EP0598694B1 - Compositions stables contenant de sels d'acide persulfurique - Google Patents

Compositions stables contenant de sels d'acide persulfurique Download PDF

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Publication number
EP0598694B1
EP0598694B1 EP93870198A EP93870198A EP0598694B1 EP 0598694 B1 EP0598694 B1 EP 0598694B1 EP 93870198 A EP93870198 A EP 93870198A EP 93870198 A EP93870198 A EP 93870198A EP 0598694 B1 EP0598694 B1 EP 0598694B1
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EP
European Patent Office
Prior art keywords
composition
present
hard
compositions
hydrophilic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP93870198A
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German (de)
English (en)
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EP0598694A1 (fr
Inventor
Giulia Ottavia Bianchetti
Sandro Campestrini
Stefano Scialla
Fulvio Di Furia
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
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Priority to EP93870198A priority Critical patent/EP0598694B1/fr
Publication of EP0598694A1 publication Critical patent/EP0598694A1/fr
Priority to CA 2133354 priority patent/CA2133354C/fr
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Publication of EP0598694B1 publication Critical patent/EP0598694B1/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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to cleaning and bleaching compositions.
  • the cleaning and bleaching compositions according to the present invention are aqueous compositions comprising nonionic surfactants and persulfate salts. Said compositions are particularly suitable for the cleaning and bleaching of hard surfaces.
  • EP-A-0 373 613 discloses the preparation of a specific monopersulfate derivative, i.e. pyridine-3-percarboxylic acid monopersulfate useful as bleaching agent in detergent formulations.
  • persulfate salts have the drawback that they decompose in aqueous detergent compositions due to the presence of metal impurities which catalyze the decomposition of said persulfate salts and ingredients present in the compositions that can be oxidized by persulfate.
  • persulfate salts in aqueous detergent compositions tend to be chemically unstable. It is therefore an object of the present invention to provide compositions comprising persulfate salts which are chemically stable.
  • the present invention meets the above objects in proposing highly acidic aqueous emulsions of nonionic surfactants, which further comprise a persulfate salt. It has been found that the storage stability of persulfate salts in the compositions of the present invention is improved compared to compositions without any nonionic surfactants.
  • Aqueous emulsions of a nonionic surfactant system have been disclosed in the art for instance in European Patent EP-B-0 092 932.
  • Said patent discloses nonionic emulsions comprising hydrogen peroxide and an emulsified organic phase comprising a specific enol ester bleach activator. Such emulsions allow to keep the hydrogen peroxyde separate from the bleach activator. Persulfate salts are not disclosed.
  • compositions of the present invention comprising nonionic surfactants and a persulfate salt, find a preferred application in the cleaning of toilet bowls.
  • compositions according to the present invention have enhanced cleaning performance in their dilute form, compared to their neat form.
  • this "pH jump" effect allows to formulate compositions which are stable upon storage (acidic pH) and effective in cleaning (pH jumped).
  • the compositions of the present invention exhibit outstanding soil solubilization and soil discolouration properties when used diluted. Particularly on soil discolouration the performance of the compositions of the present invention is better than similar compositions comprising only hydrogen peroxide.
  • CA-A- 2062006 discloses a germicide composition for deodorising, cleaning and disinfecting in a single application, consisting of potassium monoperoxysulfate (60% to 90%), malic acid (2% to 10%), sulfamic acid (2% to 6%), EDTA (0.25% to 3%) and an alkylated ether of polyethylene glycol surfactant. No highly acidic emulsions of a hydrophilic and hydrophobic nonionic surfactants and a persulfate salt are disclosed.
  • EP-A-0 188 025 discloses aqueous thickened low-pH bleaching compositions comprising a thickening surfactant selected from the group of amine oxides, amines and cationic detergent actives, a cold-water soluble inorganic peroxy compound (e.g., peroxymonosulphuric acid), a strong acid and optionally a bleach-compatible electrolyte.
  • a thickening surfactant selected from the group of amine oxides, amines and cationic detergent actives
  • a cold-water soluble inorganic peroxy compound e.g., peroxymonosulphuric acid
  • Co-surfactants like nonionic surfactants may be present. However no highly acidic emulsions of a hydrophilic and hydrophobic nonionic surfactants and a persulfate salt are disclosed.
  • EP-A-0 199 385 discloses aqueous stable thickened low-pH bleaching compositions comprising a thickening anionic surfactant of the sulphonic acid or salt type, a cold-watersoluble inorganic peroxy compound, in particular peroxymonosulphate, and a mineral acid to yield a pH of below pH 4.
  • Nonionic co-surfactants like alkoxylation products of primary and secondary fatty alcohols may be present.
  • no highly acidic emulsions of a hydrophilic and hydrophobic nonionic surfactants and a persulfate salt are disclosed.
  • JP-A-5171195 discloses a bleaching composition containing hydrogen peroxide or a peroxide that generates hydrogen peroxide in aqueous solutions, and a particular nonionic surfactant that generates organic peroxides by reacting hydrogen peroxide.
