EP0297673B1 - Hektorittonhaltige Waschmittel-/Weichspülerzusammensetzungen - Google Patents

Hektorittonhaltige Waschmittel-/Weichspülerzusammensetzungen Download PDF

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Publication number
EP0297673B1
EP0297673B1 EP88201330A EP88201330A EP0297673B1 EP 0297673 B1 EP0297673 B1 EP 0297673B1 EP 88201330 A EP88201330 A EP 88201330A EP 88201330 A EP88201330 A EP 88201330A EP 0297673 B1 EP0297673 B1 EP 0297673B1
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Prior art keywords
alkyl
detergent composition
granular detergent
clay
composition according
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French (fr)
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EP0297673A2 (de
EP0297673A3 (en
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André Baeck
Young Sik Oh
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/001—Softening 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
    • C11D3/02—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

Definitions

  • the present invention relates to detergent compositions. More specifically it relates to detergent compositions containing a fabric-softening amount of a hectorite clay, the clay being in the form of particles having a narrowly-defined layer charge distribution.
  • British Patent 1 376 379 teaches the use of synthetic hectorite clays as anti-redeposition agents. However there is no mention of addressing the problem of fabric softening, and the use of natural hectorite clays is discouraged.
  • European Patent Application 0 225 142 discloses the use of clay materials having certain swellability characteristics. The application deals exclusively with liquid detergent compositions.
  • European Patent Application 0 011 340 describes the use of a wide range of clays for fabric softening purposes in detergents.
  • the clays described are mainly smectite clays, and, although hectorite clays are mentioned in passing, there is no disclosure of hectorite clays of natural origin and of the required layer charge characteristics of the present invention.
  • British Patent 1 400 898 discloses detergent compositons 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 (TM) and Volclay BC (TM) , 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 desposited 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. It is a further object of this invention to select clay materials for use in detergent compositions that provide a signficiantly better fabric-softening performance than the clay materials used to date in commercial softeness-through-the-wash detergent compositions.
  • the present invention relates to detergent compositions containing a fabric-softening amount of a fabric-softening clay.
  • the amount of clay is from 1% to 25% by weight of the detergent composition.
  • Said fabric-softening clay is a hectorite clay of natural origin, commonly referred to as trioctahedral smectite.
  • the clay is present in the form of particles. The particles have a narrowly defined layer charge distribution, such that at least 50% of the clay has a layer charge of from 0.23 to 0.31.
  • 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, i.e. from 1% to 25% by weight of the detergent composition, of a fabric-softening clay.
  • the clay which is of the smectite-type, is selected on basis of its layer charge properties.
  • the value of (x + y) is the layer charge of the hectorite clay.
  • the hectorite clays suitable for the detergent compositions of the present invention have a layer charge distribution such that at least 50% is in the range of from 0.23 to 0.31.
  • hectorite clays of natural origin having a layer charge distribution such that at least 65% is in the range of from 0.23 to 0.31.
  • the layer charge distribution of the clay material can be determined using its swelling in the presence of cationic surfactants having specific chain lengths. This method is described in detail by Lagaly and Weiss, Zeitschrift fuer Deernaehrung und Bodentechnik, 130(1), 1971, pages 9-24.
  • the method consists of a battery of tests, known in the detergent industry as the KES-F system of Kawabata.
  • the method is described in S. Kawabata, "The Standardization and Analysis of Hand Evaluation", 2nd Ed., Textile Mach. Soc. of Japan, Osaka, 1980.
  • the shear hysteresis parameter 2HG5 is particularly useful in the characterization of fabric softening clays.
  • Preferred herein are hectorite clays which, when incoporated in detergent compositions at 10% by weight, reduce the shear hysteresis of fabrics laundered therein by at least 32%, more preferably by at least 35%.
  • the shear hysteresis parameter 2HG5 is discussed in more detail in Finnimore and Koenig, Melliand Textilberichte 67 (1986) pages 514-516.
  • Shear hysteresis is determined on cotton terry towels, with detergent compositions containing 10% (weight) of the clay to be tested. The test is described more fully in the Examples hereinbelow.
  • the hectorite clays used in the detergent compositions are further characterized by an unusually great propensity for deposition onto fabrics.
