WO2006010491A1

WO2006010491A1 - Method for the production of multi-phase sticks for wc cleaning

Info

Publication number: WO2006010491A1
Application number: PCT/EP2005/007700
Authority: WO
Inventors: Ronald Menke; Gerd Praus
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2004-07-22
Filing date: 2005-07-15
Publication date: 2006-02-02
Also published as: RU2007106495A; WO2006010491A8; EP1769061A1; DE102004035655A1

Abstract

The invention relates to a method for the production of solid multi-phase WC cleaning blocks consisting of at least two phases. Said method is characterised by the following steps; mixing the components for each individual phase, extruding the individual strands for the various phases, shortening the strands according to the length required for the individual blocks, combining the blocks for the various phases and fixing in a water-soluble, transparent film. As a result, only one extruder is required in the production of multi-phase WC cleaning blocks. Said blocks can be sold in the form of one product comprising one transparent container.

Description

Method for producing multi-phase sticks for toilet cleaning

The subject matter of the present application is a process for producing solid multi-phase WC cleaning blocks which consist of at least two phases.

Detergents and disinfectants have long been used in the toilet bowl under the edge of the pool (so-called rim blocks) as well as in the water tank (in- tank-biocks or cistern blocks). The formulations generally contain surfactants, disinfectants and bleaches, salts, acids, complexing agents, fillers, dyes and perfumes, Abspülregulatoren and / or other components. In the production, the ingredients are usually mixed, compressed and then extruded to Strän¬ gene. The strands are finally cut to the desired length and optionally placed in toilet bowls.

With such a toilet block or stick several effects can be achieved. The toilet bowl can be cleaned and / or disinfected, for example. Furthermore, e.g. It is also possible to inhibit unpleasant odors or fragrance with a perfume. However, the ingredients needed for these various effects are not always compatible with each other. For example, sensitive substances, such as dyes, can be attacked, for example, by antimicrobial bleaching agents; Also, the compatibility of acids or complexing agents, which are used to prevent lime, rust or urinary stone deposits, for example, with perfumes is often not given. Such multi-use toilet sticks are therefore advantageously designed as multi-phase sticks. The different phases can be equipped with different colors in order to signal the multiple benefit to the consumer as well. In this case, the different phases can be arranged either horizontally above one another or vertically next to or behind one another.

Polyphonic WC sticks have so far been produced in a single manufacturing process by co-extrusion of the different phases. The various strands are brought together immediately after extrusion, pressed together and cut.

This process is already described in EP 0 101 402 B1. There, a Reinigungs¬ and disinfectant tablet for the water tank is claimed flushing toilets, the consists of at least two mixtures containing ent incompatible substances and have the same or similar consistency, wherein the tablet is prepared by ge separately extruding the individual mixtures, joining the strands into a single strand and cutting this strand into pieces. Another claim is directed to the manufacturing process.

Furthermore, EP 1 165 740 B1 describes a toilet cleaning block comprising at least two phases, one phase of which contains a water-insoluble salt which makes up at least 50% by weight of the salt in this phase, and the second phase of which is a perfume and a water-soluble one Contains salt, wherein the salts in both phases should have the same anion. Other ingredients may also be included. The manufacturing process also claimed is the coextrusion of the two or more phases to form the block.

EP 0 791 047 B1 also describes multi-phase cleaning agent pieces for flushing toilets, which, however, are configured in such a way that one phase is enclosed by a second and, if appropriate, further phases. In this case, all phases can be extruded or extruded at least one phase and at least one further phase are poured, the latter in particular for liquid cores. If all phases are extruded, two or more extruders are needed, the strands of which are brought together and then cut, with a two-component or multi-component nozzle for the common extrusion of the phases enclosing each other can be used.

