EP1010751A2 - Compositions de blanchiment - Google Patents

Compositions de blanchiment Download PDF

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Publication number
EP1010751A2
EP1010751A2 EP99870220A EP99870220A EP1010751A2 EP 1010751 A2 EP1010751 A2 EP 1010751A2 EP 99870220 A EP99870220 A EP 99870220A EP 99870220 A EP99870220 A EP 99870220A EP 1010751 A2 EP1010751 A2 EP 1010751A2
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EP
European Patent Office
Prior art keywords
acid
composition
liquid bleaching
group
alkyl
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.)
Granted
Application number
EP99870220A
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German (de)
English (en)
Other versions
EP1010751A3 (fr
EP1010751B1 (fr
Inventor
Francesco Buzzaccarini (Nmn)
Patrick Firmin Delplancke
Stefano Scialla (Nmn)
Oreste Todini (Nmn)
Alessandro Gagliardini (Nmn)
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Procter and Gamble Co
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Procter and Gamble Co
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26152307&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1010751(A2) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from EP98870271A external-priority patent/EP1010750A1/fr
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP99870220A priority Critical patent/EP1010751B1/fr
Priority to JP2000588323A priority patent/JP2002532616A/ja
Priority to CZ20012005A priority patent/CZ20012005A3/cs
Priority to AU19382/00A priority patent/AU1938200A/en
Priority to CA002352140A priority patent/CA2352140C/fr
Priority to PCT/US1999/029330 priority patent/WO2000036072A1/fr
Priority to US09/857,959 priority patent/US6548470B1/en
Priority to TR2001/01700T priority patent/TR200101700T2/xx
Priority to BR9916215-6A priority patent/BR9916215A/pt
Priority to KR1020017007348A priority patent/KR20010101190A/ko
Priority to CN99816065A priority patent/CN1334860A/zh
Priority to CO99077704A priority patent/CO5210987A1/es
Priority to ARP990106369A priority patent/AR019501A1/es
Priority to PE1999001242A priority patent/PE20001470A1/es
Publication of EP1010751A2 publication Critical patent/EP1010751A2/fr
Publication of EP1010751A3 publication Critical patent/EP1010751A3/fr
Publication of EP1010751B1 publication Critical patent/EP1010751B1/fr
Application granted granted Critical
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • 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
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • 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
    • C11D3/3945—Organic per-compounds
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to a bleaching compositions which can be used to bleach various surfaces including but not limited to, hard-surfaces as well as fabrics, clothes, carpets and the like.
  • aqueous cleaning compositions for removal or cleaning stains on fabrics and/or hard-surfaces may comprise a bleaching agent.
  • bleaching agents are known in the art.
  • Halogen bleaches whilst being extremely effective bleaching agents, often also present a number of drawbacks which can sometimes dissuade a consumer from choosing the halogen-containing product.
  • halogen bleaches especially chlorine bleaches, emit a pungent odour during and after use (e.g., on consumer hands and/or surfaces treated therewith) which some consumer find disagreeable.
  • halogen bleach-containing compositions are relatively aggressive to fabrics and may cause damage when used in relatively high concentration and/or repeated usage. In particular the consumer may perceive damage to the fabric itself (e.g. loss of tensile strength) or damage to the colour intensity of the fabric. While colour and fabric damage may be minimised by employing milder oxygen bleaches such as hydrogen peroxide or hydrogen peroxide generating bleaches, the bleach performance characteristics of such peroxygen bleaches are much less desirable than those of the halogen-containing bleaching agents. Therefore, liquid aqueous activated peroxygen bleach-containing compositions have been developed containing activators, i.e., compounds which enhance peroxygen bleaching performance. However these bleaches do not perform as well as hypohalite bleaches in stain removal.
  • activators i.e., compounds which enhance peroxygen bleaching performance.
  • Peroxycarboxylic acid (peracid) bleaches are known in the art. The Applicant has found that such bleaches, in this instance, are particularly useful as they do not present the disadvantages of hypochlorite bleaches and are better performing bleaching agents than the oxygen bleaches.
  • peracid bleach-containing compositions have stability problems as the peracid prematurely begins to degrade. This premature degradation of the peracid is believed to be due to the presence of trace amounts of metal ions in the formulation which may catalyse the further degradation of the peracid.
  • the present invention thus provides a bleaching composition which is stable, safe to the surfaces treated and delivers improved bleaching performance when used in laundry applications and/or in any household application (e.g. bleaching/disinfecting of hard-surfaces).
  • solubility of the particulate pre-formed peracid is affected by the level of hardness ions.
  • 'hardness ions it is meant ions that are present in water and form insoluble salts that precipitate from solution.
  • the most predominant hardness ions are calcium and magnesium ions
  • the water may be either water used to prepare the composition of the present invention or may be the wash water into which the composition of the present invention is dispensed.
  • compositions according to the present invention may be useful in any laundry application, e.g., as a laundry detergent or a laundry additive, and when used as a laundry pre-treater.
  • a particular advantage of the compositions of the present invention is that they are suitable for the bleaching of different types of fabrics including natural fabrics, (e.g., fabrics made of cotton, and linen), synthetic fabrics such as those made of polymeric fibres of synthetic origin (e.g., polyamide-elasthane) as well as those made of both natural and synthetic fibres.
  • the bleaching compositions of the present invention herein may be used on synthetic fabrics despite a standing prejudice against using bleaches on synthetic fabrics, as evidenced by warnings on labels of clothes and commercially available bleaching compositions like hypochlorite-containing compositions.
  • compositions according to the present invention can be used in a variety of conditions, i.e., in hard as well as soft water and in either neat or diluted form. More particularly, it has been found that the liquid aqueous compositions of the present invention find a preferred application when used in their diluted form in any application and especially in any conventional laundry application. Indeed, upon dilution (typically at a dilution level of 20ml/L or more (composition:water)) the compositions of the present invention become less acidic, e.g., from a pH of about 1.5 to about 6.5 or more.
  • compositions according to the present invention although delivering effective bleaching performance in their neat form surprisingly exhibit further enhanced bleaching performance in their diluted form.
  • this "pH jump" effect allows to formulate acidic liquid aqueous compositions (i.e. pH below 7, preferably below 3 and more preferably below 2) which are physically and chemically stable upon prolonged periods of storage and which deliver outstanding bleaching performance under diluted usage conditions.
  • acidic liquid aqueous compositions i.e. pH below 7, preferably below 3 and more preferably below 2
  • compositions of the present invention exhibit also effective stain removal performance on various stains including enzymatic stains and/or greasy stains.
  • a liquid detergent composition comprising a pre-formed particulate peroxy carboxylic acid containing at least one aromatic group and a co-agent selected from the group consisting of organic acid, homo and copolymer of acidic monomers and mixtures thereof.
  • liquid bleaching product comprising a first composition comprising a peroxy carboxylic acid containing at least one aromatic group and a second composition comprising a surfactant wherein the product is packaged such that first and second compositions are separated from each other.
  • the present invention further encompasses methods of bleaching a surface with a composition according to the present invention.
  • compositions according to the present invention are liquid and preferably aqueous.
  • the composition preferably has a water content of from 10% to 99%, more preferably from 30 to 95%, more preferably 40 to 90% by weight of the composition.
  • composition according to the present invention is liquid is preferably has a pH of below 7.
  • the pH of the compositions according to the present invention is from 1 to 6, more preferably from 1 to 5, even more preferably from 2 to 4.
