EP0381397A2 - Teilchenförmige Detergenszusammensetzungen und ihre Verwendung - Google Patents

Teilchenförmige Detergenszusammensetzungen und ihre Verwendung Download PDF

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Publication number
EP0381397A2
EP0381397A2 EP19900300869 EP90300869A EP0381397A2 EP 0381397 A2 EP0381397 A2 EP 0381397A2 EP 19900300869 EP19900300869 EP 19900300869 EP 90300869 A EP90300869 A EP 90300869A EP 0381397 A2 EP0381397 A2 EP 0381397A2
Authority
EP
European Patent Office
Prior art keywords
parts
surfactant
detergent composition
detergent
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19900300869
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English (en)
French (fr)
Inventor
Johan Haverkamp
Johanna Antonia Van Der Gugten
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.)
Unilever PLC
Unilever NV
Original Assignee
Unilever PLC
Unilever NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Unilever PLC, Unilever NV filed Critical Unilever PLC
Publication of EP0381397A2 publication Critical patent/EP0381397A2/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38609—Protease or amylase in solid compositions only
    • 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38645—Preparations containing enzymes, e.g. protease or amylase containing cellulase

Definitions

  • This invention relates to particulate, e.g. granular, enzymatic detergent compositions.
  • the invention relates to detergent granulates of high density, and especially for example those that contain enzyme, e.g. lipase.
  • EP 0 219 328 discloses a granular low-phosphate detergent composition prepared by spray-drying a slurry to give a base powder containing a low to moderate level of sodium tripolyphosphate builder and low levels of inorganic salts, and then postdosing solid material including sodium sulphate of high bulk density and of smaller particle size than the base powder, thus filling the voids between base powder particles and producing a product of high bulk density.
  • JP 61-069897 discloses a batch process in which a spray-dried detergent powder containing surfactant and builder is subjected successively to pulverising and granulating treatments in a high-speed mixer, the granulation being carried out in the presence of an "agent for improving surface properties" and optionally a binder. It would appear that in the high-speed mixer, the spray-dried powder is initially broken down to a fine state of division; the surface-improving agent and optional binder are then added and the pulverised material granulated to form a final product of high bulk density.
  • the surface-improving agent which is a finely divided particulate solid such as fine sodium aluminosilicate, is apparently required in order to prevent the composition from forming into large balls or cakes:
  • the examples of spray-dried starting powders described in the Kao specification contain very high levels of surfactant (45% by weight) and relatively low levels of builder salts, and are likely to have a high tendency towards caking and balling.
  • EP 0 229 671 discloses postdosing a crystalline alkaline inorganic salt, for example, sodium carbonate, to a spray-dried base powder to produce a high bulk density product.
  • a crystalline alkaline inorganic salt for example, sodium carbonate
  • GB 1 517 713 (Unilever), which discloses a process in which a detergent powder produced by spray-drying or pan granulation is spheronised and granulated in a "marumerizer” (Trade Mark) with some increase in bulk density.
  • EP 0 220 024 (Procter & Gamble) is also concerned with the densification of a spray-dried powder containing a high level (30-85% by weight) of anionic surfactant.
  • the powder is compacted and granulated, inorganic builder (sodium tripolyphosphate, or sodium aluminosilicate and sodium carbonate) being added before compaction.
