EP0266904A2 - Composition pour le lavage machinal de la vaisselle contenant de l'acide dipicolinique - Google Patents

Composition pour le lavage machinal de la vaisselle contenant de l'acide dipicolinique Download PDF

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Publication number
EP0266904A2
EP0266904A2 EP87308797A EP87308797A EP0266904A2 EP 0266904 A2 EP0266904 A2 EP 0266904A2 EP 87308797 A EP87308797 A EP 87308797A EP 87308797 A EP87308797 A EP 87308797A EP 0266904 A2 EP0266904 A2 EP 0266904A2
Authority
EP
European Patent Office
Prior art keywords
composition according
dipicolinic acid
weight
enzyme
composition
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
EP87308797A
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German (de)
English (en)
Other versions
EP0266904A3 (fr
Inventor
Hidde Frankena
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
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 PLC filed Critical Unilever PLC
Publication of EP0266904A2 publication Critical patent/EP0266904A2/fr
Publication of EP0266904A3 publication Critical patent/EP0266904A3/fr
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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
    • 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
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38627—Preparations containing enzymes, e.g. protease or amylase containing lipase

Definitions

  • the present invention relates to machine dishwashing compositions which contain low levels of phosphate salts or which are completely phosphate-free and particularly to such compositions of the enzymatic type.
  • a more unconventional example of a phosphate salt substitute is dipicolinic acid (2,6-pyridinedicarboxylic acid) or a salt thereof, the usefulness of which in fabric-washing compositions has been described in British Patent No 1 342 095.
  • dipicolinic acid (2,6-pyridinedicarboxylic acid) or a salt thereof, the usefulness of which in fabric-washing compositions has been described in British Patent No 1 342 095.
  • dipicolinic acid has been described for use in combination with a relatively soluble magnesium salt in hand-dishwashing formulations having a high-foaming behaviour under both soft and hard water conditions and in the United States Patent No 3 956 159 dipicolinic acid has also been described as suitable stabiliser for peroxygen bleaches.
  • European Patent Specification 0 082 564 a machine dishwashing composition comprising dipicolinic acid as a sequestrant is described, although no mention of enzymes as co-additives is made.
  • dipicolinic acid-­containing compositions should comprise enzymes to improve performance, and it has now been discovered that contrary to what would be expected from the literature (Aldrich Chemie, Benelux, 1984 - Aldrich is a registered trade mark of Aldrich Chemie SA/NV), the use of dipicolinic acid does not inhibit enzymic action on soils.
  • the present invention provides a machine dishwashing composition
  • a machine dishwashing composition comprising a carboxylic acid derivative of pyridine or a water-soluble or water-dispersible salt thereof having the general formula: in which R is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a carboxyl group or a short-chain alkyl group, together with an enzyme.
  • compositions are in general formulated so as to provide a cleaning solution which removes soils, burnt materials, amylaceous products, dyes and the like, but without corrosive attack on dishware made of glass, china and metal. Moreover, formulations should be such that the formation of films and spots on the cleaned surfaces is prevented or avoided.
  • conventional machine dishwashing compositions in general contain a significant amount of inorganic, relatively alkaline salts, such as alkali metal phosphates, alkali metal silicates and alkali metal carbonates, a bleaching system providing active chlorine or oxygen and, optionally, ingredients such as proteolytic and/or amylolytic enzymes, and nonionic surfactants for foam-reduction and wetting.
  • inorganic, relatively alkaline salts such as alkali metal phosphates, alkali metal silicates and alkali metal carbonates
  • a bleaching system providing active chlorine or oxygen
  • ingredients such as proteolytic and/or amylolytic enzymes, and nonionic surfactants for foam-reduction and wetting.
