EP0268967B1 - Cleaning block for the cistern of flushing toilets - Google Patents

Cleaning block for the cistern of flushing toilets Download PDF

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Publication number
EP0268967B1
EP0268967B1 EP87116866A EP87116866A EP0268967B1 EP 0268967 B1 EP0268967 B1 EP 0268967B1 EP 87116866 A EP87116866 A EP 87116866A EP 87116866 A EP87116866 A EP 87116866A EP 0268967 B1 EP0268967 B1 EP 0268967B1
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EP
European Patent Office
Prior art keywords
weight
cleaning block
carbon atoms
acid
water
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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.)
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EP87116866A
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German (de)
French (fr)
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EP0268967A2 (en
EP0268967A3 (en
Inventor
Ronald Menke
Bernd-Dieter Holdt
Gerd Praus
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT87116866T priority Critical patent/ATE77647T1/en
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Publication of EP0268967A3 publication Critical patent/EP0268967A3/en
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
    • 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
    • C11D17/0056—Lavatory cleansing blocks
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols

Definitions

  • none of the known products is free from disadvantages; be it too high a dissolving speed, be it insufficient cohesion or inadequate adhesion to the container wall, so that the detergent is carried away in part or in total undissolved by the water, or be it a lack of cleaning ability due to uneven product delivery.
  • the object of the invention was to develop a cleaning block with better properties overall.
  • this block as a slowly soluble detergent depot in the water tank of flush toilets and a method for the production.
  • the cleaning agent blocks according to the invention are primarily characterized by a particularly uniform rinsing rate; ie, regardless of how far the cleaning blocks have already been removed, there is always approximately the same concentration of active ingredients in the rinse water. This is not least due to the fact that the blocks melt somewhat in the water with increasing service life and thereby the loss of surface area due to the mass erosion, approximately compensate. Also very noteworthy is the good adhesion of the blocks to the container walls, which means that the blocks are not carried away by the water flow even under unfavorable conditions, such as can be found in the suction toilets working with large amounts of water. Since the blocks also do not tend to disintegrate, they have an extremely long service life.
  • a long period of effectiveness is particularly desirable today because cisterns are increasingly being installed under plaster and these cisterns are difficult to open.
  • a further advantage of the formulations according to the invention is that all active ingredients are to a high degree ecologically compatible or readily biodegradable.
  • the production of the cleaning blocks according to the invention is particularly simple due to the fact that all solid raw materials are available in the form of fine powders and can therefore easily be intimately mixed in simple mixers such as barrel, Lödige or paddle mixers.
  • the liquid components can be introduced during the mixing process without the mixture clumping.
  • the result is a free-flowing, largely homogeneous premix which can be easily transferred to an extrusion system via screw conveyors, where it is pressed into dense strands. This procedure avoids energy-intensive stages such as heating and kneading.
  • the extruded strands are preferably given a square or rectangular shape, so that cleaning blocks in the form of cubes or cuboids can be produced therefrom. This shape is particularly preferred because it ensures an optimal contact surface in the water tanks and thus good adhesion.
  • the cleaning blocks preferably have weights of 50 to 150 g and have densities of about 1.2 to about 1.7 g / cm 3.
  • the cleaning blocks are used in such a way that one or, if necessary, also several cleaning blocks are thrown into the water tank of the flushing toilet.
  • the cleaning power then develops automatically by slowly dissolving the blocks in the water and transporting the dissolved active ingredients with the water into the toilet bowl.
  • the test was carried out in an automatically controlled toilet system, which released the contents of the water tank every 1 hour and refilled the tank with 9 liters of tap water of 17 ° German hardness and a temperature of approx. 15 ° C.
  • One block was placed in each case in the water tank and it was determined how many rinses were possible until the block was completely used up.
  • Table 2 shows the rounded results obtained in five parallel experiments.

Abstract

A cleaning block for the tank of flush toilets comprising: 10 to 30% by weight of monoalkyl sulfate, Na salt, 5 to 40% by weight of fatty acid alkanolamide, and 15 to 60% by weight of a water-soluble inorganic alkali salt, and optionally calcium-complexing carboxylic acids or alkali salts thereof, perfume, dye and other auxiliaries. The block is distinguished by a particularly long useful life, by uniform dissolving behavior and by high cleaning power. A method for use and process for manufacture are also afforded.

