EP0313146B1 - Compositions détergentes - Google Patents

Compositions détergentes Download PDF

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Publication number
EP0313146B1
EP0313146B1 EP88202253A EP88202253A EP0313146B1 EP 0313146 B1 EP0313146 B1 EP 0313146B1 EP 88202253 A EP88202253 A EP 88202253A EP 88202253 A EP88202253 A EP 88202253A EP 0313146 B1 EP0313146 B1 EP 0313146B1
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Prior art keywords
weight
alkyl
clay
detergent composition
composition according
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German (de)
English (en)
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EP0313146A2 (fr
EP0313146B2 (fr
EP0313146A3 (en
Inventor
Alfred Busch
Andre Baeck
Bob Dekker
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from GB878724463A external-priority patent/GB8724463D0/en
Priority claimed from GB888807013A external-priority patent/GB8807013D0/en
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to AT88202253T priority Critical patent/ATE89856T1/de
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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
    • C11D3/02—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
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions

Definitions

  • the present invention relates to detergent compositions containing a fabric-softening amount of a smectite-type clay.
  • the clay is present in the form of agglomerates which comprise from 0.5% to 30% of an organic humectant.
  • British Patent 1,572,815 discloses a detergent composition based on soap and a curd-dispersing agent.
  • the compositions comprise from 4% to 25% of a smectite-type clay.
  • the clay is agglomerated with water, an aqueous electrolyte solution, a nonionic surfactant, or an aqueous solution of an organic adhesive.
  • adhesives include dextrin, gelatine, carboxymethyl- cellulose, starch, carboxymethyl starch, and alkyl and hyroxy alkyl substituted celluloses and starches.
  • the agglomerates are disclosed to minimize dustiness while the full softening potential of the clay is preserved.
  • British Patent 1,167,037 discloses clays that have been treated with alkanolamine salts and an organic humectant.
  • the treated clays are disclosed to hydrate rapidly and to develop viscosity in a short period of time as compared to untreated clays.
  • European Patent Application 164 797 discloses detergent compositions comprising agglomerates of smectite clay which are sprayed with a dispensing aid such as quaternary ammonium compounds.
  • French Patent Application 2 524 903 discloses detergent compositions comprising agglomerates of clay with binders such as sodium silicate, gums, resins and organic polymers.
  • European Patent Application 287344 published on 19th October, 1988, is a part of the prior art according to Article 54(3) EPC. It discloses softening clay in intimate contact with a nonionic surfactant system.
  • British Patent 1,400,898 discloses detergent compositions comprising, as a fabric softening ingredient, a smectite-type clay.
  • the present invention relates to the granular detergent compositions comprising a) conventional detergent ingredients; and b) clay agglomerates comprising from 60% to 99.5% smectite-type clay and from 30% to 0.5% of an organic humectant.
  • the humectants are selected from: glycerol, ethylene glycol, propylene glycol, dimers and trimers of glycerol and mixtures thereof.
  • Highly preferred agglomerates further comprise, by weight of the clay, from 0.005% to 20% of a clay flocculating agent.
  • 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 preferred are poly (ethylene oxide) polymers having a molecular weight (weight average) in the range 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 35% by weight preferably from 3% to 15% by weight of the detergent composition, of the fabric-softening clay agglomerates herein.
  • Percentages herein are percentages by weight of the detergent compositions, unless otherwise specified.
  • 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.
  • 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 C 9 - C 1 8 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.
  • C 11 - C1 6 alkyl benzene sulfonates, C 12 - C 1 8 paraffin - sulfonates and alkyl sulfates, and the ethox - ylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
  • the 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.
  • 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 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
  • 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 - de - canoyloxybenzenesulfonate : 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 R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 8 to 20, preferably from 12 - 18 carbon atoms, R 5 is alkyl having from 1 to 10 carbon atoms, and R 6 and R 7 are each C 1 to C 4 alkyl preferably methyl : X- is an anion, e.g. chloride.
  • quaternary ammonium compounds include C12 - C1 4 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%.
  • 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 having a lath - type shape.
  • the fabric softening clay is present in the form of agglomerates.
