EP0237895B1 - Cleaning agent for lavatories - Google Patents

Cleaning agent for lavatories Download PDF

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Publication number
EP0237895B1
EP0237895B1 EP87103288A EP87103288A EP0237895B1 EP 0237895 B1 EP0237895 B1 EP 0237895B1 EP 87103288 A EP87103288 A EP 87103288A EP 87103288 A EP87103288 A EP 87103288A EP 0237895 B1 EP0237895 B1 EP 0237895B1
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EP
European Patent Office
Prior art keywords
weight
preparation
cellulose powder
water
acid
Prior art date
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Expired
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EP87103288A
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German (de)
French (fr)
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EP0237895A1 (en
Inventor
Ronald Menke
Bernd-Dieter Holdt
Gerd Praus
Petra Plantikow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT87103288T priority Critical patent/ATE46533T1/en
Publication of EP0237895A1 publication Critical patent/EP0237895A1/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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/12—Carbonates bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/08—Acids
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/40—Products in which the composition is not well defined
    • C11D7/44—Vegetable products

Definitions

  • acidic agents that allow limescale deposits to be removed quickly.
  • solid, scatterable agents have become established, particularly for household use, since they are more convenient and safer to handle.
  • these agents usually also contain a certain proportion of water-soluble carbonates, which release carbon dioxide when the agent meets water, and thereby promote the dissolution of the agent and the distribution of the active ingredients.
  • the agents can contain fillers, other active ingredients and auxiliaries.
  • a disadvantage of these powdered toilet cleaners is their tendency to clump in a moist atmosphere, which exists even when the agents are kept in plastic bottles. Presumably, one reason is that the closures of these containers which are usually used can never be absolutely moisture-tight. Especially if the products are stored for a long time or exported to countries where high levels of humidity are often present, this can lead to serious impairments in the spreadability and even complete caking of the contents of the can. To a certain extent, remedial measures can be taken by adding conventional anticaking agents, such as finely divided silicas, but then other disadvantages, such as strong dust formation and matting of the treated ceramic surfaces by adsorption, have to be accepted.
  • the invention therefore relates to solid, scatterable acidic cleaning agents for toilets which, in addition to solid water-soluble acids, water-soluble carbonates and, if appropriate, further ingredients, also contain cellulose powder.
  • the agents preferably contain inorganic salts, surfactants and perfume.
  • cellulose powder in the acidic cleaners improves the flowability of the powders and increases the storage stability considerably, even under extreme moisture conditions. This applies even if the powders are repeatedly exposed to a change from a humid to a dry climate.
  • the addition of cellulose powder does not impair the cleaning power and, although cellulose powder is insoluble in water, the gloss of the ceramic surfaces is not reduced.
  • the content of cellulose powder increases the absorption capacity of the agents for perfume oils and that the perfume oils can be incorporated more permanently than in agents without cellulose powder. In addition, neither the production nor the use of the agents are impaired by the content of cellulose powder.
  • the production can be carried out in simple mixing apparatuses, the mostly coarse-grained components either being mixed all at once, or firstly premixes made from only a part of the components and the other components being mixed in only in further steps. It is also possible, particularly in the case of very finely divided starting materials, to agglomerate all components or a part to larger grains by means of build-up granulation, in order to achieve, for example, dust-free or higher storage stability of individual components.
  • the agents can be applied in the customary manner by scattering or spraying the powders. Provided that not only the automatic cleaning due to the effervescence effect of the powders is used, but that additional mechanics are used, the cellulose powder as a mild abrasive component can have an advantageous effect on the cleaning performance.
  • the acids contained in the agents primarily serve to dissolve limestone and rust deposits on the ceramic surfaces.
  • Suitable solid water-soluble acids having a pK a below 5, such.
  • sodium bisulfate, amidosulfonic acid, tartaric acid, adipic acid, glutaric acid, succinic acid and citric acid As sodium bisulfate, amidosulfonic acid, tartaric acid, adipic acid, glutaric acid, succinic acid and citric acid.
  • the term water-soluble is intended here to mean a solubility of more than 1 g per 100 g of water at 15 ° C.
  • Acids with a pKa value below 4 are preferably used, in particular sodium bisulfate, amidosulfonic acid and citric acid.
  • the proportion of acids in the compositions is between about 3 and about 90 percent by weight and preferably between 5 and 80 percent by weight. For various reasons, when using organic acids, the acid content is usually below 30 percent by weight, while when using inorganic acids it is usually
  • Ammonium or alkali carbonates and / or bicarbonates are preferably used in the agents.
  • (NH 4 ) 2 CO 3 and in particular Na ⁇ COs and NaHCOs are particularly preferred.
  • the amount of carbonates in the agents is always chosen so that, after the CO 2 has developed completely, there is still sufficient acid available for removing limescale and rust deposits. Preferred two
  • the agents therefore contain only so much carbonate that no more than 80 percent, in particular no more than 50 percent, of the acid equivalents contained are used to develop the CO z .
  • the proportion of carbonates is usually between about 1 and about 25 percent by weight, preferably between about 3 and about 20 percent by weight.
  • organic acids usually no more than 10 percent by weight is used, while in the presence of inorganic acids, the agents usually contain at least 5 percent by weight.
  • the starting material for the cellulose powders suitable according to the invention are lignin and other contaminants, in particular bleached celluloses, from which the powders are obtained by mechanical comminution.