  • deposition onto fabrics of the claimed hectorite clays from a detergent composition is greater than the deposition of conventional smectite-type clays or of synthetic hectorites.
  • suitable hectorite clays include Bentone EW (TM) and Macaloid (TM) from NL Chemicals, NJ., and hectorites from Industrial Mineral Ventures.
  • 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. In general, such 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 5 to 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 compositons 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.
  • anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates
  • Compositions containing 4% or less nonionic surfactant are therefore preferred.
  • 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 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.
  • 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 and persilicates.
  • 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-nonanoyloxybenzene 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-chloroctanoyloxy)benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.
  • alpha-substituted alkyl or alkenyl esters such as sodium-4-(2-chloroctanoyloxy)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 No.
  • RXAOOH and RXAL compounds of the general type RXAOOH and RXAL, wherein R is a hydroxycarbyl 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.
  • 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%.
  • 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 No. 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 No 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.
  • 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.
  • the amine and amide softening ingredients may be added to the crutcher mix and spray-dried, or 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.
  • 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.
  • Softener materials of this type are preferably added to the composition as particles or agglomerates as disclosed in European patent application 0 265 187, published on April 27, 1988 (U.S. Patent Application Serial Number 922 912, filed October 24, 1986 by Baker et al).
  • a preferred cyclic amine is 1-tallowamidoethyl-2-tallow imidazoline.
  • Preferred compositions contain from 1% to 10% of the substituted cyclic amine.
  • compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additonal 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 and bleach activators.
  • compositions are typically used at a concentration of at least 500 ppm, preferably 0.10% 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 are granular.
  • the clay may be added, as a powder or as a slurry, to a crutcher mix of conventional detergent ingredients, mixed, and spray dried to form a detergent granule.
  • the clay powder can be agglomerated to a desirable agglomerate size, and then be mixed with granules containing the other detergent ingredients.
  • Clay granules for dry mixing can also be obtained by selecting a proper sieve fraction of natural agglomerates, by spraying a clay slurry onto a suitable particulate carrier, by agglomerating clay particles with sodium carbonate or by spray drying a clay slurry.
  • the commercially available material has been treated with a wetting agent.
  • a wetting agent The same material without the wetting jaunt is equally suitable.
  • Suitable is also Macaloid (TM) (NL Chemicals, NJ), also a hectorite from Hector, CA.
  • Each of the compositions was used in a laundry test as follows : 3 kg wash load and desired test swatches (cotton terry towels)* were laundered in a commercial automatic drum washing machine (MIELE W 726) using one wash cycle at 60°C.
  • the detergent compositions were used at 1,12% concentration in 0,308 g CaCO3/l water hardness.
  • the wash loads were line-dried at 20°C/65% relative humidity.
  • the test swatches then were instrumentally assessed for softness, using the Kawabata KES-F system (shear hysteresis at 5 degrees 2HG5 as best correlating parameter with softness on KES-F-1 instrument).
  • the sample size was 20 x 20 cm, whereby the area of sample which is actually subjected to shear stress is 20 x 5 cm. From the curves of shear stress against shear angle the shear hysteresis was calculated at 5° (2HG5) in N/m. Each measurement was repeated 8 times to calculate the confidence interval of the mean at 95% confidence level.
  • Supplier Santens - Belgium (type Lopez, 340 g/m2).
  • Hectorite clays of the present invention gave a shear hysteresis reduction of 40%, on average.
  • Fabrics are laundered with the above detergent compositions, in usual fashion.
  • the laundered fabrics are evaluated for handle and softness in Kawabata Evaluation System-Fabric (KES-F) with a series of test instruments for measuring parameters that determine "softeness” and "handle” of fabrics.
  • Kawabata Evaluation System-Fabric Kawabata Evaluation System-Fabric
  • shear hysteresis (2HG5) is of particular importance. The test method is described more fully in Melliand Textilberichte 67 (1986) pp 514-516.

