Continuous forming process of spherical wc stones

Abstract

The present invention relates to a continuous process for producing spherical toilet blocks and to toilet blocks obtained by this process.

Description

[0001] The present invention relates to a continuous process for the production of spherical toilet blocks.

[0002] Toilet cleaning blocks, also known as toilet blocks, have long been used to clean, disinfect, and scent toilets under the bowl (so-called rim blocks) and in the cistern (in-tank blocks or cistern blocks). In recent years, aesthetics and performance have become increasingly important. This has led, for example, to the development of gel or liquid fragranced air fresheners, some of which are offered in multi-chamber containers, thus combining a cleaning agent released when the toilet is flushed with a permanent room fragrance.

[0003] In addition, solid toilet blocks remain relevant. These were previously primarily manufactured by extrusion and then cut to size, resulting in mostly cuboid-shaped toilet rim blocks that were then inserted into corresponding baskets. A disadvantage of these rim blocks is that they swell due to the flushing water penetrating the basket, are rinsed unevenly, and lose their shape. Therefore, after a short time, an unsightly block remains.

[0004] DE 10 2015 215135 A1 describes a toilet block consisting of a shell and a core. The shell contains a first composition, while the core contains a second composition. These two compositions differ in terms of active ingredients, their concentration, or viscosity. The core protrudes and is exposed on at least one side of the toilet block. The toilet block can be designed so that the surface of the core changes when the block is removed. The method of D1 comprises mixing the ingredients for the core and shell composition, co-extrusion of the two mixtures, cutting the extruded strand into portions, and deformation into rotationally symmetrical bodies (ball rolling machine or press), with the core exposed on at least one side.

[0005] WO 2020 / 064159 A1 describes a spherical toilet block comprising two different compositions. These are produced through a non-concentric coextrusion step. The process for producing the toilet block includes a forming step in which the extrudate is formed into a sphere. The device for producing the toilet block comprises an extruder head that combines the compositions and extrudes them through a profile die.

[0006] Furthermore, spherical toilet blocks are known, for example, from EP 2638137 B1. These do not swell and, due to their round shape, always have a minimal surface area. Rinsing is therefore even, so that the original shape is retained even after numerous rinsing processes. Such spherical, preferably rotationally symmetrical toilet blocks are produced by extruding a mixture containing the respective toilet block ingredients into strands, cutting them into strands of suitable lengths, lubricating the surface, and then forming them into spherical toilet blocks.

[0007] Such manufacturing processes always produce a certain proportion of poorly formed toilet blocks. Such defects occur particularly in the sections of the extruded strands, resulting in a high proportion of returns.

[0008] The object of the present invention was therefore to provide a method for producing spherical toilet blocks which overcomes the disadvantages of conventional manufacturing processes explained above and enables economical toilet block production.

[0009] The inventors of the present invention have surprisingly discovered that this problem can be solved by a continuous toilet block manufacturing process in which the extruded mixture is shaped directly after extrusion. Such processes advantageously result in low rates of poorly formed toilet blocks and product returns. Furthermore, less lubricant is required.

[0010] The present invention and the preferred embodiments are apparent from the claims.

[0011] Therefore, in a first aspect, the invention relates to a continuous process for producing spherical toilet blocks comprising the following steps: a) Providing at least one mixture of toilet block ingredients; b) Feeding the at least one mixture obtained from step a) into a ball rolling machine, wherein the ball rolling machine comprises at least two forming screws, wherein the forming screws rotate about their longitudinal axis in the same direction when the ball rolling machine is operated and the at least two forming screws are installed in the ball rolling machine in such a way that they run essentially parallel to one another and with a pitch difference from one another; c) Deforming the mixture fed in according to step b) into spherical bodies by feeding the mixture of toilet block ingredients to the at least two rotating forming screws.

[0012] 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. Any feature from one aspect of the invention may be employed in any other aspect of the invention. For example, described features or embodiments of the method may also be applied to the product, and vice versa. Furthermore, it is to 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.

[0013] "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 statement does not refer to the absolute amount of molecules, but rather 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 may be present, without specifying the amount of the individual components.