  • the type of chemical pretreatment of cellulose is insignificant insofar as it is ensured that the purified cellulose still has the essential properties of native cellulose. This means that the celluloses should still have the fibrous structure of the native material, which is made up of partially crystalline fibrils, and they must not be soluble in water and must not swell until gel formation.
  • chemically unmodified celluloses are used as the starting material.
  • the particle size of the cellulose powder is primarily determined by the requirement that no conspicuous residues may remain in the toilet bowl after the use of the agents. Therefore, the size of the particles should generally not exceed 1000 ⁇ m, preferably 600 ⁇ m. Since the agents should not develop any disturbing dust when used, the lower limit of the fiber length is 1 ⁇ m, preferably 5 11 m. Cellulose powders are particularly preferred, the particles of which have a size of more than 90% between 5 and 300 ⁇ m, in particular between 10 and 200 11 m.
  • the dust development can also be favorably influenced by using finely divided cellulose powder in agglomerated form, ie as granules.
  • the proportion of the cellulose powder in the compositions can be between about 2 percent by weight and about 85 percent by weight; the proportion is preferably 5 to 30 and in particular 5 to 15 percent by weight.
  • the agents can contain inorganic salts in amounts of up to 90 percent by weight as builders or fillers.
  • the alkali and ammonium salts of mineral acids are suitable insofar as they do not impair the acidic reaction of the agents, in particular sodium sulfate and sodium chloride.
  • the proportion of the salts in the compositions is preferably at least 5 and up to 75 percent by weight, and if organic acids are used in the compositions, the proportion of the salts is in particular above 60 percent by weight.
  • the agents can contain anionic or nonionic surfactants in amounts of up to 5 percent by weight.
  • the surfactants are preferably present in proportions between 0.05 and 5 percent by weight, in particular not more than 1 percent by weight.
  • the anionic surfactants used in the agents according to the invention are, in particular, those of the sulfate and sulfonate type, for example alkyl sulfates (sulfuric acid half-esters of long-chain alcohols), ether sulfates (sulfuric acid half-esters of ethylene oxide adducts with long-chain alcohols), alkylbenzenesulfonates, olefin sulfonates, alkanesulfonate acid and alkanesulfonate acid.
  • the anionic surfactants are mainly used in the form of their sodium salts. Particularly preferred anionic surfactants are the alkyl benzene sulfonates, the olefin sulfonates and the alkyl sulfates.
  • nonionic surfactants are the addition products of 1 to 100, preferably 5 to 60, moles of ethylene oxide (EO) to 1 mole of an aliphatic or alkylaromatic compound having 10 to 20 carbon atoms from the group of alcohols, alkylphenols, fatty acids and fatty acid amides.
  • EO ethylene oxide
  • the adducts of 20 to 50 mol EO with primary alcohols of natural or synthetic origin as well as with secondary alcohols and with alkylphenols are particularly suitable. Of these in turn, the adducts of 20 to 50 mol EO with fatty alcohols with 12 to 18 C atoms are particularly preferred.
  • the agents according to the invention often contain a small proportion of perfume. When selecting this ingredient, care must generally be taken to avoid incompatibilities with other ingredients, especially the acid, than with other ingredients. However, by adding the cellulose powder in the agents according to the invention, the sensitivity of the perfume to chemical attacks has been significantly reduced.
  • the perfume content is usually not more than 1 percent by weight, preferably between 0.05 and 0.3 percent by weight.
  • the content of these components is generally not more than 60 percent by weight, preferably not more than 30 percent by weight.
  • Antimicrobial agents such as phenols, are said to give the agents not only the cleansing but also a germ-inhibiting effect. They are used in proportions of up to 10 percent by weight, preferably between 0.5 and 5 percent by weight.
  • polishing agents increases cleaning performance.
  • Acid-stable polishing media such as aluminum clays and glass powder, are suitable for this to a degree of fineness that does not lead to surface scratches even with frequent use.
  • the proportion of the polishing bodies can be up to 50 percent by weight, but is preferably between 5 and 15 percent by weight.
  • bleaching agents also increases cleaning performance, but also has a disinfecting effect.
  • the amount used can be up to 10 percent by weight, preferably 0.5 to 5 percent by weight.
  • Water-soluble types which have no affinity for ceramic surfaces are preferably used as dyes.
  • Food dyes are primarily used taking ecological aspects into account.
  • the proportion of the dyes in the compositions can be up to 1 percent by weight and is preferably between 0.005 and 0.5 percent by weight.
  • dedusting agents are used to bind fine dust that may be present in some of the individual components.
  • These agents are preferably liquid substances which are largely chemically inert, for example paraffin oils, silicone oils, terpenes or polyether alcohols. These agents are preferably sprayed onto the premix of the other constituents, amounts of up to 3 percent by weight, preferably 0.05-0.5 percent by weight, based on the total agent, being sufficient.
  • compositions described below in the form of their composition were produced in the following way:
  • the test was carried out in each case with 100 g of the agents listed in Table 1, each of which was stored in open powder bottles in a climate cell at 40 ° C. and 90% relative humidity for 7 days.
  • the first assessment was made after cooling to room temperature; the second assessment after drying over 24 hours at 40 ° C.
  • the free-flowing properties were assessed in grades from 1 (free-flowing properties not affected) to 5 (powder completely caked).
  • the agents listed in Table 2 were mixed in the manner given before Examples 1 to 5 and stored in portions of 1 kg each in plastic containers with pouring and spray closures in a climatic cell at 30 ° C. and 80% relative humidity. The assessment was made after cooling to room temperature after a storage period of 14 days.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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Abstract

1. A solid, powder-form acidic sprinkling preparation for cleaning toilets containing solid water-soluble acid and water-soluble carbonate, characterized in that it also contains cellulose powder.