Description

Für die selbsttätige Reinigung von Spültoiletten, die mit einem Wasserkasten als Reservoir arbeiten, sind seit langem Reinigungsmittel in Stückform gebräuchlich, die in den Wasserkasten eingelegt oder eingehängt werden und dort ihre Wirkstoffe über lange Zeit an das Spülwasser abgeben. Besonders einfach sind solche Produkte zu handhaben, die ohne weitere Hilfsmittel angewendet, d. h. direkt in den Wasserkasten eingeworfen werden können. Diese meist als Blöcke oder Tabletten geformten Reinigungsmittelstücke erreichen allein auf Grund ihrer geringen Lösegeschwindigkeit ausreichende Standzeiten. Beispiele derartiger Produkte finden sich in den deutschen Offenlegungsschriften 18 16 802, 24 07 947 und 29 07 029 sowie in der britischen Patentanmeldung 2 061 996 und den europäischen Patentanmeldungen 55 100 und 184 416.For the automatic cleaning of flush toilets that work with a water tank as a reservoir, detergent in pieces has long been in use, which are inserted or hung in the water tank and release their active ingredients there for a long time to the flushing water. Products which are used without further aids are particularly easy to handle, i. H. can be thrown directly into the water tank. These pieces of detergent, usually shaped as blocks or tablets, achieve sufficient service lives simply because of their slow dissolution rate. Examples of such products can be found in German laid-open documents 18 16 802, 24 07 947 and 29 07 029 as well as in British patent application 2 061 996 and European patent applications 55 100 and 184 416.

Keines der bekannten Produkte ist jedoch frei von Nachteilen; sei es zu hohe Lösegeschwindigkeit, seien es nicht ausreichender Zusammenhalt oder mangelnde Haftung an der Behälterwand, so daß die Mittel in Teilen oder insgesamt ungelöst vom Wasser mitgerissen werden, oder sei es mangelndes Reinigungsvermögen auf Grund ungleichmäßiger Produktabgabe.However, none of the known products is free from disadvantages; be it too high a dissolving speed, be it insufficient cohesion or inadequate adhesion to the container wall, so that the detergent is carried away in part or in total undissolved by the water, or be it a lack of cleaning ability due to uneven product delivery.

In diesem Zusammenhang lag der Erfindung die Aufgabe zu Grunde, einen Reinigungsblock mit insgesamt besseren Eigenschaften zu entwickeln.In this connection, the object of the invention was to develop a cleaning block with better properties overall.

Es wurde gefunden, daß diese Aufgabe durch eine Kombination spezieller Wirkstoffe in bestimmten ausgewählten Mengenverhältnissen gelöst werden kann, obwohl die Mehrzahl dieser Wirkstoffe durchaus schon für Produkte dieser Art vorgeschlagen oder darin verwendet worden sind.It has been found that this task is achieved by a combination of special active ingredients in certain selected proportions can be solved, although the majority of these active ingredients have already been proposed or used for products of this type.

Gegenstand der Erfindung ist ein Reinigungsblock für den Wasserkasten von Spültoiletten, der anionisches Tensid und löslichkeitsregulator enthält und aus folgenden komponenten besteht:

a) 10 bis 30 Gew.-%
Monoalkylsulfat-Na-Salz mit im Mittel 12 bis 14 C-Atomen in der Alkylgruppe,
b) 5 bis 40 Gew.-%
Mono- und/oder Dialkanolamid einer Fettsäure mit 2 bis 6 C-Atomen im Aminteil und im Mittel 12 bis 18 C-Atomen im Fettsäureteil,
c) 15 bis 60 Gew.-%
wasserlösliche anorganische Alkalisalze,
d) 0 bis 20 Gew.-%
feste wasserlösliche niedermolekulare Carbonsäure mit einer Komplexbildungskonstante für Calcium oberhalb von 10¹ oder einer äquivalenten Menge von deren Alkalisalz,
e) 0 bis 15 Gew.-%
Parfümöl,
f) 0 bis 20 Gew.-%
wasserlöslicher Farbstoff,
g) 0 bis 5 Gew.-%
keimhemmendes Mittel und
h) 0 bis 10 Gew.-%
Hilfsstoffe.
The invention relates to a cleaning block for the water tank of flush toilets, which contains anionic surfactant and solubility regulator and consists of the following components:
a) 10 to 30% by weight
Monoalkyl sulfate Na salt with an average of 12 to 14 carbon atoms in the alkyl group,
b) 5 to 40% by weight
Mono- and / or dialkanolamide of a fatty acid with 2 to 6 carbon atoms in the amine part and on average 12 to 18 carbon atoms in the fatty acid part,
c) 15 to 60% by weight
water-soluble inorganic alkali salts,
d) 0 to 20% by weight
solid water-soluble low molecular weight carboxylic acid with a complex formation constant for calcium above 10¹ or an equivalent amount of its alkali salt,
e) 0 to 15% by weight
Perfume oil,
f) 0 to 20% by weight
water-soluble dye,
g) 0 to 5% by weight
germicide and
h) 0 to 10% by weight
Auxiliaries.

Weitere Gegenstände der Erfindung sind die Verwendung dieses Blocks als langsam lösliches Reinigungsmitteldepot im Wasserkasten von Spültoiletten und ein Verfahren zur Herstellung.Further objects of the invention are the use of this block as a slowly soluble detergent depot in the water tank of flush toilets and a method for the production.

