[go: up one dir, main page]

EP0622451B1 - Perfumed hypochlorite bleaching compositions - Google Patents

Perfumed hypochlorite bleaching compositions Download PDF

Info

Publication number
EP0622451B1
EP0622451B1 EP93870070A EP93870070A EP0622451B1 EP 0622451 B1 EP0622451 B1 EP 0622451B1 EP 93870070 A EP93870070 A EP 93870070A EP 93870070 A EP93870070 A EP 93870070A EP 0622451 B1 EP0622451 B1 EP 0622451B1
Authority
EP
European Patent Office
Prior art keywords
acetal
acetate
composition
dimethyl
perfume
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.)
Revoked
Application number
EP93870070A
Other languages
German (de)
French (fr)
Other versions
EP0622451A1 (en
Inventor
Francesco Agostini
Giulia Ottavia Bianchetti
Francis Perrichon
Mauro Gallo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8215338&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0622451(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to AT93870070T priority Critical patent/ATE174054T1/en
Priority to ES93870070T priority patent/ES2127267T3/en
Priority to EP98870103A priority patent/EP0867503A3/en
Priority to DE69322375T priority patent/DE69322375T2/en
Priority to DK93870070T priority patent/DK0622451T3/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93870070A priority patent/EP0622451B1/en
Publication of EP0622451A1 publication Critical patent/EP0622451A1/en
Publication of EP0622451B1 publication Critical patent/EP0622451B1/en
Application granted granted Critical
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes

Definitions

  • the present invention relates to a liquid bleaching composition which is suitable both for laundry and household applications.
  • Compositions herein are particularly suitable in laundry applications, as a prewash bleaching composition.
  • Liquid bleaching compositions are well known In the art. Amongst the different bleaching compositions available, those relying on bleaching by hypochlorite are often preferred, mainly for performance reasons. These hypochlorite-based compositions are typically used in dilute form and are suitable both for laundry and household applications. However a major drawback associated with chlorine-based compositions is the malodor they generate during and after use. Indeed, not only does the composition itself smell chlorine bleach, but the malodor remains noticeable on fabrics or surfaces which have been treated with said compositions, as well as on the skin of the user of the composition, even after the bleaching composition has been thoroughly rinsed away.
  • Formulators have tried to solve that problem by designing perfumed chlorine-based bleaching compositions. However, this has proved difficult mainly for two reasons. Firstly, only a few perfume components are available which are stable in a strong oxidative environment such as a chlorine-based bleaching composition, resulting in limited flexibility in designing perfumes for such compositions. Secondly, chlorine bleach odor is strong and therefore difficult to mask even when perfumes are present.
  • a chlorine-based bleaching composition suitable for use in diluted form could be formulated, which exhibits a reduced chlorine odor upon use, by adding a pH buffering means, preferably a carbonate salt and/or a silicate salt in an aqueous bleaching composition, said composition comprising an alkali metal hypochlorite (2% - 10% by weight) and a bleach stable perfume and being formulated, at a pH of from 11.5 to 14.
  • a pH buffering means preferably a carbonate salt and/or a silicate salt
  • WO 88/05461 discloses a bleaching composition comprising sodium hypochlorite, sodium carbonate and sodium hydroxide.
  • US 4 287 079 discloses aqueous cleaning compositions to be applied from squirt bottle comprising a particulate abrasive, a two part thickener consisting essentially of a mixture of fumed silicon dioxide and smectite clay, an aqueous hypohalite bleach solution, an alkaline builder and perfume like isobornylacetate. Said compositions are suitable for cleaning hard surfaces, no laundry application is disclosed.
  • GB-A-2 076 010 discloses thickened aqueous bleach compositions comprising an alkali metal hypochlorite, one or more carboxylated surfactants, metal hydroxide, electrolytes such as calcium carbonate and perfume. Said compositions are suitable for cleaning vertical and inclined surfaces, no laundry application is disclosed.
  • EP-A-30 401 discloses liquid thickened chlorine bleaching compositions having a pH of from 10 to 12.5 and comprising hypochlorite, a buffering means like alkali metal salts of carbonic acid and of silicilic acid, perfume and a thickening system, i.e. a mixture of two different detergent active compounds. Said compositions are useful for bleaching hard surfaces, no laundry application is disclosed.
  • EP-A-204 472 discloses a thickened aqueous cleaning composition
  • a thickened aqueous cleaning composition comprising a specific tertiary amino oxide and an alkali metal or alkaline earth metal mono- or polyalkylated benzene or naphthalene sulphonate in which the alkyl groups contain from 1 to 4 carbon atoms.
  • Said compositions may further comprise hypochlorite, metal hydroxide, alkali metal carbonate and perfume like isobornylacetate dihydroter pincol, dihydroterpinyl acetate and isoborneol.
  • Alkali metal carbonate may be present as a contaminant of commercially available hypochlorite solution at a level of from 0.01% to 0.1% by weight of the hypochlorite solution.
  • Said compositions are suitable for cleaning non-horizontal structural surfaces, no laundry application is disclosed.
  • US 4 235 732 discloses alkaline aqueous hypochlorite cleaning compositions containing paraffin sulphonate surfactant, an inorganic colloid-forming clay, insoluble particulate abrasive, an inorganic alkaline salt capable of maintaining the composition pH within the range of from about 10 to 14 and perfume.
  • Different bleaching applications are disclosed including bleaching of textiles.
  • US 3 876 551 discloses aqueous perfumed compositions (pH 12 to 13.5) containing an alkali metal hypochlorite, a stable perfume oil and a surface active agent consisting solely of an amine oxide composition which consists essentially of one or more morpholine and/or dimethyl C 11 -C 13 straight chain alkyl amine oxides. No pH buffering means are disclosed. Said compositions are suitable for laundry and domestic bleaching.
  • EP-A-186 386 discloses an aqueous composition and having a pH above 12, comprising sodium hypochlorite, perfume, optical brighteners and amine oxides. No pH buffering means are disclosed. Said compositions are suitable for laundry applications.
  • the present invention encompasses an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising:
  • the present invention further encompasses a method of bleaching fabrics which comprises the steps of:
  • the present invention also encompasses the use of a pH buffering means, in an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising from 2% to 10% by weight of the total composition of an alkali metal hypochlorite, and a bleach stable perfume, whereby said perfume causes no more than 10% AvCl2 loss in 5 days at 50C, to reduce the chlorine odor during and after use.
  • compositions according to the present invention are aqueous bleaching compositions.
  • they comprise hypochlorite in an aqueous matrix.
  • alkali metal hypochlorite Various forms of alkali metal hypochlorite are commercially available and, although this is not critical for the present invention, it is preferred herein to use sodium hypochlorite.
  • Compositions according to the present invention comprise a bleaching amount of alkali metal hypochlorite, which represents from 2% to 10% by weight of the total composition, based on active chlorine, of alkali metal hypochlorite.
  • Preferred compositions herein comprise from 3% to 6% of alkali metal hypochlorite.
  • compositions according to the present invention have a pH as is of from 11.5 to 14, preferably from 12.5 to 14. Suitable means to achieve such a pH value include potassium and sodium hydroxide.
  • compositions according to the present invention are suitable for use in diluted form.
  • the expression "use in diluted form” herein includes dilution by the user, which occurs for instance in household application or hand laundry applications, as well as dilution by other means, such as in a washing machine. Typical dilution levels are of from 0.5% to 20% for hand laundry application, 0.1% to 10% in a washing machine, and 0.5 to 20% for household application.
  • the pH of the composition as is changes, i.e. decreases, to a certain pH value which is hereinafter referred to as the pH of the diluted composition.
  • the pH of the diluted composition is buffered to a substantially constant value throughout use, i.e. from the moment the dilution is completed and until the hypochlorite bleaching composition is started to be rinsed away.
  • composition according to the present invention comprise pH buffering means whereby the pH of the diluted composition remains constant throughout use.
  • silicate or carbonate salts or mixtures thereof.
  • Particularly useful are alkali metal salts of silicate and carbonate, preferably sodium silicate and sodium carbonate, both of which are commercially available, or mixtures thereof.
  • the compositions according to the present invention comprise a mixture of sodium carbonate and sodium silicate.
  • the compositions herein comprise from 0.2% to 5% by weight of the total composition of sodium carbonate, preferably from 0.5% to 3%, and from 0.02% to 3% by weight of the total composition of sodium silicate, preferably from 0.04% to 3%.
