WO1994000545A1 - Composition pour le lavage en machine de la vaisselle - Google Patents

Composition pour le lavage en machine de la vaisselle Download PDF

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Publication number
WO1994000545A1
WO1994000545A1 PCT/EP1993/001521 EP9301521W WO9400545A1 WO 1994000545 A1 WO1994000545 A1 WO 1994000545A1 EP 9301521 W EP9301521 W EP 9301521W WO 9400545 A1 WO9400545 A1 WO 9400545A1
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WO
WIPO (PCT)
Prior art keywords
zeolite
particle size
composition according
composition
phosphate
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.)
Ceased
Application number
PCT/EP1993/001521
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English (en)
Inventor
Willem Robert Van Dijk
Antoine Pierre A. F. Rocourt
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 NV
Original Assignee
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 NV filed Critical Unilever NV
Priority to AU43261/93A priority Critical patent/AU4326193A/en
Publication of WO1994000545A1 publication Critical patent/WO1994000545A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C11D3/02—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

  • This invention relates to machine dishwashing compositions including compositions for machine warewashing, which contain low levels of phosphate salts or which are completely phosphate-free.
  • zeolites Because of their ability to sequester calcium-ions from solution, zeolites have found widespread use as main builder component to replace phosphates in detergent compositions for the textile and fabric washing.
  • Zeolite is a crystalline alkalimetal aluminosilicate material having calcium binding capacity functioning by ion- exchange. Although many crystal forms of zeolite are known, the preferred zeolite for detergents use has always been zeolite A. Other zeolites such as X or P(B) have not found favour because their calcium ion uptake is either inadequate or too slow.
  • Zeolite A has the advantage of being a "maximum aluminium" structure containing maximum possible proportion of aluminium to silicon - or the theoretical minimum Si: Al ratio of 1.0 - so that its capacity for taking up calcium ions from aqueous solution is intrinsically greater than those of zeolite X and P which generally contain a lower proportion of aluminium (or a higher Si: Al ratio) .
  • zeolites in general, and zeolite A in particular have not found their utilization in machine dishwashing products.
  • the weaker builders, particularly citrates and carbonates are more commonly used as phosphate replacements.
  • the main reason therefor is that zeolite, being a water-insoluble particulate material, tend to cause problems of sedimentation during the wash and leaving visible residues on the washed articles, which in machine dishwashing are unacceptable.
  • zeolite in machine dishwashing compositions would have been preferred instead of or to at least partially replace citrate and/or carbonate.
  • an effective zeolite built machine dishwashing composition can be formulated with a significantly less or substantially no tendency to cause sedimentation and residue problems by using a finely divided zeolite having a particle size smaller than 6 ⁇ m, preferably smaller than 5 ⁇ m, and most preferably smaller than 4 ⁇ m.
  • the present invention provides a low phosphate to phosphate- free machine dishwashing composition
  • a low phosphate to phosphate- free machine dishwashing composition comprising finely divided zeolite having a particle size smaller than 6 ⁇ m, preferably smaller than 5 ⁇ m and most preferably smaller than 4 ⁇ m as determined by the method described hereinafter.
  • a low phosphate to phosphate-free machine dishwashing composition comprising a zeolite builder, characterized in that the zeolite is a finely divided material having a particle size smaller than 6 ⁇ m, preferably smaller than 5 ⁇ m, and most preferably smaller than 4 ⁇ m, as determined according to the Fraunhofer laser-diffraction method using a HELOS ® apparatus ex Sympatic.
  • the upper limit of the particle size is important and should be sharply defined. It is furthermore of importance that the material contains an as high as possible percentage of smaller particles i.e. the smaller the better with no limitation in the lower end of the particle size other than that as determined by constraints in preparing the material. It is thus not sufficient for the purpose of the invention to define the particle size in terms of average particle size, average particle diameter or d values. _
  • the analysis of the particle size as defined herein is carried out according to the Fraunhofer laser-diffraction method using a HELOS® apparatus ex Sympatic.
  • volume distributions are measured with 32 channels within the range of 0.18 ⁇ m to 35 ⁇ m.
  • the particle size is determined as particle size distribution expressed in cumulative volume %.
  • the zeolites should preferably have the following particle size distributions: Particle size
  • the amount of zeolite usable in the composition of the invention may vary from about 5% to about 60% by weight, preferably from about 10% to about 50% by weight of the composition.