  • inorganic builder sodium tripolyphosphate, or sodium aluminosilicate and sodium carbonate
  • EP 0 150 613 (Unilever) concerns detergent compositions involving base powder granules containing detergent-active materials and amorphous aluminosilicate together with a postdosed peroxygen bleach compound, for improved ion-exchange properties and bleach stability within a defined range of moisture contents, and discloses examples (including comparative example) of fully formulated detergent powders with 6-7% anionic active, 1.5-4% nonionic active, 0-5% soap, 5% Na silicate, 21-40% amorphous aluminosilicate, 0 or 10% NTA, 2.4-9.9% sodium sulphate, 15-20% perborate, O-18% tripolyphosphate, 0-2% TAED,and 4.1-18% moisture. It has been proposed (Research Disclosure 29056, 1988) to use lipase in connexion with detergent compositions of EP 0 150 613.
  • EP 0 168 526 discloses further aluminosilicate-­containing detergent powders and the use of enzyme (protease and/or amylase) granulates therein, comprising e.g. enzyme 15-18%, zeolite 20-31%, starch 26-36%, CMC 9-10%, and PEG and other minor additives. It has been proposed (Research Disclosure 29056, 1988) to use lipase in connexion with compositions of EP 0 168 526.
  • washing/bleaching/cleaning processes using in the wash liquor finely-divided aluminosilicates or borosilicates with calcium exchange capacity, and discloses typical washing compositions with 5-30% (especially 5-8% anonic + 2-10% nonionic) anionic/nonionic actives, 5-70% ion-exchange materials, 2-45% complex-formers for calcium, 0-50% alkaline builders, 0-50% bleaching agents.
  • washing compositions that contain 14-16.5% anionic + nonionic detergent, 10-11% cation-exchanger, 30-35% aluminosilicate, 20-26.5% Na perborate trihydrate, 6.6%-8.9% water,
  • US 4 287 101 (Lion Fat & Oil Co, assignees of Nishio et al) concerns enzyme-containing detergent compositions, including e.g. protease and optionally amylase or lipase, e.g. as powder or particles, with compsitions defined by reference to a trinagular diagram and based on at least 25% in aggregate of C10-20 alpha-olefin sulphonate plus another sulphate or sulphonate detergent active, and a pyrophosphate.
  • enzyme-containing detergent compositions including e.g. protease and optionally amylase or lipase, e.g. as powder or particles, with compsitions defined by reference to a trinagular diagram and based on at least 25% in aggregate of C10-20 alpha-olefin sulphonate plus another sulphate or sulphonate detergent active, and a pyrophosphate.
  • Comparative examples given in this specification show detergent compositions containing 8% AOS, animal fatty alkyl-11EO 0.5%, Na orthophosphate 10%, Na pyrophosphate 6%, sodium silicate 10%, Glauber's salt 4.46-4.76%, magnesium sulphate 4%, sodium perborate tetrahydrate 32%, cationic agglomerate 16.4% (based on 25.6% ditallow dimethyl ammonium chloride, 8,5% fatty alcohol, 48.8% Na montmorillonite clay, 2.6% Na pyrophosphate and 14.5% water), and minor additives.
  • JA 63-017996 discloses phosphorus-free enzyme-containing powder detergents after-blended with alkaline inorganic builder, to improve enzyme stabilisation.
  • enzyme-containing detergent powders are provided for example in JA 63-078000 (Lion), JA 63-069894 (Kao), JA 62-260900 (Sunstar), JA 62-068898 (Lion), JA 62 043499 (Kao), JA 61-291693 (Kao), JA 61-238898 (Lion), JA 59-221396 (lion) and JA 58-045300 (Lion).
  • a further aim is to incorporate into high bulk density powders and/or granulates compositions which have suitable properties to support enzyme activities, and particularly for example lipase activity.
  • detergent granulates and powders e.g. of high-bulk-density, e.g. higher than about 600 g/l, e.g. at least about 650 g/l, preferably at least about 700 g/l, e.g. about 750 g/l or about 800 g/l or more, with high levels of detergent actives, e.g. at least 15% (wt), often around 18-23% or higher.