  • the present invention is based on the finding that the addition of a pH buffering means, preferably a carbonate salt (typically at a level of 0.2% to 5% by weight) and/or a silicate salt (typically at a level of 0.02% to 3% by weight), in an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising an alkali metal hypochlorite and a bleach stable perfume as defined herein, reduces the chlorine odor during and after use.
  • a pH buffering means preferably a carbonate salt (typically at a level of 0.2% to 5% by weight) and/or a silicate salt (typically at a level of 0.02% to 3% by weight)
  • the compositions according to the present invention comprise a bleach stable perfume, whereby said perfume causes no more than 10% loss of available chlorine in 5 days at 50°c, preferably not more than 8% loss of available chlorine.
  • a bleach stable perfume whereby said perfume causes no more than 10% loss of available chlorine in 5 days at 50°c, preferably not more than 8% loss of available chlorine.
  • most perfume ingredients are incompatible for use in a strong oxidizing environment such as hypochlorite bleaching compositions.
  • the hypochlorite attacks the perfume, resulting not only in the degradation of the perfume but also in the loss of available chlorine, thus bleaching power.
  • Perfumes useful for use herein do not cause loss of available chlorine outside the limits described hereinabove.
  • the capacity of a perfume to meet this criteria is evaluated by comparing a composition with the perfume to a composition without, to account for the loss of available chlorine which is not due to the perfume.
  • the available chlorine is measured in the fresh compositions, i.e. just after they are made, and in the same compositions after 5 days storage at 50 °c, using the method described for instance in "Analyses des Eaux et Extraits de Javel” by Latica syndicalerance de L'eau de Javel et des building connexes, Pages 9-10 (1984). The % loss of available chlorine is then calculated.
  • perfume it is meant herein individual perfume components as well as mixtures thereof.
  • Bleach stable perfumes include components in the class of acetals, aldehydes, esters, alcohols, ketones, ethers, nitriles, terpenes, as well as miscellaneous materials, including materials of natural origin.
  • suitable acetals components include 1,2,3,4,6,7,8-octahydro 2,3,8,8-tetramethyl -2 acetal naphtalene, available from IFF under the trade name Iso E Super®, octane 1,1-dimethoxy acetal, commercially available from Dragoco under the trade name Resedyl Acetal ®, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, commercially available from Dragoco under the trade name Vertacetal ®, 1,3-dioxolane 2-hexyl acetal, commercially available from Dragoco under the trade name Ylamone ®, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, and acetaldehyde phenyl ethyl propyl acetal.
  • Suitable perfume components within the class of esters include dihydro terpinyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, commercially available from Dragoco under the trade name Vetikol Acetate ®, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, fenchyl acetate, iso bornyl acetate, styrallyl acetate.
  • Suitable perfume components within the class of alcohols include 4-tert-butylcyciohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, commercially available from IFF under the trade name Dimetol ®, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol.
  • Suitable perfume components from the class of ketones include menthone, iso menthone racemic, dimethyl octanone, fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone.
  • Suitable perfume components from the class of ethers include monoterpenes and cyclic monoterpenes ethers, commercially available from Givaudan Roure under the trade name Lime Oxide ®, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether.
  • Suitable perfume components in the class of nitriles include 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, commercially available from Dragoco under the trade name Cantryl ®, bicyclo [2.2.1] heptane-2 carbonitrile, commercially available from Dragoco under the trade name Romaryl ®, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile.
  • Suitable terpenes as perfume components herein include para cymene and terpinolene.
  • Suitable materials of natural origin include essential oils and resins such as eucalyptus oil, cistus oil, patchouli oil.
  • suitable miscellaneous materials include eucalyptol and 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene.
  • the compositions according to the present invention typically comprise from 0.000002% to 2% by weight of the total composition of said perfume, preferably from 0.000005% to 0.5 %.
  • compositions according to the present invention further comprise a bleach-stable perfume solubilizer, i.e. a surface active ingredient which helps the homogeneization or solubilization of the perfume in the composition.
  • Suitable bleach-stable perfume solubilizers include amine oxides, alkyl ethoxy methyl carboxylates, alkyl phenyl ethoxy methyl carboxylates, diphenyl oxide sulphonates, sarcosinates, taurates, betaines, quaternary ammoniun salts, sulphates, sulphonates, and mixtures thereof.
  • compositions according to the present invention typically comprise from 0.000001% to 20% by weight of the total composition of a perfume solubilizer, preferably from 0.000002% to 5%.
  • the present invention further encompasses a method of bleaching fabrics which comprises the steps of first contacting said fabrics with an aqueous liquid bleaching composition suitable for use in diluted form, having a pH as is of from 11.5 to 14 and comprising:
  • a composition of pH 13.1 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium carbonate, 0.02% benzophenone, 0.02% nonyl phenyl ethoxy(7) methyl carboxylate and water up to 100%.
  • the loss of available chlorine is the same with and without benzophenone and amounts to about 14% loss of available chlorine in 5 days at 50°c.
  • Said compositions is used in a method of bleaching fabrics according to the present invention.
  • a composition of pH 13.2 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium carbonate, 1.0% sodium silicate, 0.03% tetrahydromyrcenol, 0.04% nonyl phenyl ethoxy(7) methyl carboxylate, and water up to 100%.
  • the loss of available chlorine is the same with and without tetrahydromercenol and amounts to about 14% loss of available chlorine in 5 days at 50°C.
  • composition exemplified herein after (example 3 to 6) are designed for use in a method of bleaching fabrics according to the present invention.
  • a composition of pH 13.2 is prepared which contains 5% available chlorine, 0.8% sodium hydroxide, 1% sodium carbonate, 0.03% tetrahydrolynalool, 0.07% nonyl ethoxy(5) methyl carboxylate and water up to 100%.
  • the loss of available chlorine is the same with and without tetrahydrolynalool and amounts to about 16% loss of available chlorine in 5 days at 50°c.
  • a composition of pH 13.0 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium silicate, 0.03% fenchylacetate, 0.08% nonyl ethoxy(5) methyl carboxylate, and water up to 100%.
  • the loss of available chlorine is the same with and without fenchylacetate and amounts to about 16% loss of available chlorine in 5 days at 50°c.
  • a composition of pH 13.2 is prepared which contains 5% available chlorine, 0.8% sodium hydroxide, 1% sodium carbonate, 0.03% ortho tertiary amyl cyclohexanyl acetate, 0.1% diphenyl oxide, and water up to 100%.
  • the loss of available chlorine is the same with and without fenchylacetate and amounts to about 16% loss of available chlorine in 5 days at 50°c.
  • a composition of pH 13.0 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium silicate, 0.03% eucaliptol, 0.04% nonyl phenyl ethoxy(7) methyl carboxylate, and water up to 100%.
  • the loss of available chlorine is the same with and without fenchylacetate and amounts to about 16% loss of available chlorine in 5 days at 50°c.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