  • Formulating the compositions according to the present invention in the acidic pH range is critical to the chemical stability of the compositions according to the present invention.
  • the pH of the composition is preferably below the pKa of the peracid used. It is believed that the acidic pH controls/limits the formation of highly reactive species which are unstable in acidic medium upon storage, and thus contributes to the stability of the compositions for prolonged periods of storage.
  • the pH of the compositions may be adjusted by any acid or alkaline species known to those skilled in the art.
  • acidic species suitable for use herein are organic acids, such as citric acid and inorganic acids, such as sulphuric acid, sulphonic acid and/or metanesulphonic acid.
  • alkaline species are sodium hydroxide, potassium hydroxide and/or sodium carbonate.
  • the bleaching performance of the present composition may be evaluated by the following test methods on various type of bleachable stains.
  • a suitable test method for evaluating the bleaching performance on a soiled fabric under diluted conditions is the following:
  • a composition according to the present invention is diluted with water typically at a dilution level of 1 to 100 ml/L, preferably 20 ml/L (composition :water), then the soiled fabrics are soaked in it for 20 minutes to 6 hours and then rinsed.
  • the bleaching composition can be used in a washing machine at a dilution level of typically at a dilution level of 1 to 100 ml/L (composition :water). In the washing machine the soiled fabrics are washed at a temperature of from 30° to 70°C for 10 to 100 minutes and then rinsed.
  • the reference composition in this comparative test undergoes the same treatment.
  • Soiled fabrics/swatches with for example tea, coffee and the like may be commercially available from E.M.C. Co. Inc..
  • the bleaching performance is then evaluated by comparing side by side the soiled fabrics treated with a composition of the present invention with those treated with the reference, e.g., the same composition but comprising no bleach or a different bleach.
  • a visual grading may be used to assign difference in panel units (psu) in a range from 0 to 4.
  • compositions of the present invention are physically and chemically stable upon prolonged periods of storage.
  • compositions herein may be evaluated by measuring the concentration of available oxygen at given storage time after having manufactured the compositions.
  • chemically stable it is meant herein that the compositions of the present invention comprising a peracid do not undergo more than 15% AvO loss, in one month at 25°C and preferably not more than 10%.
  • the loss of available oxygen (AvO) of a peracid-containing composition over time can be measured by titration with potassium permanganate after reduction with a solution containing ammonium ferrous sulphate.
  • This 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.
  • peracid 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).
  • the bleaching composition of the present invention comprises a pre-formed particulate peroxycarboxylic acid containing at least one aromatic group (hereinafter referred to as peracid).
  • Preferred peracids are those having general formula A m -Q- A wherein Q is an aromatic group; A is P-(R) n -C(O)OOH wherein R is C1-10 alkyl, preferably C1-4 alkyl; n is from 1 to 8, preferably 1 to 5; P is either CO-NH or C(O)NC(O); and m is either 0 or 1.
  • peracid in a preferred peracid are those having general formula: where R is C1-20 alkyl group and where A, B, C and D are independently either hydrogen or substituent groups individually selected from the group consisting of alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic, sulphate, sulphonate, aldehydes or mixtures thereof.
  • R is an alkyl group having from 3 to 12 carbon atoms, more preferably from 5 to 9 carbon atoms.
  • Preferred substituent groups A, B, C and D are linear or branched alkyl groups having from 1 to 5 carbon atoms, but more preferably hydrogen.
  • Preferred peracids are selected from the group consisting of phthaloyl amido peroxy hexanoic acid (also known as phthaloyl amido-peroxy caproic acid), phthaloyl amido peroxy heptanoic acid, phthaloyl amido peroxy octanoic acid, phthaloyl amido peroxy nonanoic acid, phthaloyl amido peroxy decanoic acid and mixtures thereof.
  • phthaloyl amido peroxy hexanoic acid also known as phthaloyl amido-peroxy caproic acid
  • phthaloyl amido peroxy heptanoic acid also known as phthaloyl amido peroxy heptanoic acid
  • phthaloyl amido peroxy octanoic acid phthaloyl amido peroxy nonanoic acid
  • phthaloyl amido peroxy decanoic acid and mixtures thereof.
  • Even more preferred peracids are any of having general formula: wherein R is selected from C1-4 alkyl and n is an integer of from 1 to 5.
  • the peracid has the formula such that R is CH 2 and n is 5 i.e. phthaloyl amido-peroxy caproic acid or PAP.
  • the peracid is preferably used as a substantially water-insoluble solid or wetcake and is available from Ausimont under the trade name Euroco.
  • TPCAP N, N terephthaloyl di(6 amino percarboxy caproic acid)
  • the peracid has mean average particle size of less than 100 microns, more preferably less than 80 microns, even more preferably less than 60 microns. Most preferably PAP used herein has mean average particle size of between 20 and 50 microns.
  • the peracid is preferably present at a level of from 0.1% to 20%, more preferably from 1% to 10%, most preferably from 2% to 4%. In an alternative embodiment of the present invention the peracid may be present at a much higher level of for example 10% to 40%, more preferably from 15% to 30%, most preferably from 15% to 25%.
  • compositions of the present invention comprise a co-agent.
  • Co-agents as used herein refers to a compound selected from an organic acids, homo or copolymers of acidic monomers and mixtures thereof.
  • Suitable organic acids include those having molecular weight of less than 4000, more preferably less than 1000, most preferably less than 500.
  • the organic acid is selected from the group consisting of citric acid, maleic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, oxydiacetic acid, carboxymethyl oxysuccinic acid, carboxymethyl tartronic acid, ditartronic acid, oxydisuccinic acid, tartaric monosuccinic acid, tartaric disuccinic acid, guinaldic acid, picolinic acid, dipicolinic acid, C8-C22 saturated or unsaturated fatty acids and C8-C22 alkyl or alkenyl succinic acid, butane tri and tetracarboxylic acid, such as 1,2,3 butane tricarboxylic acid and 1,2,3,4 butane tetracarboxylic acid, and mixtures thereof.
  • a preferred organic acid is citric acid.
  • organic acids are those having pKa1 equal to or below the pH of the composition into which they are to be formulated.
  • especially preferred organic acids include oxalic acid, malonic acid, succinic acid and mixtures thereof. These latter acids are di-carboxylic acids, having pKa1 of 1.23, 2.85 and 4.15, respectively. More preferably the organic acid is selected from oxalic acid or malonic acid.
  • suitable homopolymers include polymaleic acid, polyacrylic acid and polyglyoxalic acid.
  • suitable copolymers include copolymers of maleic acid and acrylic acid.
  • An alternative copolymer may contain more than two different monomeric units for example a polymer comprising maleic acid, acrylic acid and either acrylamide or acrylic esters.
  • the co-agent is present in the composition at a level of from 0.1% to 20%, more preferably from 1% to 10% and most preferably from 2% to 5%.
  • compositions herein may further comprise a variety of other optional ingredients such as surfactants, suspending agent, chelating agents, radical scavengers, antioxidants, stabilisers, soil suspending polymer, polymeric soil release agents, pH control agents, dye transfer inhibitor, solvents, suds controlling agents, suds booster, brighteners, perfumes, pigments, dyes and the like.
  • surfactants such as surfactants, suspending agent, chelating agents, radical scavengers, antioxidants, stabilisers, soil suspending polymer, polymeric soil release agents, pH control agents, dye transfer inhibitor, solvents, suds controlling agents, suds booster, brighteners, perfumes, pigments, dyes and the like.
  • compositions of the present invention may comprise a surfactant as a preferred but optional ingredient.
  • a surfactant is selected form the group consisting of nonionic surfactants, anionic surfactants, zwitterionic surfactants, amphoteric surfactants, cationic surfactants and mixtures thereof.
  • Preferred anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • R preferably
  • alkyl chains of C10-16, more preferably C10-14 are preferred for lower wash temperatures (e.g. below approx. 50 °C ) and C16-18 alkyl chains are preferred for higher wash temperatures (e.g. above approx. 50 °C).
  • Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
