EP0530635B1 - Composition neutre pour laver la vaisselle en machine - Google Patents

Composition neutre pour laver la vaisselle en machine Download PDF

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Publication number
EP0530635B1
EP0530635B1 EP92114418A EP92114418A EP0530635B1 EP 0530635 B1 EP0530635 B1 EP 0530635B1 EP 92114418 A EP92114418 A EP 92114418A EP 92114418 A EP92114418 A EP 92114418A EP 0530635 B1 EP0530635 B1 EP 0530635B1
Authority
EP
European Patent Office
Prior art keywords
weight
dishwashing
dishwashing agent
builder system
salt
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.)
Revoked
Application number
EP92114418A
Other languages
German (de)
English (en)
Other versions
EP0530635A3 (en
EP0530635A2 (fr
Inventor
Klaus Golz
Ludwig Hertling
Harald Dr. Magg
Guido Dr. Wäschenbach
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.)
Reckitt Benckiser NV
Original Assignee
Joh A Benckiser GmbH
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=6439450&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0530635(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Joh A Benckiser GmbH filed Critical Joh A Benckiser GmbH
Publication of EP0530635A2 publication Critical patent/EP0530635A2/fr
Publication of EP0530635A3 publication Critical patent/EP0530635A3/de
Application granted granted Critical
Publication of EP0530635B1 publication Critical patent/EP0530635B1/fr
Anticipated expiration legal-status Critical
Revoked 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2086—Hydroxy carboxylic acids-salts thereof

