WO1997024430A1 - Compositions de blanchiment au peroxyde active par un oxo-piperidinium - Google Patents

Compositions de blanchiment au peroxyde active par un oxo-piperidinium Download PDF

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Publication number
WO1997024430A1
WO1997024430A1 PCT/US1996/020176 US9620176W WO9724430A1 WO 1997024430 A1 WO1997024430 A1 WO 1997024430A1 US 9620176 W US9620176 W US 9620176W WO 9724430 A1 WO9724430 A1 WO 9724430A1
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Prior art keywords
composition
agents
oxopiperidinium
bleaching
peroxygen
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Application number
PCT/US1996/020176
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English (en)
Inventor
Robert Joseph Heffner
Robert John Steltenkamp
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Colgate-Palmolive Company
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Publication date
Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to AU16859/97A priority Critical patent/AU1685997A/en
Publication of WO1997024430A1 publication Critical patent/WO1997024430A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • 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
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames

Definitions

  • This invention relates to bleach compositions containing a peroxygen bleaching compound. More particularly it relates to bleaching compositions containing inorganic peroxygen compounds activated with oxo-piperidinium salts.
  • Bleaching compositions have been used in the home and in industrial applications for bleaching stains on hard surfaces and soiled fabrics.
  • Hypochlorite bleaches are effective in removing such stains, when used in relatively high concentrations, but hypochlorite, along with other active chlorine bleaches, cause severe damage to fabric colors as well as to the textile fibers.
  • hypochlorite liquid bleaches present handling and packaging problems. Color and fabric damage can be minimized by using milder oxygen bleaches, such as, sodium perborate or potassium monopersolfate.
  • milder oxygen bleaches such as, sodium perborate or potassium monopersolfate.
  • the stain removal characteristics of these peroxygen bleaches are much less desirable than those of the harsher halogen bleaching agents.
  • bleaching compositions that contain peroxygen bleaches commonly employ activators, i.e., compounds that enhance the performance of the peroxygen bleaches.
  • activators i.e., compounds that enhance the performance of the peroxygen bleaches.
  • Bleaching compositions containing different types of bleach activators are known in the art including such compounds as esters, carboxylic acid anhydrides, quaternary ammonium salts and carboxylic acid salts.
  • U.S. 5,437,686 discloses an inorganic peroxygen compound and a bicyclic or tricyclic diketone as an activator for the peroxygen compound.
  • 3,822,114 discloses a process for the activation of peroxygen bleaching agents which comprises conjointly dissolving in aqueous solution certain peroxygen bleaching agents, certain aldehyde or ketone bleach activators and buffering agents. Concentrated dry bleach compositions containing these compounds are also disclosed. Among a host of other ketones there is also taught the use of certain piperidone compounds.
  • Another object is to provide activators for enhancing the efficiency of peroxygen bleaches.
  • a peroxygen bleaching composition which comprises a mixture by weight of: (1) about 1 to about 75% of a peroxygen bleaching compound; and (2) about 1 to about 75% of an oxo-piperidinium salt peroxygen bleaching compound activator having the formula:
  • Rl and R2 are each an alkyl having 1 to about 18 carbon atoms or an aryl monovailing group having 6 to about 10 carbon atoms
  • X is R1SO4-, Br- or Cl- and the oxo- piperidinium ring carbon atoms can be mono- or disubstituted at the 2, 3, 5 or 6 positions by one or more groups defined by Rl or R2, aryl groups having 6 to about 10 carbon atoms, and alkaryl groups having about 7 to about 20 carbon atoms.
  • the peroxygen bleaching compositions of this invention can be used directly or in aqueous solution to bleach a fabric or in the alternative the bleaching compositions can be inco ⁇ orated as an additive to a cleaning composition, such as, a powdered laundry detergent, a non-aqueous laundry detergent, a scouring powder, a hard surface cleaning composition, a powdered automatic dish washing composition, a non-aqueous automatic dish washing composition, a hair bleaching composition, a wound cleansing composition, a dental cleansing composition, a paper bleaching composition, a pre-spotter and the like.