  • R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
  • alkyl sulphonates including water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 22 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
  • R is a C 6 -C 22 linear or branched, saturated
  • Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO 3 M wherein R is an aryl, preferably a benzyl, substituted by a C 6 -C 22 linear or branched saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethy
  • alkylsulfonates and alkyl aryl sulphonates for use herein include primary and secondary alkylsulfonates and primary and secondary alkyl aryl sulphonates.
  • secondary C6-C22 alkyl or C6-C22 alkyl aryl sulphonates it is meant herein that in the formula as defined above, the SO3M or aryl-SO3M group is linked to a carbon atom of the alkyl chain being placed between two other carbons of the said alkyl chain (secondary carbon atom).
  • C14-C16 alkyl sulphonate salt is commercially available under the name Hostapur ® SAS from Hoechst and C8-alkylsulphonate sodium salt is commercially available under the name Witconate NAS 8® from Witco SA.
  • An example of commercially available alkyl aryl sulphonate is Lauryl aryl sulphonate from Su.Ma.
  • Particularly preferred alkyl aryl sulphonates are alkyl benzene sulphonates commercially available under trade name Nansa® available from Albright&Wilson.
  • anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
  • alkyl carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20, preferably from 5 to 15.
  • Suitable amphoteric surfactants for use herein include amine oxides having the following formula R 1 R 2 R 3 NO wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chain of from 1 to 30 carbon atoms.
  • Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R 1 R 2 R 3 NO wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups.
  • R1 may be a saturated, substituted or unsubstituted linear or branched hydrocarbon chain.
  • Suitable amine oxides for use herein are for instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst.
  • the surfactant where present is a C16 amine oxide.
  • Suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
  • the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
  • R 1 is a hydrophobic group
  • R 2 is hydrogen, C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group
  • R 3 is C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group which can also be joined to R 2 to form ring structures with the N, or a C 1 -C 6 carboxylic acid group or a C 1 -C 6 sulfonate group
  • R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms
  • X is the hydrophilic group which is a carboxylate or sulfonate group.
  • R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more preferably from 10 to 16. These simple alkyl groups are preferred for cost and stability reasons.
  • the hydrophobic group R 1 can also be an amido radical of the formula R a -C(O)-NH-(C(R b ) 2 ) m , wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18, more preferably up to 16, R b is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R b ) 2 ) moiety.
  • Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
  • Preferred R 3 is a C 1 -C 4 carboxylic acid group or C1-C4 sulfonate group, or a C 1 -C 3 alkyl and more preferably methyl.
  • Preferred R 4 is (CH2) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
  • betaine/sulphobetaine Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
  • alkyldimethyl betaines examples include coconutdimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
  • coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
  • Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
  • amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
  • C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
  • betaine is Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
  • Suitable cationic surfactants for use herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds.
  • Preferred cationic surfactants for use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a saturated, linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms, and more preferably of 12 to 20 carbon atoms, and wherein the other hydrocarbon groups (i.e.
  • quaternary ammonium compounds suitable for use herein are non-chloride/non halogen quaternary ammonium compounds.
  • the counterion used in said quaternary ammonium compounds are compatible with any persulfate salt and are selected from the group of methyl sulfate, or methylsulfonate, and the like.
  • compositions of the present invention are trimethyl quaternary ammonium compounds like myristyl trimethylsulfate, cetyl trimethylsulfate and/or tallow trimethylsulfate.
  • trimethyl quaternary ammonium compounds are commercially available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN CM®.
  • nonionic surfactants alkoxylated nonionic surfactants and especially ethoxylated nonionic surfactants are suitable for use herein.
  • Particularly preferred nonionic surfactants for use herein are the capped alkoxylated nonionic surfactants as they have improved stability to the persulfate salts.
  • Suitable capped alkoxylated nonionic surfactants for use herein are according to the formula: R 1 (O-CH 2 -CH 2 ) n -(OR 2 ) m -O-R 3
  • surfactants are commercially available from BASF under the trade name Plurafac®, from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
  • Preferred capped nonionic alkoxylated surfactants of the above formula are those commercially available under the tradename Genapol® L 2.5 NR from Hoechst, and Plurafac® from BASF.
  • Particularly preferred surfactants are those selected from the group consisting of alkyl sulphate, alkyl ethoxy sulphate, alkyl sulphonate, alkyl benzene sulphonate, alkyl carboxylate, alkyl ethoxy carboxylate and mixtures thereof.
  • compositions according to the present invention comprise surfactant at a level of 5% or less, preferably from 0.01% to 5%, more preferably at a level of from 0.1% to 4 % and most preferably from 0.2% to 3% by weight of the composition.
  • a product comprising two compositions, one of which comprises surfactant.
  • This surfactant composition may comprise any of the surfactants as discussed previously.
  • the surfactant or combination of surfactants of this composition makes up for 10-40% of this surfactant-containing composition.
  • composition of the present invention may preferably comprise a suspending agent.
  • a suspending agent is an ingredient which is specifically added to the composition of the present invention to suspend a solid particulate ingredient of the composition.
  • a suspending agent is particularly useful for suspending the PAP.
  • suspending agents are those known in the art.
  • suspending agents include gum-type polymers (e.g. xanthan gum), polyvinyl alcohol and derivatives thereof, cellulose and derivatives thereof and polycarboxylate polymers.
  • the suspending agent is selected from a gum-type polymer or a polycarboxylate polymer.
  • the gum-type polymer may be selected from the group consisting of polysaccharide hydrocolloids, xanthan gum, guar gum, succinoglucan gum, Cellulose, derivatives of any of the above and mixtures thereof.
  • the gum-type polymer is a xanthan gum or derivative thereof.
  • the gum-type polymer is preferably present at a level of from 0.01% to 10%, more preferably from 0.1 % to 3%.
  • the polycarobxylate polymer can be a homo or copolymer of monomer units selected from acrylic acid, methacrylic acid, maleic acid, malic acid, maleic anhydride.
  • Preferred polycarboxylate polymers are Carbopol from BF Goodrich. Suitable polymers have molecular weight in the range of from 10 000 to 10 000 000, more preferably 100 000 to 10 000 000.
  • the cross-linked polycarboxylate polymer is preferably present at a level of from 0.01% to 2%, more preferably from 0.01% to 1%, most preferably from 0.1% to 0.8%.
  • the ratio of gum-type polymer to cross-linked polycarboxylate polymer is from 100:1 to 1:100, more preferably from 10:1 to 1:10.
  • compositions of the present invention may comprise a chelating agent as a preferred optional ingredient.
  • Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, amino carboxylate chelating agents, other carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
  • chelating agents contribute to further enhance the chemical stability of the compositions.
  • a chelating agent may be also desired in the compositions of the present invention as it allows to increase the ionic strength of the compositions herein and thus their stain removal and bleaching performance on various surfaces.
  • Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
  • the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
  • Preferred phosphonate chelating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP). Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
  • Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.
  • a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
  • Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
  • Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Suitable amino carboxylates to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanoldiglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
  • R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO 2 , -C(O)R', and -SO 2 R"; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R" is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R 5 , R 6 , R 7 , and R 8 are independently selected from the group consisting of -H and alkyl.
  • Particularly preferred chelating agents to be used herein are amino aminotri(methylene phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic acid, and mixtures thereof.
  • compositions according to the present invention comprise up to 5% by weight of the total composition of a chelating agent, or mixtures thereof, preferably from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.
  • compositions of the present invention may comprise a radical scavenger or a mixture thereof.
  • Suitable radical scavengers for use herein include the well-known substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof.
  • Preferred such radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene.
  • Such radical scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories under the trade name Nip
  • Radical scavengers when used are typically present herein in amounts up to 10% by weight of the total composition and preferably from 0.001% to 0.5% by weight.
  • radical scavengers may contribute to the chemical stability of the bleaching compositions of the present invention as well as to the safety profile of the compositions of the present invention.
  • compositions according to the present invention may further comprise a suds controlling agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient.
  • a suds controlling agent such as 2-alkyl alkanol, or mixtures thereof, as a preferred optional ingredient.
  • Particularly suitable to be used in the present invention are the 2-alkyl alkanols having an alkyl chain comprising from 6 to 16 carbon atoms, preferably from 8 to 12 and a terminal hydroxy group, said alkyl chain being substituted in the ⁇ position by an alkyl chain comprising from 1 to 10 carbon atoms, preferably from 2 to 8 and more preferably 3 to 6.
  • Such suitable compounds are commercially available, for instance, in the Isofol® series such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyl decanol).
  • suds controlling agents may include alkali metal (e.g., sodium or potassium) fatty acids, or soaps thereof, containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms.
  • alkali metal e.g., sodium or potassium
  • soaps thereof containing from about 8 to about 24, preferably from about 10 to about 20 carbon atoms.
  • the fatty acids including those used in making the soaps can be obtained from natural sources such as, for instance, plant or animal-derived glycerides (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow, grease, lard and mixtures thereof).
  • plant or animal-derived glycerides e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, tallow, grease, lard and mixtures thereof.
  • the fatty acids can also be synthetically prepared (e.g., by oxidation of petroleum stocks or by the Fischer-Tropsch process).
  • Alkali metal soaps can be made by direct saponification of fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
  • tallow is used herein in connection with fatty acid mixtures which typically have an approximate carbon chain length distribution of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic (the first three fatty acids listed are saturated). Other mixtures with similar distribution, such as the fatty acids derived from various animal tallows and lard, are also included within the term tallow.
  • the tallow can also be hardened (i.e., hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
  • coconut refers to fatty acid mixtures which typically have an approximate carbon chain length distribution of about 8% C8, 7% C10, 48% C12, 17% C14, 9% C16, 2% C18, 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated).
  • Other sources having similar carbon chain length distribution such as palm kernel oil and babassu oil are included with the term coconut oil.
  • Suitable suds controlling agents are exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds controlling agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent impermeable carrier.
  • the suds controlling agent can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. U.S. Patent 3 933 672.
  • Other particularly useful suds controlling agents are the self-emulsifying silicone suds controlling agents, described in German Patent Application DTOS 2 646 126 published April 28, 1977.
  • An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer.
  • compositions can comprise a silicone/silica mixture in combination with fumed nonporous silica such as Aerosil R .
  • Especially preferred suds controlling agent are the suds controlling agent system comprising a mixture of silicone oils and the 2-alkyl-alcanols.
  • compositions herein may comprise up to 4% by weight of the total composition of a suds controlling agent, or mixtures thereof, preferably from 0.1 % to 1.5% and most preferably from 0.1% to 0.8%.
  • compositions of the present invention may further comprise up to 10%, preferably from 2% to 4% by weight of the total composition of an alcohol according to the formula HO - CR'R" - OH, wherein R' and R" are independently H or a C2-C10 hydrocarbon chain and/or cycle.
  • Preferred alcohol according to that formula is propanediol. Indeed, we have observed that these alcohols in general and propanediol in particular also improve the chemical stability of the compositions.
  • inorganic stabilizers include sodium stannate and various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate.
  • compositions herein may also comprise other polymeric soil release agents known to those skilled in the art.
  • polymeric soil release agents are characterised by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibres and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents useful herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from about 1 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100.
  • Suitable oxy C 4 -C 6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO 3 S(CH 2 ) n OCH 2 CH 2 O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellulosic polymers, co-polymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C 1 -C 4 alkyl and C 4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.
  • Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft co-polymers of poly(vinyl ester), e.g., C 1 -C 6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C 1 -C 6 vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a co-polymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units which contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are fully described in U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoaroyl, end-capped terephthalate esters.
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • soil release agents will generally comprise from 0.01% to 10.0%, by weight, of the detergent compositions herein, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.
  • compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one dyed surface to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, co-polymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and more preferably from 0.05% to 2%.
  • the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A X -P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units;
  • x is 0 or 1; and
  • R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block co-polymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate co-polymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • the most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • Co-polymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis , Vol 113.
  • the PVPVI co-polymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4:1. These co-polymers can be either linear or branched.
  • compositions may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.
  • suds boosters such as C 10 -C 16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C 10 -C 14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl 2 , MgSO 4 , and the like, can be added at levels of, for example, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • optical brighteners fluorescent whitening agents or other brightening or whitening agents known in the art can be incorporated in the instant compositions when they are designed for fabric treatment or laundering, at levels typically from about 0.05% to about 1.2%, by weight, of the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acids, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5-and 6-membered-ring heterocyclic brighteners, this list being illustrative and non-limiting. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM Tinopal PLC; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stil- benes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-napth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972, to Hamilton. Anionic brighteners are typically preferred herein.
