EP4011406A1 - Continuous forming process of spherical wc stones - Google Patents

Abstract

The present invention relates to a continuous process for the production of spherical toilet blocks and toilet blocks obtained by the process.

Description

The present invention relates to a continuous process for the production of spherical toilet blocks and toilet blocks obtained by the process.

Toilet cleaning pieces, also known as toilet blocks, have long been used to clean, disinfect and scent toilets under the edge of the pool (so-called rim blocks) and in the water tank (in-tank blocks or cistern blocks). Aesthetics and performance have become increasingly important in recent years. This led, for example, to the development of gel-like or liquid fragrance rinsing agents, some of which are offered in multi-chamber containers and thus allow the combination of a cleaning agent, which is released when the toilet is flushed, with permanent room scenting.

In addition, however, the fixed toilet blocks are still relevant. Up to now, these have mainly been produced by extrusion and then cut to size, so that mostly cuboid WC rim blocks were obtained, which were then inserted into corresponding cups. A disadvantage of these rim blocks is that they swell up as a result of the rinsing water penetrating the basket, are rinsed off unevenly and lose their shape. Therefore, an unaesthetic block remains after a short time.

Furthermore, for example, from the EP 2638137 B1 spherical toilet blocks that do not swell and always have a minimal surface area due to their round shape. The rinsing is therefore even, so that the original shape is retained even after a large number of rinsing processes. Corresponding spherical, preferably rotationally symmetrical toilet blocks are produced by extruding a mixture containing the respective toilet block ingredients in strand form, cutting it into strands of suitable lengths, applying a lubricant on the surface and then shaping it into spherical toilet blocks.

Such manufacturing processes always produce a certain proportion of poorly formed toilet blocks. Such defects occur in particular through the sections of the extruded strands, resulting in a high proportion of returns.

The object of the present invention was therefore to provide a method for producing spherical toilet blocks which overcomes the disadvantages of conventional production processes explained above and enables economical toilet block production.

The inventors of the present invention have here surprisingly found that this problem can be solved by a continuous toilet block manufacturing process in which the

Deformation of the extruded mixture takes place directly after the extrusion. Such methods result in advantageously low proportions of poorly shaped toilet blocks and product returns. In addition, less lubricant is required.

1. a) Bereitstellung mindestens einer Mischung aus WC-Stein-Inhaltsstoffen;
2. b) Extrusion der mindestens einen Mischung erhalten aus Schritt a);
3. c) Verformung der extrudierten Mischung erhalten aus Schritt b) zu kugelförmigen Körpern.

Therefore, in a first aspect, the invention relates to a continuous process for the production of spherical toilet blocks, comprising the following steps:

1. a) providing at least one mixture of toilet block ingredients;
2. b) extrusion of the at least one mixture obtained from step a);
3. c) deformation of the extruded mixture obtained from step b) into spherical bodies.

In a second aspect, the invention relates to spherical toilet blocks made by a method as described herein.

In a final aspect, the invention relates to a method for cleaning and/or scenting and/or disinfecting flush toilets using one or more spherical toilet blocks produced as described herein.

These and other aspects, features and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Each feature from one aspect of the invention can be used in any other aspect of the invention. For example, described features or embodiments of the method can also be applied to the claimed product, and vice versa. Furthermore, it should be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples.

"At least one" as used herein refers to 1 or more, for example 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of components of the compounds described herein, this specification does not refer to the absolute amount of molecules, but to the type of component. "At least one surfactant" therefore means, for example, that only one type of surfactant or several different types of surfactants can be present, without giving any information about the amount of the individual compounds.

Unless otherwise stated, all percentages are by weight, based in each case on the total weight of the corresponding composition. Numerical ranges given in the format "from x to y" include the stated values. Where multiple preferred numeric ranges are given in this format, it is understood that any ranges resulting from the combination of the different endpoints are also included.

Numerical values given herein without decimal places refer to the full stated value with one decimal place. For example, "99%" means "99.0%".

The expressions "approximately" "approx." or "approximately", in connection with a numerical value, refers to a variance of ±10% based on the stated numerical value, preferably ±5%, particularly preferably ±1%, even more preferably below ±0.1%.

Information about the molecular weight relates to the weight-average molecular weight in g/mol, unless the number-average molecular weight is explicitly mentioned. Molecular weights are preferably determined by GPC using polystyrene standards.