  • detergent granulates and powders e.g. of high-bulk-density which have a low salt (esp. neutral salt) content, e.g. those that yield a wash solution with ionic strength much lower than the ionic strength derived from standard washing powders, e.g. ionic strength of about 0.04 or less, e.g. about 0.03 or less, e.g. about 0.025 or less or about 0.02 or less, as compared with levels of about 0.06 - 0.09 or more derived from current washing powders, when used in standard quantity so as to yield a washing solution with (e.g.) about 0.8 g/l surfactant concentration.
  • the upper ionic strength limit may be up to 0.05.
  • the invention provides an enzymatic detergent composition in the form of a granulate or powder, comprising surfactant, enzyme and optionally normal detergent adjuncts, characterised in that, in combination, said composition (a) has a bulk density higher than about 600 g/l, and (b) has an electrolyte content such that said composition yields a wash solution with ionic strength lower than about 0.04, (with the proviso that the ionic strength may be up to about 0.05 when phosphate builder is present), when said composition is dissolved or dispersed in aqueous liquid in an amount that gives about 0.8 g/l surfactant concentration.
  • embodiments of this invention incorporating lipase in low-ionic-strength detergent formulations can give improved fabric wash results in respect of the odour quality/quantity of the fabrics after washing, as compared with results obtained using lipase enzyme in connection with detergents of higher ionic strength.
  • a convenient water type for comparing ionic strengths of various detergent compositions in use is for example a water having 15 degrees French hardness.
  • detergent granulates and powders e.g. of high-bulk-density which have a low or even close-to-zero content of neutral salt (e.g. sodium sulphate), e.g. usually less than 10%, often less than 5% to 2%, or even less than 1% or absent.
  • neutral salt e.g. sodium sulphate
  • the detergent compositions of the invention may for example comprise either phosphates or related builders or aluminosilicates or related builders or mixtures of the two types. Very often a level for such materials in the range of the order of about 25-40% by weight will be found useful, more broadly at least about 15% or for example up to about 45%.
  • examples of the compositions of the invention may sometimes have up to 15% neutral salt content, e.g. sodium sulphate.
  • Enzymes other than lipase include protease, amylase, oxidase and/or cellulase.
  • compositions can comprise lipase enzyme in for example an amount in the range 50 to 30,000 (LU) lipase units per gram of the surfactant system or of the detergent composition.
  • lipase units are defined as they are in EP 0 258 068 (Novo).
  • lipase enzyme shows surprisingly little inhibition.
  • the lipolytic enzyme can usefully be added in the form of a granular composition of lipolytic enzyme with carrier material (e.g. as in EP 0 258 068 and Savinase and Lipolase products of Novo).
  • carrier material e.g. as in EP 0 258 068 and Savinase and Lipolase products of Novo.
  • the added amount of lipolytic enzyme can be chosen within wide limits, for example 50 to 30,000 LU/g of granular detergent composition, e.g. often at least 100 LU/g, very usefully at least 500 LU/g, sometimes preferably above 1000, above 2000 LU/g or above 4000 LU/g or more, thus very often within the range 50-4000 LU/g and possibly within the range 200-1000 LU/g.