However, the process described in the prior art is technically complicated and thus expensive, since at least two extruders are needed. Furthermore, the consistency of the individual phases must be largely identical so that the corresponding composite can be achieved. The compatibility of the individual phases must also be ensured at the contact surfaces and the migration of the ingredients into adjacent phases must be as low as possible, so that neither functional nor aesthetic (due to migration of the dyes) impairments occur.

The object of the present invention was thus the development of a process for simplified production of multiphase WC sticks, which do not have the disadvantages mentioned with the same visual impression. Surprisingly, it has now been found that it is also possible, without changing the visual impression, to successively press the individual strands in a single extruder, then to shorten them and finally to bring the individual phases together and to form one piece by being blown into a water-soluble transparent film connect. Since only one extruder is needed in this case, this method represents a significant simplification. Due to the separate production of the individual phases, it is also possible to use phases with different consistency. The bond between the phases is initially weaker, since the fixation during storage is mainly caused by the water-soluble film. As a result, unwanted migration phenomena between the phases are likewise less pronounced. During use, ie when rinsing with water, the film dissolves, but at the same time the components stick together, so that there is still no separation of the phases. If necessary, additional fixing of the phases takes place through the surrounding container.

The invention therefore relates to a process for producing solid multi-phase WC cleaning block, consisting of at least two phases, characterized by the steps of mixing the components in each case for the individual phases, extrusion of the individual strands for the different phases, trimming the strands on the for the length of individual blocks, combining the blocks for the various phases and finally fixing in a water-soluble, transparent film.

With this method, a multi-phase WC stick can be obtained which has a water-soluble shell of PVAL.

Accordingly, a second subject of this invention is a multi-phase WC cleaning block which requires only one extruder to produce. This toilet cleaning block is inserted into a water-soluble polyvinyl alcohol (PVAL) film.

In order to secure the cleaning block to the toilet bowl rim, a suitable container, for example a basket, is required. So that the consumer can be made aware of the multiphase, it is expedient here a transparent container use. Through the container, the phases are fixed to each other even after the dissolution of the film surrounding the block.

Another subject of the invention is therefore a product of a multi-phase toilet cleaning block and a transparent container.

The terms "toilet block" or "block" or "toilet cleaning block", "toilet stick" or "stick" and "cleaning agent piece" and "means" are used synonymously below.

In the process according to the invention, the extrusion of the individual phases for all phases can take place successively on an extruder. In addition, it is also possible to perform the extrusion of the various phases on different extruders, parallel or zeit¬ offset.

Furthermore, it is possible to emboss the blocks of individual phases after extrusion and cutting in each case into a water-soluble, transparent film before they are merged and the finished toilet cleaning block is fixed in a water-soluble, transparent film.

Both the blocks for the individual phases and the finished multiphase WC sticks are preferably cuboidal. In this case, the phases can be arranged horizontally one above the other in the finished WC-stick, preferably in such a way that the larger longitudinal surfaces of the individual cuboids are in contact with each other, or vertically behind or next to each other, preferably in such a way that the smaller parallelepiped surfaces coincide with one another are in contact. In particular, in the latter case, it is preferable that the can length of the longer edges of the cuboids for the individual phases is not more than twice as large as that of the shorter edges. If three or more phases are combined to form a block, they can all be arranged one above the other, all next to each other or both above and next to each other. For example, in a three-phase block, two phases may be arranged next to or behind one another and rest on a third block, the dimensions of which are preferably chosen such that complete coincidence occurs on the common area with the other two phases. In particular, in the case of three-phase and multi-phase sticks, it is also possible to choose another than the cuboid shape for the individual phases, for example a three-sided one Prism or a cylinder segment. Because of the expenditure on equipment, however, parallelepiped shapes are also preferred here.

The composition of the individual phases, which together form the toilet cleaning blocks according to the invention, can be substantially the same except for the different contents of active substance. In this case, it is possible to first mix all two phases of common ingredients and to divide this base (the so-called masterbatch) before the addition of the phase-specific active ingredients.