[0014] Unless otherwise stated, all percentages are by weight, based on the total weight of the corresponding composition. Numerical ranges expressed in the format "from x to y" are inclusive of the stated values. Where multiple preferred numerical ranges are specified in this format, it is understood that all ranges resulting from the combination of the various endpoints are also included.

[0015] Numerical values ​​stated without decimal places refer to the full specified value with one decimal place. For example, "99%" stands for "99.0%."

[0016] The expressions "approximately," "ca.", or "about," in connection with a numerical value, refer to a variance of ±10% relative to the stated numerical value, preferably ±5%, particularly preferably ±1%, even more preferably less than ±0.1%.

[0017] Molecular weight data refer to the weight-average molecular weight in g / mol unless the number-average molecular weight is explicitly stated. Molecular weights are preferably determined by GPC using polystyrene standards.

[0018] Figure 1 shows a schematic representation of two forming screws, which run offset from each other with a pitch difference. This enables the continuous drawing, further transport, and ultimately spherical forming of a fed mixture, preferably in the form of a strand.

[0019] Figure 2 shows two profiled rollers which are used in discontinuous processes not according to the invention for the production of spherical toilet blocks. Figure 2a shows the two rollers and a strand in between. Figure 2bshows how, by reducing the distance between the two rollers, the strand is first cut into smaller segments and then, due to the rotation of the rollers, is spherically formed.

[0020] The invention relates to a continuous process for the production of spherical toilet blocks comprising the following steps: a) Providing at least one mixture of toilet block ingredients; b) Feeding the at least one mixture obtained from step a) into a ball rolling machine, wherein the ball rolling machine comprises at least two forming screws, wherein the forming screws rotate about their longitudinal axis in the same direction when the ball rolling machine is operated and the at least two forming screws are installed in the ball rolling machine in such a way that they run essentially parallel to one another and with a pitch difference from one another; c) Deforming the mixture fed in according to step b) into spherical bodies by feeding the mixture of toilet block ingredients to the at least two rotating forming screws.

[0021] The ball rolling machines comprise at least two forming screws, i.e., at least two forming screws that rotate around their longitudinal axes in the same direction when the ball rolling machine is in operation. In various embodiments, however, a suitable ball rolling machine has, in particular, three such rotating forming screws.

[0022] The ball rolling machines are further characterized by the fact that the forming screws are installed offset from one another in the ball rolling machine, which in the context of the present invention means that the screw threads of the forming screws run with a pitch difference to one another, so that they can mesh with one another ( Figure 1 ). This distinguishes the process according to the invention from the process known in the prior art, since the difference in the pitch of the forming screws allows the fed-in mass to be drawn into the ball rolling machine in a continuous manner and formed into balls.

[0023] The forming screws are installed essentially parallel to one another. "Essentially parallel to one another" in the context of the present invention means running parallel to one another with a deviation of approximately 0° to 5°, in particular approximately 0° to 3°, more preferably approximately 0° to 2°, most preferably approximately 0° to 1°, and most preferably with a deviation of approximately 0.0° to 0.5°. In various embodiments, the forming screws run exactly parallel to one another.

[0024] In particular, the method according to the invention is accordingly characterized in that the ball forming machine comprises at least two forming screws, wherein the forming screws rotate about their longitudinal axis in the same direction when the ball rolling machine is operated and the at least two forming screws are installed in the ball rolling machine in such a way that they run substantially parallel to one another and with a pitch difference to one another, and wherein the deformation according to step c) takes place by feeding the mixture of toilet block ingredients to the at least two rotating forming screws.

[0025] The two or more forming screws, preferably three forming screws, are preferably intake screws. Intake screws are generally known in the prior art and are characterized by a pitch that decreases in the feed area in the transport direction. Outside the feed area, i.e. in the context of the present invention in the area of ​​the final spherical formation, the pitch then remains identical with each turn. This principle is used for compacting intake screws. Alternatively, an intake area can also be created by the diameter of the screws becoming increasingly larger in the transport direction over a certain length of the forming screws, so that the space between the individual screws is reduced in the transport direction until it reaches a certain size that is based on the ultimately desired size of the spherical toilet blocks.

