Machine dishwashing detergent

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Dish tab

Machine dishwashing detergents are dishwashing detergents that are used in dishwashers . The pressed pieces are also called “tabs” in common parlance (short for “tablet (te)”) and are used in dishwashers in private households. In 2018, around 70% of all German households had a dishwasher; 75% of them now use "tabs", while the market share of the powdered and thus individually dosed machine dishwashing detergents is falling steadily.

The cleaning performance of conventional machine dishwashing detergents is based on surfactants in an alkaline environment , while bleaching agents , enzymes and other washing-active ingredients are also effective .

history

The first machine dishwashing detergent was Calgonit , which was developed in the company of Johann Adam Benckiser in 1929 and initially only used for commercial customers for bottle washing. It was not until 30 years later (1960) that Benckiser presented a machine dishwashing detergent in powder form for household use. In 1987 Dennis W. Weatherby developed the powdered machine dishwashing detergent Cascade with bleach while working for Procter & Gamble . In 1990 Benckiser introduced the first product in tablet form, and in 1995 the first "2-in-1" cleaner.

According to the Federal Cartel Office , consumers have paid excessive prices for dishwasher tabs for years. As a duopoly, the manufacturers Henkel and Reckitt Benckiser had agreed to raise prices between 2005 and 2007.

Major global manufacturers include Henkel ( Somat ), Reckitt Benckiser (Finish), Dalli-Werke (trademarks), Procter & Gamble (Cascade), Ecover and Ecolab .

Multiphase tabs

Multi-phase tab, here "MaxIn1"

Dishwasher cleaners are often offered in stores as multi-phase tabs.

  • 2-in-1: In addition to the dishwasher detergent, these also contain rinse aid ,
  • 3-in-1: with additional water softener (also advertised as a "salt substitute"),
  • 4-in-1: with additional glass protection
  • 5-in-1: with additional bleach activators (rinsing power boosters),
  • 7-in-1: with additional stainless steel gloss and "power decruster",
  • Even "higher quality" dishwasher cleaners are advertised with partially general properties ("fat dissolving power", "cleaning enhancer"), which tabs with "fewer" listed advantages can also provide, for example:
    • "11-in-1 dishwasher tabs": with "detergent, rinse aid, glass protection, salt function, stainless steel shine, cleaning enhancer, low temperature system, quick-drying formula, odor neutralizer, fat dissolving power, silver protection"

ingredients

Since the ingredients can change without notice due to the manufacturer's recipe changes, it is advisable to search the current pages of the manufacturers and distributors under the name of the respective product. In accordance with the Detergent Ordinance, the current recipes can be found there in the INCI code.

Machine dishwashing detergents are also used to soften the water . In contrast to ion exchangers, these bind hardness builders through permanent chemical bonds; it caused water-soluble chelate complexes of the hardness-forming alkaline earth metal ions (mainly calcium - and magnesium ion), see water hardness . Before the Detergent Ordinance was implemented , (alkali) polyphosphates were used; since January 1, 2017, machine dishwashing detergents in the EU have contained phosphate-free softeners, for example

Examples of other ingredients:

  • alkaline cleaning agents, the proportions of which influence the pH value , for example:
  • Bleach, e.g. B. Sodium percarbonate or sodium perborate (dihydrate) remove colored dirt that cannot be washed out; above 60 ° C they oxidize,  for example, humic acids (found in coffee, tea, cocoa, etc.), tannins (found in red wine and tea), anthocyanin dyes (found in berries ) in combination with:
  • Bleach activators (rinsing power boosters) that enable oxidative bleaching even below 60 ° C, such as
  • nonionic surfactants such as
  • Enzymes,
  • Builders support the effect of washing-active substances by, for example, softening water, adjusting the optimum pH value, increasing the dirt-bearing capacity. In the past, pentasodium tripolyphosphate was usually used for this purpose, nowadays it is more like zeolites and polycarboxylates ( copolymers of acrylic acid and maleic acid ) used
  • Amino acid compounds (for example of serine , threonine , ornithine , arginine , lysine , asparagine , glutamine , phenylalanine , tyrosine , glycine , alanine , valine , leucine and isoleucine ), such as glycine or alanine derivatives , as a substitute for enzymes, as Builder substances and for pH adjustment; Sulfur-containing amino acids would form insoluble silver salt deposits on silver cutlery
  • Benzotriazole or other triazoles as a corrosion inhibitor , although it is itself readily soluble in water, forms a water-insoluble protective film on metals
  • Anticorrosion agents such as zinc sulphate (which in the alkaline solution converts to insoluble zinc hydroxide and soluble hydroxo-zinc complexes, which in turn supposedly act as a glass corrosion protection agent). There are other ways to avoid clouding the glass. A low pH and salinity of the liquid and a high temperature accelerate the corrosion. Thus causes softer water in the dishwasher higher dissolution of minerals from the surface.
  • Triethanolamine as a solubilizer or, in the case of gel-like products, also as a thickener
  • Dyes to make the tabs more attractive (psychological effect, product design), without washing effect
  • Perfume substances to cover up unpleasant smells from stale lye in the pump sump, but also to cover up your own odor
  • Carboxylic acids , especially citric acid or its salts (citrates), buffer high pH values ​​and are used to form complexes of calcium and magnesium ions (hardness builders).
  • If (outside the EU) phosphates are included, for example pentasodium polyphosphate ; Phosphates keep the dirt particles in solution and ensure that the dirt particles do not settle on the dishes, but also act as softeners (i.e., complexing alkaline earth metal ions ). Because they fertilize the wastewater with soluble phosphates, they have been replaced. Typical formulations of compact and tablet-shaped machine dishwashing detergents contained 30 to 60% phosphate.

So-called "ECO programs" use the enzymes contained in conventional dishwasher detergents. The enzymes work in these longer washing programs at a lower temperature, while higher washing temperatures and more aggressive detergents are necessary in the case of short-term programs, in which the enzymes are denatured. Current multiphase tabs usually contain both types of cleaning system.

The protease subtilisin is known to sensitize the respiratory tract and is therefore in an encapsulated form in dishwasher detergents for the purpose of consumer protection.

Impact on the environment

After use, all cleaning agents end up in the canals or sewage treatment plants and rivers and cause costs or environmental damage.

Ready-made standard tabs contain a dosage that is sufficient for all degrees of water hardness in the sales area and thus prevent a lower dosage when the water hardness or the dishes are not so dirty, but they can be portioned using a knife. The economic interests of the cleaning agent producers ( sales promotion, i.e. increased sales through specified “quasi-prescribed” pack sizes) stand in contrast to avoiding unnecessary chemical release and the need to protect the environment. A reduction is only possible through the use of individually flooded modular components with appropriately adapted dishwashers.

The individual packaging ( portion packaging ) of tabs and wrappings are seen as unnecessary rubbish, a moisture-proof basic packaging and removal with a cutlery spoon for easy handling without contact would be sufficient. The water-soluble packaging made of polyvinyl alcohol film, which is occasionally offered, simplifies handling, but the water-soluble casing substances also pollute the waste water.

The corrosion inhibitors benzotriazole and tolyltriazole are relatively soluble in water, but are difficult to break down and are suspected of acting as endocrine disruptors . Only a small proportion of them are eliminated in sewage treatment plants and large quantities end up in rivers, lakes and seas.

Phosphonates and also ethylenediaminetetraacetic acid (EDTA) metal complexes are also difficult to biodegrade and therefore accumulate in the environment.

A test by Stiftung Warentest in 2015 showed that some phosphate-free dishwasher tablets already achieve a cleaning effect that is comparable to that of agents containing phosphate. The EU severely limited the use of phosphates in dishwashing detergents from early 2017; In the course of the change, there were therefore significant product changes on the supermarket shelves towards the end of 2016.

Not completely resolved tab

Unnecessary use and consumption of chemicals

In standard dishwashers, the hard tap water is pumped through ion exchange cartridges after it has been tapped; there, the dissolved alkaline earth metal ions , which interfere with washing processes, are removed and the water is "softened" . Only then does the water get into the interior of the dishwasher. In such machines, during normal operation, the softening substances that are added to the dishwasher detergent remain unused and ineffective; the rinsing water that has already been softened by an ion exchanger does not need and cannot be softened twice. This proportion of detergent was therefore bought unnecessarily and only pollutes the environment unnecessarily.