For the production of the compositions for the individual phases, it is possible to use all substances which have hitherto been used for the production of detergent pieces for toilets. These substances include in particular surfactants, disinfectants and bleaches, salts, acids, complexing agents, fillers, dyes, fragrances, Abspül¬ regulators and plasticizers. As phase-specific active substances in the sense of this invention, above all disinfectants, bleaching agents, acids, complexing agents, dyes and fragrances are considered. Accordingly, in a preferred embodiment of this invention, these are subsequently stirred into portions of the base mixture of surfactants, salts, rinse-off regulators, plasticizers and further common constituents before the portion is extruded.

Substances which also serve as ingredients of cosmetic products are hereinafter referred to, where appropriate, according to the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds carry an INCI name in English language, plant ingredients are listed exclusively in Latin after Linne, so-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names can be found in the International Cosmetic Ingredient Dictionary and Handbook - Seventh Edition (1997), The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17th Street, NW, Suite 300, Washington, DC 20036, USA , which publishes more than 9,000 INCI names and references to more than 37,000 trade names and technical names, including related distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook assigns to the ingredients one or more chemical classes (Chemical Classes), for example Polymeric Ethers, and one or more functions, for example Surfactants - Cleansing Agents, which in turn explains it in more detail and the nach¬ following, if appropriate, also referred to.

The indication CAS means that the following sequence of numbers is a name of the Chemical Abstracts Service.

surfactants

Surfactants from all known classes, namely anionic, nonionic, cationic and amphoteric surfactants can be selected for use in the compositions according to the invention, but anionic and / or nonionic surfactants are preferably used.

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

Anionic surfactants

Anionic surfactants according to the invention may be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates and aliphatic sulfonates such as alkanesulfonates, olefinsulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lignosulfonates. Also usable in the context of the present invention are alkylbenzenesulfonates, in particular having about 12 carbon atoms in the alkyl moiety, fatty acid cyanamides, sulfosuccinates (sulfosuccinic esters), in particular sulfosuccinic mono- and di-C ₈ -C ₁₈ -alkyl esters, sulfosuccinamates, sulfosuccin amides, fatty acid isethionates, acylaminoalkanesulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates, and α-sulfofatty acid salts, acyl glutamates, monoglyceride disulfates and alkyl ethers of glyceryl disulfate.

Preferred in the context of the present invention are 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 sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands by alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, for the purposes of the present invention preferably with longer-chain alcohols. As a rule, a complex mixture of addition products of 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 the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Preferred fatty alcohol ethers are the sulfates of lower ethoxylated fatty alcohols with 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 may also be present as other alkali metal or alkaline earth metal salts, for example magnesium salts, and in the form of ammonium or mono-, di-, tri- or tetraalkylammonium salts, in the case of the sulfonates also in the form their corresponding acid, eg Dode- cylbenzenesulfonic acid.

Particularly suitable anionic surfactants are sodium cocoalkyl sulfate, sodium seα-alkanesulfonate having about 15 carbon atoms and sodium dioctylsulfosuccinate. Sodium fatty alkyl sulfates and fatty alkyl + 2EO ether sulfates having 12 to 14 C atoms have proven to be particularly suitable. Anionic surfactants, in particular fatty alcohol sulfates, are preferably used in amounts of from 10 to 50% by weight, in particular in amounts of from 15 to 30% by weight, particularly preferably from 20 to 28% by weight.

Nonionic surfactants

Nonionic surfactants in the context 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. Just- if usable, 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, in particular the glycerides, such as alkyl polyglycosides and fatty acid glucamides. Particularly preferred are the alkyl polyglycosides, in particular the alkyl polyglucosides, and the fatty alcohol polyglycol ethers.

Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols by the relevant methods of preparative organic chemistry. depending on the type of production to a. Mixture of monoalkylated, oligomeric or polymeric sugar comes. Preferred alkyl polyglycosides are alkyl polyglucosides wherein particularly preferred the alcohol is a long-chain fatty alcohol or a mixture of long-chain fatty alcohols having branched or unbranched C ₈ - to C ₈ alkyl chains and the CTigomerisierungsgrad (DP) of the sugar 1-10, preferably 1 to 6, in particular 1.1 to 3, more preferably 1.1 to 1.7, is, for example, C _8- io-alkyl-1.5-glucoside (DP of 1, 5).

Preferred fatty alcohol polyglycol ethers are ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C _8-22 -AlkO- hole with a degree of alkoxylation up to 30, preferably ethoxylated C _12-22 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 C _16-18 fatty alcohol ethoxylates with 25 EO. Nonionic surfactants, in particular fatty alcohol ethoxylates and / or alkyl polyglycosides, are preferably used in amounts of from 5 to 30% by weight, in particular in amounts of from 10 to 25% by weight, particularly preferably from 14 to 20% by weight.

Preferably, a toilet stick according to the invention contains anionic and / or nonionic surfactants in a total amount of from 20 to 60% by weight, preferably from 25 to 50% by weight, in particular from 30 to 45% by weight.

Amphoteric surfactants

The amphoteric surfactants (zwitterionic surfactants) which can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are particularly preferred within the scope of the teaching according to the invention. Suitable betaines include the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines. Alkyl and alkyl amido betaines having a carboxylate group are also called carbobetaines.

Examples of suitable betaines and sulfobetaines are the following compounds designated as INCI: almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenylamine, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, Cocamidoethyl betaines, cocamidopropyl betaines, cocamidopropyl hydroxysuccinols, coco betaines, cocp hydroxysultaines, coco / olearnoprylphenyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethyl stearyl glycinates, dihydroxyethyl tallow glycinates, dimethicones propyl PG Betaines, erucamidopropyl hydroxysultaines, hydrogenated tallow betaines, isostearamidopropyl betaines, lauramidopropyl betaines, lauryl betaines, lauryl hydroxysultaines, lauryl sultaines, milkamidopropyl betaines, minkamidopropyl betaines, myristamidopropyl betaines, myristyl betaines, oleamidopropyl betaines, oleamidopropyl Hydroxysultaines, Oleyl Betaine, Olivamidopropyl Betaine, Palmamidopropyl Betaine, Palmitamidopropyl Beetaine, Palmitoyl Carnitine, Palm Kemelamidopropyl Betaine, Polytetrafluoroethylene acetoxypropyl Betaine, Ricinoleamidopropyl Betaine, Sesamidopropyl Betaine, Soyamidopropyl Betaine, Stearamidopropyl Betaine, Stearyl Betaine, Tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undeydeamidopropyl Betaine and Wheat Germamidopropyl Betaine.

The amine oxides suitable in accordance with the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides.

Examples of suitable amine oxides are the following compounds designated as INCI: Almondamidopropylamine oxides, Babassuamidopropylamine oxides, Behenamine oxides, Cocamidopropyl Amine oxides, Cocamidopropylamine oxides, Cocamine oxides, Coco-Morpholine oxides, Decylamine oxides, Decyltetradecylamine oxides, Diaminopyrimidines oxides, Dihydroxyethyl C8-10 Alkoxypropylamines oxides, dihydroxyethyl C9-11 alkoxypropylamines oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel amines oxides, hydrogenated tallowamine oxides, hydroxyethyl hydroxypropyl C12-15 Alkoxypropylamines oxides, isostearamidopro- pylamine oxides, isostearamidopropyl morpholine oxides, lauramidopropylamides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amines oxides, minkamidopropylamides oxides, myristamidopropylamine oxides, myristamine oxides, myristyl / cetyl amine oxides, oleamidopropylamine oxides, oleamine oxides, olivamidopropylamine oxides, palmitamidopropylamine oxides, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Taliowamine Oxide, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide.

