bleaching composition comprisin~
hydrogen peroxide and a li~uid hydropho~ic bleach activator, wherein said bleach activator is emùlsified in the composition by means of a specific nonionic surfactant mixture.
EP 497 337 describes suspensions of solid water-insoluble peroxyacids~in~agueous compositions comprising a mixture of two nonionic~ surfactants~ ~Compared to~the compo~itions in the '337 patent application,~the~compositions according to the present~ invention~allow for~ a ~aster dissolution of said liquid ~hydrophobic bleach~ activator in the ;wash~ ~, solution. ~
~ WO~4/11475 2 1 4 9 3 ~ O PCT/US93/10432 The present invention allows for great flexibility in formulating and provides compositions which are chemically and physically s~able. ~s an additional benefit, the nonionic surfactant mixture used to emulsify the hydrophobic activator prov.ides efficient c~eaning.
, As an additional advantage, it has been ~ound that the nonionic sur~actant ystem used to~ emulsify said hydrophobic liquid ingredient~ ~improves the storage stability o~ hydrogen peroxide.
.. .
Although the present ~invention finds a preferred application in formulating activated bleaching compositions, the present invetion is also applicable to the formulation of bl~aching compositions which comprise any hydrophobic liquid ingredient which needs to be kept separate from the hydrogen peroxide.
SummarY of the in~ntion The present invention is an aqueous cleaninq and bleaching composition ha~ing a pH of ~from 0.5 to 6, comprising hydrogen peroxide or a source ~thereof and a hydrophobic li~uid i~ edient, preferably a bleach activa~or, wherein said hydrophobic liquid ingredient :is emulsified in said composition by a mixture comprising at:least one nonionic surfactant with an HLB that is hi~her. than or equal to the HLB of said hydrophobic liquid ingredient and at least:one nonionic surfactant with an ~L~ that~is lower than or e~ual to the HLB of said hydrophobic~ liquid ingredient, pro~ided that the HLBs of said nonionic surfactants , provided that the H1Bs of said:nonionic sur~actants are not identical.
W094/1147~ PCT/US93/10432 ~ '' The present invention also encompassPs a process for the manufacture o~ said composition.
Detailed descriptlon of the invention The compositions according to: the~present invention are aqueous. :Accordingly, the compositions according to the present invention comprise from 10% to 95~ by weight of the :
total composition of water~,-preferably from 30% to 90%, most preferably~ from 60% to 80%. Deionized water is pref~rably used. - ~
The compositions ~ac~ording to the present invention are based on hydrogen peroxide. ~ccordingly/ the compositions according to the ~present invention comprise hydrogen peroxide' or a water-soluble source thereof. Suitable water-soluble sources of hydrogen; peroxide : include perborate, percarbonate, persilicate:and persulphate-salts.
In a preferred:~mbodi~ment, the compositions according to the present ~ invention : comprise hydrogen peroxide.
Typically, the compositions : ac~ording to the present invention comprise from 0.5~ to 2d~ by weight of the total compqsition of~ hydrogen~ peroxide,~ preferably from 2% to 15%, most~preferably from 3%~:to 10~
~ : : : : : ..
T~e compositions of the present invention have a pH as is of~from 0.5~ to ~6. Formulati~ng~the compositions according: ~ -to the : present ~invention: ~in this ~acidic pH range~
contributes to the ~stability of the composition. In a preferred embodimen~, ~the~compos~itions are formulated in a ~ .-pH~range~:o~::from 1 to 5.:~ The:pH of the composition can be !~
tr ~d ~by all;means; available tb~ the~:man skilled in the ~ :
:The:compositions::accordin~ to the present invention further comprise~ a hydrophobic;llquid ingredient. As used herein,; .
~ W094tll475 ~1 4 9 3 2 0 '' PCT/US93/10432 ,..................................... .
the term "hydrophobic Iiquid ingredient" refers both to liquid ingredients, and ~solid materials which are dissolved in a hydrophobic }iquid phase prior to incorporation into the compositions of the invention. By hydrophobic, it is meant herein any material which is not substantially and stab}y miscible in water. Hydrophobic materials herein typically have an HLB below ll. In a preferred embodiment, said hydrophobic li~uid ingredient is a bleach activator.
.
By bleach activator~, it is meant herein any compound which reacts with hydrogen peroxide to form a peracid. In the case of bleach activators, such hydrophobic bleach activators typ~ically belong to the class of esters, amides, imides, or anhydrides.~ A particular family of bleac~
activators of interest in ~the ~present invention were disclosed in applicant's co-pending European patent application No 91870207.7.~ Particularly preferred in that~
family is acetyl triethyl citrate which~was also disclosed in the context of bar soaps in FR 2 362 21~. Acetyl triethyl citra~te~ has the ~ advantages that it is environmentally friendly as it ~eventually degrades into citric acid and alcohol.~ Furthermore,~ acetyl triethyl citrate has a good;hydrolytical ~tability in the product upon storage ~and it is an efficient bleach activator.
Finally, it ~;provides good building capacity to the composition. ;~ As ~ usèd ~herein~ and unless otherwise specified, the term~bleach~activator includes mixtures of bleach activators. Apart from bleach activators, ;hy~oyhobic llquid ~ingredients of~;intérest herein include~
hydrophobic peroxyacids, enzymes,~brighteners~,~ perfumes~and the like.
.
As used~ herein,~the ter~hydrophobic liquid ingredient refers to~single;ingredients~or~mixtures~thereof.