Liquid aqueous bleaching compositions are disclosed which are suitable for use in diluted form. The compositions comprise an akali metal hypochlorite and a bleach stable perfume. The compositions have a pH as is of from 11.5 to 14, and comprise a buffering means, i.e., a carbonate salt and/or a silicate salt. A method of bleaching fabrics with such a composition is also disclosed.

Description

Technical field
The present invention relates to a liquid bleaching composition which is suitable both for laundry and household applications. Compositions herein are particularly suitable in laundry applications, as a prewash bleaching composition.
Background of the invention
Liquid bleaching compositions are well known In the art. Amongst the different bleaching compositions available, those relying on bleaching by hypochlorite are often preferred, mainly for performance reasons. These hypochlorite-based compositions are typically used in dilute form and are suitable both for laundry and household applications. However a major drawback associated with chlorine-based compositions is the malodor they generate during and after use. Indeed, not only does the composition itself smell chlorine bleach, but the malodor remains noticeable on fabrics or surfaces which have been treated with said compositions, as well as on the skin of the user of the composition, even after the bleaching composition has been thoroughly rinsed away.
Formulators have tried to solve that problem by designing perfumed chlorine-based bleaching compositions. However, this has proved difficult mainly for two reasons. Firstly, only a few perfume components are available which are stable in a strong oxidative environment such as a chlorine-based bleaching composition, resulting in limited flexibility in designing perfumes for such compositions. Secondly, chlorine bleach odor is strong and therefore difficult to mask even when perfumes are present.
It is thus an object of the present invention to provide a chlorine bleaching composition wherein the chlorine odor is reduced during and after use.
Various solutions to this problem have been discussed in the art. See for instance JP 63108099, where sulphamates were proposed to diminish chlorine odor. See also ES 8800652 which proposes a process for packaging chlorine bleach where perfume is injected into the container just before the container is closed. See also JP62205200 which proposes certain perfume ingredients in combination with certain surfactants.
Our invention proposes a simple solution to this problem. We have now found that a chlorine-based bleaching composition suitable for use in diluted form could be formulated, which exhibits a reduced chlorine odor upon use, by adding a pH buffering means, preferably a carbonate salt and/or a silicate salt in an aqueous bleaching composition, said composition comprising an alkali metal hypochlorite (2% - 10% by weight) and a bleach stable perfume and being formulated, at a pH of from 11.5 to 14.
WO 88/05461, discloses a bleaching composition comprising sodium hypochlorite, sodium carbonate and sodium hydroxide.
US 4 287 079 discloses aqueous cleaning compositions to be applied from squirt bottle comprising a particulate abrasive, a two part thickener consisting essentially of a mixture of fumed silicon dioxide and smectite clay, an aqueous hypohalite bleach solution, an alkaline builder and perfume like isobornylacetate. Said compositions are suitable for cleaning hard surfaces, no laundry application is disclosed.
GB-A-2 076 010 discloses thickened aqueous bleach compositions comprising an alkali metal hypochlorite, one or more carboxylated surfactants, metal hydroxide, electrolytes such as calcium carbonate and perfume. Said compositions are suitable for cleaning vertical and inclined surfaces, no laundry application is disclosed.
EP-A-30 401 discloses liquid thickened chlorine bleaching compositions having a pH of from 10 to 12.5 and comprising hypochlorite, a buffering means like alkali metal salts of carbonic acid and of silicilic acid, perfume and a thickening system, i.e. a mixture of two different detergent active compounds. Said compositions are useful for bleaching hard surfaces, no laundry application is disclosed.
EP-A-204 472 discloses a thickened aqueous cleaning composition comprising a specific tertiary amino oxide and an alkali metal or alkaline earth metal mono- or polyalkylated benzene or naphthalene sulphonate in which the alkyl groups contain from 1 to 4 carbon atoms. Said compositions may further comprise hypochlorite, metal hydroxide, alkali metal carbonate and perfume like isobornylacetate dihydroter pincol, dihydroterpinyl acetate and isoborneol. Alkali metal carbonate may be present as a contaminant of commercially available hypochlorite solution at a level of from 0.01% to 0.1% by weight of the hypochlorite solution. Said compositions are suitable for cleaning non-horizontal structural surfaces, no laundry application is disclosed.
US 4 235 732 discloses alkaline aqueous hypochlorite cleaning compositions containing paraffin sulphonate surfactant, an inorganic colloid-forming clay, insoluble particulate abrasive, an inorganic alkaline salt capable of maintaining the composition pH within the range of from about 10 to 14 and perfume. Different bleaching applications are disclosed including bleaching of textiles.
US 3 876 551 discloses aqueous perfumed compositions (pH 12 to 13.5) containing an alkali metal hypochlorite, a stable perfume oil and a surface active agent consisting solely of an amine oxide composition which consists essentially of one or more morpholine and/or dimethyl C11-C13 straight chain alkyl amine oxides. No pH buffering means are disclosed. Said compositions are suitable for laundry and domestic bleaching.
EP-A-186 386 discloses an aqueous composition and having a pH above 12, comprising sodium hypochlorite, perfume, optical brighteners and amine oxides. No pH buffering means are disclosed. Said compositions are suitable for laundry applications.
Summary of the invention
The present invention encompasses an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising:
  • a bleach stable perfume, whereby said perfume causes no more than 10 % AvCl2 loss in 5 days at 50°c,
  • from 2% to 10% by weight of the total composition of an alkali metal hypochlorite,
  • from 0.2% to 5% by weight of the total composition of a carbonate salt and from 0.02% to 3% by weight of a silicate salt,
and wherein said bleach stable perfume is selected from the group consisting of 1,2,3,4,6,7,8-octahydro 2,3,8,8- tetramethyl -2 acetal naphtalene, octane 1,1-dimethoxy acetal, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, 1,3-dioxolane 2-hexyl acetal, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, acetaldehyde, phenyl ethyl propyl acetal, dihydro terpinyl acetate, iso bornyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, Fenchyl acetate, styrallyl acetate, 4-tert-butylcyclohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, Fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol, Menthone, Iso menthone racemic, dimethyl octanone, Fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone, monoterpenes and cyclic monoterpenes ethers, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether, 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, bicyclo [2.2.1] heptane-2 carbonitrile, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile, para cymene and terpinolene, eucalyptol, 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene, essential oils and resins including eucalyptus oil, cistus oil and patchouli oil, and mixtures thereof.
The present invention further encompasses a method of bleaching fabrics which comprises the steps of:
  • first contacting said fabrics with an aqueous liquid bleaching composition suitable for use in diluted form, having a pH as is of from 11.5 to 14 and comprising:
    • a bleach stable perfume, whereby said perfume causes no more than 10 % AvCl2 loss in 5 days at 50°c,
