WO2000034432A1 - Pastilles - Google Patents

Pastilles Download PDF

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Publication number
WO2000034432A1
WO2000034432A1 PCT/EP1999/009223 EP9909223W WO0034432A1 WO 2000034432 A1 WO2000034432 A1 WO 2000034432A1 EP 9909223 W EP9909223 W EP 9909223W WO 0034432 A1 WO0034432 A1 WO 0034432A1
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WO
WIPO (PCT)
Prior art keywords
core
tablets
acid
tablet according
tablet
Prior art date
Application number
PCT/EP1999/009223
Other languages
German (de)
English (en)
Inventor
Thomas Holderbaum
Hans-Josef Beaujean
Christian Nitsch
Jürgen Härer
Markus Semrau
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP99964514A priority Critical patent/EP1135458A1/fr
Publication of WO2000034432A1 publication Critical patent/WO2000034432A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0082—Coated tablets

Definitions

  • the present invention relates to laundry detergent and cleaning product tablets which permit active ingredient separation and are designed as a special case of a core-shell molded article.
  • the invention relates to moldings made of detergents and cleaning agents and detergents and cleaning aids such as, for example, dishwasher tablets, detergent tablets, detergent tablets, bleach tablets, stain remover tablets, water softening tablets and toilet cleaning tablets.
  • Detergent tablets are widely described in the prior art and are becoming increasingly popular with consumers because of their simple meterability, their low packaging volume and their aesthetic features.
  • a large number of design options for such shaped bodies are known from the prior art and from everyday life, ranging from the most varied of shapes (angular, round, etc.) and colors to multi-phase shaped bodies.
  • multilayer tablets (“two-phase tabs”), ring-core shaped bodies or core-shell tablets have been established in the prior art.
  • Dot tablets are core-shell tablets, in which the core is not enveloped by the shell in all spatial directions, but is visible on the surface of the tablet.
  • European patent application 055 100 (Jeyes Group) describes, for example, toilet cleaning tablets in designs such as tray tablets, core-shell tablets and ring-core tablets. This document describes several possible shapes in general and does not go into special geometries in the case of point tablets. Multi-phase cores are neither described nor specified in this application.
  • the European patent application 481 547 (Unilever) describes "multilayer" - detergent tablets which have the shape of a ring-core tablet which has at least three layers (inner, barrier and outer layers). In this document, which does not deal with point tablets, no statements are made regarding geometric parameters.
  • Point tablets are not widely described in the prior art, since there are special problems in their manufacture.
  • the outlay on equipment is great, since a core must first be pressed and then placed in a premix bed with the aid of a transfer and centering device, the compression of which provides the point tablet.
  • a core must first be pressed and then placed in a premix bed with the aid of a transfer and centering device, the compression of which provides the point tablet.
  • the core visible on the surface is smaller (and therefore requires a smaller matrix) than the tablet carrying the core.
  • the core must be pre-pressed into a sufficiently stable molded body in order to be able to be moved using the transfer and centering device. This reduces the adhesion between the core and the carrying tablet and in extreme cases the core can detach from the tablet.
  • point tablets have advantages that make them particularly attractive for detergent tablets: At the core, special detergent ingredients can be pre-pressed, thereby separating incompatible components. The aesthetic aspect is also not to be neglected, since point tablets have a high level of consumer acceptance due to their "fried egg structure".
  • the present invention was based on the object of providing a detergent tablet which has the shape of a tablet and is nevertheless free from the disadvantages mentioned.
  • both the technical and the aesthetic advantages of the point tablets active ingredient separation, controlled release of ingredients, optical differentiation should be further expanded.
  • the present invention relates to a detergent tablet ("point tablet”) made of compressed particulate material, comprising a core and a jacket surrounding this core, in which the core consists of at least two phases.
  • the individual phases of the at least two-phase core can have different spatial shapes in the context of the present invention.
  • the simplest possible implementation is in two- or multi-layer cores, with each layer of the core representing a phase. According to the invention, however, it is also possible to produce multiphase cores in which individual phases have the form of inclusions in (one) other phase (s).
  • ring core tablets coated tablets or combinations of the above-mentioned embodiments are possible, for example.
  • the most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet. In the context of the present invention, it is therefore preferred that the phases of the core have the form of layers, so that point tablets are preferred in which the core consists of at least two layers.
  • a two-phase core in a point tablet according to the invention can therefore preferably have a layer structure.
  • the two-layer core can be pressed into the jacket in such a way that the layer structure lies parallel to the base area of the shaped body.
  • the top layer of the core can function as a "lid" on the bottom core layer, if this is realized on the recipe side.
  • the core can also be placed in such a way that the layers run perpendicular to the base surface of the molded body. In this way, two mutually incompatible ingredients spatially in the molded body be separated from each other, but still dissolve at the same time, since the surface for water exists for both layers.
  • the core is a core-shell tablet.
  • the shell of the core first dissolves from one side (from the surface of the molded body), while the remaining sides are initially protected from water ingress by the core carrying the molded body.
