EP0203524B1 - Composé sous forme de bloc fondu exempt d'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et son procédé de préparation - Google Patents

Composé sous forme de bloc fondu exempt d'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et son procédé de préparation Download PDF

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Publication number
EP0203524B1
EP0203524B1 EP86106943A EP86106943A EP0203524B1 EP 0203524 B1 EP0203524 B1 EP 0203524B1 EP 86106943 A EP86106943 A EP 86106943A EP 86106943 A EP86106943 A EP 86106943A EP 0203524 B1 EP0203524 B1 EP 0203524B1
Authority
EP
European Patent Office
Prior art keywords
active chlorine
detergent
content
weight
alkali
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.)
Expired - Lifetime
Application number
EP86106943A
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German (de)
English (en)
Other versions
EP0203524A3 (en
EP0203524A2 (fr
Inventor
Peter Dr. Jeschke
Theodor Dr. Altenschöpfer
Jochen Dr. Jacobs
Klaus Dr. Schumann
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to AT86106943T priority Critical patent/ATE66246T1/de
Publication of EP0203524A2 publication Critical patent/EP0203524A2/fr
Publication of EP0203524A3 publication Critical patent/EP0203524A3/de
Application granted granted Critical
Publication of EP0203524B1 publication Critical patent/EP0203524B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0052—Cast detergent 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
    • C11D3/395—Bleaching agents
    • C11D3/3958—Bleaching agents combined with phosphates