  • JP-A-63161089 discloses a bleaching agent composition containing hydrogenperoxide or a peroxide that release hydrogen peroxide in aqueous solutions, and a cyanamid compound and ⁇ -hydroxycarboxylic acid and/or alkali metal salts of ⁇ -hydroxycarboxylic acid.
  • the present invention is a stable aqueous cleaning and bleaching composition in the form of an emulsion comprising at least two selected nonionic surfactants, said aqueous composition further comprising a persulfate salt or mixtures thereof and said composition having a pH of from 0 to 4.
  • the present invention also encompasses a process of treating surfaces wherein a composition according to the present invention is used in its diluted form.
  • the present invention also encompasses a process for the manufacture of said composition.
  • compositions according to the present invention are highly acidic aqueous emulsions of nonionic surfactants, which further comprise a persulfate salt or mixtures thereof.
  • compositions according to the present invention are typically stable.
  • stable it is meant herein that a composition comprising a persulfate salt or mixtures thereof does not undergo more than 20 % persulfate loss, in one month at 25°C.
  • Persulfate concentration can be measured by titration with potassium permanganate after reduction with a solution containing ammonium ferrous sulphate. Said stability test method is well known in the art and is reported,for example, on the technical information sheet of Curox R commercially available from Interox. Alternatively persulfate concentration can also be measured using a chromatography method described in the literature for peracids (F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol 113, May 1988, p 793-795).
  • compositions according to the present invention are aqueous. Accordingly, the compositions according to the present invention comprise from 10% to 95% by weight of the total composition of water, preferably from 30% to 90%, most preferably from 60% to 85%. Deionized water is preferably used.
  • compositions according to the present invention comprise as an essential element a persulfate salt or mixtures thereof in an amount of from 0.1% to 30% by weight of the total composition.
  • the compositions according to the present invention comprise from 1% to 20%, more preferably from 2% to 10% thereof.
  • Preferred persulfate salt to be used herein is the monopersulfate salt.
  • monopersulfate salts commercially available are those commercialized by Interox under the trade name Curox R .
  • Other persulfate salts such as dipersulfate salts commercially available from Peroxide Chemie GMBH can be used in the compositions according to the present invention.
  • compositions according to the present invention comprise as a further essential element a hydrophobic and a hydrophilic nonionic surfactant, whereby said composition is in the form of an emulsion.
  • compositions according to the present invention comprise from 1% to 50% by weight of the total composition of said nonionic surfactant mixture, more preferably from 4% to 30%, most preferably from 6% to 20%.
  • Suitable nonionic surfactants to be used herein are alkoxylated alcohol nonionic surfactants which can be readily made by condensation processes which are well known in the art. However, a great variety of such alkoxylated alcohols, especially ethoxylated and/or propoxylated alcohols is also conveniently commercially available. Surfactants catalogs are available which list a number of surfactants, including nonionics, together with their respective HLB values.
  • preferred alkoxylated alcohols for use herein are nonionic surfactants according to the formula RO(E)e(P)pH where R is a hydrocarbon chain of from 6 to 22 carbon atoms, E is ethylene oxide and P is propylene oxide, and e and p which represent the average degree of respectively ethoxylation and propoxylation, are of from 0 to 60.
  • compositions according to the present invention are in the form of an emulsion of at least two nonionic surfactants.
  • Said two nonionic surfactants must have different HLB values (hydrophilic lipophilic balance) in order to form emulsions which are stable, and preferably the difference in value of the HLBs of said two surfactants is of at least 1, preferably at least 3, more preferably of at least 6.5.
  • HLB values hydrophilic lipophilic balance
  • nonionic surfactant used herein is a nonionic surfactant with an HLB above 11 (herein referred to as hydrophilic nonionic surfactant), whereas the other one is a nonionic surfactant with an HLB below 10 (herein referred to as hydrophobic nonionic surfactant).
  • alkoxylated fatty alcohols to be used herein have very different HLB values.
  • the HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
  • said hydrophobic and hydrophilic nonionic surfactants are alkoxylated alcohols according to the present invention where the R group is a hydrocarbon chain with only from 8 to 13 carbon atoms, preferably from 8 to 11.
  • Dobanol R surfactants are commercially available from Shell.
  • compositions according to the present invention may further comprise other nonionic surfactants which should however not significantly alter the weighted average HLB value of the overall composition.
  • compositions according to the present invention are their acidity.
  • said compositions need to be formulated at a pH of from 0 to 4, preferably 0 to 3 and most preferably from 0 to 2.