  • the present invention at least two phases designed cores can shape any specification are in terms matched, thus for example a circular or elliptical senfb own '-shaped plan view of the core, with the invention it is of course also possible, three-, four-, five-, hexagonal etc. to realize cross sections or top views.
  • Another core which can be used according to the invention as a "point" can also have the shape of a two-layer ring, for example, so that a circular shaped body is similar to that shown in EP 481 547.
  • the dimension of the core inserted into the molded body is advantageously chosen so that the "webs", i.e. the areas in which only the substance of the shaped body (“shell”) enclosing the core, which is at least two-phase in accordance with the invention, are visible in the vertical section, are wide enough to ensure adequate mechanical stability.
  • Dot tablets in which the ratio of the length of the core to the length of the shaped body in total is ⁇ 0.9, preferably ⁇ 0.85 and in particular ⁇ 0.8, are preferred according to the invention
  • Analogous considerations also apply to the width of the shaped bodies, so that in preferred point tablets the ratio of the width of the core to the width of the shaped body ⁇ 0.9, preferably ⁇ 0.85 and in particular ⁇ 0.8.
  • the quotient of the width of the distance can also be used to define the width of the edge regions between the molded body edge and the beginning of the core protruding from the surface from the edge of the core to the edge of the shaped body (“web width”) and the width of the shaped body. This quotient is called "relative web width” below.
  • the relative web width is a size that is independent of the geometry of the molded body and the geometry of the core.
  • the web width In the case of a rectangular molded body with a symmetrically arranged rectangular core, the web width is constant over the entire web, in the case of a round or ellipsoidal core the web width varies, since the curvature of the core results in an increased distance from the edge of the molded body.
  • the absolute web width is the smallest distance between the core edge and the edge of the molded body.
  • the web width can have a different value for a longitudinal section through the shaped body than for a cross section.
  • Technically advantageous embodiments are, for example, round tablets with a concentrically arranged circular core (a single web width), square shape body having a round core, whose center is also at the center of the square (a web width) rectangular shaped body with a round or ellipsenfb 'shaped core, which is arranged symmetrically (depending on the design, one or two web widths) and rectangular shaped bodies with a symmetrically arranged rectangular core (depending on the design, one or two web widths).
  • relative web width is illustrated by a longitudinal section through the molded body, in which L stands for the length of the rectangular molded body, L2 for the length of the core, and L1 and L3 for the web widths.
  • Ll and L3 are identical.
  • the relative web width is the quotient of L1 and L or L3 and L. Analogous considerations apply to a cross section through the rectangular shaped body, for example, ie the width B is different from the shaped body length L.
  • the web widths and relative web widths as well as the width of the trough are analogous to the longitudinal section.
  • any length dimension can be used to determine the absolute web width, since the physical unit is divided out by forming the quotient and the relative widths are therefore dimensionless. Strictly speaking, the above information can only be used for "closed" cores. If cores according to the invention are used which have cavities in the middle, one only calculates the outer dimensions of the core for the relative web widths and does not take into account the fact that in the interior Strictly speaking, there is no core, but part of the jacket.
  • Point tablets preferred in the context of the present invention have a relative web width of less than 0.4, preferably less than 0.3 and particularly preferably less than 0.25.
  • the web width can vary depending on the absolute size of the molded body. Usually, however, the relative web width is at least 0.005, preferably at least 0.01 and in particular at least 0.015. It applies here that the relative web width is chosen to be greater the smaller the shaped body itself, in order to achieve practical and safe web widths. The person skilled in the art has no problems with the selection of the web widths, so that the minimum widths mentioned are to be understood as guide values which can be varied within the scope of the present teaching.
  • Preferred dot tablets have a square, rectangular or circular shape.
  • the cores can preferably have a square, rectangular or circular shape in plan view.
  • rectangular point tablets are produced in which the relative web widths on the longitudinal and cross-section are identical.
  • the cores can preferably be round, elliptical or rectangular.
  • the identical relative web width in the longitudinal and cross-sections leads to the absolute web widths being due to the differences between length and width are different.
  • the only exception here are the shaped bodies with a square base as a special case of a rectangle, in which the same relative widths require the same absolute widths.
  • the person skilled in the art can choose both the absolute and the relative web widths identically or differently, depending on which aesthetic impression he prefers.
  • Preferred core shapes are square, circular or elliptical cores.
  • Particularly preferred tablet tablets according to the invention are detergent tablets. It is therefore preferred according to the invention that the casing of the point tablets according to the invention contains one or more substances from the group of builders, surfactants, Contains bleaching agents, bleach activators, enzymes, pH regulators, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-deposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors.
  • Preferred ingredients of the particulate premix, into which the core of at least two phases, according to the invention, is pressed and which forms the shell surrounding the core after pressing are substances from the group of builders.
  • builders are the most important ingredients of detergents and cleaning agents.
