EP0815051A1 - Compositions de blanchiment parfumees - Google Patents

Compositions de blanchiment parfumees

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Publication number
EP0815051A1
EP0815051A1 EP96908584A EP96908584A EP0815051A1 EP 0815051 A1 EP0815051 A1 EP 0815051A1 EP 96908584 A EP96908584 A EP 96908584A EP 96908584 A EP96908584 A EP 96908584A EP 0815051 A1 EP0815051 A1 EP 0815051A1
Authority
EP
European Patent Office
Prior art keywords
weight
peroxyacid
hydrophobic
perfume
compounds
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Withdrawn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
EP96908584A
Other languages
German (de)
English (en)
Inventor
Allan Campbell Mcritchie
Michael Green
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0815051A1 publication Critical patent/EP0815051A1/fr
Withdrawn legal-status Critical Current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
    • C11D3/50—Perfumes
    • 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

Definitions

  • the invention relates to perfumed bleaching compositions. More specifically, it relates to bleaching compositions comprising a hydrophobic bleach system and a stabilised perfume composition.
  • Perfumes are an important and desirable part of detergent compositions. They are used to cover up the chemical odours of the cleaning ingredients and provide an aesthetic benefit to the wash process and, preferably the cleaned fabrics.
  • EP 430315 which discloses the use of a laundry detergent composition containing a lipase and a perfume having specific fragrance materials, exemplifies such use. In said patent, the perfume composition is said to counteract the problem of the residual malodour of lipase treated laundry.
  • perfumes A problem encountered with perfumes is their volatility and many perfume ingredients can be destroyed or damaged in presence of cleaning ingredients, especially alkali and bleaches.
  • Hydrophobic bleach systems selected from a source of hydrogen peroxide combined with a hydrophobic peroxyacid bleach precursor and a hydrophobic peroxyacid bleach are known in the art as effective soil removal agents of dingy stains.
  • EP 332259 teaches the use of a liquid detergent composition containing peroxyacid bleach and perfumed silica particles which protect the perfume from oxidation by the bleach.
  • the detergent formulator thus faces the challenge of formulating a product which maximises soil/stain removal, which avoids degradation of the detergent components, which covers up the chemical odours of the cleaning ingredients, which provides an aesthetic benefit and which is also inexpensive.
  • hydrophobic peroxyacid precursor serves as a carrier material for the perfume composition.
  • compositions suitable for use in laundry washing methods which produces an excellent perfume fragrance on fabrics as well as an excellent perfume stability in presence of the hydrophobic bleaching system in the wash liquor and in the product during storage.
  • the present invention relates to a perfumed bleaching composition containing:
  • a-a hydrophobic bleaching system selected from i)-a perhydrate in amount of from 0.1 % to 60% by weight and combined with a hydrophobic peroxyacid bleach precursor in amount of from 0.1 % to 60% by weight, ii)-a hydrophobic preformed peroxyacid in amount of from 0.1 % to 60% by weight, and iii)-mixtures of i) and ii), wherein a hydrophobic peroxyacid bleach precursor is defined as a compound which produces under perhydrolysis a hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre, and wherein a hydrophobic preformed peroxyacid is defined as a compound whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre, and
  • b- a perfume composition in amount from 0.05% to 2% by weight which comprises one or more aroma chemicals selected from: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff bases, esters and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 40% by weight of the perfume.
  • aroma chemicals selected from: tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff bases, esters and mixtures thereof, wherein the total sum of the weight of said aroma chemicals in the perfume is at least 40% by weight of the perfume.
  • An essential component of the invention is a hydrophobic bleach system selected from a perhydrate combined with a hydrophobic peroxyacid bleach precursor, a preformed hydrophobic peroxyacid and any mixtures thereof.
  • the perhydrate is typically an inorganic perhydrate bleach, normally in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor.
  • This perhydrate is normally incorporated at a level of from 0.1 % to 60%, preferably from 3% to 40% by weight, more preferably from 5% to 35% by weight and most preferably from 8% to 30% by weight of the composition.
  • the perhydrate may be any of the alkalimetal inorganic salts such as perborate monohydrate or tetrahydrate, percarbonate, perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate.
  • Sodium percarbonate which is the preferred perhydrate, is an addition compound having a formula corresponding to 2Na2C ⁇ 3-3H2 ⁇ 2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1 , 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1 , 1-diphosphonic acid (HEDP) or an amino-phosphonate
  • the percarbonate can be incorporated into detergent compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material.
  • a variety of coatings can be used including borate, boric acid and citrate or sodium silicate of Si ⁇ 2:Na2 ⁇ ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate.
  • the most preferred coating is a mixture of sodium carbonate and sulphate or sodium chloride.
  • the particle size range of the crystalline percarbonate is from 350 micrometers to 1500 micrometers with a mean of approximately 500- 1000 micrometers.
