EP1129166A1 - Verfahren zum bleichen von gewebe - Google Patents

Verfahren zum bleichen von gewebe

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Publication number
EP1129166A1
EP1129166A1 EP99960264A EP99960264A EP1129166A1 EP 1129166 A1 EP1129166 A1 EP 1129166A1 EP 99960264 A EP99960264 A EP 99960264A EP 99960264 A EP99960264 A EP 99960264A EP 1129166 A1 EP1129166 A1 EP 1129166A1
Authority
EP
European Patent Office
Prior art keywords
process according
alkyl
bleaching
composition
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99960264A
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English (en)
French (fr)
Inventor
Gloria Di Capua
Pierre Antoine Dresco
Stefano Scialla
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Procter and Gamble Co
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1129166A1 publication Critical patent/EP1129166A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/44—Multi-step processes

Definitions

  • the present invention relates to a process of bleaching fabrics with a bleaching composition comprising a peroxycarboxylic acid.
  • Detergent compositions suitable for laundry applications are well known in the art. It is also known that detergent compositions relying on hypochlorite as a bleaching agent can be preferred over oxygen bleaches, mainly for performance reasons, especially at lower temperatures. Typically used oxygen bleaches are the oxygen bleach precursors perborate or percarbonate that react with an activator species to produce hydrogen peroxide.
  • hypochlorite bleaches there are some limitations to the convenience of hypochlorite bleaches.
  • 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.
  • the manufacturer is therefore faced with achieving a balance between cleaning performance and fabric and/or colour damage.
  • the Applicant has identified a bleaching agent, peroxy carboxylic acid, that is a less aggressive bleach than hypochlorite, yet still provides improved cleaning performance versus the oxygen bleach precursor bleaching agents currently used in most fully formulated detergent compositions.
  • Peroxy carboxylic acids are known in the art for example EP 435 379. However, despite the apparent suitability of this bleach, it has been found that cleaning performance is occasionally not sufficient to meet consumer expectations.
  • the present invention relates to a process of cleaning a fabric with a bleaching composition and a detergent composition comprising the separate steps of:
  • the present invention encompasses a process of bleaching fabrics as described herein after.
  • fabric any type of fabric including for example natural and synthetic fabrics and these used to make clothes, curtains, drapes, bed linens, bath linens, table cloths, sleeping bags, tents, upholstered furniture and the like.
  • 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 elasthane®), and those made of both natural and synthetic fibers.
  • the process of the present invention requires that a fabric is contacted in one step (a) with a bleaching composition and in a second separate step (b), the fabric is contacted with a detergent composition.
  • the first step may be performed prior to the second step or alternatively the second step may be performed prior to the first step.
  • washing machines have a pre-rinse cycle wherein the fabric is moistening with at least water.
  • This pre-rinse cycle may be followed by additional rinse cycles, but is normally followed with the main wash cycle. It is into the main wash cycle that detergent compositions are conventionally delivered.
  • the main wash cycle is followed with at least one post-wash rinse cycle, preferably at least 2 rinse cycles. It is preferred that step (a) is performed in the pre-rinse and/or at least one of the post-wash rinse cycle. It is preferred that step (b) is performed in the main wash cycle.
  • the bleaching composition remains in contact with the fabrics for a period of time sufficient to bleach the fabrics.
  • the acidic liquid aqueous composition herein When used in diluted form the acidic liquid aqueous composition herein remains in contact with the fabrics for up to 24 hours, preferably from 1 minute to 12 hours and more preferably from 20 minutes to 6 hours.
  • the acidic liquid aqueous composition herein When used in its neat form the acidic liquid aqueous composition herein remains in contact with the fabrics for up to 24 hours, preferably from 1 minute to 2 hours and more preferably from 1 minute to 1 hour.
  • step (a) of the bleaching processes according to the present invention is performed of a temperature of from 4°C to 60°C, preferably from 10°C to 50°C and most preferably from 20°C to 40°C.
