EP3478812B1 - Use of a piece of cleaning agent for cleaning of the toilet area - Google Patents

Use of a piece of cleaning agent for cleaning of the toilet area Download PDF

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Publication number
EP3478812B1
EP3478812B1 EP17720496.3A EP17720496A EP3478812B1 EP 3478812 B1 EP3478812 B1 EP 3478812B1 EP 17720496 A EP17720496 A EP 17720496A EP 3478812 B1 EP3478812 B1 EP 3478812B1
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EP
European Patent Office
Prior art keywords
salts
alkanecarboxylic
cleaning
less
weight
Prior art date
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Application number
EP17720496.3A
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German (de)
French (fr)
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EP3478812A1 (en
Inventor
Joachim Leipold
Antje Schirmer
Frank BRUNECKER
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Buck Chemie GmbH
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Buck Chemie GmbH
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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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0095—Solid transparent soaps or detergents
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D3/50—Perfumes
    • 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
    • C11D1/008—Polymeric surface-active agents
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols

Definitions

  • the present invention relates to the use of a toilet area cleaning agent containing soaps.
  • cleaning agents can be hung, for example, as so-called rim blocks in toilet baskets or via a hook attached to the agent on the edge of the toilet bowl, or they can also be glued to the toilet bowl.
  • Such bar-shaped cleaning agents should retain their shape even at higher temperatures, they should be cut-resistant and have a sufficiently high melting point so that they can also be transported and stored in warmer climates and in summer, without changing their shape.
  • the soaps form gels with liquids and, even in small amounts, make the agent very firm, so that lump-shaped, cut-resistant cleaning agents can be obtained.
  • Soaps are also advantageous because they can store a high proportion of perfume oils, so that the agents are also suitable for fragrancing.
  • transparent agents can be made from soaps. Such transparent means are desired by consumers because they are visually appealing.
  • the DE 197 10 635 A1 teaches a transparent gel-like, lump-like toilet cleaning agent, which is also used for permanent room scenting and comprises anionic surfactants, alkanecarboxylic acid salts such as sodium stearate as gelling agents, solvents and fragrances.
  • the means there are attached to a holder or in a basket or cage-like container in the toilet bowl at a point through which the incoming flushing water flows during each flushing process.
  • Toilet cleaning agents in lump form with particularly high transparency are known which, in addition to alkanecarboxylic acid salts, solvents, surfactants and perfume oil, also include at least one compound from the group of sugar and sugar derivatives and at least one compound from the group of reduced sugars.
  • Pastes for the sanitary sector which comprise an adhesion promoter from the group of oligo- or polyethylene oxide and / or oligo- or polypropylene oxide and / or oligo- and / or polybutylene oxide comprising block copolymers as well as water and perfume.
  • These viscous pastes are not lumpy and are not stored in a toilet basket, but rather applied directly to the sanitary item, where they adhere and are only rinsed off after a large number of flushing processes.
  • Transparent bars of soap are from the WO 01/11 001 A1 and the US 6,689,728 B2 known.
  • toilet cleaning blocks that are at least partially transparent or translucent with a carrier composition and 20 to 50% by weight of a biocide.
  • WO 2017/140511 A1 is a cleaning agent for the sanitary sector with at least two phases, the first phase being an overall gel phase and the second phase being a non-gel shaped cleaning agent tablet.
  • the object of the present invention is to provide cleaning agents for the toilet area, comprising lump-shaped alkanecarboxylic acid salts, which completely dissolve, do not whiten, their Maintain transparency and have a sufficiently high melting point. This object is achieved by the features of claim 1.
  • the invention relates to the use of a cleaning agent in lump form for cleaning the toilet area, which cleaning agent is transparent and comprises surfactants, alkanecarboxylic acid salts and solvents, and the proportion of alkanecarboxylic acid salts between 1% by weight and 5% by weight and the proportion of solvents (including perfume oils ) is less than 40% by weight in the agent and the agent contains at least 18% nonionic surfactants from the group of oligo- or polyethylene oxides and / or oligo- and / or polypropylene oxides and / or block copolymers comprising oligo- and / or polybutylene oxide.
  • a cleaning agent which has between 1% by weight and 5% by weight of salts of alkanecarboxylic acids, less than 40% by weight of solvents (including perfume oils) and at least 18% by weight of nonionic surfactants from the group the oligo- or polyethylene oxides and / or oligo- and / or polypropylene oxides and / or oligo- and / or polybutylene oxide comprising block copolymers, is transparent, cut-resistant, lumpy and sufficiently hard, has a melting point of at least 53 ° C and is also washed over many times Water remains essentially transparent and can be rinsed off completely.
  • the agent has a low proportion of a maximum of 5% by weight, preferably less than 4% by weight and particularly preferably less than 3% by weight of alkanecarboxylic acid salts. Due to the low proportion of alkanecarboxylic acid salts, which together with the alkaline earth metal ions contained in the rinse water, ultimately cause the unsightly white precipitate on the surface, whitening is avoided even if the surface is continuously washed over with water.
  • agents with melting points above 53 ° C. which are transparent, cut-resistant and do not whiten, are obtained if the agent contains a special nonionic surfactant, namely from the group of the block copolymers described above of preferably at least 18% by weight, preferably at least 20% by weight, preferably at least 25% by weight, cleaning agents with particularly high melting points being obtained in a proportion of at least 30% by weight or even at least 35% by weight of block copolymers.
  • the alkanecarboxylic acid salts and block copolymers form sufficiently hard, transparent gels with the solvents which can be rinsed off and do not whiten.
  • the agent has between 1% by weight and 5% by weight and particularly preferably between 2% by weight and 4% by weight of salts of alkanecarboxylic acids, in particular alkali stearate, between 20% by weight and 50% by weight and preferably 35% by weight. % to 45% by weight of the above block copolymers and less than 30% by weight, preferably between 18% by weight and 28% by weight of solvent. Some of these values can also be present in a mean, regardless of the presence of the other specified concentration ranges.
  • the salts of the aliphatic or unsaturated alkanecarboxylic acids are used as salts of the alkanecarboxylic acids.
  • the alkanecarboxylic acid salts preferably have a carbon chain with between 10 and 24 carbon atoms and are monocarboxylic acid salts, in particular alkali soaps.
  • Particularly preferred alkanecarboxylic acid salts are salts of stearic, lauric, myristic, palmitic, oleic acid and / or carbon fragments thereof from natural or synthetic sources. Because of their biodegradability, the even-numbered, unbranched alkanecarboxylic acid salts with natural C-source cuts are particularly suitable.
  • the agent comprises at least one alkanecarboxylic acid salt, but several alkanecarboxylic acid salts can also be combined with one another.
  • the alkanecarboxylic acid salts are preferably alkali metal salts and in particular sodium and / or potassium salts.
  • block copolymers are understood to mean macromolecules composed of blocks of several monomers that are chemically linked to one another in a linear manner, that is to say hetero- or copolymers which consist of longer sequences or blocks of each monomer.
  • the block copolymers according to the invention comprise at least one oligo- or polyethylene oxide block.
  • the block copolymer comprises a further polymer, oligo- or polypropylene oxide and / or oligo- or polybutylene oxide being preferred as copolymers in the context of the present invention.
  • a high melting point, transparency and dimensional stability of the cleaning agent are achieved, for example, with EO-PO-EO block copolymers of the following formula HO- (CH 2 -CH 2 -O) x - (CHCH 3 -CH 2 -O) y (-CH 2 - CH 2 -O) z -H achieved.
  • Such block copolymers are available, for example, from BASF under the trade name Pluronic PE 6800 or from Kolb-Chemie under the name V / 23345/2. In general, these block copolymers are either liquid at room temperature or have a low melting point of less than 50 ° C.
  • a B (utylen) O block can also be used.