  • a cleaning composition such as, a powdered laundry detergent, a non-aqueous laundry detergent, a scouring powder, a hard surface cleaning composition, a powdered automatic dish washing composition, a non-aqueous automatic dish washing composition, a hair bleaching composition, a wound cleansing composition, a dental cleansing composition, a paper bleaching composition, a pre-spotter and the like.
  • the present invention is directed to peroxygen bleaching compositions, and bleaching and/or stain removal processes carried out in an aqueous solution.
  • These peroxygen bleaching compositions exhibit many practical utilities both domestic and industrial.
  • the bleaching compound-activator compositions can be used alone or in combination with other conventional ingredients to effect (1) direct bleaching of stains on fabrics. (2) removal by bleaching of stains found on hard surfaces, and (3) inhibition of the transfer to fabrics of solubilized or suspended dyes found in fabric laundering solutions.
  • the bleach compositions of the instant invention comprise a mixture of a peroxygen bleaching compound, preferably a monoperoxysulfate and more preferably potassium monoperoxysulfate and an oxo-piperidinium salt peroxygen bleaching compound activator. in a weight ratio of peroxygen bleaching compound to oxo-piperidinium salt peroxygen bleaching compound activator (hereinafter referred to as piperidinium salt) of about 1 : 1 to about 100:1, preferably about 1 : 1 to about 50: 1, and most preferably of about 1 :1 to about 10:1.
  • the piperidinium salts used herein are N,N'-disubstituted oxo-piperidinium salts having the formula shown above.
  • the bleaching compounds used in the instant invention are inorganic peroxygen salts, organic peroxygen acids and their water soluble salts.
  • inorganic peroxygen salts include the water-soluble monopersukfates and water-soluble monoperoxyphosphates. Specific examples of such salts include sodium monopersulfate, potassium monopersulfate, disodium monope ⁇ hosphate, and dipotassium monope ⁇ hosphate.
  • Highly preferred peroxygen salts, namely, those which are most highly activated by the piperidone derivative activators used in the instant invention are the sodium and potassium monopersul fates having the generic formulae NaHSO5 and KHSO5 respectively.
  • Potassium monopersulfate is available commercially from E. I. duPont de Nemours and Company, Inc. under the trade name "Oxone". Oxone contains approximately 41.5% by weight KHSO5 with the balance being KHSO4 and K2SO4 in about equal proportions.
  • Peroxyacids which are suitable in the instant invention have the general formula:
  • R is an alkylene group containing from 1 to about 16 carbon atoms or an arylene group containing from 6 to about 8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
  • Y includes the following structures:
  • organic peroxyacids or salts thereof suitable for use in this invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
  • the organic peroxyacid is aliphatic, the unsubstituted acid has the general formula: O
  • Y' can be:
  • Preferred aliphatic peroxyacids include diperazelaic acid and diperadipic acid.
  • organic peroxyacid is aromatic, the unsubstituted acid has the general formula:
  • Y is as defined above.
  • suitable aromatic peroxy acids or salts thereof include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chloroperoxyphthalic acid and the monosodium salt of diperoxyterephthalic acid.
  • a preferred aromatic peroxyacid is diperoxyisophthalic acid.
  • Mixtures of the peroxygen salt compounds and the peroxyacids can also be employed in the instant invention.
  • the concentration of the peroxygen bleaching compound in the compositions of this invention is about 1 to about 75% by weight, preferably about 5 to about 60% by weight and most preferably about 5 to about 50% by weight.
  • the concentration of the peroxygen bleaching compound is at a sufficient level in the bleaching composition to provide about 1 ppm to about 1000 ppm, when the composition is contacted with and dissolved in water at room temperature or higher.
  • the bleaching system acts through a mechanism first involving the reaction of an oxo-piperidinium salt with a peroxygen bleaching compound, such as, a monoperoxysulfate upon contact with water to form a dioxirane intermediate.
  • a peroxygen bleaching compound such as, a monoperoxysulfate
  • the intermediate then reverts back to the original acylpiperidone liberating nascent oxygen at the same time functioning in the bleaching operation.
  • the oxo- piperidinium salt may be considered as a catalyst since it is not consumed in the process.