  • the process of bleaching fabrics according to the present invention further comprises as an essential step, the step of rinsing the fabrics with water after having been contacted with the bleaching composition and the detergent composition. This can either be performed by hand in a container of water or by placing the fabric under flowing water or in a rinse cycle of a laundry washing machine.
  • the process of the present invention requires contacting a fabric with a bleaching composition comprising a pre-formed peroxy carboxylic acid (hereafter referred to as peracid).
  • R is a linear or branched alkyl chain having at least 1 carbon atom and X is hydrogen or a substituent group selected from the group consisting of alkyl, especially alkyl chains of from 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, phosphonate, phosphonic or mixtures thereof.
  • the R group preferably comprises from 2 to 24 carbon atoms.
  • the R group may be a branched alkyl chain comprising one or more side chains which comprise substituent groups selected from the group consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, ketone or mixtures thereof.
  • X group is a phthalimido group.
  • particularly preferred peracids are those having general formula:
  • R is C1-20 alkyl group and where A, B, C and D are independently either hydrogen or substituent groups individually selected from the group consisting of alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic, sulphate, sulphonate, aldehydes or mixtures thereof.
  • R is an alkyl group having from 3 to 12 carbon atoms, more preferably from 5 to 9 carbon atoms.
  • Preferred substituent groups A, B, C and D are linear or branched alkyl groups having from 1 to 5 carbon atoms, but more preferably hydrogen.
  • Preferred peracids are selected from the group consisting of phthaloyl amido peroxy hexanoic acid (also known as phthaloyl amido-peroxy caproic acid), phthaloyl amido peroxy heptanoic acid, phthaloyl amido peroxy octanoic acid, phthaloyl amido peroxy nonanoic acid, phthaloyl amido peroxy decanoic acid and mixtures thereof.
  • phthaloyl amido peroxy hexanoic acid also known as phthaloyl amido-peroxy caproic acid
  • phthaloyl amido peroxy heptanoic acid also known as phthaloyl amido peroxy heptanoic acid
  • phthaloyl amido peroxy octanoic acid phthaloyl amido peroxy nonanoic acid
  • phthaloyl amido peroxy decanoic acid and mixtures thereof.
  • R is selected from C1-4 alkyl and n is an integer of from 1 to 5.
  • the peracid has the formula such that R is CH 2 and n is 5 i.e. phthaloyl amido-peroxy caproic acid or PAP.
  • the peracid is preferably used as a substantially water-insoluble solid or wetcake and is available from Ausimont under the trade name Euroco.
  • the peracid is present may be present at a level in the composition of from 0.1% to 10% more preferably 0.5% to 8% and most preferably 1 % to 6%. Alternatively the peracid may be present at a much higher level of for example 10% to 40%, more preferably from 15% to 30%, most preferably from 20% to 25%.
  • the bleaching composition may be in granular, but is preferably in liquid form.
  • the term liquid is to be understood as including gel-like or pasty form as well.
  • the bleaching composition is liquid, it is preferably aqueous, comprising water at a level of preferably 10 to 99%, more preferably from 50% to 98% by weight of the bleaching composition.
  • the bleaching composition may comprise other components in addition to the peracid. Examples of such components are described herein as optional ingredients.
  • Preferred optional components include surfactants, preferably anionic surfactants. In this embodiment it is also particularly preferred that the surfactant be present at a level of less than 5%.
  • suspending agent is a particularly preferred component.
  • Suspending agents are components that aid or facilitate the suspension of insoluble or partially insoluble solids in a liquid environment.
  • the peracids currently available are generally solid and substantially water insoluble. If solid particles are incorporated in a liquid composition, the particles fall to the bottom of the container holding the liquid. A way of uniformly distributing the solid (e.g. peracid) throughout the liquid composition is to incorporate suspending agent.