Die erfindungsgemäßen Reinigungsmittelblöcke zeichnen sich in erster Linie durch eine besonders gleichmäßige Abspülrate aus; d. h., unabhängig davon, wie weit die Reinigungsblöcke bereits abgetragen sind, findet sich im Spülwasser immer etwa die gleiche Konzentration an Wirkstoffen. Dies ist nicht zuletzt darauf zurückzuführen, daß die Blöcke mit zunehmender Standzeit im Wasser etwas zerfließen und dadurch den Verlust an Oberfläche, der durch den Massenabtrag zustande kommt, in etwa kompensieren. Sehr bemerkenswert ist außerdem die gute Haftung der Blöcke an den Behälterwänden, die dazu führt, daß die Blöcke selbst unter ungünstigen Bedingungen, wie sie bei den mit großen Wassermengen arbeitenden Absaugtoiletten anzutreffen sind, nicht vom Wasserstrom mitgerissen werden. Da die Blöcke außerdem nicht zum Zerfallen neigen, erreichen sie außerordentlich hohe Standzeiten. Eine lange Wirkungsdauer ist heute insbesondere deshalb erwünscht, weil im zunehmenden Maße Spülkästen unter Putz eingebaut werden und diese Spülkästen nur schwer geöffnet werden können. Als weiterer Vorteil der erfindungsgemäßen Rezepturen ist zu werten, daß alle Wirkstoffe im hohen Maße ökologisch verträglich sind bzw. leicht biologisch abgebaut werden.The cleaning agent blocks according to the invention are primarily characterized by a particularly uniform rinsing rate; ie, regardless of how far the cleaning blocks have already been removed, there is always approximately the same concentration of active ingredients in the rinse water. This is not least due to the fact that the blocks melt somewhat in the water with increasing service life and thereby the loss of surface area due to the mass erosion, approximately compensate. Also very noteworthy is the good adhesion of the blocks to the container walls, which means that the blocks are not carried away by the water flow even under unfavorable conditions, such as can be found in the suction toilets working with large amounts of water. Since the blocks also do not tend to disintegrate, they have an extremely long service life. A long period of effectiveness is particularly desirable today because cisterns are increasingly being installed under plaster and these cisterns are difficult to open. A further advantage of the formulations according to the invention is that all active ingredients are to a high degree ecologically compatible or readily biodegradable.

Es folgt nun eine Beschreibung der einzelnen Bestandteile:

  • a) Monoalkylsulfate
    Als anionisches Tensid enthalten die Reinigungsblöcke Monoalkylsulfat-Natriumsalze, die im Mittel 12 bis 14 C-Atome in der Alkylgruppe aufweisen. Es handelt sich dabei um die Mononatriumsalze von Schwefelsäurehalbestern langkettiger Alkohole, die vorzugsweise unverzweigt sind. Insbesondere sind es Abkömmlinge von Fettalkoholen, von denen wiederum das Kokosalkylsulfat und das Laurylsulfat besonders hervorzuheben sind. Andere Tenside sind höchstens in geringen Mengen enthalten, sofern sie die Eigenschaften der Blöcke nicht nachteilig beeinflussen; sie fehlen aber vorzugsweise ganz. Der Anteil der Alkylsulfate an den Blöcken liegt zwischen 10, vorzugsweise 15, Gewichtsprozent und 30, vorzugsweise 25, Gewichtsprozent.
  • b) Fettsäurealkanolamid
    Bei dieser nichtionischen Komponente handelt es sich um Fettsäureamide, die sich von Alkanolaminen mit 2 bis 6 C-Atomen und von Fettsäuren mit im Mittel 12 bis 18 C-Atomen ableiten. Als Aminkomponente werden Mono- und Diethanolamin bevorzugt; beim Fettsäureteil liegt der Vorzug bei Fettsäuren, die im Mittel 12 bis 14 C-Atome aufweisen. Besonders bevorzugt wird Kokosfettsäuremonoethanolamid. Die Komponente b) ist in den Reinigungsblöcken in Mengen zwischen 5, vorzugsweise 10, Gewichtsprozent und 40, vorzugsweise 35, Gewichtsprozent, enthalten.
  • c) Wasserlösliches anorganisches Alkalisalz
    Alkalisalze stellen die dritte notwendige Komponente der erfindungsgemäßen Reinigungsblöcke dar. Ihre Aufgabe ist es unter anderem, die Reinigungskraft zu verstärken und das spezifische Gewicht der Blöcke zu erhöhen. Vorzugsweise werden schwach sauer oder alkalisch oder aber neutral reagierende Alkalisalze verwendet, beispielsweise Natriumcarbonat, Natriumbicarbonat, Borax, Natriumsulfat und Natriumchlorid. Besondere Bedeutung besitzen die Natriumsalze und hier in erster Linie Natriumsulfat. Der Gehalt an Alkalisalzen beträgt in den Reinigungsblöcken zwischen 15, vorzugsweise 20, Gewichtsprozent und 60, vorzugsweise 55, Gewichtsprozent. Dabei bestehen vorzugsweise mehr als 50 Gew.-%, insbesondere mehr als 70 Gew.-% der Salze aus Natriumsulfat. Phosphate werden in den Blöcken in Mengen nicht über 10 Gew.-%, vorzugsweise aber gar nicht verwendet. Die eingesetzten Salze können in gewissem Umfang Kristallwasser enthalten, werden aber vorzugsweise, wie auch alle anderen Komponenten, wasserfrei eingesetzt.
  • d) Wasserlösliche Carbonsäure
    Die erfindungsgemäßen Reinigungsmittel können in Mengen bis zu 20 Gew.-% feste wasserlösliche niedermolekulare Carbonsäuren als Komplexbildner für Calcium enthalten. Geeignet sind all jene Carbonsäuren, deren erste Komplexbildungskonstante für Calciumionen (K₁) über 10¹ liegt, bestimmt bei Raumtemperatur in wäßriger Lösung der Ionenstärke 0,2. Beispiele derartiger Carbonsäuren sind Bernsteinsäure, Weinsäure, Diglykolsäure, Hydroxyethyliminodiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure. Vorzugsweise werden anstelle der Carbonsäuren oder im Gemisch mit diesen die äquivalenten Mengen der entsprechenden Salze, insbesondere der Alkalisalze eingesetzt. Bevorzugt werden weiterhin die biologisch gut abbaubaren, nur aus Kohlenstoff, Wasserstoff und Sauerstoff bestehenden Carbonsäuren, deren Komplexbildungskonstante K₁ zwischen 10¹ und 10⁴ liegt und deren Salze. Besonders bevorzugt werden Citronensäure, Äpfelsäure und Gluconsäure und, insbesondere, deren Salze. Vorzugsweise enthalten die Reinigungsblöcke 1 bis 15 Gew.-%, insbesondere 3 bis 10 Gew.-% dieser Komplexbildner, jeweils gerechnet als freie Säuren.
  • e) Parfümöl
    Die Mittel können bis zu 15 Gew.-% Parfümöl enthalten; bevorzugt sind Gehalte zwischen 3 und 8 Gew.-%.
  • f) Wasserlöslicher Farbstoff
    Diese Komponente kann in den Reinigungsmitteln in Mengen bis zu 20 Gew.-% enthalten sein. Der Farbstoff dient in erster Linie dazu, dem Verbraucher die Wirksamkeit der Mittel optisch anzuzeigen. Bevorzugt werden solche Farbstoffe, die auf Grund ihrer Löslichkeit nicht vorzeitig aus den Reinigungsblöcken ausdiffundieren. Vorzugsweise werden die Farbstoffe in Mengen zwischen 3 und 20 Gew.-% eingearbeitet.
  • g) Keimhemmende Mittel
    Obwohl die erfindungsgemäßen Produkte bereits ohne die Komponente g) eine ausgezeichnete Reinigungswirkung besitzen, kann die hygienische Wirkung durch den Zusatz keimhemmender Mittel verstärkt werden. Die Menge dieser Mittel hängt stark von der Wirksamkeit der jeweiligen Verbindung ab und kann bis zu 5 Gew.-% betragen. Vorzugsweise werden mehr als 0,1 Gew.-% in die Reinigungsblöcke eingearbeitet. Geeignet sind insbesondere Isothiazolongemische oder Kombinationen aus Natriumbenzoat und Chloracetamid, doch können auch andere antimikrobiell wirksame Verbindungen, beispielsweise Phenole oder chlorabspaltende Mittel eingesetzt werden.
  • h) Weitere Inhaltsstoffe
    Neben den unter a) bis g) aufgeführten Komponenten können die erfindungsgemäßen Reinigungsblöcke weitere Hilfs- oder Begleitstoffe enthalten, soweit sie die Eigenschaften der Blöcke nicht negativ beeinflussen. Zu erwähnen sind in erster Linie Plastifizierungshilfsstoffe, abspülregulierende Substanzen, Reinigungsverstärker und Hilfsmittel, die die Herstellung der Reinigungsblöcke erleichtern. Auch Überzugsmittel, die nachträglich auf die Blöcke aufgebracht werden, um ihre Handhabbarkeit und die Lagerfähigkeit vor Anwendung zu verbessern, gehören in diese Kategorie. Die Hilfsstoffe können in Mengen bis zu 10 Gew.-%, vorzugsweise mit Mengen zwischen 0,1 und 5 Gew.-% in den Blöcken enthalten sein; sie können insbesondere aber auch ganz fehlen.