  • the oxo-piperidinium salts of this invention are stable solids having a melting point of at least 25 °C that can be conveniently post blended with the conventional powder detergents of bleach additives, unlike liquid peroxy bleach activators. Additionally, these peroxygen bleaches of the instant invention have the advantage that they are fully activated in the presence of water over a broad range of temperatures from below room temperature to higher temperatures; are stable solids resistant to hydrolysis and are biodegradable leaving no nitrogen residues and thus are environmentally safe and acceptable.
  • the concentration of the dioxirane formed from these oxo-piperidinium salts in use in the water is about 1 to about 10,000 parts per million (ppm), more preferably about 1 to about 5,000 ppm and most preferably about 1 to about 1,000 ppm.
  • the peroxygen bleaching composition can be utilized as an additive to a fully formulated composition at a concentration level of about 1 to about 75% by weight preferably about 6 to about 60 weight % and most preferably about 5 to about 50 weight % depending upon the kind of cleaning composition.
  • a typical powder form automatic dishwashing composition (by weight) containing the claimed peroxygen bleach composition comprises:
  • a typical nonaqueous liquid automatic dishwashing composition (by weight) comprises: ( 1 ) 3-20% of an alkali metal silicate
  • a typical powder form detergent composition (by weight) comprises:
  • An exemplary nonaqueous laundry detergent comprises (by weight):
  • a typical scouring powder composition suitable for removing stains from hard surfaces comprises by weight: (1) 90.85% of White Silex
  • a typical nonconcentrated powdered bleach composition comprises by weight:
  • the bleach activator process of the instant invention is carried out in aqueous solution having a pH of about 7 to about 12. Outside of this range the bleaching performance falls off markedly. Since the aqueous solutions of the persalts or peracids of the present invention are generally acidic, it is necessary to maintain the requisite pH conditions by utilizing standard buffering agents.
  • a buffering agent is defined as any non-interfering compound which can alter and/or maintain a specified pH.
  • Useful buffers include phosphates, carbonates, or bicarbonates designed to buffer in the range of 7-12. Specific examples include sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate, and disodium hydrogen phosphate. Buffering agents generally comprise about 1% to about 85% of the instant concentrated bleaching compositions.
  • Nonionic surfactants suitable for use herein include ethoxylated and propoxylated fatty alcohols, capped or uncapped. Typical nonionic surfactants are disclosed in U.S. Patent Nos. 4,316,812 inco ⁇ orated herein by reference.
  • Foam inhibition is important to increase dishwasher and laundry machine efficiency and minimize the destabilizing effects what may occur due to the presence of excess foam within the washer during laundering.
  • the degree of foam is partly dependent on the hardness of the wash water where addition of builder salts, such as, NaTTP (sodium tripolyphosphate) which has a water softening effect may aid in providing a degree of foam inhibition.
  • builder salts such as, NaTTP (sodium tripolyphosphate) which has a water softening effect may aid in providing a degree of foam inhibition.
  • Particularly effective are silicones from Dow Chemical and the alkyl phosphoric acid esters derived from C12-C20 alkanols or ethoxylated alcohols. Commercially available examples of the latter are SAP from Hooker and LPKN from Knapsack.
  • alkali metal detergent builder salts include the polyphosphates, e.g., alkali metal pyrophosphates, alkali metal tripolyphosphates, alkali meta
  • Low molecular weight polyacrylates in the range of about 1 ,000 about 100,000 can be used in conjunction with the builder salts.
  • a preferred polyacrylate is Norasol LMW45ND sold by Norsohaas as is Acusol TM 640D from Rohm & Haas. These are employed in a range of about 0- 15% or 0.1 - 10%.
  • compositions can also contain a nonphosphate builder system comprised of a mixture of phosphate-free particles formed from a builder salt and a low molecular weight polyacrylate.
  • a preferred solid builder salt is an alkali metal carbonate, such as, sodium carbonate or sodium citrate or a mixture thereof. When a mixture is used, a weight ratio of sodium carbonate to sodium citrate of about 9:1 to about 1 :9 and preferably about 3:1 to about 1 :3 is used.
  • the alkali metal silicates serve as anti-corrosion agents functioning to make the composition anti-corrosive to eating utensils and to automatic dishwashing machine parts.