In the compositions~according ~to~ the present invention~, said~ hydrophobic liguid~ingredient~ is emulsifiéd in the composition by~ means ofma~mixture of nonio~ic surfactants:.
~ ~ .
W0~4/11475 ~4932~ ~ PCT/US93/1043~ ~ ~
Said mixture o~ nonionic surfactants comprises at least two nonionic sur~actants.
The first of said nonionic surfactant must have an HLB
which is lower than or equal to the HLB of said hydrophobic liquid ingredient, whereas the second nonionic surfactant must have an HLB~which~is higher than or equal to the HLB
of said hydrophobic liquid ingredient, provided the HLBs of said nonionic surfactants~ are not identical. In a preferred embodiment of the~ present invention the difference between the HLB values of the two nonionic surfactants herein must be of at least 3. Upon using this nonionic surfactant system, ~the hydrophobic liquid ingredient is stably emulsif~ied in the composition. The emulsion is physically stable and the hydropho~ic liguid ingredient is kept separate from the hydrogen peroxide, thus the compo~ition is also chemica}ly stable. Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols. Indeed, a great variety of such alkcxylated fatty alcohols are commercially available which have very different ~HLB values. The HLB valuas of such alkoxylated nonionic surfactants d~pend essentially on the chain length of the fatty alcohol, the nature of the alkoxyl~ation and~ the degree of alkoxylation.~ Hydrophilic nonionic~ surfactants tend to have a high degree of ethoxylation and a short chain fatty alcohol, ~while hydrophobic surfactants tend~ to~ have a low degree of ethoxylation and~a long chain ~fatty alcohol. Surfa~tants catalogs are available which~list a number of surfactants including nonionics, together' with their respective H~B
values. ; ~
The exact nonionic surfactant system to be ch~sen depends on the hydrophobic~ liquid~ ingredient to be emulsified.
Accordingly,~a~;suitable; way to proceed is~to determ~ine the HLB value of the~hydrophobic liquid ingredient, then~select two~nonionic surfactants which have H~B values below and ~ ~ t ~ WO94/11475 .~ 4 9 3 2 0 PCT/us93/l0432 above said HLB value of said hydrophobic liquid ingredient, wherein the di~ference in the H~B values of said nonionic surfactants is preferably at least 3.
In a preferred embodiment, the amount by weight of said nonionic surfactant with an HLB lower than or equal to the HLB of said hydrophobic liquid ingredient ~hould be at least equal to or higher than the weight amount of said liquid hydrophobic ingredient.
Also, the amount of said nonionic surfactant with an HLB
higher than or equa} to-the HLB of said liquid hydrophobic ingrdient should be chosen so that the weighted average of the HLB values of said nonionic surfactants is equal to the . HLB of said hydrophobic liquid ingredient.
~In other words, the emulsifying system meets the equation:
~A ~ : %B ~
H~B(X) = x HLB~A) + _ x HLB(B) and %A+~B = 100%;
: where X refers: to the hydrophobic liquid ingredient to : emulsify, A refers to one of said nonionic surfactants, and :
:~ ~ B refers to the other said nonionic surfactant.
:
.
In a~particularly preferred embodiment: of the invention, the hy~o~hobic liquid:ingredient is a bleach activator and : ; said bleach act~ivator is ~acetyl triethyl citrate. Acetyl triethyl citrate has an HLB of about lO. An adequate ~ ' nonionic surfactant~system would therefore comprise a first :~ nonionic surfactant with;an~H~B~from l to lOj and a second ' :nonionic: surfactan~ with an~ HLB of above ll. A
' particularly suitable~ Gystem comprises a :~first nonionic ; surfactant:with an ~L~ of about 6,~ for~instance a Dobanol : 23-2~and~a sécond non~ionic:~surfactant with an HLB of about lS, for instance a ~Dobanol~ ~ 9l-lO. Another suitab}e 2~93~: ' PCT/US93/10432 ~
~ i 8 nonionic surfactant system comprises a Dobanol ~ 23-6 5 (HLB about 12) and a Dobanol ~ 23 (HLB below 6~ All these Do~anol ~ surfactants are commercially available from Shell The compositions according to the present invention may further comprise other nonionic~ surfastants which should however not significantly alter the weighted average ~HLB
valu~ of the overall composition Preferably,the compositions ~ according to the present invention are' free of other surfactant types, especially anionic surfactants~
-' The compositions ~according to the present invention may further comprise the ~usual optional ingredients such ~as perfumes, dyes~ optica~ brighteners,~builders and chelants, pigments, enzymes, ~soil release agents, dye transfer inh'i~itors, solvents~,~buffering agents and~the like The present invention~further~'encompasses a process for the ma~nufacture of the; composition ~escribed herein The process according: to the present invention comprises at least thrée steps~
In'the first step,~a~hydrophobic~mixture is~prepared which comprises at least: said hydrophobiG liquid ingredient and said~;nonionic~surfactant with ~a~ 1Ow HLB This hydrophobic~
mixture preferably further~ comprises~other hydrophobic 'ingredients Which~ are~to be formulated in the composition, ~UCh as~ perfu _ s, -olvents, enzymes and polymers In~the~second~step, a~hydrophi~lic mixture is prepared which~
comprises~ at ~least~ said water,~said hydrogen peroxide~and said nonionic~surfactant with~a~hi~qh HLB Said hydrophilLc mixture~pre'ferably~further;~ comprises other hydrophilic n~ nts ~h~ r- to ~e ~mul~-ed in the~composition 1~ WO 94/1 1475 2 1 ~ ~ 3 2 0 Pcr/usg3/l0432 - : .
g such as dyes, optical brighteners, builders, chelants and buffering agents. In this second step hydrogen peroxide is pre~erably~added last, after said buffering agent has been added.