1. a) Bereitstellung mindestens einer Mischung aus WC-Stein-Inhaltsstoffen;
2. b) Extrusion der mindestens einen Mischung erhalten aus Schritt a);
3. c) Verformung der extrudierten Mischung erhalten aus Schritt b) zu kugelförmigen Körpern.

The invention relates to a continuous process for the production of spherical toilet blocks, comprising the following steps:

1. a) providing at least one mixture of toilet block ingredients;
2. b) extrusion of the at least one mixture obtained from step a);
3. c) deformation of the extruded mixture obtained from step b) into spherical bodies.

The deformation according to step c) takes place in particular with a ball rolling machine. Preferred ball rolling machines comprise at least two shaping screws, i.e. at least two shaping screws which rotate about their longitudinal axis in the same direction when the ball rolling machine is operated. In various embodiments, a suitable ball rolling machine has, in particular, three rotating shaping screws. The mixture extruded according to step b), preferably in the form of a strand, is introduced into the balling machine and cut by the roller die of the shaping screw and formed into balls. In various embodiments, the shaping worms, i.e. the shaping worms that rotate when the ball rolling machine is in operation, are installed offset to one another in the ball rolling machine. "Staggered" in the context of the present invention means that the worm threads run with a pitch difference relative to one another, so that they can engage in one another.

The individual shaping screws are preferably installed approximately parallel to one another, preferably with a deviation of approximately 0 to 10°, in particular approximately 0 to 5°, even more preferably approximately 0 to 2°, most preferably approximately 0 to 1°, most preferably approximately 0 .0 to 0.5°. In various embodiments, the shaping screws run parallel to one another.

Preferably, the two or more shaping screws, preferably three shaping screws, are intake screws. Feed screws are generally known in the prior art and are characterized by a gradient that decreases in the direction of transport in the feed area. Outside the catchment area, ie in the context of the present invention in the area of the final spherical formation, the gradient then remains identical with each winding. This principle is used with compacting augers. Alternatively, a catchment area can also be created by increasing the diameter of the screws in the direction of transport over a certain length of the shaping screws, so that the space between the individual Screws is reduced in the direction of transport until it reaches a certain size, which is based on the ultimately desired size of the spherical toilet blocks.

In various embodiments, due to the increasing diameter of the shaping worms over a certain length of the shaping worms, in addition to the spherical shaping, there is also a compaction of the extruded material to be shaped. Due to the design of the shaping screws as described above, the fed and transported strand is fed in continuously, then first cut and, with progressive transport along the length of the shaping screws, spherically shaped (rolled) and smoothed on the surface and, if necessary, compacted. In various embodiments, the spherical toilet blocks produced are rotationally symmetrical, in particular spherical. The pitch of the individual augers (the distance between two windings) must be the same as the distance between the two or three form augers. If the distance between the screws increases, ellipsoids form. Due to the progressive necking, transporting and balling, the balling of the present invention occurs in a continuous manner.

The process according to the invention is correspondingly referred to as a continuous production process. “Continuously” in the context of the present invention means that the mixture extruded according to step b), preferably in the form of an extruded strand, is fed to the shaping according to step c) directly after the extrusion according to step b). In particular, "continuous" also means that the mass of the extruded mixture is not divided into individual sections, for example by cutting an extruded strand into individual sections/segments, before it is fed to the shaping according to step c) of the method according to the invention. In this way, the proportion of badly formed spherical toilet blocks can be minimized, particularly compared to conventional discontinuous production processes, which are primarily attributable to the sections of the extruded strand which are normally fed back into the extruder. In the case of discontinuous processes, an extruded strand is fed to shaping screws that are not offset. In this case, the strand must contain a little more material than is needed to form the balls, since the strand cannot be cut with the required precision to ensure the exact formation of the first and last ball. If the two or more forming screws then move towards each other, the front and rear ends of the strand are cut off and fed back in the process. This is not the case in the present process according to the invention, since the extruded strand is fed to the ball-shaping process by means of staggered shaping screws, which enables the strand to be fed in and transported on continuously without end sections occurring.

Accordingly, a further embodiment of the present invention provides that the extruded mixture obtained from step b) is fed directly to the shaping according to step c), ie without the extruded mixture being portioned, for example by cutting an extruded strand into sections of specific lengths.

