WO1993025651A1 - Composition pour le lavage de la vaisselle en machine - Google Patents

Composition pour le lavage de la vaisselle en machine Download PDF

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Publication number
WO1993025651A1
WO1993025651A1 PCT/EP1993/001461 EP9301461W WO9325651A1 WO 1993025651 A1 WO1993025651 A1 WO 1993025651A1 EP 9301461 W EP9301461 W EP 9301461W WO 9325651 A1 WO9325651 A1 WO 9325651A1
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WO
WIPO (PCT)
Prior art keywords
clay
water
weight
composition according
finely divided
Prior art date
Application number
PCT/EP1993/001461
Other languages
English (en)
Inventor
François Delwel
Paul Michael Hill
Willem Michaël Maria MÖHLMANN
Original Assignee
Unilever N.V.
Unilever Plc
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 N.V., Unilever Plc filed Critical Unilever N.V.
Priority to AU43246/93A priority Critical patent/AU4324693A/en
Publication of WO1993025651A1 publication Critical patent/WO1993025651A1/fr

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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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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

Definitions

  • This invention relates to machine dish- and warewashing compositions. These compositions are used for the cleaning of housewares such as pots, pans, dishes, cups, saucers, bottles, glassware, crockery, cutlery and other kitchen utensils in automatic-dishwashing and warewashing machines. For brevity sake these compositions are referred to in the description as machine dishwashing compositions.
  • Machine dishwashing compositions usually contain as main components a builder or builder mixture, buffering and/or alkaline agents, a bleaching agent which may be a chlorine or oxygen bleach, and lately also enzymes. Such machine dishwashing compositions are used in the main wash step of machine dishwashing and in general have a satisfactory cleaning performance.
  • the layered clay minerals suitable for the above purpose of use belong to the geological classes of the smectites, the kaolins, the illites, the chlorites, the attapulgites and the mixed layer clays.
  • Typical examples of specific clays belonging to these classes are:
  • smectites e.g. montmorillonite, bentonite,pyrophylite, hectorite, saponite, sauconite, nontronite, talc, beidellite, volchonskoite, vermiculite; kaolins, e.g. kaolinite, dickite, nacrite, antigorite, anauxite, halloysite, indellite, chrysotile; illites, e.g. bravaisite, muscovite, paragonite, phlogopite, biotite; chlorites, e.g.
  • the layered clay minerals may be either naturally occurring or synthetic.
  • Preferred clay minerals are natural or synthetic hectorites, montmorillonites and bentonites, and of these the hectorites are especially preferred.
  • Many of the above clays are commercially available, and typical examples of commercial hectorites are the Laponites ® ex
  • Particularly preferred clays are the commercial synthetic hectorites ex Laporte Industries Ltd, known under the tradename Laponites such as Laponite S, Laponite XLS, Laponite RD, Laponite RDS and Laponite XLG.
  • the effective level of the layered clay to be included in machine dishwashing compositions generally lies within a range of 0.1 to 40%, preferably from 0.5 to 10%, and most preferably from 0.5 - 5% by weight.
  • the present invention therefore relates to machine dishwasing compositions comprising a layered clay for reducing film and spot formation on the washed articles.
  • Machine dishwashing powder compositions are not true fine powders, but consist of granules and particles of a size lying within the range of 0.2 to 2.0 mm, normally, from 0.25 to 1.5 mm. Finely divided clay powder as normally supplied cannot be used for incorporating in such granulated machine dishwashing compositions as it will segregate in the pack, with the consequence of non-uniformity of product composition in the pack upon reaching the consumer.
  • Laponite XLG standard grade
  • Laponite XLS special grade
  • It is another object of the invention to provide a machine dishwasing powder composition comprising a clay material which does not segregate in the pack and does not deposit on and blocking the dishwashing machine filter.
  • the clay material is provided in the form of granules of a size of about 0.2 - 2.0 mm, obtained by:
  • the invention provides a machine dishwashing powder composition