Description

Zur Reinigung von Toiletten verwendet man vorzugsweise säurehaltige Mittel, die es gestatten, auch Kalksteinablagerungen schnell zu entfernen. Neben flüssigen Präparaten haben sich vor allem für die Anwendung im Haushalt feste, streufähige Mittel durchgesetzt, da sie bequemer und sicherer zu handhaben sind. Diese Mittel enthalten neben einer festen wasserlöslichen Säure in der Regel auch einen gewissen Anteil an wasserlöslichen Carbonaten, die Kohlendioxid freisetzen, wenn das Mittel mit Wasser zusammentrifft, und dadurch die Auflösung des Mittels und die Verteilung der Wirkstoffe begünstigen. Zusätzlich können die Mittel Füllstoffe, weitere Wirkstoffe und Hilfsstoffe enthalten.To clean toilets, preference is given to using acidic agents that allow limescale deposits to be removed quickly. In addition to liquid preparations, solid, scatterable agents have become established, particularly for household use, since they are more convenient and safer to handle. In addition to a solid water-soluble acid, these agents usually also contain a certain proportion of water-soluble carbonates, which release carbon dioxide when the agent meets water, and thereby promote the dissolution of the agent and the distribution of the active ingredients. In addition, the agents can contain fillers, other active ingredients and auxiliaries.

Nachteilig an diesen pulverförmigen WC-Reinigern ist ihre Neigung zum Verklumpen in feuchter Atmosphäre, die selbst dann besteht, wenn die Mittel in Plastikflaschen aufbewahrt werden. Vermutlich, liegt eine Ursache darin, daß die üblicherweise verwendeten Verschlüsse dieser Behälter nie absolut feuchtigkeitsdicht sein können. Vor allem dann, wenn die Mittel lange lagern oder in Länder exportiert werden, in denen häufig hohe Luftfeuchtigkeiten herschen, kann dies zu ernsthaften Beeinträchtigungen der Streubarkeit bis hin zum vollständigen Verbacken des Doseninhaltes führen. Zwar kann durch Zugabe üblicher Anticakingmittel, wie feinteiligen Kieselsäuren, in gewissem Grade Abhilfe geschaffen werden, doch müssen dann andere Nachteile, wie starke Staubentwicklung und Mattierung der behandelten Keramikflächen durch Adsorption in Kauf genommen werden.A disadvantage of these powdered toilet cleaners is their tendency to clump in a moist atmosphere, which exists even when the agents are kept in plastic bottles. Presumably, one reason is that the closures of these containers which are usually used can never be absolutely moisture-tight. Especially if the products are stored for a long time or exported to countries where high levels of humidity are often present, this can lead to serious impairments in the spreadability and even complete caking of the contents of the can. To a certain extent, remedial measures can be taken by adding conventional anticaking agents, such as finely divided silicas, but then other disadvantages, such as strong dust formation and matting of the treated ceramic surfaces by adsorption, have to be accepted.

Es wurde nun gefunden, daß das Verklumpen der Mittel, ohne daß andere Nachteile auftreten, weitgehend bis vollständig vermieden werden kann, wenn man den Mitteln Cellulosepulver zusetzt.It has now been found that clumping of the compositions, without other disadvantages, can be largely or completely avoided by adding cellulose powder to the compositions.

Gegenstand der Erfindung sind daher feste, streubare sauer wirkende Reinigungsmittel für Toiletten, die neben festen wasserlöslichen Säuren, wasserlöslichen Carbonaten und gegebenenfalls weiteren Inhaltsstoffen auch Cellulosepulver enthalten. Vorzugsweise enthalten die Mittel darüber hinaus anorganische Salze, Tenside und Parfüm.The invention therefore relates to solid, scatterable acidic cleaning agents for toilets which, in addition to solid water-soluble acids, water-soluble carbonates and, if appropriate, further ingredients, also contain cellulose powder. In addition, the agents preferably contain inorganic salts, surfactants and perfume.

Die zusätzliche Verwendung von Cellulosepulver in den sauren Reinigern verbessert die Fließfähigkeit der Pulver und erhöht die Lagerstabilität selbst unter extremen Feuchtigkeitsbedingungen ganz beträchtlich. Dies gilt selbst dann, wenn die Pulver wiederholt einem Wechsel von feuchtem und trockenem Klima ausgesetzt sind. Dabei kommt es durch den Zusatz von Cellulosepulver nicht zu einer Beeinträchtigung der Reinigungskraft, und es wird, obwohl Cellulosepulver wasserunlöslich ist, der Glanz der Keramikoberflächen nicht gemindert. Bemerkenswert ist weiterhin, daß durch den Gehalt an Cellulosepulver das Aufnahmevermögen der Mittel für Parfümöle ansteigt und daß die Parfümöle dauerhafter eingearbeitet werden können als in Mitteln ohne Cellulosepulver. Darüber hinaus werden weder die Herstellung noch die Anwendung der Mittel durch den Gehalt an Cellulosepulver beeinträchtigt.The additional use of cellulose powder in the acidic cleaners improves the flowability of the powders and increases the storage stability considerably, even under extreme moisture conditions. This applies even if the powders are repeatedly exposed to a change from a humid to a dry climate. The addition of cellulose powder does not impair the cleaning power and, although cellulose powder is insoluble in water, the gloss of the ceramic surfaces is not reduced. It is also noteworthy that the content of cellulose powder increases the absorption capacity of the agents for perfume oils and that the perfume oils can be incorporated more permanently than in agents without cellulose powder. In addition, neither the production nor the use of the agents are impaired by the content of cellulose powder.