Naturally, said first and said~ second steps can be performed in any order, i.e second step first is also suitable.
~.
.
In the third step~of the process accordinq to the present invention, said~hydrophobic~ mixture and said hydrophilic mixture are mixed together.
The present invention is further~illustrated by the folIowing examples.
Exam~les Comp~sitions are~made which comprise~the listed ingredients in the listed~proportions (weight %).
III IV V
Dobanol ~45-7~ - 6.0 Dobanol ~ 91-10 ~ 6.6~ ~6.6 Dobanol ~ 23-2~ 8.~4 ~ 8.4 ~ 8.0 5.2 4.0 Dobanol-~ Z3-6.;5 ~ - ~ - 4~0 9.8 5.0 . .
Acetyl triethyl citrate~ 7.0 ~ 7.0 7.0 7.0 ~ 7.;0 Hyd~G~en peroxide 7.5 7.5 7.5 7-5 7-5 Citric acid 4.0 4.0 4.0 4.0 4.0 S,S-ethylene diamino ~
disuccinic a~cid~ 0.1 Brightener~4g ~ 0.1~ ~0 Deionized~water ~ balance --. : .. ~ . .
:
w094/1147~ 2 1 ~ 9 3 2 0 ' ~ ' ~ PCT/US93/10432 ~
1a Compositions I to IV are each made by preparing two mixtures. A hydrophilic mixture is prepared which comprises the water, citric acid, brightener, S,S-EDDS and the Dobanol ~ 9l-lO or Dobanol ~ 23-6.5. Hydrogen peroxide is added in said:hydrophilic mixture as last step, after the buffering agent is added. A second, hydrophobic, mixture is prepared which comprises the acetyl triethyl citrate and the Dobanol G 23-2.
Then said hydrophobic mixture is poured into said hydrophilic mixture, while mixing.
Compositions I to IV were obtained which were stable emulsions, both from a chemical and a phys~ical standpoint.
I
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:
AQUEOUS CLEANING AND BLEACHING COMPOSITION~CONTAINING
HYDROPHOBIC LIQUID, H202 AND TWO NONIONIC SURFACTANTS:WITH DIFFERENT HLBS
AAAAAil~AAAAAA
.':
: ' ;, : ' ;"
, .
;;' ':
~ ~ .
' , Technical field ~ :
The presen~ invent~ion~ relates to cl~in~ and ble~ching ~
compositions ~hich~;~re:h~F~ on hydrogen peroxide. ~ :
~ i Backqround ~ : .
Bleaching and cleaning compositions: have~ been extensively des~ribed;in the art. ;It; is:~also:~we:ll knuwn ~hat it::i~
des~irable:~ to~ us~e~: hydrogen ~peroxide rather ~han other bleachas su h~as chlorin~ type bleaches. ~ Indeed, ihydrogen peroxidP~is:much~mildèr~and there~ore safer~, both for the 'W094/11475 ~i493~~ PCT/US93/1~432 ~
, item being bleached and for the user. However, hydrogen peroxide based bleaches have the main inconvenient that they perform poorly at~low temperature. In response to ; this object, compositions have been desi~ned which further compri~e a bleach activator.~ The bleach activator reacts with hydroqen peroxide to ~yield a peraci~ which is the bleaching species.
Activate~ bleaching compositions however have the drawback that the activator and the hydrogen~peroxide ters~ to react in the composition~.~ ThUs ,~ such actlvated bleaching compositions tend to be chemically unstable upon storaqe.
It is an object of the present~ invention to provide activated bleaching ~compositions which are chemically stable.
; .
' Another problem~ is that bleach activators which are hydrophobic are problematic to use in aqueous compositions as the product tends to separate into two different layer phases which can be visualized by the consumer. Therefore, physical stability upon storage ig~a further issue.
Th~ present invention meets the above objects in proposing an aqueous cleaning and bleaching composition comprisin~
hydrogen peroxide and a li~uid hydropho~ic bleach activator, wherein said bleach activator is emùlsified in the composition by means of a specific nonionic surfactant mixture.
EP 497 337 describes suspensions of solid water-insoluble peroxyacids~in~agueous compositions comprising a mixture of two nonionic~ surfactants~ ~Compared to~the compo~itions in the '337 patent application,~the~compositions according to the present~ invention~allow for~ a ~aster dissolution of said liquid ~hydrophobic bleach~ activator in the ;wash~ ~, solution. ~
~ WO~4/11475 2 1 4 9 3 ~ O PCT/US93/10432 The present invention allows for great flexibility in formulating and provides compositions which are chemically and physically s~able. ~s an additional benefit, the nonionic surfactant mixture used to emulsify the hydrophobic activator prov.ides efficient c~eaning.
, As an additional advantage, it has been ~ound that the nonionic sur~actant ystem used to~ emulsify said hydrophobic liquid ingredient~ ~improves the storage stability o~ hydrogen peroxide.
.. .
Although the present ~invention finds a preferred application in formulating activated bleaching compositions, the present invetion is also applicable to the formulation of bl~aching compositions which comprise any hydrophobic liquid ingredient which needs to be kept separate from the hydrogen peroxide.