The amount of softener contained in a tab must be based on the average hardest natural water. If the water is soft (by nature or because it has been softened by a water softener system), the water softener will always be overdosed. If there is no ion exchange system and the tap water is particularly hard, the total amount of detergent added is usually increased - similar to detergents to improve the washing effect with extra hard water; this also increases the proportions of the other cleaners, which themselves are then overdosed and useless.

The technical term carry-over effect describes the intentional or unintentional carry-over of dissolved cleaning agents into the next wash cycle due to residual amounts in the pump sump (the deepest part of the pump system that can never be completely emptied by the pump). Powdered machine dishwashing detergents and easily soluble tabs use the carry-over effect so that substances that are still required (e.g. more effective softeners or rinse aid) are available in the second wash cycle. For this purpose, the concentration of these substances required in the main wash cycle must be high enough that the amount remaining in the pump sump is sufficient for the dilution in the second wash cycle. Most of these substances, which are only required in the second rinse, are pumped out - unused - after the first rinse. This proportion of detergent was also bought unnecessarily and only pollutes the environment unnecessarily.

In order to reduce the chemicals pumped out unused, modern dishwashers only add rinse aid from a reservoir during the last wash cycle. In this case, any rinse aid contained in the detergent is useless and pollutes the environment unnecessarily, so detergents used for such machines should not contain any rinse aid.

Because the machine load, the amount of soiling, the type of dishes, the temperature and the duration of the program can vary widely, not all of the substances contained in a tablet or powder are actually required and may remain in traces on the dishes after the last wash cycle. In general, modular systems (see also there ), which can be individually dosed depending on the local water hardness and the contamination in the specific wash cycle, would be the best solution for the environment.

literature

  • Klaus Henning: detergents and cleaning agents , 2nd edition, publishing house for chemical industry H. Ziolkowski GmbH, Thannhausen / Burg, ISBN 978-3-87846-291-0
  • Günter Wagner: detergents, chemistry, environment, sustainability , 5th edition, 2017, Wiley-VCH-Verlag, Weinheim, ISBN 978-3-527-34316-4 .

