WO1999032598A1 - Systeme perfectionne de blanchiment par l'oxygene - Google Patents

Systeme perfectionne de blanchiment par l'oxygene Download PDF

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Publication number
WO1999032598A1
WO1999032598A1 PCT/US1997/023480 US9723480W WO9932598A1 WO 1999032598 A1 WO1999032598 A1 WO 1999032598A1 US 9723480 W US9723480 W US 9723480W WO 9932598 A1 WO9932598 A1 WO 9932598A1
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WO
WIPO (PCT)
Prior art keywords
aqueous component
component chamber
aqueous
chamber
separate chambers
Prior art date
Application number
PCT/US1997/023480
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English (en)
Inventor
Shuichi Tsunetsugu
Original Assignee
The Procter & Gamble Company
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP11509766A priority Critical patent/JP2000516299A/ja
Priority to PCT/US1997/023480 priority patent/WO1999032598A1/fr
Priority to AU57095/98A priority patent/AU5709598A/en
Publication of WO1999032598A1 publication Critical patent/WO1999032598A1/fr

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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • 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
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • 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

Definitions

  • the present invention relates to methods for making and using oxygen bleaches. Specifically, the present invention relates to methods for making and using oxygen bleaching systems in cleaning compositions, and a kit for making such oxygen bleaching systems.
  • BACKGROUND Bleaching agents are highly desired in cleaning compositions because they provide improved whitening and cleaning.
  • consumers desire oxygen bleaches, because they are generally safe on fibers and fabrics, as well as hard surfaces. They are compatible with enzymes present in cleaning compositions, tend not to damage colored and/or brightly dyed fabrics, and do not damage fabric if there is accidental overuse of the oxygen bleach.
  • the cleaning and bleaching efficacy of bleaching agents, and in particular oxygen bleaches can be significantly increased by combining a bleach activator with the bleaching agent. Therefore, oxygen bleaches often consist of at least an active oxygen source and a bleach activator. In the presence of an alkalinity source and moisture, these active oxygen sources and bleach activators evolve available peroxyacid oxygen. While not intending to be limited by theory, it is believed that it is the production of this available peroxyacid oxygen which provides effective oxygen bleaching activity.
  • Non-granular cleaning compositions are sometimes preferred over granular detergents, because they have good dispersion and solubility in the wash solution.
  • the active oxygen source and/or the bleach activator contained in these non-granular cleaning compositions can sometimes degrade over time, because they are usually mixed together with the alkalinity source. This equates to a limited shelf-life for compositions containing these bleaching materials, as well as a drop in cleaning performance over time. It is therefore desired to maintain the stability of oxygen bleaches over time.
  • the present invention relates to a method for providing a plurality of separate chambers to make and use an activated bleach mixture.
  • the separate chambers include an aqueous component chamber which has from about 10% to about 90% moisture and an aqueous component, and a non-aqueous component chamber which has a non-aqueous solvent and a non-aqueous component.
  • the separate chambers maintain the contents of the aqueous component chamber and the non-aqueous component chamber in a substantially unmixed state.
  • an alkalinity source is also provided.
  • An activated bleach mixture is made by commingling the contents of the aqueous component chamber, the non-aqueous component chamber, and the alkalinity source. This forms an activated bleach mixture having an available peroxyacid oxygen level of at least about 200 ppm. The activated bleach mixture can then be used in a cleaning application.
  • the current invention also provides for a kit for making and using an activated bleach mixture.
  • Fig. 1 shows a dual chamber embodiment of the current invention.
  • Fig. 2 shows a cross-sectional view of Fig. 1 as seen along line 1-1.
  • Fig. 3 shows a triple chamber embodiment of the current invention.
  • Fig. 4 shows a triple chamber embodiment of the current invention.
  • the above drawings are for reference purposes only, and not necessarily drawn to scale.
  • DETAILED DESCRIPTION it has been found that an oxygen bleaching system can possess surprising stability over time in a cleaning composition and have improved cleaning properties.
  • the oxygen bleaching system herein physically separates at least one of the active oxygen source, the bleach activator, and the alkalinity source, until they are commingled to form an activated bleach mixture.
  • the activated bleach mixture can then be used in a cleaning application. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (°C) unless otherwise specified. All documents cited are incorporated herein by reference.
  • low-polarity indicates those non-aqueous solvents which have little, if any, tendency to dissolve the preferred types of particulate materials which can be suspended in the compositions prepared herein, e.g., the active oxygen sources, sodium perborate or sodium percarbonate.
  • moisture as used herein includes both free and bound moisture, as well as free and bound water.
  • non-aqueous refers to compositions having less than about 5% moisture, preferably less than about 1% moisture by weight.
  • ppm as used herein is an acronym for "parts per million.”
  • the bleaching system has at least two separate chambers, containing an active oxygen source, a bleach activator, moisture, and an alkalinity source.
  • the separate chambers provide a means to maintain the contents thereof in a substantially unmixed state until the user is ready to activate and use the bleaching system.
  • the user commingles the contents of the separate chambers. This commingling combines the active oxygen source, the bleach activator, the alkalinity source, and moisture, which in turn forms the activated bleach mixture.
  • the formed activated bleach mixture has an available peroxyacid oxygen level of at least 200 ppm.
  • the bleaching system of the invention is based upon three basic principles: (1) there must be at least one aqueous component chamber and at least one non-aqueous component chamber (hereinafter, "principle 1"); (2) there must be an active oxygen source, a bleach activator, and an alkalinity source (hereinafter, “principle 2"); and (3) the active oxygen source, the bleach activator, and the alkalinity source should not all be in the same separate chamber (hereinafter, "principle 3").
  • the active oxygen source, bleach activator, and alkalinity source are separated by placing them in at least two separate chambers.
  • at least one separate chamber is an aqueous component chamber which contains from about 10% to about 90% moisture and an aqueous component.
  • At least one other separate chamber is a non-aqueous component chamber containing a non-aqueous solvent and a non-aqueous component.
  • the active oxygen source can be in one of the above chambers, and a bleach activator can be in the other chamber.
  • an alkalinity source which, subject to principle 3, can be in either of the separate chambers, or both of the separate chambers.
  • the active oxygen source is part of the aqueous component and located within the aqueous component chamber, while the bleach activator and the alkalinity source are part of the non- aqueous component and located in the non-aqueous component chamber.
  • the alkalinity, moisture, bleach activator, and active oxygen source cause either the active oxygen source and/or the bleach activator to degrade.