  • a variety of suitable means can be used for adjusting the pH of the compositions, including organic or inorganic acids, alkanolamines and the like. It may be advantageous to use alkanolamines, in particular monoethanolamine, inasmuch as they have an additional effect of regulating the viscosity of the emulsion, without compromising on its physical stability.
  • composition described herein may also comprise minor ingredients such as pigment or dyes and perfumes.
  • the liquid aqueous composition of the present invention can be used to clean surfaces.
  • surfaces it is meant herein any inanimate surface. These inanimate surfaces include, but are not limited to, hard-surfaces typically found in houses like kitchens, bathrooms, or in car interiors, e.g., tiles, walls, floors, chrome, glass, smooth vinyl, any plastic, plastified wood, table top, sinks, cooker tops, dishes, sanitary fittings such as sinks, showers, shower curtains, wash basins, WCs and especially include fabrics including clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like, and carpets. Inanimate surfaces also include household appliances including, but not limited to, refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on.
  • bleaching and/or disinfecting said surfaces as the compositions of the present invention comprise a bleaching system based on a peracid compound or a mixture thereof and optionally cleaning as said compositions may comprise a surfactant or any other conventional cleaning agents.
  • the present invention also encompasses a process of treating, especially bleaching a fabric, as the inanimate surface.
  • a fabric is treated with a composition according to the present invention.
  • Such treatment can be done either in a so-called “pretreatment mode", where a liquid bleaching composition, as defined herein, is applied neat onto said fabrics before the fabrics are rinsed, or washed with a conventional detergent, then rinsed, or in a "soaking mode” where a liquid bleaching composition, as defined herein, is first diluted in an aqueous bath and the fabrics are immersed and soaked in the bath, before preferably being rinsed, or in a "through the wash mode", where a liquid bleaching composition, as defined herein, is added in to a typical laundry detergent. It is preferred in both cases, that the fabrics be rinsed after they have been contacted with said composition and before said composition has completely dried off.
  • the processes of bleaching surfaces according to the present invention delivers effective whiteness performance as well as effective stain removal performance.
  • compositions according to the present invention are preferably used to contact to fabrics in a liquid form. Indeed, by "in a liquid form”, it is meant herein the liquid compositions according to the present invention per se in neat or in their diluted form.
  • compositions according to the present invention are typically used in diluted form in a laundry operation.
  • in diluted form it is meant herein that the compositions for the bleaching of fabrics according to the present invention may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by other means such as in a washing machine.
  • Said compositions can be diluted up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times.
  • a process of bleaching fabrics according to the present invention comprises the steps of first contacting said fabrics with a bleaching composition according to the present invention, in its diluted form, then allowing said fabrics to remain in contact with said composition, for a period of time sufficient to bleach said fabrics, typically 1 to 60 minutes, preferably 5 to 30 minutes, then rinsing said fabrics with water. If said fabrics are to be washed, i.e., with a conventional composition comprising at least one surfactant, said washing is preferably conducted together with the bleaching of said fabrics by contacting said fabrics at with a bleaching composition according to the present invention and said conventional surfactant-containing detergent composition at the same time.
  • said washing may be conducted before or after said fabrics have been bleached with a bleaching composition according to the present invention.
  • said process according to the present invention allows the user to bleach fabrics and optionally to wash fabrics with a detergent composition comprising at least one surfactant before the step of contacting said fabrics with said bleaching composition and/or in the step where said fabrics are contacted with said bleaching composition and/or after the step where said fabrics are contacted with said bleaching composition and before the rinsing step and/or after the rinsing step.
  • the bleaching composition and the surfactant containing conventional laundry detergent composition are applied to the fabric at the same time. Although it is essential that in this method the two compositions are not pre-mixed.
  • the present invention also encompasses a process of treating a hard-surface, as the inanimate surface.
  • a composition as defined herein, is contacted with the hard-surfaces to be treated.
  • the present invention also encompasses a process of treating a hard-surface with a composition, as defined herein, wherein said process comprises the step of applying said composition to said hard-surface, preferably only soiled portions thereof, and optionally rinsing said hard-surface.
  • composition as defined herein, may be applied to the surface to be treated in its neat form or in its diluted form typically up to 200 times their weight of water, preferably into 80 to 2 times their weight of water, and more preferably 60 to 2 times.
  • compositions of the present invention are easy to rinse and provide good shine characteristics on the treated surfaces.
  • hard-surfaces any hard-surfaces as mentioned herein before as well as dishes.
  • compositions herein can be packaged in a variety of containers including conventional bottles, and bottles equipped with roll-on, sponge, brush or spray appliances.
  • the composition is packaged in a two-compartment container, wherein the bleaching composition as described herein is packaged in one compartment and a second composition is packaged in the second compartment.
  • the second composition is a conventional laundry detergent liquid composition, preferably comprising ingredients, particularly bleach-sensitive ingredients such as surfactants, enzymes and perfumes.
  • the invention is further illustrated by the following example which shows the stain removal benefits obtained by the combination of peracid bleach and citric acid.
  • the peracid used for the purposes of the present example is Phtaloylamido peroxycaproic acid (PAP), obtained from the supplier (Ausimont) as a 70% wet cake.
  • PAP Phtaloylamido peroxycaproic acid
  • the wetcake PAP is primarily dispersed in distilled water under gentle agitation using a lab stirrer, to form a dispersion containing 2.7g of pure PAP in 100 mls water.
  • a 1% solution of citric acid is then prepared and the pH is trimmed to 4.0 with sodium hydroxide.
  • the PAP dispersion and the citric acid solution are then mixed together to obtain a dispersion of PAP in the citric acid solutions.
  • the liquid detergent used was a commercial product marketed by the Procter & Gamble Company under the tradename Liquid Tide and was produced in summer 1998. It was used at 92 mls /wash (99 grams) as recommended.
  • compositions tested (in grams /wash) were:
  • the PAP/citric acid dispersion was delivered into the washing machine at the same time as (but without premixing with) the liquid detergent.
  • the tests were run using four identical Kenmore washing machines, using average US washing conditions, at a wash temperature of 32 C, using 64 liters water, of a hardness of 1 millimole/liter.
  • the wash pH was measured and was similar for all four treatments (between 7.6 and 7.9).
  • a piece of fabric with a total of 20 stains was introduced, together with 1.5 kg of a white ballast load of mixed (cotton/polycotton) composition.
  • Four cycles were run by scrambling the 4 products across the 4 washing machines; for each cycle new stains were used. At the end, the results of the four wash cycles were averaged.
  • the fabrics are visually graded by two expert graders using the 0-4 Panel Score Unit (psu) scale, where 0 means no difference and 4 corresponds to the highest difference. All psu grades are referred to the Liquid Tide control and positive grades mean a higher degree of stain removal vs Liquid Tide. The results were analyzed for statistical significance (at 95% confidence interval) and all grades that were significantly different vs. the Liquid Tide control are identified by the suffix "s".