  • the pH of said compositions can be trimmed by appropriate organic or/and inorganic acids which physically stabilize the compositions and may build up viscosity.
  • Said acids can be added typically from 1% to 20% by weight of the total composition.
  • organic acids to be used alone or in combination with other organic or/and inorganic acids are citric acid, succinic acid, maleic acid, tartaric acid and the like.
  • An example of inorganic acids to be used herein is sulfuric acid.
  • compositions of the present invention are free of hydrogen peroxide. Said compositions are particularly stable. In another embodiment, the compositions of the present invention further comprise from 0.5% to 20% by weight of the total composition of hydrogen peroxide, preferably from 2% to 15%, most preferably from 3% to 10%. Said compositions exhibit outstanding cleaning performances.
  • compositions according to the present invention may further comprise a variety of other ingredients including other surfactants of all types, organic or inorganic alkalis, perfumes, dyes, optical brighteners, builders, chelants, pigments, enzymes, dye transfer inhibitors, solvents, buffering agents and stabilizers.
  • the present invention further encompasses a process of treating hard-surfaces wherein a composition as hereinbefore defined is used in its diluted form.
  • a composition as hereinbefore defined is used in its diluted form.
  • the compositions according to the present invention may be diluted with water up to a pH of 6. Said dilution may occur either before, after or while said composition is applied to a hard-surface.
  • compositions according to the present invention find a preferred application in the cleaning of hard-surfaces, particularly toilet bowls and bath tubs.
  • a process of treating a hard-surface wherein a composition according to the present invention is diluted after or while it is applied to said surface.
  • said composition may be dispensed from a container onto said hard-surface, then diluted in water and left to act onto said surfaces, then removed by rinsing or flushing.
  • compositions according to the present invention are also particularly suitable to be used for denture applications.
  • a composition according to the present invention is either diluted before, after or while said composition is applied to said surface.
  • said composition may be first diluted in water before it is applied to said denture or may be diluted in water which is already in contact with a denture.
  • treating includes washing as the compositions according to the present invention comprise surfactants and bleaching as the compositions according to the present invention comprise persulfate salts.
  • the present invention further encompasses a process for the manufacture of the emulsions described herein.
  • the process according to the present invention comprises at least three steps:
  • a hydrophobic mixture which comprises said hydrophobic nonionic surfactant together with other hydrophobic ingredients which are to be formulated in the composition, such as metal chelants, perfumes, solvents, enzymes.
  • a hydrophilic mixture which comprises at least said water, said hydrophilic nonionic surfactant and said persulfate salts.
  • Said hydrophilic mixture optionally further comprises other hydrophilic ingredients which are to be formulated in the composition such as dyes, optical brighteners, builders, stabilizers, chelants, an organic acid or mixtures thereof, hydrogen peroxide and buffering agents.
  • hydrogen peroxide if present is preferably added last, after said buffering agent has been added.
  • the pH of said hydrophilic phase is adjusted to the desired value before the third step.
  • first and said second steps can be performed in any order, i.e. second step first is also suitable.
  • said hydrophobic mixture and said hydrophilic mixture are mixed together and stirred.
  • compositions are made which comprise the listed ingredients in the listed proportions (weight %).
  • compositions #1 and #2 are representative of the compositions according to the present invention.
  • Compositions #1 and #2 are emulsions of nonionic surfactants; these compositions comprise a monopersulfate salt.
  • compositions according to the present invention exhibit good stability.
  • composition #2 had virtually no persulfate loss after 3 weeks at 20°C.
  • compositions are made which comprise the listed ingredients in the listed proportions (weight %).
  • composition #1 which is representative of the present invention was evaluated for its cleaning performance on artificial toilet soils, i.e. soil solubilization efficiency and soil discolouration efficiency.
  • composition #2 which is an emulsion comprising hydrogen peroxide, is taken as the reference.
  • the evaluation (psu) used was a visual evaluation on a four points scale wherein "O” is attributed to the tested composition when no difference versus the reference is observed and wherein "4" is attributed when the tested composition is much better than the reference.
  • Artificial toilet soil discolouration (psu) Neat form of #1 3 Diluted form of #1 3
  • compositions of the present invention in the form of an emulsion exhibit outstanding cleaning performance by exploiting the pH jump that takes place upon product usage/dilution. Indeed, the cleaning performance of the composition #1 is enhanced when increasing the pH from 1 (neat product) to 2 (diluted product).
  • compositions according to the present invention provide significant benefits in toilet soils cleaning compared to hydrogen peroxide emulsions, both when used neat or diluted.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Cosmetics (AREA)

