EP0299575B1 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
EP0299575B1
EP0299575B1 EP88201455A EP88201455A EP0299575B1 EP 0299575 B1 EP0299575 B1 EP 0299575B1 EP 88201455 A EP88201455 A EP 88201455A EP 88201455 A EP88201455 A EP 88201455A EP 0299575 B1 EP0299575 B1 EP 0299575B1
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.)
Expired - Lifetime
Application number
EP88201455A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0299575A1 (en
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/en
Application granted granted Critical
Publication of EP0299575B1 publication Critical patent/EP0299575B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular 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, 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, 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 800.000, 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 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 amino-polyphosphonates (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 micrometer size zeolite (e.g. zeolite A) builders disclosed in DE-A 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 preferably a mixture of amylase and protease
  • 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 : bisphenol A diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
  • peroxygen bleach activators which are disclosed in U.S. Patents 4.483.778 and 4.539.130, are 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 o 0 116 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydrocarbyl 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 o 0 133 804,. 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 o 0 168 889.
  • 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, or is O-R13, wherein R13 is 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 softening amines.
  • 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, 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 liquor 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 Detergent compositions Expired - Lifetime EP0299575B1 (en)

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
GB8722844 1987-09-29
GB878722844A GB8722844D0 (en) 1987-09-29 1987-09-29 Detergent compositions
GB888807012A GB8807012D0 (en) 1988-03-24 1988-03-24 Detergent compositions
GB8807012 1988-03-24

Publications (2)

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

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP88201455A Expired - Lifetime EP0299575B1 (en) 1987-07-14 1988-07-08 Detergent compositions

Country Status (6)

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

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US6740713B1 (en) 1999-07-08 2004-05-25 Procter & Gamble Company Process for producing particles of amine reaction products
US6764986B1 (en) 1999-07-08 2004-07-20 Procter & Gamble Company Process for producing particles of amine reaction products
US6972276B1 (en) 1999-07-09 2005-12-06 Procter & Gamble Company Process for making amine compounds
WO2019063402A1 (en) 2017-09-29 2019-04-04 Unilever Plc LAUNDRY PRODUCTS
WO2019068472A1 (en) 2017-10-05 2019-04-11 Unilever Plc METHODS AND DEVICES FOR INDIVIDUALIZED LAUNDRY

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DE69019973T2 (de) * 1990-10-29 1995-11-16 Procter & Gamble Wäschebehandlungszusammensetzung.
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US5670475A (en) 1994-08-12 1997-09-23 The Procter & Gamble Company Composition for reducing malodor impression of inanimate surfaces
EP0709452A1 (en) 1994-10-27 1996-05-01 The Procter & Gamble Company Cleaning compositions comprising xylanases
GB2294707A (en) * 1994-11-05 1996-05-08 Procter & Gamble Bleaching composition
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DE602004013270D1 (de) 2004-02-03 2008-06-05 Procter & Gamble Zusammensetzung zum Waschen oder Behandeln von Wäsche
ATE405624T1 (de) 2004-02-03 2008-09-15 Procter & Gamble Eine zusammensetzung zur verwendung beim waschen oder bei der wäschebehandlung
ES2338322T5 (es) 2004-02-03 2018-06-25 The Procter & Gamble Company Una composición para usar en el lavado o tratamiento de tejidos, y un proceso para elaborar la composición
CN100503802C (zh) * 2004-02-13 2009-06-24 花王株式会社 洗涤方法
CN100519717C (zh) * 2004-02-13 2009-07-29 花王株式会社 洗涤剂组合物
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DE602005012946D1 (de) 2005-08-05 2009-04-09 Procter & Gamble Verfahren zur Herstellung einer Textilbehandlungshilfsmittelzusammensetzung und Verfahren zur Herstellung eines Textilbehandlungs- und Textilreinigungsmittels
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GB0518059D0 (en) 2005-09-06 2005-10-12 Dow Corning Delivery system for releasing active ingredients
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US6764986B1 (en) 1999-07-08 2004-07-20 Procter & Gamble Company Process for producing particles of amine reaction products
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Also Published As

Publication number Publication date
FI96776B (fi) 1996-05-15
IE882139L (en) 1989-01-14
JP2620318B2 (ja) 1997-06-11
IE61938B1 (en) 1994-11-30
FI96776C (fi) 1996-08-26
DK171848B1 (da) 1997-06-30
FI883340A (fi) 1989-01-15
EP0299575A1 (en) 1989-01-18
DE3887020T2 (de) 1994-06-09
DK393888D0 (da) 1988-07-14
DK393888A (da) 1989-01-15
FI883340A0 (fi) 1988-07-13
JPH0198697A (ja) 1989-04-17
DE3887020D1 (de) 1994-02-24

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