    • from 2% to 10% by weight of the total composition of an alkali metal hypochlorite,
    • from 0.2% to 5% by weight of the total composition of a carbonate salt and/or from 0.02% to 3% by weight of a silicate salt,
    • a perfume - solubilizing amount of a perfume solubilizing surfactant selected from the group consisting of amine oxides, alkyl ethoxy methyl carboxylates, alkyl phenyl ethoxy methyl carboxylates, diphenyl oxide sulphonates, sarcosinates, taurates, betaines, quarternary ammonium salts, and mixtures thereof,
    and wherein said bleach stable perfume is selected from the group consisting of 1,2,3,4,6,7,8-octahydro 2,3,8,8- tetramethyl -2 acetal naphtalene, octane 1,1-dimethoxy acetal, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, 1,3-dioxolane 2-hexyl acetal, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, acetaldehyde, phenyl ethyl propyl acetal, dihydro terpinyl acetate, iso bornyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, Fenchyl acetate, styrallyl acetate, 4-tert-butylcyclohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, Fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol, Menthone, Iso menthone racemic, dimethyl octanone, Fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone, monoterpenes and cyclic monoterpenes ethers, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether, 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, bicyclo [2.2.1] heptane-2 carbonitrile, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile, para cymene and terpinolene, eucalyptol, 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene, essential oils and resins including eucalyptus oil, cistus oil and patchouli oil, and mixtures thereof,
  • then allowing said fabrics to remain in contact with said composition for a period of time sufficient to bleach said fabrics,
  • then rinsing said fabrics in water to remove said composition.
Finally, the present invention also encompasses the use of a pH buffering means, in an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising from 2% to 10% by weight of the total composition of an alkali metal hypochlorite, and a bleach stable perfume, whereby said perfume causes no more than 10% AvCl2 loss in 5 days at 50C, to reduce the chlorine odor during and after use.
Detailed Description of the invention
The compositions according to the present invention are aqueous bleaching compositions. Thus they comprise hypochlorite in an aqueous matrix. Various forms of alkali metal hypochlorite are commercially available and, although this is not critical for the present invention, it is preferred herein to use sodium hypochlorite. Compositions according to the present invention comprise a bleaching amount of alkali metal hypochlorite, which represents from 2% to 10% by weight of the total composition, based on active chlorine, of alkali metal hypochlorite. Preferred compositions herein comprise from 3% to 6% of alkali metal hypochlorite.
As a second essential feature, the compositions according to the present invention have a pH as is of from 11.5 to 14, preferably from 12.5 to 14. Suitable means to achieve such a pH value include potassium and sodium hydroxide.
The compositions according to the present invention are suitable for use in diluted form. The expression "use in diluted form" herein includes dilution by the user, which occurs for instance in household application or hand laundry applications, as well as dilution by other means, such as in a washing machine. Typical dilution levels are of from 0.5% to 20% for hand laundry application, 0.1% to 10% in a washing machine, and 0.5 to 20% for household application. As the composition according to the present invention is diluted, the pH of the composition as is changes, i.e. decreases, to a certain pH value which is hereinafter referred to as the pH of the diluted composition. For the purpose of the present invention, it is essential that the pH of the diluted composition is buffered to a substantially constant value throughout use, i.e. from the moment the dilution is completed and until the hypochlorite bleaching composition is started to be rinsed away.
Therefore, as a third essential feature, the composition according to the present invention comprise pH buffering means whereby the pH of the diluted composition remains constant throughout use.
In order to achieve a proper buffering of the pH within the present invention, it has been found particularly useful to use silicate or carbonate salts, or mixtures thereof. Particularly useful are alkali metal salts of silicate and carbonate, preferably sodium silicate and sodium carbonate, both of which are commercially available, or mixtures thereof. The compositions according to the present invention comprise a mixture of sodium carbonate and sodium silicate. The compositions herein comprise from 0.2% to 5% by weight of the total composition of sodium carbonate, preferably from 0.5% to 3%, and from 0.02% to 3% by weight of the total composition of sodium silicate, preferably from 0.04% to 3%.
In its broader embodiment, the present invention is based on the finding that the addition of a pH buffering means, preferably a carbonate salt (typically at a level of 0.2% to 5% by weight) and/or a silicate salt (typically at a level of 0.02% to 3% by weight), in an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising an alkali metal hypochlorite and a bleach stable perfume as defined herein, reduces the chlorine odor during and after use.
As a fourth essential ingredient, the compositions according to the present invention comprise a bleach stable perfume, whereby said perfume causes no more than 10% loss of available chlorine in 5 days at 50°c, preferably not more than 8% loss of available chlorine. Indeed, it is well known that most perfume ingredients are incompatible for use in a strong oxidizing environment such as hypochlorite bleaching compositions. In such compositions, the hypochlorite attacks the perfume, resulting not only in the degradation of the perfume but also in the loss of available chlorine, thus bleaching power. Perfumes useful for use herein do not cause loss of available chlorine outside the limits described hereinabove. The capacity of a perfume to meet this criteria is evaluated by comparing a composition with the perfume to a composition without, to account for the loss of available chlorine which is not due to the perfume.
In both, the available chlorine is measured in the fresh compositions, i.e. just after they are made, and in the same compositions after 5 days storage at 50 °c, using the method described for instance in "Analyses des Eaux et Extraits de Javel" by La chambre syndicale nationale de L'eau de Javel et des produits connexes, Pages 9-10 (1984). The % loss of available chlorine is then calculated.
By perfume, it is meant herein individual perfume components as well as mixtures thereof. Bleach stable perfumes include components in the class of acetals, aldehydes, esters, alcohols, ketones, ethers, nitriles, terpenes, as well as miscellaneous materials, including materials of natural origin. More specifically, suitable acetals components include 1,2,3,4,6,7,8-octahydro 2,3,8,8-tetramethyl -2 acetal naphtalene, available from IFF under the trade name Iso E Super®, octane 1,1-dimethoxy acetal, commercially available from Dragoco under the trade name Resedyl Acetal ®, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, commercially available from Dragoco under the trade name Vertacetal ®, 1,3-dioxolane 2-hexyl acetal, commercially available from Dragoco under the trade name Ylamone ®, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, and acetaldehyde phenyl ethyl propyl acetal. Suitable perfume components within the class of esters include dihydro terpinyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, commercially available from Dragoco under the trade name Vetikol Acetate ®, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, fenchyl acetate, iso bornyl acetate, styrallyl acetate. Suitable perfume components within the class of alcohols include 4-tert-butylcyciohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, commercially available from IFF under the trade name Dimetol ®, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol. Suitable perfume components from the class of ketones include menthone, iso menthone racemic, dimethyl octanone, fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone. Suitable perfume components from the class of ethers include monoterpenes and cyclic monoterpenes ethers, commercially available from Givaudan Roure under the trade name Lime Oxide ®, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether.
