WO2017140511A1

WO2017140511A1 - Cleaning- and fragrance agent for sanitary use, and production process

Info

Publication number: WO2017140511A1
Application number: PCT/EP2017/052258
Authority: WO
Inventors: Joachim Leipold; Matthias Fritz; Antje Schirmer; Frank BRUNECKER
Original assignee: Buck-Chemie Gmbh
Priority date: 2016-02-19
Filing date: 2017-02-02
Publication date: 2017-08-24
Also published as: EP3417044A1; DE102016102949A1

Abstract

The invention relates to a cleaning- and fragrance agent for sanitary use, which comprises at least two phases, the first phase being an aggregate gel phase comprising a gelling agent, fragrance products and solvents and the second phase being a non-gel-type cleaning-agent moulded body comprising surfactants. The aggregate gel phase comprises gel sub-phases, i.e. at least one gel sub-phase of one colour A (A-gel phase) and a gel sub-phase of colour B (B-gel phase). The A-gel phase differs in colour and in at least one other physical property from the B-gel phase prior to the curing of the aggregate gel phase, or the aggregate gel phase has a colour-alteration reactant, said colour-alteration reactant being at least one chemical substance that can be converted into a coloured product or product of another colour, in particular by reacting with a reaction partner or being exposed to energy. The invention also relates to a process for the production of said agent, characterised in that the constituents of said cleaning-agent moulded body are mixed and extruded to form a hollow body in a continuous process and the hollow body is simultaneously filled with the melted gel of the aggregate gel phase by means of one or more nozzles, or the cavity is filled jointly by means of two or more nozzles with the respective melted gels of the gel sub-phases.

Description

Cleaning and perfuming preparations for sanitary purposes and

production method

The present invention relates to a piece-shaped cleaning and perfuming means for the sanitary sector, in particular for toilets, and its production method.

A large part of the known piece-shaped means are so-called "rim blocks", which are fastened in a container, in particular a basket or cage-like container, on the rim ("rim") of the toilet. The agent in the container is covered by the rinse water during each rinse. As a result, a small portion of the Rimblocks is dissolved with the release of surfactants, fragrances, etc., with each rinse, which then the desired cleaning of the toilet bowl and toilet sump and the desired scent are achieved.

The known Rimblocks consume only by the purge flow of water, and the fragrance release is dependent on the flushing of the toilet. The room scenting in the rim blocks is essentially achieved by flushing out the fragrances with the rinse water, entering the toilet sump and evaporating some of the fragrances in the toilet sump.

From DE 197 10 635 AI are piece-shaped toilet cleaning agents known that comprise gel formers, solvents and fragrances and the union with low perfume dosing a sufficient and permanent room scent even union made when no toilet flushing takes place.

A toilet cleaner comprising both a detergent tablet phase and a gel phase with a perfume are known from EP 1 418 225 B1 and EP 2 374 483 B1. With these means both the desired cleaning effect is achieved, and even with low perfume dosing, sufficient and permanent room ventilation is possible even when no toilet flushing takes place.

For the preparation of such toilet cleaning agent, a cleaning agent molding is prepared with openings or depressions, in which the liquid gel phase is introduced. The recesses may, for example, be grooves in the surface of the detergent shaped article. Also, the detergent molding can be extruded in the form of a hollow tube, in which case the liquid gel phase is filled into the interior. After cooling, the strand is then cut into individual cleaning medium discs, the outside of a detergent tablet phase and internally have a gel phase cut.

EP 1 553 162 A1 teaches a cleaning agent with a gel phase based on preferably water-insoluble polyamide resins and a cleaning agent phase. If desired, the gel phase may also contain pigments, including shimmering pigments. Toilet cleaners with gel and detergent tablet phases often have a white or colored detergent tablet phase and a different colored gel phase.

The demands of consumers on the visual effect of cleaning and fragrancing products for the sanitary sector are constantly increasing. The funds should not only cleanse and scent the room, but also be visually appealing in a modern design.

From DE 198 34 172 Al a molded body with a core is known, which may have a pH indicator.

US 2003/0003069 A teaches foaming multiphase liquid detergents and cleaners.

The object of the present invention is to provide a cleaning and perfuming agent for the sanitary sector, which meets the needs of consumers to a visually appealing, special design and g leichzeitig inexpensive to produce.

This object is solved by the features of claim 1. According to the invention, in addition to the detergent tablet phase, the detergent has an overall gel phase which, in a first variant of claim 1, consists of at least two partial gel phases of different color, namely a partial gel phase of color A (hereinafter A gel phase) and a partial gel phase of color B (hereinafter B gel phase). wherein the A-gel phase differs from the B-gel phase before curing of the total gel phase in at least one physical property.

