EP0299575A1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0299575A1
EP0299575A1 EP88201455A EP88201455A EP0299575A1 EP 0299575 A1 EP0299575 A1 EP 0299575A1 EP 88201455 A EP88201455 A EP 88201455A EP 88201455 A EP88201455 A EP 88201455A EP 0299575 A1 EP0299575 A1 EP 0299575A1
Authority
EP
European Patent Office
Prior art keywords
clay
alkyl
detergent composition
composition according
flocculating agent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP88201455A
Other languages
German (de)
English (en)
Other versions
EP0299575B1 (fr
Inventor
Hans Raemdonck
Alfred Busch
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
Priority claimed from GB878716584A external-priority patent/GB8716584D0/en
Priority claimed from GB878722844A external-priority patent/GB8722844D0/en
Priority claimed from GB888807012A external-priority patent/GB8807012D0/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT88201455T priority Critical patent/ATE100134T1/de
Publication of EP0299575A1 publication Critical patent/EP0299575A1/fr
Application granted granted Critical
Publication of EP0299575B1 publication Critical patent/EP0299575B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/12Water-insoluble compounds
    • C11D3/124Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246Silicates, e.g. diatomaceous earth
    • C11D3/1253Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3746Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the present invention relates to detergent compositions. More specifically it relates to detergent compositions containing a fabric-softening amount of a smectite-type clay.
  • the compositions further contain a polymeric clay flocculating agent.
  • British Patent 1 400 898 discloses detergent compositions comprising, as a fabric-softening ingredient, a smectite-type clay. Any smectite-type clay having a cation exchange capacity of at least 50 meq/100 g is taught to be suitable. Gelwhite GP and Volclay BC, both of which are sodium montmorillonite clays, are disclosed to be preferred for reasons of color and cation exchange capacity.
  • an object of the present invention to provide detergent compositions comprising a fabric-softening clay from which the clay particles are more efficiently deposited onto fabrics during the laundry process. It is another object of the present invention to provide detergent compositions from which clay particles are efficiently deposited, regardless of the builder system used.
  • the present invention relates to detergent compositions comprising from 5% to 40% of an organic surfactant and, as a fabric softening ingredient, from 1% to 30% of a smectite-type clay, characterized in that it further comprises a softening enhancing amount of a polymeric clay flocculating agent, typically in the range of from 0.005% to 20% by weight of the smectite-type clay.
  • Preferred clay flocculating agents are polymers like poly(ethylene oxide), poly(acryl amide) and poly(acrylate), having a weight average molecular weight of from 100.000 to 10 million, most preferably of from 150.000 to 5 million.
  • the detergent compositions of the present invention comprise conventional detersive surfactants, conventional detergent builders and, optionally, other conventional detergent ingredients.
  • the compositions further comprise a fabric-softening amount, typically from 1% to 30% by weight of the detergent composition, of a fabric-softening clay.
  • Percentages herein are percentages by weight of the detergent compositions, unless otherwise specified.
  • compositions furhter contain a polymeric clay-flocculating agent.
  • polymeric clay-flocculating agents enhance the deposition of fabric-softening clays onto fabrics.
  • the amount of clay-flocculating agent to be used in the present detergent compositions must be such that the deposition of the softening clay onto fabrics is enhanced, but remains substantially uniform.
  • the amount required in the detergent composition can be readily determined in a simple level study using the clay deposition test described hereinbelow.
  • the amount of clay-flocculating agent expressed as percent by weight of the smectite-type clay, ranges from 0.005 - 20% by weight of the clay, preferably from 0.05 - 20% by weight of the clay, for clay flocculating agents having a weight average molecular weight of from 150.000 to 800.00, and 0.005 to 2% by weigth of the clay for MW 800.000 to 5 million.
  • Clay-flocculating agents are not commonly used in detergent compositions. On the contrary, one is inclined to use clay dispersents, which aid in removing clay stains from fabrics. Such agents are, however, very well known in other industries like oil well drilling, and for ore flotation in metallurgy. Most of these materials are fairly long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are suitable as well.