Exemplary alkylamidoalkylamines are the following gene named according to INCI Verbindun¬: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoampho- dipropionate, disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoam- phocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium coco amphodipropionate , Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipro- pionate, Disodium Laureth-5 Carboxyamphodiacetate, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-amphodiacetates lsodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium tallow, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium 85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Caprylo- amphoacetate, Sodium Caprylo- amphohydroxypropylsulf onate, Sodium Capryloamphopropionate, Sodium coconut amphoacetates, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, So¬ dium Cornamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoampho- propionate, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate , Sodium Oleoamphohydroxypropylsul- sulfonates, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, amphoacetates Stearo- Sodium, Sodium Stearoamphohydroxypropylsulfonate, pionate Stearoamphopro- Sodium, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, lenoamphoacetate Undecy- Sodium, Sodium Undecylenoamphopropionate, Sodium Wheat Germampho- acetate and Trisodium Lauroampho PG-Acetate Chloride phosphates. Exemplary alkyl-substituted amino acids are the following INCI compounds: Aminopropyl Laurylglutamine, Cocaminobutyric Acid, Cocaminopropionic Acid, DEA Lauraminopropionate, Disodium Cocaminopropyl Iminodiacetate, Disodium Dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine , Lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 Alkoxypropyl Iminodipropionate, Sodium Cocaminopropionate, Sodium Lauramine Propionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA Myristaminopropionate.

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids, which bear on the amino acyl residue RCO to a saturated or ungesättig¬ th fatty acid RCOOH, wherein R is a saturated or unsaturated C _6-22 alkyl, preferably C _8- ₈ i Alkyl, in particular a saturated Ci _O -i _6- Alkylrest, for example a saturated Ci _2- i _4- Alkylrest is. The acylated amino acids can also be used as alkali metal salt, alkaline earth metal salt or alkanolammonium salt, for example mono-, di- or triethanolammonium salt. Exemplary acylated amino acids are the acyl derivatives summarized in accordance with INCI under amino acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.

Abspülregulatoren

The substances designated as rinse-off regulators serve primarily to control the consumption of the agents during use in such a way that the intended service life is maintained. Preferred regulators are 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 having molecular weights between 10,000 and 50,000. In general, not more than 25% by weight is used Abspülregulatoren required in the individual phases, preferably the WC sticks contain up to 15 wt .-% of Abspülregulatoren, in particular between 5 and 12 wt .-%, each based on the individual phases. The nature and amount of Abspülregulato¬ Ren may be different in the individual phases of the inventive compositions. However, the flushing regulators are preferably part of the common base mass and accordingly contained in all phases in the same manner and in equal parts. plasticizers

Plasticizers serve primarily to give the detergent compositions a plasticity suitable for the formation of the pieces. These are high-boiling organic substances which are liquid at the processing temperature. Suitable plasticizers are, for example, paraffin oils, 1,2-propylene glycol, silicone oils, phthalic esters, terpenes and dihydroabietic acid esters. Preference is given to using dihydro-abietic acid methyl ester, diethyl phthalate and dibutyl phthalate. Since the function of the plasticizers can in many cases be taken over by other constituents of the compositions, above all by the perfume oils, but also by nonionic surfactants or liquid acids, their presence is only necessary in a few cases. They are then used in amounts of up to 15 wt .-%.

salts

The addition of inorganic salts can also influence the consistency and the rinsing behavior of the cleaning agent pieces, but this component also improves the homogeneity of the pieces in critical cases. The salts can further enhance the cleaning action of the surfactants by means of electrolytes and as buffers, and they can, for example, the polyphosphates, act as hardness-binding agents. The salts used are generally the alkali metal or ammonium salts of mineral acids, if appropriate in hydrated form. Preference is given to using the sodium salts of sulfuric acid, phosphoric acids, carbonic acid and hydrochloric acid, in particular sodium carbonate and sodium sulfate. They are used in amounts of up to 50% by weight, preferably in amounts of from 10 to 40% by weight, in the individual compositions, and here too the nature and amount in the individual component compositions can be different.

fillers

Fillers, which may also be insoluble in water, such as cellulose powder, act, inter alia, as volume. Preferably, fillers are contained in amounts of not more than 10% by weight, in particular not more than 5% by weight.