Definitions

  • the invention relates to a neutral machine dishwashing detergent.
  • acid dishwashing detergents which have a pH of 2-6, preferably 3-5, in 0.5-0.7% aqueous solution.
  • These acidic dish detergents contain 5-80% by weight of hydroxypolycarboxylic acids such as citric acid and sodium citrate as framework substances. They also contain 0.5-5% by weight of at least one enzyme from the group of hydrolases, such as proteases and lipases, and preferably amylases.
  • DE-PS 35 32 586 relates to phosphate-free, acidic detergent in powder form for dishwashers, which contain a polymeric organic carboxylic acid, a weakly acidic organic acid, such as citric acid, a nonionic surfactant, silica and fillers.
  • DE-AS 1 151 627 discloses acidic cleaning agents, in particular for dishwashers, which contain poorly soluble mixed ethylene oxide and propylene oxide addition products with, for example, nonylphenol and additions of acidic agents, for example citric acid.
  • DE-AS 1 628 632 discloses a method for machine washing dishes, whereby a pH value of 3-6 is set in the pre-cleaning liquor by means of appropriately acidic agents and a pH value of 4-6 in the rinse aid liquor.
  • U.S. Patent 3,553,139 discloses dishwashing detergents containing an enzyme and a per compound.
  • GB-PS 1 197 446 discloses dishwashing detergents, the invention being seen in that an amylolytic enzyme is added to them.
  • dishwashing detergents have a pH of 7.0-9.0 and have a high phosphate content.
  • these agents should contain 40-60% alkali phosphate.
  • GB-PS 1 323 670 discloses washing and cleaning agents which are said to be phosphate-free and are said to contain a certain surface-active agent.
  • the pH of these agents is completely uncritical and can range from 6-10.
  • These known agents are detergents, especially for cleaning textiles.
  • the compositions can also be used as detergents in dishwashing, it is obvious to the person skilled in the art that the disclosed compositions are not very suitable for dishwashing and in particular are completely unsuitable for machine dishwashing because they are much too foaming.
  • DE-OS 1 792 359 relates to a multi-stage process for the automatic washing of dishes, with a soaking bath upstream which contains enzymes.
  • This soaking bath can have a pH of 4-12.
  • DE-OS 1 692 021 discloses dishwashing detergents which necessarily contain alkali phosphates.
  • DE-OS 2 060 485 discloses enzymatic detergents with a pH of 6.5-6.8, which are to be used as hand-held detergents or rinse aids (rinse aids). Because of their high surfactant content, they are not suitable as automatic dishwashing detergents.
  • dishwashing detergents also has some disadvantages. In part, they still largely consist of ingredients that are no longer caustic but still irritating to the skin or eyes. The bleaching effect of the oxygen system also lags behind that of the chlorine system.
  • the acidic dishwashing detergents described in DE-OS 38 33 047 have advantages in that, for example, no regenerating salt has to be used, but they have to lose a distance in the acidic pH range accept certain types of soiling. Only a formulation with strong complexing agents such as NTA or EDTA was able to largely compensate for this disadvantage. Due to their potential for the remobilization of heavy metals from sludge or sediments, such compounds should not, according to current knowledge, be released into the environment in large quantities.
  • neutral automatic dishwashing detergents of a certain composition not only offer better consumer safety and more favorable environmental behavior, but surprisingly also provide comparable or even better cleaning performance than conventional cleaners.
  • the invention therefore relates to liquid or powdered, phosphate-free automatic dishwashing agents containing a builder system, which ensure a pH of 5-8 in 1.0% aqueous solution and which are free of NTA and EDTA.
  • a builder system from the salt of a hydroxycarboxylic acid or from the mixture of a hydroxycarboxylic acid and the salt of a hydroxycarboxylic acid is particularly preferred.
  • the preferred object of the invention is a liquid or powdered automatic dishwashing detergent which contains a builder or buffer system composed of a salt of a hydroxycarboxylic acid or a mixture of a hydroxycarboxylic acid with the salt of a hydroxycarboxylic acid and has a pH of more than 1.0% in aqueous solution 6-8, preferably 6.1-7.5. A pH of 6.2-6.5 is particularly preferred.
  • the builder system preferably consists of the salt of a hydroxypolycarboxylic acid with 2-4 carboxyl groups, which can be mixed with a hydroxypolycarboxylic acid or acidic inorganic salts for pH adjustment.
  • a suitable polymer e.g. Polyacrylate.
  • Sodium citrate or a mixture of sodium citrate with citric acid is preferably used.
  • Mixtures with a predominant proportion of sodium citrate, for example 10 parts of trisodium citrate dihydrate with 1 part of citric acid, are suitable for adjusting the pH value according to the invention, up to and including systems which consist exclusively of trisodium citrate.
  • a system of 20-22 parts by weight of trisodium citrate per 1 part of citric acid is particularly preferred.
  • the dishwashing detergent according to the invention generally contains 20-98% by weight of such a builder system.
  • Liquid dishwashing detergent products generally contain 20-60% by weight, powdered dishwashing detergents naturally contain a higher proportion, generally in the range of 50-98% by weight.
  • the water content of the liquid dishwashing detergent can be about 40-80% by weight.
  • the liquid dishwashing detergents also contain 0.2-5.0% by weight, preferably 0.5-2% by weight, of a thickener.
  • a thickener preferably 0.5-2% by weight
  • Carboxyvinyl polymers such as those marketed by BF Goodrich under the product name "Carbopol”, proved to be very useful.
  • inorganic compounds in this product composition have thickening properties can be used. Examples of this are natural or synthetic thickeners based on differently structured silicate structures. Their use is described in various patents, for example in US Pat. No. 4,933,101 or EP-A2-0 407 187.
  • the liquid dishwashing detergents according to the invention are bleach-free.
  • Powdered cleaners can contain an oxygen-based bleaching or oxidizing agent.
  • bleaching or oxidizing agents come e.g. in question perborates, percarbonates, peroxymonosulfates, peroxydisulfates or peroxycarboxylic acid and their salts.
  • Boron-free bleaches such as e.g. Caroate (Peroxymonosulfate).
  • a small amount of bleach can be beneficial to prevent the formation of sulfide on silver.
  • the dishwashing detergents according to the invention can also contain a low content of generally 0.2-5, preferably 0.5-2,% by weight of a nonionic surfactant. All non-ionic surfactants customary for this purpose, in particular fatty alcohol alkoxylates, are suitable for this purpose. Anionic surfactants should preferably not be used.
  • the automatic dishwashing agents according to the invention preferably contain one or more enzymes, such as, for example, amylase, protease, lipase, cellulase.
  • amylase such as, for example, amylase, protease, lipase, cellulase.
  • protease such as, for example, amylase, protease, lipase, cellulase.
  • the best cleaning results were achieved by the combined use of amylase and protease.
  • These enzymes can be used particularly effectively in the pH ranges described here; For example, the temperature-stable amylase Termamyl (Novo) achieves the optimum of its spectrum of action at pH 7-8.
  • the enzymes come in granular form or in solution with commercially available ones Concentrations or activities are used, the content of enzymes being 0.5-6, preferably 1-4% by weight.
  • Liquid dishwashing detergents are particularly preferred according to the invention.
  • the neutral dishwashing detergents according to the invention are neither caustic nor irritating because of their neutral pH and therefore do not require any particularly secure packaging. A good washing result can be achieved with a relatively low amount of 15-20 g powder or 20-50 ml liquid cleaner. All ingredients are after current knowledge is neither toxic nor otherwise harmful to health.
  • the cleaning agents described here are therefore an environmentally and consumer-friendly alternative to conventional cleaners, which are also characterized by a surprisingly high cleaning ability.
  • the types of soiling were prepared and applied in accordance with DIN 44990.
  • the drying times of DIN 44990 were observed.
  • the evaluation was carried out in accordance with DIN 44990 according to an internal evaluation procedure, with a rating of 5 for absolutely clean dishes after cleaning, a rating of 0 if no dirt is removed.
  • rinsing with tap water of approximately 20 ° d was carried out, which was not softened in the machine.
  • the amount of detergent was 20 g for the powder detergent. 40 ml (corresponds to approx. 50 g) were added to the liquid cleaner.