  • the separate chambers of the invention help to maintain oxygen bleaching system stability, because they maintain the alkalinity, bleach activator, and active oxygen source in a substantially unmixed state.
  • the contents of the separate chambers can have many physical forms such as, for example, liquids, gels, pastes, suspensions of particles in a liquid, suspensions of particles in a gel, emulsions, etc. Least preferred for use in the separate chambers are granular and solid forms.
  • the contents of the separate chambers are commingled. This commingled mixture then forms an activated bleach mixture having an available peroxyacid oxygen level of at least 200 ppm.
  • the activated bleach mixture is then ready to be used in a cleaning application.
  • the activated bleach mixture can then be used in a laundry application as either a pre-treater, and/or added to the wash cycle. It is preferred that the activated bleach mixture be removed from the separate chambers for use and that the separate chambers do not enter the wash cycle; in a preferred embodiment, the activated bleach mixture is poured from the separate chambers into the wash cycle.
  • each separate chamber can be either an aqueous component chamber, or a non-aqueous component chamber; however, as noted in principle 1 , there must be at least one aqueous component chamber and at least one non- aqueous component chamber.
  • Aqueous components and moisture are only found in aqueous component chambers.
  • Non-aqueous components and non- aqueous solvents are only found in non-aqueous component chambers. Accordingly, the total number of separate chambers is variable, but must be at least two, because of principle 1.
  • the contents of each corresponding aqueous component and each specific non-aqueous component are also variable.
  • the active oxygen source, the bleach activator, and the alkalinity source should be divided among the aqueous component chamber(s) and the non-aqueous component chamber(s) according to principle 3, so as to provide maximum stability. It is preferred that the active oxygen source and the bleach activator be located in separate chambers.
  • the aqueous component can contain either one or two of the following: the active oxygen source, the bleach activator, and the alkalinity source. Accordingly, the non-aqueous component, subject to principle 2 and principle 3, would contain at a minimum the other remaining compound, or remaining two compounds.
  • Table 1 shows four preferred embodiments having only two chambers, with the alkalinity source contained therein.
  • AOS indicates the active oxygen source
  • BA indicates the bleach activator
  • AS indicates the alkalinity source.
  • the alkalinity source should be in at least one of the separate chambers.
  • Other non-listed embodiments are also included herein, such as, for example, when the aqueous component chamber contains an active oxygen source and bleach activator, and the non- aqueous component chamber contains an alkalinity source and a bleach activator. If a surfactant component is included, then it can be included in either the aqueous chamber, the non-aqueous chamber, or both.
  • Embodiments of the invention which have only two chambers are referred to as “dual chamber” embodiments.
  • each chamber holds either an active oxygen source, a bleach activator, or a surfactant component.
  • triple chamber embodiments not shown in Table 2 are also operable and included herein.
  • Table 2 assumes that the active oxygen source, the bleach activator, and the surfactant component are located in three separate chambers.
  • the presence of the alkalinity source is not specifically indicated; however, it will be recognized that because the bleach activator and the active oxygen source are already separated, the alkalinity source can be in any, multiple, or even all three of the separate chambers. Table 2
  • embodiment 1 in Table 2 has two aqueous component chambers (the first containing the active oxygen source, and the second containing the bleach activator), and one non-aqueous component chamber (containing the surfactant component).
  • triple chamber package embodiments are described in Fig. 3 and Fig. 4.
  • the active oxygen source, the bleach activator, the alkalinity source, and the surfactant component are located in four separate chambers. Because each separate chamber can be either aqueous or non- aqueous (subject to principle 1), the possible permutations of these further embodiments increase exponentially. It is preferred that the bleaching system described herein have from about 2 to about 5 separate chambers.
  • the separate chambers can be positioned in many different arrangements. For example, they can be made as unattached chambers, or as a single package having attached chambers and an adjoining partition, as seen for example in Fig. 1.
  • the separate chambers can also be constructed so as to be rigid, flexible, or both, as desired. Furthermore, depending upon the relative amounts and concentrations of the contents of thereof, the separate chambers can be made to contain the same volume, or different volumes.
  • the bleaching system can be designed such that the activated bleach mixture can be made either outside of the separate chambers or within a package which is divided into separate chambers, such as described below. Gas-generating ingredients, such as oxygen bleach precursors can be and are intended for use herein. Therefore, if the activated bleach mixture is to be made within the package, it is preferred that the separate chambers of the package be made or filled so as to take into account gas evolution therein.
  • a single package is divided into separate chambers via an adjoining partition, and the activated bleach mixture is made in the single package. If gas is evolved therein, the separate chambers should be sealed such that the separate chambers do not prematurely rupture due to internal pressure.
  • the separate chambers can be made of many materials, so long as the separate chambers maintain the contents thereof in a substantially unmixed state.
  • Preferred separate chamber materials are materials which are clear, flexible, and/or water and solvent-impervious. Examples of preferred separate chamber materials useful herein are plastics, coated papers, foils, membranes, nylon, and combinations thereof. More preferred separate chamber materials include laminated nylon, thin plastics, and combinations thereof.
  • the separate chambers can be made of the same materials or of different materials, as desired.
  • the means to seal the separate chambers also varies according to the type of material, but preferred sealing means for flexible portions of the separate chambers are heat sealing, ultrasonic sealing, adhesives, and combinations thereof. Preferred sealing means for rigid portions of the separate chambers are threaded screws, adhesives, hinges, snap-type closures, and combinations thereof.
  • the separate chambers are made of a flexible material, because they allow the contents of the separate chambers to be easily commingled when the seal is broken or removed. Flexible materials also allow the activated bleach mixture to be easily dispensed for use.
  • the separate chambers are made from a flexible material and are heat sealed to form one or more outer seals. An embodiment of such a seal is seen for example, in Fig. 1 at 3.
  • the separate chambers have at least one spout and/or perforation to facilitate dispensing of the contents.
  • the separate chambers may also contain, in addition to the outer seal, breaking seals and non-breaking seals to further partition the package.
  • the total number of seals present can vary according to the type of materials used for the separate chambers, the number of separate chambers, their alignment, etc.
  • one of more breaking seals can be used, especially between separate chambers which are made with a flexible material. Breaking seals are intended to prevent commingling but to give way, for example, upon the exertion of manual pressure, when the activated bleaching mixture is to be made and used. Breaking seals are therefore intended to be weaker than the outer seal.
  • Breaking seals can be achieved in many ways, such as for example, using a laminate or film which has a strong adhesive on one side and a weak adhesive on the other, a seal which is much thinner than the outer seal, weakly heat- sealing the separate chamber, utilizing a different sealing method than in the outer seals and non-breaking seals, etc.
