EP0802969A1 - Zeolith und amylase enthaltendes waschmittel - Google Patents

Zeolith und amylase enthaltendes waschmittel

Info

Publication number
EP0802969A1
EP0802969A1 EP96903400A EP96903400A EP0802969A1 EP 0802969 A1 EP0802969 A1 EP 0802969A1 EP 96903400 A EP96903400 A EP 96903400A EP 96903400 A EP96903400 A EP 96903400A EP 0802969 A1 EP0802969 A1 EP 0802969A1
Authority
EP
European Patent Office
Prior art keywords
detergent composition
enzyme
composition according
zeohte
amyiase
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.)
Granted
Application number
EP96903400A
Other languages
English (en)
French (fr)
Other versions
EP0802969B1 (de
EP0802969A4 (de
Inventor
Carolyn Jayne Brown
Jonathan Richard Clare
Johan Juliaan Serafin Wauben
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.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
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
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0802969A1 publication Critical patent/EP0802969A1/de
Publication of EP0802969A4 publication Critical patent/EP0802969A4/de
Application granted granted Critical
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Anticipated expiration legal-status Critical
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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
    • 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

Definitions

  • Detergent Composition Comprising Zeolite and Amyiase Enzyme
  • the present invention relates to a detergent composition
  • a detergent composition comprising an amyiase enzyme and a small particle size 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 21 491 A (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.
  • a problem may occur when a water insoluble zeolite having a small particle size, is used as a detergency builder in a composition formulated for use in the laundering of fabrics.
  • the problem has been found to be particularly pronounced when the zeolite is zeolite MAP.
  • a small particle size for a zeolite MAP component that is to say particles having a particle size, measured as a d50 value, of up to 1.0 micrometres has previously been taught to be preferred in the art, as represented, for example, by EP 384070 A.
  • 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.
  • the zeolite builder comprises zeolite P having a silicon to aluminium ratio of not greater than 1.33 (zeolite MAP) Detailed description of the invention
  • the first essential component of the present invention is an aluminosilicate zeohte builder, optionally in conjunction with one or more supplementary builders.
  • the zeohte builder is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.
  • the zeohte detergent builder has a particle size, expressed as a d50 value of less than 1.0 micrometres, more preferably from 0.05 to 0.9 micrometres, most preferably from 0.2 to 0.7 micrometres.
  • the d50 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.
  • Suitable aluminosilicate zeolites have the unit cell formula Na z [(Al ⁇ 2)z(Si ⁇ 2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic ciystalline aluminosilicate ion exchange materials are available under the designations Zeohte A, Zeolite B, Zeohte P, Zeohte X, Zeohte MAP, Zeohte HS and mixtures thereof.
  • Zeohte A has the formula
  • Zeolite X has the formula Nag [(Al ⁇ 2)86(Si ⁇ 2)l06]. 276 H 2 0.
  • Zeohte MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeohte P type having a silicon to alumimum 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.
  • zeohte 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.
  • Zeohte 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 zeohtes contains water of hydration, for the purposes of the present invention amounts and percentages of zeohte 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 second essential component of the compositions is an amyiase enzyme, that is to say an enzyme having amylolytic activity.
  • amyiase 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.
  • T ilo 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:
  • amyiase 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 amyiase 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 stabihty, particularly having improved stabihty 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 amyiase 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 amyiase, such as B. amyloliquefaciens, B.subtilis, or B.stearothermophilus.
  • amylases having enhanced oxidative stabihty derived from B. licheniformis NCIB806, are described by Genencor International in a paper entitled "Oxidatively Resistant ⁇ - Amylases" which was presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson.
  • Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant.
  • amylases having enhanced oxidative stabihty include those described in WO 94/18314 A (Genencor International) and WO 94/02597 A (Novo). Any other oxidative stability-enhanced amyiase 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 rninimzed 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 C5-C17 acyl-N-(C ⁇ - C alkyl) and -N-(C ⁇ -C2 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 C6-C]g 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 ⁇ -Ci 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 C5- C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C 1 5-C24 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 hydrophihc lipophilic balance (hlb) value of ⁇ 9.5, more preferably ⁇ 10.5.
  • hlb hydrophihc 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-0-(C n H 2n O)yH
  • 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 Ci 1-C15 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 C13-C15 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
  • 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.
  • 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.
  • 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, methaciyhc and/or maleic acids in neutralised form.
  • Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.
  • Suitable ciystalline layered silicates have the composition:
  • 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 is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20.
  • the synthetic material is commercially available from Hoechst AG as ⁇ -Na2 Si2 ⁇ 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 builder is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the zeohte builder to be incorporated post-tower.
  • the crystalline layered sihcate, 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 1 preferably at least 550 g/1, most preferably at least 700 g/1 and, with particular preference at least 800 g/1.
  • powders of high bulk density for example, of 700 g/1 or above.
  • Such powders may be prepared either by post-tower densification of spray- dried 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 EP340013A, EP 367 339A, EP 390 251 A 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.
  • the abbreviated component identifications have the following meanings:
  • TAS Sodium alkyl sulfate surfactant containing predominantly C ⁇ - Cj alkyl chains derived from tallow oil.
  • Zeohte A Hydrated sodium aluminosilicate zeohte A having a particle size, expressed as a d5o value, of 0.6 micrometres
  • amyiase enzyme levels relate to levels of active enzyme, expressed on a 60 KNU/g activity basis.
  • the following granular laundry detergent compositions of density 850 gram/litre are prepared (parts by weight) in accordance with the invention. All amyiase levels relate to levels of active enzyme, expressed on a 60 KNU/g activity basis.