  • These agglomerates comprise, in addition to the clay, an organic humectant.
  • the agglomerates optionally further comprise a polymeric clay flocculating agent.
  • the agglomerates comprise by weight of the agglomerate, from 60% to 99.5% of the clay; from 0.5% to 30% of the humectant; and from 0% to 10% of the clay flocculating agent.
  • the agglomerates further contain a heavy metal sequestering agent. Examples include heavy metal chelators, like EDTA and ethylenediamine tetramethylene phosphonic acid (EDTP).
  • the agglomerates typically contain from 0.1 % to 10% of the chelator.
  • the humectants are selected from glycerol, ethylene glycol, propylene glycol and the dimers and trimers of glycerol and mixtures thereof.
  • the clay agglomerates comprise from 0.5% to 30%, preferably from 2% to 15%, of the humectant.
  • the optional clay flocculating agent is selected from the optional clay flocculating agent
  • Clay-flocculating agents are not commonly used in detergent compositions. On the contrary, one is inclined to use clay dispersants, which aid in removing clay stains from fabrics. Flocculating 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. It has been found that these polymers dramatically enhance the deposition of a fabric softening clay if their molecular weights (weight average) are in the range of from 100,000 to 10 million. Preferred are such polymers having a (weight average) molecular weight of from 150.000 to 5 million.
  • the most preferred polymer is poly (ethylene oxide).
  • Molecular weight distributions can be readily determined using gel permeation chromatography, against standards of poly (ethylene oxide) of narrow molecular weight distributions.
  • the clay agglomerates herein comprise, by weight of the clay, from 0% to 20% clay flocculating agent, preferably from 0.05% to 20% by weight of the clay if the molecular weight is 150.000 - 800.000 and from 0.005% to 2% by weight of the clay if its molecular weight is from 800.000 to 5 million.
  • 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 R 1 R 2 R 3 N, wherein R 1 is C 6 to C 20 hydrocarbyl, R 2 is C 1 to C 20 hydrocarbyl, and R 3 is C 1 to C 10 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 C s to C 20 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. 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
  • R 8 and Rg are C 1 - C 20 alkyl, or ethoxylated alkyl groups of the general formula alkyl-(OCH 2 CH 2 )y, wherein the alkyl substituent is C 1 - C 20 , preferably C 8 - -C 16 , 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.
  • optional softening ingredients include the softening amides of the formula R 10 R 11 NCOR 12 , wherein R 10 and R 11 are independently selected from C 1 - C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl - aryl groups; R 12 is hydrogen, or a C 1 - C22 alkyl or alkenyl, an aryl or alkyl - aryl group.
  • R 10 and R 11 are independently selected from C 1 - C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl - aryl groups
  • R 12 is hydrogen, or a C 1 - 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
  • 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 agglomeration process itself may be performed using any of the techniques and apparatus which are conventional in the art (see e.g. "A review of Detergent Agglomeration” - M.J. DOLAN, HAPPI, April 1987 p 64-85). It can be batchwise or continuous. The optimum operating conditions (preferred granule size and moisture level) can be found by trial adjustments of process parameters such as the liquid spray-on level, rate and droplet size, the residence time, etc.
  • Granulometry 212 ⁇ m (65 mesh) ⁇ min. 80% ⁇ 850 ⁇ m (20 mesh).
  • a reference agglomerate i.e. no glycerol was made in the same way. Both agglomerates were dry mixed with a spray-dried granular detergent to yield the following composi - tions:
  • compositions A and B were then used to wash 4 Kg clean fabric loads in a MIELE washing machine.
  • the water hardness was 3.0 mmol (Ca ++ + Mg ++ )/l and the detergent concentration was 10 g/I.
  • Clean terry towel tracers were added to permit evaluation of 1 cycle and cumulative (4 cycles) softening performance.
  • Softness tracers were line dried prior to assessment by expert judges.
  • a 0 - -- 4 panel score units (p.s.u.) scale was used for grading, in which 0 means no difference and 4 stands for a very big difference.
  • Composition A was rated better for softness than B :
  • composition A in accordance with the invention is superior in fabric softening performance to the prior art composition A.
  • the clay agglomerates may also be incorporated in a laundry additive, as such or with the aid of a water soluble and/or insoluble carrier such as e.g. a sheet or a pouch. These agglomerates, as such or with a suitable carrier, can then be added to the wash liquor on top of a conventional detergent composition.
  • the laundry additive preferably also contains one or more of the additional softening ingredients specified before. The additive may thus be used in conjunction with detergent compositions that themselves do not contain such a clay and/or these other softening ingredients.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Claims (16)