  • a machine dishwashing powder composition comprising a layered clay, characterized in that said layered clay is in the form of granulated particles of a size of from about 0.2-2.0 mm, obtained by:
  • granulated clay usable in the present invention may be:
  • a co-granulate comprising a matrix of a finely divided layered clay material, a solid particulate material and a water-soluble film-forming polymeric binder material having average molecular weight of from about 500- 1,000,000;
  • a conglutinate comprising a core of sodium disilicate carrier material, a coating layer of a nonionic surface-active agent enrobing said core, and a finely divided layered clay material attached to the glutinous coating layer of the core, or
  • Preferred granulated clay is a co-granulate as defined and obtained under 1) hereinbefore.
  • Suitable solid particulate materials for use herein are for example carbonates, citrates, silicates, peroxygen bleaching agents, bleach activators, bleach catalysts and mixtures thereof. Crystalline materials which by themselves are ingredients of machine dishwashing compositions are preferred.
  • granulated clay particles obtained by co- granulation will have a composition comprising:
  • a preferred solid particulate material to co-granulate with is a bleach activator, especially N, N, N 1 , N 1 -tetraacetyl ethylene diamine (TAED) .
  • TAED tetraacetyl ethylene diamine
  • a bleach catalyst is also used this can also be incorporated in the granule composition. It is furthermore preferred that the granule composition is exempt of inert non-functional ingredients, i.e. fillers, such as sodium sulphate.
  • the preferred clays for use in the present invention are the commercially available synthetic hectorite in finely divided powdered form ex Laporte Industries Ltd, known as Laponite ® clay.
  • Film forming polymeric materials which can be used in the invention are, for example, carbohydrates and derivatives, such as carbohydrate ethers; polymers or copolymers from vinyl monomers, such as vinylacetate (and its hydrolysate vinyl alcohol) , vinyl pyrrolidone, methyl acrylate, acrylic acid, methacrylic acid, maleic acid (anhydride) , styrene, ⁇ tyrene sulphonate or mixtures thereof.
  • suitable polymeric materials are polyvinyl acetate, polyvinyl pyryolidone, copolymers of polyvinyl alcohol/polyvinyl acetate; carboxy methyl cellulose; dextrine modified vinylacetate polymers; and homo- or copoly eric polycarboxylic acids or salts thereof, such as the polyacrylic acids or polyacrylates, copolymers of maleic acid (anhydride) and acrylic or methacrylic acid, and copolymers of maleic acid (anhydride) and vinyl-methyl ether.
  • Preferred materials are the copolymers of maleic acid (anhydride) and (meth)acrylic acid , such as being sold under the trade names Sokalan® CP4 and Sokalan® CP5 ex BASF.
  • the nonionic surface-active agent for use as coating layer to render the surfaces of the core material glutinous can be any nonionic surfactant which is liquid or semi-paste-like at room temperature. Higher melting liquifiable nonionic surface-active agents may also be used.
  • nonionic surface active agents are C 8 -C 20 monohydric aliphatic alcohols condensed with 5 to 25 moles of ethylene oxide, such as tallow fatty alcohol condensed with 20-25 moles of ethylene oxide, isotridecyl alcohol condensed with 7-11 ethylene oxide, secondary C 11 -C 15 alcohols condensed with 3-10 ethylene oxide, fatty acid mono- and di- alkylolamides with 10-20 carbonatoms in the fatty acid residue and ethoxylated derivatives thereof.
  • Preferred nonionic surfactants are however the low to non-foaming nonionic surfactants, normally incorporated in machine dishwashing compositions to improve detergency and to suppress excessive foaming due to some protein soil.
  • Examples thereof are the low-to-non-foaming ethoxylated straight chain alcohols of the Plurafac ® RA series, supplied by the Eurane Company; of the Lutensol ® LF series, supplied by the BASF Company; of the Triton ® DF series, supplied by the Rohm & Haas Company; and of the Synperonic ® LF series, supplied by the ICI Company.
  • the granulated clay particles can be manufactured by using any known granulation technique e.g. with a pan granulator, a rotating drum or a Schugi ® granulator, such as the Schugi Flexomix ® 160, wherein 1) an agitated powder mixture comprising the clay is sprayed with the proper amount of polymer-solution, optionally followed by drying e.g. in a fluid bed drier; 2) a nonionic surface active agent is mixed with a granular sodium disilicate carrier material and subsequently affixing the finely divided clay thereon; or 3) an agitated clay powder is sprayed with water or an alkaline silicate solution.