SummarY of the in~ntion The present invention is an aqueous cleaninq and bleaching composition ha~ing a pH of ~from 0.5 to 6, comprising hydrogen peroxide or a source ~thereof and a hydrophobic li~uid i~ edient, preferably a bleach activa~or, wherein said hydrophobic liquid ingredient :is emulsified in said composition by a mixture comprising at:least one nonionic surfactant with an HLB that is hi~her. than or equal to the HLB of said hydrophobic liquid ingredient and at least:one nonionic surfactant with an ~L~ that~is lower than or e~ual to the HLB of said hydrophobic~ liquid ingredient, pro~ided that the HLBs of said nonionic surfactants , provided that the H1Bs of said:nonionic sur~actants are not identical.
W094/1147~ PCT/US93/10432 ~ '' The present invention also encompassPs a process for the manufacture o~ said composition.
Detailed descriptlon of the invention The compositions according to: the~present invention are aqueous. :Accordingly, the compositions according to the present invention comprise from 10% to 95~ by weight of the :
total composition of water~,-preferably from 30% to 90%, most preferably~ from 60% to 80%. Deionized water is pref~rably used. - ~
The compositions ~ac~ording to the present invention are based on hydrogen peroxide. ~ccordingly/ the compositions according to the ~present invention comprise hydrogen peroxide' or a water-soluble source thereof. Suitable water-soluble sources of hydrogen; peroxide : include perborate, percarbonate, persilicate:and persulphate-salts.
In a preferred:~mbodi~ment, the compositions according to the present ~ invention : comprise hydrogen peroxide.
Typically, the compositions : ac~ording to the present invention comprise from 0.5~ to 2d~ by weight of the total compqsition of~ hydrogen~ peroxide,~ preferably from 2% to 15%, most~preferably from 3%~:to 10~
~ : : : : : ..
T~e compositions of the present invention have a pH as is of~from 0.5~ to ~6. Formulati~ng~the compositions according: ~ -to the : present ~invention: ~in this ~acidic pH range~
contributes to the ~stability of the composition. In a preferred embodimen~, ~the~compos~itions are formulated in a ~ .-pH~range~:o~::from 1 to 5.:~ The:pH of the composition can be !~
tr ~d ~by all;means; available tb~ the~:man skilled in the ~ :
:The:compositions::accordin~ to the present invention further comprise~ a hydrophobic;llquid ingredient. As used herein,; .
~ W094tll475 ~1 4 9 3 2 0 '' PCT/US93/10432 ,..................................... .
the term "hydrophobic Iiquid ingredient" refers both to liquid ingredients, and ~solid materials which are dissolved in a hydrophobic }iquid phase prior to incorporation into the compositions of the invention. By hydrophobic, it is meant herein any material which is not substantially and stab}y miscible in water. Hydrophobic materials herein typically have an HLB below ll. In a preferred embodiment, said hydrophobic li~uid ingredient is a bleach activator.
.
By bleach activator~, it is meant herein any compound which reacts with hydrogen peroxide to form a peracid. In the case of bleach activators, such hydrophobic bleach activators typ~ically belong to the class of esters, amides, imides, or anhydrides.~ A particular family of bleac~
activators of interest in ~the ~present invention were disclosed in applicant's co-pending European patent application No 91870207.7.~ Particularly preferred in that~
family is acetyl triethyl citrate which~was also disclosed in the context of bar soaps in FR 2 362 21~. Acetyl triethyl citra~te~ has the ~ advantages that it is environmentally friendly as it ~eventually degrades into citric acid and alcohol.~ Furthermore,~ acetyl triethyl citrate has a good;hydrolytical ~tability in the product upon storage ~and it is an efficient bleach activator.
Finally, it ~;provides good building capacity to the composition. ;~ As ~ usèd ~herein~ and unless otherwise specified, the term~bleach~activator includes mixtures of bleach activators. Apart from bleach activators, ;hy~oyhobic llquid ~ingredients of~;intérest herein include~
hydrophobic peroxyacids, enzymes,~brighteners~,~ perfumes~and the like.
.
As used~ herein,~the ter~hydrophobic liquid ingredient refers to~single;ingredients~or~mixtures~thereof.
In the compositions~according ~to~ the present invention~, said~ hydrophobic liguid~ingredient~ is emulsifiéd in the composition by~ means ofma~mixture of nonio~ic surfactants:.
~ ~ .
W0~4/11475 ~4932~ ~ PCT/US93/1043~ ~ ~
Said mixture o~ nonionic surfactants comprises at least two nonionic sur~actants.
The first of said nonionic surfactant must have an HLB
which is lower than or equal to the HLB of said hydrophobic liquid ingredient, whereas the second nonionic surfactant must have an HLB~which~is higher than or equal to the HLB
of said hydrophobic liquid ingredient, provided the HLBs of said nonionic surfactants~ are not identical. In a preferred embodiment of the~ present invention the difference between the HLB values of the two nonionic surfactants herein must be of at least 3. Upon using this nonionic surfactant system, ~the hydrophobic liquid ingredient is stably emulsif~ied in the composition. The emulsion is physically stable and the hydropho~ic liguid ingredient is kept separate from the hydrogen peroxide, thus the compo~ition is also chemica}ly stable. Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols. Indeed, a great variety of such alkcxylated fatty alcohols are commercially available which have very different ~HLB values. The HLB valuas of such alkoxylated nonionic surfactants d~pend essentially on the chain length of the fatty alcohol, the nature of the alkoxyl~ation and~ the degree of alkoxylation.~ Hydrophilic nonionic~ surfactants tend to have a high degree of ethoxylation and a short chain fatty alcohol, ~while hydrophobic surfactants tend~ to~ have a low degree of ethoxylation and~a long chain ~fatty alcohol. Surfa~tants catalogs are available which~list a number of surfactants including nonionics, together' with their respective H~B
values. ; ~
The exact nonionic surfactant system to be ch~sen depends on the hydrophobic~ liquid~ ingredient to be emulsified.