[0026] In various embodiments, the diameter of the forming screws increases over a certain length, resulting in not only a spherical shape but also a compaction of the extruded and to-be-formed material. Due to the design of the forming screws as described above, the fed-in and transported strand is continuously drawn in, then first cut and, as the transport progresses along the length of the forming screws, formed into a spherical shape (rolled), and surface smoothed and, if necessary, compacted. In various embodiments, the spherical toilet blocks produced are rotationally symmetrical, in particular spherical. The pitch of the individual screws (the distance between two turns) must be equal to the distance between the two or three forming screws. If the distance between the screws is increased, ellipsoids form.

[0027] Due to the progressive drawing in, further transport and spherical forming, the spherical forming according to the invention takes place in a continuous manner.

[0028] The process according to the invention is accordingly referred to as a continuous production process. "Continuous" in the context of the present invention means that the deformation according to step c) takes place directly after the feeding according to step b), in that the fed mixture is drawn through the forming screws and simultaneously formed into spheres. In particular, "continuous" further means that the fed mass is not divided into individual sections, for example by cutting an extruded strand into individual sections / segments, before being fed to the deformation according to step c) of the process according to the invention. Instead, the entire mixture provided according to step a) is fed in continuously, i.e., without interruption, and continuously, i.e., without interruption, fed to the sphere formation.In this way, the proportion of poorly formed spherical toilet blocks can be minimized, particularly compared to conventional discontinuous manufacturing processes, which are primarily attributable to the sections of the extruded strand that are normally returned to the extruder. In discontinuous processes, a suitable mixture, primarily in the form of an extruded strand, is fed to rollers that can approach one another, with the rollers having essentially no pitch difference between them, and the ball formation takes place by reducing the distance between the rollers, so that the mass fed into the space between the rollers, for example in the form of an extruded strand, is first cut / crushed and then, due to the rolling movements of the rollers, is spherized (Fig. Figure 2). Here the strand must contain slightly more material than is needed to form the balls because the strand cutting cannot be carried out with the necessary precision to guarantee the exact formation of the first and last ball. When the two or more rollers then move towards each other the front and rear ends of the strand are cut off. These sections are then added to a fresh mixture of toilet block ingredients and returned to the process in this way to save resources. This is not the case with the present inventive method because the fed-in mass is fed to the ball forming process by forming screws with a different pitch to each other, which enables continuous feeding, further transport, cutting and spherical forming of the mass without any end sections occurring.

[0029] Accordingly, the present invention provides that the mixture fed in according to step b) is fed directly to the deformation according to step c), ie without the mixture obtained according to step a) being portioned, for example by cutting an extruded strand into sections of specific lengths.

[0030] In various embodiments of the method according to the invention, a maximum of one defect (incorrectly formed ball) occurs per approximately 200 balls. In the context of the present invention, it is particularly provided that sections are performed only by starting and stopping.

[0031] In various embodiments, the production process according to the invention produces spherical toilet blocks, of which < 10%, preferably approximately 0 to 10%, most preferably < 0.5%, are returned, in each case based on the total amount of the mixture obtained from step a).

[0032] In various embodiments, a mixture of toilet block ingredients provided according to step a) is fed into a ball forming machine in the form of an extruded mixture, preferably in the form of an extruded strand according to step b).

[0033] Steps a) and b) can also be combined in such a way that the toilet block ingredients are mixed in the extruder and fed directly as extrudate.

[0034] All process steps may take place at different temperatures, so heating or cooling steps may be added between the steps. These are at the discretion of the expert.

[0035] In various embodiments, a further process step can be carried out following step a), in which the mixture to be fed in, for example in the form of an extruded mixture, preferably in the form of an (extruded) strand, is provided with a lubricant. This can be done by means of a sponge impregnated with a lubricant, for example in the form of an impeller, and / or by spraying a lubricant and / or dripping the lubricant and / or immersing the mixture to be fed in the lubricant, for example in the form of a strand which is passed through a lubricant bath. The surface can be fully or partially coated with lubricant, preferably to a degree of 10 to 40%. The addition of the lubricant can improve the subsequent spheroidization.On the one hand, it results in better transportability of the mixture for spheroidization, and on the other hand, in improved feasibility of the spheroidization process itself. In the process according to the invention, less lubricant is consumed compared to conventional manufacturing processes, since fewer portions resulting from spheroidization are returned to the process. Suitable lubricants are, in particular, substances used, for example, as surfactants or rinsing regulators in formulations according to the invention. Particular preference is given to using a lubricant selected from the group comprising dipropylene glycol, paraffins, nonionic surfactants, polyethylene glycols, and mixtures thereof, in particular dipropylene glycol. In a process according to the invention, the amount of lubricant required can be reduced, particularly compared to conventional discontinuous processes.