  • the agent can comprise further surfactants, wherein the surfactants can be selected from the group of anionic, nonionic, cationic or amphoteric surfactants or mixtures thereof can be provided, in particular from anionic and nonionic surfactants.
  • the anionic surfactants include, in particular, the alkyl sulfates, alkyl ether sulfates, the sulfonates such as, for example, the alkyl sulfonates, the olefin sulfonates, the alkoxyalkane sulfonates, the alkylarylsulfonates such as the Alkylbenzenesulfonates or the toluenesulfonates, the sulfate esters, the alkyl carbonates, alkylether carboxylates, the fatty acid taurides, the alkyl isothionates and mixtures thereof are preferred.
  • Nonionic surfactants that can be used are, for example, alkyl ethoxylates such as C8 - C30 alcohol ethoxylate with up to 60 EO, ethoxylated alkyphenols, ethoxylated or propoxylated fatty alcohols, sugar surfactants such as alkyl polyglycosides, polyethylene glycol ethers, ethoxylated fatty acid esters, condensation products of ethylene oxides, amine alkylene oxides, or similar compounds of amine oxides with long-chain amine oxides or similar amine oxides or comparable amine oxides with long-chain amine oxides, ethoxylated alkyphenols or mixtures thereof are used.
  • alkyl ethoxylates such as C8 - C30 alcohol ethoxylate with up to 60 EO
  • ethoxylated alkyphenols ethoxylated or propoxylated fatty alcohols
  • sugar surfactants such as alkyl polyglycosides,
  • Betaines for example, can be used as amphoteric surfactants and quaternary alkylammonium compounds as cationic surfactants. In the case of cationic surfactants, care must be taken when making the selection that no cloud formation occurs due to the formation of neutral complexes.
  • the proportion of surfactants depends on the desired cleaning or foam performance and is generally between 10% by weight and 65% by weight.
  • the surfactant content in the agent is preferably between 15 and 40% by weight and particularly preferably between 20% by weight and 30% by weight.
  • the proportion of nonionic surfactants is preferably between 5 and 30% by weight, in particular between 10 and 20% by weight and particularly preferably between 11% by weight and 15% by weight.
  • the proportion of anionic surfactants is generally between 5 and 30% by weight, in particular between 10 and 20% by weight and particularly preferably between 11% by weight and 15% by weight.
  • the total proportion of surfactants (including the alkanecarboxylic acid salts and the block copolymers) in the agent should be less than 90% by weight, preferably less than 85% by weight and more than 60% by weight and particularly preferably between 65 and 75% by weight.
  • the proportion of solvent in the agent should be a maximum of 40% by weight.
  • perfume oils are counted among the solvents.
  • Solvents are required so that the alkanecarboxylic acid salts form transparent gels.
  • the proportion of solvents also affects the hardness of the agent. For this reason, the proportion of solvents in the agent should preferably be less than 30% by weight and particularly preferably between 20% by weight and 25% by weight.
  • Organic and / or inorganic solvents can be used as solvents.
  • Preferred solvents are water and alcohols, especially polyhydric alcohols.
  • alcohols for example, 1,2-propylene glycol, dipropylene glycol, butylene glycol, ethylene glycol, 1,7-heptanediol, glycerol, glycerol derivatives, monoethylene glycols, polyethylene glycols with a molecular weight of up to 8000 and the mono-C 1-4 -alkyl ethers of the preceding compounds can be selected will.
  • sorbitols are also defined as polyhydric alcohols.
  • the polyhydric alcohols help make the masses more transparent.
  • the agent can also contain perfume oils, for example in an amount of 2% by weight to 20% by weight, preferably less than 10% by weight and particularly preferably between 3% by weight and 6% by weight. This achieves a long-lasting, continuous release of fragrances and room scenting. After the perfume oils next to the fragrance also have a dissolving effect, they are also counted among the solvents in the context of the present invention.
  • ethers such as ethers, esters, aldehydes or ketones
  • perfume oils include, for example, benzyl acetate (ester), benzyl ethyl ether (ether), citral, citronellal (aldehyde), citronellol or eugenol (alcohols).
  • benzyl acetate ester
  • benzyl ethyl ether ether
  • citral citronellal
  • aldehyde citronellol
  • eugenol alcohols
  • the agent can contain inorganic salts, preferably between 0 and 5%. Cumene sulfonates can be added up to 10% as a solubilizer, hydrotrope or clarifying agent.
  • the agent can also include bleaching agents, oxidizing agents, anti-corrosive agents, nano-particles, germicidal agents, decorative colored granules and / or polymers such as PVA, cellulose or acrylamides.
  • the addition of dyes is also possible, although it must be borne in mind when adding dyes that the transparency impression decreases as a result of increasing light absorption by the dyes.
  • the components of the agent are preferably melted together and then poured into any closed mold with at least one opening in order to solidify there.
  • the filling can be carried out using the known discontinuous and continuous processes. Compared to the known extruded toilet cleaning agents, which require complex mixers and extruders, the visually appealing agent according to the invention can thus be produced in a far simpler process.
  • the agent has a melting point of at least 53 ° C, preferably at least 55 ° C and particularly preferably at least 59 ° C. Melting points above 60 ° C. are particularly preferred.
  • the agents are also characterized by adequate hardness at room temperature and temperatures of at least 53 ° C., preferably at least 55 ° C. and particularly preferably more than 59 ° C., they are cut-resistant and dimensionally stable.
  • the cleaning agents then have the required hardness if the cooled agents can be removed from the mold undamaged at room temperature and without damaging the surface.
  • a sufficient hardness is, among other things, also a prerequisite for the agent to even achieve the number of flushes required for a toilet cleaning agent.
  • the means are transparent.
  • an agent is transparent if the transmission of the agent with a layer thickness of 10 mm, measured against an empty cuvette with a layer thickness of 10 mm, is at least 60%, preferably at least 70%.
  • the transmission is determined in the visible, i.e. between 400 nm and 800 nm, and the transmission should have the above minimum transmission at least at one wavelength in the visible.
  • the flushing numbers of the agents are generally between 80 and 400 for a block of 35 g.
  • the pH value of a 1% solution of the cleaning agent in water should be above pH 9 so that the transparency is maintained and the carboxylic acids are prevented from precipitating.
  • the pH should preferably be between 9.5 and 12.
  • the formulations R1 and R2 according to the invention have a melting point above 53 ° C., in particular around 60 ° C., whereas the agents according to the comparison formulation have melting points below 50 ° C. and thus melt and become soft during transport or storage in warmer climates are therefore unsuitable as cleaning agents in the form of bars.
  • the EO-PO block polymer in the inventive recipe R1 in Table 1 was replaced by another nonionic surfactant, namely C13-C15 alcohol ethoxylate with 11 EO according to the following recipe, and the melting point was determined: ⁇ u> Table 3 ⁇ /u> substance Substance group function Were used V3 Sodium alkylbenzenesulfonate + toluenesulfonate anionic surfactants cleaning Marlon ARL (Sasol) 14.00 Sodium stearate Gel builder 2.25 C9-C11 alcohol ethoxylate with 10 EO nonionic surfactants Gel builder Imbentin C / 91/100 (Kolb) 12.40 C13-C15 alcohol ethoxylate with 11 EO Gel builder Lutensol AO 11 (BASF) 40.00 EO / PO block copolymer Gel builder - Polyoxyethylene C8-C10 glycerides Foamer Emanon XLF (Kao Chemicals) 4.00
  • the melting point of the comparison formulation V3 was 43.0 ° C and the hardness measured at 25 ° C was 940 mN.
  • the hardness values of the various recipes were determined as follows: The hardness measurements were carried out with the compression force meter PCE-FG 20SD from PCE Instruments (PCE Deutschland GmbH) and the included stainless steel measuring tip "Kegel". For the defined positioning, the compressive force measuring device was mounted on the test stand PCE-FTS50 from PCE Instruments (PCE Deutschland GmbH) in order to guarantee an exact vertical shift with a resolution of 0.01 mm.
  • the melted gel masses were poured into a Petri dish and then stored for 3 hours at 25 ° C. in order to ensure that the gel masses hardened. The samples were then examined in the measurement setup described.
  • the measuring tip was positioned just above the sample surface and the measuring tip was moved downwards in steps of 0.1 mm in the direction of the sample surface (lowering speed 0.02 mm / s) and the force value was saved at the corresponding point.
  • the measured force value in mN at a depth of penetration of the measuring tip into the sample of 2.5 mm was used as a measure of the hardness.
  • the zero point of the penetration depth was defined as the position at which a force was measured for the first time at the following position.
  • the temperature during the measurement was 25 ° C.