Accordingly,~a~;suitable; way to proceed is~to determ~ine the HLB value of the~hydrophobic liquid ingredient, then~select two~nonionic surfactants which have H~B values below and ~ ~ t ~ WO94/11475 .~ 4 9 3 2 0 PCT/us93/l0432 above said HLB value of said hydrophobic liquid ingredient, wherein the di~ference in the H~B values of said nonionic surfactants is preferably at least 3.
In a preferred embodiment, the amount by weight of said nonionic surfactant with an HLB lower than or equal to the HLB of said hydrophobic liquid ingredient ~hould be at least equal to or higher than the weight amount of said liquid hydrophobic ingredient.
Also, the amount of said nonionic surfactant with an HLB
higher than or equa} to-the HLB of said liquid hydrophobic ingrdient should be chosen so that the weighted average of the HLB values of said nonionic surfactants is equal to the . HLB of said hydrophobic liquid ingredient.
~In other words, the emulsifying system meets the equation:
~A ~ : %B ~
H~B(X) = x HLB~A) + _ x HLB(B) and %A+~B = 100%;
: where X refers: to the hydrophobic liquid ingredient to : emulsify, A refers to one of said nonionic surfactants, and :
:~ ~ B refers to the other said nonionic surfactant.
:
.
In a~particularly preferred embodiment: of the invention, the hy~o~hobic liquid:ingredient is a bleach activator and : ; said bleach act~ivator is ~acetyl triethyl citrate. Acetyl triethyl citrate has an HLB of about lO. An adequate ~ ' nonionic surfactant~system would therefore comprise a first :~ nonionic surfactant with;an~H~B~from l to lOj and a second ' :nonionic: surfactan~ with an~ HLB of above ll. A
' particularly suitable~ Gystem comprises a :~first nonionic ; surfactant:with an ~L~ of about 6,~ for~instance a Dobanol : 23-2~and~a sécond non~ionic:~surfactant with an HLB of about lS, for instance a ~Dobanol~ ~ 9l-lO. Another suitab}e 2~93~: ' PCT/US93/10432 ~
~ i 8 nonionic surfactant system comprises a Dobanol ~ 23-6 5 (HLB about 12) and a Dobanol ~ 23 (HLB below 6~ All these Do~anol ~ surfactants are commercially available from Shell The compositions according to the present invention may further comprise other nonionic~ surfastants which should however not significantly alter the weighted average ~HLB
valu~ of the overall composition Preferably,the compositions ~ according to the present invention are' free of other surfactant types, especially anionic surfactants~
-' The compositions ~according to the present invention may further comprise the ~usual optional ingredients such ~as perfumes, dyes~ optica~ brighteners,~builders and chelants, pigments, enzymes, ~soil release agents, dye transfer inh'i~itors, solvents~,~buffering agents and~the like The present invention~further~'encompasses a process for the ma~nufacture of the; composition ~escribed herein The process according: to the present invention comprises at least thrée steps~
In'the first step,~a~hydrophobic~mixture is~prepared which comprises at least: said hydrophobiG liquid ingredient and said~;nonionic~surfactant with ~a~ 1Ow HLB This hydrophobic~
mixture preferably further~ comprises~other hydrophobic 'ingredients Which~ are~to be formulated in the composition, ~UCh as~ perfu _ s, -olvents, enzymes and polymers In~the~second~step, a~hydrophi~lic mixture is prepared which~
comprises~ at ~least~ said water,~said hydrogen peroxide~and said nonionic~surfactant with~a~hi~qh HLB Said hydrophilLc mixture~pre'ferably~further;~ comprises other hydrophilic n~ nts ~h~ r- to ~e ~mul~-ed in the~composition 1~ WO 94/1 1475 2 1 ~ ~ 3 2 0 Pcr/usg3/l0432 - : .
g such as dyes, optical brighteners, builders, chelants and buffering agents. In this second step hydrogen peroxide is pre~erably~added last, after said buffering agent has been added.
Naturally, said first and said~ second steps can be performed in any order, i.e second step first is also suitable.
~.
.
In the third step~of the process accordinq to the present invention, said~hydrophobic~ mixture and said hydrophilic mixture are mixed together.
The present invention is further~illustrated by the folIowing examples.
Exam~les Comp~sitions are~made which comprise~the listed ingredients in the listed~proportions (weight %).
III IV V
Dobanol ~45-7~ - 6.0 Dobanol ~ 91-10 ~ 6.6~ ~6.6 Dobanol ~ 23-2~ 8.~4 ~ 8.4 ~ 8.0 5.2 4.0 Dobanol-~ Z3-6.;5 ~ - ~ - 4~0 9.8 5.0 . .
Acetyl triethyl citrate~ 7.0 ~ 7.0 7.0 7.0 ~ 7.;0 Hyd~G~en peroxide 7.5 7.5 7.5 7-5 7-5 Citric acid 4.0 4.0 4.0 4.0 4.0 S,S-ethylene diamino ~
disuccinic a~cid~ 0.1 Brightener~4g ~ 0.1~ ~0 Deionized~water ~ balance --. : .. ~ . .