  • machine dishwashing compositions of equal or superior efficiency to conventional compositions based on inorganic salts, bleach, enzymes and optionally a nonionic surfactant, in which the conventional phosphate component is substantially substituted by the pyridine derivative defined above.
  • dipicolinic acid proves not only to be an acceptable alternative to phosphate salts, but, contrary to many of the conventional phosphate replacers in machine dishwashing compositions, it exhibits a cleaning efficiency on a large number of soils, which is superior to the cleaning efficiency of phosphate-­containing compositions.
  • compositions of the invention comprise less than 6% by weight, preferably less than 4% by weight calculated as phosphorus, of phosphates, or are substantially phosphorus-free.
  • compositions may also include one or more alkaline salts, bleaches and nonionic surfactants, either singly or in combination.
  • the pyridine derivative comprises 5 to 50% by weight of the composition, preferably 15 to 30% by weight.
  • R is a hydrogen atom.
  • the pyridine derivative will generally be used in its salt form, in particular in the form of its alkali metal salt, such as the sodium salt. If so desired, also the ammonium or substituted ammonium salts of the pyridine derivative may be used.
  • the machine dishwashing compositions according to the invention may comprise one or more salts suitable to provide adequate alkalinity and buffering capacity.
  • they may comprise organic and/or inorganic builder and filler salts such as the alkali metal salts of silicate, in particular metasilicate, carbonate, borate, citrate, carboxymethyloxysuccinate, nitrilotriacetate and ethylenediaminotetraacetate, as well as polyelectrolytes such as polyacrylate, polymethacrylate, and polyamaleate.
  • Polyelectrolytes may be present at 0-20% by weight. Examples include Sokalan CP5, Sokalan CP7, Gantrez and Builder U. Molecular weights may range from 1 000-5 000 000. Also combinations of the above salts among themselves or with inert filler salts such as sodium sulphate are possible.
  • the amount of the above salts may vary between 10 and 90% by weight of the composition, and normally lies between 30 and 70% by weight.
  • compositions according to the invention may further comprise a bleach component, which may be of both the oxygen- and chlorine-releasing type.
  • Suitable chlorine-releasing bleaches include the well-known alkali metal hypochlorites and chlorinated cyanuric acid salts. Because the compositions also contain one or more enzymatic components, these should either be protected against attack by such chlorine-releasing bleaches, eg by encapsulating them, or, and this is preferred, oxygen-releasing bleaches should be used.
  • Particularly preferred in the present invention is the use of a peroxygen salt such as sodium perborate tetrahydrate or monohydrate, percarbonate and persilicate. It may also be advantageous to combine such a persalt with a bleach activator therefor.
  • the activators for peroxygen salts are organic compounds which react with the peroxygen salt in solution to form an organic peroxygen acid as the effective bleaching agent. Numerous examples of such activators are known in the art. Preferred activators for use in the present invention are tetraacetylethylenediamine, tetraacetylglycoluril, glucosepentaacetate and xylose tetraacetate.
  • the peroxygen salt is normally included in an amount of up to 25% by weight, in particular of from 3 to 15% by weight of the total composition.
  • the ratio between the peroxygen salt and the activator lies in the range of from 8:1 to 1:1, preferably 4:1 to 1.5:1.
  • compositions of the present invention preferably also comprise a surfactant which should be of essentially nonionic character.
  • a surfactant which should be of essentially nonionic character.
  • low- to non-foaming nonionic surfactants selected from the group consisting of alkoxylated nonionic surfactants wherein the alkoxy moiety consists of ethylene oxide, propylene oxide and/or butylene oxide or mixtures thereof may be used.
  • suitable and preferred low- to non-foaming nonionics for use in the present invention are the ethoxylated straight-chain alcohols sold under the trade names of Synperonic LF/RA 30 and Synperonic LF/RA 40 by the ICI Company, Lutensol LF 403 and Lutensol LF 1300 by the BASF Company, and Triton DF 12 by the Rohm & Haas Company.