  • a breaking seal as seen, for example, in Fig. 1 at 4, is used as an adjoining partition between the separate chambers; thus the breaking seal provides a means for forming separate chambers which possess a relatively weak seal at one or more points therebetween.
  • a non-breaking seal is shown, for example, in Fig. 4, at 20, and should be at least stronger than any breaking seals.
  • any non-breaking seals are as strong as the outer seal(s).
  • all seals, including breaking seals, outer seals, or non-breaking seals should be substantially solvent-tight and/or water-tight.
  • the separate chambers must have at least one aqueous component chamber containing from about 10% to about 90% moisture and an aqueous component.
  • Moisture is the aqueous solvent, and the aqueous component can be dissolved in solution and/or suspended therein.
  • the aqueous component chamber contains from about 10% to about 99%, preferably from about 50% to about 95%, and more preferably from about 70% to about 95% moisture, by weight.
  • the aqueous component chamber also contains from about 1% to about 90%, preferably from about 5% to about 50%, and more preferably from about 5% to about 30% of an aqueous component, by weight.
  • the aqueous component can be either one or two components selected from the active oxygen source, the bleach activator, and the alkalinity source, subject to principle 3.
  • the aqueous component can be dissolved and/or suspended in the aqueous solvent.
  • the aqueous component chamber can also contain a surfactant component, and/or other detersive ingredients.
  • the aqueous component contains one or two of: the active oxygen source, the bleach activator, and the alkalinity source, while the remaining compound(s) is/are located in the non-aqueous component chamber, as described below.
  • the aqueous component for any given chamber can contain one or more of the following: the active oxygen source, the bleach activator, the alkalinity source, and the surfactant component.
  • the possible permutations of the invention increase dramatically, but the three basic principles remain constant; (1) there must be at least one aqueous component chamber and at least one non-aqueous component chamber; (2) there must be an active oxygen source, a bleach activator, and an alkalinity source; and (3) the active oxygen source, the bleach activator, and the alkalinity source should not all be in the same separate chamber.
  • the bleaching system of the current invention must also have at least one non- aqueous component chamber (principle 1).
  • the non-aqueous component chamber contains a non-aqueous solvent and a non-aqueous component.
  • the non-aqueous component can be dissolved and/or suspended in the non-aqueous solvent.
  • Preferred non-aqueous solvents useful herein are those which are thermally stable, do not degrade the container, are easily dispersible in aqueous solution, and have less than about 5% free moisture, preferably less than about 1% free moisture, by weight of the solvent.
  • the non-aqueous component chamber contains from about 45% to about 95%, preferably from about 50% to about 95%, and more preferably from about 50% to about 70%, by weight, of a non-aqueous solvent.
  • a preferred non-aqueous solvent useful herein is one having a low polarity, such as non-vicinal C4-C8 alkylene glycol, alkylene glycol mono lower alkyl ether, lower molecular weight polyethylene glycol, lower molecular weight methyl ester and amide, and the like, and mixtures thereof.
  • a preferred type of non-aqueous, low-polarity solvent for use in the compositions prepared herein comprises non-vicinal C -C8 branched or straight chain alkylene glycol.
  • hexylene glycol (4-methyl-2,4-pentanediol), 1 ,6- hexanediol, 1 ,3-butylene glycol and 1 ,4-butylene glycol.
  • Hexylene glycol is very preferred.
  • Another preferred non-aqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl ethers.
  • the specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether, and dipropylene glycol monobutyl ether.
  • Diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether and butoxy-propoxy- propanol (BPP), and mixtures thereof are especially preferred.
  • Compounds of the type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.
  • non-aqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyethylene glycols (PEGs).
  • PEGs polyethylene glycols
  • Such materials are those having an average molecular weight of at least about 150.
  • Yet another preferred non-aqueous solvent comprises the lower molecular weight methyl esters.
  • Such materials are those of the general formula: R ⁇ -C(O)- OCH3 wherein R 1 ranges from 1 to about 18.
  • suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, methyl dodecanoate, and mixtures thereof.
  • non-aqueous solvent employed should, of course, be compatible and non-reactive with other composition components, e.g., the active oxygen source and/or bleach activators, used herein.
  • a more preferred non-aqueous solvent includes glycerol, PEG having an average molecular weight of between about 150 and about 600, 1 ,3-butylene glycol, and mixtures thereof.
  • the non-aqueous component can also contain a surfactant component, and/or other detersive ingredients.
  • the non-aqueous component chamber also contains from about 5% to about 55%, preferably from about 5% to about 50%, and more preferably from about 30% to about 50% of a non-aqueous component.
  • the exact composition of any specific non-aqueous component depends upon the aqueous component, the number of aqueous component chambers, and the number of non-aqueous component chambers.
  • dual- chamber embodiments contain in the non-aqueous component the active oxygen source, the bleach activator, and/or the alkalinity source; whichever compound(s) is/are not contained in the aqueous component chamber.
  • non-aqueous component chamber containing the same or different non-aqueous solvent(s), and non-aqueous component(s).
  • the activated bleach mixture is made by commingling the contents the aqueous component chamber, the non-aqueous component chamber, and the alkalinity source. This can occur, for example, by moving a partition, by squeezing the contents of a separate chamber into another, by pouring the contents of one separate chamber into another, by breaking the barrier between separate chambers, and/or otherwise causing the contents of the aqueous component chamber(s) and the non-aqueous component chamber(s) to combine.
  • the commingling causes the bleach activator, the active oxygen source, and the alkalinity source to mix with moisture, to make the activated bleach mixture.
  • the active oxygen source and the bleach activator will then begin generating available peroxyacid oxygen.
  • the active oxygen source and bleach activator begin to produce available peroxyacid oxygen in the activated bleach mixture.
  • the available peroxyacid oxygen level in the activated bleach mixture is at least 200 ppm, preferably from about 200 ppm to about 2000 ppm, more preferably from about 400 ppm to about 1000 ppm.
  • the available peroxyacid oxygen level is typically measurable by standard methods such as iodide/thiosulfate and/or eerie sulfate titration.
  • oxygen bleach is a peroxygen compound, it contains -O-O- linkages with one O in each such linkage being "active.”
  • Most available oxygen measurement methods measure the total available oxygen.
  • the total available oxygen is equal to the available peroxide oxygen plus the available peroxyacid oxygen. Therefore, to determine the available peroxyacid oxygen level, it is necessary to remove the available peroxide oxygen. This can be done, for example, by destroying the peroxide by adding catalase.