  • polymers of ethylene oxide, acryl amide, or acrylic acid are preferred.
  • the polymers should be fairly long chain, i.e., have a weight average molecular weight of at least 100,000.
  • weight average molecular weight of the polymers should not exceed 10 million.
  • Smectite-type clays are widely used as fabric softening ingredients in detergent compositions. Most of these clays have a cation exchange capacity of at least 50 meq/100g.
  • Montmorrillonite clays are commonly used for this purpose. It appears, however, that certain hectorite clays provide better fabric softening performance than the more commonly used montmorillonites. The hectorites exhibiting this superior fabric softening performance are hectorites of natural origin.
  • cation exchange capacity of clays is a well-known parameter and may be determined by well-established analytical techniques. See, for example, H. van Olphen, "Clay Colloid Chemistry", Interscience Publishers, 1963 and the relevant references cited therein.
  • compositions of this invention will typically contain organic surface-active agents ("surfactants”) to provide the usual cleaning benefits associated with the use of such materials.
  • surfactants organic surface-active agents
  • Detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.
  • detersive surfactants contain an alkyl group in the C9-C18 range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.
  • U.S. Patent 3 995 669 the disclosures of which are incorporated herein by reference, contains detailed listings of such typical detersive surfactants.
  • C11-C16 alkyl benzene sulfonates, C12-C18 paraffin-­sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
  • surfactant are the water-­soluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well-known in the art.
  • the surfactant component can comprise as little as 1% of the compositions herein, but preferably the composi­tions will contain 5% to 40%, preferably 10% to 30%, of surfactant. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabrics. It has previously been disclosed that high levels of nonionic surfactants (i.e., in excess of 4%) in clay-containing detergent compositions negatively affect the clay softening performance. It has now surprisingly been found that such negative interaction does not occur if the clay flocculating agent of the present invention is also present.
  • compositions herein can contain other ingredients which aid in their cleaning performance.
  • through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant.
  • detergent builders include the nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof.
  • Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino­polyphosphonates (DEQUEST) and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3 579 454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise about 0.5% to 45% of the composition.
  • the 1-10 micron size zeolite (e.g. zeolite A) builders disclosed in German patent 2 422 655 are especial­ly preferred for use in low-phosphate compositions.
  • Particularly suitable phosphate-free builders are ether carboxylate mixtures comprising
  • Typical detergent compositions contain from 5% to 35% of this builder system.
  • the laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning perfor­mance on a variety of soils and stains.
  • Amylase and prote­ase enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
  • Commercial detersive enzymes (preferivelyably a mixture of amylase and protease) are typically used at levels of 0.001% to 2%, and higher, in the present compositions.
  • Detergent cellulase enzymes provide both cleaning and softening benefits, particularly to cotton fabrics. These enzymes are highly desirable in the detergent compositions of this invention.
  • compositions herein can contain other ingredients which aid in their cleaning performance.
  • the compositions herein can advantageously contain a bleaching agent, especially a peroxyacid bleaching agent.
  • peroxyacid bleaching agent encompasses both peroxyacids per se and systems which are able to yield peroxyacids in situ .
  • Peroxyacids per se are meant to include the alkaline and alkaline-earth metal salts thereof.
  • Peroxyacids and diperoxyacids are commonly used; examples are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.
  • Systems capable of delivering peracids in situ consist of a peroxygen bleaching agent and an activator thereof.
  • the peroxygen bleaching agents are those capable of yielding hydrogen peroxide in an aqueous solution; these compounds are well-known in the art, and include hydrogen peroxide, alkali-metal peroxides, organic peroxide bleaching agents such as urea peroxide, inorganic persalt bleaching agents such as alkali metal perborates, percarbonates, perphosphates, persilicates, and the like.
  • sodium perborate commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.