Claims (12)

  1. Körnige Detergenszusammensetzung umfassend, bezogen auf das Gewicht der genannten Zusammensetzung, mindestens 1 % eines detersiven grenzflächenaktiven Mittels, 5 % bis 35 % an Detergensgerüststoffen und 1 % bis 25 % eines Hektorittones, dadurch gekennzeichnet, daß der genannte Hektoritton natürlichen Ursprungs ist und die allgemeine Formel:
    Figure imgb0012
     besitzt, worin MeIII für Al, Fe, oder B steht; oder y den Wert 0 besitzt; Mn+ ein einwertiges (n = 1) oder zweiwertiges (n = 2) Metallion darstellt, dadurch gekennzeichnet, daß der genannte Ton eine Verteilung der Schichtladung (x+y) derart besitzt, daß mindestens 50 % der Schichtladung im Bereich von 0,23 bis 0,31 liegen.
  2. Körnige Detergenszusammensetzung nach Anspruch 1, worin der genannte Hektoritton eine Verteilung der Schichtladung (x+y) derart besitzt, daß mindestens 65 % der Schichtladung im Bereich von 0,23 bis 0,31 liegen.
  3. Körnige Detergenszusammensetzung, welche 1 % bis 25 % eines Hektorittones enthält, dadurch gekennzeichnet, daß der genannte Hektoritton natürlichen Ursprungs ist, welcher Hektoritton ferner dadurch gekennzeichnet ist, daß Baumwollfrotteetücher, welche mit einer Detergenszusammensetzung gewaschen wurden, welche Zusammensetzung 10 % (bezogen auf das Gewicht) des Tones enthält, eine Verringerung der Scherungshysterese, 2HG5, von mindestens 32 % zeigen.
  4. Körnige Detergenszusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daß der Ton eine Verringerung des genannten Scherungshystereseparameters von mindestens 35 % ergibt.
  5. Körnige Detergenszusammensetzung nach einem der vorstehenden Ansprüche, welche ferner als zusätzlichen weichmachenden Bestandteil 1 % bis 10 % eines Amins der Formel R₁ R₂ R₃ N enthält, worin R₁ C₆-C₂₀ Hydrocarbyl ist, R₂ für C₁-C₂₀Hydrocarbyl oder Wasserstoff steht und R₃ C₁- C₂₀Hydrocarbyl oder Wasserstoff darstellt.
  6. Körnige Detergenszusammensetzung nach Anspruch 5, worin R₁ und R₂ jeweils Alkyl mit 10 bis 18 Kohlenstoffatomen sind und R₃ für Methyl steht.
  7. Körnige Detergenszusammensetzung nach Anspruch 6, worin das Amin in Form eines Komplexes mit einer Fettsäure der Formel R COOH vorliegt, worin R ein C₉-C₂₀Alkyl oder -Alkenyl darstellt.
  8. Körnige Detergenszusammensetzung nach Anspruch 7, worin das Amin in der Form eines Komplexes mit einem Phosphatester der Formel
    Figure imgb0013
     vorliegt, worin R₈ und R₉ C₁-C₂₀Alkylgruppen oder ethoxylierte Alkylgruppen der allgemeinen Formel Alkyl-(OCH₂CH₂)y bedeuten, worin der Alkylsubstituent C₁-C₂₀ ist und y eine ganze Zahl von 1 bis 15 bedeutet.
  9. Körnige Detergenszusammensetzung nach einem der vorstehenden Ansprüche, welche ferner 1 % bis 10 % eines Amides der Formel R₁₀R₁₁NCOR₁₂ umfaßt, worin R₁₀ und R₁₁ unabhängig voneinander unter C₁-C₂₂Alkyl-, -Alkenyl, -Hydroxyalkyl-, Aryl- und Alkylaryl-Gruppen ausgewählt sind; R₁₂ Wasserstoff oder eine C₁-C₂₂Alkyl- oder -Alkenyl-, Aryl- oder Alkylaryl-Gruppe darstellt oder O-R₁₃ ist, worin R₁₃ eine C₁-C₂₂Alkyl- oder-Alkenyl-, eine Aryl- oder Alkylaryl-Gruppe bedeutet.
  10. Körnige Detergenszussmmensetzung nach Anspruch 9, worin das Amid in Form eines Komplexes mit der Fettsäure nach Anspruch 7 vorliegt.
  11. Körnige Detergenszusammensetzung nach einem der vorstehenden Ansprüche, welche ferner 1 % bis 10 % eines 1-(Höher alkyl)amido(Niederalkyl)-2-(Höheralkyl)imidazolins umfaßt, worin Höheralkyl ein Alkyl mit 12 bis 22 Kohlenstoffatomen bedeutet und Niederalkyl ein Alkyl mit 1 bis 4 Kohlenstoffatomen ist.
  12. Körnige Detergenszusammensetzung nach einem der vorstehenden Ansprüche, welche ferner 5 % bis 35 % eines Gerüststoffsystems umfaßt, welches Gerüststoffsystem
    a) 1 Gew.-% bis 99 Gew.-% einer Tartratmonosuccinatkomponente der Struktur:
    Figure imgb0014
     worin X für H oder ein salzbildendes Kation steht; und
    b) 1 Gew.-% bis 99 Gew.-% einer Tartratdisuccinatkomponente der Struktur:
    Figure imgb0015
     umfaßt, worin X für H oder ein salzbildendes Kation steht.
EP88201330A 1987-06-30 1988-06-28 Hektorittonhaltige Waschmittel-/Weichspülerzusammensetzungen Expired - Lifetime EP0297673B1 (de)