Web links

Individual evidence

  1. ↑ a b c Klaus Ruppersberg, Wolfgang Proske: Dishwasher tabs . In: Chemistry in Our Time . tape 53 , no. 3 . Wiley-VCH, Weinheim, p. 180–186 , doi : 10.1002 / ciuz.201800816 .
  2. ^ The History of Dishwashing Detergent .
  3. ↑ Finish / Calgonit– 80 years of clean dishes (PDF file; 31 kB) ( Memento from November 12, 2013 in the Internet Archive ).
  4. ↑ n24.de , accessed on January 5, 2012.
  5. ↑ Safety data sheet 4-in-1 dishwasher detergent (PDF; 115 kB).
  6. ↑ 11-in-1 tabs .
  7. ↑ Ingredients of detergents, machine and hand dishwashing detergents ; at Industrieverband Körperpflege- und Waschmittel e. V .; ikw.org
  8. ↑ Federal Environment Agency Chemical policy and pollutants, REACH, detergents and cleaning agents, information for consumers .
  9. ↑ Expertise dishwasher ; HEA - Professional Association for Efficient Energy Use eV
  10. ↑ Entry on etidronic acid. In: Römpp Online . Georg Thieme Verlag, accessed on June 30, 2019.
  11. ↑ a b c d e f g h i 7in1 Safety data sheet in accordance with EC Directive 91/155 / E for a 7 in 1 cleaner .
  12. ↑ a b c Ecology and Household Chemistry ( Memento from June 10, 2012 in the Internet Archive ), brochure from the Umweltbüro für Berlin-Brandburg e. V.
  13. ↑ Operating instructions according to § 14 GefStoffV for tableware cleaner Tabs Ultra ( Memento from January 2, 2014 in the Internet Archive ) (PDF; 34 kB).
  14. ^ A b Karl-Heinz Lautenschläger: Taschenbuch der Chemie. German, 2007, ISBN 978-3-817-11761-1 , pp. 765–766 ( limited preview in Google book search).
  15. ↑ a b Safety data sheet in accordance with EC Directive 91/155 and 93/112 EEC Claro 4in1 tabs with protective glass formula (PDF; 115 kB).
  16. ↑ M. Paladini, G. Schnorbus: Use of phosphonates in liquid heavy-duty detergents , Seifen-Öle-Fette-Wachse, 115th year (1989), pp. 508 to 511.
  17. ↑ Detergent additive ( Memento from July 19, 2012 in the Internet Archive ), product description, English, accessed on January 4, 2012.
  18. ^ Kosswig, Stache: Die Tenside , Carl Hanser Verlag, Munich 1993
  19. ↑ H.-J. Krause, A. Syldatk, Konrad Henkel: New surfactants from mixed Guerbet alcohols. In: fats, soaps, paints. 87, 1985, p. 386, doi : 10.1002 / lipi.19850871005 .
  20. ↑ Product data sheet for a machine dishwashing detergent ( Memento from September 7, 2012 in the Internet Archive ) (PDF; 100 kB), accessed on January 3, 2012.
  21. ↑ Safety data sheet for a cleaner (PDF; 72 kB).
  22. ↑ Registration dossier on subtilisin ( GHS section ) at the European Chemicals Agency (ECHA), accessed on May 21, 2019.
  23. ↑ page 765
  24. ↑ a b patent specification for a dishwasher detergent .
  25. ↑ Patent specification ( Memento of the original dated December 13, 2015 in the Internet Archive ) Info: The archive link was inserted automatically and has not yet been checked. Please check the original and archive link according to the instructions and then remove this notice. , accessed January 4, 2012. @1@ 2Template: Webachiv / IABot / www.surechem.org
  26. ↑ Benziotriazol , accessed 3 January 2012
  27. ↑ Patent specification of rinse aid with water-soluble metal salt for use in automatic dishwashing with glass corrosion protection , accessed on January 3, 2012.
  28. ^ Dispatch manuscript Glaskorrosion (PDF; 69 kB), accessed on January 4, 2012.
  29. ↑ Stiftung Warentest : Glasses and cutlery in the dishwasher . In: test , 02/2004, accessed on February 4, 2013
  30. ↑ Machine dishwashing detergent and process for its production , patent specification.
  31. ^ Ernst Guggolz: Phosphates in dishwashing detergents - a blessing and a curse. Gesellschaft Deutscher Chemiker, press release from January 26, 2012 from Informationsdienst Wissenschaft (idw-online.de), accessed on September 15, 2015.
  32. ↑ subtilisin | 9014-01-1. Retrieved August 14, 2019 .
  33. ↑ Stiftung Warentest: waste package , accessed Feb. 4, 2013.
  34. ↑ Waste avoidance rules (PDF), accessed on January 5, 2012.
  35. ↑ Martin Heidenreich: 1H-Benzotriazole. May 10, 2016, accessed August 14, 2019 .
  36. ^ W. Giger , C. Schaffner, HP. Kohler (2006): Benzotriazole and Tolyltriazole as Aquatic Contaminants. 1. Input and Occurrence in Rivers and Lakes . Environ. Sci. Technol. 40, pp. 7186-7192. PMID 17180965
  37. ↑ Antifreeze discovered in the North Sea . In: Welt online.
  38. ↑ Hendrik Wolschke, Zhiyong Xie, Axel Möller, Renate Sturm, Ralf Ebinghaus: Occurrence, distribution and fluxes of benzotriazoles along the German large river basins into the North Sea . In: Water Research . tape 45 , no. November 18 , 2011, p. 6259-6266 , doi : 10.1016 / j.watres.2011.09.028 .
  39. ^ Willemsen, Hans-Günter (State Environment Agency North Rhine-Westphalia): EDTA in NRW - a synthetic substance in an aquatic environment . In: Environment NRW, Düsseldorf, 2003.
  40. ^ Heintz, Reinhardt: Chemistry and Environment , Vieweg-Verlag, ISBN 3-528-36349-5 .
  41. ↑ Dishwasher tabs tested by Stiftung Warentest In: test 5/2015, pp. 62–66 and test.de from April 23, 2015.
  42. ↑ Official Journal of the European Union: REGULATION (EU) No. 259/2012 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL. March 14, 2012, accessed December 5, 2018 .
  43. ↑ Buying a dishwasher: What to look out for. Retrieved August 14, 2019 .