EP0812348A1 - Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu - Google Patents

Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu

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Publication number
EP0812348A1
EP0812348A1 EP96906534A EP96906534A EP0812348A1 EP 0812348 A1 EP0812348 A1 EP 0812348A1 EP 96906534 A EP96906534 A EP 96906534A EP 96906534 A EP96906534 A EP 96906534A EP 0812348 A1 EP0812348 A1 EP 0812348A1
Authority
EP
European Patent Office
Prior art keywords
composition
manganese
iron
fabric
acid
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
EP96906534A
Other languages
German (de)
English (en)
Other versions
EP0812348A4 (fr
EP0812348B1 (fr
Inventor
Valerio Del Duca
John Scott Park
Dario Rapisarda
Barry Stoddart
Marina Trani
Taher Iqbal Yousaf
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
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP96906534A priority Critical patent/EP0812348B1/fr
Publication of EP0812348A1 publication Critical patent/EP0812348A1/fr
Publication of EP0812348A4 publication Critical patent/EP0812348A4/fr
Application granted granted Critical
Publication of EP0812348B1 publication Critical patent/EP0812348B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the present invention relates to the pretreatment of soiled fabrics, to compositions suitable to be used as pretreater, and to a pretreatment process.
  • Peroxygen bleach-containing compositions have been extensively described in laundry applications as laundry detergents, laundry additives or even laundry pretreaters.
  • peroxygen bleach-containing compositions in laundry pretreatment applications to boost the removal of encrusted stains/soils which are otherwise particularly difficult to remove such as grease, coffee, tea, grass, mud/clay-containing soils and the like.
  • a drawback associated with such peroxygen bleach- containing compositions is that said compositions may damage fabrics when used in pretreatment application, i.e. when applied directly onto the fabrics, and left to act onto said fabrics for prolonged periods of time before washing said fabrics
  • a further advantage of the present invention is that excellent laundry performance on bleachable stains is provided as well as on removing greasy stains.
  • compositions suitable to be used according to the present invention also provide excellent performance when used in other applications, apart from laundry pretreater application, such as in other laundry applications, as a laundry detergent or laundry additive, or even in hard surface cleaning applications.
  • a chelating agent like ethylenedinitrilotertrakis (methylenephosphonic acid) N,N, -dioxide, hydroxy-ethane diphosphonic acid (HEDP) and/or a chelating agent having two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co-ordination so as to form complexes with metal ions in which each metal ion is complexed by 3 molecules of chelating agents like 2-hydroxypyridine-N-oxide, allows to formulate acidic liquid compositions suitable for pretreating fabrics which exhibit improved chemical stability upon prolonged storage time.
  • a chelating agent like ethylenedinitrilotertrakis (methylenephosphonic acid) N,N, -dioxide, hydroxy-ethane diphosphonic acid (HEDP) and/or a chelating agent having two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co-ordination so as to form complexes with metal ions in which each metal
  • EP-A- 629691 discloses emulsions of nonionic surfactants comprising a silicone compound, and as optional ingredients, hydrogen peroxide, or a water soluble source thereof, and chelants.
  • the only chelant disclosed is S,S,-ethylene diamino disuccinic acid (see examples).
  • pretreatment application is disclosed for the compositions of EP-A 629691 , the use of peroxygen bleach-containing compositions comprising a compound chelating copper and/or iron and/or manganese, for pretreating fabrics, whereby the loss of tensile strength in said fabrics is reduced, is nowhere disclosed.
