Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3947—Liquid compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/391—Oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3915—Sulfur-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/3927—Quarternary ammonium compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/13—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen using inorganic agents

Definitions

• the present invention relates to the bleaching of fabrics with liquid aqueous persulfate-containing bleaching compositions having a pH below 7.
• Liquid aqueous bleaching compositions suitable for laundry applications are well known in the art. It is also known that liquid bleaching compositions relying on hypochlorite as the bleaching agent can be preferred over oxygen bleaches like hydrogen peroxide, mainly for performance reasons, especially at lower temperatures.
• hypochlorite beaches there are some limitations to the convenience of hypochlorite beaches.
• hypochlorite bleaching may cause yellowing and/or damage of the fabrics which are being bleached. This holds particularly true for synthetic fabrics and indeed there is a standing prejudice against using hypochlorite bleaches on synthetic fibers, as evidenced by warnings on labels of commercially available hypochlorite bleaches.
• fabrics made of or containing synthetic fibers are labeled by their manufacturers as non-bleachable.
• liquid aqueous hypochlorite-based bleaching compositions are also drawbacks associated to liquid aqueous hypochlorite-based bleaching compositions.
• the bleaching processes herein starting from the liquid aqueous persulfate-containing compositions as described herein provide effective bleaching performance and effective stain removal performance even under short soaking time conditions, typically below 30 minutes, more preferably below 10 minutes and most preferably below 5 minutes.
• the bleaching processes herein starting from the liquid persulfate-containing compositions as described herein provide effective bleaching performance and effective stain removal performance even under soaking conditions where the aqueous bath is made of cold water, typically down to 4°C (preferably below 40°C and most preferably from 10°C to 30°C).
• the present invention provides a process of bleaching fabrics that best needs the today consumers needs, i.e.
• an advantage of the process of bleaching a fabric herein is that the acidic liquid aqueous persulphate-containing composition herein is effective since the first instants of its dilution in the aqueous bath. This is because it quickly dissolves in the aqueous bath.
• the acidic liquid aqueous composition used preferably comprises on top of the persulfate salt, a bleach activator being an aldehyde and/or ketone and/or halide activator compound, for further improved bleaching performance and improved stain removal performance.
• the laundry bleaching operations according to the present invention are safe to the fabrics perse and/or fabrics colours. Indeed, it has been surprisingly been found that when formulating a persulfate salt and optionally an activator compound as described herein after, in a liquid aqueous composition having a pH below 7, the safety (both fabric safety and colour safety) delivered to the fabrics bleached therewith according to the process of the present invention is improved as compared to formulating the same ingredients in a granular composition.
• the process of bleaching fabrics according to the present invention has the advantage of being odour free on hands if a hand bleaching operation is carried out and/or on the fabrics so bleached.
• the present invention encompasses a process of bleaching a fabric which comprises the steps of :
• the present invention encompasses the use of a liquid aqueous bleaching composition having a pH below 7 and comprising a persulfate salt and optionally a bleach activator being an aldehyde, ketone and/or halide activator compound for the bleaching of fabrics, for reducing the loss of tensile strength in said fabrics. Furthermore, the present invention encompasses the use of a liquid aqueous bleaching composition having a pH below 7 and comprising a persulfate salt and optionally a bleach activator being an aldehyde, ketone and/or halide activator compound for the bleaching of coloured fabrics, for reducing the colour damage to said fabrics.
• the present invention encompasses a process of bleaching fabrics as described herein after.
• fabrics any types of fabrics including for example clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like.
• the process of bleaching fabrics herein is suitable for both natural fabrics and synthetic fabrics.
• natural fabrics it is meant fabrics made of cotton, viscose, linene, silk and/or wood.
• synthetic fabrics it is meant those made of synthetic fibers like polymeric fibers (polyamide, polyester, lycra® and elasthan®), and those made of both natural and synthetic fibers.
• the process of bleaching fabrics according to the present invention comprises the steps of:
• liquid compositions per se as described herein are diluted typically with water to form an aqueous bath to which the fabrics to be bleached will be contacted before being rinsed.
• the fabrics are left into contact with the aqueous bath (in the so-called "soaking step") for a period of time sufficient to bleach the fabrics.
• This period of time typically ranges from 1 minute to 24 hours, preferably from 3 minutes to 12 hours and more preferably from 4 minutes to 6 hours.
• the process of bleaching according to the present invention provides effective bleaching performance and effective stain removal performance even upon shorter soaking time, typically below 1 hour, preferably below 20 minutes and more preferably from 4 minutes to 15 minutes.