  • the liberated hydrogen peroxide reacts with a bleach activator to form the peroxyacid bleach.
  • bleach activators include esters, imides, imidazoles, oximes, and carbonates.
  • preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-nonanoxyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate : biophenol A diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
  • alpha-substituted alkyl or alkenyl esters such as sodium-4(2-chlorooctanoyloxy)benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.
  • Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application N° 0 116 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
  • quaternary ammonium compounds of the formula R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 8 to 20, preferably from 12-18 carbon atoms, R5 is alkyl having from 1 to 10 carbon atoms, and R6 and R7 are each C1 to C4 alkyl preferably methyl :
  • X ⁇ is an anion, e.g. chloride.
  • Examples of such quaternary ammonium compounds include C12-C14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.
  • the quaternary ammonium compounds can be used at levels from 0.5% to 5%, preferably from 1% to 3%.
  • the detergent compositions of the present invention may further contain, in addition to the clay material, other softening ingredients.
  • Suitable examples include amines of the formula R1R2R3N, wherein R1 is C6 to C20 hydrocarbyl, R2 is C1 to C20 hydrocarbyl, and R3 is C1 to C10 hydrocarbyl or hydrogen.
  • a preferred amine of this type is ditallowmethylamine.
  • the softening amine is present as a complex with a fatty acid of the formula RCOOH, wherein R is a C9 to C20 alkyl or alkenyl. It is desirable that the amine/fatty acid complex be present in the form of microfine particles, having a particle size in the range of from, e.g. , 0.1 to 20 micrometers. These amine/fatty acid complexes are disclosed more fully in European Patent Application N° 0 133 804, the disclosures of which are incorporated herein by reference. Preferred are compositions that contain from 1% to 10% of the amine.
  • Suitable are also complexes of the above described amine and phosphate esters of the formula wherein R8 and R9 are C1-C20 alkyl, or ethoxylated alkyl groups of the general formula alkyl-(OCH2CH2) y , wherein the alkyl substituent is C1-C20, preferably C8-C16, and y is an integer of 1 to 15, preferably 2-10, most preferably 2-5.
  • Amine/phosphate ester complexes of this type are more fully disclosed in European Patent Application N° 0 168 889, the disclosures of which are incorporated herein by reference.
  • optional softening ingredients include the softening amides of the formula R10R11NCOR12, wherein R10 and R11 are independently selected from C1-C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups; R12 is hydrogen, or a C1-C22 alkyl or alkenyl, an aryl or alkyl-aryl group.
  • R10 and R11 are independently selected from C1-C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups
  • R12 is hydrogen, or a C1-C22 alkyl or alkenyl, an aryl or alkyl-aryl group.
  • Preferred examples of these amides are ditallow acetamide and ditallow benzamide. Good results are obtained when the amides are present in the composition in the form of a composite with a fatty acid or with a phosphate ester, as described hereinbefore for the soft
  • the amides are present in the composition at 1%-10% by weight.
  • Suitable softening ingredients are also the amines disclosed in U.K. Patent Application GB 2 173 827, the disclosures of which are incorporated herein by reference, in particular the substituted cyclic amines disclosed therein.
  • Suitable are imidazolines of the general formula 1-(higher alkyl) amido (lower alkyl)-2-(higher alkyl)imidazoline wherein higher alkyl is alkyl having from 12 to 22 carbon atoms, and lower alkyl is alkyl having from 1 to 4 carbon atoms.
  • a preferred cyclic amine is 1-tallowamidoethyl-2-tallowimidazoline.
  • Preferred compositions contain from 1% to 10% of the substituted cyclic amine.
  • the amine and amide softening ingredients may be added as a dry powder to a detergent granule, or may be sprayed onto the detergent granule or onto a carrier, either in melted or in dissolved form.
  • a suitable carrier is perborate monohydrate.
  • compositions herein can contain, in addi­tion to ingredients already mentioned, various other optio­nal ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
  • Typical ingredients include pH regulants, perfumes, dyes, bleach, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.