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  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Cosmetics (AREA)
EP99870220A 1998-12-14 1999-10-25 Compositions de blanchiment Revoked EP1010751B1 (fr)

Priority Applications (14)

Application Number Priority Date Filing Date Title
EP99870220A EP1010751B1 (fr) 1998-12-14 1999-10-25 Compositions de blanchiment
CZ20012005A CZ20012005A3 (cs) 1998-12-14 1999-12-09 Kapalný bělící prostředek
TR2001/01700T TR200101700T2 (tr) 1998-12-14 1999-12-09 Ağartıcı bileşimler
CN99816065A CN1334860A (zh) 1998-12-14 1999-12-09 漂白组合物
AU19382/00A AU1938200A (en) 1998-12-14 1999-12-09 Bleaching compositions
CA002352140A CA2352140C (fr) 1998-12-14 1999-12-09 Acide peroxycarboxylique contenant compositions de blanchiment
PCT/US1999/029330 WO2000036072A1 (fr) 1998-12-14 1999-12-09 Compositions de blanchiment
US09/857,959 US6548470B1 (en) 1998-12-14 1999-12-09 Bleaching compositions
JP2000588323A JP2002532616A (ja) 1998-12-14 1999-12-09 漂白組成物
BR9916215-6A BR9916215A (pt) 1998-12-14 1999-12-09 Composições alvejantes
KR1020017007348A KR20010101190A (ko) 1998-12-14 1999-12-09 액체 표백 조성물 및 이를 사용한 직물의 세탁 방법
CO99077704A CO5210987A1 (es) 1998-12-14 1999-12-13 Composicion liquida de blanqueo que contiene acido peroxicarboxilico que tiene al menos un grupo aromatico y un coagente seleccionado de acidos organicos, homo o copolimeros de monomeros acidificantes y mezclas de ellos.
PE1999001242A PE20001470A1 (es) 1998-12-14 1999-12-14 Composicion blanqueadora acuosa, estable a base de acido peroxicarboxilico
ARP990106369A AR019501A1 (es) 1998-12-14 1999-12-14 Composiciones blanqueadoras