• the dilution level that the liquid aqueous composition as described herein, undergoes in the process of the bleaching fabrics herein is a dilution of the composition into water of up to 500 times its weight, preferably from 5 to 200 times and more preferably from 10 to 80 times. Such dilution may occur for instance in hand laundry applications as well as by the other means such as in washing machine.
• the temperature of the bleaching process does have an influence on the stain removal performance and/or bleaching performance of the liquid aqueous persulfate-containing compositions used herein, effective stain removal performance and/or bleaching performance are provided even at low temperatures typically down to 4°C. More particularly, these benefits are observed not only at low temperatures but also under short soaking periods, typically below 20 minutes. It is also understood that by increasing the temperature the bleaching process can be accelerated, i.e. the time required to bleach a given soiled fabric is reduced.
• the aqueous baths occurring in the bleaching processes according to the present invention where the persulfate bleaching compositions as described herein are diluted have a temperature of from 4°C to 60°C, preferably from 10°C to 50°C and most preferably from 15°C to 30°C.
• the process of bleaching fabrics according to the present invention provides improved bleaching performance and improved overall stain removal performance, as compared to the same process where the bleaching composition used is a liquid aqueous composition based on activated hydrogen peroxide at the same total level of bleaching agents. Also these benefits are obtained with the process of bleaching fabrics according to the present invention with short soaking time in both cold or hot aqueous baths.
• Effective bleaching performance is provided on a variety of bleachable soils, from hydrophobic to hydrophilic soils on both hydrophilic and hydrophobic fabrics. Effective bleaching performance herein also includes effective whiteness.
• the present invention provides not only effective bleaching performance but also overall effective stain removal performance on various types of stains including greasy stains (e.g., lipstick, tomato, make-up) and/or enzymatic stains (e.g. blood, choco pudding).
• greasy stains e.g., lipstick, tomato, make-up
• enzymatic stains e.g. blood, choco pudding
• said washing may be conducted together with the bleaching of said fabrics by contacting said fabrics at the same time with the liquid aqueous bleaching composition as described herein and a laundry detergent composition, or said washing may be conducted before or after that said fabrics have been bleached.
• the process according to the present invention allows to bleach fabrics and optionally to wash fabrics with a detergent composition comprising at least one surface active agent before the step of contacting said fabrics with said aqueous bath comprising the liquid aqueous composition and/or in the step where said fabrics are contacted with said aqueous bath and/or after the step where said fabrics are contacted with said aqueous bath and before the rinsing step and/or after the rinsing step.
• the fabrics are preferably washed in a separate step from the bleaching step to get optimum bleaching and stain removal performance.
• conducting the bleaching and washing with a detergent composition in the same step may cause chemical interaction between the persulfate salt coming from the liquid aqueous composition and the conventional detergent ingredients typically present in a conventional detergent composition, i.e. enzymes, surfactants and the like and thus may reduce the bleaching performance and/or overall stain removal performance.
• a typical issue associated to for example granular persulphate-containing compositions known in the art is the fabric and colour damage associated to residual persulphate that dissolves slowly in the aqueous bath obtained by diluting such a composition with water.
• a slow-dissolving granular persulphate-containing composition is used to prepare an aqueous bath (soaking bath)
• the absence of agitation that typically occurs in hand washing soaking can cause prolonged contact between the persulphate in a granular form and the fabrics.
• an advantage of the present invention is that the fast dissolution of the liquid aqueous composition as used herein reduces the fabric and colour damage typically associated to the use of granular persulphate-containing compositions.
• the tensile strength in a fabric may be measured by stretching said fabric until it breaks.
• the force needed to break the fabric is the "Ultimate Tensile Stress” and may be measured with a stress-strain INSTRON ® machine available from INSTRON.
• the loss of tensile strength is the difference between the tensile strength of a fabric taken as a reference, e.g. a fabric which has not been bleached, and the tensile strength of the same fabric after having been bleached with a composition of the present invention.
• a tensile strength loss of zero means that no fabric damage is observed.
• the colour safety can be evaluated visually by comparing side by side fabrics soaked with a composition of the present invention and a reference composition. Differences and graduations in colour can be visually assessed and ranked according to Panel Score Units (PSU) using any suitable scale. PSU data can be handled statistically using conventional techniques. Alternatively, various types of optical apparatus and procedures can be used to assess the improvement in colour safety afforded by the present invention. For example when evaluating colour safety on fabrics measurements with Hunterlab colour Quest 45/0 apparatus can be used.
• An advantage of the persulfate-containing compositions suitable for use in the process of bleaching fabrics according to the present invention is that they are physically and chemically stable upon prolonged periods of storage.