  • EP-A- 629690 discloses emulsions of nonionic surfactants comprising a terephthalate-based polymer, and as optional ingredients, hydrogen peroxide, or a water soluble source thereof, and chelants
  • the only chelant disclosed is S,S,-ethylene diamino disuccinic acid (see examples)
  • pretreatment application is disclosed for the compositions of EP-A 629690, the use of peroxygen bleach-containing compositions comprising a compound chelatmg copper and/or iron and/or manganese, for pretreating fabrics, whereby the loss of tensile strength in said fabrics is reduced, is nowhere disclosed
  • EP-B-209 228 discloses compositions comprising a peroxide source like hydrogen peroxide, an am o polyphosphonate chelant and a radical scavenger Diethylene t ⁇ amine penta methylene phosphonic acid is expressly disclosed Also EP-B-209 228 discloses that the hydrogen peroxide-containing compositions may be used as pre-spotters However, nowhere it is mentioned that peroxygen bleach-containing compositions comprising a compound chelating copper and/or iron and/or manganese, for pretreating fabrics, allow to reduce the loss of tensile strength in said fabrics
  • the present invention encompasses the use of a liquid composition comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese, for pretreating a soiled fabric before said fabric is washed, whereby the loss of tensile strength in said fabric is reduced
  • the present invention further encompasses a process of pretreating soiled fabrics with a liquid composition comprising a peroxygen bleach and a compound chelatmg copper and/or iron and/or manganese, and said process comprises the steps of applying said composition in its neat form onto the fabric and allowing said composition to remain in contact with said fabric without leaving said composition to dry onto said fabric, before said fabric is washed
  • the present invention further encompasses a liquid detergent composition comprising a peroxygen bleach and, as a compound chelating copper and/or iron and/or manganese, methyl glycine di-acetic acid, propylene diamine tetracetic acid, 2-hydroxypyridine-N-oxide, ethylenedinitrilotertrakis (methylenephosphonic acid) N,N, -dioxide, hydroxy-ethane diphosphonic acid, or mixtures thereof.
  • the present invention encompasses the use of a liquid composition comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese, for pretreating a soiled fabric before said fabric is washed, whereby the loss of tensile strength in said fabric is reduced.
  • the present invention is based on the finding that, fabric damage resulting in tensile strength loss is reduced, when compositions comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese according to the present invention are used to pretreat soiled fabrics, as compared to the use of the same compositions but without any compound chelating copper and/or iron and/or manganese, to pretreat said fabrics.
  • pretreat soiled fabrics By “to pretreat soiled fabrics” it is to be understood that the liquid composition is applied in its neat form onto the soiled fabric and left to act onto said fabric before said fabric is washed, as described herein after, in the process of pretreating soiled fabrics according to the present invention.
  • a peroxygen bleach-containing composition comprising a compound chelating copper and/or iron and/or manganese according to the present invention allows to considerably reduce the tensile strength loss caused by the presence of copper and/or iron and/or manganese on the fabric surface, even if said composition is left onto the fabric to be pretreated upon a prolonged period of time before washing said fabric, e.g. about 24 hours, and even if said fabric is contaminated by high levels of copper and/or iron and/or manganese.
  • the tensile strength loss of a fabric may be measured by employing the Tensile Strength method, as can be seen in the examples herein after. This method consists in measuring the tensile strength of a given fabric by stretching said fabric until it breaks. The force, expressed in Kg, necessary to break the fabric is the "Ultimate Tensile Stress” and may be measured with "The Stress-Strain INSTRON Machine”.
  • tensile strength loss it is to be understood the difference when comparing the tensile strength of a fabric taken as a reference, i.e. a fabric which has not been pretreated, and the tensile strength of the same fabric after having been pretreated according to the present invention. A tensile strength loss of zero means that no fabric damage is observed.
  • An advantage associated to the present invention is that the color damage is also reduced. Indeed, the color change or/and decoloration observed when pretreating soiled colored fabrics with a peroxygen bleach-containing composition comprising a compound chelating copper and/or iron and/or manganese according to the present invention, is reduced, as compared to the color change and/or decoloration observed when using the same composition but without any such compound for chelating copper and/or iron and/or manganese, this even if said composition is left onto the fabrics upon prolonged periods of time before washing said fabrics.
  • the present invention also encompasses the use of a liquid composition comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese for pretreating a soiled colored fabric before said fabric is washed, whereby the color damage of said fabric is reduced.
  • liquid compositions comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese without compromising on the bleaching performance nor on the stain removal performance delivered by said compositions.
  • the present invention further encompasses a process of pretreating soiled fabrics with a liquid composition comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese, said process comprises the steps of applying said composition in its neat form onto the fabric and allowing said composition to remain in contact with said fabric without leaving said composition to dry onto said fabric, before said fabric is washed.
  • Said composition may remain in contact with said fabric, typically for a period of 1 minute to 24 hours, preferably 1 minute to 1 hour and more preferably 5 minutes to 30 minutes.
