EP0802970B1 - Waschmittel enthaltend map-zeolith und amylasen - Google Patents

Waschmittel enthaltend map-zeolith und amylasen Download PDF

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Publication number
EP0802970B1
EP0802970B1 EP96905128A EP96905128A EP0802970B1 EP 0802970 B1 EP0802970 B1 EP 0802970B1 EP 96905128 A EP96905128 A EP 96905128A EP 96905128 A EP96905128 A EP 96905128A EP 0802970 B1 EP0802970 B1 EP 0802970B1
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EP
European Patent Office
Prior art keywords
detergent composition
composition according
zeolite
enzyme
amylase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96905128A
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English (en)
French (fr)
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EP0802970A4 (de
EP0802970A1 (de
Inventor
Carolyn Jayne Brown
Jonathan Richard Clare
Johan Juliaan Serafin Wauben
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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

Definitions

  • the present invention relates to a detergent composition
  • a detergent composition comprising an amylase enzyme and a zeolite component as a sequestering agent for water hardness.
  • water soluble inorganic phosphates such as sodium tripolyphosphate
  • sodium tripolyphosphate have been used as builders for laundry detergents.
  • alkali metal aluminosilicate ion-exchangers particularly crystalline water insoluble sodium aluminosilicate zeolites, have been proposed as replacements for the inorganic phosphates.
  • EP 21 491A (Procter & Gamble) discloses detergent compositions containing a builder system which includes zeolite A, X or P (B) or a mixture thereof.
  • EP 384070A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes their use as detergency builders.
  • the problem relates to the formation of white residues, which adhere to the fabrics and remain thereon at the end of a laundry washing process.
  • the degree of residue formation may vary. On coloured fabrics the appearance of the white residues tends to be visually more apparent than on white fabrics. White residues frequently form on areas of fabric where there is a stain present, interfering with and preventing the complete removal of the stain. As a result of the visible contrast between the white residues and the coloured fabric, the stained area on which white deposits have formed may be more noticeable that the original stain.
  • a detergent composition selected from liquid compositions and granular compositions having a bulk density of at least 550 g/l and containing
  • the first essential component of the present invention is a zeolite MAP builder, optionally in conjunction with one or more supplementary builders.
  • the zeolite MAP is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
  • Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.
  • Zeolite P having a Si:Al ratio of 1.33 or less may be prepared by the following steps:
  • Preferred drying methods are spray-drying and flash drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity of the product under certain circumstances.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel).
  • the calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.
  • zeolite MAP like other zeolites contains water of hydration, for the purposes of the present invention amounts and percentages of zeolite are expressed in terms of the notional anhydrous material.
  • the amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.
  • the zeolite MAP detergent builder has a particle size, expressed as a d 50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.
  • the d 50 value indicates that 50% by weight of the particles have a diameter smaller than that figure.
  • the particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d 50 values are disclosed in EP 384070A.
  • the second essential component of the compositions is an amylase enzyme, that is to say an enzyme having amylolytic activity.
  • the amylase enzyme is typically incorporated into the compositions in accordance with the invention at a level of from 0.01% to 5%, preferably from 0.1 % to 3%, more preferably from 0.2% to 2%, most preferably from 0.3% to 1.5% active enzyme by weight of the composition, on a 60KNU/g (Kilo Novo Units/gram) activity basis.
  • KNU/g The units of 'Kilo Novo Units/gram (KNU/g)' are a well known means of defining amylolytic enzyme activity and are described in GB-1,269,839 A (Novo).
  • 1 KNU is the amount of enzyme which breaks down 5.25 grams of starch (Merck, Amylum Solubile Erg. B.6, Batch 9947275) per hour in the method described in GB-1,269,839 A, which has the following standard conditions: Substrate Soluble starch Calcium content in solvent 0.0043 M Reaction time 7-20 minutes Temperature 37°C pH 5.6
  • the amylase enzyme may be fungal or bacterial in origin. Amylases obtained by chemical or genetic manipulation of fungal or bacterial derived strains are also useful herein.
  • the amylase enzyme is preferably an ⁇ -amylase.
  • Preferred amylases include, for example, ⁇ -amylases obtained from a special strain of B. licheniformis, described in more detail in GB-1,269,839 A.
  • Reported deposit numbers for B. licheniformis strains capable of producing ⁇ -amylases include NCIB 8061, NCIB 8059, ATCC 6634, ATCC 6598, ATCC 11945, ATCC 8480 and ATCC 9945a.
  • Preferred commercially available ⁇ -amylases include for example, those sold under the tradename Rapidase and Maxamyl by Gist-Brocades; those sold under the tradename Taka-Therm L-340 by Miles Laboratories, Elkhart, Indiana; those sold under the tradename Rohalase AT by Rohm and Haas, West Philadelphia, PA; and those sold under the tradenames Termamyl 60T and 120T, Fungamyl and BAN by Novo Industries A/S.
  • the amylases have been designed to have improved stability, particularly having improved stability to oxidation, for example in a bleaching environment, and improved thermal stability. Stability can be measured using any of the technical tests known in the art including those referred to in WO 94/02597 A. Stability-enhanced amylases are commercially available from Novo Industries A/S or from Genencor International.