  • compositions are typically used at a concentration of at least 400 ppm, preferably 0.05% to 1.5%, in an aqueous laundry bath at pH 7-11 to launder fabrics.
  • the laundering can be carried out over the range from 5°C to the boil, with excellent results.
  • the detergent compositions of the present invention can be formulated as granular or as liquid detergents. It has been found that clays having a high swelling capacity can be easily incorporated in a liquid detergent composition, while maintaining phase stability.
  • the polymeric clay-flocculating agent can be mixed with the other detergent ingredients under stirring.
  • the polymeric clay-flocculating agent can be added in a variety of ways. It may be added to the crutcher mix prior to spray-drying; or it may be sprayed onto a granular detergent from solution in water or an organic solvent; or it may be dry-mixed, in the form of particles, with a granular detergent.
  • the release of the flocculating agent can be controlled by incorporating it in a prill, or by microencapsulating it in a suitable microencapsulating agent.
  • agglomerates are formed of the fabric softening clay and the clay-flocculating agent. These agglomerates are dry mixed with the granular detergent composition.
  • the chemical stability of the clay-flocculating agent is improved by the addition of small amounts (typically from 0.05% to 1% by weight of the detergent composition) of a chelating agent.
  • a preferred chelating agent is ethylenediamine tetramethylene phosphonic acid.
  • the clay-flocculating agent may also be incorporated in a detergent additive, e.g. in the form of a sheet or a pouch, that is to be added to the wash liquour on top of a conventional detergent composition.
  • the laundry additive preferably also contains a fabric-softening clay and/or other fabric softening ingredients described hereinabove, so it may be used in conjunction with detergent compositions that themselves do not contain such a clay or such other softening ingredients.
  • the polymeric clay-flocculating agent is formed into a water-soluble film.
  • the film is formed into a pouch which is filled with a single dose of a clay-containing detergent composition.
  • the pouch will dissolve and release the detergent composition.
  • the dissolved polymer will interact with the softening clay to enhance its deposition onto fabrics.
  • Polymers of ethylene oxide are particularly suitable for use in this embodiment of the invention.
  • a fabric-softening clay and a softness enhancing amount of a polymeric clay-flocculating agent can also be incorporated into a rinse-added softener composition.
  • Other softening agents like quaternary ammonium compounds, may also be present.

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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)
EP88201455A 1987-07-14 1988-07-08 Compositions détergentes Expired - Lifetime EP0299575B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88201455T ATE100134T1 (de) 1987-07-14 1988-07-08 Detergenszusammensetzungen.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB8716584 1987-07-14
GB878716584A GB8716584D0 (en) 1987-07-14 1987-07-14 Detergent compositions
GB878722844A GB8722844D0 (en) 1987-09-29 1987-09-29 Detergent compositions
GB8722844 1987-09-29
GB8807012 1988-03-24
GB888807012A GB8807012D0 (en) 1988-03-24 1988-03-24 Detergent compositions

Publications (2)

Publication Number Publication Date
EP0299575A1 true EP0299575A1 (fr) 1989-01-18