Claims (14)

  1. Composition aqueuse formulée à un pH de 0 à 4 et comprenant de 0,1% à 30%, en poids de la composition totale, d'un sel ou mélange de sels d'acide persulfurique, de 10% à 95% en poids d'eau et un tensioactif non ionique hydrophile et un tensioactif non ionique hydrophobe, afin que ladite composition soit sous forme d'une émulsion.
  2. Composition selon la revendication 1, dans laquelle ledit sel d'acide persulfurique et un sel d'acide monopersulfurique.
  3. Composition selon l'une quelconque des revendications précédentes, dans laquelle la proportion dudit sel ou mélange de sels d'acide persulfurique est de 1 à 20% en poids de la composition totale, de préférence de 2% à 10%.
  4. Composition selon l'une quelconque des revendications précédentes qui a un pH de 0 à 3, de préférence de 0 à 2.
  5. Composition selon l'une quelconque des revendications précédentes qui comprend de 1% à 50%, en poids de la composition totale, desdits tensioactifs non ioniques ou de mélanges de ceux-ci, mieux encore de 4% à 30%, tout particulièrement de 6% à 20%.
  6. Composition selon l'une quelconque des revendications précédentes, dans laquelle lesdits tensioactifs non ioniques hydrophiles et hydrophobes sont des alcools alcoxylés de formule RO(E)e(P)pH, dans laquelle R représente une chaíne hydrocarbonée de 6 à 22 atomes de carbone, de préférence de 8 à 13, mieux encore de 8 à 11, E est l'oxyde d'éthylène et P est l'oxyde de propylène, et e et p qui représentent le degré moyen, respectivement, d'éthoxylation et de propoxylation, valent de 0 à 60.
  7. Composition selon l'une quelconque des revendications précédentes, dans laquelle ladite composition est dépourvue de peroxyde d'hydrogène.
  8. Composition selon l'une quelconque des revendications 1 à 6, dans laquelle ladite composition comprend en outre de 0,5% à 20%, en poids de la composition totale, de peroxyde d'hydrogène, de préférence de 2% à 15%, mieux encore de 3% à 10%.
  9. Procédé de traitement d'une surface dure, dans lequel une composition selon l'une quelconque des revendications précédentes est utilisée sous sa forme diluée.
  10. Procédé de traitement d'une surface dure selon la revendication 9, dans lequel ladite composition est diluée avant d'être appliquée sur ladite surface.
  11. Procédé de traitement d'une surface dure selon la revendication 10, dans lequel ladite surface dure est une prothèse dentaire.
  12. Procédé de traitement d'une surface dure selon la revendication 9, dans lequel ladite composition est diluée après ou pendant son application sur ladite surface.
  13. Procédé de traitement d'une surface dure selon la revendication 12, dans lequel ladite surface dure est une prothèse dentaire ou une cuvette de toilette.
  14. Procédé de fabrication d'une émulsion selon l'une quelconque des revendications 1 à 8, dans lequel:
    un mélange hydrophobe est préparé qui comprend au moins ledit tensioactif non ionique hydrophobe;
    un mélange hydrophile est préparé qui comprend au moins de l'eau, ledit sel d'acide persulfurique, ledit tensioactif non ionique hydrophile et un acide organique ou des mélanges de ceux-ci;
    ledit mélange hydrophobe et ledit mélange hydrophile sont mélangés l'un avec l'autre.
EP93870198A 1992-11-16 1993-10-04 Compositions stables contenant de sels d'acide persulfurique Expired - Lifetime EP0598694B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP93870198A EP0598694B1 (fr) 1992-11-16 1993-10-04 Compositions stables contenant de sels d'acide persulfurique
CA 2133354 CA2133354C (fr) 1993-10-04 1994-09-30 Compositions surfactives, non ioniques, aqueuses, stables, renfermant des sels persulfates

