EP0812348B1 - Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage - Google Patents
Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage Download PDFInfo
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- EP0812348B1 EP0812348B1 EP96906534A EP96906534A EP0812348B1 EP 0812348 B1 EP0812348 B1 EP 0812348B1 EP 96906534 A EP96906534 A EP 96906534A EP 96906534 A EP96906534 A EP 96906534A EP 0812348 B1 EP0812348 B1 EP 0812348B1
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Classifications
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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 art of pretreatment of soiled fabrics before laundry.
- 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 compound for chelating copper and/or iron and/or manganese iono selected from the group consisting of diethylene triamine penta methylene phosphonic acid (DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamine N,N'-disuccinic acid (EDDS), methyl glycine di-acetic acid (MGDA), diethylene triamine penta acetic acid (DTPA), propylene diamine tetracetic acid (PDTA), 2-hydroxypyridine-N-oxide (HPNO), or ethylenedinitrilotertrakis (methylenephosphonic acid) N,N,-dioxide, in a peroxygen bleach-containing composition, considerably reduces the damage on a fabric pretreated with such a composition.
- An advantage associated to the use of a peroxygen bleach-containing composition comprising such a compound for chelating copper and/or iron and/or manganese, in laundry pretreatment application, is that color damage is also reduced.
- 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 and/or hydroxy-ethane diphosphonic acid (HEDP) 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 and/or hydroxy-ethane diphosphonic acid (HEDP) 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
- 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 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-209 228 discloses compositions comprising a peroxide source like hydrogen peroxide, an amino polyphosphonate chelant and a radical scavenger. Diethylene triamine penta methylene phosphonic acid is expressly disclosed. Also EP-A-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 relates to a use as defined in claim 1.
- 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.
- the 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.
- 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 are selected from the group listed below and mixtures thereof.
- Phosphonate chelants in terms of hydroxy-ethane diphosphonic acid (HEDP) and ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-oxide as well as alkali metal ethane 1-hydroxy diphosphonates, 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-oxide have been found to be particularly resistant to protonation and oxidation.
- hydroxy-ethane diphosphonic acid and ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-oxide 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-oxide 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.
- another chelating agent e.g. diethylene triamine penta methylene phosphonic acid
- a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substituted 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.
- Amino carboxylates useful according to the invention as compounds chelating copper and/or iron and/or manganese are diethylene triamine penta acetic acid (DTPA), 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).
- DTPA diethylene triamine penta acetic acid
- PDTA propylene diamine tetracetic acid
- MGDA methyl glycine di-acetic acid
- Said chelating agents having 'two electron-donor groups able to occupy adjacent co-ordination sites in the metal ions sphere of co-ordination include chelating agents having at least an ionised carboxylate directly adjacent to one of the following groups: an unionised carboxylate, a hydroxyl group, an amino group or an N-oxide group. Particularly suitable to be used herein is 2-hydroxypyridine-N-oxide, or mixtures thereof.
- 2-hydroxy-pyridine-N-oxide is, for instance, commercially available from Pyrion Chemie (Germany) under the trade name 2-hydroxy-pyridine-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), ethylenediamine N,N'- disuccinic acid (EDDS), 2-hydroxypyridine-N-oxide (HPNO), and/or ethylenedinitrilotertrakis (methylenephosphonic acid) N,N-oxide, 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.
- PDTA propylene diamine tetracetic acid
- MGDA methyl glycine di-acetic acid
- DTPMP diethylene triamine penta methylene phosphonate
- compositions relate to the compositions used according to the present invention for pretreating soiled fabrics
- 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 hydrogen 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.
- 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.
- 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-(C 2 H 4 O) n (C 3 H 6 O) m H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 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 8 to C 22 alkyl chains.
- Dobanol R 23-3 or Dobanol R 23-2, Lutensol R TO3, or mixtures thereof.
- These Dobanol R surfactants are commercially available from SHELL.
- These 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 RO-(C 2 H 4 O) n (C 3 H 6 O) m H, wherein R is a C 6 to C 22 alkyl chain or a C 6 to C 28 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 C 8 to C 22 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 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).
- 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-, trimethylammonium 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.
