EP0224136B1 - Détergents à plusieurs couches sous forme moulée - Google Patents

Détergents à plusieurs couches sous forme moulée Download PDF

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Publication number
EP0224136B1
EP0224136B1 EP86115766A EP86115766A EP0224136B1 EP 0224136 B1 EP0224136 B1 EP 0224136B1 EP 86115766 A EP86115766 A EP 86115766A EP 86115766 A EP86115766 A EP 86115766A EP 0224136 B1 EP0224136 B1 EP 0224136B1
Authority
EP
European Patent Office
Prior art keywords
layer
weight
sodium metasilicate
detergents
anhydrous
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
EP86115766A
Other languages
German (de)
English (en)
Other versions
EP0224136A2 (fr
EP0224136A3 (en
Inventor
Peter Dr. Jeschke
Theodor Dr. Altenschöpfer
Jochen Dr. Jacobs
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 AT86115766T priority Critical patent/ATE61400T1/de
Publication of EP0224136A2 publication Critical patent/EP0224136A2/fr
Publication of EP0224136A3 publication Critical patent/EP0224136A3/de
Application granted granted Critical
Publication of EP0224136B1 publication Critical patent/EP0224136B1/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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates

Definitions

  • the invention relates to multi-layer detergents in the form of a melting block, in particular for the automatic cleaning of dishes, a method for producing the detergents and the use of the detergents in the automatically running pre-washing and cleaning process of household dishwashers (HGSM).
  • HGSM household dishwashers
  • the detergent metered into the cleaning zone which is carried over by the continuous operation according to the countercurrent principle into the so-called pre-clearing zone, which corresponds to a pre-rinse cycle, there for supporting cleaning of adhering food residues is being used.
  • a pre-clearing zone with detergent content is more effective than a pre-clearing that is only supplied with fresh water.
  • the cleaning agents used in this sector are very strongly alkaline. They mainly contain alkali hydroxides. The pH value is above about 12 at normal application concentrations.
  • the aim of the present invention to develop a cleaning agent which also serves to support cleaning in the pre-rinse cycle of a domestic dishwasher. Since the pre-rinse cycle, which works at tap water inlet temperatures, only takes a few minutes, the cleaning agent must be soluble as quickly as possible. It must also not be too strongly alkaline, since this is not permitted in the household sector for health reasons as well as for decor-damaging reasons. The pH should therefore not exceed 12 if possible. Contents of free caustic alkali must be excluded.
  • melt-block detergents are suitable for simultaneous use in the pre-rinse and main cleaning cycle, the total in the pre-rinse and cleaning cycle during different times and water temperatures have different solubilities, which is ensured by two or more differently acting layers.
  • melt-block detergents for automatic dishwashing have been described, which can be obtained by simply mixing together all the alkaline-reacting active substances, such as. 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 mildly heating the mixture with stirring to 90 to 100 ° 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 were not mentioned there.
  • Example 8 Melting-block agents for machine dishwashing 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 components, but mostly the active chlorine carrier is added in the form of a separate core. The content of cleaning-active substances in this example is only 60% by weight, based on the total agent, which is too low for use in household dishwashers.
  • the composition of the cleaning layer for the pre-rinse cycle consists of cold water-soluble alkali dispensers, in particular of differently hydrated alkali metal silicates, which cause swelling and wetting of dried-on food residues, which cannot be removed from the dishes by the water mechanics alone.
  • this layer has a flow rate in flowing water of 25 to 40, preferably 28 to 38, grams per hour.
  • the invention therefore relates to detergents in the form of a melt block, in particular for the mechanical cleaning of dishes, containing alkali metal silicates and pentaalkali polyphosphates, and to conventional additives of the type of active chlorine compounds, surfactants and / or electrolytes, which are characterized in that they are in the form of multilayer, in particular two-layer, structures are present and that the layers have a different dissolution rate at the mechanically predetermined time-temperature curve, at least one of the layers consisting entirely or predominantly of differently hydrated alkali metal silicates and this layer at 15 ° C.