  • Sodium silicates of Na2/SiO2 ratios of from 1 :1 to 1 :3.4 especially about 1 :2 to 1 :3 are preferred. Potassium silicates of the same ratios can also be used.
  • the preferred silicates are sodium disilicate (hydrated or anhydrous) and sodium metasilicate.
  • Thickening agents that can be used to ensure the physical stability of the suspension and to enhance its viscosity are those that will swell and develop thixotropic properties in a nonaqueous environment. These include organic polymers and inorganic and organic modified clays. Essentially, any clay can be used as long as it will swell in a nonaqueous environment and exhibits thixotropic properties. A preferred clay is bentonite. A swelling agent is used with the bentonite clay. A preferred swelling agent is a combination of propylene carbonate and tripropylene glycol methyl ether. However, any other substance that will cause bentonite to swell in a nonaqueous environment and to develop thixotropic properties can be used.
  • nonaqueous liquid carrier materials that can be used for formulating nonaqueous liquid compositions include the higher glycols, polyglycols, polyoxides and glycol ethers. Examples are propylene glycol, polyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, tripropylene glycol methyl ether, propylene glycol methyl ether acetate, and the like.
  • a preferred nonaqueous carrier is polyethylene glycol 200 (PEG 200) or polyethylene glycol 300 (PEG 300).
  • the system that can be used in the instant compositions to ensure phase stability can comprise a finely divided silica, such as, Cab-O-Sil M5, Cab-O-Sil EH5 or Aerosil 200 used at a level of about 0 to about 4.0 weight % and preferably about 0.5 to about 3.0 weight %.
  • a finely divided silica such as, Cab-O-Sil M5, Cab-O-Sil EH5 or Aerosil 200 used at a level of about 0 to about 4.0 weight % and preferably about 0.5 to about 3.0 weight %.
  • the detergent formulation can also contain a mixture of a proteolytic enzyme and an amylolytic enzyme and optionally, a lipolytic enzyme that serves to attack and remove the organic residues on glasses, plates, pots, pans, and other eating utensils.
  • Proteolytic enzymes attack protein residues, lipolytic enzymes fat residues and amylolytic enzymes starches.
  • Proteolytic enzymes include the protease enzymes subtilism, bromelin, papain, trypsin mad pepsin.
  • Amylolytic enzymes include amylase enzymes.
  • Lipolytic enzymes include the lipase enzymes.
  • the preferred amylase enzyme is available under the name Maxamyl, derived from Bacillus lichenformis, from Gist-Brocades of the Netherlands in the form of a nonaqueous slurry (18% of enzyme) having an activity of about 40.000 TAU/g.
  • Maxatase is a preferred protease enzyme.
  • compositions include perfumes, hydrotropic agents, such as. sodium benzene, toluene, and cumene sulphonates, preservatives, dyestuffs. pigments and the like.
  • hydrotropic agents such as. sodium benzene, toluene, and cumene sulphonates
  • preservatives dyestuffs. pigments and the like.
  • Especially preferred for coloring are the chlorinated phthalocyanines and polysulfides of aluminosilicate which provide, respectively, green and blue tints. Titanium dioxide may be used for whitening or neutralizing off-shades.
  • EXAMPLE 1 In order to test the efficacy of the claimed compositions, the following compositions were prepared and the described procedures performed. A solution of 350 mg of potassium monopersulfate (Oxone) and 1.0 g of Fab Ultra detergent in one liter of water was prepared to which was added 10 mg of l,3-dimethyl-4- oxopiperidinium methosulfate.
  • Bleaching tests were performed in a six bucket (1 -liter) terg-o-tometer at 80° F and 120° F. Tests were run in tap water. Dioxiranes were generated in situ by the addition of Oxone (0.35 g) and the stained swatches were added to the terg-o-tometer which contained the Fab Ultra detergent. After 10 seconds of agitation of the above solution, stained swatches were added to the solution and agitation was continued for 15 minutes. The stains were then rinsed in tap water, dried and their reflectance measured on a reflectometer to determine the average soil removal (% ASR). The following four stained swatches were evaluated for bleaching in the test:
  • the % Average Soil Removal (% ASR) value is calculated by averaging the individual % Soil Removal (%SR) values ofthe four stains evaluated.