[0036] A method according to the invention may, in some embodiments, in addition to the predefined steps a)-c) and an optional step of applying lubricant, as described and explained above, further comprise 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 optionally f) closing the plastic holder include.

[0037] Preferably, the toilet blocks are temporarily stored in a container between steps c) and d). The container acts as a buffer, allowing the production of the toilet blocks to be separated from the production of the toilet baskets. Preferably, the toilet blocks used in the baskets come from at least two containers, with the containers containing toilet blocks with different compositions. Thus, a toilet basket can be produced that can release active ingredients from different toilet blocks with different compositions.

[0038] In various embodiments, the mixture obtained from step a) has a viscosity in the range of approximately 500,000 to 50,000,000 mPas, preferably in the range of 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, 15,000,000, 16,000,000, 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. Viscosity can be determined using a rotational viscometer "IKA Rotavisc hi-vi I" from IKA-Werke GmbH & Co. KG at 20-40°C.

[0039] The mixture which is provided according to step a) of the process according to the invention preferably comprises one, more preferably at least two ingredients selected from the group consisting of perfume, surfactants, dyes, rinse regulators, bleaching agents, builders, acids and / or bases, antimicrobial agents, polymers, salts, thickeners, preservatives, complexing agents, agents for reducing malodors, perfume boosters, fillers, corrosion inhibitors, rinse regulators, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for inhibiting limescale deposits, active ingredients for reducing dirt adhesion, active ingredients for improving processability and active ingredients for reducing 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 comprise two or more different types of toilet blocks, which can differ in terms of their respective composition and / or size and / or shape and / or color. perfume

[0040] The mixture obtained according to step a) of the process according to the invention preferably contains one or more fragrances. These are preferably present in the mixture in an amount of 0.01 to 10 wt. %, in particular 0.05 to 8 wt. %, particularly preferably 0.1 to 5 wt. d-Limonene can be present as a perfume component. In a particularly preferred embodiment, the mixture contains long-lasting fragrances, in particular essential oils (also referred to as volatile oils). Pine, citrus, jasmine, patchouli, rose, or ylang-ylang oil, for example, can be used as such within the meaning of this invention. Also suitable are clary sage oil, chamomile oil, lavender oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden 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. But also other persistent fragrances, such as the higher boiling orSolid fragrances of natural or synthetic origin, or also more volatile fragrances, in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures, can be used advantageously within the scope of the present invention. Surfactants

[0041] Preferably, at least one surfactant is included. This is selected from the group of anionic surfactants, nonionic surfactants, amphoteric or zwitterionic surfactants, cationic surfactants, and mixtures thereof. Preferably, at least one anionic surfactant is included.

[0042] In the context of the present invention, fatty acids or fatty alcohols or their derivatives - unless stated otherwise - represent branched or unbranched carboxylic acids or alcohols or their derivatives having preferably 6 to 22 carbon atoms, in particular 8 to 20 carbon atoms, particularly preferably 10 to 18 carbon atoms, extremely preferably 12 to 16 carbon atoms, for example 12 to 14 carbon atoms. The former are particularly preferred for ecological reasons because of their plant-based nature as they are based on renewable raw materials, without, however, limiting the teaching of the invention to them. In particular, the oxo alcohols or oxo alcohols obtainable, for example, by the Roelen oxo synthesis are also suitable.their derivatives having preferably 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.

[0043] Solid toilet blocks generally preferably contain at least one alkylbenzenesulfonate and at least one olefinsulfonate. They may also contain other surfactants, particularly from the group of anionic and / or nonionic surfactants.