Suitable perfume components in the class of nitriles include 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, commercially available from Dragoco under the trade name Cantryl ®, bicyclo [2.2.1] heptane-2 carbonitrile, commercially available from Dragoco under the trade name Romaryl ®, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile. Suitable terpenes as perfume components herein include para cymene and terpinolene. Suitable materials of natural origin include essential oils and resins such as eucalyptus oil, cistus oil, patchouli oil. Finally, suitable miscellaneous materials include eucalyptol and 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene. The compositions according to the present invention typically comprise from 0.000002% to 2% by weight of the total composition of said perfume, preferably from 0.000005% to 0.5 %.
As a highly preferred ingredient, the compositions according to the present invention further comprise a bleach-stable perfume solubilizer, i.e. a surface active ingredient which helps the homogeneization or solubilization of the perfume in the composition. Suitable bleach-stable perfume solubilizers include amine oxides, alkyl ethoxy methyl carboxylates, alkyl phenyl ethoxy methyl carboxylates, diphenyl oxide sulphonates, sarcosinates, taurates, betaines, quaternary ammoniun salts, sulphates, sulphonates, and mixtures thereof. Preferred for use herein are amine oxides, alkyl ethoxy methyl carboxylates, alkyl phenyl ehtoxy methyl carboxylates, diphenyl oxides and mixtures thereof. The compositions according to the present invention typically comprise from 0.000001% to 20% by weight of the total composition of a perfume solubilizer, preferably from 0.000002% to 5%.
The present invention further encompasses a method of bleaching fabrics which comprises the steps of first contacting said fabrics with an aqueous liquid bleaching composition suitable for use in diluted form, having a pH as is of from 11.5 to 14 and comprising:
  • a bleach stable perfume, whereby said perfume causes no more than 10 % AvCl2 loss in 5 days at 50°c,
  • from 2% to 10% by weight of the total composition of an alkali metal hypochlorite,
  • from 0.2% to 5% by weight of the total composition of a carbonate salt and/or from 0.02% to 3% by weight of a silicate salt,
  • a perfume - solubilizing amount of a perfume solubilizing surfactant selected from the group consisting of amine oxides, alkyl ethoxy methyl carboxylates, alkyl phenyl ethoxy methyl carboxylates, diphenyl oxide sulphonates, sarcosinates, taurates, betaines, quarternary ammonium salts, and mixtures thereof,
and wherein said bleach stable perfume is selected from the group consisting of 1,2,3,4,6,7,8-octahydro 2,3,8,8- tetramethyl -2 acetal naphtalene, octane 1,1-dimethoxy acetal, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, 1,3-dioxolane 2-hexyl acetal, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, acetaldehyde phenyl ethyl propyl acetal, dihydro terpinyl acetate, iso bornyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, Fenchyl acetate, styrallyl acetate, 4-tert-butylcyclohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, Fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol, Menthone, Iso menthone racemic, dimethyl octanone, Fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone, monoterpenes and cyclic monoterpenes ethers, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether, 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, bicyclo [2.2.1] heptane-2 carbonitrile, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile, para cymene and terpinolene, eucalyptol, 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene, essential oils and resins including eucalyptus oil, cistus oil and patchouli oil, and mixtures thereof, then allowing said fabrics to remain in contact with said composition for a period of time sufficient to bleach said fabrics, typically 5 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics in water to remove said composition. If said fabrics are to be washed, i.e. with a conventional composition comprising at least one surface active agent, it is preferred to perform the method herein before said fabrics are washed. Indeed, it has been observed that bleaching said fabrics with the compositions according to the present invention prior to washing them with a detergent composition provides superior whitenesss and stain removal with less energy and detergent than if said fabrics are washed first, then bleached. Accordingly, said method according to the present invention further comprises a subsequent step where said fabrics are washed with a detergent composition comprising at least one surface active agent.
The present invention will be further illustrated by the following examples.
Example 1
A composition of pH 13.1 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium carbonate, 0.02% benzophenone, 0.02% nonyl phenyl ethoxy(7) methyl carboxylate and water up to 100%. In said composition, the loss of available chlorine is the same with and without benzophenone and amounts to about 14% loss of available chlorine in 5 days at 50°c. Said compositions is used in a method of bleaching fabrics according to the present invention.
Example 2
A composition of pH 13.2 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium carbonate, 1.0% sodium silicate, 0.03% tetrahydromyrcenol, 0.04% nonyl phenyl ethoxy(7) methyl carboxylate, and water up to 100%. In said composition, the loss of available chlorine is the same with and without tetrahydromercenol and amounts to about 14% loss of available chlorine in 5 days at 50°C.
The composition exemplified herein after (example 3 to 6) are designed for use in a method of bleaching fabrics according to the present invention.
Example 3
A composition of pH 13.2 is prepared which contains 5% available chlorine, 0.8% sodium hydroxide, 1% sodium carbonate, 0.03% tetrahydrolynalool, 0.07% nonyl ethoxy(5) methyl carboxylate and water up to 100%. In said composition, the loss of available chlorine is the same with and without tetrahydrolynalool and amounts to about 16% loss of available chlorine in 5 days at 50°c.
Example 4
A composition of pH 13.0 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium silicate, 0.03% fenchylacetate, 0.08% nonyl ethoxy(5) methyl carboxylate, and water up to 100%. In said composition, the loss of available chlorine is the same with and without fenchylacetate and amounts to about 16% loss of available chlorine in 5 days at 50°c.
Example 5
A composition of pH 13.2 is prepared which contains 5% available chlorine, 0.8% sodium hydroxide, 1% sodium carbonate, 0.03% ortho tertiary amyl cyclohexanyl acetate, 0.1% diphenyl oxide, and water up to 100%. In said composition, the loss of available chlorine is the same with and without fenchylacetate and amounts to about 16% loss of available chlorine in 5 days at 50°c.
Example 6
A composition of pH 13.0 is prepared which contains 5% available chlorine, 0.7% sodium hydroxide, 1% sodium silicate, 0.03% eucaliptol, 0.04% nonyl phenyl ethoxy(7) methyl carboxylate, and water up to 100%. In said composition, the loss of available chlorine is the same with and without fenchylacetate and amounts to about 16% loss of available chlorine in 5 days at 50°c.