  • One form of the essential hydrophobic bleach system component of the invention is a hydrophobic peroxyacid bleach precursor which produces upon perhydrolysis hydrophobic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 25 °C.
  • the peroxyacid backbone chain contains at least 7 carbons which may be linear or partly or totally branched or cyclic and any mixtures thereof.
  • the peroxyacid bleach precursors are normally incorporated at a level of from 0.1 % to 60%, preferably from 3% to 40% and most preferably 3 to 25% by weight of the perfumed bleaching composition.
  • hydrophobic peroxyacid bleach precursor compounds are selected from bleach precursor compounds which comprise at least one acyl group forming the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.
  • Suitable peroxyacid bleach precursors for the purpose of the invention are the amide substituted compounds of the following general formulae:
  • R ⁇ is an aryl or alkaryl group with from about 1 to about 14 carbon atoms
  • R ⁇ is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • Rl preferably contains from about 6 to 12 carbon atoms.
  • R ⁇ preferably contains from about 4 to 8 carbon atoms.
  • Rl may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2.
  • R2 can include alkyl, aryl, wherein said R ⁇ may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g. , a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • Preferred L groups are selected from:
  • R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms
  • R is an alkyl chain containing from 1 to 8 carbon atoms
  • R is H or R
  • Y is H or a solubilizing group.
  • Any of R 1 , R and R 4 may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammmonium groups
  • the preferred solubilizing groups are -SOg ' M , -CO2 M , -S0 4 " M + , -N + (R 3 ) 4 X " and 0 ⁇ -N(R 3 ) 3 and most preferably -SO ⁇ ' M and -CO2 M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • L group for use herein, include a leaving group selected from a caprolactam leaving group, a valerolactam leaving group and mixture thereof.
  • bleach precursors of the above formulae include amide substituted peroxyacid precursor compounds selected from (6- octanamido-caproy oxybenzenesulfonate, (6-nonanamidocaproyl)oxy benzene sulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in EP-A-0170386.
  • Still another class of bleach precursor is the class of alkyl percarboxylic acid bleach precursors.
  • Preferred alkyl percarboxylic acid precursors include nonanoyl oxy benzene sulphonate (NOBS described in US 4,412,934) and 3,5,5-tri-methyl hexanoyl oxybenzene sulfonate (ISONOBS described in EP120,591) and salts thereof.
  • peroxyacid bleach precursor herein before described
  • conventional peroxyacid bleach precursors such as the tetraacetyl ethylene diamine (TAED) bleach precursor may be added to the bleaching composition of the invention so as to produce an enhanced soil removal performance.
  • TAED tetraacetyl ethylene diamine
  • Another form of the essential hydrophobic bleach system component of the invention is a preformed hydrophobic peroxyacid bleaching agent and salt thereof whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 25 °C.
  • the peroxyacid backbone chain contains at least 7 carbons which may be linear, partly or totally branched, or cyclic and any mixtures thereof.
  • hydrophobic peroxyacid bleach compounds are selected from peroxyacid bleach compounds which comprise at least one acyl group forming the peroxyacid moiety bonded to a leaving group through an -O- or-N- linkage.
  • Preformed hydrophobic peroxyacid compounds will typically be in amount of from 0.1 % to 60% , preferably from 3% to 20% by weight.
  • Suitable examples of this class of agents include (6-octylamino)-6-oxo- caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6- oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781 , U.S. Patent 4,634,551, EP 0,133,354, U.S. Patent 4,412,934 and EP 0,170,386.
  • a preferred hydrophobic preformed peroxyacid bleach compound for the purpose of the invention is monononylamido peroxycarboxylic acid.
  • the other essential component of the invention is a perfume composition comprising one or more aroma chemicals selected from tertiary alcohols, nitriles, lactones, ketones, acetals, ethers, schiff bases, esters and mixtures thereof.
  • the perfume composition is incorporated in the bleaching composition of the invention at a level of from 0.05% to 2% by weight, preferably from 0.01 % to 1 % by weight of the bleaching composition.
  • the total sum of the weight of said aroma chemicals present in the perfume composition is at least 40%, preferably at least 50% and more preferably at least 60% by weight of the perfume.
  • aroma chemicals selected from tertiary alcohols, nitriles, lactones, ketones, acetals, ethers and schiffs bases can be either saturated or unsaturated. When in unsaturated form, they comprise a group selected from an aromatic ring and an alkenyl group and mixtures thereof.
  • aroma chemicals of the ester class can be saturated or unsaturated. When in unsaturated form, they either comprise an alkenyl group or are esters of salicylic acid.
  • Non-limiting tertiary alcohols suitable for the purpose of the invention include tetrahydro linalool, tetrahydro myrcenol, tetrahydro muguol and tetrahydro geraniol compounds and mixtures thereof.
  • tertiary alcohol compounds When used such tertiary alcohol compounds will be at a level of up to 50%, preferably at a level of up to 30% and more preferably up to 20% by weight of the perfiime composition.
  • Non-limiting examples of nitriles suitable for the purpose of the invention include lauric nitrile, myristic nitrile and tridecene-2-nitrile compounds, and mixtures thereof.
