EP0530635A2 - Composition neutre pour laver la vaisselle en machine - Google Patents
Composition neutre pour laver la vaisselle en machine Download PDFInfo
- Publication number
- EP0530635A2 EP0530635A2 EP92114418A EP92114418A EP0530635A2 EP 0530635 A2 EP0530635 A2 EP 0530635A2 EP 92114418 A EP92114418 A EP 92114418A EP 92114418 A EP92114418 A EP 92114418A EP 0530635 A2 EP0530635 A2 EP 0530635A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- dishwashing detergent
- detergent according
- 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.)
- Granted
Links
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 automatic dishwasher detergent.
- acid dishwashing detergents which have a pH of 2-6, preferably 3-5, in 0.5-0.7% aqueous solution.
- These acidic dishwashing detergents contain 5-80% by weight of hydroxypolycarboxylic acids such as citric acid and sodium citrate as builders. 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, a pH of 3-6 being set in the pre-cleaning liquor by means of appropriately acidic agents and a pH 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 disclosed 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 machine washing dishes, whereby a soaking bath containing enzymes is connected upstream.
- 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 dishwashing detergents or rinse aids (rinse aid). 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 regeneration 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 detergents which contain a builder system which ensures a pH of 5-9, preferably above 6-8, 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 to adjust the pH.
- 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.
- enzymes such as, for example, amylase, protease, lipase, cellulase.
- amylase ase
- protease ase
- lipase ase
- cellulase e.g., cellulase.
- the 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 activity 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 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 hazardous 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 process, with a rating of 5 for absolutely clean dishes after cleaning, a rating of 0 if no dirt is removed.
- tap water of about 20 ° d was used, 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.
Landscapes
- 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)
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 true EP0530635A2 (fr) | 1993-03-10 |
EP0530635A3 EP0530635A3 (en) | 1993-08-04 |
EP0530635B1 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 (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994007981A1 (fr) * | 1992-09-25 | 1994-04-14 | Henkel Kommanditgesellschaft Auf Aktien | Detergent faiblement alcalin pour lave-vaisselle |
WO1997008281A1 (fr) * | 1995-08-25 | 1997-03-06 | Henkel Kommanditgesellschaft Auf Aktien | Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine |
EP0636170B1 (fr) * | 1992-04-13 | 1997-08-06 | The Procter & Gamble Company | Composition thixotrope liquide contenant des enzymes, pour le lavage automatique de la vaisselle |
US5786314A (en) * | 1993-11-03 | 1998-07-28 | The Procter & Gamble Company | Control of calcium precipitation in automatic dishwashing |
US5786315A (en) * | 1993-11-03 | 1998-07-28 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
EP0863199A2 (fr) * | 1997-03-03 | 1998-09-09 | Henkel Kommanditgesellschaft auf Aktien | Composition détergente ayant un pH acide |
US5898025A (en) * | 1992-09-25 | 1999-04-27 | Henkel Kommanditgesellschaft Auf Aktien | Mildly alkaline dishwashing detergents |
WO2003006594A1 (fr) * | 2001-07-07 | 2003-01-23 | Henkel Kommanditgesellschaft Auf Aktien | Detergents aqueux '3 en 1' pour lave-vaisselle |
DE10311429A1 (de) * | 2003-03-13 | 2004-09-23 | Thomas Hartl | Kombinations-Spülmittel (Fettlöser und Kalklöser) |
US7153816B2 (en) | 2001-08-17 | 2006-12-26 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Dishwasher detergent with improved protection against glass corrosion |
US7192911B2 (en) | 2001-07-07 | 2007-03-20 | Henkel Kgaa | Nonaqueous 3 in 1 dishwasher products |
WO2010049187A1 (fr) * | 2008-10-31 | 2010-05-06 | Henkel Ag & Co. Kgaa | Agent de lavage pour lave-vaisselle |
WO2011049945A2 (fr) | 2009-10-23 | 2011-04-28 | Danisco Us Inc. | Procédés destinés à réduire le saccharide donnant une couleur bleue |
EP2428572A2 (fr) | 2007-03-09 | 2012-03-14 | Danisco US, Inc., Genencor Division | Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation |
US8323945B2 (en) | 2008-06-06 | 2012-12-04 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof |
US8507243B2 (en) | 2008-09-25 | 2013-08-13 | Danisco Us Inc. | Alpha-amylase blends and methods for using said blends |
US9040278B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Production of glucose from starch using alpha-amylases from Bacillus subtilis |
US9040279B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Saccharification enzyme composition and method of saccharification thereof |
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 |
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 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2016272A1 (en) * | 1968-08-23 | 1970-05-08 | Henkel & Cie Gmbh | Enzymatic pretreatment of dishes before - cleaning in dish washers |