1. Composition détergente granulée comprenant:
a) des ingrédients détergents classiques et
b) des agglomérats d'argile comprenant de 60% à 99,5% en poids d'argile de type smectite et caractérisée en ce qu'elle comprend en outre de 30 à 0,5% en poids d'un agent mouillant organique choisi parmi: le glycérol, l'éthylèneglycol, le propylèneglycol, les dimères et les trimères de glycérol, et leurs mélanges.
2. Composition détergente selon la revendication 1, dans laquelle les agglomérats d'argile comprennent de 2 à 15% en poids de l'agent mouillant organique.
3. Composition détergente selon l'une quelconque des revendications 1 ou 2, caractérisée en ce que les agglomérats d'argile comprennent en outre de 0,005% à 20% en poids de l'argile d'un agent de floculation polymère d'argile.
4. Composition détergente selon la revendication 3, caractérisée en ce que les agglomérats d'argile comprennent en outre de 0,1% à 10% en poids d'un complexant, de préférence l'EDTA, l'EDTP, et leurs mélanges.
5. Composition détergente selon la revendication 3, dans laquelle l'agent de floculation polymère de l'argile a une masse moléculaire moyenne en poids de 150 000 à 5 millions.
6. Composition détergente selon la revendication 3 ou 5, dans laquelle le polymère est dérivé de monomères choisis parmi l'oxyde d'éthylène, l'acrylamide, et l'acide acrylique.
7. Composition détergente selon l'une quelconque des revendications précédentes, comprenant en outre de 0,5% à 5% en poids d'un ammonium quaternaire de formule R4R5R6R7N+X-, dans laquelle R4 représente un alkyle ayant de 10 à 20 atomes de carbone, Rs, R6 et R7 représentent chacun un alkyle en Ci à C4, et X- représente un anion.
8. Composition détergente selon l'une quelconque des revendications précédentes, comprenant en outre de 1 à 10% d'un amide de formule R10 R11 NCOR12, dans laquelle R10 et R11 sont choisis indépendamment parmi les groupes alkyle en Ci à C22, alcényle, hydroxy alkyle, aryle, et alkyl aryle; R12 représente un atome d'hydrogène, ou un groupe alkyle ou alcényle en Ci à C22 ou un groupe aryle ou alkyl aryle, ou représente O - R13, dans laquelle R13 représente un groupe alkyle ou alcényle en Ci à C22, aryle ou alkyl aryle.
9. Composition détergente selon l'une quelconque des revendications précédentes, comprenant en outre de 1 à 10% en poids d'imidazolines de formule 1 - -(R14)amido (R15)-2-(R16)-imidazoline dans laquelle R14, R16, sont choisis indépendamment dans le groupe alkyle en C12 2 à C22 et R15 parmi le groupe alkyle en Ci à C4.
10. Composition détergente selon l'une quelconque des revendications précédentes, comprenant de 1 à 10% en poids d'amines de formule R1 R2 R3 N dans laquelle R1 représente un hydrocarbyle en C6 à C20, R2 représente un hydrocarbyle de Ci à C20; et R3 représente un hydrocarbyle en Ci à C10 ou un atome d'hydrogène.
11. Composition détergente selon l'une quelconque des revendications précédentes, comprenant en outre de 5 à 35% en poids d'un système d'adjuvants, ledit système d'adjuvants comprenant
a) de 1 % à 99% en poids d'un composant de tartrate monosuccinate de structure :
Figure imgb0012
dans laquelle X représente H ou un cation formant sel; et
b) de 1 % à 99% en poids d'un composant tartrate disuccinate de structure:
Figure imgb0013
dans laquelle X représente H ou un cation formant sel.
12. Additif de lessive contenant un agglomérat d'argile comprenant de 70% à 99,5% en poids d'argile de type smectite et de 30% à 0,5% en poids d'un agent mouillant organique tel que défini dans la revendication 1.
13. Additif selon la revendication 12, dans lequel l'agent mouillant organique représente de 2 à 15% en poids.
14. Additif selon les revendications 12 et 13, qui comprend en outre de 0,005% à 20% en poids de l'argile d'un agent polymère de floculation d'argile.
15. Additif selon les revendications 12 à 14, qui en outre contient un ingrédient supplémentaire adoucissant tel que défini dans les revendications 8, 9, et 10 à raison de 2% à 50% en poids, de préférence de 5 à 30% en poids.
16. Additif selon les revendications 12 à 15, qui est déposé sur/contenu dans un support approprié hydrosoluble ou insoluble dans l'eau.
EP88202253A 1987-10-19 1988-10-10 Compositions détergentes Expired - Lifetime EP0313146B2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88202253T ATE89856T1 (de) 1987-10-19 1988-10-10 Reinigungsmittel.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8724463 1987-10-19
GB878724463A GB8724463D0 (en) 1987-10-19 1987-10-19 Detergent compositions
GB8807013 1988-03-24
GB888807013A GB8807013D0 (en) 1988-03-24 1988-03-24 Detergent compositions

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EP0313146A2 EP0313146A2 (fr) 1989-04-26
EP0313146A3 EP0313146A3 (en) 1989-08-09
EP0313146B1 true EP0313146B1 (fr) 1993-05-26
EP0313146B2 EP0313146B2 (fr) 2001-09-05