  • compositions according to the present invention may be rubbed and/or brushed more or less intensively, for example, by means of a sponge or a brush or simply by rubbing two pieces of fabric each against the other
  • washing it is to be understood herein to simply rinse the fabrics with water, or the fabrics may be washed with conventional compositions comprising at least one surface active agent, this by means of a washing machine or simply by hand
  • compositions described herein are applied onto the fabrics to be pretreated without undergoing any dilution, i e they are applied as described herein
  • the liquid compositions used in said process should not be left to dry onto the fabrics Indeed, it has been found that water evaporation contributes to increase the concentration of free radicals onto the surface of the fabrics and, consequently, the rate of chain reaction It is also speculated that an auto-oxidation reaction occurs upon evaporation of water when the liquid compositions are left to dry onto the fabrics Said reaction of auto-oxidation generates peroxy-radicals which may contribute to the degradation of cellulose Thus, not leaving the liquid compositions, as described herein, to dry onto the fabric, in the process of pretreating soiled fabrics according to the present invention, contributes to the benefits according to the present invention, i e to reduce the tensile strength loss when pretreating fabrics with liquid peroxygen bleach-containing compositions
  • compositions suitable to be used according to the present invention comprise a peroxygen bleach
  • Preferred peroxygen bleach is hydrogen peroxide, or a water soluble source thereof, or mixtures thereof
  • Hydrogen peroxide is most preferred to be used in the compositions according to the present invention
  • a hydrogen peroxide source refers to any compound which produces hydrogen peroxide when said compound is in contact with water
  • Suitable water-soluble sources of hydrogen peroxide for use herein include percarbonates, persilicate, persulphate such as monopersulfate, perborates and peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphthalatic acid and mixtures thereof.
  • percarbonates persilicate, persulphate such as monopersulfate, perborates and peroxyacids such as diperoxydodecandioic acid (DPDA), magnesium perphthalatic acid and mixtures thereof.
  • DPDA diperoxydodecandioic acid
  • compositions suitable to be used herein comprise from 0.5% to 20% by weight of the total composition of said peroxygen bleach, preferably from 2% to 15% and most preferably from 3% to 10%.
  • peroxygen bleach preferably hydrogen peroxide provides strong cleaning benefits which are particularly noticeable in laundry applications.
  • the compositions suitable to be used according to the present invention comprise a compound chelating copper and/or iron and/or manganese.
  • the compositions suitable to be used herein comprise from 0.005% to 2% by weight of the total composition of said compound chelating copper and/or iron and/or manganese, or mixtures thereof, preferably from 0.01 % to 1 % and most preferably from 0.01 % to 0.5%.
  • Said compounds chelating copper and/or iron and/or manganese may be any compound capable of binding copper and/or iron and/or manganese.
  • Such compounds chelating copper and/or iron and/or manganese can be selected from the group comprising phosphonate chelants, amino carboxylate chelants, polyfunctionally-substituted aromatic chelating agents or polycarboxylic acids of pyridine and the like, or mixtures thereof.
  • Such phosphonate chelants may include ethydronic acid, hydroxy-ethane diphosphonic acid (HEDP) and ethylenedinitrilotertrakis
  • amino phosphonate compounds such as amino alkylene poly (alkylene phosphonate), alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates.
  • 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.
  • Phosphonate chelants are commercially available from Monsanto under the trade name DEQUEST® Preferred phosphonate chelants to be used herein are diethylene triamine penta methylene phosphonates, hydroxy-ethane diphosphonic acid (HEDP) and ethylenedinitrilotertrakis (methylenephosphonic acid) N.N-oxide
  • Hydroxy-ethane diphosphonic acid and ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-ox ⁇ de have been found to be particularly resistant to protonation and oxidation
  • hydroxy-ethane diphosphonic acid and ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-ox ⁇ de are particularly suitable for application in acidic liquid compositions as a compound for chelating copper and/or iron and/or manganese according to the present invention whereby fabrics safety is improved
  • hydroxy- ethane diphosphonic acid and/or ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-ox ⁇ de allow to formulate liquid acidic peroxygen bleach-containing compositions with improved chemical stability as compared to the same compositions without said chelating agent, or as compared to the same compositions but with another chelating agent, e g diethylene triamine penta methylene phosphonic acid, instead of said chelating agent
  • 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-d ⁇ hydroxy -3,5-d ⁇ sulfobenzene
  • a preferred biodegradable chelatmg 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
  • Ethylenediamme 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 Ethylenediamme N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
  • Such amino carboxylates useful as compounds chelating copper and/or iron and/or manganese include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentoacetate (DTPA), N- hydroxyethylethylenediamine triacetates, nitrilot -acetates, ethylenediamine tetraprophonates, 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
  • DTPA diethylene triamine penta acetic acid
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Suitable polycarboxylic acids of pyridine to be used herein include dipicolinic acid.