  • preferred suspending agents are polymers for example natural-gum polymers (e.g. xanthan gum), cross-linked polycarboxylic acids, polyvinyl polymers (PVA, PVP etc).
  • the suspending agent of the present invention is selected from xanthan gum, cross-linked polycarboxylic acid and mixtures thereof.
  • the bleaching composition is preferably acidic i.e. the bleaching composition preferably has a pH of less than 7, more preferably from 1 to 8.5, most preferably from 3 to 4.
  • diluted form it is meant herein that the composition as described herein after, may be diluted by the user, preferably with water. Such dilution may occur for instance in hand laundry applications as well as by the other means such as in washing machine. Said compositions can be diluted up to 500 times, preferably from 5 to 200 times and more preferably from 10 to 80 times. In a preferred embodiment herein said composition is used in its diluted form.
  • An advantage of the bleaching 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 may be evaluated by measuring the concentration of available oxygen at given storage time after having manufactured the compositions.
  • chemically stable it is meant herein that the compositions used herein comprising a peracid do not undergo more than 15% AvO loss, in one month at 25°C and preferably not more than 10%.
  • AvO loss of a peracid-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 ⁇ commercially available from Interox. Alternatively peracid concentration can also be measured using a chromatography method described in the literature for peracids (F. Di Furia et al., Gas-liquid Chromatography Method for Determination of Peracids, Analyst, Vol 113, May 1988, p 793-795).
  • the process of the present invention requires contacting a fabric with a detergent composition.
  • detergent composition it is understood fully formulated detergent compositions currently available on the market. These compositions are those that are generally expected to be used in the wash cycle of a laundry washing machine.
  • the detergent composition comprises conventional detergent ingredients.
  • Suitable conventional detergent ingredients for use in such detergent compositions are described for example in co-pending patent applications UK 96/16112.0, UK 97/13946.3, or WO 96/28531 and or EP-B-707626.
  • Such liquid detergent and/or granular detergent compositions may also comprise at least one or more other conventional detergent ingredients, preferably selected from builders (up to 80%), organic polymeric compounds (up to 20%), bleaching agents (up to 25%), bleach activators (up to 15%) , enzymes (typically 0.0001% to 2%), suds suppressers (up to 4%), dispersants (up to 15%), lime- soap dispersants (up to 15%), soil suspending agents (up to 20%), antiredepositions agents (up to 20%), corrosion inhibitors (up to 10%), solvents (up to 20%), chelating agents (up to 15%), dyes, pigments, perfumes and the like.
  • additional conventional detergent ingredients and levels of incorporation thereof will depend on the physical form of the detergent composition and the end characteristics of the composition desired.
  • the detergent composition of the present invention does not comprise a peracid, although it may comprise another mild bleach or bleach system such as a bleach precursor and a bleach activator.
  • the detergent composition may be in granular or liquid form.
  • the detergent composition comprises surfactant and where present the surfactant is present at a level of greater than 5%.
  • the detergent composition when in liquid form or a l % solution thereof when in granular form preferably has a pH of greater than 7, more preferably greater than 9, most preferably in the range of from 9 to 11.5.
  • the pH of both the bleaching and detergent compositions may be adjusted using any acidic or alkaline agent known to those skilled in the art.
  • acidic agents are organic acids such as citric acid and inorganic acids such as sulphuric acid, sulphonic acid and/or methane sulphonic acid.
  • alkaline agents are sodium hydroxide, potassium hydroxide and/or sodium carbonate.
  • liquid detergent compositions and/or granular detergent compositions may be diluted up to 250 times their weight of water to provide an alkaline solution as described herein, preferably from 2 to 200 and more preferably from 10 to 160. Such dilution may occur for instance in hand laundry application as well as by other means such as in washing machine.
  • the bleaching compositions used in the process of bleaching fabrics according to the present invention may comprise a variety of optional ingredients such as surfactants, chelating agents, radical scavengers, antioxidants, stabilisers, builders, soil suspenders, polymeric soil release agents, dye transfer agents, solvents, suds controlling agents, brighteners, perfumes, pigments, dyes and the like.