Definitions

  • Powder, granule or tablet detergents for dishes in dishwashers consist essentially of pentasodium triphosphate, alkali silicate, predominantly alkali metasilicate and optionally a low-foaming, preferably chlorine-stable, nonionic surfactant and bleaching agents, preferably those which release active chlorine in an aqueous solution. They are mainly used to facilitate the removal of stains from tea, coffee or fruit juices.
  • the agents are strongly alkaline due to their high content of alkali silicates and pentasodium triphosphate. Their working solutions have a pH of around 11 to 12. An addition of sodium hydroxide is not intended, because in the contact times customary in household dishwashers, porcelain, frosting decorations and glasses are then attacked by the high alkalinity. This attack is called corrosion.
  • Silicate on the other hand, synergistically supports the cleaning power of triphosphate and inhibits corrosion in certain concentrations in the total triphosphate / silicate mixture.
  • the known agents are generally produced by customary production processes, such as mixing or granulating. They are also used in powder or granule form usual concentrations, ie in amounts of about 30 to 50 g per machine filling.
  • a disadvantage of the production of a tablet on the basis of compressed individual substances is that mechanical strength and dissolution speed are in opposite directions. For this reason, it is necessary to add tableting aids and so-called "disintegrants". On the one hand, these bring about a homogeneity of the pulverulent or granulated raw materials during the pressing process, on the other hand the tablet is broken up by contact with water by swelling of the disintegrant, whereby a better solubility is achieved.
  • both additives are useless for the cleaning process as such, so they represent dietary fiber, the incorporation of which is also time-consuming.
  • melt-block detergents for machine dishwashing have already been described, which can be obtained by simply mixing together all the alkaline-reacting active substances, such as, for. B. up to 65 wt .-%, based on the total agent, of sodium silicates and pentasodium triphosphate and optionally water, if the preferred water of hydration of the compounds mentioned is not sufficient, and then gentle heating of the mixture with stirring to 90 to 100 o C until Achieving a uniformly molten mass and casting it in molds and allowing it to solidify to form a dense crystal aggregate.
  • Additions of active chlorine-releasing compounds have not been mentioned there. This is understandable because the agents themselves are strongly alkaline and it was to be expected that, like many substances whose addition would be desirable, but which are sensitive to alkali, they would be rendered ineffective during the melting process.
  • Block-shaped agents for machine dishwashing obtained from solidified aqueous solution are also described in EP-PS 3,769. They mostly contain high proportions of alkali hydroxides. However, Example 8 also gives a composition that is free of alkali hydroxide. There, the active chlorine carrier is stirred directly into the later solidifying aqueous solution of the constituents at 55 to 60 ° C., but mostly the active chlorine carrier is added in the form of a separate core. In this example, the AS content is only 60% by weight, based on the total agent, which is too low for use in household dishwashers. Since the patent repeatedly refers to the known alkali sensitivity of the active chlorine carriers, also in comparative experiments, it could not be assumed that active chlorine carriers could be incorporated directly into strongly alkaline, alkali hydroxide-free melt block cleaners.
  • melting blocks form alkali hydroxide-free agents for the mechanical cleaning of dishes containing a mixture of alkali silicates and pentaalkalitriphosphates and having a homogeneously distributed content of, preferably organic, active chlorine-releasing compounds.
  • the present invention thus relates to a block-shaped, alkali hydroxide-free, active chlorine-containing agent obtained by means of a melting process at 45 to 55 ° C. for the automatic cleaning of dishes, based on a content of 65 to 85% by weight and calculated on the total Agents and on crystal water-free compounds, a mixture of alkali silicates, advantageously in the form of their hydrates or in the form of mixtures of hydrates and the anhydrous compounds, and pentaalkali nitride phosphates, as hexahydrate, as a mixture of hexahydrate with small amounts of the anhydrous compound or as an anhydrous compound homogeneously distributed content of 0.2 to 4% by weight, based on the active chlorine content and the total composition, of an active chlorine-releasing compound, and a total water content, preferably as the crystal water content of the alkaline-reacting active substances, of 11 to 34.8% by weight is marked.
  • Alkali silicates are preferred as alkali silicates, advantageously in the form of sodium metasilicate . 9 H20, sodium metasilicate . 6 H20 and sodium metasilicate . 5 H20 used.
  • the amounts used are in particular 5 to 60, preferably 10 to 50,% by weight, based on the total composition. But you can also replace some of the hydrate-containing alkali metal silicates with the anhydrous compound. This is even desirable since it enables high active substance contents to be set with an optimal ratio of alkali silicate to pentaalkali metal phosphate.
  • pentaalkalide triphosphate which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate, has been used as the pentaalkali metal triphosphate , so that a total water content of 5.5 mol is calculated.
  • pentaalkalide triphosphate which is used as hexahydrate or as a mixture of hexahydrate with small amounts of anhydrous pentasodium triphosphate
  • the optimal ratio of pentasodium triphosphate to sodium metasilicate, in each case anhydrous, is 1: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
  • inorganic active chlorine carriers such as. Chlorinated lime, lithium or calcium hypochlorite can be used. They are in amounts of 0.2 to 4, preferably from 0.5 to 2 wt .-%, based on the active chlorine content, the z. B. to be determined by iodometric titration, and the entire mean used.
  • the total water content of the melt-block-shaped cleaning agents is 11 to 34.8, preferably 18 to 29.5% by weight. It is preferably introduced by the crystal water content of the alkaline reacting active substances. The calculations of the water content must therefore be based on these compounds. Small amounts of free water for weight compensation can be added, but are not within the scope of the invention.
  • the solidification process takes a few minutes to about an hour depending on the size of the mold.
  • the melting blocks are very hard, hard or less hard, but in any case consistently and thoroughly composed and quickly soluble when used.
  • 150 g of cleaning agent each were produced with the following compositions (data in% by weight). The procedure was such that first Na2Si03. 9 H20 was heated to about 53 o C until a clear melt formed. Then the other active ingredients were added, stirred and poured. The melt solidified within a few minutes.
  • the active substance content (AS) - according to the definition given - was: After 24 hours, the active chlorine content (A-Cl) was determined, which gave the theoretically calculated value for all 3 compositions.
  • the active substance content (AS) was 72.5%.
  • the active chlorine content was determined after 24 hours. It was 0.93% (theory 0.91%).
  • a Melting block produced with the following composition (data in% by weight):
  • the cleaner block was produced as described in Example 2.
  • the composition was made using a combination of Na2Si03. 9 H20 and Na2Si03. 5 H20 chosen so that a total of the same amounts of water as in Example 8 of EP-PS 3 769 were present. It was found that had to be stirred to make the melt after diesum Example 8 for about 30 minutes at 55 to 60 o C until the suspension began to become viscous and could be cast revealed. Such measures are cost-intensive and therefore disadvantageous for technical processes. Storage at 25 o C and 85% rel. Moisture resulted in the following active chlorine losses: The results showed a clear advantage for Example 3 according to the invention. It must also be taken into account that compositions with a lower water content have even better stabilities.