  • dipicolinic acid is used in mixture with another compound for chelating copper and/or iron and/or manganese according to the present invention.
  • dipicolinic acid is preferably added on top of other chelants herein in a liquid composition according to the present invention to improve the chemical stability of said composition.
  • chelating agents suitable to be used herein as compounds chelating copper and/or iron and/or manganese include chelating agents having two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co-ordination so as to form complexes with metal ions in which each metal ion is complexed by 3 molecules of chelating agents (3:1 chelating agent:metal ion stoichiometrie). In other words, said chelating agents occupy the co-ordination sphere of the metal ion, making it thereby catalytically inactive. Said chelating agents have been found to be particularly resistant to protonation and/or oxidation.
  • Said chelating agents are thus particularly suitable for application in acidic liquid compositions as a compound for chelating copper and/or iron and/or manganese according to the present invention whereby fabrics safety is improved.
  • said chelating agents having two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co-ordination allow to formulate acidic peroxygen bleach-containing compositions with improved chemical stability as compared to the same compositions without any such chelatmg agents or as compared to the same compositions with another chelating agent, e g diethylene triamine penta methylene phosphonic acid, instead of said chelating agents
  • another aspect of the present invention is the use of chelatmg agents having two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co ⁇ ordination so as to form complexes with metal ions in which each metal ion is complexed by 3 molecules of said chelatmg agents, in an acidic liquid peroxygen bleach-containing composition,
  • Said chelating agents having two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co-ordination include chelatmg agents having at least an ionised carboxylate directly adjacent to one of the following groups an unionised carboxylate, a hydroxyl group, an ammo group or an N-oxide group Particularly suitable to be used herein are malonic acid, 2-hydroxypyr ⁇ d ⁇ ne-N-ox ⁇ de, or mixtures thereof
  • 2-hydroxy-py ⁇ d ⁇ ne-N-ox ⁇ de is, for instance, commercially available from Pynon Chemie (Germany) under the trade name 2-hydroxy-pyr ⁇ dme-N- oxide
  • liquid compositions comprising a peroxygen bleach and, as a compound chelating copper and/or iron and/or manganese, propylene diamine tetracetic acid (PDTA), methyl glycine di- acetic acid (MGDA), diethylene triamine penta methylene phosphonate (DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamme N,N'- disuccinic acid (EDDS), 2-hydroxypyr ⁇ d ⁇ ne-N-ox ⁇ de (HPNO), and/or ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-ox ⁇ de, provide virtually no tensile strength loss in fabrics pretreated therewith, i e the fabric resistance is not reduced, even upon prolonged contact periods of said compositions onto said fabrics, e g 24 hours
  • the present invention accordingly further encompasses liquid compositions comprising a peroxygen bleach, as described herein before and, as the compound chelating copper and/or iron and
  • compositions of the present invention relate to the compositions of the present invention claimed per se, to the compositions used according to the present invention for pretreating soiled fabrics and to the compositions applied onto the fabrics according to the process of pretreating soiled fabrics of the present invention.
  • compositions according to the present invention are aqueous liquid cleaning compositions.
  • Said aqueous compositions have a pH as is of from 1 to 9, preferably from 2 to 6 and more preferably from 3 to 5.
  • the pH of the compositions can be adjusted by using organic or inorganic acids, or alkalinising agents.
  • compositions according to the present invention may further comprise a variety of optional ingredients such as radical scavengers, surfactants, builders, stabilisers, other chelants, soil suspenders, dye transfer agents, solvents, brighteners, perfumes, antioxidants, foam suppressors and dyes.