- 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 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary or secondary alkanesulfonates, 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.
- salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
- C 9 -C 20 linear alkylbenzenesulfonates C 8 -C 22 primary or secondary alkanesulfonates
- 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).
- 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).
- 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®.
- 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).
- Compositions VII VIII IX X XI XII XIII XIV H 2 O 2 7.0 7.0 7.0 7.0 7.0 7.0 Alkylsulphate (1) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 Dobanol R 91-10 1.6 1.6 1.6 1.6 1.6 1.6 Dobanol R 23-3 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 1.1 BHT 0.03 0.03 0.03 0.03 ⁇ - ⁇ - 0.09 0.09 2-Butyl Octanol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 S,S EDDS 0.5 --- --- --- --- --- --- --- --- PDTA --- 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 S,S EDDS 0.5 --- ---
- 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 in examples VII-XIX are according to the present invention.
- a pretreatment process was carried out according to the present invention with compositions VII-XIX 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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- Oil, Petroleum & Natural Gas (AREA)
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96906534A EP0812348B1 (en) | 1995-02-28 | 1996-02-20 | Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95870018 | 1995-02-28 | ||
EP95870018 | 1995-02-28 | ||
PCT/US1996/002219 WO1996026999A1 (en) | 1995-02-28 | 1996-02-20 | Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage |
EP96906534A EP0812348B1 (en) | 1995-02-28 | 1996-02-20 | Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage |
Publications (3)
Publication Number | Publication Date |
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EP0812348A1 EP0812348A1 (en) | 1997-12-17 |
EP0812348A4 EP0812348A4 (en) | 2000-04-12 |
EP0812348B1 true EP0812348B1 (en) | 2002-12-18 |
Family
ID=8222114
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP96906534A Expired - Lifetime EP0812348B1 (en) | 1995-02-28 | 1996-02-20 | Laundry pretreatment with peroxide bleaches containing chelators for iron, copper or manganese for reduced fabric damage |
Country Status (19)
Country | Link |
---|---|
EP (1) | EP0812348B1 (fi) |
JP (1) | JPH11502549A (fi) |
KR (1) | KR100249610B1 (fi) |
CN (1) | CN1176656A (fi) |
AT (1) | ATE230042T1 (fi) |
AU (1) | AU711340B2 (fi) |
BR (1) | BR9607400A (fi) |
CA (1) | CA2213633C (fi) |
CZ (1) | CZ270297A3 (fi) |
DE (1) | DE69625471T2 (fi) |
ES (1) | ES2185764T3 (fi) |
FI (1) | FI973517A (fi) |
HU (1) | HUP9800073A2 (fi) |
NO (1) | NO973910L (fi) |
PL (1) | PL322021A1 (fi) |
SK (1) | SK115597A3 (fi) |
TR (1) | TR199700867T1 (fi) |
WO (1) | WO1996026999A1 (fi) |
ZA (1) | ZA961586B (fi) |
Families Citing this family (29)
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EP0752469B1 (en) * | 1995-07-05 | 2004-09-22 | The Procter & Gamble Company | Laundry pre-treatment with improved fabric/colour safety |
GB2311536A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Dishwashing and laundry detergents |
GB2311537A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Rinse composition for dishwashers |