A description of the individual components now follows:
  • a) Monoalkyl sulfates
    As an anionic surfactant, the cleaning blocks contain monoalkyl sulfate sodium salts which have an average of 12 to 14 carbon atoms in the alkyl group. These are the monosodium salts of sulfuric acid half-esters of long-chain alcohols, which are preferably unbranched. In particular, there are descendants of fatty alcohols, of which coconut alkyl sulfate and lauryl sulfate are particularly noteworthy. Other surfactants are contained in small amounts at most, provided they do not adversely affect the properties of the blocks; however, they are preferably entirely absent. The proportion of the alkyl sulfates in the blocks is between 10, preferably 15, percent by weight and 30, preferably 25, percent by weight.
  • b) fatty acid alkanolamide
    This nonionic component is a fatty acid amide derived from alkanolamines with 2 to 6 carbon atoms and from fatty acids with an average of 12 to 18 carbon atoms. Mono- and diethanolamine are preferred as the amine component; in the fatty acid part, preference is given to fatty acids which have an average of 12 to 14 carbon atoms. Coconut fatty acid monoethanolamide is particularly preferred. Component b) is contained in the cleaning blocks in amounts between 5, preferably 10, percent by weight and 40, preferably 35, percent by weight.
  • c) Water-soluble inorganic alkali salt
    Alkali salts represent the third necessary component of the cleaning blocks according to the invention. Their task is, inter alia, to increase the cleaning power and to increase the specific weight of the blocks. Weakly acidic or alkaline or neutral reacting alkali salts are preferably used, for example sodium carbonate, sodium bicarbonate, borax, sodium sulfate and sodium chloride. The sodium salts and especially sodium sulfate are of particular importance. The content of alkali salts in the cleaning blocks is between 15, preferably 20, percent by weight and 60, preferably 55, percent by weight. In this case, preferably more than 50% by weight, in particular more than 70% by weight, of the salts consist of sodium sulfate. Phosphates are used in the blocks in amounts of not more than 10% by weight, but preferably not at all. The salts used can contain water of crystallization to a certain extent, but, like all other components, are preferably used anhydrous.
  • d) Water soluble carboxylic acid
    The cleaning agents according to the invention can contain up to 20% by weight of solid, water-soluble, low molecular weight carboxylic acids contain as complexing agent for calcium. Suitable are all those carboxylic acids whose first complexation constant for calcium ions (K₁) is above 10¹, determined at room temperature in an aqueous solution of ionic strength 0.2. Examples of such carboxylic acids are succinic acid, tartaric acid, diglycolic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid. Instead of the carboxylic acids or in a mixture with these, the equivalent amounts of the corresponding salts, in particular the alkali salts, are preferably used. Preference is furthermore given to the readily biodegradable carboxylic acids consisting only of carbon, hydrogen and oxygen, the complex formation constant of which K₁ is between 10¹ and 10⁴ and the salts thereof. Citric acid, malic acid and gluconic acid and, in particular, their salts are particularly preferred. The cleaning blocks preferably contain 1 to 15% by weight, in particular 3 to 10% by weight, of these complexing agents, each calculated as free acids.
  • e) perfume oil
    The agents can contain up to 15% by weight of perfume oil; contents between 3 and 8% by weight are preferred.
  • f) Water soluble dye
    This component can be contained in the cleaning agents in amounts of up to 20% by weight. The primary purpose of the dye is to visually indicate to the consumer the effectiveness of the agents. Preferred dyes are those which, owing to their solubility, do not diffuse out of the cleaning blocks prematurely. The dyes are preferably incorporated in amounts between 3 and 20% by weight.
  • g) germicides
    Although the products according to the invention already have an excellent cleaning action without component g), the hygienic effect can be enhanced by the addition of germ-inhibiting agents. The amount of these agents depends heavily on the effectiveness of the particular compound and can be up to 5% by weight. Preferably more than 0.1% by weight are incorporated into the cleaning blocks. Isothiazolone mixtures or combinations of sodium benzoate and chloroacetamide are particularly suitable, but other antimicrobial compounds, for example phenols or chlorine-releasing agents, can also be used.
  • h) Other ingredients
    In addition to the components listed under a) to g), the cleaning blocks according to the invention may contain further auxiliaries or accompanying substances, provided that they do not adversely affect the properties of the blocks. First and foremost, plasticization aids, rinse-regulating substances, cleaning enhancers and aids are to be mentioned which facilitate the manufacture of the cleaning blocks. Coating agents that are subsequently applied to the blocks in order to improve their manageability and storage stability before use also belong to this category. The auxiliaries can be present in the blocks in amounts of up to 10% by weight, preferably in amounts of between 0.1 and 5% by weight; in particular, however, they can also be completely absent.