[0044] Among the alkylbenzenesulfonates, those with approximately 12 carbon atoms in the alkyl moiety are particularly preferred, such as linear sodium C10-13 alkylbenzenesulfonate. Preferred olefinsulfonates have a carbon chain length of 14 to 16. The toilet cleaning block preferably contains 10 to 70 wt.%, preferably 20 to 65 wt.%, particularly preferably 20 to 30 wt.% of alkylbenzenesulfonate and preferably 10 to 30 wt.%, preferably 15 to 30 wt.%, particularly preferably 15 to 25 wt.% of olefinsulfonate.

[0045] Other anionic surfactants that may be present in the toilet cleaning block include aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates, and aliphatic sulfonates such as alkanesulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, and lignin sulfonates. Also usable within the scope of the present invention are 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, as well as α-sulfofatty acid salts, acylglutamates, monoglyceride disulfates, and alkyl ethers of glycerol disulfate.

[0046] Preferred within the scope of the present invention are fatty alcohol sulfates and / or fatty alcohol ether sulfates, in particular fatty alcohol sulfates. Fatty alcohol sulfates are products of sulfation reactions on corresponding alcohols, whereas fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. In this context, the skilled person generally understands alkoxylated alcohols to be the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably with longer-chain alcohols within the meaning of the present invention. Depending on the reaction conditions, n moles of ethylene oxide and one mole of alcohol generally form a complex mixture of addition products with varying degrees of ethoxylation. Another embodiment of the alkoxylation involves the use of mixtures of alkylene oxides, preferably a mixture of ethylene oxide and propylene oxide.Preferred fatty alcohol ether sulfates are the sulfates of low-ethoxylated fatty alcohols with 1 to 4 ethylene oxide units (EO), in particular 1 to 2 EO, for example 1.3 EO.

[0047] 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, as well as in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, and in the case of sulfonates also in the form of their corresponding acid, e.g. dodecylbenzenesulfonic acid.

[0048] In various embodiments, the mixture of toilet block ingredients as defined above contains at least one alkylbenzenesulfonic acid, preferably in the form of its sodium salt, in an amount of approximately 10 to 30 wt.%, preferably approximately 20 to 25 wt.%, in each case based on the total weight of said mixture.

[0049] 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. Ethylene oxide / propylene oxide block polymers, fatty acid alkanolamides, and fatty acid polyglycol ethers can also be used. Another important class of nonionic surfactants that can be used according to the invention are polyol surfactants, particularly glycosurfactants such as alkyl polyglycosides and fatty acid glucamides. Alkyl polyglycosides, especially alkyl polyglucosides, and especially fatty alcohol alkoxylates (fatty alcohol polyglycol ethers) are particularly preferred.

[0050] Preferred fatty alcohol alkoxylates are unbranched or branched, saturated or unsaturated Cs-22 alcohols alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO) and having a degree of alkoxylation of up to 30, preferably ethoxylated Cs-22 fatty alcohols having a degree of ethoxylation of less than 30, preferably 12 to 28, in particular 20 to 28, particularly preferably 25, for example Cs-16-18 fatty alcohol ethoxylates with 25 EO.

[0051] Alkyl polyglycosides are surfactants that 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 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 Cs-alkyl chains, and the degree of oligomerization (DP) of the sugar being between 1 and 10, preferably 1 to 6, in particular 1.1 to 3, and most preferably 1.1 to 1.7, for example C8-10-alkyl-1,5-glucoside (DP of 1.5).

[0052] Fatty alcohol ethoxylates are preferably used in amounts of up to 20 wt.%, particularly preferably 4 to 12 wt.%, particularly preferably 7 to 9 wt.%. In addition, other nonionic surfactants, such as fatty acid monoalkanolamides and / or alkyl polyglycosides, may be present in amounts of up to 10 wt.%.

[0053] In addition to the surfactant types mentioned above, the mixture may also contain cationic surfactants and / or amphoteric or zwitterionic surfactants.

[0054] 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 optionally interrupted by heteroatoms or heteroatom groups having 8 to 25, preferably 10 to 21 carbon atoms 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.