  • Highly preferred amylases with enhanced oxidative stability are derived using site-directed mutagenesis from one or more of the Baccillus amylases, especialy the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors.
  • Preferred amylases of this type are described in WO 94/02597 A, and comprise a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis ⁇ -amylase, sold under the tradename Termamyl, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus.
  • amylases having enhanced oxidative stability include those described in WO 94/18314 A (Genencor International) and WO 94/02597 A (Novo). Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other enzyme modifications are acceptable including those described in WO 95/09909 A (Novo).
  • enzymes for incorporation into solid detergent compositions are generally sold commercially as enzyme prills containing active enzyme supported on a variety of inert host materials, which for example, can include alkali metal sulfates, carbonates and silicates.
  • organic binder materials are also incorporated.
  • the calcium content of these enzyme prills is minimzed to ensure good in-product storage stability of the enzyme.
  • the detergent composition according to the invention may contain other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • other detergent components such as surfactants, cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.
  • the detergent composition according to the invention preferably includes a surfactant selected from anionics, nonionics, zwitterionics, ampholytics and cationics.
  • the surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, preferably from 3% to 30%, most preferably from 5% to 20% by weight of the compositions.
  • Suitable additional anionic surfactants include anionic sulfates, olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates.
  • Sodium salts are generally preferred.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5 -C 17 acyl-N-(C 1 -C 4 alkyl) and -N-(C 1 -C 2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C 6 -C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C 6 -C 18 alkyl sulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C 5 -C 20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C 6 -C 22 primary or secondary alkane sulfonates, C 6 -C 24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • the nonionic surfactant is preferably a hydrophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of ⁇ 9.5, more preferably ⁇ 10.5.
  • hlb hydrophilic lipophilic balance
  • hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule.
  • the alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.
  • Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those of the general formula: R-O-(C n H 2n O)yH wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.
  • Preferred nonionic surfactants include primary C 11 -C 15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.
  • a particularly preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.
  • alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C 13 -C 15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.
  • Another class of nonionic sufactants comprises alkyl polyglucoside compounds of general formula RO(C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
  • the builder system may contain an organic or inorganic cobuilder.
  • Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form.
  • Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.
  • Suitable crystalline layered silicates have the composition: NaMSi x O 2x +1 . y H 2 0 where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • M sodium or hydrogen, preferably sodium
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20.
  • Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
  • the synthetic material is commercially available from Hoechst AG as ⁇ - Na 2 Si 2 O 5 (SKS6) and is described in US Patent No. 4664830.
  • the total amount of detergency builder in the granular composition typically ranges from 10 to 80 wt. %, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.
  • Detergent compositions according to the invention may also suitably contain a bleach system.
  • a bleach system preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.
  • the bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor.
  • Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.
  • Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.
  • TAED tetraacetylethylene diamine
  • the detergent composition according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.
  • the detergent compositions of the invention may be prepared by any suitable method.
  • the particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.
  • a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).
  • the zeolite MAP is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeolite MAP to be incorporated post-tower.
  • the crystalline layered silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.
  • particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.
  • the granular detergent compositions of the invention may be prepared to any suitable bulk density.
  • the compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g/l.
  • powders of high bulk density for example, of 700 g/l or above.
  • Such powders may be prepared either by post-tower densification of spraydried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used.
  • Processes using high-speed mixer/granulators are disclosed, for example, in EP340 013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
  • the detergent composition of the invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous.
  • liquid used herein includes pasty viscous formulations such as gels.
  • the liquid detergent composition generally has a pH of from 6.5 to 10.5.
  • the total amount of detergency builder in the liquid composition is preferably from 5 to 70% of the total liquid composition.
  • compositions according to the present invention are presented in the following Examples.

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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)

Claims (9)