So kann die Herstellung in einfachen Mischapparaturen vorgenommen werden, wobei die meist grobkömigen Bestandteile entweder alle auf einmal vermischt werden, oder zunächst Vorgemische aus nur einem Teil der Komponenten hergestellt und erst in weiteren Schritten die übrigen Bestandteile zugemischt werden. Es ist ebenfalls möglich, insbesondere bei sehr feinteiligen Ausgangsmaterialien, alle Komponenten oder einen Teil durch Aufbaugranulation zu größeren Körnern zu agglomerieren, um dadurch beispielsweise Staubfreiheit oder höhere Lagerstabilität einzelner Bestandteile zu erreichen.Thus, the production can be carried out in simple mixing apparatuses, the mostly coarse-grained components either being mixed all at once, or firstly premixes made from only a part of the components and the other components being mixed in only in further steps. It is also possible, particularly in the case of very finely divided starting materials, to agglomerate all components or a part to larger grains by means of build-up granulation, in order to achieve, for example, dust-free or higher storage stability of individual components.

Die Anwendung der Mittel kann in üblicher Weise durch Streuen oder Sprühen der Pulver erfolgen. Sofern nicht allein die selbsttätige Reinigung durch den Sprudeleffekt der Pulver genutzt, sondern zusätzlich Mechanik angewandt wird, kann sich das Cellulosepulver als milde Abrasivkomponente vorteilhaft bei der Reinigungsleistung bemerkbar machen.The agents can be applied in the customary manner by scattering or spraying the powders. Provided that not only the automatic cleaning due to the effervescence effect of the powders is used, but that additional mechanics are used, the cellulose powder as a mild abrasive component can have an advantageous effect on the cleaning performance.

Es folgt nun eine Beschreibung der einzelnen Inhaltsstoffe. Sie werden in der Regel in wasserfreier Form verwendet:There now follows a description of the individual ingredients. They are usually used in anhydrous form:

a Säurena acids

Die in den Mitteln enthaltenen Säuren dienen in erster Linie der Auflösung von Kalkstein und Rostablagerungen auf den Keramikoberflächen. Geeignet sind feste wasserlösliche Säuren, die einen pKs-Wert unter 5 aufweisen, wie z. B. Natriumbisulfat, Amidosulfonsäure, Weinsäure, Adipinsäure, Glutarsäure, Bernsteinsäure und Citronensäure. Der Ausdruck wasserlöslich soll hier eine Löslichkeit von mehr als 1 g pro 100 g Wasser bei 15 °C bedeuten. Bevorzugt werden Säuren mit einem pKs-Wert unter 4 verwendet, insbesondere Natriumbisulfat, Amidosulfonsäure und Citronensäure. Der Anteil der Säuren in den Mitteln liegt zwischen etwa 3 und etwa 90 Gewichtsprozent und vorzugsweise zwischen 5 und 80 Gewichtsprozent. Aus verschiedenen Gründen liegt beim Einsatz von organischen Säuren der Säureanteil meist unter 30 Gewichtsprozent, während er bei Verwendung anorganischer Säuren meistens wenigstens 10 Gewichtsprozent beträgt.The acids contained in the agents primarily serve to dissolve limestone and rust deposits on the ceramic surfaces. Suitable solid water-soluble acids having a pK a below 5, such. As sodium bisulfate, amidosulfonic acid, tartaric acid, adipic acid, glutaric acid, succinic acid and citric acid. The term water-soluble is intended here to mean a solubility of more than 1 g per 100 g of water at 15 ° C. Acids with a pKa value below 4 are preferably used, in particular sodium bisulfate, amidosulfonic acid and citric acid. The proportion of acids in the compositions is between about 3 and about 90 percent by weight and preferably between 5 and 80 percent by weight. For various reasons, when using organic acids, the acid content is usually below 30 percent by weight, while when using inorganic acids it is usually at least 10 percent by weight.

b) Carbonateb) carbonates

Vorzugsweise werden in den Mitteln Ammonium- oder Alkalicarbonate und/oder -bicarbonate eingesetzt. Besonders bevorzugt werden (NH4)2C03 und insbesondere NaεCOs und NaHCOs. Die Menge an Carbonaten wird in den Mitteln stets so gewählt, daß nach vollständiger Entwicklung des C02 noch genügend Säure für die Entfernung von Kalk- und Rostablagerungen zur Verfügung steht. Vorzugsweise enthalten die Mittel deshalb nur soviel Carbonat, daß nicht mehr als 80 Prozent, insbesondere nicht mehr als 50 Prozent der enthaltenen Säureäquivalente zur Entwicklung des COz verbraucht werden. Der Anteil der Carbonate liegt üblicherweise zwischen etwa 1 und etwa 25 Gewichtsprozent, vorzugsweise zwischen etwa 3 und etwa 20 Gewichtsprozent. Bei Verwendung organischer Säuren werden meist nicht mehr als 10 Gewichtsprozent eingesetzt, während bei Anwesenheit anorganischer Säuren meist wenigstens 5 Gewichtsprozent in den Mitteln enthalten sind..Ammonium or alkali carbonates and / or bicarbonates are preferably used in the agents. (NH 4 ) 2 CO 3 and in particular NaεCOs and NaHCOs are particularly preferred. The amount of carbonates in the agents is always chosen so that, after the CO 2 has developed completely, there is still sufficient acid available for removing limescale and rust deposits. Preferred two The agents therefore contain only so much carbonate that no more than 80 percent, in particular no more than 50 percent, of the acid equivalents contained are used to develop the CO z . The proportion of carbonates is usually between about 1 and about 25 percent by weight, preferably between about 3 and about 20 percent by weight. When using organic acids, usually no more than 10 percent by weight is used, while in the presence of inorganic acids, the agents usually contain at least 5 percent by weight.