Soweit bei der vorstehenden Beschreibung der Einzelkomponenten in einigen Fällen auf den Beitrag der jeweiligen Komponente zu den Eigenschaften der Mittel Bezug genommen worden ist, sollen diese Angaben nur als Hinweis auf einen Wirkungsschwerpunkt verstanden werden. Insgesamt scheinen alle Komponenten zu jeder einzelnen Eigenschaft der Blöcke, insbesondere der Beständigkeit, dem Auflöseverhalten und dem Reinigungsvermögen beizutragen, wobei erst das Zusammenwirken in der erfindungsgemäßen Komposition zu den positiven Eigenschaften der neuen Mittel führt.Insofar as reference was made in some cases to the contribution of the respective component to the properties of the composition in the above description of the individual components, this information should only be understood as an indication of a focus of action. All in all, all components seem to contribute to each individual property of the blocks, in particular the durability, the dissolution behavior and the cleaning ability, the interaction in the composition according to the invention only leading to the positive properties of the new agents.

Die Herstellung der erfindungsgemäßen Reinigungsblöcke gestaltet sich besonders einfach durch die Tatsache, daß sämtliche festen Rohstoffe in Form feiner Pulver verfügbar sind und dadurch leicht in einfachen Mischern, wie Faß-, Lödige- oder Paddel-Mischern innig vermengt werden können. Während des Mischvorganges können die flüssigen Komponenten eingetragen werden, ohne daß die Mischung verklumpt. Es entsteht eine rieselfähige, weitgehend homogene Vormischung, die problemlos über Förderschnecken in eine Extrudieranlage übergeführt werden kann, wo sie zu dichten Strängen verpreßt wird. Bei dieser Arbeitsweise werden energieaufwendige Stufen, wie Aufheizen und Kneten vermieden.The production of the cleaning blocks according to the invention is particularly simple due to the fact that all solid raw materials are available in the form of fine powders and can therefore easily be intimately mixed in simple mixers such as barrel, Lödige or paddle mixers. The liquid components can be introduced during the mixing process without the mixture clumping. The result is a free-flowing, largely homogeneous premix which can be easily transferred to an extrusion system via screw conveyors, where it is pressed into dense strands. This procedure avoids energy-intensive stages such as heating and kneading.

Den extrudierten Strängen wird vorzugsweise eine quadratische oder rechteckige Form gegeben, so daß sich daraus Reinigungsblöcke in Würfel- oder Quaderform herstellen lassen. Diese Form wird besonders bevorzugt, da sie eine optimale Auflagefläche in den Wasserkästen und damit eine gute Haftung gewährleistet. Vorzugsweise weisen die Reinigungsblöcke Gewichte von 50 bis 150 g auf und besitzen Dichten von etwa 1,2 bis etwa 1,7 g/cm³.The extruded strands are preferably given a square or rectangular shape, so that cleaning blocks in the form of cubes or cuboids can be produced therefrom. This shape is particularly preferred because it ensures an optimal contact surface in the water tanks and thus good adhesion. The cleaning blocks preferably have weights of 50 to 150 g and have densities of about 1.2 to about 1.7 g / cm 3.

Die Anwendung der Reinigungsblöcke geschieht in der Weise, daß man einen oder gegebenenfalls auch mehrere Reinigungsblöcke in den Wassertank der Spültoilette einwirft. Die Reinigungskraft entfaltet sich dann selbsttätig durch langsame Auflösung der Blöcke im Wasser und Transport der gelösten Wirkstoffe mit dem Wasser in die Toilettenschüssel.The cleaning blocks are used in such a way that one or, if necessary, also several cleaning blocks are thrown into the water tank of the flushing toilet. The cleaning power then develops automatically by slowly dissolving the blocks in the water and transporting the dissolved active ingredients with the water into the toilet bowl.

BeispieleExamples 1. Herstellung der Reinigungsblöcke A bis E 1. Production of cleaning blocks A to E

Die Rezepturen der Blöcke A bis E wiesen die in Tabelle 1 aufgeführten Komponenten auf. Tabelle 1 Bestandteile (in Gewichtsprozent) A B C D E Natriumlaurylsulfat 22,0 19,0 22,0 19,0 22,0 Kokosfettsäuremonoethanolamid 12,0 35,0 11,0 10,0 14,0 Borax (10 H₂O) 2,0 - 2,0 2,0 2,0 Natriumsulfat, wasserfrei 48,0 18,0 48,37 48,0 44,0 Natriumcarbonat - 2,0 - - - Trinatriumcitrat, wasserfrei 5,0 5,0 5,0 - 4,0 Citronensäureanhydrat-Pulver - - - - 2,0 Natriumgluconat - - - 5,0 - Pinienöl 70 französisch 6,0 4,0 4,0 - - Isobornylacetat - 2,0 2,0 - - Geißblatt-Note 81-2467 - - - 6,0 - Acidofix Apfelbouquet, säurestabil - - - - 6,0 Basacid Blau 755 (C. I. 42090) 5,0 15,0 5,0 2,0 4,5 Basacid Gelb (C.I.....) - - - 8,0 1,5 Kathon® 886 MW⁺ - - 0,42 - - Kathon® 893⁺ - - 0,21 - - + Antimikrobielle Isothiazolonverbindungen (wäßrige Lösungen) The formulations of blocks A to E had the components listed in Table 1. Table 1 Ingredients (in percent by weight) A B C. D E Sodium lauryl sulfate 22.0 19.0 22.0 19.0 22.0 Coconut fatty acid monoethanolamide 12.0 35.0 11.0 10.0 14.0 Borax (10 H₂O) 2.0 - 2.0 2.0 2.0 Sodium sulfate, anhydrous 48.0 18.0 48.37 48.0 44.0 sodium - 2.0 - - - Trisodium citrate, anhydrous 5.0 5.0 5.0 - 4.0 Citric acid anhydrate powder - - - - 2.0 Sodium gluconate - - - 5.0 - Pine oil 70 French 6.0 4.0 4.0 - - Isobornyl acetate - 2.0 2.0 - - Honeysuckle note 81-2467 - - - 6.0 - Acidofix apple bouquet, acid-stable - - - - 6.0 Basacid Blue 755 (CI 42090) 5.0 15.0 5.0 2.0 4.5 Basacid Yellow (CI ....) - - - 8.0 1.5 Kathon® 886 MW⁺ - - 0.42 - - Kathon® 893⁺ - - 0.21 - - + Antimicrobial isothiazolone compounds (aqueous solutions)