  • nitrile compounds When used such nitrile compounds will be at a level of up to 10%, preferably at a level of up to 5 % by weight of the perfume composition.
  • lactones suitable for the purpose of the invention include undecalactone, hexadecanolide and cyclopentadecanolide compounds.
  • lactones When used such lactones will be at a level of up to 30% , preferably at a level of up to 20% by weight of the perfume composition.
  • ketones suitable for the purpose of the invention include methyl beta naphtyl ketone, methyl phenyl ethyl ketone and 7-acetyl 1 ,2,3,4,5,6,7,8 octanhydro 1 ,1 ,6,7 tetra methyl naphtalene compounds.
  • ketones When used such ketones will be at a level of from up to 40% , preferably at a level of up to 30% and more preferably up to 20% by weight of the perfume composition.
  • Non-limiting examples of acetals suitable for the purpose of the invention include (indan-alpha-ole, 2-hydroxy methylene) formald acetal, acetaldehyde: phenyl ethyl propyl acetal and 4-phenyI-2,4,6- trimethyl-l-3-dioxane compounds.
  • acetals When used such acetals will be at a level of up to 20% , preferably at a level of up to 10% by weight of the perfiime composition.
  • Non-limiting examples of ethers suitable for the purpose of the invention include iso-amyl phenyl ethyl ether, phenyl ethyl methyl ether, cedryl methyl ether and 3,3,5 trimethyl cyclohexyl ethyl ether compounds.
  • ethers When used such ethers will be at a level of up to 20%, preferably at a level of up to 10% by weight of the perfume composition.
  • Non-limiting examples of schiffs bases suitable for the purpose of the invention include lyral/methyl anthranilate, helional/methyl anthranilate and triplal/methyl anthranilate. When used such schiffs bases will be at a level of up to 15% , preferably at a level of up to 10% and more preferably up to 5% by weight of the perfume composition.
  • esters suitable for the purpose of the invention include 2-tertiary butyl cyclohexyl acetate, 4-tertiary butyl cyclohexyl acetate, hexahydro 4-7-methano-inden-5-yl acetate, hexahydro 4-7-methano-inden-6-yl acetate, hexahydro 4-7-methano- inden-5-yl propionate, hexahydro 4-7-methano-inden-6-yl propionate, hexyl salicylate and amyl salicylate compounds.
  • esters When used such esters will be at a level of up to 60% , preferably at a level of up to 40% and more preferably up to 30% by weight of the perfume composition.
  • a perfumed bleaching composition consists of a bleaching composition and a perf ime composition, wherein said perfume is incorporated by any means in a composition selected from: i)-the bleaching composition as a finished product, ii)-the bleaching composition during its making process, or any mixtures thereof.
  • a detergent composition incorporating a perfumed bleaching composition consists of a bleaching composition, a perfume composition, one or more surfactants, one or more builders and optionally other conventional detergent ingredients, wherein said perfume is incorporated by any means in a composition selected from:
  • a detergent composition during its making process, and incorporating a bleaching composition, v) a bleaching composition as defined hereinbefore in i) and/or ii) and further incorporated in a detergent composition and any mixtures thereof.
  • Processes for incorporating the perfume in the bleaching composition are not critical to the present invention. This can be done by spray-on, admixture with one or more components of the bleaching composition or other means known to the man skilled in the art. A preferred process, for cost and practicability reasons, is a spray-on process.
  • the bleaching composition of the invention may also contain additional components which are not detrimental to the perfume composition.
  • additional compounds may include fillers such as sodium sulphate.
  • the detergent composition aspect of the invention comprises the incorporation of the herein before described perfumed bleaching composition together with a surfactant material, a builder, and optionally other components conventional in detergent compositions.
  • Detergent compositions incorporating the perfumed bleaching composition will normally contain from 0.1 % to 60% of said perfumed bleaching composition, more frequently from 2% to 40% and most preferably from 5% to 30%, on a composition weight basis.
  • Such detergent compositions will contain a surfactant material, a builder and preferably will also contain other components conventional in detergent compositions.
  • preferred detergent compositions will incorporate one or more surfactants, builders together with one or more soil suspending and anti-redeposition agents, suds suppressors, enzymes, fluorescent whitening agents, photoactivated bleaches and colours.
  • Detergent compositions incorporating the perfumed bleaching composition of the invention of the present invention will include one or more surfactants.
  • the total amount of surfactants will be generally up to 70% , typically 1 to 55% , preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 20% by weight of the total composition.
  • Nonlimiting examples of surfactants useful herein include the conventional C ⁇ ⁇ -C ⁇ % alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates (“AS”), the Cj ⁇ "Cl8 secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOS ⁇ 3"M+) CH3 and CH3(CH2) y (CHOSO3-M + ) CH2CH3 where x and (y -I- 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10- 8 ⁇ yl alkoxy sulfates ("AExS”; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylate
  • the conventional nonionic and amphoteric surfactants such as th Ci2-Ci8 alkyl ethoxylates ("AE"), including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxy lates (especially ethoxylates and mixed ethoxy /propoxy), Ci2"Cl8 betaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions.