  • the build-up tablets according to the invention can contain all builders commonly used in detergents and cleaning agents, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - the phosphates.
  • the builders mentioned can also be used in surfactant-free moldings, so that it is possible according to the invention to produce point tablets which can be used for water softening.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x +] ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and preferred values for x 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 'yH 2 O are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • Amorphous sodium silicates with a NajO: SiO 2 module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are delayed in dissolution, can also be used and have secondary washing properties.
  • the dissolution delay compared to conventional amorphous sodium silicates can be done in different ways, for example be caused by surface treatment, compounding, compacting / compaction or overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite that can be used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Coun- ter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Alkali carriers can be present as further constituents.
  • Alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium quartz carbonate, preferably being used for the purposes of this invention.
  • water-soluble builders are preferred since they generally have less tendency to form insoluble residues on dishes and hard surfaces.
  • Customary builders which can be present in the course of the production of machine dishwashing detergents according to the invention between 10 and 90% by weight, based on the premix to be pressed, for the jacket are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates.
  • Trisodium citrate and / or pentasodium tripolyphosphate are preferred for the production of moldings for automatic dishwashing and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicate and / or metasilicate.
  • a builder system containing a mixture of tripolyphosphate and sodium carbonate is particularly preferred.
  • a builder system which contains a mixture of tripolyphosphate and sodium carbonate and sodium disilicate is also particularly preferred.
  • the jacket builder surrounding the core usually contains in amounts of 20 to 80% by weight, preferably 25 to 75% by weight and in particular 30 to 70% by weight, based in each case on the Premix, the compression of which provides the jacket.
  • the premix can also contain the above-mentioned detergent substances, which are particularly important ingredients for detergent tablets.
  • the molded article to be produced different answers are possible when answering the questions as to whether and if so which surfactants are used.
  • Moldings for washing textiles can usually contain a wide variety of surfactants from the groups of anionic, nonionic, cationic and amphoteric surfactants, while moldings for machine dishwashing preferably contain only low-foaming nonionic surfactants and water softening tablets or bleach tablets are free of surfactants.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • C 9 - I3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 , 8 monoolefins with an end or internal double bond by sulfonating, are preferably used as the surfactants of the sulfonate type with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerin esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half-esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 -Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 6 alkyl sulfates and C 2 -C 15 alkyl sulfates and also C ] 4 -C 15 alkyl sulfates are preferred from a washing-technical point of view.
  • 2,3-alkyl sulfates which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • the Schwefelklasted Acidmonoester the ethoxylated with 1 to 6 moles of ethylene oxide chain or branched C 7-21 alcohols, such as 2-methyl-branched C. 9 n alcohols containing on average 3.5 mol ethylene oxide (EO) or C 12 _ 18 fatty alcohols with 1 to 4 EO, are also suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8.18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • preferred detergent tablets have a soap content which exceeds 0.2% by weight, based on the total weight of the molded article.
  • the preferred anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates, preferred detergent tablets 2 to 20% by weight, preferably 2.5 to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), based in each case on the Molded body weight included
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a linear or preferably 2-methyl branching may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include, for example, C 12 _ 14 alcohols with 3 EO or 4 EO, C 9 _ "- alcohol with 7 EO, C] 3-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C, 2nd 18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 .
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
  • the detergent tablets according to the invention can preferably contain alkylpolyglycosides, with APG contents of more than 0.2% by weight, based on the tablet as a whole, being preferred.
  • Particularly preferred detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5% by weight and in particular 0.5 to 3% by weight.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or represents an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred
  • [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • all surfactants can also be used as surfactants in the production of moldings for automatic dishwashing.
  • the nonionic surfactants described above, and above all the low-foaming nonionic surfactants are preferred for this purpose.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C 10 to C 8 , preferably between C 12 and C 16 , such as C ⁇ -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 - alcohols).
  • C 10 to C 8 the longer-chain alcohols
  • C 10 to C 8 preferably between C 12 and C 16 , such as C ⁇ -, C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 - alcohols.
  • 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 consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • final etherification with short-chain alkyl groups can also give the class of "closed" alcohol ethoxylates, which can also be used in the context of the invention.
  • Highly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