In the context of the present invention, it is provided in particular that the amount of sections of the extruded mixture obtained from step b) is in the range of approximately 0 to 10%, preferably <0.5%, in each case based on the total amount of the mixture obtained from step a) , lies. In various embodiments of the method according to the invention, there is a maximum of one fault (improperly shaped ball) per approximately 200 balls. In the context of the present invention, it is particularly provided that sections only take place by starting and stopping and/or interrupting the extruded strand, preferably only by starting and stopping.

In various embodiments, spherical toilet blocks are obtained with the production method according to the invention, of which <10%, preferably approximately 0 to 10%, most preferably <0.5%, based in each case on the total amount of the mixture obtained from step a), is returned will.

Steps a) and b) can also be combined, ie mixing the ingredients in the extruder. All process steps may take place at different temperatures, so that heating or cooling steps can be interposed between the steps. These are at the discretion of the professional.

In various embodiments, a further process step can be carried out after step b), in which the extruded mixture, preferably in the form of a strand, is provided with a lubricant. This can be done by means of a sponge soaked with a lubricant, for example in the form of an impeller, and/or by spraying on a lubricant and/or dripping the lubricant and/or immersing the extruded mixture in the lubricant, for example in the form of a strand which is passed through a lubricant bath is performed. The surface can be fully or partially, preferably 10 to 40%, covered with lubricant. The addition of the lubricant can improve the subsequent balling. On the one hand, it results in better transportability of the extruded mixture for spheronization, on the other hand in improved feasibility of the spheronization process itself. In the method according to the invention, compared to conventional production methods, less lubricant is consumed because fewer sections resulting from spheronization are recycled. Suitable lubricants are, in particular, substances that are used, for example, as surfactants or rinsing regulators in formulations according to the invention. A lubricant selected from the group consisting of dipropylene glycol, paraffins, nonionic surfactants, polyethylene glycols and mixtures thereof is particularly preferably used, in particular dipropylene glycol. In a process according to the invention, the amount of lubricant required can be reduced, in particular compared with conventional batch processes.

• d) Bereitstellens einer Kunststoffhalterung, vorzugsweise durch Spritzgussverfahren;
• e) Einlegens der kugelförmigen WC-Steine erhalten aus Schritt c) in die Kunststoffhalterung; und optional
• f) Verschließens der Kunststoffhalterung

umfassen.A method according to the invention can, in some embodiments, in addition to the predefined steps a)-c) and an optional step of applying the lubricant, as described and explained above, also the steps of

• d) providing a plastic holder, preferably by injection molding;
• e) inserting the spherical toilet blocks obtained from step c) into the plastic holder; and optional
• f) Closing the plastic holder

include.

The toilet blocks are preferably stored temporarily in a container between steps c) and d). The container forms a kind of buffer and this means that the production of the toilet blocks can be decoupled from the production of the toilet basket. Preferably, the toilet blocks used in the baskets come from at least two containers, the containers having stored toilet blocks of different compositions. A toilet basket can thus be produced which can release active ingredients from different toilet blocks with different compositions.

In various embodiments, the mixture obtained from step a) has a viscosity in the range from approximately 500,000 to 50,000,000 mPas, preferably in the range from approximately 1,000,000 to 25,000,000 mPas, for example approximately 1,000,000, 1,500,000, 2,000,000 , 2,500,000, 3,000,000, 3,500,000, 4,000,000, 4,500,000, 5,000,000, 5,500,000, 6,000,000, 6,500,000. 7,000,000, 7,500,000, 8,000,000, 8,500,000, 9,000,000, 9,500,000, 10,000,000, 11,000,000, 12,000,000, 13,000,000, 14,000,000,0,60,100,000,10,100,000 000, 17,000,000, 18,000,000, 19,000,000, 20,000,000, 21,000,000, 22,000,000, 23,000,000, 24,000,000 or 25,000,000 mPas. The viscosity can be determined at 20-40° C. using an "IKA Rotavisc hi-vi I" rotational viscometer from IKA-Werke GmbH & Co. KG.

The mixture which is provided according to step a) of the method according to the invention preferably comprises one, more preferably at least two ingredients selected from the group consisting of perfume, surfactants, dyes, rinsing regulators, bleaching agents, builders, acids and/or bases, antimicrobial agents, Polymers, salts, thickeners, preservatives, complexing agents, agents to reduce bad smells, perfume boosters, fillers, bleaches, corrosion inhibitors, rinse-off regulators, enzymes, microorganisms, agents to remove biofilms, agents to inhibit limescale deposits, agents to reduce dirt adhesion, agents to improve Processability and active ingredients to reduce stickiness. As already explained above, a toilet cleaning system, for example enclosed in a plastic holder, for example in the form of a basket, can also include two or more different types of toilet blocks, which differ in terms of their respective composition and/or size and/or Shape and/or color may differ.