  • AE Ci2-Ci8 alkyl ethoxylates
  • C6-C12 alkyl phenol alkoxy lates especially ethoxylates and mixed ethoxy /propoxy
  • Ci2"Cl8 betaines and sulfobetaines sultaines
  • C10-C18 amine oxides and the like
  • the C ⁇ o-Ci8 N-alkyl polyhydroxy fatty acid amides can also be used
  • sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl C12-C1 glucamides can be used for low sudsing.
  • C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C- . 6 soaps may be used.
  • Suitable surfactants suitable for the purpose of the invention are the anionic alkali metal sarcosinates of formula: wherein R is a C9-C17 linear or branched alkyl or alkenyl group, R ⁇ is a C1-C4 alkyl group and M is an alkali metal ion.
  • R is a C9-C17 linear or branched alkyl or alkenyl group
  • R ⁇ is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • Still another class of surfactant which may be suitable for the purpose of the invention are the cationic surfactant.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C - Ci6, preferably ⁇ - ⁇ Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
  • Inorganic or phosphate-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates). Non-phosphate builders may also be used.
  • polycarboxylic acids can include, but are not restricted to phytic acid, silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric poly carboxy lates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates).
  • phytic acid silicates, alkali metal carbonates (including bicarbonates and sesquicarbonates), sulphates, aluminosilicates, monomeric poly carboxy lates, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates).
  • compositions herein also function in the presence of the so-called "weak” builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders are the so called 'amorphous' alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ ratio in the range 1.6:1 to 3.2: 1 and crystalline layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Na SKS-6 silicate builder does not contain aluminium.
  • NaSKS-6 has the delta-Na2Si2 ⁇ 5 mo ⁇ hology form of layered silicate. It can be prepared by methods such as those described in German DE-A- 3,417,649 and DE-A-3, 742,043.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 , as the alpha, beta and gamma forms.
  • the delta-Na2S-2 ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilising agent for oxygen bleaches, and as a component of suds control systems.
  • carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973. Such carbonate builders act as builders to remove divalent metal ions such as calcium and additionally provides alkalinity and aids in soil removal.
  • Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amo ⁇ hous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Organic detergent builders suitable for the pu ⁇ oses of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxy lates.
  • Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralised salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of polycarboxylate builders encompasses the ether polycarboxy lates, including oxydisuccinate, as disclosed in U.S. Patent 3,128,287 and U.S. Patent 3,635,830. See also "TMS/TDS" builders of U.S. Patent 4,663,071.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxypolycarboxy lates copolymers of maleic anhydride with ethylene or vinyl methyl ether, or acrylic acid, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxy methyloxy succinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxy methyloxysuccinic acid, and soluble salts thereof.
  • Citrate builders e.g. , citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in EP 0,200,263.
  • Fatty acids e.g., C12-C1 monocarboxylic acids
  • the aforesaid builders especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium ortho- phosphate can be used.
  • Phosphonate builders such as ethane- 1 - hydroxy- 1 ,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021 ; 3,400,148 and 3,422,137) can also be used.
  • Chelating agents generally comprise from 0.1 % to 10% by weight of the compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1 % to 3.0% by weight of such compositions.
  • a chelating agent can be selected from amino carboxylate, organic phosphonate, poly functionally-substituted aromatic compound, nitriloacetic acid and mixture thereof. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove transition metal ions such as iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, ethylenediamine disuccinate, N- hy droxy ethy lethy lenediaminetriacetates , 2-hydroxypropy lene diamine disuccinate, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, ethylene triamine pentaacetate, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Preferred amino carboxylates chelants for use herein are ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, ethylenediamine-N,N'-diglutamate (EDDG) and 2-hydroxypropylene-diamine-N,N' -disuccinate (HPDDS) compounds.
  • EDDS ethylenediamine disuccinate
  • EDDG ethylenediamine-N,N'-diglutamate
  • HPDDS 2-hydroxypropylene-diamine-N,N' -disuccinate
  • a most preferred amino carboxylate chelant is ethylenediamine disuccinate.
  • Organic phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) available under the trademark DEQUEST from Monsanto, diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate), ⁇ -hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1 ,1-hexylidene, vinylidene 1 ,1 diphosphonate, 1,2 dihydroxyethane 1 , 1 diphosphonate and hydroxy-ethane 1 , 1 diphosphonate.
  • methylenephosphonates ethylenediaminetetrakis
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.