[0055] 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< represent four identical or different, in particular two long-chain and two short-chain, alkyl radicals, and X- represents an anion, in particular a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride, and mixtures thereof. Quaternary ammonium compounds with an antimicrobial effect are preferred.

[0056] In various embodiments, it is preferred if, in addition to at least one perfume and at least one surfactant, as defined above, a total of not more than 60% by weight of further ingredients is present, preferably 0.01 to 60% by weight, in particular 0.2 to 15% by weight, in each case based on the total weight of the mixture obtained according to step a). Acids

[0057] To enhance the cleaning performance against limescale 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. Particularly suitable acids are therefore 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, as well as mixtures thereof. In addition, the inorganic acids hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, or even amidosulfonic acid or mixtures thereof, can also be used. The acids and / or their salts are particularly preferably selected from the group comprising citric acid, lactic acid, formic acid, their salts, and mixtures thereof. They are preferably used in amounts of 0.01 to 10 wt.%, particularly preferably 0.2 to 5 wt.%.

[0058] In addition, inorganic salts may be present in the mixture, preferably alkali or alkaline earth metal salts, in particular carbonates, sulfates, halides, or phosphates, as well as mixtures thereof. Particular preference is given to using sodium sulfate and / or sodium carbonate. Sodium sulfate may be present in an amount of up to 60 wt.%, preferably 0.01 to 60 wt.%, particularly preferably 20 to 60 wt.%, in particular 35 to 55 wt.%. Sodium carbonate and other salts may be present in an amount of up to 30 wt.%, preferably up to 10 wt.%, particularly preferably up to 5 wt.%. Bases

[0059] Alkalis may also be included. Bases preferably used are those from the group of alkali and alkaline earth metal hydroxides and carbonates, especially sodium carbonate or sodium hydroxide. However, ammonia and / or alkanolamines with up to 9 carbon atoms per molecule can also be used, preferably ethanolamines, especially monoethanolamine. Antimicrobial agents

[0060] 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 process 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 wt.%, in particular 0.1 to 3.5 wt.%, particularly preferably 0.5 to 3 wt.%, in each case based on the total weight of the mixture.

[0061] The terms disinfection, sanitation, antimicrobial effect, and antimicrobial agent have the usual technical meaning within the context of the teaching of the invention. While disinfection in the narrower sense of medical practice means the killing of – theoretically all – infectious germs, sanitation is understood to mean the elimination of all germs as far as possible, including saprophytic germs that are normally harmless to humans. The extent of disinfection or sanitation depends on the antimicrobial effect of the agent used, which decreases with decreasing antimicrobial agent content or increasing dilution of the agent used.

[0062] Suitable according to the invention are, for example, antimicrobial active ingredients from the groups of alcohols, aldehydes, antimicrobial acids or 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, iodophores, active chlorine-releasing compounds and peroxides.Preferred antimicrobial active ingredients are preferably selected from the group comprising ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, 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 quaternary surfactants contain an ammonium, sulfonium, phosphonium, iodonium, or arsonium group.Furthermore, antimicrobially active essential oils can also be used, which also provide a fragrance for the cleaning agent. However, particularly preferred antimicrobial agents are selected from the group comprising 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 particularly preferred. Preservatives

[0063] Preservatives may also be included. These include, in particular, the substances listed under antimicrobial active ingredients. Complexing agents

[0064] Chelating agents (INCI: chelating agents), also known as sequestering agents, are ingredients that can complex and inactivate metal ions to prevent their adverse effects on the stability or appearance of the product, such as cloudiness. On the one hand, it is important to complex the calcium and magnesium ions that cause water hardness, which are incompatible with many ingredients. On the other hand, complexing the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished product. Furthermore, the complexing agents support the cleaning effect.

[0065] Geeignet sind beispielsweise die folgenden gemäß INCI bezeichneten Komplexbildner: 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, Sodium 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 und Trisodium Phosphate., Polymere

[0066] Other suitable toilet block ingredients are polymers. These can be used, for example, to reduce limescale formation and the tendency to re-soil (so-called soil repellent polymers). Preferred polymers are acrylic polymers, such as those commercially available from Rhodia under the trade name Mirapol. Dyes

[0067] One or more dyes (INCI colorants) may be included as additional ingredients. Both water-soluble and oil-soluble dyes can be used as dyes, whereby compatibility with other ingredients, for example bleaching agents, must be taken into account and the dye used should not have a substantive effect on the toilet ceramic, even after prolonged exposure. A water-soluble dye that colors the flush water is preferred, with a blue color being preferred. The flush water colored with this dye remains in the toilet sump, i.e. in the residual flush water remaining in the toilet bowl, in sufficient concentration after the actual flushing process to give it a color, preferably blue. The dyes are preferably added 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.-%, contain.