  • a pan granulator e.g. with a pan granulator, a rotating drum or a Schugi ® granulator, such as the Schugi Flexomix ® 160
  • an agitated powder mixture comprising the clay is sprayed with the proper amount of polymer-solution, optionally followed by drying e.g.
  • the granulated clay particles disperse well and do not cause deposits of clay material on or blocking of the micro-filter of dishwashing machines, provided the clay material used in the granulation process is a powder of a size that is smaller than the micro-filter mesh size. Finely divided clay powder as supplied by manufacturers have particle size of about 20 to 200 ⁇ m, which is normally suitable for use in the present invention.
  • the machine dishwashing powder of the invention will normally also contain a builder or builder mixture, buffering and/or alkaline agents, and a bleaching agent, and optionally but preferably also an enzyme or mixtures of enzymes.
  • Builder materials are well-known in the art and many types of organic and inorganic compounds have been described in literature. They are normally used in all sorts of cleaning compositions to provide alkalinity and buffering capacity, prevent flocculation, maintain ionic strength, extract metals from soils and/or remove alkaline-earth metal ions from washing solutions.
  • the builder material usable herein can be any one or mixture of the various phosphate and preferably non-phosphate builder materials, such as for example the alkalimetal citrates, carbonates and bicarbonates; nitrilotriacetic acid (NTA) ; dipicolinic acid (DPA) ; oxydisuccinic acid (ODS) ; alkenylsuccinates (AKS) ; and zeolites. They may be present in the composition of the invention in an amount of from 10% up to about 90% by weight, preferably from 20% to 80% by weight.
  • Particularly preferred builders are citrates, alkenylsuccinates, carbonates, bicarbonates, zeolites, and mixtures thereof.
  • the buffering and/or alkaline agent is the buffering and/or alkaline agent
  • This is normally an alkalimetal silicate, preferably sodium silicate at a level of from about 1 to about 70% by weight, preferably from 5 to 40% by weight.
  • This material is employed as a cleaning ingredient, source of alkalinity, metal corrosion inhibitor and protector of glaze on china tableware.
  • sodium silicate having a mol ratio of Si0 2 :Na 2 0 of from about 1.0 to about 3.3., preferably from about 1.8 to about 2.5, normally referred to as sodium disilicate.
  • the bleaching agent The amount of bleaching agent will preferably lie in a range from 1 to 30% by weight.
  • Alkali metal hypochlorite may be incorporated in liquid compositions.
  • Other chlorine bleaches which may be incorporated are alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids.
  • Preferred bleaches are the peroxygen bleaches, such as sodium perborate (tetra- or monohydrate) or sodium percarbonate. These are preferably used in conjunction with a bleach activator which allows the liberation of active oxygen species at a lower temperature. Numerous examples of activators of this type, often also referred to as bleach or peracid precursors, are known in the art.
  • Preferred bleach activators are tetraacetyl ethylene diamine (TAED) , glucose pentaacetate (GPA) and the mono-long chain acyl tetraacetyl glucoses as disclosed in WO 91/10719, but other activators such as choline sulphophenylcarbonate (CSPC) as disclosed in US Patents 4,751,015 and 4,818,426 can be used.
  • TAED tetraacetyl ethylene diamine
  • GPA glucose pentaacetate
  • CSPC choline sulphophenylcarbonate
  • the amounts of sodium perborate or percarbonate and bleach activator in the compositions preferably do not exceed 20% and 10% by weight respectively, e.g. from 4-20% and from 2-10% by weight respectively.
  • peroxygen_bleach is potassium monopersulphate.
  • Further peroxygen bleaches which may be used are the solid organic peroxyacids and their metal salts.
  • Typical peroxy- acids include: (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy- ⁇ -naphthoic acid;
  • a bleach catalyst such as the manganese complexes of EP-A-458,397 and the sulphonimines of US Patents 5,041,232 and 5,047,163 may also be added.
  • amylolytic and proteolytic enzymes are normally used.