  • At least one further layer has a substantial content of sodium metasilicate and anhydrous pentasodium triphosphate and in addition further cleaning substances and that this layer has an L at 15 ° C. Has loosening speed below 25 grams per hour, especially in the range of 24.5 to 15 grams per hour.
  • the alkali metal silicates, preferably sodium metasilicates, of the layer provided for the pre-rinse cycle are used in the anhydrous and therefore most alkaline form and the nonahydrate, the most easily soluble form.
  • the mixture can also contain proportions of pentahydrate.
  • the composition of the pre-rinse cleaning agent layer consists of 20 to 100, preferably 30 to 80% by weight sodium metasilicate nonahydrate, 0 to 60, preferably 10 to 50% by weight sodium metasilicate pentahydrate and 0 to 60, preferably 10 to 58% by weight to achieve higher alkalinity. on anhydrous sodium metasilicate.
  • Electrolytes can be added to the layer provided for the pre-rinse cycle to further improve solubility, but also to optimize costs. Electrolytes are to be understood as alkali salts of inorganic or organic acids such as, for example, pentasodium triphosphate, sodium sulfate, sodium acetate and sodium citrate. Their share in the total weight of the detergent layer provided for the pre-rinse cycle can be 2 to 10, preferably 2 to 5% by weight.
  • the layer for the actual cleaning cycle preferably contains a substantial content of sodium metasilicate and anhydrous pentasodium triphosphate and also additional cleaning substances, such as an active chlorine compound.
  • Their rate of dissolution in flowing water at 15 ° C. is preferably below 25 grams per hour, in particular in the range from 24.5 to 15 grams per hour.
  • anhydrous pentaalkali metal phosphate preferably pentasodium triphosphate
  • the alkali metal silicates are advantageously used in the layer provided for the cleaning cycle with the lower dissolution rate in the form of sodium metasilicate nonahydrate, sodium metasilicate hexahydrate and sodium metasilicate pentahydrate.
  • the amounts used are 5 to 60% by weight, preferably 10 to 50% by weight, calculated on anhydrous compounds and based on the layer intended for the cleaning cycle. However, it is also possible to add an anhydrous compound, which increases the content of cleaning-active substances.
  • the optimal weight ratio of pentasodium triphosphate to sodium metasilicate, calculated in each case without water, for the layer for the cleaning cycle, is 2: 1 to 1: 2, preferably 1: 1 to 1: 1.7.
  • Inorganic active chlorine carriers such as chlorine lime, lithium or calcium hypochlorite can also 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 layer used.
  • the total water content of the melt block-shaped cleaning agent layer is 11 to 35, preferably 18 to 30% by weight. It is preferably introduced by the crystal water content of the alkaline substances. The calculations of the water content must therefore start from these compounds.
  • a surfactant component can advantageously be accommodated in the layer provided for the pre-rinsing cycle. This increases the wetting effect in the pre-rinse cycle and better penetrates the dirt dissolved by the alkalis.
  • Suitable surfactant components are the known low-foaming nonionic surfactants, such as the ethoxylation products of long-chain alcohols and alkylphenols, where the free hydroxyl groups of the polyethylene glycol ether residue can be substituted by ether or acetal groups or by polypropylene glycol ether residues to reduce the tendency to foam.
  • the block polymers of ethylene oxide with polypropylene oxide are also suitable.
  • the proportion of surfactants in the total weight of the layer provided for the pre-rinse cycle can be 1 to 5, preferably 1 to 4,% by weight.
  • the rate of dissolution of the substances for the individual layers of the melt-block-shaped cleaning agents was determined after the raw material melts solidified in one Laboratory equipment.
  • 15 g of the cleaning agent to be tested which was present as a solid, compact mass in the form of a cuboid (approx. 25 ⁇ 95 ⁇ 15 mm)
  • the wash bottle was then closed with a Drechsel wash bottle insert and secured with a cut holder. Water was passed through the bottle at an average temperature of 15 ° C.
  • the dissolving behavior was defined as the dissolving rate in g / h (see table, quantities in% by weight)