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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)
EP96903400A 1995-01-14 1996-01-05 Zeolith und amylase enthaltendes waschmittel Expired - Lifetime EP0802969B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9500738.1A GB9500738D0 (en) 1995-01-14 1995-01-14 Detergent composition
GB9500738 1995-01-14
PCT/US1996/000281 WO1996021717A1 (en) 1995-01-14 1996-01-05 Detergent composition comprising zeolite and amylase enzyme

Publications (3)

Publication Number Publication Date
EP0802969A1 true EP0802969A1 (de) 1997-10-29
EP0802969A4 EP0802969A4 (de) 1999-12-01
EP0802969B1 EP0802969B1 (de) 2003-10-08

Family

ID=10768053

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96903400A Expired - Lifetime EP0802969B1 (de) 1995-01-14 1996-01-05 Zeolith und amylase enthaltendes waschmittel

Country Status (9)

Country Link
EP (1) EP0802969B1 (de)
AR (1) AR000717A1 (de)
AT (1) ATE251664T1 (de)
BR (1) BR9606758A (de)
CA (1) CA2210293C (de)
DE (1) DE69630279T2 (de)
ES (1) ES2206559T3 (de)
GB (1) GB9500738D0 (de)
WO (1) WO1996021717A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0756000A1 (de) * 1995-07-24 1997-01-29 The Procter & Gamble Company Waschmittelzusammensetzungen enthaltend eine spezifische Amylase und lineares Alkylbenzolsulfonattensid
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

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA767170B (en) * 1975-12-15 1978-07-26 Colgate Palmolive Co Detergent composition and method for use
US4900475A (en) * 1985-07-26 1990-02-13 Colgate-Palmolive Co. Stabilized built liquid detergent composition containing enzyme
CA2001927C (en) * 1988-11-03 1999-12-21 Graham Thomas Brown Aluminosilicates and detergent compositions
US5030377A (en) * 1988-11-11 1991-07-09 Kao Corporation Detergent compositions containing starch debranching enzymes
DE4034131C2 (de) * 1990-10-26 1999-08-26 Henkel Kgaa Gerüststoff für Waschmittel
CA2083331C (en) * 1991-11-26 1998-08-11 Johannes H. M. Akkermans Detergent compositions
CZ280524B6 (cs) * 1992-01-17 1996-02-14 Unilever Nv Částicové detergenční směsi
WO1994000545A1 (en) * 1992-06-25 1994-01-06 Unilever N.V. Machine dishwashing composition
AU669900B2 (en) * 1992-07-20 1996-06-27 Colgate-Palmolive Company, The Stabilized built aqueous liquid softergent compositions

Also Published As

Publication number Publication date
BR9606758A (pt) 1998-01-06
MX9705327A (es) 1997-10-31
CA2210293C (en) 2001-07-24
DE69630279D1 (de) 2003-11-13
AR000717A1 (es) 1997-08-06
WO1996021717A1 (en) 1996-07-18
ES2206559T3 (es) 2004-05-16
ATE251664T1 (de) 2003-10-15
DE69630279T2 (de) 2004-07-22
CA2210293A1 (en) 1996-07-18
GB9500738D0 (en) 1995-03-08
EP0802969B1 (de) 2003-10-08
EP0802969A4 (de) 1999-12-01

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