  • the lipolytic enzyme can be chosen from among a wide range of lipases: in particular the lipases described in for example the following patent specifications, EP 0 214 761 (Novo), EP 0 258 068 (Novo) and especially lipases showing immunological cross-reactivity with antisera raised against lipase from Thermomyces lanuginosus ATCC 22070, EP 0 205 208 (Unilever) and EP 0 206 390 (Unilever), and especially lipases showing immunological cross-reactivity with antisera raised against lipase from Chromobacter viscosum var lipolyticum NRRL B-3673, or against lipase from Alcaligenes PL-679, ATCC 31371 and FERM-P 3783, also the lipases described in specifications WO 87/00859 (Gist-Brocades) and EP 0 204 284 (Sapporo Breweries).
  • Suitable in particular are for example the following commercially available lipase preparations: Novo Lipolase, Amano lipases CE, P, B, AP, M-AP, AML, and CES, and Meito lipases MY-30, OF, and PL, also esterase MM, Lipozym, SP225, SP285, Saiken lipase, Enzeco lipase, Toyo Jozo lipase and Diosynth lipase (Trade Marks).
  • Lipase gene e.g. the gene for lipase from Thermomyces lanuginosus or from a mutant thereof, and introduction and expression of the gene or derivative thereof in a suitable producer organism such as an Aspergillus.
  • a suitable producer organism such as an Aspergillus.
  • the techniques described in WO 88/02775 (Novo), EP 0 243 338 (Labofina) and EP 0 268 452 (Genencor) may be applied and adapted.
  • Amylase can for example be used when present in an amount in the range about 1 to about 100 MU (maltose units) per gram of detergent composition, (or 0.014-1.4, e.g. 0.07-0.7, KNU/g (Novo units)).
  • Cellulase can for example be used when present in an amount in the range about 0.3 to about 35 CEVU units per gram of the detergent composition.
  • Protease can for example be used when present in an amount in the range about 0.0002 to about 0.05 Anson units per gram of the detergent composition.
  • the detergent compositions may be based on non-soap surfactant, e.g. usually at least partially anionic surfactant.
  • Suitable anionic surfactants are well known to those skilled in the art, and include linear alkylbenzene sulphonates, primary alcohol sulphates, alkyl ether sulphates, alpha-olefin sulphonates, internal olefin sulphonates, fatty acid ester sulphonates and combinations thereof. It is preferred that (e.g. alpha-) olefin sulphonates are absent or not used in substantial or appreciable quantity, e.g. less than 10-15%, e.g. less than 5%, of the total surfactant of the composition.
  • nonionic surfactant such as alkoxylated fatty alcohols may also be present, preferably in a minor amount.
  • surfactant component of the compositions of the invention may be constituted by 10 to 35% by weight of anionic surfactant preferably alkylbenzene sulphonate and/or primary alcohol sulphate and 0 to 10% by weight of nonionic surfactant.
  • the detergent compositions may furthermore include the following usual detergent ingredients in the usual amounts. They may be built or unbuilt, and may be of the zero-P type (i.e. not containing any phosphorus-­containing builders). Thus the composition may contain in aggregate for example from 1-50%, e.g. at least about 5% and often up to about 35-40% by weight, of one or more organic and/or inorganic builders.
  • Typical examples of such builders include those already mentioned above, and more broadly include alkali metal ortho, pyro, and tripolyphosphates, alkali metal carbonates, either alone or in admixture with calcite, alkali metal citrates, alkali metal nitrilotriacetates, carboxymethyloxy succinates, zeolites, polyacetal carboxylates and so on.
  • the detergent compositions may contain from 1-35% of a bleaching agent or a bleach precursor or a system comprising bleaching agent and/or precursor with activator therefor.
  • Further optional ingredients are lather boosters, foam depressors, anticorrosion agents, soil-suspending agents, sequestering agents, anti-soil redeposition agents, perfumes, dyes, stabilising agents for the enzymes and so on.