Disinfectant and bleach

Disinfectants are verwen¬ det in the detergent pieces according to the invention, if in addition to the toilet cleanliness and a germ-inhibiting treatment is intended sicht¬. For this purpose, the produced in the process according to the invention ten WC block in one or more of the phases preferably up to 10 wt .-%, and in particular between 0.5 and 5 wt .-% Qeweil based on the weight of the phases) of antimicrobial agents. These active ingredients can come from a variety of chemical classes, but when choosing, as well as in the selection of other active ingredients and ingredients, to ensure the compatibility with the other components of the respective masses. Examples of suitable classes of active ingredients are phenols, active chlorine-releasing substances and active oxygen-containing substances. As individual examples from these classes are 1,3-dichloro-5,5-dimethylhydantoin, bromochloro-5,5-dimethylhydantoin, 1, 3-dichloro-5-ethyl-5-methylhydantoin, sodium dichloroisocyanurate, sodium percarbonate, sodium perborate (mono- and tetrahydrate ) and magnesium monoperphthalate. Other suitable disinfectants are, in particular, isothiazoline mixtures (for example: Kathon® or Bodoxin®), sodium benzoate or salicylic acid. Active chlorine-releasing substances, for example the already mentioned sodium dichloroisocyanurate, and active oxygen-containing substances, such as peroxides, peracids and perborates, can also be used as bleaching active substances in the compositions according to the invention.

complexing

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

Suitable examples are the following according to INCI complexing agents: aminotrimethylene, phosphonic acid, beta-alanines diacetic acid, calcium disodium EDTA, citric acid, cyclodextrin, cyclohexanediamines tetraacetic acid, diammonium citrate, diammonium EDTA, diethylenetriamine pentamethylene phosphonic acid, dipotassium EDTA , Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Penta- sodium Aminotrimethylene Phosphonate, Pentasodium Ethylenediamine Tetramethylene Phosphonates, Pentasodium Pentetates, Pentasodium Triphosphates, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium EDTMP, Potassium Gluconate, Potassium Polyphosphate, Potassium Trisphosphonomethylamine Oxides, Ribonic Acid, Sodium Chitosan Methylene Phosphonates, Sodium Citrate, Sodium Diethylenetriamine Pentamethylene Phosphonates, Sodium Dihydroxyethyl Glycinate , 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 ₁ Trisodium Dicarboxymethyl Alaninate, Trisodium EDTA, Trisodium HEDTA, Trisodium NTA and Trisodium Phosphate.

acids

To prevent limestone deposits and, above all, to remove old deposits from the toilet bowls, it is also possible to add acids or their water-soluble salts to the compositions prepared by the process according to the invention as optional active ingredients. Suitable acids are, for example, sulfamic acid, phosphoric acid, citric acid, lactic acid, acetic acid, formic acid and gluconic acid. Their proportion of the individual phases of the cleaning agent pieces according to the invention can be up to 30 wt .-% and is preferably between 0 and about 20 wt .-%, in particular between 5 and 15 wt .-%, based on the single phase.

dyes

The funds can further dyes (INCI Colorants) are added. Both water-soluble and oil-soluble dyes can be used here. Preferably, however, oil-soluble dyes are used, in particular when a masterbatch (a base material identical for all phases) is prepared in the process according to the invention, which is further processed to form the individual phases while admixing the phase-specific ingredients. Care must be taken in the selection of dyes to be compatible with the other ingredients in the same phase of the composition but also to ensure that they do not appear substantive to the ceramic surfaces of the toilet bowls.