  • the bleaching compositions suitable for use in the process of bleaching fabrics herein preferably comprise a surfactant selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants and mixtures thereof.
  • the surfactant is present at a level of less than 5%, more preferably from 0.1% to 4% and most preferably from 1% to 3%.
  • Suitable anionic surfactants for use in the compositions herein include water- soluble salts or acids of the formula ROSO3M wherein R preferably is a CI Q- C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10- 20 alkyl component, more preferably a C12-C18 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 SO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10- 24 alkyl component, preferably a C12- 20 alkyl or hydroxyalkyl, more preferably C ⁇ i2-C-
  • R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10- 24 alkyl component, preferably a C12- 20 alkyl or hydroxyal
  • Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
  • Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
  • Exemplary surfactants are C12- 18 alkyl polyethoxylate (1.0) sulfate, Ci2- i8 E ( 1 -°) M )' C12-C18 alkyl polyethoxylate (2.25) sulfate, C12- C ⁇ i8E(2.25)M), C12-C18 alkyl polyethoxylate (3.0) sulfate C-
  • alkyl sulphonates including water-soluble salts or acids of the formula RSO3M wherein R is a C6-C22 linear or branched, saturated or unsaturated alkyl group, preferably a C12-C-18 alkyl group and more preferably a C-14-C16 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).
  • RSO3M alkyl sulphonates including water-soluble salts or acids
  • Suitable alkyl aryl sulphonates for use herein include water- soluble salts or acids of the formula RSO3M wherein R is an aryl, preferably a benzyl, substituted by a C6-C22 linear or branched saturated or unsaturated alkyl group, preferably a C12-C18 alkyl group and more preferably a C-14-C16 alkyl group, and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium, calcium, magnesium etc) or ammonium or substituted ammonium (e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations, such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine,
  • 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.
  • salts including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts
  • soap C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C ⁇ . ⁇ Q methyl ester sulfonates; acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C5-C-14 diesters), sulfates of alkylpolysaccharides such as the sulfates of
  • 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 R1R2R3NO 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 R1R2R3NO 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.
  • a generic formula for the zwitterionic surfactants to be used herein is :
  • is a hydrophobic group
  • R2 is hydrogen, C-i-Cg alkyl, hydroxy alkyl or other substituted C ⁇ -CQ alkyl group
  • R3 is C- -CQ alkyl, hydroxy alkyl or other substituted C-j-Cg alkyl group which can also be joined to R2 to form ring structures with the N, or a C-i-Cg carboxylic acid group or a C-i-C ⁇ sulfonate group
  • R4 is a moiety joining the cationic nitrogen atom to the hydrophilic group and is typically an alkylene, hydroxy alkylene, or polyalkoxy group containing from 1 to 10 carbon atoms
  • X is the hydrophilic group which is a carboxylate or sulfonate group.
  • 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-j 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 ⁇ can also be an amido radical of the formula R a -C(O)-NH-(C(Rb)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 ⁇ 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 )2) moiety.
  • Preferred R2 is hydrogen, or a C1-C3 alkyl and more preferably methyl.
  • Preferred R3 is a C1-C4 carboxylic acid group or C1-C4 sulfonate group, or a C1-C3 alkyl and more preferably methyl.
  • Preferred R4 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 peracid 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 can also provide a suds suppression benefit.
  • Suitable capped alkoxylated nonionic surfactants for use herein are according to the formula:
  • is a C8-C-24 linear or branched alkyl or alkenyl group, aryl group, alkaryl group, preferably R-
  • R2 is a C1-C10 linear or branched alkyl group, preferably a C2-C10 linear or branched alkyl group ;
  • R3 is a C ⁇ -C-i o alkyl or alkenyl group, preferably a C1-C5 alkyl group, more preferably methyl;
  • n and m are integers independently ranging in the range of from 1 to 20, preferably from 1 to 10, more preferably from 1 to 5; or mixtures thereof.