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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)
  • Coloring Foods And Improving Nutritive Qualities (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Claims (5)

  1. Produit pour le lavage de la vaisselle à la machine, en forme de blocs, contenant du chlore actif, exempt d'hydroxyde alcalin, obtenu par la voie d'un processus de fusion, caractérisé par une teneur de 65 à 85 % en poids, par rapport ou calculé sur la base du produit total et de composés exempts d'eau de cristallisation, en un mélange de silicates alcalins, avantageusement sous forme de leurs hydrates ou sous forme de mélanges d'hydrates et des composés anhydres, et de triphosphates penta-alcalins, sous forme d'hexahydrate, sous forme de mélanges d'hexahydrate avec de faibles quantités du composé anhydre ou sous forme de composé anhydre, par une teneur, répartie de façon homogène, de 0,2 à 4 % en poids, par rapport à la teneur en chlore actif et en produit total, en un composé libérant du chlore actif, et par une teneur totale en eau , de préférence sous forme de teneur en eau de cristallisation des substances actives à réaction alcaline, allant de 11 à 34,8 % en poids.
  2. Produit selon la revendication 1, caractérisé en ce que le rapport du triphosphate pentasodique en tant que phosphate alcalin, au métasilicate de sodium en tant que silicate alcalin, chacun anhydre, va de 1:1 à 1:2, de préférence de 1:1 à 1:1,7.
  3. Produit selon la revendication 1 ou 2, caractérisé en ce que la teneur en composé libérant du chlore actif va de 0,5 à 2 % en poids, par rapport au chlore actif et au produit total.
  4. Produit selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'il contient un composé organique contenant du chlore actif.
  5. Procédé pour la préparation du produit selon la revendication 1 à 4, caractérisé en ce que l'on fait fondre du métasilicate de sodium x 9 H₂O par chauffage à 45-55°C, on ajoute sous agitation ou avec malaxage tous les autres composants éventuellement contenant de l'eau d'hydratation, dont en dernier lieu le triphosphate pentasodique et le composé libérant du chlore actif, et on verse les masses fondues encore liquides dans des moules de forme quelconque, de préférence flexibles et on les laisse se solidifier en blocs dans ceux-ci.
EP86106943A 1985-05-30 1986-05-22 Composé sous forme de bloc fondu exempt d'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et son procédé de préparation Expired - Lifetime EP0203524B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86106943T ATE66246T1 (de) 1985-05-30 1986-05-22 Schmeltblockfoermiges alkalihydroxidfreies mittel fuer das maschinelle reinigen von geschirr und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3519354 1985-05-30
DE19853519354 DE3519354A1 (de) 1985-05-30 1985-05-30 Schmelzblockfoermiges alkalihydroxidfreies mittel fuer das maschinelle reinigen von geschirr und verfahren zu seiner herstellung

Publications (3)

Publication Number Publication Date
EP0203524A2 EP0203524A2 (fr) 1986-12-03
EP0203524A3 EP0203524A3 (en) 1988-03-23
EP0203524B1 true EP0203524B1 (fr) 1991-08-14

Family

ID=6271985

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86106943A Expired - Lifetime EP0203524B1 (fr) 1985-05-30 1986-05-22 Composé sous forme de bloc fondu exempt d'hydroxyde de métaux alcalins pour le lavage de la vaisselle en machine et son procédé de préparation

Country Status (4)