Dyes preferably used are those selected from the group consisting of Solvent Yellow 114 (Disperse Yellow 54, Cl 47020;., For example, Macrolex Yellow G ^® from Lanxess, previously Bayer), Solvent Yellow 174 (for example, Sudan Yellow 172 ^® of BASF), Solvent Yellow 16 (CI 12700, eg Fat Yellow 3 G), Solvent Yellow 179 pεperse Yellow 201; for example, Macrolex ^® Yellow 6G from Lanxess, previously Bayer), Solvent Green 3 (D & C Green No. 6, Cl 61565;., for example, Macrolex ^® Green 5B from Lanxess, previously Bayer), Solvent Green 7 (Cl 59040;. for example pyranine 120% .), Solvent Blue 104 (CI 61568; example, Sandoplast Blue 2B Clariant), Acid Blue 9 (CI: 42090; example Iragon Blue ^® 9 ABL ex Ciba Specialty Chemicals) and Solvent Blue 35 (Cl: 61554; for example, fat Blue B01). Particularly preferred are Solvent Yellow 114 (Macrolex ^® Yellow G), Solvent Green 3 (Macrolex ^® Green 5 B) and Solvent Blue 104 (Sandoplast Blue 2B). Dyes are preferably added to the individual phases in amounts of not more than 1% by weight, in particular less than 0.1% by weight, particularly preferably less than 0.01% by weight. added, in each case based on the single phase.

fragrances

Another preferred active ingredient in the toilet blocks made in the process of the invention is perfume. A uniform delivery of fragrances in the funds is a particularly good perceptible advantage. The choice of suitable fragrances is essentially limited only by possible interactions with other constituents of the individual phases of the detergent pieces. The total content of fragrances in the individual phases is preferably not more than 10% by weight; In particular, it is between 1 and 8% by weight, based on the individual phase.

Other ingredients

In addition to the ingredients already mentioned, the WC sticks may contain further additives customary in lump-shaped toilet cleaners which round off the property pattern of the cleaning agents. Examples include preservatives, corrosion inhibitors or enzymes.

Water-soluble, transparent film

To wrap the toilet sticks, a water-soluble, transparent film is used. The polymer used here is preferably selected from the group comprising polyvinyl alcohol (PVAL), acetalized polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, starch and derivatives of the abovementioned substances, in particular derivatives of polyvinyl alcohol (PVAL), acetalated polyvinyl alcohol, cellulose and / or mixtures of the aforementioned polymers, with PVAL and partially hydrolyzed polyvinyl acetate being particularly preferred, in particular PVAL. Such polyvinyl alcohols are commercially available, for example under the Waren¬ Mowiol ^® ex Clariant sign (risen in the Kuraray Specialties Europe KSE). Particularly suitable in the context of the present invention, polyvinyl alcohols are, for example Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and L648, L734, Mowiflex LPTC 221 ex Clariant / KSE and under the trademark VINEX® vertriebe¬ NEN compounds of Texas polymer, for example Vinex 2034. More geeig¬ designated polyvinyl alcohols are ELVANOL ^® 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T -66, 90- 50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.) and Gohsenol ^® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH -26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK). Also the manufacturer Aquafilm Ltd. and MonoSol offer suitable water-soluble films primarily from PVAL, for example M-3030 from MonoSol LLC.

The multi-phase WC cleaning agent piece produced in the process according to the invention is introduced into a suitable container in order to be able to fasten it to the edge of the basin. For this purpose, known from the prior art toilet bowls are suitable. In order to make clear to the consumer the multiphase and thus the multiple benefits, the stick should be as visible as possible, so that advantageously a transparent basket is used.

embodiments

Three possible embodiments of two-phase toilet sticks produced according to the invention are presented below. All quantities are in wt .-%.