c) Cellulosepulverc) cellulose powder

Ausgangsmaterial für die erfindungsgemäß geeigneten Cellulosepulver sind von Lignin und anderen Verunreinigungen befreite, insbesondere gebleichte Cellulosen, aus denen die Pulver durch mechanische Zerkleinerung gewonnen werden. Die Art der chemischen Vorbehandlung der Cellulose ist in soweit unerheblich, wie sichergestellt ist, daß die gereinigte Cellulose noch die hier wesentlichen Eigenschaften der nativen Cellulose aufweist. Das heißt, die Cellulosen sollen noch die faserartige Struktur des nativen Materials, die aus partiell kristallinen Fibrillen aufgebaut ist, besitzen, und sie dürfen in Wasser nicht löslich sein und nicht bis zur Gelbildung quellen. Insbesondere werden chemisch nicht modifizierte Cellulosen als Ausgangsmaterial eingesetzt.The starting material for the cellulose powders suitable according to the invention are lignin and other contaminants, in particular bleached celluloses, from which the powders are obtained by mechanical comminution. The type of chemical pretreatment of cellulose is insignificant insofar as it is ensured that the purified cellulose still has the essential properties of native cellulose. This means that the celluloses should still have the fibrous structure of the native material, which is made up of partially crystalline fibrils, and they must not be soluble in water and must not swell until gel formation. In particular, chemically unmodified celluloses are used as the starting material.

Die Teilchengröße des Cellulosepulvers wird in erster Linie durch die Forderung bestimmt, daß in der Toilettenschüssel keine auffälligen Rückstände nach der Anwendung der Mittel verbleiben dürfen. Daher sollte die Größe der Teilchen im allgemeinen 1000 µm, vorzugsweise 600 µm nicht überschreiten. Da die Mittel bei der Anwendung möglichst keinen störenden Staub entwickeln sollen, liegt die Untergrenze der Faserlänge bei 1 µm, vorzugsweise bei 5 11m. Besonders bevorzugt werden Cellulosepulver, deren Teilchen zu mehr als 90 % eine Größe zwischen 5 und 300 µm, insbesondere zwischen 10 und 200 11m aufweisen. Die Staubentwicklung kann auch dadurch günstig beeinflußt werden, daß feinteiliges Cellulosepulver in agglomerierter Form, d. h. als Granulat, verwendet wird.The particle size of the cellulose powder is primarily determined by the requirement that no conspicuous residues may remain in the toilet bowl after the use of the agents. Therefore, the size of the particles should generally not exceed 1000 μm, preferably 600 μm. Since the agents should not develop any disturbing dust when used, the lower limit of the fiber length is 1 µm, preferably 5 11 m. Cellulose powders are particularly preferred, the particles of which have a size of more than 90% between 5 and 300 μm, in particular between 10 and 200 11 m. The dust development can also be favorably influenced by using finely divided cellulose powder in agglomerated form, ie as granules.

Der Anteil des Cellulosepulvers kann in den Mitteln zwischen etwa 2 Gewichtsprozent und etwa 85 Gewichtsprozent liegen; vorzugsweise beträgt der Anteil 5 bis 30 und insbesondere 5 bis 15 Gewichtsprozent.The proportion of the cellulose powder in the compositions can be between about 2 percent by weight and about 85 percent by weight; the proportion is preferably 5 to 30 and in particular 5 to 15 percent by weight.

d) Gerüststoffe (Salze)d) builders (salts)

Neben den unter a) bis c) genannten obligatorischen Bestandteilen können die Mittel als Gerüst- oder Füllstoffe anorganische Salze in Mengen bis zu 90 Gewichtsprozent enthalten. Geeignet sind die Alkali-und Ammoniumsalze von Mineralsäuren, soweit sie die saure Reaktion der Mittel nicht beeinträchtigen, insbesondere Natriumsulfat und Natriumchlorid. Der Anteil der Salze an den Mitteln beträgt vorzugsweise wenigstens 5 und bis zu 75 Gewichtsprozent, wobei dann, wenn organische Säuren in den Mitteln verwendet werden, der Anteil der Salze insbesondere über 60 Gewichtsprozent liegt.In addition to the mandatory components mentioned under a) to c), the agents can contain inorganic salts in amounts of up to 90 percent by weight as builders or fillers. The alkali and ammonium salts of mineral acids are suitable insofar as they do not impair the acidic reaction of the agents, in particular sodium sulfate and sodium chloride. The proportion of the salts in the compositions is preferably at least 5 and up to 75 percent by weight, and if organic acids are used in the compositions, the proportion of the salts is in particular above 60 percent by weight.

e) Tensidee) surfactants

Zur Unterstützung der Reinigungswirkung können die Mittel anionische oder nichtionische Tenside in Mengen bis zu 5 Gewichtsprozent enthalten. Bevorzugt liegen die Tenside mit Anteilen zwischen 0,05 und 5 Gewichtsprozent, insbesondere nicht mehr als 1 Gewichtsprozent vor.To support the cleaning action, the agents can contain anionic or nonionic surfactants in amounts of up to 5 percent by weight. The surfactants are preferably present in proportions between 0.05 and 5 percent by weight, in particular not more than 1 percent by weight.