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP98870271A EP1010750A1 (fr) 1998-12-14 1998-12-14 Compositions de blanchiment
EP98870271 1998-12-14
EP99870220A EP1010751B1 (fr) 1998-12-14 1999-10-25 Compositions de blanchiment

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EP1010751A2 true EP1010751A2 (fr) 2000-06-21
EP1010751A3 EP1010751A3 (fr) 2000-08-09
EP1010751B1 EP1010751B1 (fr) 2005-04-20

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JP (1) JP2002532616A (fr)
KR (1) KR20010101190A (fr)
CN (1) CN1334860A (fr)
AR (1) AR019501A1 (fr)
AU (1) AU1938200A (fr)
BR (1) BR9916215A (fr)
CA (1) CA2352140C (fr)
CO (1) CO5210987A1 (fr)
CZ (1) CZ20012005A3 (fr)
PE (1) PE20001470A1 (fr)
TR (1) TR200101700T2 (fr)
WO (1) WO2000036072A1 (fr)

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EP1074607A1 (fr) * 1999-08-04 2001-02-07 Ausimont S.p.A. Dispersions aqueuses d'acides percarboxyliques
WO2001016281A1 (fr) * 1999-08-27 2001-03-08 The Procter & Gamble Company Compositions detergentes liquides aqueuses comprenant un systeme de stabilisation polymerique
DE10257387A1 (de) * 2002-12-06 2004-06-24 Henkel Kgaa Mehrkomponenten-Flüssigwaschmittel
DE10257389A1 (de) * 2002-12-06 2004-06-24 Henkel Kgaa Flüssiges saures Waschmittel
DE10259262B3 (de) * 2002-12-17 2004-08-05 Henkel Kgaa Verfahren zur Herstellung von bleichmittelhaltigen Suspensionen
US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system
WO2005035705A2 (fr) * 2003-10-06 2005-04-21 The Procter & Gamble Company Composition a lessive a deux compartiments contenant une solution de peracide a l'equilibre
WO2005090544A1 (fr) * 2004-03-16 2005-09-29 Solvay Solexis S.P.A. Processus de dilution d'acides imidopercarboxyliques
DE102004019138A1 (de) * 2004-04-16 2005-11-10 Henkel Kgaa Bleichmittelhaltiges Wasch- oder Reinigungsmittel in wasserlöslicher oder wasserdispergierbarer Portionsverpackung
WO2006097666A1 (fr) * 2005-03-15 2006-09-21 Reckitt Benckiser Inc. Ameliorations portant sur des compositions nettoyantes ou en rapport avec ces compositions
US7119055B2 (en) 2001-08-31 2006-10-10 Reckitt Benckiser Inc. Hard surface cleaners comprising a thickening gum mixture
US7186676B2 (en) 2003-02-22 2007-03-06 Reckitt Benckiser Inc. Hard surface cleaning compositions comprising alginate materials and xanthan gum
US7196046B2 (en) 2001-08-31 2007-03-27 Reckitt Benckiser Inc. Hard surface cleaner comprising a suspension of alginate beads
US7291586B2 (en) 2003-02-22 2007-11-06 Reckitt Benckiser Inc. Hard surface cleaning compositions comprising suspended alginate inclusions
WO2011026718A1 (fr) * 2009-09-02 2011-03-10 Unilever Nv Composition et procédé pour le traitement d'un tissu

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ITMI20040004A1 (it) * 2004-01-08 2004-04-08 Solvay Solexis Spa Foemulazione acquose di acidi inmidoalcampercarbonbossilici
EP1593733A1 (fr) * 2004-04-05 2005-11-09 The Procter & Gamble Company Compositions liquides de blanchiment
WO2005100529A1 (fr) * 2004-04-05 2005-10-27 The Procter & Gamble Company Compositions liquides de blanchiment
MX345512B (es) * 2010-12-17 2017-02-01 Procter & Gamble Composiciones de limpieza con polímeros de policarboxilato anfotéricos.

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EP0442549A2 (fr) * 1990-02-13 1991-08-21 Unilever N.V. Composition de blanchiment aqueuse
EP0484095A2 (fr) * 1990-11-02 1992-05-06 The Clorox Company Détergent liquide non aqueux contenant un peroxide stable solubilisé
EP0564250A2 (fr) * 1992-03-31 1993-10-06 Unilever Plc Compositions détergentes liquides structurées contenant des amido- et imido-peroxyacides
WO1995016023A1 (fr) * 1993-12-07 1995-06-15 Unilever Plc Composition de nettoyage a deux parties comprenant au moins un compose de peroxyde
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WO1997038618A1 (fr) * 1996-04-17 1997-10-23 S.C. Johnson & Son, Inc. Nettoyage de tissu
EP0816481A2 (fr) * 1996-06-26 1998-01-07 Unilever N.V. Granulés peracides contenant l'acide citrique de monohydrate pour l'amélioration de la vitesse de dissolution
WO1998000507A2 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Compositions detergentes non aqueuses contenant des precurseurs de blanchiment