  • the amount of the nonionic surfactant should be such that detergency and wetting are improved, and excessive foaming due to certain proteinaceous soils is reduced or suppressed. In general, amounts will be between 0.2 and 10% by weight, in particular between 0.5 and 5% by weight of the total composition.
  • compositions according to the present invention should be substantially free from other types of surfactants, such as anionic or cationic surfactants.
  • the enzymes may be of the amylolytic, proteolytic and lipolytic type or mixtures thereof.
  • the amylolytic enzymes for use in the present invention can be those derived from bacteria or fungi.
  • Preferred amylolytic enzymes are those described in British Patent Specification No 1 296 839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11 945, ATCC 8480 and ATCC 9945 A.
  • a particularly preferred enzyme is an amylolytic enzyme produced and distributed under the trade name Termamyl by Novo Industri A/S, Copenhagen, Denmark.
  • amylolytic enzymes are generally sold as granules and may have activities from about 2 to 10 Maltose units/milligram.
  • the amylolytic enzyme is normally included in an amount of from 0.1 to 5% by weight, in particular of from 0.3 to 1.5% by weight.
  • the composition may, and preferably does, also contain a proteolytic enzyme.
  • suitable proteolytic enzymes are the subtilisins which are obtained from particular strains of B subtilis and B . licheniformis , such as those commercially available under the trade names Maxatase, supplied by Gist-Brocades NV, Delft, Netherlands, and Alcalase, supplied by Novo Industri A/S, Copenhagen, Denmark.
  • Particularly preferred are the proteases obtained from a strain of Bacillus having maximal activity throughout the pH range of 8-12, being commercially available under th trade names of Esperase and Savinase, sold by Novo Industri A/S. The preparation of these and analogous enzymes is described in the British Patent No 1 243 784.
  • proteolytic enzymes are generally sold as granules and may have enzyme activities of from about 500 to 1700 glycine units/milligram.
  • the proteolytic enzyme is normally included in an amount of from 0.1 to 5% by weight, in particular of from 0.3 to 1.5% by weight.
  • compositions may further contain useful additives conventional in the machine dishwashing art, such as enzyme-stabilising agents, hydrotropes, perfumes, colouring agents, germicides, soil-suspending agents, aminopolyphosphonic acids and the alkali metal or alkaline earth metal salts thereof, anti-corrosion agents such as fatty acids, benzatriazole and so on.
  • useful additives conventional in the machine dishwashing art, such as enzyme-stabilising agents, hydrotropes, perfumes, colouring agents, germicides, soil-suspending agents, aminopolyphosphonic acids and the alkali metal or alkaline earth metal salts thereof, anti-corrosion agents such as fatty acids, benzatriazole and so on.
  • the products of the present invention should be formulated such that they provide in the wash liquor a pH in the range of from 7 to 12.5, preferably of from 9.5 to 12.0 at a use concentration of about 3 grams/litre in water.
  • the products of the invention may be in powder, gel or liquid form.
  • Machine dishwashing formulations having the following composition were prepared by conventional granulating and mixing procedures:
  • the builder salts used are shown below with the designations used for them in the following tables: Sodium carbonate/calcite carb/calc Sodium Zeolite 4 zeol Sodium dipicolinate DPA Sodium citrate cit Sodium nitrilotriacetate NTA Sodium carboxymethyloxymalonate CMOM Sodium carboxymethyloxysuccinate CMOS
  • the following tables show the percentage of the surfaces of the articles from which the soil had not been removed.
  • a negative value of ⁇ therefore shows an advantage for the test compositions in cleaning performance.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Washing And Drying Of Tableware (AREA)
EP87308797A 1986-10-07 1987-10-05 Composition pour le lavage machinal de la vaisselle contenant de l'acide dipicolinique Ceased EP0266904A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8624050 1986-10-07
GB868624050A GB8624050D0 (en) 1986-10-07 1986-10-07 Machine dishwashing compositions