The different physical property of the differently colored partial gel phases causes, in the case of a heterogeneous total gel phase, the partial gel phases to not completely mix during the curing process and, in the case of a homogeneous total gel phase, at least in some areas separates again before the solidification into the differently colored partial gel phases, so that different colored areas of the Total gel phase can be obtained. Because the partial gel phases differ not only in color but also in a physical property, a force counteracting homogenization acts in the total gel phase.

Is from the two A and B gel phases z. B. obtained by co-spraying total gel phase heterogeneous, so despite the diffusion and other mixing phenomena in the Gesamtgelphase by the different union physical properties partially a certain separation of the A and B gel phases is obtained. However, these forces which counteract homogenization are superimposed by the "homogenizing" processes, the diffusion, the stirring processes caused by the injection, etc.

As a result of these processes, the partial gel phase A slowly passes into the partial gel phase B, since two counteracting processes take place, in particular in the region of the phase boundaries. After the initially liquid total gel phase cools down progressively, transport and diffusion processes in the total gel phase become increasingly difficult, i. H . the partially separated and partially mixed A- and B-Teilgelphasen be "frozen" in this form, where by an attractive watercolor-like color gradient is achieved.

If the differently colored partial gel phases are supplied in the form of a heterogeneous total gel phase mixture during the filling process, then the different physical properties of the two partial gel phases prevent them from completely mixing together during the filling process and a homogeneous monochromatic phase is produced.

If the differently colored partial gel phases are supplied in the form of a homogeneous total gel phase mixture during the filling process, then the different physical properties bring about a partial separation of the differently colored partial gel phases. However, after the melt of the total gel phase cools, there is no complete separation of the total gel phase into two sharply separated partial gel phases. Rather, the fact that the Teilgelphasen segregate somewhat due to the physically different properties, the segregation, however, more difficult with increasing cooling As the viscosity increases and separation becomes difficult, a color transition between the A and B phases is achieved, which is optically very attractive.

Both in the case of a heterogeneous as well as in the case of a homogeneous total gel phase can thus be filled with one phase, namely the total gel phase, cavities in the detergent tablet phase, which can be achieved in a simple manner by the different colored Teilgelphasen after solidification an attractive appearance.

As a result of the addition of the total gel phase, the metering rate of the total gel phase and due to diffusion processes, a certain thorough mixing of the partial gel phases takes place, optically very appealing soft watercolor-like color gradients are achieved with a multiplicity of intermediate colors.

In the context of the present invention, a color gradient is understood to mean that the extinction measured over the surface of the total gel phase changes continuously in an absorption band, i. that the extinction at any edge of the total gel phase is different from the extinction at another edge of the total gel phase and the absorbance does not change abruptly.

Since according to the invention only one liquid total gel phase has to be added in order to produce a multicolored agent, the preparation can be carried out in conventional systems. This eliminates the need for complex conversions of manufacturing machines, as would be the case when filling with two separate colored gel phases.

The composition according to the invention is thus easy to prepare, since the preparation with a gel phase mixture in a conventional apparatus can be carried out continuously and not two separate gel phases must be filled with a time delay.

The two partial gel phases have a different color if the colors of the partial gel phases differ or a partial gel phase phase has a color and the other partial gel phase is not absorbed in the visible, that is not colored.

In the context of the present invention, a total gel phase is understood to mean any phase which at least partially also contains gels or is a gel and which comprises at least one gelling agent, a perfume and a solvent. An overall gel phase in the context of the present invention is also present if the partial gel phases from different nozzles are nevertheless injected together into the cavity of the detergent tablet phase.

Detergent tablets are understood to mean a solid body which is preferably obtained by extrusion, compression or solidification from a melt in accordance with the customary production methods of

Rimblocks is made. Detergent tablets may be, for example, an extruded detergent tablet or a soap phase.

In order to achieve or maintain the desired partial separation of the two A and B gel phases, the differences in physical properties that cause separation or counteract homogenization must be in the temperature range between the fill temperature of the molten total gel mixture and the cooled one Total gel phase exist. In the context of the present invention, this temperature range is referred to as "before solidification." After solidification, the agent is cut-resistant.

The separation of the partial gel phases or maintaining their heterogeneity can be done on the basis of different physical properties.

The different physical properties of the A and B gel phases should allow under the respective conditions at least partial phase separation or maintain a partially existing phase separation by counteracting the different physical properties of a diffusion-controlled homogeneous mixing of the A and B gel phase. In principle, the liquid total gel phase can be introduced into the hollow space in the cleaning agent body as a heterogeneous mixture of the two part-phases, the heterogeneity of which being substantially maintained around the different physical properties. Also, a homogeneous colored total gel phase can be filled, which then separates in the course of cooling due to the different union physical properties in a heterogeneous mixture of the two sub-phases.