Description

Die vorliegende Erfindung betrifft die Verwendung eines stückförmigen Reinigungsmittels für den WC-Bereich, die Seifen enthalten. Solche Reinigungsmittel können beispielsweise als sogenannte Rimblocks in WC-Körbchen oder über einen an dem Mittel befestigten Haken am Rande der Toilettenschüssel eingehängt werden oder aber auch an der Toilettenschüssel angeklebt werden.The present invention relates to the use of a toilet area cleaning agent containing soaps. Such cleaning agents can be hung, for example, as so-called rim blocks in toilet baskets or via a hook attached to the agent on the edge of the toilet bowl, or they can also be glued to the toilet bowl.

Solche stückförmigen Reinigungsmittel sollten auch bei höheren Temperaturen ihre Form beibehalten, sie sollten schnittfest sein und einen hinreichend hohen Schmelzpunkt aufweisen, damit sie auch in wärmeren Klimazonen und im Sommer transportiert und gelagert werden können, ohne ihre Form zu verändern.Such bar-shaped cleaning agents should retain their shape even at higher temperatures, they should be cut-resistant and have a sufficiently high melting point so that they can also be transported and stored in warmer climates and in summer, without changing their shape.

Die Verwendung von Seifen in Toilettenreinigungsmitteln ist bekannt.The use of soaps in toilet detergents is known.

Die Seifen bilden mit Flüssigkeiten Gele und bewirken bereits in geringen Mengen eine hohe Festigkeit des Mittels, so dass stückförmige, schnittfeste Reinigungsmittel erhalten werden können. Seifen sind weiterhin vorteilhaft, da sie einen hohen Anteil an Parfümölen einlagern können, so dass sich die Mittel auch zur Beduftung eignen.The soaps form gels with liquids and, even in small amounts, make the agent very firm, so that lump-shaped, cut-resistant cleaning agents can be obtained. Soaps are also advantageous because they can store a high proportion of perfume oils, so that the agents are also suitable for fragrancing.

Zudem können aus Seifen transparente Mittel hergestellt werden. Solche transparenten Mittel werden von den Verbrauchern gewünscht, da sie optisch ansprechend sind.In addition, transparent agents can be made from soaps. Such transparent means are desired by consumers because they are visually appealing.

Die DE 197 10 635 A1 lehrt ein transparentes gelförmiges, stückförmiges Toilettenreinigungsmittel, das auch zur permanenten Raumbeduftung dient und anionische Tenside, Alkancarbonsäuresalze wie beispielsweise Natriumstearat als Gelbildner, Lösemittel und Duftstoffe umfasst. Die dortigen Mittel werden an einem Halter oder in einem Korb oder käfigartigen Behälter im Toilettenbecken an einer Stelle angebracht, die bei jedem Spülvorgang vom zulaufenden Spülwasser durchströmt wird.the DE 197 10 635 A1 teaches a transparent gel-like, lump-like toilet cleaning agent, which is also used for permanent room scenting and comprises anionic surfactants, alkanecarboxylic acid salts such as sodium stearate as gelling agents, solvents and fragrances. The means there are attached to a holder or in a basket or cage-like container in the toilet bowl at a point through which the incoming flushing water flows during each flushing process.

Aus der EP 1 953 215 A1 sind stückförmige Toilettenreinigungsmittel mit besonders hoher Transparenz bekannt, die neben Alkancarbonsäuresalzen, Lösemitteln, Tensiden und Parfümöl auch wenigstens eine Verbindung aus der Gruppe der Zucker und Zuckerderivate und wenigstens eine Verbindung aus der Gruppe der reduzierten Zucker umfassen.From the EP 1 953 215 A1 Toilet cleaning agents in lump form with particularly high transparency are known which, in addition to alkanecarboxylic acid salts, solvents, surfactants and perfume oil, also include at least one compound from the group of sugar and sugar derivatives and at least one compound from the group of reduced sugars.

Durch das bei der Anwendung des Toilettenreinigungsmittels in der Toilettenschüssel häufige Überspülen mit Spülwasser nimmt allerdings mit der Zeit die Transparenz des Mittels ab. Auf dem Reinigungsmittel bildet sich eine weißliche Schicht, die Reinigungsmittel "verweißen". Zudem wird mit zunehmender Zahl von Spülvorgängen beim Überspülen mit Wasser immer weniger Reinigungsmittel von der Oberfläche abgelöst, und häufig verbleibt ein unlöslicher, unansehnlicher, weißlicher Rest des ursprünglich transparenten Mittels in dem Behältnis, der dann von Hand entfernt werden muss. Dieses Problem ist aus dem Stand der Technik bekannt. Versuche im Hause der Anmelderin, ein Verweißen des Mittels nach einer Vielzahl von Spülgängen durch Zugabe von Komplexbildnern oder Dispergiermitteln zu verhindern, führte nicht zum gewünschten Erfolg.However, due to the frequent flushing with flushing water when the toilet cleaning agent is used in the toilet bowl, the transparency of the agent decreases over time. A whitish layer forms on the cleaning agent, which "fuses" the cleaning agent. In addition, as the number of rinsing processes increases, less and less cleaning agent is detached from the surface when rinsing with water, and an insoluble, unsightly, whitish residue of the originally transparent agent often remains in the container, which then has to be removed by hand. This problem is known from the prior art. Attempts in the applicant's house to weld the agent after a large number of rinsing cycles by adding complexing agents or preventing dispersants did not lead to the desired success.

Aus der EP 1 318 191 B1 sind Pasten für den Sanitärbereich bekannt, die einen Haftvermittler aus der Gruppe der Oligo- oder Polyethylenoxid und/oder Oligo- oder Polypropylenoxid und/oder Oligo- und/oder Polybutylenoxid umfassenden Blockcopolymere sowie Wasser und Parfüm umfassen. Diese viskosen Pasten sind nicht stückförmig und werden auch nicht in einem Toilettenkörbchen bevorratet sondern direkt auf den Sanitärgegenstand appliziert, wo sie haften und erst nach einer Vielzahl von Spülvorgängen abgespült werden.From the EP 1 318 191 B1 Pastes for the sanitary sector are known which comprise an adhesion promoter from the group of oligo- or polyethylene oxide and / or oligo- or polypropylene oxide and / or oligo- and / or polybutylene oxide comprising block copolymers as well as water and perfume. These viscous pastes are not lumpy and are not stored in a toilet basket, but rather applied directly to the sanitary item, where they adhere and are only rinsed off after a large number of flushing processes.

Transparente Seifenstücke sind aus der WO 01/11 001 A1 und der US 6 689 728 B2 bekannt.Transparent bars of soap are from the WO 01/11 001 A1 and the US 6,689,728 B2 known.

Aus der DE 696 22 170 T2 sind Riegel-Zusammensetzungen mit minimalen Anteilen von Polyalkylenglycol zum Strukturieren der Riegel bekannt.From the DE 696 22 170 T2 For example, bar compositions with minimal levels of polyalkylene glycol to structure the bars are known.

Die DE 694 21 172 T2 lehrt synthetische Waschmittelstücke und Waschmittel-Zusammensetzungen, die zu Stücken geformt werden können.the DE 694 21 172 T2 teaches synthetic detergent bars and detergent compositions that can be formed into bars.

Die WO 2008/125407 A1 lehrt Toilettenreinigungsblöcke, die wenigstens teilweise transparent oder transluzent sind mit einer Trägerzusammensetzung und 20 bis 50 Gew.% eines Biozids.the WO 2008/125407 A1 teaches toilet cleaning blocks that are at least partially transparent or translucent with a carrier composition and 20 to 50% by weight of a biocide.

Aus der älteren Patentanmeldung WO 2017/140511 A1 ist ein Reinigungsmittel für den Sanitärbereich mit wenigstens zwei Phasen, wobei die erste Phase eine Gesamtgelphase und die zweite Phase ein nicht gelförmiger Reinigungsmittelformkörper ist, bekannt.From the older patent application WO 2017/140511 A1 is a cleaning agent for the sanitary sector with at least two phases, the first phase being an overall gel phase and the second phase being a non-gel shaped cleaning agent tablet.

Die Aufgabe der vorliegenden Erfindung besteht darin, stückförmige Alkancarbonsäuresalze umfassende Reinigungsmittel für den WC-Bereich bereitzustellen, die sich vollständig auflösen, nicht verweißen, ihre Transparenz beibehalten und einen hinreichend hohen Schmelzpunkt aufweisen. Diese Aufgabe wird durch die Merkmale des Anspruchs 1 gelöst.The object of the present invention is to provide cleaning agents for the toilet area, comprising lump-shaped alkanecarboxylic acid salts, which completely dissolve, do not whiten, their Maintain transparency and have a sufficiently high melting point. This object is achieved by the features of claim 1.

Die Erfindung betrifft die Verwendung eines stückförmigen Reinigungsmittels zur Reinigung des WC-Bereichs, welches Reinigungsmittel transparent ist und Tenside, Alkancarbonsäuresalze und Lösemittel umfasst, und der Anteil an Alkancarbonsäuresalzen zwischen 1 Gew.% und 5 Gew.% und der Anteil an Lösemitteln (einschließlich Parfümölen) weniger als 40 Gew.% in dem Mittel beträgt und das Mittel wenigstens 18 % nichtionischer Tenside aus der Gruppe der Oligo- oder Polyethylenoxide und/oder Oligo- und/oder Polypropylenoxide und/oder Oligo- und/oder Polybutylenoxid umfassenden Blockcopolymere enthält.The invention relates to the use of a cleaning agent in lump form for cleaning the toilet area, which cleaning agent is transparent and comprises surfactants, alkanecarboxylic acid salts and solvents, and the proportion of alkanecarboxylic acid salts between 1% by weight and 5% by weight and the proportion of solvents (including perfume oils ) is less than 40% by weight in the agent and the agent contains at least 18% nonionic surfactants from the group of oligo- or polyethylene oxides and / or oligo- and / or polypropylene oxides and / or block copolymers comprising oligo- and / or polybutylene oxide.