  • the sodium metasilicate nonahydrate is first heated to about 55 ° C. and, if necessary, dye is added for identification purposes. Subsequently, sodium metasilicate pentahydrate and / or electrolyte and / or anhydrous sodium metasilicate and / or nonionic surfactant is added, if necessary, with vigorous stirring and stirring is continued until the melt and the solid particles distributed therein are essentially homogeneous.
  • the melt for the pre-rinse cleaning agent layer preferably also contains at least one of the other compounds specified.
  • sodium metasilicate nonahydrate is first heated to 55 ° C., all other constituents containing hydrate water, in particular sodium metasilicate pentahydrate, then anhydrous pentasodium triphosphate, anhydrous sodium metasilicate and finally the active chlorine-releasing compounds are added and homogenized with stirring or kneading.
  • Easily pourable melts preferably have viscosities of approx. 500 to 1,500 mPas, but higher and lower viscosities can also be processed.
  • the melts are filled into the form provided in the quantities to be metered via a spray nozzle and run there one after the other to form a shaped body with a smooth surface.
  • the shape consists of a z. B. made of polyethylene, polypropylene or polyvinyl chloride deep-drawn part, which also serves as packaging. With commercial machines, several casting molds can be drawn from film webs in one work process, which then can be filled at the same time using appropriate metering devices.
  • the layer corresponding to the smaller portion of the total melt block is cast first.
  • the first layer has solidified or must be so viscous that the two layers are not mixed when the second layer is poured. It is sufficient if the first layer has only solidified on the surface or has formed a firm skin. Cooling can be accelerated by conventional measures (cooling channel, air convection, etc.).
  • the mold can be sealed with a film, preferably with a release film.
  • the invention therefore also relates, on the other hand, to a process for the production of multilayer, in particular two-layer, detergents in the form of a melt block, in particular for the machine cleaning of dishes, which is characterized in that sodium metasilicate nonahydrate is first heated to 55 ° C.
  • the melting blocks can be opened before the pre-rinse cycle into a zone which exposes the melting block to the dissolving power of the tap water flow, e.g. B. in the cutlery basket of a household dishwasher and the automatically controlled cleaning process can be started.
  • the invention therefore also relates to the use of the multi-layer detergent in the form of a melting block for cleaning dishes in automatic domestic dishwashers, which is characterized in that the melting block is open in the machine before the pre-rinse cycle begins, in a zone which exposes the melting block to the dissolving power of the tap water flow , for example by placing it in the cutlery basket, and then initiating the automatically controlled cleaning process.
  • the dishes cleaned in this way indicate difficult soiling such as burnt milk or baked baked oatmeal has better cleaning results than the traditionally treated one.
  • composition corresponds to Example 1 in the table.
  • the two melts were each prepared in heated stirred containers with vigorous stirring.
  • composition 1 the nonahydrate was first melted and heated to about 55 ° C. and then the dye was stirred in.
  • the anhydrous metasilicate and sodium sulfate were then stirred in with further vigorous stirring.
  • the surfactant was added and the melt obtained was homogenized at 55 to 60 ° C.
  • composition 2 the nonahydrate was heated to 57 ° C.
  • the metasilicate pentahydrate, the anhydrous triphosphate and the anhydrous metasilicate were then stirred in in as short a time sequence as possible and the temperature was adjusted to 57 to 60.degree.
  • intensive processing of the melt masses with a powerful stirrer was necessary. Shortly before the pouring process started, the trichloroisocyanuric acid was stirred in.
  • any melt-block-shaped multilayer cleaning agents can be produced, e.g. B. with constant composition 2 according to the above example and one of the compositions given in the table 4 to 15 for the 1st layer.
  • multilayer melt block-shaped cleaning agents whose individual layers dissolve at different temperatures at different speeds and / or separate the components that are incompatible with each other, e.g. B. surfactants and active chlorine carriers.
  • Any composition according to German application P 35 19 354.9 can also be used for layer 2.
  • the thickness of the individual layers can easily be varied with the determined dissolving speed of the composition for the first layer.