• compositions used herein comprising a persulfate salt or mixtures thereof and optionally an activator compound do not undergo more than 15% AvO loss, in one month at 25°C and preferably not more than 10%.
• AvO loss of a persulfate containing composition can be measured by titration with potassium permanganate after reduction with a solution containing ammonium ferrous sulphate. Said stability test method is well known in the art and is reported, for example, on the technical information sheet of Curox R commercially available from Interox. Alternatively persulfate concentration can also be measured using a chromatography method described in the literature for peracids (F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol 113, May 1988, p 793-795).
• liquid aqueous compositions used in the process of bleaching fabrics
• liquid persulfate-containing compositions for use in the process of bleaching fabrics according to the present invention are liquid compositions as opposed to a solid or a gas.
• liquid includes "pasty” compositions.
• These liquid compositions herein are aqueous compositions.
• These liquid compositions according to the present invention have a pH below 7, preferably from 0.1 to 6, more preferably from 0.5 to 4, even more preferably from 1 to 3 and most preferably from 1 to 2. Formulating these compositions in the acidic pH range is critical to the chemical stability of these compositions upon prolonged periods of storage before their use in the process of bleaching fabrics according to the present invention.
• the pH of these compositions may be adjusted by any acidifying or alkalinising agents known to those skilled in the art.
• acidifying agents are organic acids such as citric acid and inorganic acids such as sulphuric acid, sulphonic acid and/or methanesulphonic acid.
• alkalinising agents are sodium hydroxide, potassium hydroxide and/or sodium carbonate.
• liquid aqueous compositions for use in the process of bleaching fabrics according to the present invention comprise a persulfate salt or a mixture thereof.
• Suitable persulfate salts include any alkali metal persulfate salt including sodium persulfate salts and/or potassium persulfate salts.
• Preferred persulfate salt to be used herein is the monopersulfate salt.
• monopersulfate salts commercially available are those commercialised by Interox under the trade name Curox®, by Degussa under the trade name Caroat® or by DuPont under the trade name Oxone®. It is to understand herein that when the commercially available Curox® , Caroat® and/or Oxone® are used, the % weights of persulfate salts mentioned herein, refer to the total weight of said Curox® , Caroat® and/or Oxone® .
• the active concentration is approximately 1/2 of the total weight.
• Other persulfate salts such as dipersulfate salts commercially available among others from Peroxide Chemie GMBH can be used in the compositions according to the present invention.
• Another suitable persulphate salt is ammonium persulphate.
• the liquid compositions for use in the process of bleaching fabrics according to the present invention comprise from 0.01% to 50% by weight of the total composition of the persulfate salt or mixtures thereof, preferably from 0.5% to 20%, more preferably from 1% to 15% and most preferably from 2% to 10%.
• the liquid aqueous persulfate-containing compositions used in the process of bleaching fabrics according to the present invention may comprise a variety of optional ingredients such as bleach activator compounds, surfactants, chelating agents, radical scavengers, antioxidants, other stabilisers, builders, soil suspenders, polymeric soil release agents, catalysts, dye transfer agents, solvents, suds controlling agents, brighteners, perfumes, pigments, dyes and the like.
• optional ingredients such as bleach activator compounds, surfactants, chelating agents, radical scavengers, antioxidants, other stabilisers, builders, soil suspenders, polymeric soil release agents, catalysts, dye transfer agents, solvents, suds controlling agents, brighteners, perfumes, pigments, dyes and the like.
• Suitable bleach activators for use in these liquid persulfate-containing compositions include aldehyde activator compounds, ketone activator compounds, halide activator compounds and a mixture thereof.
• aldehyde it is meant herein any compound which contains at least one carbonyl group and has two hydrogen atoms or carbon atom and a hydrogen atom attached directly to at least one of the carbonyl carbon atoms.
• ketone it is meant herein any compound which contains at least one carbonyl group and has two carbon atoms attached directly to at least one of the carbonyl carbon atoms.
• These compounds can be aliphatic or aromatic substituted or unsubstituted, saturated or unsaturated, or acyclic, carbocyclic or heterocyclic.
• halide it is meant chloride, bromide and/or iodide.
• activator it is meant herein ketone, aldehyde and halide compounds and mixtures thereof that react with persulfate salt to form an activated bleaching specie, i.e. a dioxirane (when the activator compound is ketone or aldehyde) or a hypohalogenite (when the activator compound is a halide).
• activated bleaching specie i.e. a dioxirane (when the activator compound is ketone or aldehyde) or a hypohalogenite (when the activator compound is a halide).