FR2130382A1 (fr) * | 1971-03-18 | 1972-11-03 | Procter & Gamble | |
FR2184726A1 (en) * | 1972-05-12 | 1973-12-28 | Continental Oil Co | Detergent compsns - contg sulphated alcohol ethoxylate but no phosphate nor nitroltriacetic builders |
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 |
EP0368341B1 (fr) * | 1988-11-11 | 1996-01-31 | Kao Corporation | Composition détergente contenant des enzymes |
-
1992
- 1992-08-24 DE DE59208478T patent/DE59208478D1/de not_active Revoked
- 1992-08-24 DK DK92114418.4T patent/DK0530635T3/da active
- 1992-08-24 EP EP92114418A patent/EP0530635B1/fr not_active Revoked
- 1992-08-24 ES ES92114418T patent/ES2100985T3/es not_active Expired - Lifetime
- 1992-08-24 AT AT92114418T patent/ATE153056T1/de not_active IP Right Cessation
-
1997
- 1997-06-26 GR GR970401540T patent/GR3023893T3/el unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2016272A1 (en) * | 1968-08-23 | 1970-05-08 | Henkel & Cie Gmbh | Enzymatic pretreatment of dishes before - cleaning in dish washers |
FR2130382A1 (fr) * | 1971-03-18 | 1972-11-03 | Procter & Gamble | |
FR2184726A1 (en) * | 1972-05-12 | 1973-12-28 | Continental Oil Co | Detergent compsns - contg sulphated alcohol ethoxylate but no phosphate nor nitroltriacetic builders |
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 |
EP0368341B1 (fr) * | 1988-11-11 | 1996-01-31 | Kao Corporation | Composition détergente contenant des enzymes |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0636170B1 (fr) * | 1992-04-13 | 1997-08-06 | The Procter & Gamble Company | Composition thixotrope liquide contenant des enzymes, pour le lavage automatique de la vaisselle |
US5898025A (en) * | 1992-09-25 | 1999-04-27 | Henkel Kommanditgesellschaft Auf Aktien | Mildly alkaline dishwashing detergents |
WO1994007981A1 (fr) * | 1992-09-25 | 1994-04-14 | Henkel Kommanditgesellschaft Auf Aktien | Detergent faiblement alcalin pour lave-vaisselle |
US5786314A (en) * | 1993-11-03 | 1998-07-28 | The Procter & Gamble Company | Control of calcium precipitation in automatic dishwashing |
US5786315A (en) * | 1993-11-03 | 1998-07-28 | The Procter & Gamble Company | Control of calcium carbonate precipitation in automatic dishwashing |
WO1997008281A1 (fr) * | 1995-08-25 | 1997-03-06 | Henkel Kommanditgesellschaft Auf Aktien | Utilisation de lipase dans des agents faiblement alcalins pour le lavage de vaisselle en machine |
EP0863199A2 (fr) * | 1997-03-03 | 1998-09-09 | Henkel Kommanditgesellschaft auf Aktien | Composition détergente ayant un pH acide |
EP0863199A3 (fr) * | 1997-03-03 | 1999-09-15 | Henkel Kommanditgesellschaft auf Aktien | Composition détergente ayant un pH acide |
WO2003006594A1 (fr) * | 2001-07-07 | 2003-01-23 | Henkel Kommanditgesellschaft Auf Aktien | Detergents aqueux '3 en 1' pour lave-vaisselle |
US7041628B2 (en) | 2001-07-07 | 2006-05-09 | Henkel Kommanditgesellschaft Auf Aktien | Aqueous 3 in 1 dishwasher products |
US7192911B2 (en) | 2001-07-07 | 2007-03-20 | Henkel Kgaa | Nonaqueous 3 in 1 dishwasher products |
US7153816B2 (en) | 2001-08-17 | 2006-12-26 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Dishwasher detergent with improved protection against glass corrosion |
DE10311429A1 (de) * | 2003-03-13 | 2004-09-23 | Thomas Hartl | Kombinations-Spülmittel (Fettlöser und Kalklöser) |
EP2428572A2 (fr) | 2007-03-09 | 2012-03-14 | Danisco US, Inc., Genencor Division | Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation |
US9090887B2 (en) | 2008-06-06 | 2015-07-28 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of use, thereof |
US9040279B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Saccharification enzyme composition and method of saccharification thereof |
US8323945B2 (en) | 2008-06-06 | 2012-12-04 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof |
US8975056B2 (en) | 2008-06-06 | 2015-03-10 | Danisco Us Inc. | Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof |
US9040278B2 (en) | 2008-06-06 | 2015-05-26 | Danisco Us Inc. | Production of glucose from starch using alpha-amylases from Bacillus subtilis |
US8507243B2 (en) | 2008-09-25 | 2013-08-13 | Danisco Us Inc. | Alpha-amylase blends and methods for using said blends |
WO2010049187A1 (fr) * | 2008-10-31 | 2010-05-06 | Henkel Ag & Co. Kgaa | Agent de lavage pour lave-vaisselle |
WO2011049945A2 (fr) | 2009-10-23 | 2011-04-28 | Danisco Us Inc. | Procédés destinés à réduire le saccharide donnant une couleur bleue |
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 |
US9840683B2 (en) | 2013-10-09 | 2017-12-12 | Basf Se | Alkaline detergent composition containing a carboxylic acid/polyalkylene oxide copolymer for hard water scale control |
US10364409B2 (en) | 2013-10-09 | 2019-07-30 | Ecolab Usa Inc. | Solidification matrix comprising a carboxylic acid terpolymer |
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 |
Also Published As
Publication number | Publication date |
---|---|
DE59208478D1 (de) | 1997-06-19 |
EP0530635A3 (en) | 1993-08-04 |
DK0530635T3 (da) | 1997-09-29 |
GR3023893T3 (en) | 1997-09-30 |
ATE153056T1 (de) | 1997-05-15 |
EP0530635B1 (fr) | 1997-05-14 |
ES2100985T3 (es) | 1997-07-01 |
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