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)

Claims (8)

  1. Produit de lavage en forme de bloc fondant, en particulier pour le nettoyage en machine de la vaisselle, contenant des métasilicates alcalins et des polyphosphates pentaalcalins, ainsi que les additifs habituels du type des composés de chlore actif, des agents tensio-actifs et/ou des électrolytes, caractérisé en ce qu'il est formé de plusieurs couches, en particulier deux couches, et que les couches possèdent une vitesse de dissolution différente selon la courbe temps-température donnée par la machine et où au moins une des couches se compose totalement ou partiellement de métasilicates alcalins d'hydratation variable et que cette couche possède a 15 °C une vitesse de dissolution de 25 à 40, de préférence de 28 à 38 grammes par heure et ou au moins une autre couche possède un taux important de métasilicates de sodium et de triphsophate pentasodique anhydre et présente encore d'autres substances à action lavante et possède à une température de 15 °C une vitesse de dissolution inférieure à 25 g par heure, en particulier variant entre 24,5 et 15 grammes par heure.
  2. Produit de lavage selon la revendication 1, caractérisé en ce que la couche possédant la vitesse de dissolution la plus élevée se compose de 20 à 100, de préférence de 30 à 80 % en poids de métasilicate nonahydrate de sodium, 0 à 60, de préférence 10 a 50 % en poids de métasilicate pentahydrate de sodium et 0 à 60, de préférence 10 à 58 % en poids de métasilicate de sodium anhydre.
  3. Produit de lavage selon une des revendications 1 ou 2, caractérisé en ce que la couche possédant la vitesse de dissolution la plus élevée comprend en plus 1 à 5, de préférence 1 à 4 % en poids d'agents tensio-actifs non ioniques faiblement moussants.
  4. Produit selon une des revendications 1 à 3, caractérisé en ce que la couche possédant la vitesse de dissolution la plus faible selon la revendication 2 se compose, outre le métasilicate nonahydrate de sodium et le triphosphate pentasodique anhydre, d'au moins un autre élément du groupe des métasilicates de sodium anhydres et hydratés ainsi que d'un composé de chlore actif.
  5. Produit de lavage selon une des revendications 1 a 4, caractérisé en ce que la couche possédant la vitesse de dissolution la plus faible contient de 5 à 5C, de préférenc de 5 à 45 % en poids de triphosphate pentasodique anhydre et 5 à 60, de préférence de 10 a 50 % en poids de métasilicate de sodium, calculé en composés anhydres, et 0,2 à 4, de préférence 0,5 à 2 % en poids, par rapport au taux de chlore actif, de composés de chlore actif et 11 à 35, de préférence 18 à 30 % en poids d'eau, en ce compris l'eau de cristallisation.
  6. Produit de lavage selon une des revendications 1 à 5. caractérisé en ce que le rapport de poids entre le triphosphate pentasodique et le métasilicate de sodium, calculés chacun en produit anhydre, est de 2 : 1 à 1 : 2, de préférence de 1 : 1 à 1 : 1,7 dans la couche possédant la vitesse de dissclution la plus faible pour le cycle de lavage.
  7. Procédé de fabrication du produit de lavage en forme de bloc fondant selon une des revendications 1 à 6, caractérisé en ce que pour la fusion de la couche du produit pour le cycle de lavage, il faut d'abord chauffer le métasilicate nonahydrate de sodium à 55 °C, incorporer ensuite en malaxant ou mélangeant et homogénéiser tous les autres éléments contenant de l'eau d'hydratation, en particulier le métasilicate pentahydrate de sodium, ensuite le triphosphate pentasodique anhydre et le métasilicate de sodium anhydre et enfin les composés de décomposition du chlore actif, ensuite, que pour la fusion de la couche du produit pour le cycle de lavage, il faut également d'abord chauffer le métasilicate nonahydrate de sodium à environ 55 °C, y ajouter éventuellement un colorant en guise de marquage, incorporer ensuite le plus rapidement possible en mélangeant vigoureusement le métasilicate pentahydrate de sodium, éventuellement l'électrolyte, le métasilicate de sodium anhydre et un agent tensio-actif non ionique et mélanger jusqu'à ce que la masse en fusion et les particules solides qui y sont incorporées soient essentiellement homogènes, ensuite couler dans un moule quelconque, de préférence carré, la masse en fusion qui correspond à la plus petite partie de l'ensemble du bloc fondant en premier lieu de préférence, laisser se solidifier cette masse par refroidissement du moins à sa surface, couler ensuite la deuxième couche et, enfin, laisser se solidifier toute la masse pour qu'elle forme un bloc fondant en deux couches.
  8. Utilisation du produit de lavage en forme de bloc fondant selon une des revendications 1 à 6 pour le nettoyage de la vaisselle dans des lave-vaisselle ménagers automatiques, caractérisée en ce qu'un ou plusieurs blocs fondants sont disposés librement dans la machine avant le début du cycle de prélavage dans une zone où ils sont exposés à la force de dissolution du flux de l'eau de distribution, par exemple dans le panier à couverts et le programme de lavage à déroulement automatique de la machine est ensuite mis en route.
EP86115766A 1985-11-21 1986-11-13 Détergents à plusieurs couches sous forme moulée Expired - Lifetime EP0224136B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86115766T ATE61400T1 (de) 1985-11-21 1986-11-13 Mehrschichtige reinigungsmittel in schmelzblockform.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853541153 DE3541153A1 (de) 1985-11-21 1985-11-21 Mehrschichtige reinigungsmittel in schmelzblockform
DE3541153 1985-11-21