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP92870188 1992-11-16
EP92870188A EP0598170B1 (fr) 1992-11-16 1992-11-16 Compositions de nettoyage et de blanchiment
EP93870198A EP0598694B1 (fr) 1992-11-16 1993-10-04 Compositions stables contenant de sels d'acide persulfurique

Publications (2)

Publication Number Publication Date
EP0598694A1 EP0598694A1 (fr) 1994-05-25
EP0598694B1 true EP0598694B1 (fr) 1998-02-04

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Family Applications (2)

Application Number Title Priority Date Filing Date
EP92870188A Expired - Lifetime EP0598170B1 (fr) 1992-11-16 1992-11-16 Compositions de nettoyage et de blanchiment
EP93870198A Expired - Lifetime EP0598694B1 (fr) 1992-11-16 1993-10-04 Compositions stables contenant de sels d'acide persulfurique

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP92870188A Expired - Lifetime EP0598170B1 (fr) 1992-11-16 1992-11-16 Compositions de nettoyage et de blanchiment

Country Status (12)

Country Link
EP (2) EP0598170B1 (fr)
JP (1) JP3285868B2 (fr)
AT (2) ATE163037T1 (fr)
AU (1) AU683858B2 (fr)
BR (1) BR9307462A (fr)
CA (1) CA2149320C (fr)
DE (2) DE69224389T2 (fr)
DK (2) DK0598170T3 (fr)
ES (2) ES2113421T3 (fr)
GR (2) GR3026437T3 (fr)
RU (1) RU2135558C1 (fr)
WO (1) WO1994011475A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6248705B1 (en) 1996-01-12 2001-06-19 The Procter & Gamble Company Stable perfumed bleaching compositions
US6992053B2 (en) 2001-03-26 2006-01-31 The Procter & Gamble Company Hard surface cleaning composition comprising a bleach, acid, and silicone glycol polymer