Perfume

The mixture obtained according to step a) of the process according to the invention preferably contains one or more fragrances. These are preferably contained in the mixture in an amount of 0.01 to 10% by weight, in particular 0.05 to 8% by weight, particularly preferably 0.1 to 5% by weight. D-limonene can be present as a perfume component. In a particularly preferred embodiment, the mixture contains adherent fragrances, in particular essential oils (also referred to as essential oils). For example, pine, citrus, jasmine, patchouli, rose or ylang-ylang oil can be used as such for the purposes of this invention. Also suitable are clary sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. However, other adherent fragrances, such as the higher-boiling or solid fragrances of natural or synthetic origin, or more volatile fragrances, in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures, are advantageous in the context of the present invention usable.

surfactants

At least one surfactant is preferably included. This is selected from the group of anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants and mixtures thereof. At least one anionic surfactant is preferably present.

In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless otherwise stated - represent branched or unbranched carboxylic acids or alcohols or their derivatives with preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, most preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are preferred in particular because of their vegetable basis as based on renewable raw materials for ecological reasons, but without restricting the teaching according to the invention to them. In particular, the oxo-alcohols or derivatives thereof obtainable, for example, by ROELEN's oxo synthesis, preferably having 7 to 19 carbon atoms, in particular 9 to 19 carbon atoms, particularly preferably 9 to 17 carbon atoms, extremely preferably 11 to 15 carbon atoms, for example 9 to 11 , 12 to 15 or 13 to 15 carbon atoms, can be used accordingly.

Solid toilet blocks containing generally preferably at least one alkyl benzene sulfonate and at least one olefin sulfonate. In addition, further surfactants can be present, in particular from the group of anionic and/or nonionic surfactants.

In the case of the alkylbenzene sulfonates, preference is given in particular to those having about 12 carbon atoms in the alkyl moiety, for example linear sodium C10-13 alkylbenzene sulfonate. Preferred olefin sulfonates have a carbon chain length of 14-16. The toilet cleaning block contains preferably 10 to 70% by weight, preferably 20 to 65% by weight, particularly preferably 20 to 30% by weight, of alkyl benzene sulfonate and preferably 10 to 30% by weight, preferably 15 to 30% by weight. -%, more preferably 15 to 25% by weight of olefin sulfonate.

Other anionic surfactants in the toilet cleaning block can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkane sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignin sulfonates. Fatty acid cyanamides, sulfosuccinates (sulfosuccinic acid esters), in particular sulfosuccinic acid mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccinamides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention and α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates and alkyl ethers of glycerol disulfate.

In the context of the present invention, preference is given to the fatty alcohol sulfates and/or fatty alcohol ether sulfates, in particular the fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, while fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably with relatively long-chain alcohols for the purposes of the present invention. As a rule, a complex mixture of addition products with different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment of the alkoxylation consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ether sulfates are the sulfates of lower ethoxylated fatty alcohols having 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.

The anionic surfactants are preferably used as sodium salts, but can also be present as other alkali or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, and in the case of sulfonates also in the form its corresponding acid, e.g. dodecylbenzenesulfonic acid.

In various embodiments, the mixture of toilet block ingredients as defined above contains at least one alkyl benzene sulfonic acid, preferably in the form of its sodium salt, in an amount of about 10 to 30% by weight, preferably about 20 to 25% by weight, in each case based on the total weight of said mixture.

Nonionic surfactants within the scope of the invention can be alkoxylates such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Also useful are ethylene oxide/propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers. Another important class of nonionic surfactants which can be used according to the invention are the polyol surfactants and here in particular the glycosurfactants such as alkyl polyglycosides and fatty acid glucamides. The alkyl polyglycosides, in particular the alkyl polyglucosides, and above all the fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are particularly preferred.

Preferred fatty alcohol alkoxylates are ethylene oxide (EO) and/or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated Cs-22 alcohols with a degree of alkoxylation up to 30, preferably ethoxylated C _12-22 fatty alcohols with a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example C _16-18 fatty alcohol ethoxylates with 25 EO.