  • the jacket, individual phases of the core or the entire core can contain other conventional ingredients of detergents and cleaning agents, in particular from the groups of disintegration aids, bleaching agents, bleach activators, enzymes, fragrances, perfume - Contain carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors, corrosion inhibitors, etc. These substances are described below.
  • disintegration aids so-called tablet disintegrants
  • tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Preferred tablet tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, of one or more disintegration auxiliaries, in each case based on the weight of the shaped body.
  • Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, represents a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
  • Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but used in a mixture with cellulose.
  • the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
  • the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
  • Detergent tablets which contain disintegrants in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • Subsequent disaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m. and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
  • bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
  • bleaching agents from the group of organic bleaching agents can also be used.
  • Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimoxy acid phthalimidoxanoic oxoacid (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocyseboxyacidoxy acid, diperoxic acid, 2-Decyldiperoxybutane-l, 4-diacid
  • Chlorine or bromine-releasing substances can also be used as bleaching agents in moldings for automatic dishwashing.
  • Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromine and N- Chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid,
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated into the premix to be pressed.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylene
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof.
  • Bacterial strains or are particularly well suited Fungi such as Bacillus subtilis, Bacillus hcheniformis and Streptomyces griseus are enzymatic active ingredients.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the premix to be pressed for the production of detergent tablets may also contain components which have a positive influence on the ability to wash oil and fat out of textiles (so-called soil repellents). This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and of hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, and the polymers of phthalic acid and / or terephthalic acid or of their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the premix to be pressed can, if one wishes to produce molded textile detergent articles, contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5- triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Dyes and fragrances can be added to the premix in the process according to the invention in order to improve the aesthetic impression of the resulting products and, in addition to the softness, provide the consumer with a visually and sensorially "typical and unmistakable" product.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepyl propionate, allyl cyclohexyl propyl pionate.
  • the ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, oc -Isomethyl ionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile 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.
  • the fragrances can be incorporated directly into the premix, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance for the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the premix (or parts thereof) can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and have no pronounced substantivity towards textile fibers or dishes, in order not to stain them.
  • the premix to be pressed can be used to protect the dishes or the machine from corrosion inhibitors, silver protection agents in particular being of particular importance in the area of automatic dishwashing.
  • the known substances of the prior art can be used.
  • silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
  • Benzotriazole and or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
  • oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds.
  • Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
  • transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate.
  • Zinc compounds can also be used to prevent corrosion on the wash ware.
  • ingredients described above can be used both in the premix for the jacket and in any premix for individual phases of the core of the tablet.
  • An exemplary list of embodiments can be found below.
  • Point tablets preferred in the context of the present invention are characterized in that at least one of the phases of the core contains at least one component for solubility control.
  • solubility of individual shaped body areas or of the entire tablet can be influenced by components and / or compounds for accelerating solubility (disintegrant) or for delaying solubility.
  • disintegrants known in the prior art can be used as disintegrants. Particular reference is made to the textbooks Rompp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology” (6th edition, 1987). Substances such as starch, cellulose and cellulose derivatives, alginates, Dextrans, cross-linked polyvinylpyrrolidones and others; systems made from weak acids and carbonate-containing agents, in particular citric acid and tartaric acid in combination with hydrogen carbonate or carbonate as well as polyethylene glycol sorbitan fatty acid esters.
  • EP-A-0 466 485, EP-A-0 522 766, EP-A-0 711 827, EP-A-0 711 828 and EP-A-0 716 144 describe the production of cleaning-active tablets , where compact, particulate material with a particle size between 180 and 2000 microns is used.
  • the resulting tablets can have both a homogeneous and a heterogeneous structure.
  • EP-A-0 522 766 at least the particles which contain surfactants and builders are coated with a solution or dispersion of a binder / disintegrant, in particular polyethylene glycol.
  • binders / disintegrants are in turn the disintegrants which have already been described several times, for example starches and starch derivatives, commercially available cellulose derivatives such as crosslinked and modified cellulose, microcrystalline cellulose fibers, crosslinked polyvinylpyrrolidones, layered silicates, etc.