  • a still further improvement to the effect that substantially no deposit on glasses is observed can be obtained if all particles of the zeolite used are of a size smaller than 2 ⁇ m.
  • zeolite MAP maximum aluminium zeolite P
  • the zeolite MAP as preferably used herein is described and claimed in EP-A-0,384,070 (Unilever) .It is defined as an alkalimetal aluminosilicate of the zeolite P type having a silicon to aluminium ratio (Si: Al) not greater than 1.33, preferably within the range of 0.9 to 1.33, and more preferably within the range of 0.9 to 1.2.
  • zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and having a tetragonally distorted cubic crystal structure.
  • Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per gram of anhydrous alumino-silicate.
  • zeolite MAP is that, unlike most other known zeolite types of the art e.g. zeolite 4A, its calcium binding capacity is independent of particle size, and is substantially unaffected by size reduction.
  • the zeolite can be used as the sole builder or, if desired, may be used in conjunction with other inorganic or organic builder materials.
  • Builder materials that may be present include the phosphate salts, such as sodium triphosphate; sodium carbonate and/or sodium bicarbonate; alkalimetal citrates, especially sodium citrate; nitrilotriacetate (NTA) ; dipicolinic acid; oxydisuccinic acid (ODS) ; alkenylsuccinates (AKS) ; the poly carboxylate polymers such as poly-acrylates, acrylic/maleic copolymers and acrylic phosphonates; and the various organic polyphosphonates such as ethylene diamine tetra-methylene phosphonates, ethylene hydroxy diphosphonates, known under the Dequest ® Trade mark series. Each of these supplementary builder may be used alone or in various combinations thereof and may be present in amounts of from 1% to about 25% by weight.
  • phosphate salts such as sodium triphosphate; sodium carbonate and/or sodium bicarbonate
  • alkalimetal citrates especially sodium citrate
  • NTA nitrilotriacetate
  • Phosphate builders if present, should be used in only small amounts e.g. up to about 12% by weight, preferably up to 10% by weight.
  • composition of the invention should be entirely phosphate-free.
  • composition of the invention may and preferably further contains one or more of the following specialized components for specific purposes during the multi-step wash cycle typical for machine dishwashing composition.
  • 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 55% 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 sulphates and sulphonate surfactants, and the alkyl polyglycoside class of surfactant, may be used in lower builder containing active- based composition.
  • Alkalimetal silicate Preferably sodium silicate at a level of from about 1 to about 40% by weight, preferably from 5 to 35% 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.
  • Bleach system If present the amount 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.
  • peroxygen bleach is potassium monopersulphate.
  • Further peroxygen bleaches which may be used are the organic peroxyacids and their metal salts. Typical peroxy-acids include :
  • aliphatic and substituted aliphatic monoperoxy acids e.g. peroxylauric acid and peroxystearic 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 lichenifor is 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 Ter anyl ® 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 Esperase ® and Savinase ® . The preparation of these and analogues enzymes is described in GB Patent No. 1,243,784.
  • proteolytic enzyme activity can be determined by the method as described by M.L. Anson in "Journal of General
  • 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.
  • clay minerals particularly the layered clay minerals to reduce film- and spot formation on washed articles.
  • Typical and particularly preferred commercial clay products are the synthetic hectorites manufactured and supplied by Laporte Industries Ltd, England as Laponite ® clays e.g. Laponite S, Laponite XLS, Laponite RD and Laponite RDS.
  • 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.
  • composition of the invention should be formulated such that they provide in the wash liquor a pH in the range of from about 7 to 12.0, preferably of from 9-11.5 at a use concentration of about 3 gram/liter in water.
  • composition can be in any product-form, such as in powder, gel, aqueous and non-aqueous liquids.
  • zeolite particularly zeolite MAP according to the invention can be of special importance to machine dishwashing products in an aqueous liquid form.
  • compositions in powder form are within the purview of the present invention:
  • the zeolite MAP used in Examples I-V was zeolite P of Example 2 of EP-A-0,384, 070 and had the following particle size distribution:
  • Zeolite deposits on inverted standard wine glasses were determined in washing machine appraisal tests using the prototype liquid formulation of Example V containing zeolite MAP and commercial zeolite 4A ex Degussa respectively.