Alkyl polyglycosides are surfactants which can be obtained by reacting sugars and alcohols using the relevant methods of preparative organic chemistry, resulting in a mixture of monoalkylated, oligomeric or polymeric sugars, depending on the type of preparation. Preferred alkyl polyglycosides are the alkyl polyglucosides, with the alcohol particularly preferably being a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched Cs to Cis-alkyl chains and the degree of oligomerization (DP) of the sugars between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, most preferably 1.1 to 1.7, e.g. Cs _-10 -alkyl-1.5-glucoside (DP of 1.5).

Fatty alcohol ethoxylates are preferably used in amounts of up to 20% by weight, particularly preferably 4 to 12% by weight, particularly preferably 7 to 9% by weight. In addition, other nonionic surfactants, such as fatty acid monoalkanolamides and/or alkyl polyglycosides, can be present in amounts of up to 10% by weight.

In addition to the types of surfactants mentioned so far, the mixture can also contain cationic surfactants and/or amphoteric or zwitterionic surfactants.

Suitable amphoteric surfactants are, for example, betaines of the formula (R ⁱⁱⁱ )(R ^iv )(R ^v )N ⁺ CH ₂ COO ^- , in which R ⁱⁱⁱ is an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and which is optionally interrupted by heteroatoms or heteroatom groups, and R ^iv and R ^v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C ₁₀ -C ₁₈ -alkyldimethylcarboxymethylbetaine and C ₁₁ -C ₁₇ -alkylamidopropyldimethylcarboxymethylbetaine.

Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R ^vi ) (R ^vii ) (R ^viii ) (R ^ix ) N ⁺ X ^- , in which R ^vi to R ^ix are four identical or different, in particular two long and two short-chain alkyl radicals and X- is an anion, in particular a halide ion, for example didecyl-dimethyl-ammonium chloride, alkyl-benzyl-didecyl-ammonium chloride and mixtures thereof. Quaternary ammonium compounds with an antimicrobial effect are preferred.

In various embodiments, it is preferred if, in addition to at least one perfume and at least one surfactant, as defined above, no more than 60% by weight of other ingredients are present, preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight, based in each case on the total weight of the mixture obtained in step a).

acids

To improve the cleaning performance against lime and urine scale, the mixture of toilet block ingredients according to step a) can contain one or more acids and/or their salts. The acids are preferably produced from renewable raw materials. Organic acids such as formic acid, acetic acid, citric acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid and gluconic acid and mixtures thereof are therefore particularly suitable as acids. In addition, however, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid or amidosulfonic acid or mixtures thereof can also be used. The acids and/or their salts are particularly preferably selected from the group consisting of citric acid, lactic acid, formic acid, their salts and mixtures thereof. They are preferably used in amounts of 0.01 to 10% by weight, particularly preferably 0.2 to 5% by weight.

In addition, inorganic salts can be present in the mixture, preferably alkali metal or alkaline earth metal salts, in particular carbonates, sulfates, halides or phosphates, and mixtures thereof. Sodium sulfate and/or sodium carbonate are particularly preferably used. Sodium sulphate can be present in an amount of up to 60% by weight, preferably 0.01 to 60% by weight, particularly preferably 20 to 60% by weight, in particular 35 to 55% by weight. Sodium carbonate and other salts can be present in an amount of up to 30% by weight, preferably up to 10% by weight, particularly preferably up to 5% by weight.

bases

Furthermore, alkalis can be included. The bases used are preferably those from the group of alkali metal and alkaline earth metal hydroxides and carbonates, in particular sodium carbonate or sodium hydroxide. In addition, however, it is also possible to use ammonia and/or alkanolamines having up to 9 carbon atoms in the molecule, preferably the ethanolamines, in particular monoethanolamine.

Antimicrobial Agents

Disinfection and sanitation represent a special form of cleaning. In a corresponding special embodiment of the invention, the mixture obtained according to step a) of the method according to the invention therefore contains one or more antimicrobial active ingredients, preferably in an amount of 0.01 to 5 wt. %, preferably 0.02 to 4% by weight, in particular 0.1 to 3.5% by weight, particularly preferably 0.5 to 3% by weight, based in each case on the total weight of the mixture.