  • the amylolytic enzymes usable herein can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those prepared and described in GB Patent No. 1,296,839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945 A.
  • Examples of such amylolytic enzymes are those produced and distributed under the Trade-names of SP- 95 ® and Termamyl ® by Novo Industri A/S, Copenhagen, Denmark.
  • amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose units/milligram. They may be present in the composition of the invention in amounts such that the final composition has amylolytic enzyme activity of from 10 3 to 10 6 Maltose Units/Kilogram.
  • amylolytic activity as referred to herein can be determined by the method as described by P. Bernfeld in "Method of Enzymology” Volume I (1955) page 149.
  • the proteolytic enzymes usable herein are for example the subtilisins which are obtained from particular strains of B. Subtilis and B. licheniformis, such as the commercially available substilisins Maxatase ® supplied by Gist-Brocades NV, Delft, Holland, and Alcalase ® , supplied by NOVO Industri A/S Copenhagen, Denmark. Particularly suitable are proteases obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from NOVO Industri A/S under the Trade names of E ⁇ perase ® and Savinase ® . The preparation of these and analogues enzymes is described in GB Patent No. 1,243,784.
  • proteolytic enzymes may be present in amounts such that the final composition has proteolytic enzyme activity of from about 10 6 to 10 8 Glycine Units/Kilogram.
  • lipolytic enzymes may also be incorporated to improve fat removal.
  • Typical examples of commercial lipolytic enzymes are Lipase YL, Amano CE, Wallerstein AW, Lipase My, and Lipolase ex Novo Ind.
  • Surfactants though not strictly essential may also be present for detergency, soil removal, foam depression and/or as rinse aids. If present they can be used in an amount of up to about 60% by weight depending upon their type and properties. Normally in a properly built or highly built composition as is conventional, only small amounts of low- to non-foaming nonionic surfactant in the order of 0.1-5% by weight are preferably used, to aid detergency and particularly to suppress excessive foaming caused by some protein soil. Higher amounts i.e.
  • highly detersive surfactants such as the high HLB nonionic surfactants, the anionic sulphate or sulphonate surfactants and the alkyl polyglycoside class of surfactants, may be used in normally lower builder containing active-based compositions.
  • Zinc salts both soluble and insoluble zinc salts, can also be incorporated as adjuncts for minimizing glass corrosion.
  • An inert particulate filler especially sodium sulphate may also be incorporated, though in compact powdered composition it should desirably be omitted as practically possible.
  • alkali-metal or alkaline earth metal salts of amino polyphosphonic acids such as the sodium or calcium salt of ethylene diamine tetra methylene phosphonic acid, and ethylene hydroxy dimethylene phosphonate may also be preferred because of their stabilizing effect on percompound bleaches and/or their anti-scaling properties.
  • polycarboxylate polymeric substances such as the maleic acid/methacrylic acid copolymers, known under the Trade Name Sokalan CP5 ® may be present to aid in the inhibition of scaling.
  • the products of the present invention are preferably formulated such that they provide a wash liquor with a pH of between 9 and 11, more preferably from 9.5-10.5 (at a concentration of 0.3% by weight in water).
  • a 2:1 w/w TAED/Laponite powder mix was dosed to a Schugi Flexomix 160 equipment (3000 rpm; blades at +2 degrees) at 420 kg/hr.
  • a 30% Sokalan CP5 solution was used as liquid binder and in another experiment a 34% Sokalan CP5 solution was used.
  • the liquid binder was dosed at a gradually increasing flow rate, until (after approx. 2 minutes) the granulates looked good. Then the liquid feed was kept constant and the wet granulate was charged to the fluid bed drier. At a reasonable fill of the fluid bed (approx. 30 kg) the granulation was stopped and drying continued until the bed temperature was 50°C.
  • Each experiment was dried at two water contents of 5% and 10% by weight .
  • the appearance of the filter and weight of residue on the filter were determined after 20 repeat washes.
  • Laponite clay granulated according to the invention gave no or substantially no clay build-up on the filter.