:
w094/1147~ 2 1 ~ 9 3 2 0 ' ~ ' ~ PCT/US93/10432 ~
1a Compositions I to IV are each made by preparing two mixtures. A hydrophilic mixture is prepared which comprises the water, citric acid, brightener, S,S-EDDS and the Dobanol ~ 9l-lO or Dobanol ~ 23-6.5. Hydrogen peroxide is added in said:hydrophilic mixture as last step, after the buffering agent is added. A second, hydrophobic, mixture is prepared which comprises the acetyl triethyl citrate and the Dobanol G 23-2.
Then said hydrophobic mixture is poured into said hydrophilic mixture, while mixing.
Compositions I to IV were obtained which were stable emulsions, both from a chemical and a phys~ical standpoint.
I
; ~ , :
:
: ~ , :: :
:
r : ~ ' ~ :
: '
Claims (10)
1. An aqueous cleaning and bleaching composition having a pH of from about 0.5 to about 6, comprising hydrogen peroxide or a source thereof and a hydrophobic liquid ingredient, characterized in that said hydrophobic liquid ingredient is emulsified in said composition by a mixture comprising at least one nonionic surfactant with an HLB that is higher than or equal to the HLB of said hydrophobic liquid ingredient and at least one nonionic surfactant with an HLB that is lower than or equal to the HLB of said hydrophobic liquid ingredient, provided that the HLBs of said nonionic surfactants are not identical.
2. A composition according to claim 1 wherein said hydrophobic liquid ingredient is a bleach activator.
3. A composition according to claim 2 wherein said bleach activator is acetyl triethyl citrate.
4. A composition according to claim 1 which has a pH of from about 1 to about 5.
5. A composition according to claim 1 which comprises from about 0.5% to about 20% by weight of the total composition of hydrogen peroxide.
6. A composition according to claim 3 wherein said nonionic surfactant with a high HLB has an HLB above about 11.
7. A composition according to claim 3 wherein said nonionic surfactant with a low HLB has an HLB of from about 1 to about 10.
8. A composition according to claim 1 wherein said emulsifying system meets the equation:
where X refers to the hydrophobic liquid ingredient to emulsify, A
refers to one of said nonionic surfactants, and B refers to the other said nonionic surfactant.
where X refers to the hydrophobic liquid ingredient to emulsify, A
refers to one of said nonionic surfactants, and B refers to the other said nonionic surfactant.
9. A process for the manufacture of a composition according to claim 1 wherein:
- a hydrophobic mixture is prepared which comprises at least said hydrophobic liquid ingredient and said nonionic surfactant with a low HLB;
- a hydrophilic mixture is prepared which comprises at least said water, said hydrogen peroxide or source thereof and said nonionic surfactant with a high HLB;
- said hydrophobic mixture and said hydrophilic mixture are mixed together.
- a hydrophobic mixture is prepared which comprises at least said hydrophobic liquid ingredient and said nonionic surfactant with a low HLB;
- a hydrophilic mixture is prepared which comprises at least said water, said hydrogen peroxide or source thereof and said nonionic surfactant with a high HLB;
- said hydrophobic mixture and said hydrophilic mixture are mixed together.
10. A process according to claim 9 wherein said hydrogen peroxide or source thereof is added last in the preparation of said hydrophilic mixture.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP92870188A EP0598170B1 (en) | 1992-11-16 | 1992-11-16 | Cleaning and bleaching compositions |
| EP92870188.7 | 1992-11-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2149320A1 CA2149320A1 (en) | 1994-05-26 |
| CA2149320C true CA2149320C (en) | 1999-02-02 |
Family
ID=8212286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002149320A Expired - Fee Related CA2149320C (en) | 1992-11-16 | 1993-10-29 | Aqueous cleaning and bleaching composition containing hydrophobic liquid, h2o2 and two nonionic surfactants with different hlbs |
Country Status (12)
| Country | Link |
|---|---|
| EP (2) | EP0598170B1 (en) |
| JP (1) | JP3285868B2 (en) |
| AT (2) | ATE163037T1 (en) |
| AU (1) | AU683858B2 (en) |
| BR (1) | BR9307462A (en) |
| CA (1) | CA2149320C (en) |
| DE (2) | DE69224389T2 (en) |
| DK (2) | DK0598170T3 (en) |
| ES (2) | ES2113421T3 (en) |
| GR (2) | GR3026437T3 (en) |
| RU (1) | RU2135558C1 (en) |
| WO (1) | WO1994011475A1 (en) |
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| DE69322744T2 (en) * | 1992-11-16 | 1999-07-22 | The Procter & Gamble Co., Cincinnati, Ohio | Stable, nonionic surfactant emulsions that contain viscosity control agents |