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EP (1) EP0313146B2 (fr)
JP (1) JP2620338B2 (fr)
DE (1) DE3881329T3 (fr)
DK (1) DK581988A (fr)
GR (1) GR3007979T3 (fr)
IE (1) IE61345B1 (fr)
IN (1) IN174322B (fr)
MX (1) MX169939B (fr)

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GB8924294D0 (en) * 1989-10-27 1989-12-13 Unilever Plc Detergent compositions
DE69019973T2 (de) * 1990-10-29 1995-11-16 Procter & Gamble Wäschebehandlungszusammensetzung.
ES2080241T3 (es) * 1991-09-27 1996-02-01 Procter & Gamble Composiciones suavizantes de tejidos concentradas.
DE69327654T2 (de) * 1993-11-11 2000-08-31 The Procter & Gamble Company, Cincinnati Beim Waschen weichmachende Zusammensetzungen
EP0709452A1 (fr) 1994-10-27 1996-05-01 The Procter & Gamble Company Compositions de nettoyage contenant des xylanases
WO1997009406A1 (fr) * 1995-09-01 1997-03-13 The Procter & Gamble Company Composition detergente renfermant un polymere floculant l'argile avec taille des particules inferieure a 250 microns
DE69739020D1 (de) 1996-11-04 2008-11-13 Novozymes As Subtilase varianten und verbindungen
JP4044143B2 (ja) 1996-11-04 2008-02-06 ノボザイムス アクティーゼルスカブ ズブチラーゼ変異体及び組成物
EP1086211B1 (fr) 1998-06-10 2011-10-12 Novozymes A/S Nouvelles mannanases
GB2348435A (en) * 1999-04-01 2000-10-04 Procter & Gamble Softening compositions
US6881717B1 (en) 1999-04-01 2005-04-19 The Procter & Gamble Company Fabric softening component
GB2349390A (en) * 1999-04-30 2000-11-01 Procter & Gamble Cleaning compositions comprising compressed clay
US6764986B1 (en) 1999-07-08 2004-07-20 Procter & Gamble Company Process for producing particles of amine reaction products
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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
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JP2006517989A (ja) 2003-02-18 2006-08-03 ノボザイムス アクティーゼルスカブ 洗剤組成物
TW200540263A (en) * 2004-02-13 2005-12-16 Kao Corp Process for washing
ES2960774T3 (es) * 2006-01-23 2024-03-06 Procter & Gamble Composiciones que contienen enzima y agente de matizado de tejidos
EP1894993A1 (fr) * 2006-08-28 2008-03-05 Süd-Chemie Ag Additif détergent au base de minéraux d'argile et des copolymers contenant du PVP
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
EP2138563A1 (fr) * 2008-06-25 2009-12-30 The Procter and Gamble Company Composition de détergent de blanchisserie fine, contenant un agent de surface détersif anionique, et comprenant en outre de l'argile
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
GB0918914D0 (en) 2009-10-28 2009-12-16 Revolymer Ltd Composite
EP2380958A1 (fr) * 2010-04-19 2011-10-26 The Procter & Gamble Company Composition détergente solide comprenant du carbonate de glycérol
EP2712363A1 (fr) 2011-04-29 2014-04-02 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
US20140073548A1 (en) 2011-04-29 2014-03-13 Danisco Us Inc. Detergent compositions containing bacillus sp. mannanase and methods of use thereof
EP2935573A1 (fr) 2012-12-19 2015-10-28 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.
JP7364330B2 (ja) 2015-11-05 2023-10-18 ダニスコ・ユーエス・インク パエニバチルス（Ｐａｅｎｉｂａｃｉｌｌｕｓ）属種及びバチルス（Ｂａｃｉｌｌｕｓ）属種のマンナナーゼ
CN109689197B (zh) 2016-09-16 2023-06-23 国际香料和香精公司 用粘度控制剂稳定的微胶囊组合物
WO2024050339A1 (fr) 2022-09-02 2024-03-07 Danisco Us Inc. Variants de mannanases et procédés d'utilisation

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Also Published As

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DK581988A (da) 1989-04-20
DE3881329T3 (de) 2002-05-23
JPH01221495A (ja) 1989-09-04
GR3007979T3 (fr) 1993-08-31
MX169939B (es) 1993-08-02
DE3881329D1 (de) 1993-07-01
IE61345B1 (en) 1994-11-02
EP0313146A2 (fr) 1989-04-26
JP2620338B2 (ja) 1997-06-11
EP0313146B2 (fr) 2001-09-05
EP0313146A3 (en) 1989-08-09
IN174322B (fr) 1994-11-05
DK581988D0 (da) 1988-10-19
IE883161L (en) 1989-04-19
DE3881329T2 (de) 1993-12-16

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