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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)

Abstract

L'invention concerne des compositions en poudre pour le lavage en machine de la vaisselle se composant d'argile stratifiée se présentant sous la forme de particules granulées obtenues par: 1) cogranulation d'une argile finement divisée avec une matière particulaire solide, au moyen d'une matière polymère soluble dans l'eau utilisée comme liant; 2) conglutination d'une argile finement divisée avec du disilicate de sodium en tant que liant, au moyen d'un agent tensioactif non ionique soluble dans l'eau utilisé comme liant; ou 3) granulation d'une argile finement divisée avec de l'eau ou une solution de silicate alcalin. Les particules d'argile granulées se dispersent bien, ne se déposent pas sur le filtre du lave-vaisselle et ne risquent donc pas de le boucher.
PCT/EP1993/001461 1992-06-18 1993-06-09 Composition pour le lavage de la vaisselle en machine WO1993025651A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43246/93A AU4324693A (en) 1992-06-18 1993-06-09 Machine dishwashing composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92201772.8 1992-06-18
EP92201772 1992-06-18

Publications (1)

Publication Number Publication Date
WO1993025651A1 true WO1993025651A1 (fr) 1993-12-23

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19640759A1 (de) * 1996-10-02 1998-04-09 Herbert Schmitz Verfahren zur Herstellung eines Reinigungsmittels, insbesondere eines Maschinengeschirreinigers in Pulverform
US5998360A (en) * 1994-09-22 1999-12-07 Crosfield Limited Granules based on silicate antiredeposition agent mixtures and method for manufacturing same
WO2000052130A1 (fr) * 1999-03-04 2000-09-08 The Procter & Gamble Company Pastilles detergentes
US6770616B1 (en) 1999-03-04 2004-08-03 The Procter & Gamble Company Detergent tablet
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4166039A (en) * 1973-10-15 1979-08-28 The Proctor & Gamble Company Detergent composition and process
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
EP0140435A2 (fr) * 1983-10-20 1985-05-08 Unilever N.V. Compositions pour laver la vaisselle
EP0240057A1 (fr) * 1986-03-25 1987-10-07 Unilever N.V. Compositions d'activateurs de blanchiment, granulaires, libres de phosphore et leur utilisation dans des compositions détergentes de blanchiment granulaires
GB2190921A (en) * 1986-05-27 1987-12-02 Unilever Plc Granular detergent composition
EP0267371A1 (fr) * 1986-08-16 1988-05-18 Hoechst Aktiengesellschaft Agent pour le lavage de la vaisselle exempt de phosphate
EP0299575A1 (fr) * 1987-07-14 1989-01-18 The Procter & Gamble Company Compositions détergentes
EP0419970A2 (fr) * 1989-09-23 1991-04-03 Henkel KGaA Produit granulaire, exempt de phosphate, pour adoucir l'eau
WO1991009927A1 (fr) * 1989-12-27 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Additif d'agent de lavage granulaire, a effet avivant et procede pour sa fabrication
GB2249104A (en) * 1990-10-23 1992-04-29 Bp Chem Int Ltd Bleach activators

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4166039A (en) * 1973-10-15 1979-08-28 The Proctor & Gamble Company Detergent composition and process
FR2500475A1 (fr) * 1981-02-26 1982-08-27 Colgate Palmolive Co Perles de base destinees a la fabrication de compositions detergentes, procede et melanges pour leur fabrication et compositions detergentes les contenant
EP0140435A2 (fr) * 1983-10-20 1985-05-08 Unilever N.V. Compositions pour laver la vaisselle
EP0240057A1 (fr) * 1986-03-25 1987-10-07 Unilever N.V. Compositions d'activateurs de blanchiment, granulaires, libres de phosphore et leur utilisation dans des compositions détergentes de blanchiment granulaires
GB2190921A (en) * 1986-05-27 1987-12-02 Unilever Plc Granular detergent composition
EP0267371A1 (fr) * 1986-08-16 1988-05-18 Hoechst Aktiengesellschaft Agent pour le lavage de la vaisselle exempt de phosphate
EP0299575A1 (fr) * 1987-07-14 1989-01-18 The Procter & Gamble Company Compositions détergentes
EP0419970A2 (fr) * 1989-09-23 1991-04-03 Henkel KGaA Produit granulaire, exempt de phosphate, pour adoucir l'eau
WO1991009927A1 (fr) * 1989-12-27 1991-07-11 Henkel Kommanditgesellschaft Auf Aktien Additif d'agent de lavage granulaire, a effet avivant et procede pour sa fabrication
GB2249104A (en) * 1990-10-23 1992-04-29 Bp Chem Int Ltd Bleach activators

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5998360A (en) * 1994-09-22 1999-12-07 Crosfield Limited Granules based on silicate antiredeposition agent mixtures and method for manufacturing same
DE19640759A1 (de) * 1996-10-02 1998-04-09 Herbert Schmitz Verfahren zur Herstellung eines Reinigungsmittels, insbesondere eines Maschinengeschirreinigers in Pulverform
WO2000052130A1 (fr) * 1999-03-04 2000-09-08 The Procter & Gamble Company Pastilles detergentes
US6770616B1 (en) 1999-03-04 2004-08-03 The Procter & Gamble Company Detergent tablet
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue

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