• the bleaching performance and overall stain removal performance is further improved.
• activated species i.e. dioxirane and hypohalogenite
• these activation mechanisms mainly occur upon dilution of the compositions herein with water and are emphased with the pH jump in the neutral to alkaline pH range (i.e. around 6 and higher) associated to this dilution. It is at those pHs that more dioxiranes and/or hypohalogenites are generated thereby outstandingly improving the bleaching performance of the process of bleaching fabrics herein.
• Suitable aldehyde activator compounds for use herein include chloral-hydrate, acetaldehyde, butyraldehyde, benzaldehyde, and/or 4-trimethylammonio benzaldehyde methyl sulfate.
• Particularly preferred aldehyde activator compounds for use herein are acetaldehyde, butyraldehyde and/or, benzaldehyde and most preferred is acetaldehyde.
• Aldehyde activator compounds are in general less preferred than the ketone activators compounds as they may be oxidised during prolonged storage periods.
• acetaldehyde may be commercially available from Aldrich.
• Suitable aliphatic ketone activator compounds for use herein include acetacetone, 2,3-hexanedione, trimethylammonio acetone nitrate, 5-diethylbenzylammonio 2-pentanone nitrate, 5-diethylmethylammonio 2-pentanone nitrate, methyl pyruvate, diethyl keto malonate, 3-hydroxy-2-butanone, acetol, hexachloracetone, 2,5-hexanedione, phenylacetone, ethyl levulinate, 3-hydroxy-2-pentanone, acetone, 3-penten-2-one, methyl ethyl ketone, 4-hydroxy-3-methyl-2-butanone, 3-pentanone, and/or 2-heptanone.
• acetacetone may be commercially available from Aldrich under its chemical name.
• Suitable aromatic ketone activator compounds for use herein include hydroxyquinoline, 4-acetyl-1-methylpyridinium nitrate, di-2-pyridyl ketone N-oxide, 2-acetylquinoxaline, 2-acetyl-3-methylquinoxaline oxaline, di-2- pyridyl ketone, 6-acetyl-1,2,4-trimethyl quinolinium nitrate, 8-hydroxyquinoline N-oxide, methyl phenyl glyoxalate, N-methyl-p-morpholinio acetophenone methyl sulfate, 3-acetyl pyridine N-oxide, p-nitroacetophenone, m-nitroacetophenone, sodium p-acetyl benzene sulfonate, p-acetylbenzonitrile, 3,5-dinitroacetophenone, 4-trimethylammonioacetophenone nitrate, 4-methoxy-3-
• Suitable cyclic ketone activator compounds for use herein include cyclohexanone, 2-methylcyclohexanone, 2,6-dimethyl cyclohexanone, 3-methyl cyclohexanone, 4-ethyl cyclohexanone, 4-t-butyl cyclohexanone, 4,4-dimethyl cyclohexanone, methyl 4-oxo-cyclohexanone carboxylate, sodium 4-oxo-cyclohexanone carboxylate, 2-trimethylammoniocyclohexanone nitrate, 4-trimethylammonio cyclohexanone nitrate, 3 oxo-cyclohexyl acetic acid, cycloheptanone, 1,4-cyclohexadione, dehydrochloric acid, tropinone methonitrate, N-methyl-3-oxoquinuclidinium nitrate, cyclooctanone and/or cyclopentan
• cyclohexanone may be commercially available from Aldrich under its chemical name.
• Suitable heterocyclic ketone activator compounds for use herein include, 2,2,6,6-tetramethyl-4-piperidone hydrate, 1-methyl-4-piperidone N-oxide, N-carbethoxy 4-piperidone, tetrahydrothiopyran-4-one methonitrate, tetrahydrothiopyran-4-one S,S- dioxide, tetrahydrothiopyran-3-one,S,S,-dioxide, and/or 4-oxacyclohexanone.
• Particularly preferred bleach activators for use herein are the ketone activator compounds and highly preferred are the ketones activator compounds bearing a positive charge.