Claims (10)

  1. An aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising:
    a bleach stable perfume, whereby said perfume causes no more than 10 % AvCl2 loss in 5 days at 50°c,
    from 2% to 10% by weight of the total composition of an alkali metal hypochlorite,
    from 0.2% to 5% by weight of the total composition of a carbonate salt and from 0.02% to 3% by weight of a silicate salt,
    and wherein said bleach stable perfume is selected from the group consisting of 1,2,3,4,6,7,8-octahydro 2,3,8,8- tetramethyl -2 acetal naphtalene, octane 1,1-dimethoxy acetal, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, 1,3-dioxolane 2-hexyl acetal, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, acetaldehyde, phenyl ethyl propyl acetal, dihydro terpinyl acetate, iso bomyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, Fenchyl acetate, styrallyl acetate, 4-tert-butylcyclohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, Fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol, Menthone, Iso menthone racemic, dimethyl octanone, Fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone, monoterpenes and cyclic monoterpenes ethers, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether, 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, bicyclo [2.2.1] heptane-2 carbonitrile, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile, para cymene and terpinolene, eucalyptol, 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene, essential oils and resins including eucalyptus oil, cistus oil and patchouli oil, and mixtures thereof.
  2. A composition according to claim 1 which comprises from 3% to 6% by weight of the total composition, based on active chlorine, of hypochlorite.
  3. A composition according to claims 1 and 2 wherein said perfume causes no more than 8% loss of available chlorine in 5 days at 50 °c.
  4. A composition according to the preceding claims wherein said pH is of from 12.5 to 14.
  5. A composition according to the preceding claims which comprises from 0.000002% to 2%, preferably from 0.000005% to 0.5% by weight of the total composition of said bleach stable perfume.
  6. A composition according to the preceding claims which further comprises from 0.000001% to 20% by weight of the total composition of a perfume solubilizer, preferably 0.000002% to 5%.
  7. A method of bleaching fabrics which comprises the steps of:
    first contacting said fabrics with an aqueous liquid bleaching composition suitable for use in diluted form, having a pH as is of from 11.5 to 14 and comprising:
    a bleach stable perfume, whereby said perfume causes no more than 10 % AvCl2 loss in 5 days at 50°c,
    from 2% to 10% by weight of the total composition of an alkali metal hypochlorite,
    from 0.2% to 5% by weight of the total composition of a carbonate salt and/or from 0.02% to 3% by weight of a silicate salt,
    a perfume - solubilizing amount of a perfume solubilizing surfactant selected from the group consisting of amine oxides, alkyl ethoxy methyl carboxylates, alkyl phenyl ethoxy methyl carboxylates, diphenyl oxide sulphonates, sarcosinates, taurates, betaines, quarternary ammonium salts, and mixtures thereof,
    and wherein said bleach stable perfume is selected from the group consisting of 1,2,3,4,6,7,8-octahydro 2,3,8,8- tetramethyl -2 acetal naphtalene, octane 1,1-dimethoxy acetal, 1,3-dioxane 2,4,6-trimethyl 4-phenyl acetal, 1,3-dioxolane 2-hexyl acetal, phenylacetaldehyde dimethyl acetal, aldehyde dimethyl acetal, citral diethyl acetal, acetaldehyde, phenyl ethyl propyl acetal, dihydro terpinyl acetate, iso bornyl acetate, tetrahydro linalyl acetate, benzene propanoltrimethyl acetate, ortho tertiary butyl cyclohexanol acetate, ortho tertiary amyl cyclohexanyl acetate, Fenchyl acetate, styrallyl acetate, 4-tert-butylcyclohexanol, dihydro terpineol, tetrahydro geraniol, tetrahydro myrcenol, tetrahydro linaleol, Fenchyl alcohol, dimethyl octanol, 2,5-dimethyl heptan-2-ol, phenyl methyl ethyl carbinol, dimethyl benzyl carbinol, dimethyl phenyl ethyl carbinol, Menthone, Iso menthone racemic, dimethyl octanone, Fenchone-1,1,3-trimethyl bicyclo-1,2,2-heptanone 2, benzophenone, monoterpenes and cyclic monoterpenes ethers, diphenyl oxide, iso amyl phenyl ethyl ether, paracrasyl methyl ether, phenyl ethyl methyl ether, beta naphtol methyl ether, methyl diphenyl ether, 3-cyclopentane 2,2,3-trimethyl 1-acetonitrile, bicyclo [2.2.1] heptane-2 carbonitrile, 5-phenyl-3-methyl-pentaneacid nitrile, dodecanenitrile, tetrahydro geranyl nitrile, para cymene and terpinolene, eucalyptol, 2,4,6-trinitro-3,5-dimethyl-tert-butyl benzene, essential oils and resins including eucalyptus oil, cistus oil and patchouli oil, and mixtures thereof,
    then allowing said fabrics to remain in contact with said composition for a period of time sufficient to bleach said fabrics,
    then rinsing said fabrics in water to remove said composition.
  8. A method according to claim 7 which further comprises a subsequent step where said fabrics are washed with a detergent composition comprising at least one surface active agent.
  9. The use, in an aqueous liquid bleaching composition suitable for use in diluted form, said composition having a pH as is of from 11.5 to 14 and comprising from 2% to 10% by weight of the total composition of an alkali metal hypochlorite, and a bleach stable perfume, whereby said perfume causes no more than 10% AvCl2 loss in 5 days at 50C, of a pH buffering means, to reduce the chlorine odor during and after use.
  10. The use according to claim 9 wherein said pH buffering means is a carbonate salt at a level of 0.2% to 5% by weight of the total composition and/or a silicate salt at a level of 0.02% to 3% by weight of the total composition.
EP93870070A 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions Revoked EP0622451B1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
ES93870070T ES2127267T3 (en) 1993-04-26 1993-04-26 HYPOCHLORITE SCENTED WHITENING COMPOSITIONS.
EP98870103A EP0867503A3 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions
DE69322375T DE69322375T2 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleach
DK93870070T DK0622451T3 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions
AT93870070T ATE174054T1 (en) 1993-04-26 1993-04-26 PERFUMED HYPOCHLORITE BLEACHES
EP93870070A EP0622451B1 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP93870070A EP0622451B1 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP98870103A Division EP0867503A3 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions

Publications (2)

Publication Number Publication Date
EP0622451A1 EP0622451A1 (en) 1994-11-02
EP0622451B1 true EP0622451B1 (en) 1998-12-02

Family

ID=8215338

Family Applications (2)

Application Number Title Priority Date Filing Date
EP93870070A Revoked EP0622451B1 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions
EP98870103A Withdrawn EP0867503A3 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP98870103A Withdrawn EP0867503A3 (en) 1993-04-26 1993-04-26 Perfumed hypochlorite bleaching compositions

Country Status (5)

Country Link
EP (2) EP0622451B1 (en)
AT (1) ATE174054T1 (en)
DE (1) DE69322375T2 (en)
DK (1) DK0622451T3 (en)
ES (1) ES2127267T3 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7067153B2 (en) 2000-09-25 2006-06-27 Cognis France S.A. Microcapsule powder
EP2179748A1 (en) 2008-10-27 2010-04-28 The Procter & Gamble Deodorizing system
EP2179747A1 (en) 2008-10-27 2010-04-28 The Procter & Gamble Company Method of reducing malodors

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0743391A1 (en) * 1995-05-16 1996-11-20 The Procter & Gamble Company A process of bleaching fabrics
DE69528185D1 (en) 1995-12-22 2002-10-17 Procter & Gamble hypochlorite bleach
DE19700799C2 (en) * 1997-01-13 1999-02-04 Henkel Kgaa Aqueous textile bleach
EP0867501A1 (en) * 1997-03-27 1998-09-30 The Procter & Gamble Company Bleaching compositions
US5939368A (en) * 1997-10-08 1999-08-17 Firmenich Sa Use of 1-methoxy-2-methyl-3-phenylpropane, 1-(2-methoxypropyl)-4-methylbenzene and 3-methoxy-2,2,3-trimethyl-1-phenylbutane in perfumery
WO1999058635A1 (en) * 1998-05-08 1999-11-18 Henkel Kommanditgesellschaft Auf Aktien Bleaching and disinfecting agents
DE19855329A1 (en) 1998-12-01 2000-06-08 Henkel Kgaa Preparations containing active chlorine with stabilized optical brighteners
DE19855347C1 (en) * 1998-12-01 2000-09-21 Henkel Kgaa Preparations containing active chlorine with stabilized fragrances
ES2213948T3 (en) 1999-07-02 2004-09-01 Cognis Iberia, S.L. MICROCAPSULES II.
ATE258417T1 (en) 1999-07-02 2004-02-15 Cognis Iberia Sl MICRO CAPSULES - I
ES2247749T3 (en) 1999-07-02 2006-03-01 Cognis Ip Management Gmbh MICROCAPSULES III.
EP1064910B1 (en) 1999-07-02 2005-09-14 Cognis IP Management GmbH Microcapsules
US6824705B1 (en) * 2003-05-19 2004-11-30 Colgate-Palmolive Co. Bleach odor reducing composition
DE102005062008B3 (en) 2005-12-22 2007-08-30 Henkel Kgaa Odor reduction of hypochlorite-containing agents
DE102005063177A1 (en) 2005-12-30 2007-07-05 Henkel Kgaa Use of diethylene-penta-methylene phosphonic acid for the stabilization of optical brightener in aqueous liquid detergent containing alkali hypochlorite
DE102007034539A1 (en) * 2007-07-20 2009-01-22 Henkel Ag & Co. Kgaa Gentle bleach
US10465149B2 (en) 2016-03-02 2019-11-05 Harris Research, Inc. Stain and odor treatment
JP6781866B2 (en) * 2018-01-12 2020-11-11 加地貿易 株式会社 Deodorant and cleaning method for chlorine odor in residual scent of chlorine-based cleaning agent