Im Rahmen der vorliegenden Erfindung wurde festgestellt, dass ein Reinigungsmittel, das zwischen 1 Gew.% und 5 Gew.% Salze von Alkancarbonsäuren aufweist, weniger als 40 Gew.% Lösemittel (einschließlich Parfümöle) und wenigstens 18 Gew.% nichtionische Tenside aus der Gruppe der Oligo- oder Polyethylenoxide und/oder Oligo- und/oder Polypropylenoxide und/oder Oligo- und/oder Polybutylenoxid umfassenden Blockcopolymere, transparent, schnittfest, stückförmig und ausreichend hart ist, einen Schmelzpunkt von wenigstens 53 °C aufweist und auch bei vielfachem Überspülen mit Wasser im Wesentlichen transparent bleibt und sich vollständig abspülen lässt.In the context of the present invention, it was found that a cleaning agent which has between 1% by weight and 5% by weight of salts of alkanecarboxylic acids, less than 40% by weight of solvents (including perfume oils) and at least 18% by weight of nonionic surfactants from the group the oligo- or polyethylene oxides and / or oligo- and / or polypropylene oxides and / or oligo- and / or polybutylene oxide comprising block copolymers, is transparent, cut-resistant, lumpy and sufficiently hard, has a melting point of at least 53 ° C and is also washed over many times Water remains essentially transparent and can be rinsed off completely.

Das Mittel weist einen geringen Anteil von maximal 5 Gew.%, vorzugsweise weniger als 4 Gew.% und besonders bevorzugt weniger als 3 Gew.% Alkancarbonsäuresalze auf. Aufgrund des geringen Anteils an Alkancarbonsäuresalzen, die letztendlich zusammen mit den im Spülwasser enthaltenen Erdalkaliionen den unansehnlichen weißen Niederschlag auf der Oberfläche bewirken, wird auch beim fortwährenden Überspülen mit Wasser ein Verweißen vermieden.The agent has a low proportion of a maximum of 5% by weight, preferably less than 4% by weight and particularly preferably less than 3% by weight of alkanecarboxylic acid salts. Due to the low proportion of alkanecarboxylic acid salts, which together with the alkaline earth metal ions contained in the rinse water, ultimately cause the unsightly white precipitate on the surface, whitening is avoided even if the surface is continuously washed over with water.

Grundsätzlich geht eine Reduzierung des Anteils an Alkancarbonsäuresalzen jedoch mit einer Erniedrigung des Schmelzpunktes des Mittels einher (vgl. US 4,666,671 ), so dass solche Reinigungsmittel bereits unterhalb von 50 °C schmelzen und somit für den Transport und die Lagerung in heißeren Klimata oder im Sommer nicht geeignet sind.In principle, however, a reduction in the proportion of alkanecarboxylic acid salts is accompanied by a lowering of the melting point of the agent (cf. U.S. 4,666,671 ), so that such cleaning agents melt below 50 ° C and are therefore unsuitable for transport and storage in hotter climates or in summer.

Im Rahmen der vorliegenden Erfindung wurde erstaunlicherweise festgestellt, dass Mittel mit Schmelzpunkten über 53° C, die transparent und schnittfest sind und nicht verweißen, erhalten werden, wenn das Mittel ein spezielles nichtionisches Tensid, nämlich aus der Gruppe der zuvor beschriebenen Blockcopolymere, in einem Anteil von vorzugsweise wenigstens 18 Gew.%, vorzugsweise wenigstens 20 Gew.%, bevorzugt wenigstens 25 Gew.% umfasst, wobei Reinigungsmittel mit besonders hohen Schmelzpunkten bei einem Anteil von wenigstens 30 Gew.% oder gar wenigstens 35 Gew.% Blockcopolymere erhalten werden.In the context of the present invention, it was surprisingly found that agents with melting points above 53 ° C., which are transparent, cut-resistant and do not whiten, are obtained if the agent contains a special nonionic surfactant, namely from the group of the block copolymers described above of preferably at least 18% by weight, preferably at least 20% by weight, preferably at least 25% by weight, cleaning agents with particularly high melting points being obtained in a proportion of at least 30% by weight or even at least 35% by weight of block copolymers.

In dem erfindungsgemäßen Konzentrationsbereich von Alkancarbonsäuresalzen, Blockcopolymeren und Lösemitteln bilden die Alkancarbonsäuresalze und Blockcopolymere mit den Lösemitteln hinreichend harte, transparente Gele, die abspülbar sind und nicht verweißen.In the concentration range of alkanecarboxylic acid salts, block copolymers and solvents according to the invention, the alkanecarboxylic acid salts and block copolymers form sufficiently hard, transparent gels with the solvents which can be rinsed off and do not whiten.

Das Mittel weist zwischen 1 Gew.% und 5 Gew.% und besonders bevorzugt zwischen 2 Gew.% und 4 Gew.% Salze von Alkancarbonsäuren, insbesondere Alkalistearat, auf, zwischen 20 Gew.% und 50 Gew.% und vorzugsweise 35 Gew. % bis 45 Gew. % der obigen Blockcopolymere und weniger als 30 Gew.%, vorzugsweise zwischen 18 Gew. % und 28 Gew. % Lösemittel. Einzelne dieser Werte können auch in einem Mittel, unabhängig von dem Vorliegen der anderen angegebenen Konzentrationsbereiche, vorliegen.The agent has between 1% by weight and 5% by weight and particularly preferably between 2% by weight and 4% by weight of salts of alkanecarboxylic acids, in particular alkali stearate, between 20% by weight and 50% by weight and preferably 35% by weight. % to 45% by weight of the above block copolymers and less than 30% by weight, preferably between 18% by weight and 28% by weight of solvent. Some of these values can also be present in a mean, regardless of the presence of the other specified concentration ranges.

Als Salze der Alkancarbonsäuren werden im Rahmen der vorliegenden Erfindung die Salze der aliphatischen oder ungesättigten Alkancarbonsäuren eingesetzt. Vorzugsweise weisen die Alkancarbonsäuresalze eine Kohlenstoffkette mit zwischen 10 und 24 Kohlenstoffatomen auf und sind Monocarbonsäuresalze, insbesondere Alkaliseifen. Besonders bevorzugte Alkancarbonsäuresalze sind Salze von Stearin-, Laurin-, Myristin-, Palmitin-, Ölsäure und/oder C-Schnitze derselben aus natürlichen oder synthetischen Quellen. Wegen der biologischen Abbaubarkeit sind insbesondere die geradzahligen, unverzweigten Alkancarbonsäuresalze mit natürlichen C-Quellen-Schnitten besonders geeignet.In the context of the present invention, the salts of the aliphatic or unsaturated alkanecarboxylic acids are used as salts of the alkanecarboxylic acids. The alkanecarboxylic acid salts preferably have a carbon chain with between 10 and 24 carbon atoms and are monocarboxylic acid salts, in particular alkali soaps. Particularly preferred alkanecarboxylic acid salts are salts of stearic, lauric, myristic, palmitic, oleic acid and / or carbon fragments thereof from natural or synthetic sources. Because of their biodegradability, the even-numbered, unbranched alkanecarboxylic acid salts with natural C-source cuts are particularly suitable.

Das Mittel umfasst wenigstens ein Alkancarbonsäuresalz, es können jedoch auch mehrere Alkancarbonsäuresalze miteinander kombiniert werden.The agent comprises at least one alkanecarboxylic acid salt, but several alkanecarboxylic acid salts can also be combined with one another.

Die Alkancarbonsäuresalze sind vorzugsweise Alkalisalze und insbesondere Natrium- und/oder Kaliumsalze.The alkanecarboxylic acid salts are preferably alkali metal salts and in particular sodium and / or potassium salts.

Im Rahmen der vorliegenden Erfindung werden unter Blockcopolymer Makromoleküle aus linear miteinander chemisch verknüpften Blöcken aus mehreren Monomeren, das heißt Hetero- oder Copolymere, die aus längeren Sequenzen oder Blöcken eines jeden Monomers bestehen, verstanden. Die erfindungsgemäßen Blockcopolymere umfassen wenigstens einen Oligo- oder Polyethylenoxidblock. Weiterhin umfasst das Blockcopolymer ein weiteres Polymer, wobei Oligo- oder Polypropylenoxid und/oder Oligo- oder Polybutylenoxid als Copolymere im Rahmen der vorliegenden Erfindung bevorzugt sind.In the context of the present invention, block copolymers are understood to mean macromolecules composed of blocks of several monomers that are chemically linked to one another in a linear manner, that is to say hetero- or copolymers which consist of longer sequences or blocks of each monomer. The block copolymers according to the invention comprise at least one oligo- or polyethylene oxide block. Furthermore, the block copolymer comprises a further polymer, oligo- or polypropylene oxide and / or oligo- or polybutylene oxide being preferred as copolymers in the context of the present invention.