| US5409632A (en) * | 1992-11-16 | 1995-04-25 | The Procter & Gamble Company | Cleaning and bleaching composition with amidoperoxyacid |
| EP0600847B2 (en) * | 1992-11-26 | 2001-10-31 | The Procter & Gamble Company | Cleaning compositions with combined highly hydrophilic and highly hydrophobic nonionic surfactants |
| EP0598973A1 (en) * | 1992-11-26 | 1994-06-01 | The Procter & Gamble Company | Multi-purpose liquid cleaning composition |
| ATE169953T1 (en) * | 1993-06-09 | 1998-09-15 | Procter & Gamble | METHOD FOR BLEACHING TISSUES |
| US5713962A (en) * | 1993-06-09 | 1998-02-03 | The Procter & Gamble Company | Process for the bleaching of fabrics |
| US5902354A (en) * | 1994-04-12 | 1999-05-11 | The Procter & Gamble Company | Bleaching compositions |
| EP0686691B1 (en) * | 1994-06-10 | 2001-08-08 | The Procter & Gamble Company | Aqueous emulsions with brighteners |
| DE69423613T2 (en) * | 1994-06-17 | 2000-11-02 | The Procter & Gamble Company, Cincinnati | Bleaching compositions |
| US5880079A (en) * | 1994-06-17 | 1999-03-09 | The Procter & Gamble Company | Bleaching compositions |
| US5879584A (en) * | 1994-09-10 | 1999-03-09 | The Procter & Gamble Company | Process for manufacturing aqueous compositions comprising peracids |
| GB9423374D0 (en) * | 1994-11-19 | 1995-01-11 | Procter & Gamble | Peroxyacid bleach precursor compositions |
| AU4370896A (en) * | 1994-11-25 | 1996-06-19 | Procter & Gamble Company, The | Thickened bleaching compositions, method of use and process for making them |
| GB9425882D0 (en) * | 1994-12-21 | 1995-02-22 | Solvay Interox Ltd | Thickened peracid compositions |
| EP0751214A1 (en) * | 1995-06-30 | 1997-01-02 | The Procter & Gamble Company | Stable peroxygen bleach-containing compositions |
| DE69525526T2 (en) | 1995-03-27 | 2002-10-31 | The Procter & Gamble Company, Cincinnati | Liquid activated bleaching compositions |
| EP0742279A1 (en) * | 1995-05-10 | 1996-11-13 | The Procter & Gamble Company | Acidic aqueous liquid compositions |
| EP0745663A1 (en) * | 1995-05-31 | 1996-12-04 | The Procter & Gamble Company | Colored acidic aqueous liquid compositions comprising a peroxy-bleach |
| EP0751210A1 (en) * | 1995-06-27 | 1997-01-02 | The Procter & Gamble Company | Bleaching compositions |
| EP0779357A1 (en) * | 1995-12-16 | 1997-06-18 | The Procter & Gamble Company | Stable emulsions comprising a hydrophobic liquid ingredient |
| EP0784091A1 (en) | 1996-01-12 | 1997-07-16 | The Procter & Gamble Company | Stable perfumed bleaching composition |
| US6248705B1 (en) | 1996-01-12 | 2001-06-19 | The Procter & Gamble Company | Stable perfumed bleaching compositions |
| US5879409A (en) * | 1996-02-23 | 1999-03-09 | The Procter & Gamble Company | Bleach additive and bleaching compositions having glycine anhydride activators |
| DE19635070A1 (en) * | 1996-08-30 | 1998-03-05 | Clariant Gmbh | Liquid bleach suspension |
| EP0913463A1 (en) * | 1997-10-31 | 1999-05-06 | The Procter & Gamble Company | Multi-purpose liquid aqueous bleaching compositions |
| WO1999038481A1 (en) * | 1998-01-29 | 1999-08-05 | The Procter & Gamble Company | Method for cleaning dentures |
| US6613726B1 (en) | 1998-11-10 | 2003-09-02 | Leo Gagliardi | Bleaching compositions |
| DE60114361T2 (en) | 2001-03-26 | 2006-07-20 | The Procter & Gamble Company, Cincinnati | Process for cleaning hard surfaces with a bleach-containing liquid detergent |
| DE10136208A1 (en) * | 2001-07-25 | 2003-02-13 | Henkel Kgaa | Acidic aqueous detergent |
| RU2371532C1 (en) * | 2008-08-18 | 2009-10-27 | Институт прикладной механики УрО РАН | Method of express cleaning of blood stains off clothes |
| US8969283B2 (en) | 2009-02-05 | 2015-03-03 | American Sterilizer Company | Low odor, hard surface sporicides and chemical decontaminants |
| US20110166370A1 (en) | 2010-01-12 | 2011-07-07 | Charles Winston Saunders | Scattered Branched-Chain Fatty Acids And Biological Production Thereof |
| EP2678410B1 (en) | 2011-02-17 | 2017-09-13 | The Procter and Gamble Company | Composiitons comprising mixtures of c10-c13 alkylphenyl sulfonates |
| WO2012112828A1 (en) | 2011-02-17 | 2012-08-23 | The Procter & Gamble Company | Bio-based linear alkylphenyl sulfonates |
| WO2023049927A1 (en) * | 2021-09-27 | 2023-03-30 | Quaker Chemical Corporation | Stable resin methods and compositions for aqueous treatments |