[0068] Furthermore, active ingredients can be used to prevent or reduce unpleasant odors, so-called malodor repellents. These are generally substances that adsorb, complex, oxidize, or form inclusion compounds with the volatile substances that cause the unpleasant odor, thus inactivating them (so-called deodorants). Alternatively, they are fragrances that mask the unpleasant odor with their own odor, thus neutralizing it (so-called odor enhancers). Builder

[0069] The agents produced according to the invention may optionally contain water-soluble and / or water-insoluble builders. Water-soluble builders are preferred, as they generally have less tendency to leave insoluble residues on hard surfaces. Common builders that may be present in the context of the invention are low-molecular-weight polycarboxylic acids and their salts, homopolymeric and copolymeric polycarboxylic acids and their salts, citric acid and its salts, carbonates, phosphates, and silicates. Water-insoluble builders include zeolites, which may also be used, as well as mixtures of the aforementioned builder substances. Bleach

[0070] 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 are particularly preferred. Alkali metal hypochlorites such as sodium hypochlorite, on the other hand, are less suitable for acidic cleaning agents due to the release of toxic chlorine gas vapors, but can be used in alkaline cleaning agents. Trichloroisocyanuric acid and, in particular, sodium dichloroisocyanurate are also suitable. In some circumstances, a bleach activator may also be required in addition to the bleaching agent. Corrosion inhibitors

[0071] Geeignete Korrosionsinhibitoren (INCI Corrosion Inhibitors) sind beispielsweise folgende gemäß INCI benannte Substanzen: Cyclohexylamine, Diammonium Phosphate, Dilithium Oxalate, Dimethylamino Methylpropanol, Dipotassium Oxalate, Dipotassium Phosphate, Disodium Phosphate, Disodium Pyrophosphate, Disodium Tetrapropenyl Succinate, Hexoxyethyl Diethylammonium, Phosphate, Nitromethane, Potassium Silicate, Sodium Aluminate, Sodium Hexametaphosphate, Sodium Metasilicate, Sodium Molybdate, Sodium Nitrite, Sodium Oxalate, Sodium Silicate, Stearamidopropyl Dimethicone, Tetrapotassium Pyrophosphate, Tetrasodium Pyrophosphate, Triisopropanolamine. Abspülregulatoren

[0072] The substances known as rinse regulators primarily serve to control the consumption of the detergent during use so 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

[0073] To improve processability during the production according to the invention, an active agent can be added to the mixture to reduce stickiness. For example, the addition of dolomite powder or titanium dioxide powder with a fine particle size distribution improves processing behavior during sphere molding and significantly reduces abrasion and stickiness. The results with such active agents are better than with other conventional measures, such as coating the spheres with a lubricant, powdering, or coating the molding rollers with Teflon. Enzymes

[0074] Other suitable components for toilet blocks are enzymes, preferably proteases, lipases, amylases, hydrolases, and / or cellulases. They can be added in any form established by the state of the art. This includes enzyme solutions, advantageously as concentrated as possible, low in water, and / or containing stabilizers. Alternatively, the enzymes can be encapsulated, for example, by spray-drying or extrusion of the enzyme solution together with a polymer, preferably natural, or in the form of capsules, for example, those in which the enzymes are enclosed as if in a solidified gel, or in core-shell capsules, in which an enzyme-containing core is coated with a protective layer impermeable to water, air, and / or chemicals. Additional active ingredients, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers.Advantageously, such granules are low in dust, for example by applying polymeric film formers, and are storage-stable due to the coating.