  • Preferred chelants are the diphosphonate derivatives selected from ⁇ - hydroxy-2 phenyl ethyl diphosphonate, methylene diphosphonate, hydroxy 1 ,1-hexylidene, vinylidene 1 ,1 diphosphonate, 1 ,2 dihydroxyethane 1 ,1 diphosphonate and hydroxy-ethane 1,1 diphosphonate.
  • a most preferred is hydroxy-ethane 1 ,1 diphosphonate.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044.
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.
  • Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering pu ⁇ oses, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of fugitive dye transfer, and for fabric restoration.
  • the enzymes to be inco ⁇ orated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability and stability versus active detergents and builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Enzymes are normally inco ⁇ orated at levels sufficient to provide up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5% by weight of a commercial enzyme preparation.
  • Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniforms.
  • Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 of Novo.
  • proteases suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other proteases include Protease A (see EP 130,756) and Protease B (see EP257189). Preferred levels of proteases are from 0.01 % to 4.0% by weight of the detergent composition herein.
  • Amylases include, for example, ⁇ -amylases described in GB 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries. Fungamyl (Novo) is especially useful. Preferred levels of amylases are from 0.01 % to 2.0% by weight of the detergent composition herein.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. ENDO A, CAREZYME both from Novo Industries A/S are especially useful. Preferred levels of cellulases are from 0.01 % to 1.0% by weight of the detergent composition herein.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also Upases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial lipases include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Co ⁇ ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • the LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo is a preferred lipase for use herein.
  • Preferred levels of lipases are from 0.01 % to 2.0% by weight of the detergent composition herein.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase- containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by O. Kirk, assigned to Novo Industries A/S.
  • a wide range of enzyme materials and means for their inco ⁇ oration into synthetic detergent compositions are also disclosed in U.S. Patent 3,553,139. Enzymes are further disclosed in U.S. Patent 4,101,457 and in U.S. Patent 4,507,219. Enzyme materials useful for liquid detergent formulations, and their inco ⁇ oration into such formulations, are disclosed in U.S. Patent 4,261,868. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. Patent 3,600,319 and EP 0 199 405. Enzyme stabilisation systems are also described, for example, in U.S. Patent 3,519,570.
  • Enzyme Stabilisers The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of various other art-disclosed stabilisers, especially borate species: see Severson, U.S. 4,537,706. Typical detergents, especially liquids, will comprise from 1 to 30, preferably from 2 to 20, more preferably from 5 to 15, and most preferably from 8 to 12, millimoles of calcium ion per litre of finished composition.
  • the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
  • a small amount of calcium ion generally from 0.05 to 0.4 millimoles per litre, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from 0.05% to 2% by weight of a water-soluble source of calcium or magnesium ions, or both.
  • the amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • additional stabilizers especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from 0.25% to 10% , preferably from 0.5% to 5% , more preferably from 0.75% to 3% , by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g. , sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • Polymeric Dispersing Agents can advantageously be utilized at levels from 0.5% to 8% , by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by particulate soil release peptization, and anti- redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein or monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacry lates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1 :1 , more preferably from 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts.
  • Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate.
  • Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol te ⁇ olymers.
  • Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 te ⁇ olymer of acrylic/maleic/vinyl alcohol.
  • PEG polyethylene glycol
  • PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
  • Typical molecular weight ranges for these pu ⁇ oses range from 500 to 100,000, preferably from 1 ,000 to 50,000, more preferably from 1,500 to 10,000.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of 10,000.
  • compositions according to the present invention can also optionally contain water- soluble ethoxylated amines having clay soil removal and antire- deposition properties.
  • Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble ethoxylates amines; liquid detergent compositions typically contain 0.01 % to 5% .
  • the most preferred soil release and anti-redeposition agent is ethoxy lated tetraethylenepentamine. Exemplary ethoxy lated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
  • Another group of preferred clay soil removal- antiredeposition agents are the cationic compounds disclosed in EP 111 ,965.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in EP 1 11 ,984; the zwitterionic polymers disclosed in EP 112,592; and the amine oxides disclosed in U.S. Patent 4,548,744.
  • Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterised by having both hydrophilic segments, to hy- drophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • Soil release agents characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cj-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones (see EP 0 219 048).
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays and U.S. Patent 3,893,929.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units which contains 10-15 % by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a poly oxy ethylene glycol of average molecular weight 300-5,000.
  • this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, the anionic end-capped oligomeric esters of U.S. Patent 4,721 ,580 and the block polyester oligomeric compounds of U.S. Patent 4,702,857.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from 0.01 % to 10.0%, by weight, of the compositions herein, typically from 0.1 % to 5% , preferably from 0.2% to 3.0% .
  • Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units.
  • the repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l ,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxy ethoxy )- ethanesulfonate.
  • Said soil release agent also comprises from 0.5% to 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • a crystalline-reducing stabilizer preferably selected from xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof.
  • compositions according to the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5% , and more preferably from 0.05% to 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures:
  • Rj, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N- oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are poly vinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
  • polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1 : 1 ,000,000.
  • the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization.
  • the average molecular weight is within the range of 500 to 1 ,000,000; more preferred 1 ,000 to 500,000; most preferred 5,000 to 100,000. This preferred class of materials can be referred to as "PVNO".
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferred for use herein.
  • the PVPVI has an average molecular weight range from 5,000 to 1 ,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis. Vol 113.
  • the PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1, more preferably from 0.8:1 to 0.3:1 , most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.
  • compositions also may employ a poly- vinylpyrrolidone (“PVP”) having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 200,000, and more preferably from 5,000 to 50,000.
  • PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A- 256,696.
  • Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from 500 to 100,000, preferably from 1 ,000 to 10,000.
  • PEG polyethylene glycol
  • the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2: 1 to 50: 1 , and more preferably from 3: 1 to 10:1.
  • the detergent compositions herein may also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from 0.01 % to 1.2% by weight of such optical brighteners.
  • hydrophilic optical brighteners useful in the present invention are those having the structural formula:
  • Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxy ethyl
  • R2 is selected from N-2-bis-hydroxy ethyl, N-2- hydroxy ethyl-N-methylamino, mo ⁇ hilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • the brightener is 4,4',- bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'- stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA- GX by Ciba-Geigy Co ⁇ oration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the compositions herein.
  • Rj is anilino
  • R2 is N-2- hydroxyethyl-N-2-methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)- s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Co ⁇ oration.
  • Rj is anilino
  • R2 is mo ⁇ hilino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4-anilino-6- mo ⁇ hilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Co ⁇ oration.
  • Other specific optical brightener species which may be used in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described.
  • the exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
  • optical brighteners or other brightening or whitening agents known in the art can be inco ⁇ orated at levels typically from 0.005% to 5%, preferably from 0.01 % to 1.2% and most preferably from 0.05% to 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents.
  • optical brightener examples include naphthalimide, benzoxazole, benzofuran, benzimidazole and any mixtures thereof.
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD; the 2-(4-styryl-phenyl)-2H- naptho[l ,2-d]triazoles; 4,4'-bis(l ,2,3-triazol-2-yl)-stilbenes; 4,4'- bis(styryl)bisphenyls; and the aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; 1,2- bis(-benzimidazol-2-yl)ethylene; 1 ,3-diphenyl-pyrazolines; 2,5- bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho-[l ,2-d]oxazole; and 2- (stilbene-4-yl)-2H-naphtho[l ,2-d]triazole. See also U.S. Patent 3,646,015.
  • Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be inco ⁇ orated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" and in front- loading European-style washing machines.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc. , 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non- surfactant suds suppressors.
  • non- surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g. , fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g., stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of -40°C and 50°C, and a minimum boiling point not less than 110°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779.