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| GB1589866A (en) * | 1976-08-20 | 1981-05-20 | Unilever Ltd | Detergent bars for personal washing |
| US4146499A (en) * | 1976-09-18 | 1979-03-27 | Rosano Henri L | Method for preparing microemulsions |
| GB8310081D0 (en) * | 1983-04-14 | 1983-05-18 | Interox Chemicals Ltd | Peroxygen compounds |
| GB8500116D0 (en) * | 1985-01-03 | 1985-02-13 | Unilever Plc | Liquid bleaching compositions |
| GB8508010D0 (en) * | 1985-03-27 | 1985-05-01 | Unilever Plc | Liquid bleaching compositions |
| US4909962A (en) * | 1986-09-02 | 1990-03-20 | Colgate-Palmolive Co. | Laundry pre-spotter comp. providing improved oily soil removal |
| NZ221505A (en) * | 1986-09-09 | 1989-08-29 | Colgate Palmolive Co | Liquid detergent compositions with peroxygen bleach and calcium cyanamide activator |
| US4764302A (en) * | 1986-10-21 | 1988-08-16 | The Clorox Company | Thickening system for incorporating fluorescent whitening agents |
| US4804491A (en) * | 1986-11-03 | 1989-02-14 | The Clorox Company | Aqueous based acidic hard surface cleaner |
| JPS63161089A (en) * | 1986-12-24 | 1988-07-04 | ライオン株式会社 | bleach composition |
| US4889651A (en) * | 1988-01-21 | 1989-12-26 | Colgate-Palmolive Company | Acetylated sugar ethers as bleach activators and detergency boosters |
| US5047168A (en) * | 1988-01-21 | 1991-09-10 | Colgate-Palmolive Co. | Sugar ethers as bleach stable detergency boosters |
| SU1682432A1 (en) * | 1988-06-14 | 1991-10-07 | Московский Текстильный Институт Им.А.Н.Косыгина | Composition for bleaching cotton fabrics |
| US4891147A (en) * | 1988-11-25 | 1990-01-02 | The Clorox Company | Stable liquid detergent containing insoluble oxidant |
| DE3842007A1 (en) * | 1988-12-14 | 1990-06-21 | Henkel Kgaa | FLUID TO PASTOESES, BLEACHING DETERGENT |
| DE3907131A1 (en) * | 1989-03-06 | 1990-09-13 | Henkel Kgaa | BLEACH SUSPENSION |
| GB8928631D0 (en) * | 1989-12-19 | 1990-02-21 | Procter & Gamble | Concentrated aqueous liquid bleach compositions |
| TW291496B (en) * | 1991-02-01 | 1996-11-21 | Hoechst Ag | |
| JPH05171195A (en) * | 1991-12-25 | 1993-07-09 | Lion Corp | Bleachable composition |
| CA2062006C (en) * | 1992-02-27 | 1996-12-10 | Lucien Vallieres | Disinfectant with wide spectrum germicidal activity |
-
1992
- 1992-11-16 EP EP92870188A patent/EP0598170B1/en not_active Expired - Lifetime
- 1992-11-16 AT AT92870188T patent/ATE163037T1/en not_active IP Right Cessation
- 1992-11-16 ES ES92870188T patent/ES2113421T3/en not_active Expired - Lifetime
- 1992-11-16 DE DE69224389T patent/DE69224389T2/en not_active Expired - Lifetime
- 1992-11-16 DK DK92870188.7T patent/DK0598170T3/en active
-
1993
- 1993-10-04 AT AT93870198T patent/ATE163038T1/en not_active IP Right Cessation
- 1993-10-04 DE DE69316842T patent/DE69316842T2/en not_active Expired - Fee Related
- 1993-10-04 EP EP93870198A patent/EP0598694B1/en not_active Expired - Lifetime
- 1993-10-04 DK DK93870198.4T patent/DK0598694T3/en active
- 1993-10-04 ES ES93870198T patent/ES2113521T3/en not_active Expired - Lifetime
- 1993-10-29 CA CA002149320A patent/CA2149320C/en not_active Expired - Fee Related
- 1993-10-29 WO PCT/US1993/010432 patent/WO1994011475A1/en not_active Ceased
- 1993-10-29 JP JP51213494A patent/JP3285868B2/en not_active Expired - Fee Related
- 1993-10-29 RU RU95113166A patent/RU2135558C1/en active
- 1993-10-29 BR BR9307462A patent/BR9307462A/en not_active Application Discontinuation
- 1993-10-29 AU AU54559/94A patent/AU683858B2/en not_active Ceased
-
1998
- 1998-03-24 GR GR980400624T patent/GR3026437T3/en unknown
- 1998-04-07 GR GR980400752T patent/GR3026562T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| GR3026437T3 (en) | 1998-06-30 |
| EP0598170B1 (en) | 1998-02-04 |
| JPH08503017A (en) | 1996-04-02 |
| ATE163038T1 (en) | 1998-02-15 |
| DK0598694T3 (en) | 1998-03-02 |
| EP0598694A1 (en) | 1994-05-25 |
| EP0598170A1 (en) | 1994-05-25 |
| AU5455994A (en) | 1994-06-08 |
| WO1994011475A1 (en) | 1994-05-26 |
| DE69224389T2 (en) | 1998-08-13 |
| ES2113421T3 (en) | 1998-05-01 |
| RU2135558C1 (en) | 1999-08-27 |
| DK0598170T3 (en) | 1998-03-02 |
| ES2113521T3 (en) | 1998-05-01 |
| ATE163037T1 (en) | 1998-02-15 |
| DE69316842T2 (en) | 1998-09-10 |
| RU95113166A (en) | 1997-01-10 |
| DE69316842D1 (en) | 1998-03-12 |
| BR9307462A (en) | 1999-08-24 |
| CA2149320A1 (en) | 1994-05-26 |
| GR3026562T3 (en) | 1998-07-31 |
| DE69224389D1 (en) | 1998-03-12 |
| AU683858B2 (en) | 1997-11-27 |
| JP3285868B2 (en) | 2002-05-27 |
| EP0598694B1 (en) | 1998-02-04 |
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