  • compositions as described in the present specification can show advantage in supporting the activity of enzymes such as lipase, and in providing improved odour performance.
  • enzymes such as lipase
  • compositions may in practice be formulated to achieve low ionic strengths.
  • formulation examples mentioned in the earlier specification may be so formulated.
  • compositions can for example be prepared by any suitable processing technique, for example by adaptation of the techniques disclosed in the documents cited above for making concentrated powders and granulates, which are hereby specifically incorporated by reference.
  • a zero-phosphate high-bulk density composition is made up with the following constitution (% wt): Alkylbenzenesulphonate 10 C12-C15 alkyl-3EO Nonionic 6 C12-C15 alkyl-7EO Nonionic 5 Na carbonate 12 zeolite (Degussa A or equivalent) 32 Sokolan CP5 maleic/acrylic polymer co-builder 5 Na perborate tetrahydrate 15.5 TAED 4 Protease (e.g. Savinase T grade ) 1 Lipase (e.g. Lipolase T grade ) 1 Minor additives, perfumes, etc.
  • Protease e.g. Savinase T grade
  • Lipase e.g. Lipolase T grade
  • the composition can be prepared as follows: first, a detergent base is obtained by spray-drying an aqueous slurry comprising the bulk constituents other than the bleach precursors, enzymes and minors.
  • the base powder is passed through an airlift and fed into a Lödige recycler (type Lödige CB30 - Trade Mark), operated at a rotational speed of about 1600 rpm, and processed therein with a mean residence time of about 10 seconds, after which it is passed to a plough-share mixer (type Lödige KM300 - Trade Mark), a continuous moderate-speed granulator/densifier, operated at a rotational speed of about 120 rpm, with a mean residence time of about 3 minutes.
  • a Lödige recycler type Lödige CB30 - Trade Mark
  • a plough-share mixer type Lödige KM300 - Trade Mark
  • a continuous moderate-speed granulator/densifier operated at a rotational speed of about 120 rpm, with
  • the resulting high-density granulate is dried in a fluid-bed dryer and sieved if desired.
  • a particulate base of high bulk density and small particle size there is formed a particulate base of high bulk density and small particle size; the high-density base is post-dosed with the remaining constituents.
  • the processing conditions can be adjusted to control the final bulk density, e.g. to about 800 g/l.
  • composition is found to give an ionic strength in use of less than about 0.02 under the conditions mentioned above.
  • a phosphate-built high-bulk density composition is made up with the following constitution (% wt) and processing as in Example 1 to a final bulk density of about 800 g/l: Linear alkylbenzenesulphonate 10 C12-C15 alkyl-3EO Nonionic 4.5 C12-C15 alkyl-7EO Nonionic 5.5 Na perborate tetrahydrate 16 TAED 83% 4.3 Dequest 2047 0.3 Na tripolyphosphate (STPP) 33 Blue speckles (STPP) 2 Na silicate 6 Na carbonate 2 Protease (Savinase 6T) 0.5 Lipase (Lipolase 100T) 0.5 with minor additives including perfumes, and water content 9.6%.
  • This composition provides an ionic strength of about 0.045 when used at a rate which provides 0.8 g/l surfactant in a wash liquor.
  • a zero-phosphate high-bulk density composition is made up with the following constitution (% wt) and processing as in Example 1 to a final bulk density of about 800 g/l: Linear alkylbenzenesulphonate 9 C12-C15 alkyl-3EO Nonionic 5 C12-C15 alkyl-7EO Nonionic 6 Na perborate tetrahydrate 14 TAED 83% 3.6 Dequest 2047 0.7 Zeolite (Degussa A or equivalent) 30 Speckles 0.5 Na carbonate 9 Protease (Savinase 6T) 0.6 Lipase (Lipolase 100T) 0.7 Silicone oil antifoam carried on particulate Na carbonate carrier 3 with minor additives including perfumes, and water content 11%.
  • This composition provides an ionic strength of less than about 0.02 when used at a rate which provides 0.8 g/l surfactant in a wash liquor.