  • an aliquot of the solution is removed, and the peroxide destroyed by adding catalase.
  • the solution can then be reacted with iodide at about 80°C under argon, and further titrated with thiosulfate. The titration can be done in aqueous solution, or the solution can be extracted with propyl acetate.
  • Iodine formation can be measured by measuring absorption at 420 nm, using a spectrometer, and the concentration calculated by multiplying by the dilution factor. Electrometric titration methods can also be used to determine the available peroxyacid titration level.
  • the activated bleach mixture is ready and can be used in a cleaning application.
  • the active oxygen source useful herein includes compounds which form available peroxyacid oxygen when exposed to a bleach activator, an alkalinity source, and moisture.
  • An active oxygen source can be hydrophilic, hydrophobic, or both.
  • the active oxygen source useful in the present invention can be any of the oxidizing agents known for laundry, hard surface cleaning, automatic dishwashing, or denture cleaning purposes, including oxygen.
  • a preferred active oxygen source of the peroxygen type includes hydrogen peroxide, inorganic per- compounds, inorganic peroxohydrates, organic peroxohydrates, and mixtures thereof; a more preferred active oxygen source includes hydrogen peroxide, perborate, percarbonate, and mixtures thereof.
  • an active oxygen source is also useful herein as an active oxygen source.
  • the inorganic peroxides such as Na2 ⁇ 2, superoxides such as KO2, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacids and their salts such as the peroxosulfuric acid salts, especially the potassium salts of peroxodisulfuric acid and mixtures thereof; more preferably, of peroxomonosulfuric acid including the commercial triple-salt form sold as OXONETM by DuPont and also any equivalent commercially available forms such as CUROXTM from Akzo or CAROATTM from Degussa.
  • organic peroxides such as dibenzoyl peroxide
  • a preferred active oxygen source includes peroxohydrates, sometimes known as peroxyhyd rates or peroxohydrates. These are organic or, more commonly, inorganic salts capable of releasing hydrogen peroxide readily. They include types in which hydrogen peroxide is present as a true crystal hydrate, and types in which hydrogen peroxide is incorporated covalently and is released chemically, for example by hydrolysis. Typically, peroxohydrates deliver hydrogen peroxide readily enough that it can be extracted in measurable amounts into the ether phase of an ether/water mixture.
  • Peroxohydrates are characterized in that they fail to give the Riesenfeld reaction, in contrast to certain other active oxygen sources. Peroxohydrates are the most common examples of "hydrogen peroxide source” materials and include the perborates, percarbonates, perphosphates, and persilicates.
  • peroxohydrates include sodium carbonate peroxyhydrate and equivalent commercial "percarbonate” bleaches, and any of the so-called sodium perborate hydrates, the "tetrahydrate” and “monohydrate” being preferred; though sodium pyrophosphate peroxyhydrate can be used.
  • Many such peroxohydrates are available in processed forms with coatings, such as of silicate and/or borate and/or waxy materials and/or surfactants, or have particle geometries, such as compact spheres, which improve storage stability.
  • Percarbonate bleach includes, for example, dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1 ,250 micrometers. These percarbonates are compatible with non-aqueous solvents. Percarbonates and perborates are widely available in commerce, for example from FMC, Solvay and Tokai Denka.
  • Another suitable hydrogen peroxide generating system is a combination of a C1-C4 alkanol oxidase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol (the corresponding bleach activators).
  • MOX methanol oxidase
  • ethanol the corresponding bleach activators.
  • enzymatic materials related to bleaching such as peroxidases, haloperoxidases, oxidases, superoxide dismutases, catalases and their enhancers or, more commonly, inhibitors, may be used as optional ingredients in the instant compositions.
  • a preferred active oxygen source includes perborate, percarbonate, and mixtures thereof. If an active oxygen source is present in a aqueous component chamber, then a preferred active oxygen source is hydrogen peroxide.
  • the active oxygen source herein can have any physical form compatible with the intended application; more particularly, liquid-forms and solid-forms.
  • Liquids can be included in solid detergents, for example by adsorption onto an inert support; and solids can be included in liquid detergents, for example by use of compatible suspending agents.
  • An active oxygen source will typically be at a level of from about 1% to about 30%, more typically from about 5% to about 20%, of the cleaning composition, especially for fabric laundering.
  • a bleach activator useful herein includes amides, imides, esters, anhydrides, and mixtures thereof.
  • at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C(O)-L.
  • the atom in the leaving group connecting to the peracid-forming acyl moiety R(C)O- is most typically O or N.
  • a bleach activator can have non-charged, positively or negatively charged peracid- forming moieties and/or noncharged, positively or negatively charged leaving groups.
  • One or more peracid-forming moieties or leaving-groups can be present. See, for example, U.S. 5,595,967 to Kellett, et al., issued January 21 , 1997, U.S. 5,561 ,235 to Burns, et al., issued October 1 , 1996, U.S. 5,560,862 to Burns, et al., issued October 1 , 1996 or the bis-(peroxy-carbonic) system of U.S. 5,534,179 to Kellett, et al., issued July 9, 1996.
  • Examples of a cationic bleach activator includes quaternary carbamate-, quaternary carbonate-, quaternary ester-, quaternary amide-, and mixtures thereof, delivering a range of cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acids to the wash.
  • An analogous but non-cationic palette of bleach activators is available when quaternary derivatives are not desired.
  • examples of a cationic bleach activator includes the quaternary ammonium-substituted bleach activators of WO 96-06915 to Baillely, et al., published March 7, 1996, U.S.
  • cationic nitriles as disclosed in EP-B1 -303,520 to Aoyagi, et al., issued April 20, 1994 and in European Patent Specification 458,396 to Oakes, et al., published November 27, 1991 and 464,880 to Adams, et al., issued December 14, 1994.
  • Other nitrile types such as 3,5- dimethoxybenzonitrile and 3,5-dinitrobenzonitrile can also be used.
  • bleach activator disclosures include GB 836,988 to Davies, et al., published June 9, 1960; GB 864,798 to Hampson and McDonnell, published April 6,1961 ; GB 907,356 to Maddox, et al., published October 3, 1962; GB 1 ,003,310 to Chase and Samuels, published September 2, 1965 and GB 1 ,519,351 to Wellwood, published July 26, 1978; German Patent 3,337,921 to Balzer, et al., published May 2, 1985; EP-B-0185522 to Fong and Kong, issued November 7, 1990; EP-B-0174132 to Divo, issued December 14, 1988; U.S. Pat. No.