Families Citing this family (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409632A (en) * 1992-11-16 1995-04-25 The Procter & Gamble Company Cleaning and bleaching composition with amidoperoxyacid
EP0598693B1 (fr) * 1992-11-16 1998-12-23 The Procter & Gamble Company Emulsions stables d'agents tensioactifs non-ioniques contenant un agent de contrÔle de la viscosité
EP0598973A1 (fr) * 1992-11-26 1994-06-01 The Procter & Gamble Company Composition de nettoyage liquide pour tous usages
EP0600847B2 (fr) * 1992-11-26 2001-10-31 The Procter & Gamble Company Compositions de nettoyage avec des agents tensio-actifs non-ioniques hautement hydrophiles et hautement hydrophobes combinés
DE69320462T2 (de) * 1993-06-09 1999-04-22 The Procter & Gamble Co., Cincinnati, Ohio Verfahren zur Bleichung von Geweben
US5713962A (en) * 1993-06-09 1998-02-03 The Procter & Gamble Company Process for the bleaching of fabrics
US5902354A (en) * 1994-04-12 1999-05-11 The Procter & Gamble Company Bleaching compositions
ES2158878T3 (es) * 1994-06-10 2001-09-16 Procter & Gamble Emulsiones acuosas con abrillantadores.
US5880079A (en) * 1994-06-17 1999-03-09 The Procter & Gamble Company Bleaching compositions
ATE191002T1 (de) * 1994-06-17 2000-04-15 Procter & Gamble Bleichmittelzusammensetzungen
US5879584A (en) * 1994-09-10 1999-03-09 The Procter & Gamble Company Process for manufacturing aqueous compositions comprising peracids
GB9423374D0 (en) * 1994-11-19 1995-01-11 Procter & Gamble Peroxyacid bleach precursor compositions
ES2189834T3 (es) * 1994-11-25 2003-07-16 Procter & Gamble Composiciones decolorantes espesadas, metodo de empleo y procedimiento para fabricarlas.
GB9425882D0 (en) * 1994-12-21 1995-02-22 Solvay Interox Ltd Thickened peracid compositions
EP0751214A1 (fr) * 1995-06-30 1997-01-02 The Procter & Gamble Company Compositions de blanchiment stables contenant des agents de blanchiment péroxydés
ES2173151T3 (es) * 1995-03-27 2002-10-16 Procter & Gamble Composiciones blanqueantes liquidas activadas.
EP0742279A1 (fr) * 1995-05-10 1996-11-13 The Procter & Gamble Company Compositions acides, aqueuses, liquides
EP0745663A1 (fr) * 1995-05-31 1996-12-04 The Procter & Gamble Company Compositions liquides colorées, acides, aqueuses contenant un agent de blanchiment peroxydant
EP0751210A1 (fr) * 1995-06-27 1997-01-02 The Procter & Gamble Company Compositions de blanchiment
EP0779357A1 (fr) 1995-12-16 1997-06-18 The Procter & Gamble Company Emulsions stables contenant un ingrédient hydrophobe liquide
EP0784091A1 (fr) 1996-01-12 1997-07-16 The Procter & Gamble Company Composition de blanchiment stable parfumée
US5879409A (en) * 1996-02-23 1999-03-09 The Procter & Gamble Company Bleach additive and bleaching compositions having glycine anhydride activators
DE19635070A1 (de) * 1996-08-30 1998-03-05 Clariant Gmbh Flüssige Bleichmittelsuspension
EP0913463A1 (fr) * 1997-10-31 1999-05-06 The Procter & Gamble Company Compositions de blanchiment liquide aqueux à multi-usage
AU6255098A (en) * 1998-01-29 1999-08-16 Procter & Gamble Company, The Method for cleaning dentures
US6613726B1 (en) 1998-11-10 2003-09-02 Leo Gagliardi Bleaching compositions
DE10136208A1 (de) * 2001-07-25 2003-02-13 Henkel Kgaa Saures wässriges Reinigungsmittel
US8969283B2 (en) 2009-02-05 2015-03-03 American Sterilizer Company Low odor, hard surface sporicides and chemical decontaminants
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
BR112013019684A2 (pt) 2011-02-17 2016-10-18 Procter & Gamble alquil-fenil-sulfonatos lineares biobaseados
CN103380204B (zh) 2011-02-17 2016-02-03 宝洁公司 包含c10-c13烷基苯基磺酸盐的混合物的组合物