In allen Fällen wurde die Herstellung im Technikumsmaßstab mit Ansätzen von jeweils 150 kg durchgeführt. Die festen Komponenten wurden gemeinsam in einem 500 Liter fassenden Paddel-Mischer 2,5 Minuten vorgemischt, ehe das Parfümöl und gegebenenfalls die wäßrige Lösung der antimikrobiellen Wirkstoffe im Verlauf von etwa einer Minute auf die bewegte Mischung aufgesprüht wurden. Die entstehende rieselfähige körnige Vormischung wurde dann mit Hilfe einer Vibrations-Förderrinne einem 2-Schnecken-Extruder zugeführt und zu einem kompakten Strang mit quadratischem Querschnitt von ca. 11,5 cm² verpreßt. Durch ein automatisches Messer wurden quaderförmige Blöcke von 50 bzw. 100 g Gewicht geschnitten.In all cases, the production was carried out on a pilot plant scale with batches of 150 kg each. The solid components were premixed together in a 500 liter paddle mixer for 2.5 minutes before the perfume oil and optionally the aqueous solution of the antimicrobial agents were sprayed onto the agitated mixture over the course of about one minute. The resulting free-flowing granular premix was then fed to a 2-screw extruder with the aid of a vibrating conveyor trough and pressed into a compact strand with a square cross section of approximately 11.5 cm 2. Cuboid blocks weighing 50 or 100 g were cut by an automatic knife.

2. Prüfung der Standzeiten 2. Checking the service life

Die Prüfung erfolgte in einer automatisch gesteuerten Toilettenanlage, die in Abständen von 1 Stunde den Inhalt des Wasserkastens abgab und den Kasten neu mit 9 Litern Leitungswasser von 17 ° deutscher Härte und einer Temperatur von ca. 15 °C füllte. Es wurde jeweils 1 Block in den Wasserkasten eingelegt und festgestellt, wieviel Spülungen bis zum vollständigen Verbrauch des Blocks möglich waren. Tabelle 2 gibt die gerundeten Ergebnisse wieder, die in fünf Parallelversuchen erhalten wurden.

Figure imgb0001
The test was carried out in an automatically controlled toilet system, which released the contents of the water tank every 1 hour and refilled the tank with 9 liters of tap water of 17 ° German hardness and a temperature of approx. 15 ° C. One block was placed in each case in the water tank and it was determined how many rinses were possible until the block was completely used up. Table 2 shows the rounded results obtained in five parallel experiments.
Figure imgb0001

Die in allen Fällen außergewöhnlich langen Standzeiten wurden u. a. dadurch ermöglicht, daß die Blöcke bis zum völligen Verbrauch fest am Boden des Reservoirs hafteten und nicht zerfielen.The exceptionally long service lives in all cases have been a. thereby allowing the blocks to adhere firmly to the bottom of the reservoir until they were completely used up and not to disintegrate.

3. Prüfung der Wirkstoffabgabe 3. Checking the drug delivery

Die Bestimmung der Wirkstoffabgabe wurde in einer Absaugtoilettenanlage, wie sie vor allem in den USA üblich ist, durch colorimetrische Messung der Farbstoffkonzentration im Spülwasser vorgenommen. Die Füllmenge des Wasserkastens betrug hier 14 Liter; zusätzlich wurden bei jeder Spülung (im Abstand von 1 Stunde) 5 l Frischwasser durch den Wasserkasten abgegeben. Tabelle 3 gibt die Ergebnisse der Messungen wieder, die mit einem Block gemäß Beispiel 1 B im Verlauf des Verbrauchs durchgeführt wurden.

Figure imgb0002
The determination of the release of active ingredient was carried out in a suction toilet system, as is customary above all in the USA, by colorimetric measurement of the dye concentration in the rinsing water. The volume of the water tank here was 14 liters; in addition, 5 l of fresh water were dispensed through the water tank with each flush (every 1 hour). Table 3 shows the results of the measurements which were carried out with a block according to Example 1B in the course of consumption.
Figure imgb0002

Aus den Werten ist erkennbar, daß, abgesehen von einer kurzen Startphase, die Wirkstoffe weitgehend gleichmäßig bis zum fast vollständigen Verbrauch abgegeben werden. Dies wird nicht zuletzt darauf zurückgeführt, daß der Block ganz langsam zerfließt und dadurch gegen Ende in Form einer breiten flachen Masse noch immer eine große Oberfläche besitzt.From the values it can be seen that, apart from a short start-up phase, the active ingredients are released largely evenly until almost complete consumption. This is not least attributed to the fact that the block flows away very slowly and thus still has a large surface towards the end in the form of a broad, flat mass.