Ein hoher Schmelzpunkt, Transparenz und Formstabilität des Reinigungsmittels werden beispielsweise mit EO-PO-EO-Blockcopolymeren der folgenden Formel HO-(CH2-CH2-O)x-(CHCH3-CH2-O)y(-CH2-CH2-O)z-H erzielt. Solche Blockcopolymere sind beispielsweise bei der Firma BASF unter dem Handelsnamen Pluronic PE 6800 oder der Firma Kolb-Chemie unter der Bezeichnung V/23345/2 erhältlich. Im Allgemeinen sind diese Blockcopolymere entweder bei Raumtemperatur flüssig oder weisen einen niederen Schmelzpunkt von weniger als 50 °C auf.A high melting point, transparency and dimensional stability of the cleaning agent are achieved, for example, with EO-PO-EO block copolymers of the following formula HO- (CH 2 -CH 2 -O) x - (CHCH 3 -CH 2 -O) y (-CH 2 - CH 2 -O) z -H achieved. Such block copolymers are available, for example, from BASF under the trade name Pluronic PE 6800 or from Kolb-Chemie under the name V / 23345/2. In general, these block copolymers are either liquid at room temperature or have a low melting point of less than 50 ° C.

Anstelle des PO-Blockes kann auch ein B(utylen)O-Block verwendet werden.Instead of the PO block, a B (utylen) O block can also be used.

Das Mittel kann neben den Alkancarbonsäuresalzen und den Blockcopolymeren weitere Tenside umfassen, wobei die Tenside aus der Gruppe der anionischen, nichtionischen, kationischen oder amphoteren Tenside ausgewählt werden können oder Mischungen derselben vorgesehen sein können, insbesondere aus anionischen und nichtionischen Tensiden.In addition to the alkanecarboxylic acid salts and the block copolymers, the agent can comprise further surfactants, wherein the surfactants can be selected from the group of anionic, nonionic, cationic or amphoteric surfactants or mixtures thereof can be provided, in particular from anionic and nonionic surfactants.

Unter den anionischen Tensiden sind insbesondere die Alkylsulfate, Alkylethersulfate, die Sulfonate wie beispielsweise die Alkylsulfonate, die Olefinsulfonate, die Alkoxyalkansulfonate, die Alkylarylsulfonate wie die Alkylbenzolsulfonate oder die Toluolsulfonate, die Sulfatester, die Alkylcarbonate, Alkyethercarboxylate, die Fettsäuretauride, die Alkylisothionate und deren Mischungen bevorzugt.The anionic surfactants include, in particular, the alkyl sulfates, alkyl ether sulfates, the sulfonates such as, for example, the alkyl sulfonates, the olefin sulfonates, the alkoxyalkane sulfonates, the alkylarylsulfonates such as the Alkylbenzenesulfonates or the toluenesulfonates, the sulfate esters, the alkyl carbonates, alkylether carboxylates, the fatty acid taurides, the alkyl isothionates and mixtures thereof are preferred.

Als nichtionische Tenside können beispielsweise Alkylethoxylate wie C8 - C30-Alkoholethoxylat mit bis zu 60 EO, ethoxylierte Alkyphenole, ethoxylierte oder propoxylierte Fettalkohole, Zuckertenside wie Alkylpolyglycoside, Polyethylenglykolether, ethoxylierte Fettsäureester, Kondensationsprodukte von Ethylenoxid mit langkettigen Aminen oder Amiden oder vergleichbare Verbindungen, Aminoxide, Trisiloxanalkoxylate oder deren Mischungen eingesetzt werden.Nonionic surfactants that can be used are, for example, alkyl ethoxylates such as C8 - C30 alcohol ethoxylate with up to 60 EO, ethoxylated alkyphenols, ethoxylated or propoxylated fatty alcohols, sugar surfactants such as alkyl polyglycosides, polyethylene glycol ethers, ethoxylated fatty acid esters, condensation products of ethylene oxides, amine alkylene oxides, or similar compounds of amine oxides with long-chain amine oxides or similar amine oxides or comparable amine oxides with long-chain amine oxides, ethoxylated alkyphenols or mixtures thereof are used.

Als amphotere Tenside können beispielsweise Betaine eingesetzt werden und als kationische Tenside quartäre Alkylammoniumverbindungen. Im Falle von kationischen Tensiden muss bei der Auswahl darauf geachtet werden, dass keine Wolkenbildung durch die Bildung von Neutralkomplexen erfolgt.Betaines, for example, can be used as amphoteric surfactants and quaternary alkylammonium compounds as cationic surfactants. In the case of cationic surfactants, care must be taken when making the selection that no cloud formation occurs due to the formation of neutral complexes.

Der Anteil an Tensiden (ohne die Alkancarbonsäuresalze und die Blockcopolymere) hängt von der gewünschten Reinigungs- bzw. Schaumleistung ab und liegt im Allgemeinen zwischen 10 Gew.% und 65 Gew.%.The proportion of surfactants (excluding the alkanecarboxylic acid salts and the block copolymers) depends on the desired cleaning or foam performance and is generally between 10% by weight and 65% by weight.

Vorzugsweise beträgt der Tensidanteil in dem Mittel (ohne Alkancarbonsäuresalze und ohne Blockcopolymere) zwischen 15 und 40 Gew.% und besonders bevorzugt zwischen 20 Gew.% und 30 Gew.%.The surfactant content in the agent (without alkanecarboxylic acid salts and without block copolymers) is preferably between 15 and 40% by weight and particularly preferably between 20% by weight and 30% by weight.

Der Anteil an nichtionischen Tensiden (ohne Blockcopolymere) liegt vorzugsweise zwischen 5 und 30 Gew.%, insbesondere zwischen 10 und 20 Gew.% und besonders bevorzugt zwischen 11 Gew.% und 15 Gew.%.The proportion of nonionic surfactants (without block copolymers) is preferably between 5 and 30% by weight, in particular between 10 and 20% by weight and particularly preferably between 11% by weight and 15% by weight.

Der Anteil an anionischen Tensiden liegt (ohne die Alkancarbonsäuresalze) im Allgemeinen zwischen 5 und 30 Gew.%, insbesondere zwischen 10 und 20 Gew.% und besonders bevorzugt zwischen 11 Gew.% und 15 Gew.%.The proportion of anionic surfactants (excluding the alkanecarboxylic acid salts) is generally between 5 and 30% by weight, in particular between 10 and 20% by weight and particularly preferably between 11% by weight and 15% by weight.

Der Gesamtanteil an Tensiden (einschließlich der Alkancarbonsäuresalze und der Blockcopolymeren) in dem Mittel sollte weniger als 90 Gew.%, vorzugsweise weniger als 85 Gew.% und mehr als 60 Gew.% und besonders bevorzugt zwischen 65 und 75 Gew.% betragen.The total proportion of surfactants (including the alkanecarboxylic acid salts and the block copolymers) in the agent should be less than 90% by weight, preferably less than 85% by weight and more than 60% by weight and particularly preferably between 65 and 75% by weight.

Um ein hinreichend hartes Mittel zu erhalten, sollte der Lösemittelanteil in dem Mittel maximal 40 Gew.% betragen. Im Rahmen der vorliegenden Erfindung werden Parfümöle zu den Lösemitteln gerechnet. Lösemittel sind erforderlich, damit die Alkancarbonsäuresalze transparente Gele bilden. Der Anteil an Lösemitteln wirkt sich zudem auf die Härte des Mittels aus. Aus diesem Grund sollte der Anteil an Lösemitteln in dem Mittel vorzugsweise weniger als 30 Gew.% und besonders bevorzugt zwischen 20 Gew. % und 25 Gew.% betragen.In order to obtain a sufficiently hard agent, the proportion of solvent in the agent should be a maximum of 40% by weight. In the context of the present invention, perfume oils are counted among the solvents. Solvents are required so that the alkanecarboxylic acid salts form transparent gels. The proportion of solvents also affects the hardness of the agent. For this reason, the proportion of solvents in the agent should preferably be less than 30% by weight and particularly preferably between 20% by weight and 25% by weight.