• oxopiperidinium salts particularly suitable for use herein include 1,1-dimethyl-3-oxopiperidinium nitrate, 1,1-dimethyl-4-oxopiperidinium triflate, 1,1-dimethyl-3-oxopiperidinium triflate, 1,1-dimethyl-4-oxopiperidinium nitrate, 1-benzyl-4-piperidone methonitrate, 1-t-butyl-1-methyl-4-oxopiperidinium nitrate, 1-(4-dodecylbenzyl) 1-methyl-4 oxopiperidinium chloride, 3-(N-methyl-4 oxopiperidinium)-propane sulfonate, 1-allyl-1-methyl-4- oxopiperidinium chloride, 1-methyl-1-(1-naphthyl-methyl)-4- oxopiperidinium chloride, 1-methyl-1-pentamethylbenzyl-4-oxopiperidinium chloride, N,N'-
• ketone activator compounds bearing a positive charge suitable for use herein are for example the ammonium acetophenone salts according to the following formula: wherein the ammonium group can be either at the 2 , at the 3 position or at the 4 position ;
• R1, R2 and R3 are each independently a substituted or unsubstituted hydrocarbon group having from 1 to 20 carbon atoms, preferably a substituted or unsubstituted alkyl, or alkenyl or alkinyl group containing from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms, or a substituted or unsubstituted aryl group containing from 6 to 10 atoms or a C1-C20 alkyl aryl group wherein the aryl group contains from 6 to 10 carbon atoms;
• R4 is a substituted or nonsubstituted halogenate alkyl group having from 1 to 20 carbon atoms, preferably from 1 to 12 carbon atoms and more preferably is
• ammonium acetophenone salts for use herein include 4-trimethylammonium acetophenone nitrate, 2-trimethylammoniumacetophenone nitrate, 4-triethylammoniumacetophenone mesilate, 3-trimethylammoniumacetophenone mesilate, trihalogenatedmethylphenyl ketone like trifluoromethylphenylketone, trichloromethylphenylketone, tribromomethylphenylketone or a mixture thereof.
• Suitable halide activator compounds for use herein include chloride, bromide, iodide and mixtures thereof. Particularly preferred halide activator compounds for use herein is an alkali metal of chloride. For example sodium chloride may be commercially available from Aldrich under its chemical name.
• compositions herein comprise up to 10% by weight of the total composition of said ketone, aldehyde and/or halide activator compound, preferably from 0.05% to 5%, more preferably from 0.1% to 2% and most preferably from 0.2% to 1.5%.
• liquid persulfate-containing compositions suitable for use in the process of bleaching fabrics herein may comprise a surfactant or a mixture thereof including nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants and/or amphoteric surfactants.
• these surfactants do not contain functional groups that can be oxidised by the persulphate salt, or that can substantially hydrolize at a low pH.
• compositions according to the present invention may comprise from 0.01% to 50% by weight of the total composition of a surfactant or a mixture thereof, preferably from 0.1% to 30 % and more preferably from 0.2% to 10%.
• Suitable anionic surfactants for use in the compositions herein include water-soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
• Suitable anionic surfactants for use herein are water-soluble salts or acids of the formula RO(A) m SO 3 M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 12 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation.
• R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C
• Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
• Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
• Exemplary surfactants are C 12 -C 18 alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 E(1.0)M), C 12 -C 18 alkyl polyethoxylate (2.25) sulfate, C 12 -C 18 E(2.25)M), C 12 -C 18 alkyl polyethoxylate (3.0) sulfate C 12 -C 18 E(3.0), and C 12 -C 18 alkyl polyethoxylate (4.0) sulfate C 12 -C 18 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
• alkyl sulphonates including water-soluble salts or acids of the formula RSO 3 M wherein R is a C 6 -C 22 linear or branched, saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
• R is a C 6 -C 22 linear or branched, saturated
• Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO 3 M wherein R is an aryl, preferably a benzyl, substituted by a C 6 -C 22 linear or branched saturated or unsaturated alkyl group, preferably a C 12 -C 18 alkyl group and more preferably a C 14 -C 16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quatemary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethy
• alkylsulfonates and alkyl aryl sulphonates for use herein include primary and secondary alkylsulfonates and primary and secondary alkyl aryl sulphonates.
• secondary C6-C22 alkyl or C6-C22 alkyl aryl sulphonates it is meant herein that in the formula as defined above, the SO3M or aryl-SO3M group is linked to a carbon atom of the alkyl chain being placed between two other carbons of the said alkyl chain (secondary carbon atom).
• C14-C16 alkyl sulphonate salt is commercially available under the name Hostapur ® SAS from Hoechst and C8-alkylsulphonate sodium salt is commercially available under the name Witconate NAS 8® from Witco SA.
• An example of commercially available alkyl aryl sulphonate is Lauryl aryl sulphonate from Su.Ma.
• Particularly preferred alkyl aryl sulphonates are alkyl benzene sulphonates commercially available under trade name Nansa® available from Albright&Wilson.