Als anionische Tenside finden in den erfindungsgemäßen Mitteln insbesondere solche vom Sulfat-und Sulfonat-Typ Verwendung, beispielsweise Alkylsulfate (Schwefelsäurehalbester von langkettigen Alkoholen), Ethersulfate (Schwefelsäurehalbester von Ethylenoxidaddukten an langkettige Alkohole), Alkylbenzolsulfonate, Olefinsulfonate, Alkansulfonate und Alpha-Sulfofettsäureester. Die anionischen Tenside werden vorwiegend in Form ihrer Natriumsalze verwendet. Besonders bevorzugte anionische Tenside sind die Alkylbenzolsulfonate, die Olefinsulfonate und die Alkylsulfate.The anionic surfactants used in the agents according to the invention are, in particular, those of the sulfate and sulfonate type, for example alkyl sulfates (sulfuric acid half-esters of long-chain alcohols), ether sulfates (sulfuric acid half-esters of ethylene oxide adducts with long-chain alcohols), alkylbenzenesulfonates, olefin sulfonates, alkanesulfonate acid and alkanesulfonate acid. The anionic surfactants are mainly used in the form of their sodium salts. Particularly preferred anionic surfactants are the alkyl benzene sulfonates, the olefin sulfonates and the alkyl sulfates.

Als nichtionische Tenside eignen sich besonders die Anlagerungsprodukte von 1 bis 100, vorzugsweise 5 bis 60 Mol Ethylenoxid (EO) an 1 Mol einer aliphatischen oder alkylaromatischen Verbindung mit 10 bis 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Alkylphenole, Fettsäuren und Fettsäureamide. Besonders geeignet sind die Anlagerungsprodukte von 20 bis 50 Mol EO an primäre Alkohole natürlichen oder synthetischen Ursprungs sowie an sekundäre Alkohole und an Alkylphenole. Von diesen wiederum werden die Anlagerungsprodukte von 20 bis 50 Mol EO an Fettalkohole mit 12 bis 18 C-Atomen besonders bevorzugt.Particularly suitable as nonionic surfactants are the addition products of 1 to 100, preferably 5 to 60, moles of ethylene oxide (EO) to 1 mole of an aliphatic or alkylaromatic compound having 10 to 20 carbon atoms from the group of alcohols, alkylphenols, fatty acids and fatty acid amides. The adducts of 20 to 50 mol EO with primary alcohols of natural or synthetic origin as well as with secondary alcohols and with alkylphenols are particularly suitable. Of these in turn, the adducts of 20 to 50 mol EO with fatty alcohols with 12 to 18 C atoms are particularly preferred.

f) Parfümf) perfume

Häufig enthalten die erfindungsgemäßen Mittel einen kleinen Anteil an Parfüm. Bei der Auswahl dieses Bestandteils ist im allgemeinen mehr noch als bei anderen Inhaltsstoffen darauf zu achten, daß Unverträglichkeiten mit anderen Bestandteilen, insbesondere der Säure, vermieden werden. Durch den Zusatz des Cellulosepulvers in den erfindungsemäßen Mitteln ist allerdings die Empfindlichkeit des Parfüms gegenüber chemischen Angriffen deutlich vermindert worden. Der Gehalt an Parfüm liegt überlicherweise nicht über 1 Gewichtsprozent, vorzugsweise zwischen 0,05 und 0,3 Gewichtsprozent.The agents according to the invention often contain a small proportion of perfume. When selecting this ingredient, care must generally be taken to avoid incompatibilities with other ingredients, especially the acid, than with other ingredients. However, by adding the cellulose powder in the agents according to the invention, the sensitivity of the perfume to chemical attacks has been significantly reduced. The perfume content is usually not more than 1 percent by weight, preferably between 0.05 and 0.3 percent by weight.

0) weitere fakultative Bestandteile 0 ) other optional components

Hier sind in erster Linie antimikrobielle Wirkstoffe, Polierkörper, Bleichmittel, Farbstoffe und Mittel zur Verhinderung der Staubbildung zu nennen. Der Gehalt an diesen Bestandteilen liegt im allgemeinen nicht über 60 Gewichtsprozent, vorzugsweise nicht über 30 Gewichtsprozent.Primarily antimicrobial agents, polishing agents, bleaching agents, dyes and agents to prevent dust formation should be mentioned here. The content of these components is generally not more than 60 percent by weight, preferably not more than 30 percent by weight.

Antimikrobielle Wirkstoffe, beispielsweise Phenole, sollen den Mitteln neben der reinigenden auch eine keimhemmende Wirkung verleihen. Sie werden in Anteilen bis zu 10 Gewichtsprozent, vorzugsweise zwischen 0,5 und 5 Gewichtsprozent eingesetzt.Antimicrobial agents, such as phenols, are said to give the agents not only the cleansing but also a germ-inhibiting effect. They are used in proportions of up to 10 percent by weight, preferably between 0.5 and 5 percent by weight.

Die Zugabe von Poliermitteln dient der Verstärkung der Reinigungsleistung. Hierzu eignen sich säurestabile Polierkörper, wie Aluminiumtonerden und Glasmehle in einem Feinheitsgrad, der auch bei häufiger Anwendung nicht zu Oberflächenverkratzungen führt. Der Anteil der Polierkörper kann bis zu 50 Gewichtsprozent betragen, liegt vorzugsweise aber zwischen 5 und 15 Gewichtsprozent.The addition of polishing agents increases cleaning performance. Acid-stable polishing media, such as aluminum clays and glass powder, are suitable for this to a degree of fineness that does not lead to surface scratches even with frequent use. The proportion of the polishing bodies can be up to 50 percent by weight, but is preferably between 5 and 15 percent by weight.

Auch der Zusatz von Bleichmitteln verstärkt die Reinigungsleistung, wirkt aber zusätzlich desinfizierend. Man verwendet entweder Aktivsauerstoffträger, wie Perborat oder Persulfat, oder Aktivchlorträger, wie Natriumdichlorisocyanurat. Die Einsatzmenge kann bis zu 10 Gewichtsprozent, vorzugsweise 0,5 bis 5 Gewichtsprozent, betragen.The addition of bleaching agents also increases cleaning performance, but also has a disinfecting effect. Either active oxygen carriers, such as perborate or persulfate, or active chlorine carriers, such as sodium dichloroisocyanurate, are used. The amount used can be up to 10 percent by weight, preferably 0.5 to 5 percent by weight.