Claims (10)

  1. A cleaning block for the cistern of flush toilets containing an anionic surfactant and a solubility regulator, characterized in that it consists of the following components:
    a) 10 to 30% by weight monoalkyl sulfate, Na salt, containing on average 12 to 14 carbon atoms in the alkyl group,
    b) 5 to 40% by weight mono- and/or dialkanolamide of a fatty acid containing 2 to 6 carbon atoms in the amine part and, on average, 12 to 18 carbon atoms in the fatty acid part,
    c) 15 to 60% by weight water-soluble inorganic alkali metal salts,
    d) 0 to 20% by weight of a solid, water-soluble, low molecular weight carboxylic acid having a complexing constant for calcium above 10¹ or an equivalent quantity of an alkali metal salt thereof,
    e) 0 to 15% by weight perfume oil,
    f) 0 to 20% by weight water-soluble dye,
    g) 0 to 5% by weight antimicrobial agent and
    h) 0 to 10% by weight auxiliaries.
  2. A cleaning block as claimed in claim 1, wherein component a) consists of fatty alcohol sulfate sodium salt.
  3. A cleaning block as claimed in claim 1 or 2, wherein component b) consists of a mono- or diethanolamide.
  4. A cleaning block as claimed in any of claims 1 to 3, wherein component b) is a monoethanolamide of a fatty acid containing on average 12 to 14 carbon atoms in the fatty acid part.
  5. A cleaning block as claimed in any of claims 1 to 4, wherein more than 50% by weight and preferably more than 70% by weight of component c) consists of Na₂SO₄.
  6. A cleaning block as claimed in any of claims 1 to 5, wherein component d) is present in quantities of 1 to 15% by weight and preferably in quantities of 3 to 10% by weight.
  7. A cleaning block as claimed in any of claims 1 to 6, wherein component d) consists of at least one of the following carboxylic acids or, preferably, of at least one salt thereof: citric acid, malic acid, gluconic acid.
  8. A cleaning block as claimed in claim 1, consisting of:
    a) 15 to 25% by weight fatty alcohol sulfate, sodium salt, containing on average 12 to 14 carbon atoms,
    b) 10 to 35% by weight fatty acid monoethanolamide containing on average 12 to 14 carbon atoms in the fatty acid part,
    c) 20 to 55% by weight water-soluble inorganic alkali metal salts of which more than 70% by weight are present as Na₂SO₄,
    d) 3 to 10% by weight of an alkali metal salt of citric acid, malic acid, gluconic acid or mixtures of these alkali metal salts,
    e) 3 to 8% by weight perfume oil and
    f) 3 to 20% by weight water-soluble dye.
  9. The use of the cleaning block claimed in any of claims 1 to 8 as a slowly dissolving source of toilet cleaner in the cistern of flush toilets.
  10. A process for the production of the cleaning blocks claimed in any of claims 1 to 8, characterized in that the solid constituents are mixed in powder form, liquid components are optionally sprayed in, the granular material formed is extruded into strands in an extruder and the strands obtained are cut into blocks.
EP87116866A 1986-11-24 1987-11-16 Cleaning block for the cistern of flushing toilets Expired - Lifetime EP0268967B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87116866T ATE77647T1 (en) 1986-11-24 1987-11-16 CLEANING BLOCK FOR THE WATER TANK OF FLUSHING TOILET.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3640090 1986-11-24
DE19863640090 DE3640090A1 (en) 1986-11-24 1986-11-24 CLEANING BLOCK FOR THE WATER CASE OF SINK TOILETS

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EP0268967A2 EP0268967A2 (en) 1988-06-01
EP0268967A3 EP0268967A3 (en) 1990-06-13
EP0268967B1 true EP0268967B1 (en) 1992-06-24

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EP (1) EP0268967B1 (en)
AT (1) ATE77647T1 (en)
DE (2) DE3640090A1 (en)
ES (1) ES2032423T3 (en)
GR (1) GR3005752T3 (en)

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US6683035B1 (en) 1998-11-18 2004-01-27 Cognis Deutschland Gmbh & Co. Kg Gel compositions containing alkoxylated carboxylic acid esters, their use in cleaning toilets and toilet cleaning products containing the same
US6521578B1 (en) 1999-04-22 2003-02-18 Cognis Deutschland Gmbh Cleaning agents for hard surfaces
WO2004084697A1 (en) 2003-03-27 2004-10-07 Henkel Kommanditgesellschaft Auf Aktien Device for dispensing at least one water-soluble active substance onto a cleaning brush
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Also Published As

Publication number Publication date
GR3005752T3 (en) 1993-06-07
ES2032423T3 (en) 1993-02-16
EP0268967A2 (en) 1988-06-01
US4820449A (en) 1989-04-11
ATE77647T1 (en) 1992-07-15
EP0268967A3 (en) 1990-06-13
DE3780003D1 (en) 1992-07-30
DE3640090A1 (en) 1988-06-01

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