Within the scope of the teaching according to the invention, the terms disinfection, sanitation, antimicrobial effect and antimicrobial active ingredient have the customary meaning. While disinfection in the narrower sense of medical practice means killing - theoretically all - infectious germs, sanitation means the greatest possible elimination of all - including the saprophytic germs that are normally harmless to humans. The extent of the disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with a decreasing content of antimicrobial active ingredient or increasing dilution of the agent for use.

Suitable according to the invention are, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids and their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen and nitrogen acetals and formals, benzamidines, isothiazoles and their Derivatives such as isothiazolines and isothiazolinones, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo-2-propynyl-butyl-carbamate, iodine, iodophors, active chlorine-releasing compounds and peroxides. Preferred antimicrobial agents are preferably selected from the group consisting of ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, citric acid, lactic acid, benzoic acid, salicylic acid, thymol, 2- Benzyl-4-chlorophenol, 2,2'-methylene-bis(6-bromo-4-chlorophenol), 2,4,4'-trichloro-2'-hydroxydiphenyl ether, N-(4-chlorophenyl)-N-( 3,4-dichlorophenyl)urea, N,N'-(1,10-decanediyldi-1 -pyridinyl-4-ylidene)bis(1 -octanamine)dihydrochloride, N,N'-bis(4- chlorophenyl)-3,12-diimino-2,4,11,13-tetraazatetradecanediimidamide, antimicrobial quaternary surfactants, guanidines and sodium dichloroisocyanurate (DCI, 1,3-dichloro-5H-1,3,5-triazine-2 ,4,6-trione sodium salt). Preferred antimicrobial surface-active quaternary compounds contain an ammonium, sulfonium, phosphonium, iodonium or arsonium group. Furthermore, essential oils with an antimicrobial effect can also be used, which at the same time ensure that the cleaning agent is scented. However, particularly preferred antimicrobial agents are selected from the group consisting of salicylic acid, quaternary surfactants, especially benzalkonium chloride, peroxo compounds, especially sodium percarbonate, phthalimidoperoxyhexanoic acid or hydrogen peroxide, alkali metal hypochlorite, trichloroisocyanuric acid, sodium dichloroisocyanurate and mixtures thereof. Sodium dichloroisocyanurate is very particularly preferred here.

preservatives

Preservatives may also be included. As such, essentially the substances mentioned for the antimicrobial agents can be used.

complexing agent

Complexing agents (INCI chelating agents), also called sequestering agents, are ingredients that are able to complex and inactivate metal ions in order to prevent their adverse effects on the stability or the appearance of the agent, for example cloudiness. On the one hand, it is important to complex the calcium and magnesium ions of the water hardness, which are incompatible with numerous ingredients. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished product. In addition, the complexing agents support the cleaning effect.

For example, the following complexing agents designated according to INCI are suitable:
Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonate, Pentasodium Pentetate, Pentasodium Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxide, Ribonic Acid, Sodium Chitosan Methylene Phosphonate, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonate, Sodium Dihydroxyethylglycinate, Sodium EDTMP, Sodium Gluceptate, Sodium Gluconate, Sod ium Glycereth-1 Polyphosphate, Sodium Hexametaphosphate, Sodium Metaphosphate, Sodium Metasilicate, Sodium Phytate, Sodium Polydimethylglycinophenolsulfonate, Sodium Trimetaphosphate, TEA-EDTA, TEA-Polyphosphate, Tetrahydroxyethyl Ethylenediamine, Tetrahydroxypropyl Ethylenediamine, Tetrapotassium Etidronate, Tetrapotassium Pyrophosphate, Tetrasodium EDTA, Tetrasodium Etidronate, Tetrasodium Pyrophosphate, Tripotassium EDTA, Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

polymers

Other suitable toilet block ingredients are polymers. These can be used, for example, to reduce limescale formation and the tendency to become soiled again (so-called soil repellent polymers). to serve. Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol.

dyes

One or more colorants (INCI colorants) can be included as further ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, whereby on the one hand the compatibility with other ingredients, for example bleaches, must be taken into account and on the other hand the dye used should not have a substantive effect on the toilet ceramic even after prolonged exposure. A water-soluble dye which colors the rinsing water can be preferred, with a blue color being preferred. The flushing water colored with this dye remains in sufficient concentration in the toilet sump, ie in the rest of the flushing water remaining in the toilet bowl, after the actual flushing process has ended, in order to give it a color, preferably blue. The dyes are preferably present in an amount of 0.0001 to 0.1% by weight, in particular 0.0005 to 0.05% by weight, particularly preferably 0.001 to 0.01% by weight.