  • weak acids such as citric acid or tartaric acid, which in In connection with carbonate-containing sources, when they come into contact with water, lead to effervescent effects and, according to the definition according to Römpp, belong to the second class of disintegrants can be used as a coating material.
  • disintegrants whose particle size distribution (sieve analysis) is designed in such a way that a maximum of 1% by weight, preferably less, of dust components is present and overall (including any dust components present) less than 10% by weight of the disintegrant granules are smaller than 0.2 mm.
  • at least 90% by weight of the disintegrant granules have a particle size of at least 0.2 mm and a maximum of 3 mm.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are also described in German patent applications DE 197 09 991 (Stefan Herzog) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
  • the above and described in more detail in the documents cited coarser disintegration aids are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ® TF-30-HG from Rettenmaier available in the present invention.
  • the dissolution time of the entire shaped body is preferably shorter than the duration of the main wash cycle of a conventional dishwasher, i.e. shorter than 40 min, particularly preferably shorter than 30 min, very particularly preferably shorter than 20 min and extremely preferably shorter than 10 min.
  • an area of the tablet, in particular at least one phase of the core is soluble much more quickly than the rest of the shaped body.
  • This more rapidly soluble region preferably contains at least one acidifying agent.
  • suitable acidifying agents are boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • organic acidifying agents are preferably used, citric acid being a particularly preferred acidifying agent.
  • the other solid mono-, oligo- and polycarboxylic acids can also be used in particular.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are preferred from this group.
  • Organic sulfonic acids such as amidosulfonic acid can also be used.
  • Commercially available and also preferably used as an acidifying agent in the context of the present invention Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight) can be used.
  • shaped tablets and detergents in which a substance from the group of the organic di-, tri- and oligocarboxylic acids or mixtures thereof are used as the acidifying agent in the more rapidly soluble region, citric acid being particularly preferred is preferred.
  • the acidifying agents mentioned are preferably either sole component I or at least part of the same. It is therefore preferred within the scope of the present invention if at least 80% by weight, preferably more than 90% by weight, particularly preferably more than 95% by weight and very particularly preferably the total amount of the acidifying agent contained in the shaped body is faster soluble area.
  • the more readily soluble region in preferred embodiments of the present invention may contain other ingredients.
  • Other ingredients are, for example, carbonates and or bicarbonates, the use of which in combination with acidifying agents leads to gas release on contact with water, which further reduces the dissolution times.
  • Such an effervescent system can be formulated with an excess of acidifying agent, which enables an acidic pre-rinse cycle, but other ingredients can also be incorporated into the more rapidly soluble area, so that the effervescent system releases the other ingredients more quickly.
  • the dissolution time of the more rapidly dissolving area is preferably still below the values mentioned above, ie below 10 min, preferably below 5 min and in particular below 2 min.
  • the solubility control component is a solubility accelerator selected from the group of organic acids, such as. B. citric acid, or a mixture of citric acid / bicarbonate and / or the celluloses and cellulose derivatives.
  • Paraffins and / or microwaxes and / or the high molecular weight polyethylene glycols which are described in detail in the prior art, are generally customary as the material for delaying dissolution, so that point tablets according to the invention are preferred in which the component for solubility control is a solubility retarder selected from the group of Paraffins, the micro waxes and the high molecular weight polyethylene glycols.
  • the dissolution time of the entire molded body in 20 ° C. cold water is longer than the pre-rinse cycle of a commercially available dishwasher, that is to say longer than 5 min, preferably longer than 10 min.
  • a smaller area of the shaped body can be delayed in release, so that the majority of the shaped body constitutes the more rapidly soluble area.
  • Such measures to delay dissolution can only release certain ingredients, for example, only in the rinse cycle, whereby further advantages in cleaning performance can be achieved.
  • assemble at least one of the phases of the core with the aid of a solubility control component so that the corresponding ingredients of this core phase are released in a delayed or accelerated manner.
  • Dot tablets according to the invention in which the component for solubility control in a phase of the core is packaged together with one or more substances from the groups of surfactants, bleaching agents, bleach activators, enzymes or silver protection agents, are therefore preferred embodiments of the present invention.
  • the core in particularly preferred point tablets, consists of two phases sen, preferably layers, one of which contains one or more bleaching agents, while the other phase of the core contains the bleaching agent-incompatible ingredients, in particular from the groups of enzymes, bleach activators, perfumes and silver protection agents.
  • solubility control agents such as polyethylene glycols, instead of paraffin.
  • the agents according to the invention are produced by the customary methods of molding production.
  • the core is first produced by methods familiar to the person skilled in the art, in particular tableting, and then transferred with a transfer and centering device into a larger die, in which the premix for the coating of the point tablet is located.
  • the center of the ring is then filled in before the final compression to the point tablet takes place.