• anionic surfactants useful for detersive purposes can also be used herein. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 8 -C 24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
• alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C 14-16 methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12 -C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6 -C 14 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolysaccharides such as
• Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are given in "Surface Active Agents and Detergents" Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975, to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
• alkyl carboxylates and alkyl alkoxycarboxylates having from 4 to 24 carbon atoms in the alkyl chain, preferably from 8 to 18 and more preferably from 8 to 16, wherein the alkoxy is propoxy and/or ethoxy and preferably is ethoxy at an alkoxylation degree of from 0.5 to 20, preferably from 5 to 15.
• Suitable amphoteric surfactants for use herein include amine oxides having the following formula R 1 R 2 R 3 NO wherein each of R1, R2 and R3 is independently a saturated substituted or unsubstituted, linear or branched hydrocarbon chains of from 1 to 30 carbon atoms.
• Preferred amine oxide surfactants to be used according to the present invention are amine oxides having the following formula R 1 R 2 R 3 NO wherein R1 is an hydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from 6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, and wherein R2 and R3 are independently substituted or unsubstituted, linear or branched hydrocarbon chains comprising from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, and more preferably are methyl groups.
• R1 may be a saturated substituted or unsubstituted linear or branched hydrocarbon chain.
• Suitable amine oxides for use herein are for instance natural blend C8-C10 amine oxides as well as C12-C16 amine oxides commercially available from Hoechst.
• Suitable zwitterionic surfactants for use herein contain both a cationic hydrophilic group, i.e., a quaternary ammonium group, and anionic hydrophilic group on the same molecule at a relatively wide range of pH's.
• the typical anionic hydrophilic groups are carboxylates and sulfonates, although other groups like sulfates, phosphonates, and the like can be used.
• R 1 -N + (R 2 )(R 3 )R 4 X - wherein R 1 is a hydrophobic group; R 2 is hydrogen, C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group; R 3 is C 1 -C 6 alkyl, hydroxy alkyl or other substituted C 1 -C 6 alkyl group which can also be joined to R 2 to form ring structures with the N, or a C 1 -C 6 carboxylic acid group or a C 1 -C 6 sulfonate group; R 4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; and X is the hydrophilic group which is a carboxylate or sulfonate group.
• R 1 are aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chains that can contain linking groups such as amido groups, ester groups. More preferred R 1 is an alkyl group containing from 1 to 24 carbon atoms, preferably from 8 to 18, and more preferably from 10 to 16. These simple alkyl groups are preferred for cost and stability reasons.
• the hydrophobic group R 1 can also be an amido radical of the formula R a -C(O)-NH-(C(R b ) 2 ) m , wherein R a is an aliphatic or aromatic, saturated or unsaturated, substituted or unsubstituted hydrocarbon chain, preferably an alkyl group containing from 8 up to 20 carbon atoms, preferably up to 18, more preferably up to 16, R b is selected from the group consisting of hydrogen and hydroxy groups, and m is from 1 to 4, preferably from 2 to 3, more preferably 3, with no more than one hydroxy group in any (C(R b ) 2 ) moiety.
• Preferred R 2 is hydrogen, or a C 1 -C 3 alkyl and more preferably methyl.
• Preferred R 3 is a C 1 -C 4 carboxylic acid group or C1-C4 sulfonate group, or a C 1 -C 3 alkyl and more preferably methyl.
• Preferred R 4 is (CH2) n wherein n is an integer from 1 to 10, preferably from 1 to 6, more preferably is from 1 to 3.
• betaine/sulphobetaine Some common examples of betaine/sulphobetaine are described in U.S. Pat. Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.
• alkyldimethyl betaines examples include coconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethyl betaine, 2-(N-decyl-N, N-dimethyl-ammonia)acetate, 2-(N-coco N, N-dimethylammonio) acetate, myristyl dimethyl betaine, palmityl dimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine.
• coconut dimethyl betaine is commercially available from Seppic under the trade name of Amonyl 265®.
• Lauryl betaine is commercially available from Albright & Wilson under the trade name Empigen BB/L®.
• amidobetaines include cocoamidoethylbetaine, cocoamidopropyl betaine or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine.
• C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine is commercially available from Sherex Company under the trade name "Varion CAS® sulfobetaine".
• betaine is Lauryl-immino-dipropionate commercially available from Rhone-Poulenc under the trade name Mirataine H2C-HA ®.
• Suitable cationic surfactants for use herein include derivatives of quaternary ammonium, phosphonium, imidazolium and sulfonium compounds.
• Preferred cationic surfactants for use herein are quaternary ammonium compounds wherein one or two of the hydrocarbon groups linked to nitrogen are a saturated, linear or branched alkyl group of 6 to 30 carbon atoms, preferably of 10 to 25 carbon atoms, and more preferably of 12 to 20 carbon atoms, and wherein the other hydrocarbon groups (i.e.