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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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Claims (14)

  1. Produits liquides ou en poudre de lavage de la vaisselle en machine qui sont dépourvus de phosphate, de NTA et d'EDTA et contiennent un système adjuvant, caractérisés en ce qu'ils présentent, en solution aqueuse à 1,0%, un pH de 5 à 8.
  2. Produit de lavage de la vaisselle selon la revendication 1, caractérisé en ce que le système adjuvant se compose
    a) du sel d'un acide hydroxycarboxylique ou
    b) du mélange d'un acide hydroxycarboxylique et du sel d'un acide hydroxycarboxylique ou
    c) du mélange d'un acide hydrocarboxylique et du sel d'un acide hydroxycarboxylique et d'un polymère.
  3. Produit de lavage de la vaisselle selon la revendication 2, caractérisé en ce qu'il présente un pH de plus de 6 à 8, de préférence de 6,1 à 7,5 et contient un système adjuvant se composant du sel d'un acide hydroxycarboxylique ou du mélange d'un acide hydrocarboxylique et d'un sel de celui-ci.
  4. Produit de lavage de la vaisselle selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient, en tant que système adjuvant, du citrate de sodium ou un mélange d'acide citrique et de citrate de sodium.
  5. Produit de lavage de 1a, vaisselle selon la revendication 4, caractérisé en ce qu'il contient 20 à 98% en poids de citrate de sodium ou du mélange d'acide citrique et de citrate de sodium.
  6. Produit liquide de lavage de la vaisselle selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient 20 à 60% en poids du système adjuvant.
  7. Produit liquide de lavage de la vaisselle selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il contient 0,2 à 5, de préférence 0,5 à 2% en poids d'un épaississant.
  8. Produit en poudre de lavage de la vaisselle selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il contient 1 à 20% en poids d'un agent de blanchiment ou d'un oxydant.
  9. Produit en poudre de lavage de la vaisselle selon l'une quelconque des revendications 1 à 5 et 8, caractérisé en ce qu'il contient 50 à 98% en poids du système adjuvant.
  10. Produit de lavage de la vaisselle selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il contient 0,2 à 5, de préférence 0,5 à 2% en poids d'un tensio-actif non ionique.
  11. Produit de lavage de la vaisselle selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'il contient au moins une enzyme.
  12. Produit de lavage de la vaisselle selon la revendication 11, caractérisé en ce qu'il contient une amylase et une protéase.
  13. Produit liquide de lavage de la vaisselle selon la revendication 1, se composant essentiellement de
    a) 20 à 60% en poids d'un système adjuvant se composant de citrate de sodium et d'acide citrique,
    b) 0,5 à 2% en poids d'un tensio-actif non ionique,
    c) 0,5 à 2% en poids d'une ou de plusieurs enzymes,
    d) 0,5 à 2% en poids d'un épaississant,
    e) 38 à 78% en poids d'eau.
  14. Utilisation d'un produit liquide ou en poudre de lavage, dépourvu de phosphate et contenant un système adjuvant, qui présente, en solution aqueuse à 1,0%, un pH de plus de 6 à 8 et est dépourvu de NTA et d'EDTA, pour le lavage de vaisselle à la machine.
EP92114418A 1991-08-29 1992-08-24 Composition neutre pour laver la vaisselle en machine Revoked EP0530635B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4128767 1991-08-29
DE4128767 1991-08-29

Publications (3)

Publication Number Publication Date
EP0530635A2 EP0530635A2 (fr) 1993-03-10
EP0530635A3 EP0530635A3 (en) 1993-08-04
EP0530635B1 true EP0530635B1 (fr) 1997-05-14

Family

ID=6439450

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92114418A Revoked EP0530635B1 (fr) 1991-08-29 1992-08-24 Composition neutre pour laver la vaisselle en machine

Country Status (6)

Country Link
EP (1) EP0530635B1 (fr)
AT (1) ATE153056T1 (fr)
DE (1) DE59208478D1 (fr)
DK (1) DK0530635T3 (fr)
ES (1) ES2100985T3 (fr)
GR (1) GR3023893T3 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8314056B2 (en) 2008-10-31 2012-11-20 Henkel Ag & Co. Kgaa Automatic dishwashing agent
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Families Citing this family (19)