  • the % Soil Removal (%SR) of a stained swatch was determined by manipulating its reflectance values which are measured from a swatch both before and after washing. A reflectance value is the amount of light that a surface (such as a swatch) will reflect. The following procedure will illustrate this protocol. Coffee/Tea (Cotton Percal) stained swatches were bleached in the Dioxirane system DMOP- Oxone) using the procedure above. Table A provides the measured reflectance values of the swatches without stain (No Soil), with the stain (Soiled), and after washing (Washed). For each stain there are two swatches evaluated in order that there be an average value calculated.
  • the % SR value for the coffee/tea stained swatch is calculated by inserting the average ofthe measured reflectance values into the equation presented in below.
  • the % SR value for the coffee/tea stained swatch at 70° F is 72.70.
  • the individual % SR values of all four stains were added up and the sum is divided by four as shown in Table B below where the % ASR value for the DMOP/Oxone (10/350 ppm) system is shown to be 53.50.
  • This protocol is usually done in replicates of two or three to provide an overall average value and standard deviation as illustrated in Tables 1 through 6.
  • Tables 1, 2, 3 and 4 contain the % Soil Removal Values obtained at 50° F, 70° F, 100° F and 120° F respectively for Oxone alone at a concentration of 350 ppm (Control), 10 ppm of l,l-dimethyl-4-oxopiperidinium salt (DMOP) plus Oxone (350 ppm), Oxone (350 ppm) plus 1000 ppm of NF FAB, a commercial washing composition and 100 ppm of SNOBS (an acronym for sodium p-nonanoyloxybenzene sulfonate a prior art bleach activator (U.S. 4,678,594 at Column 4, lines 3-11) plus 127 ppm of sodium perborate monohydrate a prior art bleach.
  • SNOBS an acronym for sodium p-nonanoyloxybenzene sulfonate a prior art bleach activator (U.S. 4,678,594 at Column 4, lines 3-11) plus 127 ppm of sodium perborate monohydrate a prior art
  • NP FAB is a commercially available washing machine composition, comprising 28% of sodium aluminum silicate, 18% of sodium sulfate, 30% of sodium carbonate. 22% of nonionic detergents, 1.2% of a sodium anionic copolymer of maleic acid and alkyl acrylate end-capped with acrvlamide, 1.4% of triethanolamine together with minor amounts of sodium toluene sulfonate. sodium citrate, sodium sulfate, soil release polymer, and the remainder tap water.
  • Table 1 The dioxirane system of l,l-dimethyl-4- oxo-piperidinium methosuifate (DMOP) with Oxone exhibits superior bleach performance com pared to the perborate activator system of SNOBS at 50°F.
  • DMOP dioxirane system of l,l-dimethyl-4- oxo-piperidinium methosuifate
  • the specificity of the structure of the bleaching compound activator is evinced by the ineffectiveness of analogous compounds such as 2,2,6,6-tetramethyl piperidone (TMP) and N- methyl-4-piperidone with Oxone at 80° F as shown in Tables 5 and 6.
  • TMP 2,2,6,6-tetramethyl piperidone
  • Oxone 80° F
  • other useful compounds include the 1,1 -diethyl, 1.1 -dipropy 1, 1 -methyl- 1 -lauryl, 1 ,1-distearyl, 1,1,2,6-tetramethyl, l,l-diethyl-2,5-dipropyl, l,l-dimethyl-2-ethyl-6-phenyl-4-oxopiperidinium salts as well as their 3-oxopiperidinium salt isomers and the like.
  • compositions of this invention inhibit dye transfer from taking place from aqueous media in which soiled fabrics are being cleaned by the bleaching ofthe fabrics.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne des compositions de blanchiment à base d'un composé de blanchiment et d'un sel oxopipéridinium, de préférence présents l'un et l'autre à raison d'environ 1 % à environ 75 % en poids. Ces compositions peuvent également comporter des additifs tels que, notamment, des agents tensio-actifs, des agents anti-mousse, des assouplissants, des stabilisants, des adjuvants minéraux de détergence, des tampons, des enzymes et autres. En outre, ces compositions peuvent être formulées notamment en mélanges concentrés secs encapsulés ou en poudre en vrac, en solutions aqueuses, en solutions aqueuses contenant des solvants non aqueux, et sous des formes équivalentes. Efficaces comme agents de blanchiment à des températures comprises entre une température inférieure à la température ambiante et des températures bien plus élevées, ces compositions sont biodégradables et ne présentent aucun risque de nature écologique.