• quaternary ammonium compounds suitable for use herein are non-chloride/non halogen quaternary ammonium compounds.
• the counterion used in said quaternary ammonium compounds are compatible with any persulfate salt and are selected from the group of methyl sulfate, or methylsulfonate, and the like.
• compositions of the present invention are trimethyl quaternary ammonium compounds like myristyl trimethylsulfate, cetyl trimethylsulfate and/or tallow trimethylsulfate.
• trimethyl quaternary ammonium compounds are commercially available from Hoechst, or from Albright & Wilson under the trade name EMPIGEN CM®.
• nonionic surfactants alkoxylated nonionic surfactants and especially ethoxylated nonionic surfactants are suitable for use herein.
• Particularly preferred nonionic surfactants for use herein are the capped alkoxylated nonionic surfactants as they have improved stability to the persulfate salts.
• Suitable capped alkoxylated nonionic surfactants for use herein are according to the formula:
• surfactants are commercially available from BASF under the trade name Plurafac®, from HOECHST under the trade name Genapol® or from ICI under the trade name Symperonic®.
• Preferred capped nonionic alkoxylated surfactants of the above formula are those commercially available under the tradename Genapol® L 2.5 NR from Hoechst, and Plurafac® from BASF.
• the liquid aqueous persulfate-containing compositions suitable for use in the process of bleaching fabrics herein may comprise a chelating agent as a preferred optional ingredient.
• Suitable chelating agents may be any of those known to those skilled in the art such as the ones selected from the group comprising phosphonate chelating agents, amino carboxylate chelating agents, other carboxylate chelating agents, polyfunctionally-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
• a cheating agent may be also desired in the compositions herein as it allows to increase the ionic strength of the compositions and thus their stain removal and bleaching performance on various surfaces.
• Suitable phosphonate chelating agents for use herein may include alkali metal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylene phosphonate), as well as amino phosphonate compounds, including amino aminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylene phosphonates (NTP), ethylene diamine tetra methylene phosphonates, and diethylene triamine penta methylene phosphonates (DTPMP).
• the phosphonate compounds may be present either in their acid form or as salts of different cations on some or all of their acid functionalities.
• Preferred phosphonate cheating agents to be used herein are diethylene triamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxy diphosphonate (HEDP).
• DTPMP diethylene triamine penta methylene phosphonate
• HEDP ethane 1-hydroxy diphosphonate
• Such phosphonate chelating agents are commercially available from Monsanto under the trade name DEQUEST®.
• Polyfunctionally-substituted aromatic chelating agents may also be useful in the compositions herein. See U.S. patent 3,812,044, issued May 21, 1974, to Connor et al.
• Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
• a preferred biodegradable chelating agent for use herein is ethylene diamine N,N'- disuccinic acid, or alkali metal, or alkaline earth, ammonium or substitutes ammonium salts thereof or mixtures thereof.
• Ethylenediamine N,N'- disuccinic acids, especially the (S,S) isomer have been extensively described in US patent 4, 704, 233, November 3, 1987, to Hartman and Perkins.
• Ethylenediamine N,N'- disuccinic acids is, for instance, commercially available under the tradename ssEDDS® from Palmer Research Laboratories.
• Suitable amino carboxylates for use herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol-diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine diacetic 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 diacetic acid
• Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
• PDTA propylene diamine tetracetic acid
• MGDA methyl glycine di-acetic acid
• carboxylate chelating agents for use herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
• R 1 , R 2 , R 3 , and R 4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -Cl, -Br, -NO 2 , -C(O)R', and -SO 2 R''; wherein R' is selected from the group consisting of -H, -OH, alkyl, alkoxy, aryl, and aryloxy; R'' is selected from the group consisting of alkyl, alkoxy, aryl, and aryloxy; and R 5 , R 6 , R 7 , and R 8 are independently selected from the group consisting of -H and alkyl.
• Particularly preferred cheating agents to be used herein are amino aminotri(methylene phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene phosphonate, 1-hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic acid, and mixtures thereof.
• liquid aqueous persulfate-containing compositions suitable for use in the process of bleaching fabrics herein comprise up to 5% by weight of the total composition of a chelating agent, or mixtures thereof, preferably from 0.01% to 1.5% by weight and more preferably from 0.01% to 0.5%.
• the liquid aqueous persulfate-containing compositions suitable for use in the process of bleaching fabrics herein may comprise a radical scavenger or a mixture thereof.