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1589866A (en) * 1976-08-20 1981-05-20 Unilever Ltd Detergent bars for personal washing
US4146499A (en) * 1976-09-18 1979-03-27 Rosano Henri L Method for preparing microemulsions
GB8310081D0 (en) * 1983-04-14 1983-05-18 Interox Chemicals Ltd Peroxygen compounds
GB8500116D0 (en) * 1985-01-03 1985-02-13 Unilever Plc Liquid bleaching compositions
GB8508010D0 (en) * 1985-03-27 1985-05-01 Unilever Plc Liquid bleaching compositions
US4909962A (en) * 1986-09-02 1990-03-20 Colgate-Palmolive Co. Laundry pre-spotter comp. providing improved oily soil removal
NZ221505A (en) * 1986-09-09 1989-08-29 Colgate Palmolive Co Liquid detergent compositions with peroxygen bleach and calcium cyanamide activator
US4764302A (en) * 1986-10-21 1988-08-16 The Clorox Company Thickening system for incorporating fluorescent whitening agents
US4804491A (en) * 1986-11-03 1989-02-14 The Clorox Company Aqueous based acidic hard surface cleaner
JPS63161089A (ja) * 1986-12-24 1988-07-04 ライオン株式会社 漂白剤組成物
US4889651A (en) * 1988-01-21 1989-12-26 Colgate-Palmolive Company Acetylated sugar ethers as bleach activators and detergency boosters
US5047168A (en) * 1988-01-21 1991-09-10 Colgate-Palmolive Co. Sugar ethers as bleach stable detergency boosters
US4891147A (en) * 1988-11-25 1990-01-02 The Clorox Company Stable liquid detergent containing insoluble oxidant
DE3842007A1 (de) * 1988-12-14 1990-06-21 Henkel Kgaa Fluessiges bis pastoeses, bleichmittelhaltiges waschmittel
DE3907131A1 (de) * 1989-03-06 1990-09-13 Henkel Kgaa Bleichmittelsuspension
GB8928631D0 (en) * 1989-12-19 1990-02-21 Procter & Gamble Concentrated aqueous liquid bleach compositions
TW291496B (fr) * 1991-02-01 1996-11-21 Hoechst Ag
JPH05171195A (ja) * 1991-12-25 1993-07-09 Lion Corp 漂白性組成物
CA2062006C (fr) * 1992-02-27 1996-12-10 Lucien Vallieres Desinfectant a action germicide tres etendue

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6248705B1 (en) 1996-01-12 2001-06-19 The Procter & Gamble Company Stable perfumed bleaching compositions
US6992053B2 (en) 2001-03-26 2006-01-31 The Procter & Gamble Company Hard surface cleaning composition comprising a bleach, acid, and silicone glycol polymer

Also Published As

Publication number Publication date
WO1994011475A1 (fr) 1994-05-26
ES2113521T3 (es) 1998-05-01
EP0598170A1 (fr) 1994-05-25
AU683858B2 (en) 1997-11-27
GR3026562T3 (en) 1998-07-31
EP0598170B1 (fr) 1998-02-04
DE69316842D1 (de) 1998-03-12
BR9307462A (pt) 1999-08-24
JP3285868B2 (ja) 2002-05-27
ATE163038T1 (de) 1998-02-15
ES2113421T3 (es) 1998-05-01
CA2149320A1 (fr) 1994-05-26
RU95113166A (ru) 1997-01-10
JPH08503017A (ja) 1996-04-02
DE69316842T2 (de) 1998-09-10
DE69224389T2 (de) 1998-08-13
GR3026437T3 (en) 1998-06-30
EP0598694A1 (fr) 1994-05-25
DK0598170T3 (da) 1998-03-02
RU2135558C1 (ru) 1999-08-27
DK0598694T3 (da) 1998-03-02
DE69224389D1 (de) 1998-03-12
AU5455994A (en) 1994-06-08
ATE163037T1 (de) 1998-02-15
CA2149320C (fr) 1999-02-02

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