PCT/US1996/020176 1995-12-28 1996-12-18 Compositions de blanchiment au peroxyde active par un oxo-piperidinium WO1997024430A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU16859/97A AU1685997A (en) 1995-12-28 1996-12-18 Peroxygen bleach composition activated by oxo-piperidinium salts

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US939995P 1995-12-28 1995-12-28
US60/009,399 1995-12-28
US1148896P 1996-02-12 1996-02-12
US60/011,488 1996-02-12

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WO1997024430A1 true WO1997024430A1 (fr) 1997-07-10

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0913462A1 (fr) * 1997-10-31 1999-05-06 The Procter & Gamble Company Compositions de blanchiment liquides aqueuses emballées dans un conteneur résistant aux UV
EP0913463A1 (fr) * 1997-10-31 1999-05-06 The Procter & Gamble Company Compositions de blanchiment liquide aqueux à multi-usage
EP0915150A1 (fr) * 1997-10-31 1999-05-12 The Procter & Gamble Company Procédés de trempage de tissus avec un composition liquide aqueuse contenant un sel de persulfate
WO2008095558A2 (fr) * 2007-02-08 2008-08-14 Henkel Ag & Co. Kgaa Agents d'éclaircissement contenant une ou plusieurs pipéridones et imidazoles
US7456275B2 (en) 2002-04-18 2008-11-25 Chugai Seiyaku Kabushiki Kaisya Hyaluronic acid modification product

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006092A (en) * 1971-08-05 1977-02-01 The Procter & Gamble Company Laundering aid
US4421664A (en) * 1982-06-18 1983-12-20 Economics Laboratory, Inc. Compatible enzyme and oxidant bleaches containing cleaning composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4006092A (en) * 1971-08-05 1977-02-01 The Procter & Gamble Company Laundering aid
US4421664A (en) * 1982-06-18 1983-12-20 Economics Laboratory, Inc. Compatible enzyme and oxidant bleaches containing cleaning composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0913462A1 (fr) * 1997-10-31 1999-05-06 The Procter & Gamble Company Compositions de blanchiment liquides aqueuses emballées dans un conteneur résistant aux UV
EP0913463A1 (fr) * 1997-10-31 1999-05-06 The Procter & Gamble Company Compositions de blanchiment liquide aqueux à multi-usage
EP0915150A1 (fr) * 1997-10-31 1999-05-12 The Procter & Gamble Company Procédés de trempage de tissus avec un composition liquide aqueuse contenant un sel de persulfate
WO1999023196A1 (fr) * 1997-10-31 1999-05-14 The Procter & Gamble Company Compositions de blanchiment aqueuses liquides conditionnees dans un conteneur resistant aux uv
WO1999023197A1 (fr) * 1997-10-31 1999-05-14 The Procter & Gamble Company Procedes de trempage de tissus a l'aide d'une composition liquide aqueuse contenant un sel de persulfate
WO1999023195A1 (fr) * 1997-10-31 1999-05-14 The Procter & Gamble Company Compositions de blanchiment liquides aqueuses a usages multiples
US7456275B2 (en) 2002-04-18 2008-11-25 Chugai Seiyaku Kabushiki Kaisya Hyaluronic acid modification product
WO2008095558A2 (fr) * 2007-02-08 2008-08-14 Henkel Ag & Co. Kgaa Agents d'éclaircissement contenant une ou plusieurs pipéridones et imidazoles
WO2008095558A3 (fr) * 2007-02-08 2009-05-22 Henkel Ag & Co Kgaa Agents d'éclaircissement contenant une ou plusieurs pipéridones et imidazoles

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AU1685997A (en) 1997-07-28

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