EP0299575B1 EP0299575B1 (fr) 1994-01-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP88201455A Expired - Lifetime EP0299575B1 (fr) 1987-07-14 1988-07-08 Compositions détergentes

Country Status (6)

Country Link
EP (1) EP0299575B1 (fr)
JP (1) JP2620318B2 (fr)
DE (1) DE3887020T2 (fr)
DK (1) DK171848B1 (fr)
FI (1) FI96776C (fr)
IE (1) IE61938B1 (fr)

Cited By (48)

* Cited by examiner, † Cited by third party
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US4844824A (en) * 1988-02-08 1989-07-04 The Procter & Gamble Company Stable heavy duty liquid detergent compositions which contain a softener and antistatic agent
EP0387426A2 (fr) * 1988-12-21 1990-09-19 The Procter & Gamble Company Composition adoucissante textile contenant une argile hectorite naturelle
EP0483411A1 (fr) * 1990-10-29 1992-05-06 The Procter & Gamble Company Composition pour le traitement du linge
WO1993001267A1 (fr) * 1991-07-08 1993-01-21 The Procter & Gamble Company Compositions detersives contenant des agents tensioactifs a base d'amides d'acide gras polyhydroxyles et un systeme d'assouplissement a base d'argile
WO1993025651A1 (fr) * 1992-06-18 1993-12-23 Unilever N.V. Composition pour le lavage de la vaisselle en machine
WO1995027037A1 (fr) * 1994-03-30 1995-10-12 The Procter & Gamble Company Detergent en pains pour lessive contenant de l'argile adoucissant le tissu
EP0709452A1 (fr) 1994-10-27 1996-05-01 The Procter & Gamble Company Compositions de nettoyage contenant des xylanases
GB2294707A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
EP0711825A1 (fr) * 1994-11-05 1996-05-15 The Procter & Gamble Company Compositions de blanchiment
WO1998020116A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants de subtilase et compositions
WO1998020115A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants et compositions de subtilase
EP0653480B1 (fr) * 1993-11-11 2000-01-19 The Procter & Gamble Company Compositions adoucissants pour le lavage simultané
WO2000060039A1 (fr) * 1999-04-01 2000-10-12 The Procter & Gamble Company Composant d'adoucissant de textiles
WO2003031266A1 (fr) 2001-10-08 2003-04-17 The Procter & Gamble Company Procede permettant la production de sachets solubles dans l'eau et sachets ainsi obtenus
US6689739B1 (en) 1999-04-01 2004-02-10 The Procter & Gamble Company Detergent compositions
US6713442B2 (en) 2001-10-10 2004-03-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
WO2004053039A2 (fr) 2002-12-11 2004-06-24 Novozymes A/S Composition detergente
US6794349B2 (en) 2001-10-10 2004-09-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions
US6881717B1 (en) 1999-04-01 2005-04-19 The Procter & Gamble Company Fabric softening component
US7074754B2 (en) 2004-02-03 2006-07-11 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics
EP1749877A1 (fr) 2005-08-05 2007-02-07 The Procter and Gamble Company Composition particulaire de traitement des textiles comprenant une silicone, d'argile et un agent tensioactif anionique
EP1749879A1 (fr) 2005-08-05 2007-02-07 The Procter & Gamble Company Composition de nettoyage ou de traitement de tissus, et procédé de préparation de la composition
US7182941B2 (en) 1994-08-12 2007-02-27 The Procter & Gamble Company Method for reducing malodor impression on inanimate surfaces comprising uncomplexed cyclodextrin
US7304024B2 (en) 2004-02-03 2007-12-04 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics, and a process for making the composition
WO2008025505A1 (fr) 2006-08-28 2008-03-06 Süd-Chemie AG Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp
EP1923455A2 (fr) 2003-02-18 2008-05-21 Novozymes A/S Compositions détergents
DE102007012909A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, reaktive Polyorganosiloxane
DE102007012910A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, verzweigte Polyorganosiloxane
US7459423B2 (en) 2004-02-03 2008-12-02 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics
CN100503802C (zh) * 2004-02-13 2009-06-24 花王株式会社 洗涤方法
US7638478B2 (en) 2005-08-05 2009-12-29 The Procter & Gamble Company Process for preparing a textile treatment auxiliary composition and a process for preparing a composition for the laundering and treatment of fabric
DE102008050360A1 (de) 2008-10-02 2010-04-08 Süd-Chemie AG Waschmitteladditiv auf der Basis von Tonmineralien, sowie dessen Verwendung und Verfahren zu dessen Herstellung
EP2261359A1 (fr) 1998-06-10 2010-12-15 Novozymes A/S Mannanases
WO2011051681A1 (fr) 2009-10-28 2011-05-05 Revolymer Limited Composite
WO2012149317A1 (fr) 2011-04-29 2012-11-01 Danisco Us Inc. Compositions détergentes contenant mannanase dérivée de bacillus agaradhaerens et leurs procédés d'utilisation
WO2012149333A1 (fr) 2011-04-29 2012-11-01 Danisco Us Inc. Compositions détergentes contenant mannanase dérivée de bacillus sp. et leurs procédés d'utilisation
WO2012149325A1 (fr) 2011-04-29 2012-11-01 Danisco Us Inc. Compositions détergentes contenant une mannanase de geobacillus tepidamans et leurs procédés d'utilisation
US8754155B2 (en) 2005-09-06 2014-06-17 Dow Corning Corporation Delivery system for releasing silicone ingredients
WO2014100018A1 (fr) 2012-12-19 2014-06-26 Danisco Us Inc. Nouvelle mannanase, compositions et procédés pour les utiliser
US20140336029A1 (en) * 2013-05-07 2014-11-13 The Procter & Gamble Company Process for laser puncturing holes into water-soluble films
WO2017079751A1 (fr) 2015-11-05 2017-05-11 Danisco Us Inc Mannanases de paenibacillus sp.
WO2017079756A1 (fr) 2015-11-05 2017-05-11 Danisco Us Inc Mannanases de paenibacillus et bacillus spp.
WO2019045958A1 (fr) * 2017-09-04 2019-03-07 Dow Global Technologies Llc Formulation de détergent à lessive en poudre
US11131055B2 (en) 2018-02-26 2021-09-28 Conopco, Inc. Methods and system for monitoring and replenishing one or more laundry components
EP4209264A1 (fr) 2016-09-16 2023-07-12 International Flavors & Fragrances Inc. Compositions de microcapsules stabilisées avec des agents de contrôle de la viscosité
US11807974B2 (en) 2017-10-05 2023-11-07 Conopco, Inc. Methods and devices for individualized laundry
US11910982B2 (en) 2019-11-01 2024-02-27 Conopco Inc. Recyclable auto-dosing container
WO2024050339A1 (fr) 2022-09-02 2024-03-07 Danisco Us Inc. Variants de mannanases et procédés d'utilisation

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JP2009500279A (ja) * 2005-07-04 2009-01-08 ジュート−ヒェミー アクチェンゲゼルシャフト 高い固形成分含有率を有する層状珪酸塩スラリ
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EP0387426A2 (fr) * 1988-12-21 1990-09-19 The Procter & Gamble Company Composition adoucissante textile contenant une argile hectorite naturelle
EP0387426A3 (fr) * 1988-12-21 1991-11-21 The Procter & Gamble Company Composition adoucissante textile contenant une argile hectorite naturelle
EP0483411A1 (fr) * 1990-10-29 1992-05-06 The Procter & Gamble Company Composition pour le traitement du linge
TR25527A (tr) * 1990-10-29 1993-05-01 Procter & Gamble Yumusatici killeri yumusatici polisiloksanlari ve pihtilastirici maddeleri iceren kumas muamele bilesimleri.