Als Farbstoffe werden vorzugsweise wasserlösliche Typen verwendet, die keine Affinität zu Keramikoberflächen aufweisen. In erster Linie werden unter Berücksichtigung ökologischer Aspekte Lebensmittelfarbstoffe eingesetzt. Der Anteil der Farbstoffe an den Mitteln kann bis zu 1 Gewichtsprozent betragen und liegt vorzugsweise zwischen 0,005 und 0,5 Gewichtsprozent.Water-soluble types which have no affinity for ceramic surfaces are preferably used as dyes. Food dyes are primarily used taking ecological aspects into account. The proportion of the dyes in the compositions can be up to 1 percent by weight and is preferably between 0.005 and 0.5 percent by weight.

Entstaubungsmittel schließlich dienen zur Bindung von Feinstaubanteilen, die in einigen der Einzelbestandteile vorhanden sein können. Bei diesen Mitteln handelt es sich vorzugsweise um flüssige Substanzen, die chemisch weitgehend inert sind, beispielsweise Paraffinöle, Silikonöle, Terpene- oder Polyetheralkohole. Diese Mittel werden vorzugsweise auf das Vorgemisch der übrigen Bestandteile aufgesprüht, wobei Mengen bis zu 3 Gewichtsprozent, vorzugsweise 0,05 - 0,5 Gewichtsprozent, bezogen auf das gesamte Mittel, ausreichen.Finally, dedusting agents are used to bind fine dust that may be present in some of the individual components. These agents are preferably liquid substances which are largely chemically inert, for example paraffin oils, silicone oils, terpenes or polyether alcohols. These agents are preferably sprayed onto the premix of the other constituents, amounts of up to 3 percent by weight, preferably 0.05-0.5 percent by weight, based on the total agent, being sufficient.

BeispieleExamples

Die im folgenden in Form ihrer Zusammensetzung beschriebenen Mittel wurden auf folgende Weise herstellt:The compositions described below in the form of their composition were produced in the following way:

Cellulose, Natriumchlorid, Natriumsulfat und das Tensid wurden in einem Taumelmischer oder Draismischer vorgelegt und dann gemischt, wobei über eine Düse das Parfüm eingesprüht wurde. Anschließend erfolgte die Zugabe der übrigen Komponenten. Als letztes wurde das Entstaubungsmittel eingesprüht. Die Mittel gemäß Beispielen 1 bis 3 wurden in Kunststoffflaschen mit 1 kg Inhalt und Streueinsatz, die Mittel nach Beispielen 4 und 5 in Gebinde mit kindergesichertem Sprüh/Schüttverschluß abgefüllt.Cellulose, sodium chloride, sodium sulfate and the surfactant were placed in a tumble mixer or drain mixer and then mixed, with the perfume being sprayed in through a nozzle. The remaining components were then added. Finally, the dedusting agent was sprayed in. The agents according to Examples 1 to 3 were filled in plastic bottles with a content of 1 kg and a sprinkling insert, the agents according to Examples 4 and 5 in containers with child-resistant spray / pouring caps.

Soweit nicht anders angegeben, beziehen sich die Zahlenangaben im folgenden auf Gewichtsprozente. Beim Cellulosepulver ist jeweils die obere Grenze der Faserlänge angegeben.

Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
 Unless otherwise stated, the figures below relate to percentages by weight. The upper limit of the fiber length is specified for cellulose powder.
Figure imgb0001
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005

6. 13. Überprüfung der Rieselfähickeit nach dem Einwirken hoher Luftfeuchtigkeit.6. 13. Checking the pourability after exposure to high humidity.

Die Prüfung erfolgte mit jeweils 100 g der in Tabelle 1 aufgeführten Mittel, die jeweils in offenen Pulverflaschen in einer Klimazelle bei 40 °C und 90 % relativer Feuchtigkeit 7 Tage gelagert wurden. Die erste Beurteilung erfolgte nach dem Abkühlen auf Raumtemperatur; die zweite Beurteilung nach Trocknung über 24 Stunden bei 40 °C. Die Bewertung der Rieselfähigkeit erfolgte in Noten von 1 (Rieselfähigkeit nicht beeinflußt) bis 5 (Pulver vollständig verbackt).The test was carried out in each case with 100 g of the agents listed in Table 1, each of which was stored in open powder bottles in a climate cell at 40 ° C. and 90% relative humidity for 7 days. The first assessment was made after cooling to room temperature; the second assessment after drying over 24 hours at 40 ° C. The free-flowing properties were assessed in grades from 1 (free-flowing properties not affected) to 5 (powder completely caked).

Aus den Bewertungen in Tabelle 1 geht der außerordentliche positive Einfluß des Cellulosepulvers klar hervor.

Figure imgb0006
The evaluations in Table 1 clearly show the extraordinary positive influence of the cellulose powder.
Figure imgb0006

14. -17. Überprüfung der Lagerstabilität in Originalvepackung14-17 Checking the storage stability in the original packaging

Die in Tabelle 2 aufgeführten Mittel wurden in der vor den Beispielen 1 bis 5 angegebenen Weise aufgemischt und in Portionen von je 1 kg in Plastikgebinden mit Schütt- und Sprühverschluß in einer Klimazelle bei 30 °C und 80 % relativer Feuchtigkeit gelagert. Die Beurteilung erfolgte nach Abkühlung auf Raumtemperatur nach einer Lagerzeit von 14 Tagen.The agents listed in Table 2 were mixed in the manner given before Examples 1 to 5 and stored in portions of 1 kg each in plastic containers with pouring and spray closures in a climatic cell at 30 ° C. and 80% relative humidity. The assessment was made after cooling to room temperature after a storage period of 14 days.