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62205200A (en) * 1986-03-03 1987-09-09 花王株式会社 Aromatic liquid bleaching composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3876551A (en) * 1972-02-14 1975-04-08 Int Flavors & Fragrances Inc Perfumed aqueous hypochlorite composition and method for preparation of same
NL7908798A (en) * 1979-12-05 1981-07-01 Unilever Nv LIQUID, THICKENED CHLORINE BLEACH.
GB2076010B (en) * 1980-05-13 1984-05-16 Sandoz Products Ltd Bleach composition
US4287079A (en) * 1980-06-02 1981-09-01 Purex Corporation Liquid cleanser formula
EP0186386B1 (en) * 1984-12-28 1992-03-04 The Procter & Gamble Company Liquid hypochlorite bleach containing optical brightener solubilized by amine oxide
GB8513293D0 (en) * 1985-05-28 1985-07-03 Procter & Gamble Ntc Ltd Cleaning compositions
JPS62205199A (en) * 1986-03-03 1987-09-09 花王株式会社 Stable liquid bleaching composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62205200A (en) * 1986-03-03 1987-09-09 花王株式会社 Aromatic liquid bleaching composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 198742, Derwent World Patents Index; Class D25, AN 1987-294545 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7067153B2 (en) 2000-09-25 2006-06-27 Cognis France S.A. Microcapsule powder
EP2179748A1 (en) 2008-10-27 2010-04-28 The Procter & Gamble Deodorizing system
EP2179747A1 (en) 2008-10-27 2010-04-28 The Procter & Gamble Company Method of reducing malodors

Also Published As

Publication number Publication date
DK0622451T3 (en) 1999-08-16
EP0867503A2 (en) 1998-09-30
ATE174054T1 (en) 1998-12-15
DE69322375D1 (en) 1999-01-14
EP0622451A1 (en) 1994-11-02
DE69322375T2 (en) 1999-06-24
EP0867503A3 (en) 1999-01-20
ES2127267T3 (en) 1999-04-16

Similar Documents

Publication Publication Date Title
EP0622451B1 (en) Perfumed hypochlorite bleaching compositions
US5236614A (en) Stable microemulsion disinfecting detergent composition
US4789495A (en) Hypochlorite compositions containing a tertiary alcohol
US4576738A (en) Hard surface cleaning compositions containing pianane
JPS58132097A (en) Liquid detergent composition
IE57235B1 (en) Liquid scouring cleansers containing solvent system
GB1590744A (en) Cleansing compositions
US5804545A (en) Stable alkaline chlorine compositions
EP0820503B1 (en) Improvements relating to light duty cleaning
CA1113966A (en) Surfactant for an automatic dishwasher
CA2258130C (en) Cleaning compositions
AU2004242126B2 (en) Bleach odor reducing chlorine bleach composition
JPH05171198A (en) Solid cleaning agent
US6140300A (en) Low-foaming cleaning compositions comprising a hypochlorite bleaching component
JPS636098A (en) Detergent composition
JP3875292B2 (en) Cleaning composition for athletic shoes
US6051676A (en) Method for reducing bleach malodor on skin
EP1123375B1 (en) Thickened liquid hydrogen peroxide bleach compositions
EP0730628B1 (en) Limescale removing composition
MXPA94003045A (en) Whitening liquid aqueous compositions
JP3443500B2 (en) Cleaning composition for washing machine tub
ZA200105008B (en) Process and product for the treatment of textile fabrics.
CA2168769C (en) A process of cleaning carpets using active oxygen compounds in an acidic aqueous medium
GB2255352A (en) Liquid detergent compositions and their use
JPH051839B2 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: THE PROCTER & GAMBLE COMPANY

17P Request for examination filed

Effective date: 19950406

17Q First examination report despatched

Effective date: 19950519

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

REF Corresponds to:

Ref document number: 174054

Country of ref document: AT

Date of ref document: 19981215

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69322375

Country of ref document: DE

Date of ref document: 19990114

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: RITSCHER & SEIFERT

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

ITF It: translation for a ep patent filed
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2127267

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 19990218

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: UNILEVER N.V.

Effective date: 19990902

NLR1 Nl: opposition has been filed with the epo

Opponent name: UNILEVER N.V.

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 20000314

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20000315

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20000317

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20000320

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20000324

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20000327

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20000405

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IE

Payment date: 20000418

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000427

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20000512

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20000621

Year of fee payment: 8

PLBO Opposition rejected

Free format text: ORIGINAL CODE: EPIDOS REJO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010426

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010426

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010426

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010426

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010426

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010430

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

APAE Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOS REFNO

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010525

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20010525

APAC Appeal dossier modified

Free format text: ORIGINAL CODE: EPIDOS NOAPO

BERE Be: lapsed

Owner name: THE PROCTER & GAMBLE CY

Effective date: 20010430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011101

EUG Se: european patent has lapsed

Ref document number: 93870070.5

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20010426

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20011101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020201

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: PT

Ref legal event code: MM4A

Free format text: LAPSE DUE TO NON-PAYMENT OF FEES

Effective date: 20011031

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20040402

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20040422

Year of fee payment: 12

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20040518

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 20050421

Year of fee payment: 13

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20060430

Year of fee payment: 14