  • Suitable bleach activators include any acetylated diamine types, whether hydrophilic or hydrophobic in character.
  • Japanese Laid-Open Patent Application (Kokai) No. 4-28799 to Yamada, et al., published January 31 , 1992 for example describes a bleaching agent and a bleaching cleaning composition comprising an organic peracid precursor described by a general formula and illustrated by compounds which may be summarized more particularly as conforming to the formula:
  • L is sodium p-phenolsulfonate
  • R 1 is CH3 or C12H25 and R 2 is H.
  • Analogs of these compounds having any of the leaving-groups identified herein and/or having R1 being linear or branched C6-C16 are also useful.
  • Another bleach activator herein are those derivable from acyclic imidoperoxycarboxylic acids and salts thereof of the formula: and (iii) mixtures of said compounds, (i) and (ii); wherein M is selected from hydrogen and bleach-compatible cations having charge q; and y and z are integers such that said compound is electrically neutral; E, A and X comprise hydrocarbyl groups; and said terminal hydrocarbyl groups are contained within E and A.
  • the structure of the corresponding bleach activator is obtained by deleting the peroxy moiety and the metal and replacing it with a leaving-group L, which can be any of the leaving-group moieties defined elsewhere herein.
  • X is a linear C3-C8 alkyl; A is selected from:
  • Another suitable bleach activator includes sodium-4-benzoyloxy benzene sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoyloxy benzoate; trimethyl ammonium toluyloxy- benzene sulfonate; sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS), and mixtures thereof.
  • SBOBS sodium-4-benzoyloxy benzene sulfonate
  • STHOBS 3,5,5-trimethyl hexanoyloxybenzene sulfonate
  • a preferred bleach activator includes N,N,N'N'-tetraacetyl ethylene diamine (TAED) or any of its close relatives including the triacetyl or other unsymmetrical derivatives, and mixtures thereof.
  • TAED and the acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred.
  • acetyl triethyl citrate a liquid, also has some utility, as does phenyl benzoate.
  • a highly preferred bleach activator useful herein is amide-substituted and has either of the formulae:
  • a preferred bleach activator includes those of the formulae, hereinabove, for example the amide-substituted formulae,
  • R is a linear or branched alkyl, aryl, or alkaryl
  • R is an alkyl chain
  • Preferred solubilizing groups include -SO3 " M + , -CO2 " M + , -SO4 " M + , -N + (R)4X " and O ⁇ - N(R 3 )2, more preferably -SO3 " M + and -CO2 " M + wherein R 3 is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a bleach-stable cation and X is a bleach-stable anion, each of which is selected consistent with maintaining solubility of the bleach activator.
  • a preferred bleach activator also includes those of the above general formula wherein L is selected from the group consisting of:
  • hydrophobic activator NOBS and the hydrophilic TAED activator are typical, and mixtures thereof can also be used.
  • a preferred bleach activator includes para- acetoxybenzene sulphonate, triacetyl cyanurate, and tetra acetyl glycol uril.
  • acyl lactam bleach activators are also very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A to Burns, et al., published December 8, 1994) and acyl valerolactams (see ) of the formulae:
  • R ⁇ is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1 to about 12 carbon atoms, or substituted phenyl containing from about 6 to about 18 carbons.
  • acyl caprolactams including benzoyl caprolactam adsorbed into sodium perborate.
  • a NOBS, lactam bleach activator, imide bleach activator, or amide- functional bleach activator, especially the more hydrophobic derivatives are desirably combined with a hydrophilic bleach activator such as TAED, typically at weight ratios of hydrophobic bleach activator : TAED in the range of 1:5 to 5:1 , preferably about 1 :1.
  • lactam bleach activator alpha-modified, see WO 96-22350 A1 to Burekett, et al., published July 25, 1996.
  • a lactam bleach activator, especially the more hydrophobic types, are desirably used in combination with TAED, typically at weight ratios of amido- derived or caprolactam bleach activator : TAED in the range of 1 :5 to 5:1 , preferably about 1 :1.
  • TAED typically at weight ratios of amido- derived or caprolactam bleach activator : TAED in the range of 1 :5 to 5:1 , preferably about 1 :1.
  • the bleach activator having a cyclic amidine leaving-group disclosed in U.S. 5,552,556 to Burns, et al., issued September 3, 1996.
  • An additional bleach activator useful herein include those of U.S. 5,545,349 to Itoh, et al., issued August 13, 1996.
  • Examples include esters of an organic acid and ethylene glycol, diethylene glycol or glycerin, or the acid imide of an organic acid and ethylenediamine; wherein the organic acid is selected from methoxyacetic acid, 2-methoxypropionic acid, p-methoxybenzoic acid, ethoxyacetic acid, 2-ethoxypropionic acid, p-ethoxybenzoic acid, propoxyacetic acid, 2-propoxypropionic acid, p-propoxybenzoic acid, butoxyacetic acid, 2- butoxypropionic acid, p-butoxybenzoic acid, 2-methoxyethoxyacetic acid, 2- methoxy-1-methylethoxyacetic acid, 2-methoxy-2-methylethoxyacetic acid, 2- ethoxyethoxyacetic acid, 2-(2-ethoxyethoxy)propionic
  • the bleach activator may be used in an amount of up to about 20%, preferably from about 0.1% to about 10% by weight, of the activated bleach mixture, though higher levels, such as 40% or more, are acceptable in highly concentrated bleaching systems.
  • the method for making and using the activated bleach mixture of the current invention includes the step of providing an alkalinity source.
  • the bleach activator requires an alkalinity source to rapidly activate the active oxygen source and rapidly evolve available peroxyacid oxygen.
  • the alkalinity source should be in one or more of the separate chambers.
  • An alkalinity source useful herein is one which maintains the commingled contents of the aqueous component chamber, if it is present therein, at a pH of from about 7 to about 14, preferably from about 9 to about 12.
  • a preferred alkalinity source maintains the pH of the activated bleach mixture at from about 7 to about 14, preferably from about 9 to about 12.
  • a preferred alkalinity source useful herein includes sodium and potassium hydroxide, carbonate, and mixtures thereof. Generally, the higher the pH of the commingled contents of the separate chambers, the faster the evolution of available peroxyacid oxygen.
  • An optional feature of the invention described herein is the providing of a surfactant component to improve cleaning efficacy, and the making of an activated bleach mixture by commingling the contents of the aqueous component chamber, the non-aqueous component chamber, the alkalinity source, and the surfactant component.
  • the surfactant component can be included with the aqueous component and/or with the non-aqueous component.