Wie aus Tabelle 2 hervorgeht, bewirkte diese Klimabelastung bei Mitteln ohne Zusatz von Cellulosepulver und auch mit Zusatz herkömmlicher Anticakingmittel, wie gefällter Kieselsäure, oder pyrogener Kieselsäure bereits eine starke Beeinträchtigung der Rieselfähigkeit. Nur das erfindungsgemäße Produkt 17 wurde in seiner Rieselfähigkeit nicht beeinflußt.

Figure imgb0007
As can be seen from Table 2, this climatic load already caused a severe impairment of the free-flowing properties of agents without the addition of cellulose powder and also with the addition of conventional anticaking agents, such as precipitated silica or pyrogenic silica. Only the product 17 according to the invention was not influenced in its flowability.
Figure imgb0007

Claims (9)

1. A solid, powder-form acidic sprinkling preparation for cleaning toilets containing solid water-soluble acid and water-soluble carbonate, characterized in that it also contains cellulose powder.
2. A preparation as claimed in Claim 1, characterized in that it contains from 2 to 85% by weight of a cellulose powder having particle sizes of from 1 to 1000 µm.
3. A preparation as claimed in Claim 2, characterized in that it contains from 5 to 30% by weight of a cellulose powder in which more than 90% of the particles are between 5 and 300 µm and preferably between 10 and 200 µm in size.
4. A preparation as claimed in any of Claims 1 to 3, characterized in that the cellulose powder is incorporated in granulated form.
5. A preparation as claimed in any of Claims 1 to 4, characterized in that it additionally contains alkali or ammonium salts of mineral acids, anionic or nonionic surfactants and perfume.
6. A preparation as claimed in Claim 5 containing
from 3 to 90% by weight of solid water-soluble acid having a pKa-value below 5,
from 1 to 25% by weight of alkali and/or ammonium carbonate and/or bicarbonate,
from 2 to 85% by weight of cellulose powder having particle sizes of from 1 to 1000 wm,
from 5 to 90% by weight of alkali and/or ammonium salts of mineral acids,
from 0.05 to 5% by weight of anionic or nonionic surfactants,
from 0.05 to 1% by weight of perfume and
from 0 to 60% by weight of additives from the group comprising antimicrobial agents, polishes, dyes, bleaches and dust inhibitors,

with the proviso that the quantities of acid and carbonate are selected so that less than 80% and preferably less than 50% of the acid equivalents are consumed in the release of C02.
7. A preparation as claimed in Claim 6 containing
from 3 to 30% by weight solid, water-soluble organic acid,
from 1 to 10% by weight Na2COs and/or NaHCOs,
from 5 to 30% by weight cellulose powder,
from 60 to 90% by weight NazS04 and/or NaCI,
from 0.05 to 1% by weight anionic and/or nonionic surfactants,
from 0.05 to 0.3% by weight perfume and
from 0 to 30% by weight additives.
8. A preparation as claimed in Claim 6 containing
from 10 to 80% by weight solid, water-soluble inorganic acid,
from 5 to 25% by weight Na2CO3 and/or NaHCOs,
from 5 to 30% by weight cellulose powder,
from 5 to 75% by weight NazS04 and/or NaCI,
from 0.05 to 1% by weight anionic and/or nonionic surfactants,
from 0.05 to 0.3% by weight perfume and
from 0 to 30% by weight additives.
9. A process for the production of solid, acidic sprinkling preparations for cleaning toilets containing solid, water-soluble acid and water-soluble carbonate, characterized in that cellulose powder is added during mixing or granulation of the preparation.
EP87103288A 1986-03-15 1987-03-07 Cleaning agent for lavatories Expired EP0237895B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87103288T ATE46533T1 (en) 1986-03-15 1987-03-07 CLEANING AGENTS FOR TOILETS.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3608799 1986-03-15
DE19863608799 DE3608799A1 (en) 1986-03-15 1986-03-15 CLEANER FOR TOILETS

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EP0237895A1 EP0237895A1 (en) 1987-09-23
EP0237895B1 true EP0237895B1 (en) 1989-09-20

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Publication number Priority date Publication date Assignee Title
DE3941994C2 (en) * 1989-12-20 2002-10-31 Henkel Kgaa Powdered sanitary cleaning agent
DE102010042346A1 (en) * 2010-10-12 2012-04-12 Henkel Ag & Co. Kgaa Foaming powdered cleaner with disinfecting properties
US8859482B2 (en) * 2011-02-14 2014-10-14 Chemlink Laboratories, Llc Method for preparing a solid form of acetic acid and products thereof
ITMI20130697A1 (en) * 2013-04-29 2014-10-30 Fem2 Ambiente S R L ECO-SUSTAINABLE DETERGENT PRODUCT BASED ON CITRIC ACID

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Publication number Priority date Publication date Assignee Title
FR872573A (en) * 1940-11-18 1942-06-12 Maison Auziere & Co Process for the manufacture of a detergent product for toilet and cleaning
GB1049051A (en) * 1964-01-17 1966-11-23 Jeyes Group Ltd Improvements in and relating to cleaning preparations
GB2073233B (en) * 1980-04-03 1983-10-05 Arrow Chem Ltd Cleaning compositions

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GR3000174T3 (en) 1990-12-31
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ES2011271B3 (en) 1990-01-01
EP0237895A1 (en) 1987-09-23
ATE46533T1 (en) 1989-10-15

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