1. toilet stick with cleaning phase and antibacterial phase

From each phase, sticks were cut with a mass of 20g, so that the total mass of the finished toilet stick was 40g. The finished Mehphasen toilet sticks were then individually wrapped in water-soluble transparent film of polyvinyl alcohol (PVAL). The durability of these 2-phase sticks under standard conditions, i. 21 flushes per day, is 250-300 flushes.

2nd WC stick with cleaning phase and active chlorine phase

From each phase sticks were cut with a mass of 25g, so that the total mass of the finished toilet stick was 50g. The finished Mehphasen toilet sticks were then individually wrapped in water-soluble transparent film of polyvinyl alcohol (PVAL). The durability of these 2-phase sticks under standard conditions, ie 21 rinses per day, is 300-350 rinses.

3. Toilet stick with cleaning phase and lime-dissolving citric acid phase

From each phase, sticks were cut with a mass of 20g, so that the total mass of the finished toilet stick was 40g. The finished multi-phase toilet sticks were then individually wrapped in water-soluble transparent film of polyvinyl alcohol (PVAL). The durability of these 2-phase sticks under standard conditions, i. 21 flushes per day, is 250-300 flushes.

Claims

claims

1. A process for preparing solid multi-phase WC cleaning block, consisting of at least two phases, characterized by the steps a) mixing the components in each case for the individual phases b) extrusion of the individual strands for the different phases, c) truncation of the strands on the for length required for the individual blocks, d) combining the blocks for the different phases, e) fixing in a water-soluble, transparent film.

^~ 2. ^~ method according to claim 1, characterized in that the different phases of a basic mixture of the two phases common ingredients are prepared, wherein subsets of this masterbatch are then added je¬ the phase-specific ingredients.

3. The method according to claim 2, characterized in that the components used in the Grund¬ mixture, all phases common components are preferably selected from the group comprising surfactants, salts, Abspülregulatoren, plasticizers, fillers and mixtures thereof.

4. The method according to any one of claims 2 or 3, characterized in that the phase-specific ingredients are preferably selected from the group comprising dyes, fragrances, disinfectants, bleaches, Säu¬ ren, complexing agents and mixtures thereof.

5. The method according to any one of claims 1 to 4, characterized in that step b) takes place successively on an extruder for all phases.

6. The method according to any one of claims 1 to 4, characterized in that step b) for the different phases on different extruders, simultaneously or with a time delay expires.

7. The method according to any one of claims 1 to 6, characterized in that after step c) the individual blocks are each wrapped in a water-soluble, transparent film before they are brought together and fixed together.

8. The method according to any one of claims 1 to 7, characterized in that a polyvinyl alcohol film (PVAL) is used as the water-soluble, transparent film.

9. The method according to any one of claims 3 to 8, characterized in that the surfactants used are preferably selected from the group comprising anionic surfactants, in particular fatty alcohol sulfates, and / or nonionic Ten¬ side, especially fatty alcohol ethoxylates, alkyl polyglycosides and mixtures der¬ same.

10. The method according to any one of the preceding claims, characterized in that the dyes used are oil-soluble.

11. The method according to any one of the preceding claims, characterized in that - ^■ - that- are in step c) block obtained cuboid.

12. The method according to any one of the preceding claims, characterized in that the at least two phases are arranged horizontally one above the other.

13. The method according to any one of claims 1 to 11, characterized in that the at least two phases are arranged vertically one behind the other.

14. Polyphase, produced in an extrusion process toilet cleaning block, characterized in that it is produced with only one extruder.

15. Polyphonic toilet cleaning block according to claim 14, characterized gekennzeich¬ net, that it is wrapped in a water-soluble polyvinyl alcohol (PVAL) film.

16. Polyphonic toilet cleaning block according to any one of claims 14 or 15, da¬ characterized in that it contains one or more antimicrobial and / or bleaching and / or lime-dissolving active ingredients in at least one phase.

17. Product of a multi-phase toilet cleaning block according to one of claims 14 to 16 and a transparent container.