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US4992194A (en) * 1989-06-12 1991-02-12 Lever Brothers Company, Division Of Conopco Inc. Stably suspended organic peroxy bleach in a structured aqueous liquid
EP0442549A2 (fr) * 1990-02-13 1991-08-21 Unilever N.V. Composition de blanchiment aqueuse
EP0484095A2 (fr) * 1990-11-02 1992-05-06 The Clorox Company Détergent liquide non aqueux contenant un peroxide stable solubilisé
EP0564250A2 (fr) * 1992-03-31 1993-10-06 Unilever Plc Compositions détergentes liquides structurées contenant des amido- et imido-peroxyacides
US5503765A (en) * 1993-08-27 1996-04-02 Lever Brothers Company, Division Of Conopco, Inc. Stable non-aqueous compositions containing peracids which are substantially insoluble
WO1995016023A1 (fr) * 1993-12-07 1995-06-15 Unilever Plc Composition de nettoyage a deux parties comprenant au moins un compose de peroxyde
WO1995033816A1 (fr) * 1994-06-08 1995-12-14 Unilever Plc Compositions aqueuses de blanchiment comprenant des acides peroxycarboxyliques
WO1997038618A1 (fr) * 1996-04-17 1997-10-23 S.C. Johnson & Son, Inc. Nettoyage de tissu
EP0816481A2 (fr) * 1996-06-26 1998-01-07 Unilever N.V. Granulés peracides contenant l'acide citrique de monohydrate pour l'amélioration de la vitesse de dissolution
WO1998000507A2 (fr) * 1996-06-28 1998-01-08 The Procter & Gamble Company Compositions detergentes non aqueuses contenant des precurseurs de blanchiment

Cited By (22)

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US6333300B1 (en) 1999-08-04 2001-12-25 Ausimont S.P.A. Water based dispersions of percarboxylic acids
EP1074607A1 (fr) * 1999-08-04 2001-02-07 Ausimont S.p.A. Dispersions aqueuses d'acides percarboxyliques
WO2001016281A1 (fr) * 1999-08-27 2001-03-08 The Procter & Gamble Company Compositions detergentes liquides aqueuses comprenant un systeme de stabilisation polymerique
US6844305B1 (en) 1999-08-27 2005-01-18 The Proctor & Gamble Company Aqueous liquid detergent compositions comprising a polymeric stabilization system
US7119055B2 (en) 2001-08-31 2006-10-10 Reckitt Benckiser Inc. Hard surface cleaners comprising a thickening gum mixture
US7256167B2 (en) 2001-08-31 2007-08-14 Reckitt Benckiser Inc. Hard surface cleaner comprising suspended particles and oxidizing agent
US7196046B2 (en) 2001-08-31 2007-03-27 Reckitt Benckiser Inc. Hard surface cleaner comprising a suspension of alginate beads
DE10257387A1 (de) * 2002-12-06 2004-06-24 Henkel Kgaa Mehrkomponenten-Flüssigwaschmittel
DE10257389A1 (de) * 2002-12-06 2004-06-24 Henkel Kgaa Flüssiges saures Waschmittel
US7179778B2 (en) 2002-12-06 2007-02-20 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Liquid acid detergent comprising a phthaloylamino peroxy caproic acid
DE10259262B3 (de) * 2002-12-17 2004-08-05 Henkel Kgaa Verfahren zur Herstellung von bleichmittelhaltigen Suspensionen
US7183247B2 (en) 2002-12-17 2007-02-27 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Method for the production of suspensions comprising phthalimidoperoxyhexanoic acid
US7186676B2 (en) 2003-02-22 2007-03-06 Reckitt Benckiser Inc. Hard surface cleaning compositions comprising alginate materials and xanthan gum
US7291586B2 (en) 2003-02-22 2007-11-06 Reckitt Benckiser Inc. Hard surface cleaning compositions comprising suspended alginate inclusions
WO2005035705A3 (fr) * 2003-10-06 2005-05-19 Procter & Gamble Composition a lessive a deux compartiments contenant une solution de peracide a l'equilibre
WO2005035705A2 (fr) * 2003-10-06 2005-04-21 The Procter & Gamble Company Composition a lessive a deux compartiments contenant une solution de peracide a l'equilibre
WO2005090544A1 (fr) * 2004-03-16 2005-09-29 Solvay Solexis S.P.A. Processus de dilution d'acides imidopercarboxyliques
DE102004019138A1 (de) * 2004-04-16 2005-11-10 Henkel Kgaa Bleichmittelhaltiges Wasch- oder Reinigungsmittel in wasserlöslicher oder wasserdispergierbarer Portionsverpackung
WO2006097666A1 (fr) * 2005-03-15 2006-09-21 Reckitt Benckiser Inc. Ameliorations portant sur des compositions nettoyantes ou en rapport avec ces compositions
WO2011026718A1 (fr) * 2009-09-02 2011-03-10 Unilever Nv Composition et procédé pour le traitement d'un tissu
AU2010291392B2 (en) * 2009-09-02 2013-07-11 Unilever Plc Composition and process for treatment of a fabric
EA022063B1 (ru) * 2009-09-02 2015-10-30 Юнилевер Нв Жидкая композиция для обработки ткани, способ ее получения и способ стирки ткани с ее использованием

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BR9916215A (pt) 2001-09-11
EP1010751A3 (fr) 2000-08-09
KR20010101190A (ko) 2001-11-14
AU1938200A (en) 2000-07-03
CA2352140A1 (fr) 2000-06-22
PE20001470A1 (es) 2001-01-16
CO5210987A1 (es) 2002-10-30
CA2352140C (fr) 2007-10-09
EP1010751B1 (fr) 2005-04-20
WO2000036072A1 (fr) 2000-06-22
TR200101700T2 (tr) 2002-01-21
CZ20012005A3 (cs) 2002-06-12
AR019501A1 (es) 2002-02-20
JP2002532616A (ja) 2002-10-02
CN1334860A (zh) 2002-02-06

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