Publications (3)

Publication Number Publication Date
EP0224136A2 EP0224136A2 (fr) 1987-06-03
EP0224136A3 EP0224136A3 (en) 1988-03-09
EP0224136B1 true EP0224136B1 (fr) 1991-03-06

Family

ID=6286459

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86115766A Expired - Lifetime EP0224136B1 (fr) 1985-11-21 1986-11-13 Détergents à plusieurs couches sous forme moulée

Country Status (6)

Country Link
US (1) US4828745A (fr)
EP (1) EP0224136B1 (fr)
JP (1) JPS62129393A (fr)
AT (1) ATE61400T1 (fr)
CA (1) CA1277888C (fr)
DE (2) DE3541153A1 (fr)

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DE2963759D1 (en) * 1978-02-07 1982-11-11 Economics Lab Cast detergent-containing article and method of making and using
FR2529876A1 (fr) * 1982-07-09 1984-01-13 Rhone Poulenc Chim Base Nouveaux granules de metasilicate de sodium, leur procede d'obtention et leur utilisation dans les compositions detergentes pour lave-vaisselle
DE3519354A1 (de) * 1985-05-30 1986-12-04 Henkel KGaA, 4000 Düsseldorf Schmelzblockfoermiges alkalihydroxidfreies mittel fuer das maschinelle reinigen von geschirr und verfahren zu seiner herstellung

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Publication number Publication date
CA1277888C (fr) 1990-12-18
ATE61400T1 (de) 1991-03-15
DE3541153A1 (de) 1987-05-27
DE3677903D1 (de) 1991-04-11
JPS62129393A (ja) 1987-06-11
EP0224136A2 (fr) 1987-06-03
JPH0455638B2 (fr) 1992-09-03
US4828745A (en) 1989-05-09
EP0224136A3 (en) 1988-03-09

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