  • the surfactant component can be contained within a separate surfactant component chamber which is distinct from both the active oxygen source and the bleach activator.
  • the surfactant component can contain any surfactants useful in cleaning applications.
  • a preferred surfactant component is selected from amphoteric surfactants, anionic surfactants, cationic surfactants, nonionic surfactants, zwitterionic surfactants, and mixtures thereof.
  • Nonlimiting examples of a surfactant component particularly useful in the cleaning composition includes, the conventional C-
  • the conventional nonionic and amphoteric surfactants such as the C-12-C18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12- 18 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • the C10-C-I8 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C-12- 18 N-methylglucamides.
  • sugar- derived surfactant component includes the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing.
  • C10- 20 conventional soaps may also be used. If high sudsing is desired, the branched- chain C-10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
  • the cleaning composition preferably comprises at least about 1%; more preferably at least about 10%; more preferably at least about 20%; more preferably still, from about 20% to about 60% of a surfactant component, by weight of the activated bleach mixture.
  • Surfactant Component Chamber preferably comprises at least about 1%; more preferably at least about 10%; more preferably at least about 20%; more preferably still, from about 20% to about 60% of a surfactant component, by weight of the activated bleach mixture.
  • An optional feature of the bleaching system described herein is a surfactant component chamber. While not required, it is preferred that when more than two separate chambers are present, the surfactant component is located in a surfactant component chamber.
  • This chamber is a separate chamber which preferably contains a solvent and a surfactant component.
  • the solvent can be either aqueous or non- aqueous.
  • the surfactant component chamber comprises moisture as a solvent.
  • the surfactant component chamber can further contain a bleach activator, an active oxygen source, and/or an alkalinity source.
  • the surfactant component chamber can contain other detersive ingredients.
  • the contents of the surfactant component chamber can be commingled with the contents of the other separate chambers to produce the activated bleach mixture.
  • the contents of the surfactant component chamber can be used separately in a cleaning application, such as, for example, when the activated bleach mixture is used as a pre-treater, while the contents of the surfactant component chamber are used in the regular wash cycle. It is preferred that the contents of the surfactant component chamber be commingled with the contents of the other separate chambers so as to form the activated bleach mixture.
  • Optional Detersive Ingredients The following illustrates various other optional detersive ingredients which may be used herein, but is not intended to be limiting thereof. Viscosity Controller
  • a viscosity controller such as a polymer, or mixtures of polymers can be optionally included in the contents of the separate chambers described herein. They can serve to increase or decrease the viscosity of the contents of any separate chamber. It is preferred that a viscosity controller be used in non- aqueous component chambers to adjust the viscosity of the contents thereof.
  • polyethylene glycols PEGs
  • Preferred PEGs have an average molecular weight of from about 100 to 1500, more preferably from about 200 to about 600.
  • a detergent builder can optionally be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
  • the builder can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than the surfaces of articles to be cleaned.
  • Builder level can vary widely depending upon end use and physical form of the composition.
  • Built detergents typically comprise at least 1% builder.
  • Liquid cleaning compositions typically comprise 5% to 50%, more typically 5% to 35% builder by weight. Lower or higher levels of builders are not excluded.
  • a suitable builder herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured- liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured- liquid types
  • borates e.g., for pH-buffering purposes
  • sulfates especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing cleaning compositions.
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, alkalinity sources or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
  • Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 , including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under the tradename BRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layered aluminium-free ⁇ -Na2Si ⁇ 5 morphology silicate marketed by Hoechst.
  • silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
  • magnesium silicate which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
  • synthesized crystalline ion exchange materials or hydrates thereof as taught in U.S. 5,427,711 , Sakaguchi et al, June 27, 1995.
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals may be useful.
  • Aluminosilicate builders are can also be incorporated in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [M z (Al ⁇ 2)z(Si ⁇ 2) ]'*H2 ⁇ wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Aluminosilicates can be crystalline or amorphous, naturally-occurring or synthetically derived.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the formula: Na-
  • 2[( l ⁇ 2)i2(Si ⁇ 2)i2] xH2 ⁇ wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x 0 - 10) may also be used.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Suitable organic detergent builders include ether polycarboxylates, polycarboxylate, including water-soluble nonsurfactant dicarboxylate and tricarboxylate compounds. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1 , 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • Citrates e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to their availability from renewable resources and biodegradability.
  • compositions herein will typically comprise from 0.001% to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic compositions comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • proteases include those of WO 9510591 A to Procter & Gamble .
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble.
  • a recombinant trypsin-like protease for compositions suitable herein is described in WO 9425583 to Novo.
  • Any other oxidative stability-enhanced amylases can also be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. See also WO 9509909 A to Novo.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
  • Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS- 2.247.832.
  • CAREZYME® and CELLUZYME® are especially useful. See also WO 9117243 to Novo. Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used as oxygen bleach activators in combination with oxygen precursors, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen precursors e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing cleaning compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid cleaning compositions, and their incorporation into such compositions, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981. Enzymes for use in cleaning compositions can be stabilised by various techniques.
  • Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo. Enzyme Stabilizing System
  • Stabilizing systems of certain cleaning compositions may further comprise from 0 to 10%, preferably from 0.01 % to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions.
  • Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc.
  • SRA polymeric soil release agent
  • SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the composition.
  • SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with SRA to be more easily cleaned in later washing procedures.
  • SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S. 4,956,447), as well as noncharged monomer units and structures may be linear, branched or even star-shaped.
  • Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide.
  • esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without of course forming a densely crosslinked overall structure.
  • Suitable SRA's include: a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyi and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to Scheibel and Gosselink.
  • SRA's also include simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et al.
  • Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10-15% by weight of ethylene terephthalate together with 90- 80% by weight of polyoxyethylene terephthalate, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Clav Soil Removal/Anti-redeposition Agents
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • a preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
  • Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
  • Also preferred are the cationic compounds disclosed in European Patent Application 111 ,965, Oh and Gosselink, published June 27, 1984; the ethoxylated amine polymers disclosed in European Patent Application 111 ,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
  • CMC carboxy methyl cellulose
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.01% to 1.2%, by weight, into the cleaning compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners useful herein are identified in U.S. Patent 4,790,856, to Wixon, issued December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, the 2-(4- styryl-phenyl)-2H-naptho[1 ,2-djtriazoles; 4,4'-bis-(1 ,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; 1 ,2-bis(benzimidazol-2- yl)ethylene; 1 ,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2- styryl-naptho[1,2-d]oxazole; and 2-(stilben-4-yl)-2H-naphtho[1 ,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Dye Transfer Inhibiting Agents
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 2%.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine- hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • a preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins; also preferred are water- soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates. If utilized, these chelating agents will generally comprise from 0.1 % to
  • the chelating agents will comprise from 0.1% to 3.0% by weight of such compositions.