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Publication number Priority date Publication date Assignee Title
DE69312924D1 (de) * 1992-04-13 1997-09-11 Procter & Gamble Enzym enthaltendes, flüssiges, thixotropes maschinengeschirrspülmittel
US5898025A (en) * 1992-09-25 1999-04-27 Henkel Kommanditgesellschaft Auf Aktien Mildly alkaline dishwashing detergents
DE4232170C2 (de) * 1992-09-25 1999-09-16 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
CA2175331C (fr) * 1993-11-03 2000-02-01 Eugene Steven Sadlowski Limitation de la precipitation de carbonate de calcium dans les lave-vaisselle
AU7932094A (en) * 1993-11-03 1995-05-23 Procter & Gamble Company, The Control of calcium carbonate precipitation in automatic dishwashing
ES2143777T3 (es) * 1995-08-25 2000-05-16 Henkel Kgaa Empleo de lipasas en agentes de baja alcalinidad para el fregado a maquina de la vajilla.
DE19708500A1 (de) * 1997-03-03 1998-09-10 Henkel Kgaa Waschmittel mit saurem pH-Wert
DE10153553A1 (de) 2001-07-07 2003-06-12 Henkel Kgaa Nichtwäßrige "3in1"-Geschirrspülmittel II
DE10153554A1 (de) 2001-07-07 2003-05-15 Henkel Kgaa Wäßrige "3in1"-Geschirrspülmittel II
PL202632B1 (pl) 2001-08-17 2009-07-31 Henkel Ag & Co Kgaa Środek do maszynowego natryskowego zmywania naczyń
DE10311429A1 (de) * 2003-03-13 2004-09-23 Thomas Hartl Kombinations-Spülmittel (Fettlöser und Kalklöser)
KR20100014954A (ko) 2007-03-09 2010-02-11 다니스코 유에스 인크. 호알칼리성 바실러스 종 α-아밀라아제 변이체, α-아밀라아제 변이체를 함유하는 조성물 및 사용 방법
CN102112605B (zh) 2008-06-06 2014-02-26 丹尼斯科美国公司 来自枯草芽孢杆菌的变体α-淀粉酶及其使用方法
MX2010013122A (es) 2008-06-06 2011-01-21 Danisco Inc Composicion de enzima de sacarificacion y metodo de sacarificacion de la misma.
JP5560266B2 (ja) 2008-06-06 2014-07-23 ダニスコ・ユーエス・インク バシルススブチリス（Ｂ．ｓｕｂｔｉｌｉｓ）由来アルファ‐アミラーゼを用いるデンプンからのグルコースの生産
CA2738447C (fr) 2008-09-25 2019-01-08 Danisco Us Inc. Melanges d'alpha-amylases, et leurs methodes d'utilisation
CN102803481A (zh) 2009-10-23 2012-11-28 丹尼斯科美国公司 用于减少蓝色糖的方法
EP3034588B1 (fr) 2014-12-17 2019-04-24 The Procter and Gamble Company Composition de détergent
DE102022131908A1 (de) 2022-12-01 2024-06-06 Henkel Ag & Co. Kgaa Geschirrspülmaschinenreiniger mit verbesserter Kalkentfernung und zusätzlicher Fettentfernung

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DE1792359A1 (de) * 1968-08-23 1973-02-08 Henkel & Cie Gmbh Verfahren zum maschinellen spuelen von geschirr
CA966751A (en) * 1971-03-18 1975-04-29 Charles R. Ries Phosphorus-free detergent composition
CA981555A (en) * 1972-05-12 1976-01-13 William L. Groves (Jr.) Phosphate and nitrilotriacetic acid-free, heavy-duty detergent powder
DE2230453A1 (de) * 1972-06-22 1974-01-17 Benckiser Gmbh Joh A Grundstoffansatz fuer wasch- und reinigungsmittel
DE3532586C1 (de) * 1985-09-11 1986-09-11 almaca Bioprodukte Herstellungs GmbH, 7901 Illerrieden Phosphatfreies,sauer eingestelltes Spuelmittel in Pulverform fuer Geschirrspuelmaschinen
US5030377A (en) * 1988-11-11 1991-07-09 Kao Corporation Detergent compositions containing starch debranching enzymes

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8314056B2 (en) 2008-10-31 2012-11-20 Henkel Ag & Co. Kgaa Automatic dishwashing agent
US9127235B2 (en) 2013-10-09 2015-09-08 Ecolab Usa Inc. Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control
US9487738B2 (en) 2013-10-09 2016-11-08 Ecolab Usa Inc. Solidification matrix comprising a carboxylic acid terpolymer

Also Published As

Publication number Publication date
DK0530635T3 (da) 1997-09-29
EP0530635A3 (en) 1993-08-04
DE59208478D1 (de) 1997-06-19
ES2100985T3 (es) 1997-07-01
ATE153056T1 (de) 1997-05-15
GR3023893T3 (en) 1997-09-30
EP0530635A2 (fr) 1993-03-10

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