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

Abstract

Composition à faible teneur en phosphates ou entièrement dépourvue de phosphates, destinée au lavage en machine de la vaisselle. Elle comporte une zéolithe finement divisée dont la grosseur des particules est inférieure à 6 νm, de préférence inférieure à 5 νm, et plus préférablement inférieure à 4 νm. De préférence, la zéolithe est la zéolithe d'aluminium maximale P décrite dans EP-A-0,384,070, dans laquelle le rapport silicium/aluminium est égal ou inférieur à 1,33, et de préférence égal ou inférieur à 1,15.
PCT/EP1993/001521 1992-06-25 1993-06-15 Composition pour le lavage en machine de la vaisselle Ceased WO1994000545A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU43261/93A AU4326193A (en) 1992-06-25 1993-06-15 Machine dishwashing composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP92201873.4 1992-06-25
EP92201873 1992-06-25

Publications (1)

Publication Number Publication Date
WO1994000545A1 true WO1994000545A1 (fr) 1994-01-06

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WO (1) WO1994000545A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2287948A (en) * 1994-03-31 1995-10-04 Procter & Gamble Laundry detergent composition
WO1995027027A1 (fr) * 1994-03-31 1995-10-12 The Procter & Gamble Company Composition detergente comprenant un adjuvant tel que la zeolite map
WO1997029172A1 (fr) * 1996-02-09 1997-08-14 The Procter & Gamble Company Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux
EP0753044A4 (fr) * 1994-03-31 1999-06-16 Procter & Gamble Composition detergente comprenant la zeolite map et l'enzyme protease
EP0808356A4 (fr) * 1995-02-07 1999-12-01 Procter & Gamble Composition detergente contenant de la zeolithe map et mineral d'argile
EP0802969A4 (fr) * 1995-01-14 1999-12-01 Procter & Gamble Composition detergente comprenant de la zeolite et une enzyme amylase
WO2000053710A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
WO2000053709A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
US6440922B1 (en) 1995-01-14 2002-08-27 The Procter & Gamble Company Detergent composition comprising zeolite and amylase enzyme
US8114343B1 (en) 2010-12-21 2012-02-14 Ecolab USA, Inc. Corrosion inhibition of hypochlorite solutions using Zn and Ca
US8496853B2 (en) 2010-12-21 2013-07-30 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions
US8557178B2 (en) 2010-12-21 2013-10-15 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions in saturated wipes
US8603392B2 (en) 2010-12-21 2013-12-10 Ecolab Usa Inc. Electrolyzed water system

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2269575A1 (fr) * 1974-05-03 1975-11-28 Henkel & Cie Gmbh
EP0015024A1 (fr) * 1979-02-16 1980-09-03 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant un système d'adjuvant binaire
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
WO1989004360A1 (fr) * 1987-11-04 1989-05-18 Unilever Nv Zeolites contenues dans des preparations detergentes liquides
EP0357989A1 (fr) * 1988-08-12 1990-03-14 Degussa Aktiengesellschaft Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides
EP0384070A2 (fr) * 1988-11-03 1990-08-29 Unilever Plc Zéolite P, son procédé de préparation et son utilisation dans les compositions détergentes
EP0392400A2 (fr) * 1989-04-10 1990-10-17 Lonza Ag Procédé de préparation de poudre de zéolithe cristalline de type 4A finement divisée avec une répartition de grosseur des grains déterminée d'avance
EP0521635A1 (fr) * 1991-06-25 1993-01-07 Unilever Plc Composition détergente ou composition sous forme particulaire

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2269575A1 (fr) * 1974-05-03 1975-11-28 Henkel & Cie Gmbh
EP0015024A1 (fr) * 1979-02-16 1980-09-03 THE PROCTER & GAMBLE COMPANY Compositions détergentes contenant un système d'adjuvant binaire
US4405483A (en) * 1982-04-27 1983-09-20 The Procter & Gamble Company Stable liquid detergents containing aluminosilicate ion exchange material
WO1989004360A1 (fr) * 1987-11-04 1989-05-18 Unilever Nv Zeolites contenues dans des preparations detergentes liquides
EP0357989A1 (fr) * 1988-08-12 1990-03-14 Degussa Aktiengesellschaft Zéolite Na A en poudre pour l'utilisation dans les produits détergents liquides
EP0384070A2 (fr) * 1988-11-03 1990-08-29 Unilever Plc Zéolite P, son procédé de préparation et son utilisation dans les compositions détergentes
EP0392400A2 (fr) * 1989-04-10 1990-10-17 Lonza Ag Procédé de préparation de poudre de zéolithe cristalline de type 4A finement divisée avec une répartition de grosseur des grains déterminée d'avance
EP0521635A1 (fr) * 1991-06-25 1993-01-07 Unilever Plc Composition détergente ou composition sous forme particulaire

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0753044A4 (fr) * 1994-03-31 1999-06-16 Procter & Gamble Composition detergente comprenant la zeolite map et l'enzyme protease
WO1995027027A1 (fr) * 1994-03-31 1995-10-12 The Procter & Gamble Company Composition detergente comprenant un adjuvant tel que la zeolite map
GB2287948A (en) * 1994-03-31 1995-10-04 Procter & Gamble Laundry detergent composition
GB2287948B (en) * 1994-03-31 1998-04-08 Procter & Gamble Detergent composition
EP0802969A4 (fr) * 1995-01-14 1999-12-01 Procter & Gamble Composition detergente comprenant de la zeolite et une enzyme amylase
US6440922B1 (en) 1995-01-14 2002-08-27 The Procter & Gamble Company Detergent composition comprising zeolite and amylase enzyme
EP0808356A4 (fr) * 1995-02-07 1999-12-01 Procter & Gamble Composition detergente contenant de la zeolithe map et mineral d'argile
WO1997029172A1 (fr) * 1996-02-09 1997-08-14 The Procter & Gamble Company Compositions pour le lavage de la vaisselle en machine comprenant des mesopores et des macropores siliceux
WO2000053710A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
WO2000053709A1 (fr) * 1999-03-09 2000-09-14 The Procter & Gamble Company Compositions de detergents
US8114343B1 (en) 2010-12-21 2012-02-14 Ecolab USA, Inc. Corrosion inhibition of hypochlorite solutions using Zn and Ca
US8496853B2 (en) 2010-12-21 2013-07-30 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions
US8557178B2 (en) 2010-12-21 2013-10-15 Ecolab Usa Inc. Corrosion inhibition of hypochlorite solutions in saturated wipes
US8603392B2 (en) 2010-12-21 2013-12-10 Ecolab Usa Inc. Electrolyzed water system

Also Published As

Publication number Publication date
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