GB2311538A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Detergent compositions |
GB2311535A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Detergent compositions |
GB2311542A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Percarbonate bleach composition |
GB2311541A (en) * | 1996-03-29 | 1997-10-01 | Procter & Gamble | Oxygen-releasing bleach composition |
EP0839903B1 (en) * | 1996-10-31 | 2002-12-11 | The Procter & Gamble Company | Liquid aqueous bleaching compositions and pretreatment process |
US6242407B1 (en) * | 1996-11-22 | 2001-06-05 | The Procter & Gamble Company | Laundry bleaching compositions |
US5968884A (en) * | 1997-04-07 | 1999-10-19 | Basf Corporation | Concentrated built liquid detergents containing a biodegradable chelant |
EP0924292B1 (en) * | 1997-11-24 | 2005-05-25 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
US6692536B1 (en) | 1997-11-24 | 2004-02-17 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
EP0918088A1 (en) * | 1997-11-24 | 1999-05-26 | The Procter & Gamble Company | Use of a crystal growth inhibitor to reduce fabric abrasion |
GB2333772A (en) * | 1998-01-31 | 1999-08-04 | Procter & Gamble | Complexing agents (eg ethylenediamine disuccinic acid) for use in selectively complexing copper, iron, zinc, nickel and cobalt in the presence of calcium |
US6204233B1 (en) * | 1998-10-07 | 2001-03-20 | Ecolab Inc | Laundry pre-treatment or pre-spotting compositions used to improve aqueous laundry processing |
CN1384869A (zh) * | 1999-09-01 | 2002-12-11 | 荷兰联合利华有限公司 | 受污织物的预处理和漂白方法 |
JP3857082B2 (ja) * | 2001-07-24 | 2006-12-13 | 花王株式会社 | 衣料用洗濯前処理剤組成物 |
US6767881B1 (en) | 2003-03-19 | 2004-07-27 | Ecolab, Inc. | Cleaning concentrate |
JP5401034B2 (ja) * | 2007-12-19 | 2014-01-29 | ライオン株式会社 | 漂白助剤、および該漂白助剤を含有する漂白助剤粒子 |
DE102008023014A1 (de) | 2008-05-09 | 2009-11-12 | Henkel Ag & Co. Kgaa | Wäßriges Textilbehandlungsmittel |
JP5544716B2 (ja) * | 2009-01-13 | 2014-07-09 | 栗田工業株式会社 | 鉄鋼製造工程における循環冷却水の洗浄方法 |
EP2334776B1 (en) * | 2009-09-15 | 2012-11-14 | The Procter & Gamble Company | Detergent composition comprising mixture of chelants |
RU2549930C2 (ru) | 2009-10-30 | 2015-05-10 | Акцо Нобель Кемикалз Интернэшнл Б.В. | Применение металлосодержащей добавки в корме для животных |
MX2013001095A (es) * | 2010-07-27 | 2013-03-12 | Clariant Finance Bvi Ltd | Composiciones que comprenden peroxido de hidrogeno o sustancias donadoras de peroxido de hidrogeno. |
CH703870B1 (de) * | 2010-09-29 | 2014-11-28 | Genossenschaft Coop | Desinfizierende Reinigungszusammensetzung. |
EP2744881B1 (en) * | 2011-08-15 | 2016-01-20 | The Procter and Gamble Company | Detergent compositions containing pyridinol-n-oxide compounds |
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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GB926639A (en) * | 1960-05-31 | 1963-05-22 | Courtaulds Ltd | Improvements relating to the treatment of cellulosic fabrics |
JPS599662B2 (ja) * | 1980-08-18 | 1984-03-03 | 三菱瓦斯化学株式会社 | 繊維織物の糊抜方法 |
DE3218889A1 (de) * | 1982-05-19 | 1983-11-24 | Hoechst Ag, 6230 Frankfurt | Verfahren zum gleichzeitigen entschlichten und bleichen von textilmaterial aus cellulosefasern |
FR2545854B1 (fr) * | 1983-05-10 | 1985-07-26 | Ugine Kuhlmann | Procede de blanchiment des textiles en presence de particules de fer ou de metaux ferreux |
DE3346578A1 (de) * | 1983-12-23 | 1985-07-18 | Sandoz-Patent-GmbH, 7850 Lörrach | Mittel und verfahren zum einbadigen einstufigen alkalischen vorbehandeln von cellulosehaltigen textilmaterialien |