  • optional ingredients such as radical scavengers, surfactants, builders, stabilisers, other chelants, soil suspenders, dye transfer agents, solvents, brighteners, perfumes, antioxidants, foam suppressors and dyes.
  • a preferred optional ingredient of the compositions according to the present invention is a radical scavenger or mixtures thereof.
  • Suitable radical scavengers for use herein include the well-known substituted mono and di hydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof.
  • Preferred radical scavengers for use herein include butyl hydroxy toluene, 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, commercially available under the trade name Topanol CA® ex ICI, as well as n-propyl-gallate.
  • Radical scavengers when used, are typically present herein in amounts ranging from 0.001 % to 2% by weight of the total composition and preferably from 0.001% to 0.5% by weight.
  • compositions according to the present invention may further comprise any surfactant known to those skilled in the art including nonionic, anionic, cationic, zwitterionic, or amphoteric surfactants.
  • the compositions according to the present invention preferably comprise any of the nonionic surfactants or mixtures thereof described herein after and/or any of the anionic surfactants or mixtures thereof described herein after.
  • the compositions according to the present invention may comprise up to 50% by weight of the total composition of a surfactant, or mixtures thereof.
  • compositions of the present invention may also comprise a liquid hydrophobic bleach activator, as a highly preferred optional ingredient.
  • bleach activator it is meant herein a compound which reacts with hydroger peroxide to form a peracid. The peracid thus formed constitutes the activated bleach.
  • hydrophobic bleach activator it is meant herein an activator which is not substantially and stably miscible with water. Typically, such hydrophobic bleach activators have an HLB of below 11.
  • Such suitable liquid hydrophobic bleach activators typically belong to the class of esters, amides, imides, or anhydrides.
  • ATC acetyl triethyl citrate
  • ATC has the other advantages that it is environmentally friendly in that it eventually degrades into citric acid and alcohol. Also, ATC has good hydrolytical stability in the compositions herein, and it is an efficient bleach activator. Finally, it provides good building capacity to the compositions. It is also possible to use mixtures of liquid hydrophobic bleach activators herein.
  • the compositions herein may comprise up to 20% by weight of the total composition of said bleach activator or mixtures thereof, preferably from 2% to 10%, most preferably from 3% to 7%.
  • the peroxygen bleach-containing compositions according to the present invention further comprise a liquid hydrophobic bleach activator it is highly desired herein for stability purpose to formulate said compositions either as aqueous emulsions of surfactants which comprise said liquid hydrophobic bleach activator, or as microemulsions of said liquid hydrophobic bleach activator in a matrix comprising water, the peroxygen bleach and a hydrophilic surfactant system comprising an anionic and a nonionic surfactant.
  • peroxygen bleach-containing compositions of the present invention further comprise said bleach activator and are formulated as aqueous emulsions
  • said peroxygen bleach-containing emulsions comprise an emulsifying surfactant system of at least two different surfactants, i.e. at least a hydrophobic surfactant having an HLB up to 9 and at least a hydrophilic surfactant having an HLB above 10 in order to emulsify the liquid hydrophobic bleach activator.
  • said two different surfactants in order to form emulsions which are stable must have different HLB values (hydrophilic lipophilic balance), and preferably the difference in value of the HLBs of said two surfactants is at least 1 , preferably at least 3.
  • HLB values hydrophilic lipophilic balance
  • the emulsions according to the present invention comprise from 2 % to 50 % by weight of the total composition of said hydrophilic and hydrophobic surfactants, preferably from 5 % to 40 % and more preferably from 8 % to 30%.
  • the emulsions according to the present invention comprise at least from 0.1 % by weight of the total emulsion of said hydrophobic surfactant, or mixtures thereof, preferably at least 3 % and more preferably at least 5 % and at least from 0.1 % by weight of the total emulsion of said hydrophilic surfactant, or mixtures thereof, preferably at least 3 %, and more preferably at least 6 %.
  • hydrophobic nonionic surfactants and hydrophilic nonionic surfactants are the hydrophobic nonionic surfactants and hydrophilic nonionic surfactants.