Als Lösemittel können organische und/oder anorganische Lösemittel eingesetzt werden. Bevorzugte Lösemittel sind Wasser und Alkohole, insbesondere mehrwertige Alkohole. Als Alkohole können beispielsweise 1,2-Propylenglykol, Dipropylenglykol, Butylenglykol, Ethylenglykol, 1,7-Heptandiol, Glycerin, Glycerinderivate, Monoethylenglykole, Polethylenglykole mit einem Molekulargewicht von bis zu 8000 sowie die Mono-C1-4-Alkylether der vorangegangenen Verbindungen ausgewählt werden. Sorbitole werden im Rahmen der vorliegenden Erfindung auch als mehrwertige Alkohole definiert.Organic and / or inorganic solvents can be used as solvents. Preferred solvents are water and alcohols, especially polyhydric alcohols. As alcohols, for example, 1,2-propylene glycol, dipropylene glycol, butylene glycol, ethylene glycol, 1,7-heptanediol, glycerol, glycerol derivatives, monoethylene glycols, polyethylene glycols with a molecular weight of up to 8000 and the mono-C 1-4 -alkyl ethers of the preceding compounds can be selected will. In the context of the present invention, sorbitols are also defined as polyhydric alcohols.

Vorzugsweise werden zwischen 10 Gew.% und 20 Gew.% Wasser und zwischen 3 Gew.% und 10 Gew.% mehrwertige Alkohole eingesetzt. Die mehrwertigen Alkohole tragen dazu bei, dass die Massen transparenter werden.Preferably between 10% by weight and 20% by weight of water and between 3% by weight and 10% by weight of polyhydric alcohols are used. The polyhydric alcohols help make the masses more transparent.

Das Mittel kann weiterhin Parfümöle enthalten, beispielsweise in einer Menge von 2 Gew.% bis 20 Gew.%, vorzugsweise weniger als 10 Gew. % und besonders bevorzugt zwischen 3 Gew. % und 6 Gew. %. Hierdurch wird eine langanhaltende kontinuierliche Duftabgabe und Raumbeduftung erreicht. Nachdem die Parfümöle neben der Beduftung auch lösend wirken, werden sie im Rahmen der vorliegenden Erfindung auch zu den Lösemitteln gerechnet.The agent can also contain perfume oils, for example in an amount of 2% by weight to 20% by weight, preferably less than 10% by weight and particularly preferably between 3% by weight and 6% by weight. This achieves a long-lasting, continuous release of fragrances and room scenting. After the perfume oils next to the fragrance also have a dissolving effect, they are also counted among the solvents in the context of the present invention.

Generell können als Parfümöle einzelne synthetische Produkte wie Ether, Ester, Aldehyde oder Ketone eingesetzt werden. Hierzu zählen beispielsweise Benzylacetat (Ester), Benzylethylether (Ether), Citral, Citronellal (Aldehyd), Citronellol oder Eugenol (Alkohole). Bevorzugt werden Mischungen eingesetzt, die ein typisches sensorisches Profil liefern.In general, individual synthetic products such as ethers, esters, aldehydes or ketones can be used as perfume oils. These include, for example, benzyl acetate (ester), benzyl ethyl ether (ether), citral, citronellal (aldehyde), citronellol or eugenol (alcohols). Mixtures which provide a typical sensory profile are preferably used.

Das Mittel kann anorganische Salze enthalten, vorzugsweise zwischen 0 und 5 %. Cumolsulfonate können bis zu 10 % als Lösevermittler, Hydrotrop bzw. Klarstellmittel zugesetzt werden. Wahlweise kann das Mittel auch noch Bleichmittel, Oxidationsmittel, Korrosionsschutzmittel, Nano-Partikel, keimtötende Mittel, dekorative Farbgranulate und/oder Polymere wie PVA, Cellulose oder Acrylamide umfassen. Auch der Zusatz von Farbstoffen ist möglich, wobei bei der Zugabe von Farbstoffen allerdings bedacht werden muss, dass der Transparenzeindruck infolge von zunehmender Lichtabsorption durch die Farbstoffe abnimmt.The agent can contain inorganic salts, preferably between 0 and 5%. Cumene sulfonates can be added up to 10% as a solubilizer, hydrotrope or clarifying agent. Optionally, the agent can also include bleaching agents, oxidizing agents, anti-corrosive agents, nano-particles, germicidal agents, decorative colored granules and / or polymers such as PVA, cellulose or acrylamides. The addition of dyes is also possible, although it must be borne in mind when adding dyes that the transparency impression decreases as a result of increasing light absorption by the dyes.

Die Komponenten des Mittels werden vorzugsweise zusammen geschmolzen und dann in eine beliebige, geschlossene Form mit wenigstens einer Öffnung gegossen, um dort zu erstarren. Die Befüllung kann mit den bekannten diskontinuierlich und kontinuierlich arbeitenden Verfahren erfolgen. Im Vergleich zu den bekannten extrudierten Toilettenreinigungsmitteln, die aufwändige Mischer und Extruder erforderlich machen, kann das erfindungsgemäße optisch ansprechende Mittel somit in einem weitaus einfacheren Verfahren hergestellt werden.The components of the agent are preferably melted together and then poured into any closed mold with at least one opening in order to solidify there. The filling can be carried out using the known discontinuous and continuous processes. Compared to the known extruded toilet cleaning agents, which require complex mixers and extruders, the visually appealing agent according to the invention can thus be produced in a far simpler process.

Das Mittel weist einen Schmelzpunkt von wenigstens 53 °C, vorzugsweise wenigstens 55 °C und besonders bevorzugt wenigstens 59 °C auf. Besonders bevorzugt sind Schmelzpunkte über 60 °C. Die Mittel zeichnen sich auch durch eine hinreichende Härte bei Raumtemperatur und Temperaturen von wenigstens 53 °C, vorzugsweise wenigstens 55 °C und besonders bevorzugt von mehr als 59 °C aus, sie sind dabei schnittfest und formstabil.The agent has a melting point of at least 53 ° C, preferably at least 55 ° C and particularly preferably at least 59 ° C. Melting points above 60 ° C. are particularly preferred. The agents are also characterized by adequate hardness at room temperature and temperatures of at least 53 ° C., preferably at least 55 ° C. and particularly preferably more than 59 ° C., they are cut-resistant and dimensionally stable.

Die Reinigungsmittel weisen dann die erforderliche Härte auf, wenn die erkalteten Mittel bei Raumtemperatur unverletzt und ohne Beschädigung der Oberfläche aus der Form entnommen werden können. Eine solche hinreichende Härte ist unter anderem auch eine Voraussetzung dafür, dass das Mittel überhaupt die für ein Toilettenreinigungsmittel erforderlichen Spülzahlen erreicht.The cleaning agents then have the required hardness if the cooled agents can be removed from the mold undamaged at room temperature and without damaging the surface. Such a sufficient hardness is, among other things, also a prerequisite for the agent to even achieve the number of flushes required for a toilet cleaning agent.

Die Mittel sind transparent. Ein Mittel ist im Sinne der vorliegenden Erfindung transparent, wenn die Transmission des Mittels mit einer Schichtdicke von 10 mm gemessen gegen eine leere Küvette der Schichtdicke von 10 mm wenigstens 60 %, vorzugsweise wenigstens 70 %, beträgt. Die Transmission wird dabei im Sichtbaren, d.h. zwischen 400 nm und 800 nm bestimmt, und die Transmission sollte wenigstens bei einer Wellenlänge im Sichtbaren die obige Mindesttransmission aufweisen.The means are transparent. In the context of the present invention, an agent is transparent if the transmission of the agent with a layer thickness of 10 mm, measured against an empty cuvette with a layer thickness of 10 mm, is at least 60%, preferably at least 70%. The transmission is determined in the visible, i.e. between 400 nm and 800 nm, and the transmission should have the above minimum transmission at least at one wavelength in the visible.

Die Spülzahlen der Mittel liegen im Allgemeinen zwischen 80 und 400 bei einem Block von 35 g.The flushing numbers of the agents are generally between 80 and 400 for a block of 35 g.

Der pH-Wert einer 1 % Lösung des Reinigungsmittels in Wasser sollte über pH 9 liegen, damit die Transparenz erhalten bleibt und ein Ausfällen der Carbonsäuren vermieden wird. Vorzugsweise sollte der pH-Wert zwischen 9,5 und 12 betragen.The pH value of a 1% solution of the cleaning agent in water should be above pH 9 so that the transparency is maintained and the carboxylic acids are prevented from precipitating. The pH should preferably be between 9.5 and 12.

Die Erfindung wird nachfolgend anhand von Ausführungsbeispielen und Vergleichsversuchen näher beschrieben.The invention is described in more detail below on the basis of exemplary embodiments and comparative tests.