Furthermore, active ingredients for preventing or reducing bad smells, so-called malodor repellents, can be used. These are usually substances that adsorb, complex, oxidize or form inclusion compounds with the volatile substances that produce the bad odor, so that they are olfactorily inactivated (so-called deodorants), or fragrances with their own odor mask the annoying bad odor and neutralize it in this way (so-called odor improvers).

Builders

If necessary, water-soluble and/or water-insoluble builders can be contained in the agents produced according to the invention. Water-soluble builders are preferred because they tend to be less likely to leave insoluble residues on hard surfaces. Customary builders that can be present in the context of the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, citric acid and its salts, the carbonates, phosphates and silicates. Water-insoluble builders include the zeolites, which can also be used, as well as mixtures of the aforementioned builders.

bleach

Bleaching agents can also be used according to the invention. Suitable bleaching agents include peroxo compounds, in particular peroxides, peracids, percarbonates and/or perborates, sodium percarbonate, phthalimidoperoxyhexanoic acid or hydrogen peroxide being particularly preferred. Alkali metal hypochlorites such as sodium hypochlorite, on the other hand, are acidic less suitable for formulated cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. Also suitable are trichloroisocyanuric acid and in particular sodium dichloroisocyanurate. In some cases, a bleach activator may be needed in addition to the bleach.

corrosion inhibitors

Suitable corrosion inhibitors (INCI Corrosion Inhibitors) are, for example, the following substances named according to INCI: cyclohexylamine, diammonium phosphate, dilithium oxalate, dimethylaminomethylpropanol, dipotassium oxalate, dipotassium phosphate, disodium phosphate, disodium pyrophosphate, disodium tetrapropenyl succinate, hexoxyethyl diethylammonium, phosphate, nitromethane, potassium Silicates, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine.

rinse regulators

The substances referred to as rinsing regulators primarily serve to control the consumption of the agents during use in such a way that the intended service life is maintained. Suitable regulators are preferably solid, long-chain fatty acids, such as stearic acid, but also salts of such fatty acids, fatty acid ethanolamides, such as coconut fatty acid monoethanolamide, or solid polyethylene glycols, such as those with molecular weights between 10,000 and 50,000.

Active ingredients to reduce stickiness

In order to improve the processability in the preparation according to the invention, an active ingredient to reduce stickiness can be added to the mixture. For example, the addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves the processing behavior during ball molding and significantly reduces abrasion and stickiness. The results with such active substances are better than with other usual measures, for example coating the balls with a lubricant, powdering or coating the mold rollers with Teflon.

enzymes

Other suitable components for toilet stones are enzymes, preferably proteases, lipases, amylases, hydrolases and/or cellulases. They can be added in any form established in the prior art. These include solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers. Alternatively, the enzymes can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural, polymer or in the form of capsules, for example those in which the Enzymes are encapsulated as in a set gel or in the core-shell type in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer. Additional active substances, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can also be applied in superimposed layers. Advantageously, such granules, for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.

Furthermore, enzyme stabilizers can be present in agents containing enzymes in order to protect an enzyme contained in an agent according to the invention from damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage. Depending on the enzyme used, particularly suitable enzyme stabilizers are: benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters, especially derivatives with aromatic groups, such as substituted phenylboronic acids or their salts or esters; Peptide aldehydes (oligopeptides with a reduced C-terminus), amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of the acids mentioned; end-capped fatty acid amide alkoxylates; lower aliphatic alcohols and especially polyols, for example glycerol, ethylene glycol, propylene glycol or sorbitol; and reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known from the prior art. Combinations of stabilizers are preferably used, for example the combination of polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts.

Multi-layer toilet cleaning blocks

From the prior art, for example EP 791047B1 , it is known to produce toilet blocks from masses of different composition, with one of the masses being completely or partially enclosed by the other masses. For example, the inner mass can have a higher perfume concentration than the outer one in order to ensure a constant scent impression over the period of use as the ball mass decreases, or the inner mass contains a different fragrance than the outer one.