WO1993001267A1 (fr) * 1991-07-08 1993-01-21 The Procter & Gamble Company Compositions detersives contenant des agents tensioactifs a base d'amides d'acide gras polyhydroxyles et un systeme d'assouplissement a base d'argile
WO1993025651A1 (fr) * 1992-06-18 1993-12-23 Unilever N.V. Composition pour le lavage de la vaisselle en machine
EP0653480B1 (fr) * 1993-11-11 2000-01-19 The Procter & Gamble Company Compositions adoucissants pour le lavage simultané
WO1995027037A1 (fr) * 1994-03-30 1995-10-12 The Procter & Gamble Company Detergent en pains pour lessive contenant de l'argile adoucissant le tissu
US7182941B2 (en) 1994-08-12 2007-02-27 The Procter & Gamble Company Method for reducing malodor impression on inanimate surfaces comprising uncomplexed cyclodextrin
EP0709452A1 (fr) 1994-10-27 1996-05-01 The Procter & Gamble Company Compositions de nettoyage contenant des xylanases
GB2294707A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
EP0710712A1 (fr) * 1994-11-05 1996-05-08 The Procter & Gamble Company Compositions de blanchiment
EP0711825A1 (fr) * 1994-11-05 1996-05-15 The Procter & Gamble Company Compositions de blanchiment
WO1998020116A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants de subtilase et compositions
WO1998020115A1 (fr) 1996-11-04 1998-05-14 Novo Nordisk A/S Variants et compositions de subtilase
EP2278001A1 (fr) 1996-11-04 2011-01-26 Novozymes A/S Variants et compositions de protéase
EP2284272A1 (fr) 1998-06-10 2011-02-16 Novozymes A/S Mannanases
EP2287318A1 (fr) 1998-06-10 2011-02-23 Novozymes A/S Mannanases
EP2261359A1 (fr) 1998-06-10 2010-12-15 Novozymes A/S Mannanases
US6881717B1 (en) 1999-04-01 2005-04-19 The Procter & Gamble Company Fabric softening component
US6689739B1 (en) 1999-04-01 2004-02-10 The Procter & Gamble Company Detergent compositions
WO2000060039A1 (fr) * 1999-04-01 2000-10-12 The Procter & Gamble Company Composant d'adoucissant de textiles
WO2003031266A1 (fr) 2001-10-08 2003-04-17 The Procter & Gamble Company Procede permettant la production de sachets solubles dans l'eau et sachets ainsi obtenus
US6713442B2 (en) 2001-10-10 2004-03-30 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Detergent compositions
US6794349B2 (en) 2001-10-10 2004-09-21 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent compositions
WO2004053039A2 (fr) 2002-12-11 2004-06-24 Novozymes A/S Composition detergente
EP2311941A1 (fr) 2002-12-11 2011-04-20 Novozymes A/S Detergent comprenant une endoglucanase
EP1923455A2 (fr) 2003-02-18 2008-05-21 Novozymes A/S Compositions détergents
US7572760B2 (en) 2004-02-03 2009-08-11 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics, and a process for making the composition
US7754673B2 (en) 2004-02-03 2010-07-13 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics, and a process for making the composition
US7459423B2 (en) 2004-02-03 2008-12-02 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics
US7074754B2 (en) 2004-02-03 2006-07-11 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics
US7919450B2 (en) 2004-02-03 2011-04-05 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics, and a process for making the composition
US7304024B2 (en) 2004-02-03 2007-12-04 The Procter & Gamble Company Composition for use in the laundering or treatment of fabrics, and a process for making the composition
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US7638478B2 (en) 2005-08-05 2009-12-29 The Procter & Gamble Company Process for preparing a textile treatment auxiliary composition and a process for preparing a composition for the laundering and treatment of fabric
US7696144B2 (en) 2005-08-05 2010-04-13 The Procter & Gamble Co. Particulate textile treatment composition comprising silicone, clay and anionic surfactant