• Suitable radical scavengers for use herein include the well-known substituted mono and dihydroxy benzenes and their analogs, alkyl and aryl carboxylates and mixtures thereof.
• Preferred such radical scavengers for use herein include di-tert-butyl hydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone, mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid, toluic acid, catechol, t-butyl catechol, benzylamine, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallate or mixtures thereof and highly preferred is di-tert-butyl hydroxy toluene.
• BHT di-tert-butyl hydroxy toluene
• hydroquinone di-tert-butyl hydroquinone
• mono-tert-butyl hydroquinone tert-butyl-hydroxy anysole
• benzoic acid toluic acid
• catechol t-butyl catechol
• radical scavengers like N-propyl-gallate may be commercially available from Nipa Laboratories under the trade name Nipanox S1 ®. Radical scavengers when used, are typically present herein in amounts ranging from up to 10% by weight of the total composition and preferably from 0.001% to 0.5% by weight.
• radical scavengers may contribute to the chemical stability of the bleaching compositions herein as well as to the safety profile of these compositions.
• the bleaching performance may be evaluated by the following test methods on various type of bleachable stains.
• a suitable test method for evaluating the bleaching performance on a soiled fabric under soaking conditions is the following:
• a composition according to the present invention is diluted with water typically at a dilution level of 1 to 100 ml/L, preferably 20 ml/L (composition :water), then the soiled fabrics are soaked in it for 20 minutes to 6 hours and then rinsed.
• the bleaching composition can be used in a washing machine at a dilution level of typically at a dilution level of 1 to 100 ml/L (composition :water). In the washing machine the soiled fabrics are washed at a temperature of from 30° to 70°C for 10 to 100 minutes and then rinsed.
• the reference composition in this comparative test undergoes the same treatment.
• Soiled fabrics/swatches with for example tea, coffee and the like may be commercially available from E.M.C. Co. Inc..
• the bleaching performance is then evaluated by comparing side by side the soiled fabrics treated with the composition used in the present invention with those treated with the reference, e.g., the same composition but comprising another bleaching system, e.g., hydrogen peroxide and acetyl triethyl citrate at equal bleaching agents total level.
• a visual grading may be used to assign difference in panel units (psu) in a range from 0 to 4.
• compositions (% weight) I II III IV V
• Compositions (% weight) VI VII VIII IX X XI Akyposoft 100 NV® 0.5 0.5 0.5 0.2 0.2 - Curox® 5 7 10 10 6 9.5 Acetylacetone 0.5 0.5 0.5 - -
• compositions I to XXV 100 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 20 minutes before being rinsed with water.
• compositions I to XXV 200 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 20 minutes before being rinsed with water for 20 minutes.
• compositions I to XXV 300 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 20 minutes before being rinsed with water for 20 minutes.
• compositions I to XXV 100 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 1 hour before being rinsed with water for 20 minutes.
• compositions I to XXV 100 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 6 hours before being rinsed with water for 20 minutes.
• compositions I to XXV 100 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 24 hours before being rinsed with water for 20 minutes.
• compositions I to XXV 100 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then soiled fabrics were contacted with the aqueous bath so obtained for 1 hour before being rinsed with water for 20 minutes. Finally the fabrics so bleached were contacting for 1 hour with 40g of Dash Futur® diluted in 5L of water and subsequently rinsed with water.
• compositions I to XXV 100 ml of a liquid persulphate composition as exemplified above (compositions I to XXV) was diluted in 5L of water. Then the fabrics were contacted with the aqueous bath so obtained for 1 hour before being rinsed with water for 20 minutes.
• compositions I to XXV 100 ml of a liquid persulfate-containing composition as exemplified above (compositions I to XXV) was diluted in 5L of water to obtain an aqueous bath to which the soiled fabrics were contacted for 20 minutes. The fabrics were then rinsed for 2 minutes than washed in a washing machine (e.g. San Giorgio 352 ZX®, main cycle) with 225g of Dash Futur®.
• a washing machine e.g. San Giorgio 352 ZX®, main cycle

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• 1997
  • 1997-10-31 EP EP97870172A patent/EP0915150A1/fr not_active Withdrawn
• 1998
  • 1998-10-29 ZA ZA989888A patent/ZA989888B/xx unknown
  • 1998-10-30 MA MA25323A patent/MA24813A1/fr unknown
  • 1998-11-02 WO PCT/US1998/023378 patent/WO1999023197A1/fr active Application Filing
  • 1998-11-02 JP JP2000519057A patent/JP2001521996A/ja not_active Withdrawn
  • 1998-11-02 AU AU13015/99A patent/AU1301599A/en not_active Abandoned

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