Abstract

L'invention concerne des pastilles, qui comparativement aux pastilles à deux phases classiques, présentent des avantages aussi bien au plan technique, qu'esthétique (séparation du principe actif, libération contrôlée des constituants, différenciation optique). Ces pastilles comprennent un noyau et une enveloppe renfermant ledit noyau, ce dernier se composant d'au moins deux phases.
PCT/EP1999/009223 1998-12-05 1999-11-26 Pastilles WO2000034432A1 (fr)

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DE19856213.6 1998-12-05
DE1998156213 DE19856213A1 (de) 1998-12-05 1998-12-05 Punkttabelle

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006070209A1 (fr) 2004-12-31 2006-07-06 Jeyes Group Limited Pastille de nettoyage de toilettes

Families Citing this family (5)

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Publication number Priority date Publication date Assignee Title
DE10062265A1 (de) * 2000-12-14 2002-07-11 Henkel Kgaa Zuführbare Tablettenkerne
DE10110886A1 (de) * 2001-03-07 2002-09-26 Henkel Kgaa Wasch- und/oder Reinigungsmittel
DE10125441A1 (de) * 2001-05-25 2002-12-05 Henkel Kgaa Verfahren und benötigte Zusätze zur Erhöhung der Stabilität von Tabletten
DE102004011256B4 (de) * 2004-03-09 2007-11-15 Henkel Kgaa Mehrphasentabletten mit verbesserter Duftwahrnehmung
DE102004051557A1 (de) * 2004-10-22 2006-04-27 Henkel Kgaa Wasch- oder Reinigungsmitteldosiereinheit

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Publication number Priority date Publication date Assignee Title
EP0055100A1 (fr) * 1980-12-18 1982-06-30 Jeyes Group Limited Blocs pour le nettoyage de toilettes
EP0481547A1 (fr) * 1990-10-17 1992-04-22 Unilever N.V. Comprimés détergents pour le lavage de la vaisselle en machine
EP0716144A2 (fr) * 1994-11-14 1996-06-12 Unilever Plc Détergent sous forme de tablette ayant un revêtement soluble dans l'eau
WO1999027069A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Pastille de detergent
DE19806220A1 (de) * 1998-02-16 1999-08-19 Henkel Kgaa Mehrphasen-Formkörper mit optimiertem Phasensplit
US5972870A (en) * 1997-08-21 1999-10-26 Vision International Production, Inc. Multi-layered laundry tablet
WO2000006688A1 (fr) * 1998-07-29 2000-02-10 Reckitt Benckiser N.V. Composition s'utilisant dans un lave-vaisselle
EP0979862A1 (fr) * 1998-08-13 2000-02-16 The Procter & Gamble Company Comprimés détergents multicouches à dureté différente

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0055100A1 (fr) * 1980-12-18 1982-06-30 Jeyes Group Limited Blocs pour le nettoyage de toilettes
EP0481547A1 (fr) * 1990-10-17 1992-04-22 Unilever N.V. Comprimés détergents pour le lavage de la vaisselle en machine
EP0716144A2 (fr) * 1994-11-14 1996-06-12 Unilever Plc Détergent sous forme de tablette ayant un revêtement soluble dans l'eau
US5972870A (en) * 1997-08-21 1999-10-26 Vision International Production, Inc. Multi-layered laundry tablet
WO1999027069A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Pastille de detergent
DE19806220A1 (de) * 1998-02-16 1999-08-19 Henkel Kgaa Mehrphasen-Formkörper mit optimiertem Phasensplit
WO2000006688A1 (fr) * 1998-07-29 2000-02-10 Reckitt Benckiser N.V. Composition s'utilisant dans un lave-vaisselle
EP0979862A1 (fr) * 1998-08-13 2000-02-16 The Procter & Gamble Company Comprimés détergents multicouches à dureté différente

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006070209A1 (fr) 2004-12-31 2006-07-06 Jeyes Group Limited Pastille de nettoyage de toilettes
AU2006203732B2 (en) * 2004-12-31 2011-04-21 Henkel Ltd Lavatory cleansing block

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