In der nachfolgenden Tabelle 1 sind zwei erfindungsgemäße Rezepturen R1 und R2 zwei Vergleichsrezepturen V1 und V2 gegenüber gestellt. Tabelle 1 Substanz Erfindungsgemäße Rezepturen Vergleichsrezepturen R1 R2 V1 V2 Natriumalkylbenzolsulfonat + Toluolsulfonat 14,00 10,00 10,00 10,00 Natriumstearat 2,25 2,25 2,25 2,25 C9-C11 Alkohol-Ethoxylat mit 10 EO 12,40 12,00 21,00 37,00 C13-C15 Alkohol-Ethoxylat mit 11 EO 16,00 EO/PO-Blockcopolymer 40,00 40,00 15,10 15,10 Polyoxyethylene C8-C10 Glyceride 4,00 Natriumchlorid 2,00 2,00 2,00 2,00 Trinatriumcitrat 0,10 0,10 0,10 0,10 Natriumcumolsulfonat 6,00 6,00 6,00 Wasser 14,50 16,80 16,80 16,80 1,2 Propylenglycol 6,70 6,70 6,70 6,70 Chinolingelb (2 %ige wäss. Lösung) <0,1 <0,1 <0,1 <0,1 Prociontürkisblau (6 %ige wäss. Lösung) <0,1 <0,1 <0,1 <0,1 Cairo Lavender 4,00 4,00 4,00 4,00 Summe 100,0 100,0 100,0 100,0 Schmelzpunkt 59,5 °C 60,5 °C 48,5 °C 48,0 °C Härte / mN (T = 25 °C) 1670 1640 990 900 Verhältnis Natriumstearat : Blockcopolymer 1:17,8 1:17,8 1:6,7 1:6,7 Gesamtlösemittelmenge in Gew. % 18,5 20,8 20,8 20,8 Gesamttensidmenge in Gew. % 68,65 64,25 64,35 64,35 In the following table 1 , two formulations according to the invention R1 and R2 are compared with two comparison formulations V1 and V2. <u> Table 1 </u> substance Formulations according to the invention Comparison formulations R1 R2 V1 V2 Sodium alkylbenzenesulfonate + toluenesulfonate 14.00 10.00 10.00 10.00 Sodium stearate 2.25 2.25 2.25 2.25 C9-C11 alcohol ethoxylate with 10 EO 12.40 12.00 21.00 37.00 C13-C15 alcohol ethoxylate with 11 EO 16.00 EO / PO block copolymer 40.00 40.00 15.10 15.10 Polyoxyethylene C8-C10 glycerides 4.00 Sodium chloride 2.00 2.00 2.00 2.00 Trisodium citrate 0.10 0.10 0.10 0.10 Sodium cumene sulfonate 6.00 6.00 6.00 water 14.50 16.80 16.80 16.80 1,2 propylene glycol 6.70 6.70 6.70 6.70 Quinoline yellow (2% aqueous solution) <0.1 <0.1 <0.1 <0.1 Procion turquoise blue (6% aqueous solution) <0.1 <0.1 <0.1 <0.1 Cairo Lavender 4.00 4.00 4.00 4.00 total 100.0 100.0 100.0 100.0 Melting point 59.5 ° C 60.5 ° C 48.5 ° C 48.0 ° C Hardness / mN (T = 25 ° C) 1670 1640 990 900 Sodium stearate: block copolymer ratio 1: 17.8 1: 17.8 1: 6.7 1: 6.7 Total amount of solvent in% by weight 18.5 20.8 20.8 20.8 Total amount of surfactant in% by weight 68.65 64.25 64.35 64.35

Die erfindungsgemäßen Rezepturen R1 und R2 weisen einen Schmelzpunkt über 53 °C, insbesondere von etwa 60 °C auf, wohingegen die Mittel gemäß der Vergleichsrezeptur Schmelzpunkte unterhalb von 50 °C aufweisen und somit beim Transport oder der Lagerung in wärmeren Klimata schmelzen und weich werden und somit als stückförmige Reinigungsmittel ungeeignet sind.The formulations R1 and R2 according to the invention have a melting point above 53 ° C., in particular around 60 ° C., whereas the agents according to the comparison formulation have melting points below 50 ° C. and thus melt and become soft during transport or storage in warmer climates are therefore unsuitable as cleaning agents in the form of bars.

In der nachfolgenden Tabelle 2 sind für die in Tabelle 1 aufgelisteten Substanzen die Stoffgruppen, die Funktionen der jeweiligen Substanzen und die eingesetzten Chemikalien aufgeführt. Tabelle 2 Substanz Stoffgruppe Funktion Eingesetzt wurden Natriumalkylbenzolsulfonat + Toluolsulfonat anionische Tenside Reinigung Marlon ARL (Sasol) Natriumstearat anionische Tenside Gelbildner C9-C11 Alkohol-Ethoxylat mit 10 EO nichtionische Tenside Gelbildner Imbentin C/91/100 (Kolb) C13-C15 Alkohol-Ethoxylat mit 11 EO nichtionische Tenside Gelbildner Lutensol AO 11 (BASF) EO/PO-Blockcopolymer nichtionische Tenside Gelbildner V/23345/2 (Kolb-Chemie) oder Pluronic PE6800 (BASF) Polyoxyethylene C8-C10 Glyceride Schäumer Emanon XLF (Kao Chemicals) Natriumchlorid anorganische Salze Stellmittel Trinatriumcitrat Oligocarbonsäuresalze Komplexbildner Natriumcumolsulfonat Hyd rotrop Klarstellmit- Eltesol SCS tel 93 (Rhodia) Wasser Lösemittel Zur Gelbildung 1,2 Propylenglycol Lösemittel Zur Gelbildung Chinolingelb (2 %ige wäss. Lösung) Farbstoffe Prociontürkisblau (6 %ige wäss. Lösung) Farbstoffe Cairo Lavender Duftstoffe In Table 2 below, the substance groups, the functions of the respective substances and the chemicals used are listed for the substances listed in Table 1. <u> Table 2 </u> substance Substance group function Were used Sodium alkylbenzenesulfonate + toluenesulfonate anionic surfactants cleaning Marlon ARL (Sasol) Sodium stearate anionic surfactants Gel builder C9-C11 alcohol ethoxylate with 10 EO nonionic surfactants Gel builder Imbentin C / 91/100 (Kolb) C13-C15 alcohol ethoxylate with 11 EO nonionic surfactants Gel builder Lutensol AO 11 (BASF) EO / PO block copolymer nonionic surfactants Gel builder V / 23345/2 (Kolb-Chemie) or Pluronic PE6800 (BASF) Polyoxyethylene C8-C10 glycerides Foamer Emanon XLF (Kao Chemicals) Sodium chloride inorganic salts Thickening agent Trisodium citrate Oligocarboxylic acid salts Complexing agents Sodium cumene sulfonate Hyd rotrop Clarification Eltesol SCS tel 93 (Rhodia) water Solvent For gel formation 1,2 propylene glycol Solvent For gel formation Quinoline yellow (2% aqueous solution) Dyes Procion turquoise blue (6% aqueous solution) Dyes Cairo Lavender Fragrances

Darüber hinaus zeigen die nachfolgenden Vergleichsversuche, dass nur mit den erfindungsgemäßen Blockcopolymeren, nicht aber anderen nichtionischen Tensiden Reinigungsmittel mit einem hinreichend hohen Schmelzpunkt erhalten werden können.In addition, the following comparative experiments show that cleaning agents with a sufficiently high melting point can be obtained only with the block copolymers according to the invention, but not with other nonionic surfactants.

Zum Vergleich wurde das EO-PO-Blockpolymer in der erfindungsgemäßen Rezeptur R1 in Tabelle 1 durch ein anderes nichtionisches Tensid, nämlich C13-C15 Alkoholethoxylat mit 11 EO gemäß der nachfolgenden Rezeptur ersetzt und der Schmelzpunkt bestimmt: Tabelle 3 Substanz Stoffgruppe Funktion Eingesetzt wurden V3 Natriumalkylbenzolsulfonat + Toluolsulfonat anionische Tenside Reinigung Marlon ARL (Sasol) 14,00 Natriumstearat Gelbildner 2,25 C9-C11 Alkohol-Ethoxylat mit 10 EO nichtionische Tenside Gelbildner Imbentin C/91/100 (Kolb) 12,40 C13-C15 Alkohol-Ethoxylat mit 11 EO Gelbildner Lutensol AO 11 (BASF) 40,00 EO/PO-Blockcopolymer Gelbildner - Polyoxyethylene C8-C10 Glyceride Schäumer Emanon XLF (Kao Chemicals) 4,00 Natriumchlorid anorganische Salze Stellmittel 2,00 Trinatriumcitrat Oligocarbonsäuresalze Komplexbildner 0,10 Natriumcumolsulfonat Hyd rotrop Klarstellmittel Eltesol SCS 93 (Rhodia) - Wasser Lösemittel Gelbildner 14,50 1,2 Propylenglycol Gelbildner 6,70 Chinolingelb (2 %ige wäss. Lösung) Farbstoffe <0,1 Prociontürkisblau (6 %ige wäss. Lösung) <0,1 Cairo Lavender Duftstoffe 4,00 Summe 100,0 For comparison, the EO-PO block polymer in the inventive recipe R1 in Table 1 was replaced by another nonionic surfactant, namely C13-C15 alcohol ethoxylate with 11 EO according to the following recipe, and the melting point was determined: <u> Table 3 </u> substance Substance group function Were used V3 Sodium alkylbenzenesulfonate + toluenesulfonate anionic surfactants cleaning Marlon ARL (Sasol) 14.00 Sodium stearate Gel builder 2.25 C9-C11 alcohol ethoxylate with 10 EO nonionic surfactants Gel builder Imbentin C / 91/100 (Kolb) 12.40 C13-C15 alcohol ethoxylate with 11 EO Gel builder Lutensol AO 11 (BASF) 40.00 EO / PO block copolymer Gel builder - Polyoxyethylene C8-C10 glycerides Foamer Emanon XLF (Kao Chemicals) 4.00 Sodium chloride inorganic salts Thickening agent 2.00 Trisodium citrate Oligocarboxylic acid salts Complexing agents 0.10 Sodium cumene sulfonate Hyd rotrop Clarifying agent Eltesol SCS 93 (Rhodia) - water Solvent Gel builder 14.50 1,2 propylene glycol Gel builder 6.70 Quinoline yellow (2% aqueous solution) Dyes <0.1 Procion turquoise blue (6% aqueous solution) <0.1 Cairo Lavender Fragrances 4.00 total 100.0