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JP (1) JP2595052B2 (de)
KR (1) KR950013916B1 (de)
CN (1) CN1025870C (de)
AT (1) ATE97691T1 (de)
AU (1) AU624577B2 (de)
DE (1) DE3885801T2 (de)
DK (1) DK171868B1 (de)
EG (1) EG18674A (de)
FI (1) FI92495C (de)
IE (1) IE61343B1 (de)
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CN100554398C (zh) * 2003-12-26 2009-10-28 花王株式会社 柔软洗涤剂组合物

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GB8816112D0 (en) * 1988-07-06 1988-08-10 Unilever Plc Detergent compositions
GB2224035A (en) * 1988-09-30 1990-04-25 Unilever Plc Detergent composition
GB8900027D0 (en) 1989-01-03 1989-03-01 Procter & Gamble Rinse-added fabric-softening compositions
CA2004165C (en) * 1988-12-21 1997-12-16 The Procter & Gamble Company Fabric conditioning compositions
EP0387426B1 (de) * 1988-12-21 1996-10-02 The Procter & Gamble Company Textil-Wäscheweichmacher, enthaltend natürlichen Hektoritten
CA2017671C (en) * 1989-06-02 1996-12-10 Roger Brace Detergent composition
US5443750A (en) * 1991-01-16 1995-08-22 The Procter & Gamble Company Detergent compositions with high activity cellulase and softening clays
ATE219136T1 (de) * 1991-01-16 2002-06-15 Procter & Gamble Kompakte waschmittelzusammensetzungen mit hochaktiven cellulasen
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Also Published As

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DE3885801D1 (de) 1994-01-05
IE61343B1 (en) 1994-11-02
IE881972L (en) 1988-12-30
FI92495B (fi) 1994-08-15
EG18674A (en) 1993-10-30
AU624577B2 (en) 1992-06-18
FI92495C (fi) 1994-11-25
KR890000652A (ko) 1989-03-16
NZ225217A (en) 1991-07-26
DK361688D0 (da) 1988-06-30
JP2595052B2 (ja) 1997-03-26
CN1025870C (zh) 1994-09-07
MX169171B (es) 1993-06-23
JPS6465199A (en) 1989-03-10
DK361688A (da) 1988-12-31
MY103738A (en) 1993-09-30
ATE97691T1 (de) 1993-12-15
AU1858588A (en) 1989-01-05
DK171868B1 (da) 1997-07-21
CN1031561A (zh) 1989-03-08
FI883106A0 (fi) 1988-06-29
EP0297673A2 (de) 1989-01-04
TR24454A (tr) 1991-10-10
KR950013916B1 (ko) 1995-11-18
FI883106A (fi) 1988-12-31
DE3885801T2 (de) 1994-05-19
EP0297673A3 (en) 1990-04-25

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