  1. Detergenszusammensetzung, gewählt aus flüssigen Zusammensetzungen und granulären Zusammensetzungen mit einer Schüttdichte von mindestens 550 g/l und enthaltend
    (a) einen Zeolith-Builder, umfassend Zeolith P mit einem Silicium-zu-Aluminium-Verhältnis von nicht größer als 1,33 (Zeolith MAP) und mit einer Teilchengröße, ausgedrückt als d50-Wert, von 1 bis 5 µm, und
    (b) ein Amylaseenzym, das in einer Menge von 0,1% bis 2% aktives Enzym bezogen auf Gewicht der Zusammensetzung auf einer Aktivitätsbasis von 60 KNU/g vorliegt.
  2. Zusammensetzung nach Anspruch 1, welche eine teilchenförmige Wäschewaschmittelzusammensetzung ist, umfassend nichtionisches Tensid, den Zeolith-Builder, organischen oder anorganischen Co-Builder und das Amylaseenzym.
  3. Detergenszusammensetzung nach mindestens einem vorangehenden Anspruch, wobei der Zeolith-Builder kristallin ist und in einem Anteil von 15 bis 40 Gew.-% der Zusammensetzung vorliegt.
  4. Detergenszusammensetzung nach mindestens einem vorangehenden Anspruch, wobei das Amylaseenzym eine α-Amylase ist.
  5. Detergenszusammensetzung nach mindestens einem vorangehenden Anspruch, wobei das Amylaseenzym modifiziert worden ist, um seine oxidative Stabilität zu erhöhen.
  6. Detergenszusammensetzung nach mindestens einem vorangehenden Anspruch, enthaltend ein Tensid in einem Anteil von 5 bis 50 Gew.-% der Zusammensetzung.
  7. Detergenszusammensetzung nach mindestens einem vorangehenden Anspruch, enthaltend einen Co-Builder, welcher ein kristallines Schichtsilicat ist.
  8. Detergenszusammensetzung nach mindestens einem vorangehenden Anspruch, enthaltend ein Bleichsystem, umfassend eine Peroxy-Bleichverbindung und einen Peroxysäure-Bleichvorläufer.
  9. Detergenszusammensetzung nach Anspruch 8, wobei die Peroxy-Bleichverbindung Natriumpercarbonat ist.
EP96905128A 1995-01-14 1996-01-05 Waschmittel enthaltend map-zeolith und amylasen Expired - Lifetime EP0802970B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9500737 1995-01-14
GBGB9500737.3A GB9500737D0 (en) 1995-01-14 1995-01-14 Detergent composition
PCT/US1996/000284 WO1996021718A1 (en) 1995-01-14 1996-01-05 Detergent composition comprising zeolite map and amylase enzymes

Publications (3)

Publication Number Publication Date
EP0802970A1 EP0802970A1 (de) 1997-10-29
EP0802970A4 EP0802970A4 (de) 1999-01-07
EP0802970B1 true EP0802970B1 (de) 2004-03-17

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Application Number Title Priority Date Filing Date
EP96905128A Expired - Lifetime EP0802970B1 (de) 1995-01-14 1996-01-05 Waschmittel enthaltend map-zeolith und amylasen

Country Status (8)

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EP (1) EP0802970B1 (de)
AR (1) AR000716A1 (de)
AT (1) ATE262025T1 (de)
BR (1) BR9606759A (de)
CA (1) CA2210646C (de)
DE (1) DE69631873T2 (de)
GB (1) GB9500737D0 (de)
WO (1) WO1996021718A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE50107849D1 (de) 2000-07-28 2005-12-01 Henkel Kgaa Neues amylolytisches enzym aus bacillus sp. a 7-7 (dsm 12368) sowie wasch- und reinigungsmittel mit diesem neuen amylolytischen enzym
DE102004007468A1 (de) * 2004-02-13 2005-09-01 De-Sta-Co Metallerzeugnisse Gmbh Spannvorrichtung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753043A1 (de) * 1994-03-31 1997-01-15 The Procter & Gamble Company Waschmitellzusammensetzung

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9108136D0 (en) * 1991-04-17 1991-06-05 Unilever Plc Concentrated detergent powder compositions
GB9113674D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Detergent compositions
SK278834B6 (sk) * 1992-01-17 1998-03-04 Unilever Nv Časticová bieliaca detergentná zmes
CZ280524B6 (cs) * 1992-01-17 1996-02-14 Unilever Nv Částicové detergenční směsi
GB9305599D0 (en) * 1993-03-18 1993-05-05 Unilever Plc Detergent compositions
GB2287948B (en) * 1994-03-31 1998-04-08 Procter & Gamble Detergent composition
USH1468H (en) * 1994-04-28 1995-08-01 Costa Jill B Detergent compositions containing cellulase enzyme and selected perfumes for improved odor and stability

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753043A1 (de) * 1994-03-31 1997-01-15 The Procter & Gamble Company Waschmitellzusammensetzung

Also Published As

Publication number Publication date
EP0802970A4 (de) 1999-01-07
DE69631873T2 (de) 2005-03-03
BR9606759A (pt) 1998-01-06
MX9705326A (es) 1997-10-31
EP0802970A1 (de) 1997-10-29
DE69631873D1 (de) 2004-04-22
CA2210646C (en) 2001-07-31
GB9500737D0 (en) 1995-03-08
WO1996021718A1 (en) 1996-07-18
AR000716A1 (es) 1997-08-06
CA2210646A1 (en) 1996-07-18
ATE262025T1 (de) 2004-04-15

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