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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)
  • Detergent Compositions (AREA)
EP19900300869 1989-01-30 1990-01-29 Teilchenförmige Detergenszusammensetzungen und ihre Verwendung Withdrawn EP0381397A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8902009 1989-01-30
GB898902009A GB8902009D0 (en) 1989-01-30 1989-01-30 Particulate detergent compositions and their use

Publications (1)

Publication Number Publication Date
EP0381397A2 true EP0381397A2 (de) 1990-08-08

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EP19900300869 Withdrawn EP0381397A2 (de) 1989-01-30 1990-01-29 Teilchenförmige Detergenszusammensetzungen und ihre Verwendung

Country Status (7)

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EP (1) EP0381397A2 (de)
JP (1) JPH02245100A (de)
AU (1) AU4890990A (de)
BR (1) BR9000376A (de)
CA (1) CA2008948A1 (de)
GB (1) GB8902009D0 (de)
ZA (1) ZA90670B (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495258A1 (de) * 1991-01-16 1992-07-22 The Procter & Gamble Company Waschmittelzusammensetzungen mit hochaktiven Cellulasen und Tonweichmachern
EP0495554A1 (de) * 1991-01-16 1992-07-22 The Procter & Gamble Company Waschmittelzusammensetzungen mit hochaktiven Cellulasen und quaternären Ammoniumverbindungen
EP0540784A1 (de) * 1991-11-06 1993-05-12 The Procter & Gamble Company Zusammensetzungen zur Verhinderung der Farbstoffübertragung
US5443750A (en) * 1991-01-16 1995-08-22 The Procter & Gamble Company Detergent compositions with high activity cellulase and softening clays
EP0686186A4 (de) * 1993-02-26 1995-09-19 Procter & Gamble Enzymgranulate hoher aktivität
WO1996008554A1 (de) * 1994-09-16 1996-03-21 Henkel Kommanditgesellschaft Auf Aktien Pulverförmiges, enzymhaltiges bleich- und waschmittel
US5520838A (en) * 1991-01-16 1996-05-28 The Procter & Gamble Company Compact detergent compositions with high activity cellulase
WO1996016154A1 (en) * 1994-11-18 1996-05-30 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5698508A (en) * 1994-12-22 1997-12-16 Kao Corporation Powdered detergent composition
WO1999029821A1 (en) * 1997-12-05 1999-06-17 Genencor International, Inc. Method for enhancing activity of cellulase in industrial applications by adjusting ionic strength
EP2199386A1 (de) 1993-10-08 2010-06-23 Novozymes A/S Amylasevarianten
WO2014092950A1 (en) * 2012-12-11 2014-06-19 The Dial Corporation Cleansing compositions and products including soap flakes and methods for making the same
AU2021204239B2 (en) * 2016-03-02 2023-04-20 Chem-Dry, Inc. Stain and odor treatment

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU7333196A (en) * 1996-10-17 1998-05-15 Showa Denko Kabushiki Kaisha Lipase, process for producing the same, microorganism producing the same, and use of the lipase

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495257A1 (de) * 1991-01-16 1992-07-22 The Procter & Gamble Company Kompakte Waschmittelzusammensetzungen mit hochaktiven Cellulasen
EP0495554A1 (de) * 1991-01-16 1992-07-22 The Procter & Gamble Company Waschmittelzusammensetzungen mit hochaktiven Cellulasen und quaternären Ammoniumverbindungen
US5443750A (en) * 1991-01-16 1995-08-22 The Procter & Gamble Company Detergent compositions with high activity cellulase and softening clays
US5520838A (en) * 1991-01-16 1996-05-28 The Procter & Gamble Company Compact detergent compositions with high activity cellulase
EP0495258A1 (de) * 1991-01-16 1992-07-22 The Procter & Gamble Company Waschmittelzusammensetzungen mit hochaktiven Cellulasen und Tonweichmachern
EP0540784A1 (de) * 1991-11-06 1993-05-12 The Procter & Gamble Company Zusammensetzungen zur Verhinderung der Farbstoffübertragung
EP0686186A4 (de) * 1993-02-26 1995-09-19 Procter & Gamble Enzymgranulate hoher aktivität
USH1653H (en) * 1993-02-26 1997-06-03 The Procter & Gamble Company High active enzyme granulates
EP2199386A1 (de) 1993-10-08 2010-06-23 Novozymes A/S Amylasevarianten
WO1996008554A1 (de) * 1994-09-16 1996-03-21 Henkel Kommanditgesellschaft Auf Aktien Pulverförmiges, enzymhaltiges bleich- und waschmittel
WO1996016154A1 (en) * 1994-11-18 1996-05-30 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5707950A (en) * 1994-11-18 1998-01-13 The Procter & Gamble Company Detergent compositions containing lipase and protease
US5698508A (en) * 1994-12-22 1997-12-16 Kao Corporation Powdered detergent composition
WO1999029821A1 (en) * 1997-12-05 1999-06-17 Genencor International, Inc. Method for enhancing activity of cellulase in industrial applications by adjusting ionic strength
WO2014092950A1 (en) * 2012-12-11 2014-06-19 The Dial Corporation Cleansing compositions and products including soap flakes and methods for making the same
AU2021204239B2 (en) * 2016-03-02 2023-04-20 Chem-Dry, Inc. Stain and odor treatment

Also Published As

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GB8902009D0 (en) 1989-03-22
CA2008948A1 (en) 1990-07-30
BR9000376A (pt) 1990-12-04
AU4890990A (en) 1990-08-02
JPH02245100A (ja) 1990-09-28
ZA90670B (en) 1991-09-25

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