  • Alkoxylated Polycarboxylates Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2O) m (CH2)nCH3 wherein m is 2-3 and n is 6-12.
  • the side-chains are ester-linked to the polyacrylate "backbone” to provide a "comb” polymer type structure.
  • the molecular weight can vary, but is typically in the range of 2000 to 50,000.
  • Such alkoxylated polycarboxylates can comprise from 0.05% to 10%, by weight, of the compositions herein.
  • compositions herein A wide variety of other ingredients useful in cleaning compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, etc.
  • suds boosters such as the C ⁇ ⁇ o-C-
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • water-soluble magnesium and/or calcium salts such as MgC , MgSO4, CaC-2 CaSO4, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • Fig. 1 shows a package, 1 , having separate chambers, 2.
  • the outer seal, 3, runs along the outside edge of the package, 1 , while a breaking seal, 4, separates the package, 1 , into separate chambers, 2.
  • Breaking seal, 4, is weaker than outer seal, 3, so as to allow the contents of the separate chambers, 2, to be commingled by using pressure to cause the breaking seal, 4, to give way, thereby creating one large chamber from the two separate chambers, 2.
  • the commingling can be enhanced by, for example, shaking, squeezing, or agitating the package.
  • Fig. 1 also shows a perforation, 5, at which the package, 1 , can be torn and/or cut so as to allow the contents thereof to be dispensed.
  • Fig. 2 is a cross-sectional view of Fig. 1 as seen along line 1-1.
  • Fig. 2 shows that the package, 1 , is constructed of a top layer, 10, and a bottom layer, 1 1.
  • the top layer, 10 and the bottom layer, 1 1 are each made of an outer layer,
  • Fig. 4 shows a triple chamber embodiment having separate chambers, 2, separated by breaking seals, 4, and non-breaking seal 20.
  • Non-breaking seal, 20, is stronger than the breaking seal, 4.
  • Outer seal, 3, is formed so as to provide a spout, 15, from which the contents of the package, 1 , can be dispensed, for example, by cutting along line 3-3.
  • the aqueous component chamber contains as its primary components, by weight: 50% moisture, 44% surfactant and builder, and 6% hydrogen peroxide as an active oxygen source, while the non-aqueous component chamber contains by weight, 87% glycerol as a non-aqueous solvent, 3% NOBS as a bleach activator, and 10% sodium bicarbonate as an alkalinity source.
  • the breaking seal is broken and the contents of the aqueous component chamber and the non-aqueous component chamber commingle and form an activated bleach mixture having an available peroxyacid oxygen level of at least 200 ppm.
  • the activated bleach mixture is then used in a cleaning application.
  • a non-aqueous detergent paste is made by homogenizing in a blender the following ingredients: 60% base detergent powder, 10% alkalinity source, 5% nonionic surfactant, 5% of polyethylene glycol (molecular weight of about 300), 0.1% suds supressor, 4.9% bleach activator, and 15% glycerol. This paste is sealed into a non-aqueous component chamber.
  • the aqueous component contains a 6% solution of hydrogen peroxide.
  • the aqueous component is sealed into an aqueous component chamber.
  • the two separate chambers are not connected.
  • the contents of the non-aqueous component chamber are poured into the aqueous component chamber, and an available peroxyacid oxygen of greater than 400 ppm is formed therein.
  • the activated bleach mixture is then added to the wash cycle of a laundry application.
  • the aqueous component is made by making a 6% by weight solution of hydrogen peroxide. This is sealed into a first aqueous component chamber.
  • a second aqueous component is made by preparing a mixture of 15% bleach activator (TAED) in distilled water. This is sealed into a second aqueous component chamber.
  • TAED bleach activator
  • the separate chambers are made as described in Example 1 , except that there are three adjoining chambers as described in Fig. 4.
  • the volume ratio of the non-aqueous component chamber to first aqueous component chamber to second aqueous component chamber is about 8.5:2:1.
  • the activated bleach mixture is made and used as a pre-treater in a laundry application.
  • a clamp is attached to the end of the package opposite the spout. The spout is then cut open. The flexible package is then rolled around the clamp so that the package contents are forced out of the spout.
  • a preferred dual chamber embodiment is made as in Example 1 , except that 3% TAED is used as a bleach activator.
  • EXAMPLE 5 A preferred triple chamber embodiment is made as in Example 3, except that perborate is used in place of hydrogen peroxide, and instead of being placed in the first aqueous component chamber, the perborate is placed in the non- aqueous component chamber. Conversely, the alkalinity source is removed from the non-aqueous component chamber and placed in the first aqueous component chamber.
  • the separate chambers are made as in Example 4, except that the outer seal and the non-breaking sea are ultrasonically sealed.

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  • 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)

Abstract

L'invention concerne un procédé utilisant une pluralité de chambres séparées en vue de préparer et d'utiliser un mélange de blanchiment activé. Les chambres séparées comprennent une chambre à composant aqueux renfermant environ 10 % à environ 90 % d'humidité et un composant aqueux, et une chambre à composant non aqueux renfermant un solvant non aqueux et un composant non aqueux. Les chambres séparées maintiennent les contenus de la chambre à composant aqueux et de la chambre à composant non aqueux dans des conditions sensiblement non mélangées. Il est également prévu une source d'alcalinité. Un mélange de blanchiment activé est obtenu en homogénéisant les contenus de la chambre du composant aqueux, de la chambre du composant non aqueux et la source d'alcalinité, ce qui conduit à la formation d'un mélange de blanchiment activé d'une teneur en oxygène peroxyacide disponible d'au moins environ 200 ppm. Le mélange de blanchiment activé peut alors être utilisé pour le nettoyage. L'invention concerne en outre un nécessaire pour la préparation et l'utilisation d'un mélange de blanchiment activé.