Publications (2)

Publication Number Publication Date
EP0266904A2 true EP0266904A2 (fr) 1988-05-11
EP0266904A3 EP0266904A3 (fr) 1988-08-31

Family

ID=10605377

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87308797A Ceased EP0266904A3 (fr) 1986-10-07 1987-10-05 Composition pour le lavage machinal de la vaisselle contenant de l'acide dipicolinique

Country Status (4)

Country Link
EP (1) EP0266904A3 (fr)
JP (1) JPS63101490A (fr)
GB (1) GB8624050D0 (fr)
NO (1) NO168487C (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0346137A1 (fr) * 1988-06-09 1989-12-13 Unilever Plc Composition à base d'enzymes pour le lavage de la vaisselle
AU616558B2 (en) * 1988-09-07 1991-10-31 Unilever Plc Detergent compositions
WO1994005763A1 (fr) * 1992-09-08 1994-03-17 Unilever N.V. Composition liquide pour lave-vaisselle automatique
EP0615543A1 (fr) * 1992-10-02 1994-09-21 Colgate-Palmolive Company Compositions d'hypohalite stabilisees
EP0634476A1 (fr) * 1993-07-12 1995-01-18 The Procter & Gamble Company Emulsions stables aqueuses de surfactants non-ioniques avec un agent controlant la viscosité
EP0640684A1 (fr) * 1993-08-26 1995-03-01 Colgate-Palmolive Company Composition en poudre séchée par pulvérisation contenant des enzymes pour lave-vaisselle
EP0653482A1 (fr) * 1993-11-11 1995-05-17 The Procter & Gamble Company Composition de blanchiment à base d'hypochlorite
US5759989A (en) * 1993-07-12 1998-06-02 The Procter & Gamble Company Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
EP0271155B2 (fr) † 1986-12-10 2000-09-06 Unilever N.V. Procédé enzymatique pour le lavage et le rinçage de la vaisselle
EP2199386A1 (fr) 1993-10-08 2010-06-23 Novozymes A/S Variants d'amylase
US12545865B2 (en) 2023-07-20 2026-02-10 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch
US12545867B2 (en) 2023-07-20 2026-02-10 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch
US12553013B2 (en) 2023-07-20 2026-02-17 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12280217B2 (en) 2019-06-06 2025-04-22 Vincent Medical (Dong Guan) Manufacturing Co., Ltd. Heater plate

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1342095A (en) * 1971-01-05 1973-12-25 Unilever Ltd Detergent compositions
US3966649A (en) * 1972-09-28 1976-06-29 Colgate-Palmolive Company Liquid detergents containing chelidamic acids and salts thereof
GB1513550A (en) * 1975-05-05 1978-06-07 Unilever Ltd Hard surface cleaning compositions

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0271155B2 (fr) † 1986-12-10 2000-09-06 Unilever N.V. Procédé enzymatique pour le lavage et le rinçage de la vaisselle
WO1989012089A1 (fr) * 1988-06-09 1989-12-14 Unilever Plc Composition enzymatique de lavage de vaisselle
AU616780B2 (en) * 1988-06-09 1991-11-07 Unilever Plc Enzymatic dishwashing composition
EP0346137A1 (fr) * 1988-06-09 1989-12-13 Unilever Plc Composition à base d'enzymes pour le lavage de la vaisselle
AU616558B2 (en) * 1988-09-07 1991-10-31 Unilever Plc Detergent compositions
WO1994005763A1 (fr) * 1992-09-08 1994-03-17 Unilever N.V. Composition liquide pour lave-vaisselle automatique
EP0615543A1 (fr) * 1992-10-02 1994-09-21 Colgate-Palmolive Company Compositions d'hypohalite stabilisees
US5759989A (en) * 1993-07-12 1998-06-02 The Procter & Gamble Company Stable aqueous emulsions of nonionic surfactants with a viscosity controlling agent
EP0634476A1 (fr) * 1993-07-12 1995-01-18 The Procter & Gamble Company Emulsions stables aqueuses de surfactants non-ioniques avec un agent controlant la viscosité
WO1995002667A1 (fr) * 1993-07-12 1995-01-26 The Procter & Gamble Company Emulsions aqueuses stables de tensioactifs non ioniques comprenant un agent regulant la viscosite
EP0640684A1 (fr) * 1993-08-26 1995-03-01 Colgate-Palmolive Company Composition en poudre séchée par pulvérisation contenant des enzymes pour lave-vaisselle
EP2199386A1 (fr) 1993-10-08 2010-06-23 Novozymes A/S Variants d'amylase
EP0653482A1 (fr) * 1993-11-11 1995-05-17 The Procter & Gamble Company Composition de blanchiment à base d'hypochlorite
US12545865B2 (en) 2023-07-20 2026-02-10 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch
US12545867B2 (en) 2023-07-20 2026-02-10 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch
US12553013B2 (en) 2023-07-20 2026-02-17 The Procter & Gamble Company Water-soluble automatic dishwashing detergent pouch

Also Published As

Publication number Publication date
NO168487C (no) 1992-02-26
JPS63101490A (ja) 1988-05-06
EP0266904A3 (fr) 1988-08-31
NO874170D0 (no) 1987-10-05
GB8624050D0 (en) 1986-11-12
NO874170L (no) 1988-04-08
NO168487B (no) 1991-11-18

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