In addition, other active ingredients can also be incorporated into different layers, which are released at different times depending on the degree of rinsing. Such a layered structure is in principle also possible with toilet blocks produced according to the invention. In embodiments in which the production of multi-layer spherical toilet blocks is provided, at least two different mixtures of toilet block ingredients are provided in step a) according to the invention. In the extrusion according to step b) of the invention The method then involves co-extrusion of the at least two different mixtures, which are then, as described and defined herein, fed to the shaping according to step c) of the method according to the invention in order to obtain multilayer spherical bodies.

In various embodiments, the spherical toilet blocks produced in a method according to the invention are rotationally symmetrical, in particular spherical.

In various embodiments, the toilet blocks produced according to the invention have a sphericity Ψ between 0.8 and 1, in particular between 0.85 and 1, particularly preferably between 0.9 and 1.

wobei V_p das Volumen des Körpers und A_p seine Oberfläche bezeichnet.The sphericity Ψ of a body K is the ratio of the surface area of the body to the surface area of a sphere of equal volume: $$\mathrm{\Psi }=\frac{{\pi }^{\frac{1}{3}}{\left(6V_p\right)}^{\frac{2}{3}}}{A_p}$$

where V _p denotes the volume of the body and A _p denotes its surface area.

The almost ideal spherical shape of the toilet cleaning block results in a uniform rinsing of the toilet cleaning block in such a way that the toilet cleaning block essentially retains its spherical shape even during or after the rinsing processes and a corresponding removal of the toilet cleaning block. It has been shown that, in particular, a high sphericity Ψ of the toilet cleaning block at the beginning of the application of flushing water is decisive for maintaining the spherical shape during and after the flushing processes. The malleability of the mass and thus the possibility of optimal rounding can be adjusted by adding a small amount of liquid. In particular, water, dipropylene glycol or paraffin can be used as liquids in an amount of 0.1 to 1% by weight.

The diameter of the spherical toilet block is preferably between 1 mm and 10 cm, preferably between 5 mm and 5 cm, particularly preferably between 1 cm and 3 cm.

Accordingly, in a further aspect, the present invention relates to spherical toilet blocks produced in a method as defined and described above.

Furthermore, the present invention also relates to a method for cleaning and/or scenting and/or disinfecting flush toilets using one or more spherical toilet blocks, produced as described herein and as defined above.

Claims (11)

Continuous process for the production of spherical toilet blocks comprising the following steps: a) providing at least one mixture of toilet block ingredients; b) extrusion of the at least one mixture obtained from step a); c) deformation of the extruded mixture obtained from step b) into spherical bodies. The method according to claim 1, characterized in that step c) takes place by means of a ball rolling machine comprising at least 2 rotating forming screws. The method according to claim 2, characterized in that the ball rolling machine has 3 rotating shaping screws. The method according to claim 2 or claim 3, characterized in that the shaping screws are installed offset to one another in the ball rolling machine. The method according to any one of the preceding claims, characterized in that the mixture obtained from step a) has a viscosity in the range from about 500,000 to 50,000,000 mPas, preferably in the range from about 1,000,000 to 25,000,000 mPas. The method according to any one of the preceding claims, characterized in that the method obtains sections of the extruded mixture from step b) in the range of approximately 0 to 10%, preferably <0.5%, each based on the total amount of the mixture obtained from step a ), includes. The method according to any one of the preceding claims, characterized in that the method further comprises the steps of d) providing a plastic holder, preferably by injection molding; e) inserting the spherical toilet blocks obtained from step c) into the plastic holder; and optional f) Closing the plastic holder
includes. The method according to any one of the preceding claims, characterized in that the mixture obtained from step a) at least one, preferably at least two ingredients selected from the group consisting of perfume, surfactants, dyes, rinsing regulators, bleaching agents, builders, acids and / or bases, antimicrobial Active ingredients, polymers, salts, thickeners, preservatives, complexing agents, active ingredients to reduce bad smells, perfume boosters, fillers, bleaching agents, corrosion inhibitors, rinsing regulators, enzymes, microorganisms, active ingredients to remove biofilms, active ingredients to inhibit limescale deposits, active ingredients to reduce dirt adhesion, active ingredients to Processability improvement and tack reducing agents. The method according to any one of the preceding claims, characterized in that the spherical toilet blocks are rotationally symmetrical. Spherical toilet blocks produced by a method according to any one of claims 1 to 9. Method for cleaning and/or scenting and/or disinfecting flush toilets using one or more spherical toilet blocks according to claim 10.