  • 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 bleaching 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, polyfu notional ly-substituted aromatic chelating agents, ethylenediamine N,N'- disuccinic acids, or mixtures thereof.
  • chelating agents contribute to further enhance the chemical stability of the compositions.
  • a chelating agent may be also desired in the compositions 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 chelating agents for use 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 to be used herein include ethylene diamine tetra acetates, diethylene triamine pentaacetates, diethylene triamine pentaacetate (DTPA),N- hydroxyethylethylenediamine triacetates, nitrilotri-acetates, ethylenediamine tetrapropionates, triethylenetetraaminehexa-acetates, ethanol- diglycines, propylene diamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both in their acid form, or in their alkali metal, ammonium, and substituted ammonium salt forms.
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • Particularly suitable amino carboxylates to be used herein are diethylene triamine penta acetic acid, propylene diamine tetracetic acid (PDTA) which is, for instance, commercially available from BASF under the trade name Trilon FS® and methyl glycine di-acetic acid (MGDA).
  • PDTA propylene diamine tetracetic acid
  • MGDA methyl glycine di-acetic acid
  • carboxylate chelating agents to be used herein include salicylic acid, aspartic acid, glutamic acid, glycine, malonic acid or mixtures thereof.
  • Another chelating agent for use herein is of the formula:
  • , R2, R3, and R4 are independently selected from the group consisting of -H, alkyl, alkoxy, aryl, aryloxy, -CI, -Br, -NO2, -C(O)R', and -SO2R"; 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 R5, RQ, R7, and Rs are independently selected from the group consisting of -H and alkyl.
  • Particularly preferred chelating agents to be used herein are amino aminotri(methylene phosphonic acid), di-ethylene-triamino-pentaacetic acid, diethylene triamine penta methylene phosphonate, 1 -hydroxy ethane diphosphonate, ethylenediamine N, N'-disuccinic acid, and mixtures thereof.
  • compositions 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 bleaching 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 according to the process of bleaching of the present invention is the following: First a typical step (b) is carried out either in a washing-machine (e.g., by introducing 225 g of a conventional detergent, e.g.
  • Ariel future® in the detergent dispenser of a typical washing machine e.g., Sangiorgio Exacta 352ZX ® and running a washing cycle with the soiled fabrics
  • a hand soaking operation e.g., by contacting soiled fabrics with a soaking solution typically obtained by diluting a conventional detergent, e.g., Ariel a mano®, at a dilution level of 140ml/1 Outers of water -typical soaking time is 1 minute to several hours).
  • a bleaching composition as described herein is diluted with water typically at a dilution level of 1 to 100 ml/L, preferably 20 ml/L (composition :water), then the fabrics having previously undergone step (b) as described herein above, are soaked in the bleaching composition for 20 minutes to 6 hours (i.e. step (a)) and then rinsed (i.e. step (c)).
  • the bleaching composition can be used in the washing machine at a dilution level of typically at a dilution level of 1 to 100 ml/L (composition :water).
  • the soiled fabrics are bleached at a temperature of from 30° to 90°C for 10 to 100 minutes and then rinsed.
  • Soiled fabrics/swatches with for example tea, coffee and the like may be commercially available from E.M.C. Co. Inc..
  • step (b) The bleaching performance is then evaluated by comparing side by side the soiled fabrics treated accordingly to where the cleaning process only involves cleaning with a detergent composition in step (b) and step (a) is not used.
  • a visual grading may be used to assign difference in panel units (psu) in a range from 0 to 4.
  • the stain removal performance may be evaluated with the same test method but with soiled fabrics soiled by different types of stains like enzymatic ones and/or greasy ones.
  • compositions were made by mixing the listed ingredients in the listed proportions (weight % unless otherwise specified). These compositions are suitable to be used in the "bleaching step" of the bleaching processes of the present invention.