EP1749879A1 (fr) 2005-08-05 2007-02-07 The Procter & Gamble Company Composition de nettoyage ou de traitement de tissus, et procédé de préparation de la composition
EP1749877A1 (fr) 2005-08-05 2007-02-07 The Procter and Gamble Company Composition particulaire de traitement des textiles comprenant une silicone, d'argile et un agent tensioactif anionique
US8754155B2 (en) 2005-09-06 2014-06-17 Dow Corning Corporation Delivery system for releasing silicone ingredients
WO2008025505A1 (fr) 2006-08-28 2008-03-06 Süd-Chemie AG Additif pour détergent à base de minéraux argileux et de copolymères contenant de la pvp
DE102007012910A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, verzweigte Polyorganosiloxane
DE102007012909A1 (de) 2007-03-19 2008-09-25 Momentive Performance Materials Gmbh Mit Duftstoffen modifizierte, reaktive Polyorganosiloxane
DE102008050360A1 (de) 2008-10-02 2010-04-08 Süd-Chemie AG Waschmitteladditiv auf der Basis von Tonmineralien, sowie dessen Verwendung und Verfahren zu dessen Herstellung
WO2011051681A1 (fr) 2009-10-28 2011-05-05 Revolymer Limited Composite
WO2012149333A1 (fr) 2011-04-29 2012-11-01 Danisco Us Inc. Compositions détergentes contenant mannanase dérivée de bacillus sp. et leurs procédés d'utilisation
WO2012149325A1 (fr) 2011-04-29 2012-11-01 Danisco Us Inc. Compositions détergentes contenant une mannanase de geobacillus tepidamans et leurs procédés d'utilisation
WO2012149317A1 (fr) 2011-04-29 2012-11-01 Danisco Us Inc. Compositions détergentes contenant mannanase dérivée de bacillus agaradhaerens et leurs procédés d'utilisation
US8802388B2 (en) 2011-04-29 2014-08-12 Danisco Us Inc. Detergent compositions containing Bacillus agaradhaerens mannanase and methods of use thereof
US8986970B2 (en) 2011-04-29 2015-03-24 Danisco Us Inc. Detergent compositions containing Bacillus agaradhaerens mannanase and methods of use thereof
WO2014100018A1 (fr) 2012-12-19 2014-06-26 Danisco Us Inc. Nouvelle mannanase, compositions et procédés pour les utiliser
US20140336029A1 (en) * 2013-05-07 2014-11-13 The Procter & Gamble Company Process for laser puncturing holes into water-soluble films
WO2014182602A1 (fr) 2013-05-07 2014-11-13 The Procter & Gamble Company Procédé de perforation laser de trous dans des films hydrosolubles
WO2017079756A1 (fr) 2015-11-05 2017-05-11 Danisco Us Inc Mannanases de paenibacillus et bacillus spp.
WO2017079751A1 (fr) 2015-11-05 2017-05-11 Danisco Us Inc Mannanases de paenibacillus sp.
EP4141113A1 (fr) 2015-11-05 2023-03-01 Danisco US Inc Paenibacillus sp. mannanases
EP4209264A1 (fr) 2016-09-16 2023-07-12 International Flavors & Fragrances Inc. Compositions de microcapsules stabilisées avec des agents de contrôle de la viscosité
WO2019045958A1 (fr) * 2017-09-04 2019-03-07 Dow Global Technologies Llc Formulation de détergent à lessive en poudre
CN111032841A (zh) * 2017-09-04 2020-04-17 陶氏环球技术有限责任公司 粉末状洗衣清洁剂调配物
US11807974B2 (en) 2017-10-05 2023-11-07 Conopco, Inc. Methods and devices for individualized laundry
US11131055B2 (en) 2018-02-26 2021-09-28 Conopco, Inc. Methods and system for monitoring and replenishing one or more laundry components
US11910982B2 (en) 2019-11-01 2024-02-27 Conopco Inc. Recyclable auto-dosing container
WO2024050339A1 (fr) 2022-09-02 2024-03-07 Danisco Us Inc. Variants de mannanases et procédés d'utilisation

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FI883340A0 (fi) 1988-07-13
DE3887020T2 (de) 1994-06-09
EP0299575B1 (fr) 1994-01-12
DE3887020D1 (de) 1994-02-24
DK171848B1 (da) 1997-06-30
JP2620318B2 (ja) 1997-06-11
FI883340A (fi) 1989-01-15
DK393888A (da) 1989-01-15
IE61938B1 (en) 1994-11-30
FI96776C (fi) 1996-08-26
FI96776B (fi) 1996-05-15
IE882139L (en) 1989-01-14
DK393888D0 (da) 1988-07-14
JPH0198697A (ja) 1989-04-17

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