  • Said hydrophobic nonionic surfactants to be used herein have an HLB up to 9, preferably below 9, more preferably below 8 and said hydrophilic surfactants have an HLB above 10, preferably above 11 , more preferably above 12.
  • the hydrophobic nonionic surfactants to be used herein have excellent grease cutting properties, i.e. they have a solvent effect which contributes to hydrophobic soils removal.
  • the hydrophobic surfactants act as carrier of the hydrophobic brighteners onto the fabrics allowing thereby said brighteners to work in close proximity with the fabrics surface since the beginning of the wash.
  • Suitable nonionic surfactants for use herein include alkoxylated fatty alcohols preferably, fatty alcohol ethoxylates and/or propoxylates. Indeed, a great variety of such alkoxylated fatty alcohols are commercially available which have very different HLB values (hydrophilic lipophilic balance).
  • HLB values of such alkoxylated nonionic surfactants depend essentially on the chain length of the fatty alcohol, the nature of the alkoxylation and the degree of alkoxylation. Hydrophilic nonionic surfactants tend to have a high degree of alkoxylation and a short chain fatty alcohol, while hydrophobic surfactants tend to have a low degree of alkoxylation and a long chain fatty alcohol.
  • Surfactants catalogs are available which list a number of surfactants including nonionics, together with their respective HLB values.
  • Suitable chemical processes for preparing the nonionic surfactants for use herein include condensation of corresponding alcohols with alkylene oxide, in the desired proportions. Such processes are well known to the man skilled in the art and have been extensively described in the art. As an alternative, a great variety of alkoxylated alcohols suitable for use herein is commercially available from various suppliers.
  • Preferred hydrophobic nonionic surfactants to be used according to the present invention are surfactants having an HLB up to 9 and being according to the formula RO-(C2H4 ⁇ ) n (C3H6 ⁇ ) m H, wherein R is a C5 to C22 a, M chain or a C ⁇ to C28 alkyl benzene chain, and wherein n+m is from 0.5 to 5 and n is from 0 to 5 and m is from 0 to 5 and preferably n+m is from 0.5 to 4 and, n and m are from 0 to 4.
  • the preferred R chains for use herein are the C ⁇ to C22 a 'M chains.
  • Dobanol R 23-3 or Dobanol R 23- 2, Lutensol R T03, or mixtures thereof.
  • Dobanol R surfactants are commercially available from SHELL.
  • Lutensol R surfactants are commercially available from BASF and these Tergitol R surfactants are commercially available from UNION CARBIDE.
  • Other suitable hydrophobic nonionic surfactants to be used herein are non alkoxylated surfactants.
  • An example is Dobanol R 23 (HLB ⁇ 3 ).
  • Preferred hydrophilic nonionic surfactants to be used according to the present invention are surfactants having an HLB above 10 and being according to the formula O-(C2H4 ⁇ ) n (C3H5 ⁇ ) m H, wherein R is a CQ to C22 a'kyl chain or a CQ to C28 alkyl benzene chain, and wherein n+m is from 5 to 11 and n is from 0 to 11 and m is from 0 to 11 , preferably n+m is from 6 to 10 and, n and m are from 0 to 10.
  • n and m refer to the average degree of the ethoxylation/propoxylation.
  • the preferred R chains for use herein are the Cs to C22 alkyl chains.
  • Dobanol R 91-10 or Dobanol R 45-7, Dobanol R 23- 6.5, or mixtures thereof .
  • These Dobanol R surfactants are commercially available from SHELL.
  • hydrophilic nonionic surfactants other hydrophilic surfactants may further be used in the emulsions of the present invention such as anionic surfactants described herein after.
  • the emulsions according to the present invention may further comprise other surfactants which should however not significantly alter the weighted average HLB value of the overall emulsion.
  • an adequate nonionic surfactant system would comprise a hydrophobic nonionic surfactant with for instance an HLB of 6, such as a Dobanol R 23-2 and a hydrophilic nonionic surfactant with for instance an HLB of 15, such as a Dobanol R 91-10.
  • said peroxygen bleach- containing microemulsions according to the present invention comprise a hydrophilic surfactant system comprising an anionic surfactant and a nonionic surfactant.