DE3665482D1 (en) * | 1985-06-17 | 1989-10-12 | Clorox Co | Stabilized liquid hydrogen peroxide bleach compositions |
US4900468A (en) * | 1985-06-17 | 1990-02-13 | The Clorox Company | Stabilized liquid hydrogen peroxide bleach compositions |
JP2602563B2 (ja) * | 1989-12-15 | 1997-04-23 | 花王株式会社 | 液体酸素系漂白剤組成物 |
GB9027429D0 (en) * | 1990-12-18 | 1991-02-06 | Kodak Ltd | Effluent treatment |
US5362412A (en) * | 1991-04-17 | 1994-11-08 | Hampshire Chemical Corp. | Biodegradable bleach stabilizers for detergents |
GB9216408D0 (en) * | 1992-08-01 | 1992-09-16 | Procter & Gamble | Stabilized bleaching compositions |
JP2819487B2 (ja) * | 1992-10-05 | 1998-10-30 | 富士写真フイルム株式会社 | 写真用処理組成物及び処理方法 |
SG55157A1 (en) * | 1993-06-09 | 1998-12-21 | Procter & Gamble | Stable aqueous emulsions of nonionic surfactants |
ATE186324T1 (de) * | 1993-06-09 | 1999-11-15 | Procter & Gamble | Stabile wässrige nichtionische tensidemulsionen |
GB2294707A (en) * | 1994-11-05 | 1996-05-08 | Procter & Gamble | Bleaching composition |
-
1996
- 1996-02-20 HU HU9800073A patent/HUP9800073A2/hu unknown
- 1996-02-20 AU AU49882/96A patent/AU711340B2/en not_active Ceased
- 1996-02-20 CZ CZ972702A patent/CZ270297A3/cs unknown
- 1996-02-20 BR BR9607400A patent/BR9607400A/pt not_active Application Discontinuation
- 1996-02-20 AT AT96906534T patent/ATE230042T1/de not_active IP Right Cessation
- 1996-02-20 DE DE69625471T patent/DE69625471T2/de not_active Expired - Lifetime
- 1996-02-20 ES ES96906534T patent/ES2185764T3/es not_active Expired - Lifetime
- 1996-02-20 CA CA002213633A patent/CA2213633C/en not_active Expired - Fee Related
- 1996-02-20 EP EP96906534A patent/EP0812348B1/en not_active Expired - Lifetime
- 1996-02-20 WO PCT/US1996/002219 patent/WO1996026999A1/en active IP Right Grant
- 1996-02-20 KR KR1019970705972A patent/KR100249610B1/ko not_active IP Right Cessation
- 1996-02-20 TR TR97/00867T patent/TR199700867T1/xx unknown
- 1996-02-20 PL PL96322021A patent/PL322021A1/xx unknown
- 1996-02-20 SK SK1155-97A patent/SK115597A3/sk unknown
- 1996-02-20 CN CN96192233A patent/CN1176656A/zh active Pending
- 1996-02-20 JP JP8526295A patent/JPH11502549A/ja active Pending
- 1996-02-28 ZA ZA961586A patent/ZA961586B/xx unknown
-
1997
- 1997-08-26 NO NO973910A patent/NO973910L/no not_active Application Discontinuation
- 1997-08-27 FI FI973517A patent/FI973517A/fi unknown
Also Published As
Publication number | Publication date |
---|---|
HUP9800073A2 (hu) | 1998-04-28 |
ES2185764T3 (es) | 2003-05-01 |
DE69625471T2 (de) | 2003-11-06 |
NO973910D0 (no) | 1997-08-26 |
AU4988296A (en) | 1996-09-18 |
EP0812348A4 (en) | 2000-04-12 |
BR9607400A (pt) | 1998-06-30 |
PL322021A1 (en) | 1998-01-05 |
WO1996026999A1 (en) | 1996-09-06 |
CZ270297A3 (cs) | 1998-01-14 |
ATE230042T1 (de) | 2003-01-15 |
DE69625471D1 (de) | 2003-01-30 |
FI973517A (fi) | 1997-10-27 |
KR100249610B1 (ko) | 2000-03-15 |
CN1176656A (zh) | 1998-03-18 |
FI973517A0 (fi) | 1997-08-27 |
EP0812348A1 (en) | 1997-12-17 |
CA2213633C (en) | 2002-01-22 |
NO973910L (no) | 1997-08-26 |
ZA961586B (en) | 1996-09-06 |
MX9706537A (es) | 1997-11-29 |
TR199700867T1 (xx) | 1998-01-21 |
SK115597A3 (en) | 1998-06-03 |
KR19980702566A (ko) | 1998-07-15 |
JPH11502549A (ja) | 1999-03-02 |
CA2213633A1 (en) | 1996-09-06 |
AU711340B2 (en) | 1999-10-14 |
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