Der Schmelzpunkt der Vergleichsrezeptur V3 betrug 43,0 °C und die bei 25 °C gemessene Härte 940 mN.The melting point of the comparison formulation V3 was 43.0 ° C and the hardness measured at 25 ° C was 940 mN.

Dies zeigt, dass hohe Schmelzpunkte nicht mit irgendwelchen nichtionischen Tensiden, sondern nur mit den EO-PO-Blockpolymeren erhalten werden.This shows that high melting points are not obtained with any nonionic surfactants, but only with the EO-PO block polymers.

Härtemessung:Hardness measurement:

Die Härtewerte der verschiedenen Rezepturen wurden wie folgt bestimmt:
Die Härtemessungen wurden mit dem Druckkraftmesser PCE-FG 20SD von PCE Instruments (PCE Deutschland GmbH) und der enthaltenen Edelstahl-Messspitze "Kegel" durchgeführt. Zur definierten Positionierung war das Druckkraftmessgerät am Teststand PCE-FTS50 von PCE Instruments (PCE Deutschland GmbH) montiert, um eine exakte vertikale Verschiebung mit einer Auflösung von 0,01 mm zu gewährleisten.The hardness values of the various recipes were determined as follows:
The hardness measurements were carried out with the compression force meter PCE-FG 20SD from PCE Instruments (PCE Deutschland GmbH) and the included stainless steel measuring tip "Kegel". For the defined positioning, the compressive force measuring device was mounted on the test stand PCE-FTS50 from PCE Instruments (PCE Deutschland GmbH) in order to guarantee an exact vertical shift with a resolution of 0.01 mm.

Die aufgeschmolzenen Gelmassen wurden in eine Petrischale gegossen und anschließend für 3 Stunden bei 25 °C gelagert, um das Aushärten der Gelmassen sicherzustellen. Anschließend wurden die Proben im beschriebenen Messaufbau untersucht.The melted gel masses were poured into a Petri dish and then stored for 3 hours at 25 ° C. in order to ensure that the gel masses hardened. The samples were then examined in the measurement setup described.

Zur Härtemessung wurde die Messspitze knapp oberhalb der Probenoberfläche positioniert und die Messspitze in Schritten von 0,1 mm in Richtung Probenoberfläche nach unten bewegt (Absenkgeschwindigkeit 0,02 mm/s) und der Kraftwert an der entsprechenden Stelle gespeichert. Als Messgröße der Härte wurde der gemessene Kraftwert in mN bei einer Eindringtiefe der Messspitze in die Probe von 2,5 mm verwendet. Als Nullpunkt der Eindringtiefe wurde die Position definiert, bei der an der darauf folgenden Position erstmals eine Kraft gemessen wurde. Die Temperatur während der Messung betrug 25 °C.To measure the hardness, the measuring tip was positioned just above the sample surface and the measuring tip was moved downwards in steps of 0.1 mm in the direction of the sample surface (lowering speed 0.02 mm / s) and the force value was saved at the corresponding point. The measured force value in mN at a depth of penetration of the measuring tip into the sample of 2.5 mm was used as a measure of the hardness. as The zero point of the penetration depth was defined as the position at which a force was measured for the first time at the following position. The temperature during the measurement was 25 ° C.

Claims (14)

  1. Use of a cleaning composition in block form for cleaning the WC area, said cleaning composition is transparent and comprises surfactants, alkanecarboxylic salts, and solvents, and the fraction of alkanecarboxylic salts is between 1 wt% and 5 wt% and the fraction of solvents (including perfume oils) is less than 40 wt% and the composition comprises at least 18% of nonionic surfactants from the group of block copolymers comprising oligoethylene or polyethylene oxides and/or oligopropylene and/or polypropylene oxides and/or oligobutylene and/or polybutylene oxide.
  2. The use as claimed in claim 1, characterized in that the melting point of the cleaning composition is at least 53°C, preferably at least 55°C, and more preferably more than 59°C.
  3. The use as claimed in either of the preceding claims, characterized in that the composition comprises less than 4 wt% and preferably less than 3 wt% of alkanecarboxylic salts.
  4. The use as claimed in any of the preceding claims, characterized in that the cleaning composition comprises at least 20 wt%, preferably at least 25 wt%, and more preferably at least 30 wt%, more particularly more than 35 wt%, of block copolymers.
  5. The use as claimed in any of the preceding claims, characterized in that the alkanecarboxylic salts are alkali metal salts of the aliphatic saturated or unsaturated alkanecarboxylic acids having a carbon chain with between 10 and 24 carbon atoms and are particularly preferred alkali metal salts of lauric, myristic, palmitic, oleic and/or stearic acid.
  6. The use as claimed in any of the preceding claims, characterized in that the block copolymers comprise at least one oligoethylene or polyethylene oxide block.
  7. The use as claimed in any of the preceding claims, characterized in that the weight percentage ratio of the alkanecarboxylic salts to the block copolymers is less than 1:7, preferably less than 1:10, and more preferably less than 1:15.
  8. The use as claimed in any of the preceding claims, characterized in that the cleaning composition comprises less than 30 wt%, preferably between 20 wt% and 25 wt%, of solvents (including perfume oils) .
  9. The use as claimed in any of the preceding claims, characterized in that the perfume fraction is between 2 wt% and 20 wt%, preferably less than 10 wt%, and more preferably between 3 wt% and 6 wt%.
  10. The use as claimed in any of the preceding claims, characterized in that the total fraction of surfactants (including the alkanecarboxylic salts and the block copolymers) in the composition is less than 90 wt%, preferably less than 85 wt% and more than 60 wt%, and more preferably between 65 and 75 wt%.
  11. The use as claimed in any of the preceding claims, characterized in that the fraction of surfactants without the alkanecarboxylic salts and the block copolymers is between 15 and 40 wt% and more preferably between 20 and 30 wt%.
  12. The use as claimed in any of the preceding claims, characterized in that the composition comprises between 10 wt% and 20 wt% of water and/or between 3 wt% and 10 wt% of polyhydric alcohols.
  13. The use as claimed in any of the preceding claims, characterized in that the cleaning composition is transparent, i.e., the transmittance of the cleaning composition with a layer thickness of 10 mm is at least 60% at at least one wavelength between 400 nm and 800 nm, measured against an empty cuvette with a path length of 10 mm.
  14. The use of a composition as claimed in any of the preceding claims, for cleaning the WC area, characterized in that transmittance of the composition with a layer thickness of 10 mm, measured against an empty cuvette with a path length of 10 mm, is at least 60%, wherein the transmittance is determined at a wavelength range between 400 nm and 800 nm, and the transmittance at at least one wavelength between 400 nm and 800 nm has the minimum transmittance of at least 60%.
EP17720496.3A 2016-06-29 2017-05-02 Use of a piece of cleaning agent for cleaning of the toilet area Active EP3478812B1 (en)

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PCT/EP2017/060355 WO2018001603A1 (en) 2016-06-29 2017-05-02 Granular cleaning agent for bathrooms

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DE102016118944A1 (en) 2016-10-06 2018-04-12 Buck Service Gmbh Scent additive for laundry
DE102017105339A1 (en) 2017-03-14 2018-09-20 Buck Group AG Scent additive for laundry
DE102018123920A1 (en) 2018-09-27 2020-04-02 Buck Service Gmbh Laundry detergents

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