  • a key factor in order to stably incorporate the hydrophobic activator is that at least one of said surfactants must have a different HLB value to that of the hydrophobic activator. Indeed, if all said surfactants had the same HLB value as that of the hydrophobic activator, a continuous single phase might be formed thus lowering the chemical stability of the bleach/bleach activator system.
  • at least one of said surfactants has an HLB value which differs by at least 1.0 HLB unit, preferably 2.0 to that of said bleach activator.
  • Suitable anionic surfactants herein include water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10- 20 alkyl component, more preferably a C12-C18 a 'ky' 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).
  • Suitable anionic surfactants for use herein are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 a ' ⁇ v ' component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12- 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 C10-C24 alkyl or hydroxyalkyl group having a C10-C24 a ' ⁇ v ' component, preferably a
  • 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 C12-C18 alkyl polyethoxylate (1.0) sulfate, C-
  • 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 -C20 linear alkylbenzenesulfonates, CQ- C22 primary or secondary alkanesulfonates, C8-C24 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.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • C -C20 linear alkylbenzenesulfonates CQ- C22 primary or secondary alkanesulfonates
  • C8-C24 olefinsulfonates C8
  • 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 C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as the
  • 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).
  • Suitable nonionic surfactants for use in the microemulsions herein include the hydrophilic nonionic surfactants as defined herein before.
  • the preferred making of the microemulsions of the present invention which comprises a liquid hydrophobic bleach activator includes premixing the surfactants with water and subsequently adding the other ingredients including hydrogen peroxide and said hydrophobic bleach activator. Irrespective of this preferred order of addition, it is important that during the mixing of the ingredients, the microemulsions be constantly kept under stirring under relatively high stirring energies, preferably 30 minutes at 750 rpm, most preferably 30 minutes at 1000 rpm.
  • compositions are macroscopically transparent in the absence of opacifiers and dyes.
  • said microemulsions In centrifugation examination, it was observed that said microemulsions herein showed no phase separation after 15 minutes at 6000 RPM. Under microscopic examination, said microemulsions appeared as a dispersion of droplets in a matrix.
  • the matrix is the hydrophilic matrix described hereinbefore, and the droplets are constituted by the liquid hydrophobic bleach activator. We have observed that the particles had a size which is typically around or below 3 micron diameter.
  • compositions suitable to be used according to the present invention may further comprise a foam suppressor such as 2-alkyl alkanol, or mixtures thereof, as a highly preferred optional ingredient.
  • a foam suppressor such as 2-alkyl alkanol, or mixtures thereof, as a highly 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.
  • compositions suitable to be used herein comprise from 0.05 % to 2 % by weight of the total composition of a 2-alkyl alkanol, or mixtures thereof, preferably from 0.1 % to 1.5 % and most preferably from 0.1 % to 0.8 %.
  • compositions described herein may also be used as a laundry detergent or as a laundry detergent booster as well as a household cleaner in the bathroom or in the kitchen.
  • a laundry detergent or as a laundry detergent booster as well as a household cleaner in the bathroom or in the kitchen.
  • a laundry detergent booster When used as hard surface cleaners, such compositions are easy to rinse and provide good shine characteristics on the cleaned surfaces.
  • compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • compositions I II III IV V VI Compositions I II III IV V VI
  • Alkylsulphate 1 1..22 1 1..22 1 1..22 1 1..22 1 1..22 1 1..22 1 1..22 1 1..22 1 1..22
  • S,S EDDS is ethylenediamine -N,N'-disuccinic acid (S,S isomer).
  • DTPMP is diethylene triamine penta methylene phosphonate marketed by
  • MGDA is methyl glycine di-acetic acid.
  • PDTA is propylene diamine tetracetic acid marketed by BASF under the trade name Trilon FS®.
  • Composition I comprises only hydrogen peroxide and is free of compounds chelating copper and/or iron and/or manganese.
  • Compositions II to VI are representative of the present invention, they comprise hydrogen peroxide and a compound chelating copper and/or iron and/or manganese.
  • a tensile strength test method was carried out with the compositions mentioned herein above. This test method was carried out on metal- polluted fabrics.