Country Link
US (1) US4690770A (fr)
EP (1) EP0203524B1 (fr)
AT (1) ATE66246T1 (fr)
DE (2) DE3519354A1 (fr)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3541153A1 (de) * 1985-11-21 1987-05-27 Henkel Kgaa Mehrschichtige reinigungsmittel in schmelzblockform
DE8613092U1 (de) * 1986-05-14 1987-08-06 Henkel KGaA, 40589 Düsseldorf Vorratspackung eines in einer gewerblichen Geschirrspülmaschine einzusetzenden Reinigers
DE3634812A1 (de) * 1986-10-13 1988-04-14 Henkel Kgaa Verfahren zur herstellung schmelzblockfoermiger, alkalihydroxid- und gegebenenfalls auch aktivchlorhaltiger mittel fuer das maschinelle reinigen von geschirr
DE3721461A1 (de) * 1987-06-30 1989-01-12 Hoechst Ag Formstabile und spezifisch leichte alkalische reinigungsmittel sowie ein verfahren zu ihrer herstellung
AU605573B2 (en) * 1987-08-12 1991-01-17 Ecolab Inc. Solid cast warewashing composition
US5066416A (en) * 1987-08-31 1991-11-19 Olin Corporation Process for producing moldable detergents having a stable available chlorine concentration
DE3832885A1 (de) * 1988-09-28 1990-04-05 Ifah Inst Fuer Angewandte Hygi Verfahren zum maschinellen reinigen, desinfizieren und klarspuelen von geschirr und dafuer geeignetes mittel
US5133892A (en) * 1990-10-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Machine dishwashing detergent tablets
NZ239112A (en) 1991-01-29 1994-12-22 Ecolab Inc Solid alkaline compositions containing the reaction product in water of alkali metal hydroxide and alkali metal silicate; process of manufacture
US5407598A (en) * 1993-02-26 1995-04-18 Ecolab Inc. Shaped solid bleach with encapsulate source of bleach
US6689305B1 (en) 1993-05-05 2004-02-10 Ecolab Inc. Process for consolidating particulate solids and cleaning products therefrom II
US5858299A (en) * 1993-05-05 1999-01-12 Ecolab, Inc. Process for consolidating particulate solids
DE4440142C2 (de) 1994-11-10 1999-03-11 Iscon Hygiene Gmbh Verfahren zur Herstellung von Reinigungsmitteln in Schaumblockform
US6083895A (en) * 1995-03-11 2000-07-04 The Procter & Gamble Company Detergent compositions in tablet form
CN1055494C (zh) * 1996-04-24 2000-08-16 中国人民解放军第二五一医院 一种防锈防腐消毒精
US6007735A (en) * 1997-04-30 1999-12-28 Ecolab Inc. Coated bleach tablet and method
US6471974B1 (en) 1999-06-29 2002-10-29 S.C. Johnson & Son, Inc. N-chlorosulfamate compositions having enhanced antimicrobial efficacy

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
US2412819A (en) * 1945-07-21 1946-12-17 Mathieson Alkali Works Inc Detergent briquette
US3390092A (en) * 1965-03-30 1968-06-25 Fmc Corp Dishwashing detergent preparations containing sodium or potassium dichloroisocyanurate
US3816320A (en) * 1972-11-24 1974-06-11 Fmc Corp Stable dishwashing compositions containing sodium dichloroisocyanurate dihydrate
IT1020170B (it) * 1973-10-06 1977-12-20 Benckiser Gmbh Joh A Detersivi a cloro stabile
US3933670A (en) * 1973-11-12 1976-01-20 Economic Laboratories, Inc. Process for making agglomerated detergents
FR2298599A2 (fr) * 1975-01-24 1976-08-20 Sifrance Nouvelles compositions detergentes solides non corrosives
CA1120819A (fr) * 1977-06-01 1982-03-30 Jurgen W.K. Gromer Comprime detersif
US4329246A (en) * 1977-11-07 1982-05-11 The Procter & Gamble Company Alkaline dishwasher detergent
DE2963759D1 (en) * 1978-02-07 1982-11-11 Economics Lab Cast detergent-containing article and method of making and using

Also Published As

Publication number Publication date
ATE66246T1 (de) 1991-08-15
EP0203524A3 (en) 1988-03-23
DE3680823D1 (de) 1991-09-19
EP0203524A2 (fr) 1986-12-03
DE3519354A1 (de) 1986-12-04
US4690770A (en) 1987-09-01

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