PCT/US1997/023480 1997-12-22 1997-12-22 Systeme perfectionne de blanchiment par l'oxygene WO1999032598A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP11509766A JP2000516299A (ja) 1997-12-22 1997-12-22 改良された酸素漂白系
PCT/US1997/023480 WO1999032598A1 (fr) 1997-12-22 1997-12-22 Systeme perfectionne de blanchiment par l'oxygene
AU57095/98A AU5709598A (en) 1997-12-22 1997-12-22 Improved oxygen bleaching system

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/023480 WO1999032598A1 (fr) 1997-12-22 1997-12-22 Systeme perfectionne de blanchiment par l'oxygene

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Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000061712A1 (fr) * 1999-04-12 2000-10-19 Unilever N.V. Compositions multicomposant de nettoyage de surfaces dures
US6472360B1 (en) 1999-04-12 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Multiple component hard surface cleaning compositions
WO2004053042A1 (fr) * 2002-12-06 2004-06-24 Henkel Kommanditgesellschaft Auf Aktien Detergent liquide a plusieurs composants
WO2005035707A1 (fr) * 2003-10-06 2005-04-21 The Procter & Gamble Company Composition de lessive comprenant des peroxyacides contenue dans deux compartiments
WO2005035705A2 (fr) * 2003-10-06 2005-04-21 The Procter & Gamble Company Composition a lessive a deux compartiments contenant une solution de peracide a l'equilibre
WO2011051418A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
WO2011051417A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
WO2011051415A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
WO2020030517A1 (fr) * 2018-08-07 2020-02-13 Henkel Ag & Co. Kgaa Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment

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CN106860032B (zh) * 2016-10-25 2021-04-09 咏达生医材料股份有限公司 一种气态皮肤供氧美白产品及其应用
EP4296345A3 (fr) * 2017-06-22 2024-03-13 Ecolab USA Inc. Blanchiment à l'aide d'acide peroxyformique et d'un catalyseur à l'oxygène

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EP0744462A2 (fr) * 1995-05-25 1996-11-27 The Clorox Company Dispersions colloidales de précurseur peracide liquide: microémulsions
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WO1997045519A2 (fr) * 1996-05-28 1997-12-04 Warwick International Group Ltd. Composition de detergent liquide, alcalin et contenant du peroxyde

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EP0414462A2 (fr) * 1989-08-23 1991-02-27 Unilever Plc Produit de traitement pour le linge
GB2254857A (en) * 1991-02-22 1992-10-21 Unilever Plc Sachet for laundry treatment
EP0744462A2 (fr) * 1995-05-25 1996-11-27 The Clorox Company Dispersions colloidales de précurseur peracide liquide: microémulsions
WO1997031087A1 (fr) * 1996-02-23 1997-08-28 The Clorox Company Composition pour nettoyage de surfaces et appareil correspondant
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Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000061712A1 (fr) * 1999-04-12 2000-10-19 Unilever N.V. Compositions multicomposant de nettoyage de surfaces dures
US6472360B1 (en) 1999-04-12 2002-10-29 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Multiple component hard surface cleaning compositions
WO2004053042A1 (fr) * 2002-12-06 2004-06-24 Henkel Kommanditgesellschaft Auf Aktien Detergent liquide a plusieurs composants
WO2005035707A1 (fr) * 2003-10-06 2005-04-21 The Procter & Gamble Company Composition de lessive comprenant des peroxyacides contenue dans deux compartiments
WO2005035705A2 (fr) * 2003-10-06 2005-04-21 The Procter & Gamble Company Composition a lessive a deux compartiments contenant une solution de peracide a l'equilibre
WO2005035705A3 (fr) * 2003-10-06 2005-05-19 Procter & Gamble Composition a lessive a deux compartiments contenant une solution de peracide a l'equilibre
US10323218B2 (en) 2008-03-28 2019-06-18 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9540598B2 (en) 2008-03-28 2017-01-10 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US10077415B2 (en) 2008-03-28 2018-09-18 Ecolab Usa Inc. Detergents capable of cleaning, bleaching, sanitizing and/or disinfecting textiles including sulfoperoxycarboxylic acids
US9676711B2 (en) 2008-03-28 2017-06-13 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11827867B2 (en) 2008-03-28 2023-11-28 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US11015151B2 (en) 2008-03-28 2021-05-25 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9253978B2 (en) 2008-03-28 2016-02-09 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10669512B2 (en) 2008-03-28 2020-06-02 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9290448B2 (en) 2008-03-28 2016-03-22 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US10017720B2 (en) 2008-03-28 2018-07-10 Ecolab Usa Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
US9359295B2 (en) 2008-03-28 2016-06-07 Ecolab USA, Inc. Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents
WO2011051417A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
WO2011051418A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
WO2011051415A1 (fr) * 2009-10-30 2011-05-05 Henkel Ag & Co. Kgaa Procédé de lavage en machine
US10477862B2 (en) 2010-12-29 2019-11-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US8729296B2 (en) 2010-12-29 2014-05-20 Ecolab Usa Inc. Generation of peroxycarboxylic acids at alkaline pH, and their use as textile bleaching and antimicrobial agents
US9763442B2 (en) 2010-12-29 2017-09-19 Ecolab Usa Inc. In situ generation of peroxycarboxylic acids at alkaline pH, and methods of use thereof
US9321664B2 (en) 2011-12-20 2016-04-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9902627B2 (en) 2011-12-20 2018-02-27 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US9242879B2 (en) 2012-03-30 2016-01-26 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10017403B2 (en) 2012-03-30 2018-07-10 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing enzymes for treatment of drilling fluids, frac fluids, flowback water and disposal water
US10023484B2 (en) 2012-03-30 2018-07-17 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US9926214B2 (en) 2012-03-30 2018-03-27 Ecolab Usa Inc. Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water
US11939241B2 (en) 2012-10-05 2024-03-26 Ecolab Usa Inc. Stable percarboxylic acid compositions and uses thereof
US11180385B2 (en) 2012-10-05 2021-11-23 Ecolab USA, Inc. Stable percarboxylic acid compositions and uses thereof
US11026421B2 (en) 2013-03-05 2021-06-08 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9288992B2 (en) 2013-03-05 2016-03-22 Ecolab USA, Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US10893674B2 (en) 2013-03-05 2021-01-19 Ecolab Usa Inc. Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids
US9585397B2 (en) 2013-03-05 2017-03-07 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US9675076B2 (en) 2013-03-05 2017-06-13 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10165774B2 (en) 2013-03-05 2019-01-01 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US11206826B2 (en) 2013-03-05 2021-12-28 Ecolab Usa Inc. Defoamer useful in a peracid composition with anionic surfactants
US8822719B1 (en) 2013-03-05 2014-09-02 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
US10031081B2 (en) 2013-03-05 2018-07-24 Ecolab Usa Inc. Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring
WO2020030517A1 (fr) * 2018-08-07 2020-02-13 Henkel Ag & Co. Kgaa Détergent ou agent de nettoyage liquide contenant un précurseur de blanchiment

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