  • the tensile strength loss mentioned above for the different compositions tested is expressed in percentage and is obtained by comparing the tensile strength of a given fabric taken as a reference, i.e. a fabric which has not been pretreated, to the tensile strength of the same fabric measured after said fabric has been pretreated as mentioned herein before.
  • compositions according to the present invention comprising a peroxygen bleach and a compound chelating copper and/or iron and/or manganese, as compared to the use of the same compositions but without any compound chelating copper and/or iron and/or manganese (composition I).
  • compositions II to VI there is virtually no tensile strength loss observed when pretreating fabrics with compositions according to the present invention (see compositions II to VI), this even upon a long contact period, i.e. 24 hours and in presence of a high concentration of copper on the surface of said fabrics, i.e. 50 ppm per gram of cotton fabric.
  • compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified).
  • H2SO4 up to pH 4 S,S EDDS is ethylenediamine -N,N'-disuccinic acid (S,S isomer).
  • DTPMP is diethylene triamine penta methylene phosphonate marketed by Monsanto under the trade name DEQUEST®.
  • MGDA is methyl glycine di-acetic acid.
  • PDTA is propylene diamine tetracetic acid marketed by BASF under the trade name Trilon FS®.
  • HPNO is 2-hydroxy pyridine-N-oxide.
  • HEDP is hydroxy-ethane diphosphonic acid.
  • DTPA is diethylene triamine penta acetic acid.
  • compositions IX X XI XII XIII Compositions IX X XI XII XIII
  • compositions in examples I to XIII are according to the present invention.
  • a pretreatment process was carried out according to the present invention with compositions I to XIII with virtually no tensile strength loss of the fabrics treated, even when leaving the compositions to act onto said fabrics for 24 hours before washing said fabrics.

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Abstract

La présente invention concerne l'utilisation d'une composition liquide contenant un peroxyde comme agent de blanchiment et un composé chélatant pour le cuivre et/ou le fer et/ou le manganèse, destinée au prétraitement de tissus salis avant leur lavage. Ce prétraitement permet de diminuer la perte de la résistance des tissus à la rupture. Cette invention concerne également un procédé pour le prétraitement de tissus salis ainsi que des compositions convenant audit procédé.
EP96906534A 1995-02-28 1996-02-20 Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu Expired - Lifetime EP0812348B1 (fr)

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EP96906534A EP0812348B1 (fr) 1995-02-28 1996-02-20 Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu

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Application Number Priority Date Filing Date Title
EP95870018 1995-02-28
EP95870018 1995-02-28
PCT/US1996/002219 WO1996026999A1 (fr) 1995-02-28 1996-02-20 Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu
EP96906534A EP0812348B1 (fr) 1995-02-28 1996-02-20 Pretraitement du linge avec des chelateurs contenant un agent de blanchiment peroxyde pour le fer, le cuivre ou le manganese, pour diminuer la deterioration du tissu

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JP5850582B2 (ja) * 2010-07-27 2016-02-03 クラリアント・ファイナンス・（ビーブイアイ）・リミテッド 過酸化水素または過酸化水素供与性物質を含む組成物
CH703870B1 (de) * 2010-09-29 2014-11-28 Genossenschaft Coop Desinfizierende Reinigungszusammensetzung.
WO2013025742A1 (fr) * 2011-08-15 2013-02-21 The Procter & Gamble Company Compositions détergentes contenant des composés pyridinol-n-oxydes
CN103290670A (zh) * 2013-05-16 2013-09-11 辽宁腾达集团股份有限公司 一种利用漂后热能去除纯棉针织物残留氧的方法
US10060073B2 (en) 2013-05-23 2018-08-28 Washing Systems, Llc Method of laundering industrial garments
PL224478B1 (pl) 2013-06-03 2016-12-30 Eko Styl Spółka Z Ograniczoną Odpowiedzialnością Sposób apreturowania tkanin w procesie ich prania

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AU711340B2 (en) 1999-10-14
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ATE230042T1 (de) 2003-01-15
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MX9706537A (es) 1997-11-29
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AU4988296A (en) 1996-09-18
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BR9607400A (pt) 1998-06-30
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CN1176656A (zh) 1998-03-18
ZA961586B (en) 1996-09-06
DE69625471D1 (de) 2003-01-30

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