  • compositions I II III IV V Compositions I II III IV V
  • Akyposoft 100 NV® is a C12-C14 alkyl ethoxy 10 carboxylate commercially available from Kao Chemicala Gmbh.
  • Witkonate NAS 8® is an alkylsulphonate available from Witco AS
  • HEDP is ethane 1 -hydroxy diphosphonate commercially available from
  • PAP is phthalimidoperoxyhexanoic acid available from Ausimont under the tradename Euroco®
  • Carbopol®ETD 2623 and 2991 are polymers available from BFGoodrich
  • compositions are representative of the granular detergent compositions suitable to be diluted with water to provide an alkaline solution suitable to be used in the first step (alkaline step) of the process herein.
  • Pectin degrading enzyme 0.05 0.005 0.02
  • Density (g/litre) 700 700 700 The following compositions are representative of the liquid detergent compositions suitable to be used diluted with water to provide an alkaline solution suitable to be used in the first step of the process of bleaching fabrics according to the present invention.
  • Carbonate Anhydrous sodium carbonate with a particle size between 200 ⁇ m and 900 ⁇ m.
  • Bicarbonate Anhydrous sodium bicarbonate with a particle size between 400 ⁇ m and 1200 ⁇ m.
  • DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060.
  • PVNO Poly(4-vinylpyridine)-N-Oxide PVPVI Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl- imidazole and vinyl-pyrrolidone.
  • “Bleaching step” Addition step Peracid composition (ml) during rinse cycle 50 during rinse cycle 100 during main wash * 50 during main wash * 100 .
  • washing cycle is run with the bleaching composition in absence of detergent composition, the bleaching composition being introduced directly in the detergent dispenser without the presence of the detergent or in the bleach dispenser if the machine is so provided.
  • the alkaline detergent used in the processes of bleaching fabrics as exemplified herein above can be any of the conventional detergent compositions available on the market, e.g. Ariel future, Dash future® when used in a washing machine, or Ariel a Mano® when used in a hand washing application.
  • the peracid containing compositions used in these processes can be any of the ones exemplified herein before, compositions I to V.
  • washing machine may be used herein include European types as well as US types or Japanese types.
  • An example is for instance San Giorgio Exacta 252 ZX.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP99960264A 1998-11-10 1999-11-10 Verfahren zum bleichen von gewebe Withdrawn EP1129166A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
PCT/US1998/023982 WO2000027963A1 (en) 1998-11-10 1998-11-10 Processes of bleaching fabrics
WOPCT/US98/23982 1998-11-10
PCT/US1999/026609 WO2000027974A1 (en) 1998-11-10 1999-11-10 Processes of bleaching fabrics

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EP (1) EP1129166A1 (de)
JP (1) JP2003520907A (de)
AU (2) AU1699099A (de)
CO (1) CO5211000A1 (de)
TR (1) TR200101317T2 (de)
WO (2) WO2000027963A1 (de)

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DE10150403A1 (de) * 2001-10-11 2003-04-30 Ecolab Gmbh & Co Ohg Verfahren zum desinfizierenden Waschen mit Persäuren

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DE3709348A1 (de) * 1987-03-21 1988-10-06 Degussa Peroxycarbonsaeure enthaltende waessrige bleichmittelsuspensionen, verfahren zu ihrer herstellung und ihre verwendung
EP0435379A3 (en) * 1989-12-22 1991-07-31 Akzo N.V. Suspension, coating, agglomeration and uses of imidoperoxycarboxylic acids
WO1995013352A1 (en) * 1993-11-12 1995-05-18 Unilever N.V. Imine quaternary salts as bleach catalysts

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See references of WO0027974A1 *

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WO2000027963A1 (en) 2000-05-18
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AU1699099A (en) 2000-05-29
CO5211000A1 (es) 2002-10-30
AU1717400A (en) 2000-05-29

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