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds suppressors comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779 and EP 354016.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672 and in U.S. Patent 4,652,392.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:
  • polydimethylsiloxane fluid having a viscosity of from 20 cs. to 1 ,500 cs. at 25°C;
  • siloxane resin composed of (CH3)3SiO ⁇ /2 units of Si ⁇ 2 units in a ratio of from (CH3)3 SiO ⁇ /2 units and to Si ⁇ 2 units of from 0.6: 1 to 1.2:1 ;
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and preferably not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from 0.001 to 1 , preferably from 0.01 to 0.7, most preferably from 0.05 to 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin- producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene- polypropylene glycol having a solubility in water at room temperature of more than 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than 1 ,000, preferably between 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than 2 weight % , preferably more than 5 weight % .
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than 1 ,000, more preferably between 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.
  • Preferred is a weight ratio of between 1 :1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene glycol: copolymer of polyethylene-polypropylene glycol.
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the Cfr C ⁇ alkyl alcohols having a C J-CJ ⁇ chain.
  • a preferred alcohol is 2- butyl octanol, which is available from Condea under the trademark ISOFOL 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
  • suds should not form to the extent that they overflow the washing machine.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • compositions herein will generally comprise from 0% to 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to 5%, by weight, of the detergent composition.
  • from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.
  • Silicone suds suppressors are typically utilized in amounts up to 2.0% , by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5% .
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2% , by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01 % to 5.0% , although higher levels can be used.
  • the alcohol suds suppressors are typically used at 0.2%-3 % by weight of the finished compositions.
  • Fabric Softeners Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% , preferably from 0.5% to 2% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416 and U.S. Patent 4,291 ,071.
  • compositions herein A wide variety of other functional ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions.
  • suds boosters such as the Cjo-Cl6 alkanolamides can be inco ⁇ orated into the compositions, typically at 1 %-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgC-2, MgS ⁇ 4, and the like, can be added at levels of, typically, 0.1 %-2% , to provide additional suds and to enhance grease removal performance.
  • detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13- 15 ethoxy lated alcohol (EO 7) nonionic surfactant.
  • the enzyme/surfactant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11 , preferably between 7.5 and 10.5. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc. , and are well known to those skilled in the art.
  • compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions of the invention can be formulated in any desirable form such as powders, granulates, pastes, liquids, and gels.
  • the detergent compositions of the present invention may be formulated as liquid detergent compositions.
  • Such liquid detergent compositions typically comprise from 94% to 35% by weight, preferably from 90% to 40% by weight, most preferably from 80% to 50% by weight of a liquid carrier, e.g. , water, preferably a mixture of water and organic solvent.
  • the detergent compositions of the present invention may also be in the form of gels.
  • Such compositions are typically formulated with polyakenyl polyether having a molecular weight of from about 750,000 to about 4,000,000.
  • the detergent compositions of the invention may also be in the form of solids, such as powders and granules.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.4mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the bulk density of granular detergent compositions in accordance with the present invention are particularly useful in concentrated granular detergent compositions that are characterised by a relatively high density in comparison with conventional laundry detergent compositions.
  • Such high density compositions typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre, most preferably from 800g/litre to lOOOg/litre.
  • Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel.
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.
  • granular detergent compositions in accordance with the present invention can be made via a variety of methods including dry mixing, spray drying, agglomeration and granulation.
  • the abbreviated component identifications have the following meanings: CXYAS Sodium C14-C15 predominantly linear alkyl sulphate
  • TAE 50 Tallow alcohol ethoxylated with 50 moles of ethylene oxide per mole of alcohol
  • Silicone antifoam Polydimethylsiloxane foam controller with Siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1.
  • Lipolase Lipolytic enzyme of activity lOOkLU/g
  • Endolase Endoglucanase A of activity 2T/g all sold by NOVO Industries A/S
  • PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole
  • compositions in accordance with the invention were all seen having an enhanced perfume stability as well as producing an effective soil removal performance.