[0075] Furthermore, enzyme stabilizers may be present in enzyme-containing agents in order to protect an enzyme contained in an agent according to the invention from damage such as inactivation, denaturation or degradation, for example due to physical influences, oxidation or proteolytic cleavage.Particularly suitable enzyme stabilizers, depending on the enzyme used, 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; as well as reducing agents and antioxidants such as sodium sulfite and reducing sugars. Other suitable stabilizers are known from the prior art.Preferably, combinations of stabilizers are 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

[0076] From the prior art, for example, EP 791047B1, it is known to produce toilet blocks from masses of different compositions, with one of the masses being completely or partially enclosed by the other mass(es). For example, the inner mass may have a higher perfume concentration than the outer one to ensure a consistent fragrance impression throughout its service life as the ball mass decreases, or the inner mass may contain a different fragrance than the outer one.

[0077] 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 also possible in principle for toilet blocks produced according to the invention. In embodiments in which the production of multi-layered spherical toilet blocks is envisaged, at least two different mixtures of toilet block ingredients are prepared in a step a) according to the invention and fed into a spherical forming machine according to step b).In various embodiments in which the mixture from step a) is fed in the form of an extruded mixture, preferably in the form of an extruded strand according to step b), the extrusion is then co-extrusion of the at least two different mixtures, which are subsequently, as described and defined herein, fed to the deformation according to step c) of the process according to the invention in order to obtain multi-layer spherical bodies in this way.

[0078] In various embodiments, the spherical toilet blocks produced by a method according to the invention are rotationally symmetrical, in particular spherical.

[0079] 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.

[0080] 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 the same volume: Ψ = π 1 3 6 V p 2 3 A p where V p is the volume of the body and A p is its surface area.

[0081] The almost ideal spherical shape of the toilet cleaning block ensures even rinsing, meaning the toilet cleaning block essentially retains its spherical shape even during and after the rinsing process and the corresponding wear of the toilet cleaning block. It has been shown that a high sphericity Ψ of the toilet cleaning block at the beginning of the flushing water exposure is particularly crucial for maintaining the spherical shape during and after the rinsing process. The formability of the mass and thus the possibility of optimal rounding can be adjusted by adding a small amount of liquid. Suitable liquids include, in particular, water, dipropylene glycol, or paraffin in an amount of 0.1 to 1 wt.%.

[0082] 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.

Claims

1. A continuous method for producing spherical toilet rim blocks, comprising the following steps: a) providing at least one mixture of toilet rim block ingredients; b) feeding the at least one mixture obtained from step a) into a ball forming machine, wherein the ball forming machine comprises at least two forming screws, wherein the forming screws rotate about their longitudinal axis in the same direction during operation of the ball rolling machine, and the at least two forming screws are installed in the ball rolling machine such that they extend substantially in parallel with one another and with a path difference with respect to one another; c) deforming the mixture fed in according to step b) into spherical bodies by supplying the mixture of toilet rim block ingredients to at least two rotating forming screws.

2. The method according to claim 1, characterized in that the ball rolling machine has three forming screws.

3. The method according to one of the preceding claims, characterized in that the mixture obtained from step a) has a viscosity in the range of approximately 500,000 to 50,000,000 mPas, preferably in the range of approximately 1,000,000 to 25,000,000 mPas.

4. The method according to one of the preceding claims, characterized in that the method further comprises the steps of d) providing a plastics holder, preferably by means of injection molding; e) inserting the spherical toilet rim blocks obtained from step c) into the plastics holder; and optionally f) closing the plastics holder.

5. The method according to one of the preceding claims, characterized in that the mixture obtained from step a) comprises at least one, preferably at least two ingredients selected from the group consisting of perfume, surfactants, dyes, rinse regulators, bleaching agents, builders, acids and / or bases, antimicrobial active ingredients, polymers, salts, thickeners, preservatives, complexing agents, active ingredients for reducing malodors, perfume boosters, fillers, corrosion inhibitors, rinse regulators, enzymes, microorganisms, active ingredients for biofilm removal, active ingredients for inhibiting limescale deposits, active ingredients for reducing dirt adhesion, active ingredients for improving processability, and active ingredients for reducing stickiness.

6. The method according to one of the preceding claims, characterized in that the spherical toilet rim blocks are rotationally symmetrical.

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