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  • Chemical & Material Sciences (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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fats And Perfumes (AREA)

Abstract

L'invention concerne une composition de blanchiment parfumée contenant: (a) un système de blanchiment hydrophobe choisi parmi (i) un perhydrate, à raison de 0,1 - 60 % en poids, combiné à un précurseur de blanchiment hydrophobe du type peroxyacide, à raison de 0,1 - 60 % en poids, (ii) un peroxyacide hydrophobe préformé, à raison de 0,1 - 60 % en poids, et (iii) des mélanges de (i) et de (ii), où un 'précurseur de blanchiment hydrophobe du type peroxyacide' est un composé qui fournit par perhydrolyse un peroxyacide hydrophobe dont l'acide carboxylique père a une concentration micellaire critique inférieure à 0,5 moles/litre, et un 'peroxyacide hydrophobe préformé' est un composé dont l'acide carboxylique père a une concentration micellaire critique inférieure à 0,5 moles/litre, et (b) une composition de parfum à raison de 0,05 % - 2 % en poids comprenant un ou plusieurs arômes chimiques choisis parmi les alcools tertiaires, les nitriles, les lactones, les cétones, les acétals, les éthers, les bases de Schiff, les esters et leurs mélanges, le total en poids des arômes chimiques correspondant au moins à 40 % en poids de la composition de parfum.
EP96908584A 1995-03-18 1996-03-01 Compositions de blanchiment parfumees Withdrawn EP0815051A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9505518.2A GB9505518D0 (en) 1995-03-18 1995-03-18 Perfumed bleaching compositions
GB9505518 1995-03-18
PCT/US1996/002768 WO1996029281A1 (fr) 1995-03-18 1996-03-01 Compositions de blanchiment parfumees

Publications (1)

Publication Number Publication Date
EP0815051A1 true EP0815051A1 (fr) 1998-01-07

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EP (1) EP0815051A1 (fr)
JP (1) JPH11502252A (fr)
AR (1) AR001262A1 (fr)
BR (1) BR9607983A (fr)
CA (1) CA2215669A1 (fr)
CO (1) CO4700546A1 (fr)
CZ (1) CZ290097A3 (fr)
GB (1) GB9505518D0 (fr)
HU (1) HUP9800464A3 (fr)
PE (1) PE60596A1 (fr)
WO (1) WO1996029281A1 (fr)

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Publication number Priority date Publication date Assignee Title
EP0778342A1 (fr) * 1995-12-06 1997-06-11 The Procter & Gamble Company Compositions détergentes
GB2307914A (en) * 1995-12-06 1997-06-11 Procter & Gamble Detergent compositions
JP4375814B2 (ja) † 1997-01-24 2009-12-02 クエスト・インターナショナル・ビー・ブイ 大環状ムスク混合物
DE19822232A1 (de) * 1998-05-07 1999-11-11 Dragoco Gerberding Co Ag 2,4,6-Trimethyl-4-phenyl-1,3-dioxan
GB2341553A (en) * 1998-09-15 2000-03-22 Procter & Gamble Peroxyacid treatment
DE10058459A1 (de) 2000-11-24 2002-06-06 Haarmann & Reimer Gmbh Rhinologica
DE102005054565A1 (de) * 2005-11-14 2007-05-16 Henkel Kgaa Oxidationsmittel enthaltende,wohlriechende Verbrauchsprodukte
WO2014093828A2 (fr) 2012-12-14 2014-06-19 The Procter & Gamble Company Compositions antitranspirantes et déodorantes
CN105350277A (zh) * 2015-12-16 2016-02-24 上海市纺织科学研究院 一种用于纤维素纤维水刺无纺布的低温漂白配方及其工艺

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GB8716219D0 (en) * 1987-07-09 1987-08-12 Unilever Plc Perfume compositions
GB8910725D0 (en) * 1989-05-10 1989-06-28 Unilever Plc Bleach activation and bleaching compositions
US5248434A (en) * 1992-04-20 1993-09-28 The Proctor & Gamble Company Liquid or gel bleaching composition containing amidoperoxyacid bleach and perfume
US5234617A (en) * 1992-04-20 1993-08-10 Kathleen B. Hunter Aqueous liquid bleach compositions with fluorescent whitening agent and polyvinyl pyrrolidone or polyvinyl alcohol

Non-Patent Citations (1)

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Title
See references of WO9629281A1 *

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PE60596A1 (es) 1997-01-13
MX9707074A (es) 1997-11-29
AR001262A1 (es) 1997-09-24
BR9607983A (pt) 1998-06-23
CO4700546A1 (es) 1998-12-29
CA2215669A1 (fr) 1996-09-26
GB9505518D0 (en) 1995-05-03
CZ290097A3 (cs) 1998-04-15
WO1996029281A1 (fr) 1996-09-26
JPH11502252A (ja) 1999-02-23
HUP9800464A2 (hu) 1998-07-28
HUP9800464A3 (en) 1999-03-01

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