The A and B gel phases may preferably differ, for example, in terms of density, viscosity, physical state, solubility, magnetic and / or electrical properties and / or their hydrophilicity and / or their internal energy or entropy. Also, it is sufficient if the temperature dependence of the respective physical size of the A gel phase and B gel phase differs, i. H . when the respective physical property changes differently with the temperature in the A-gel phase than in the B-gel phase. This also allows a partial separation into different colors can be achieved.

In a first preferred variant, the difference Liche physical property is the density, the partial gel phase of the color A has a higher density than the partial gel phase of the color B. Both partial gel phases are added together as a liquid total gel phase, for example, by injecting the two partial gel phases through two nozzles into the feed tube for the total gel phase. Due to the different densities, the lighter partial gel phase B tends to be in the upper part of the feed tube and the heavier partial gel phase A tends to be in the lower part of the feed tube, due to the transport speed (eg in an extrusion process) and the diffusion of the particles Gelphase a certain mixing of the colors at the boundary layer and a soft watercolor-like transition is achieved.

Different densities of the A-gel phase and the B-gel phase can be adjusted, for example, via the concentration of individual ingredients, for example via a different perfume content in the two phases. Likewise, the two phases in the Art and / or amount of the solvent or solvents and / or the type and / or amount of the gelling agent.

Preferably, the density difference between the A gel phase and the B gel phase is between 2% and 50%, preferably between 5% and 30% and most preferably between 7% and 15%.

The larger the difference between the densities (or other physical property) of the individual gel phases is set, the sharper the color transitions between the individual phases can be made.

Additional interesting optical effects may result from the temperature difference between the areas in the middle of the total gel phase and the outer areas adjacent to the detergent tablet phase. The outer regions cool faster after casting the Gesamtgelphase to the solidification temperature, so that the gel phases in the middle can separate longer.

In addition, special sintering processes can be incorporated during the cooling process or temperature profiles can be run during the cooling process.

According to the invention, the A-gel phase and the B-gel phase may also have different solidification temperatures or be combined at different temperatures.

A particularly preferred variant of different tempered partial gel phases is that a partial gel phase A is cured at room temperature and divided into small pieces combined with a liquid hot Teilgelphase B. It has been found that, due to differences in the state of aggregation and different viscosities of the partial gel phases, it is possible to produce further optically appealing effects in the total gel phase, namely areas with a crystal-like structure which partly run along the edges and change into transparent areas of different colors. This is achieved, inter alia, by the fact that due to the liquid and therefore hotter partial gel phase B, the surface of the Partial yellow phase A is dissolved, so that in turn creates a color gradient.

The average particle size of the divided pieces of the partial gel phase A is preferably between 1 × 10 × 10 mm and 10 × 10 × 10 mm, preferably about 5 × 5 × 5 mm, whereby the pieces can not be cube-shaped but of course also be shaped differently.

In a modification of the variant with the divided solid gel pieces, the total gel phase according to claim 2 has a liquid partial gel phase of a color A (liquid A gel phase) and solid pieces of the partial gel phase A. The solid and the liquid part gel phase differ in their viscosity and in their temperature. Although they may have the same dye A, the pieces of the solidified A gel phase in the matrix of liquid A gel phase after their solidification in the optical properties differ, because the pieces produced from the solidified A gel phase are not frozen in motion and thus have other optical properties such as refraction. Thus, even with an A-gel phase formulation, when added to the total gel phase on the one hand as cold chunks and on the other hand as hot liquid A gel phase, a visually appealing interesting product can be obtained.

In a further modification of the first variant, the total gel phase according to claim 3 has a partial gel phase of color A (A gel phase) and a partial phase of color B, wherein the partial phase of color B need not be a gel phase. The properties of the A gel phase also differ from the B phase prior to curing of the total gel phase in at least one physical property, as previously explained. In such B-phase, which is not a gel phase, for example, similar to the above pieces of the solid partial gel phase A may be solid pieces of a B-phase, for example soap bar of a color B, which also on its surface as described previously by d The hot A-gel phase are dissolved, so that in the edge region of each piece of the partial gel phase B, a color gradient is achieved. In a further alternative, the partial phase of the paint B can also be a slurry of pigments in water with a thickener or other colored particles which differ from the A phase in a physical property which effects a separation. Such a B-phase portion may then be injected from a nozzle together with the A-gel phase into the cavity in the detergent tablet. Due to the different properties, for example the density, a color gradient in the total gel phase is achieved, for example, by the increased sedimentation of the pigments, such that the heavy particles in the B phase tend to migrate downwards and this state increases with the downward increasing concentration of B Phase is then frozen by the cooling total gel phase (or vice versa). This process is also superimposed by the dynamics caused by the dosing and the diffusion. As a total gel phase, a gel phase with the colored components (B phase) is obtained, which are not statistically distributed over the total gel phase after curing but show a color gradient. In contrast to the B-gel phase, such a B-phase generally contains no gelling agent and also no fragrances, but in most cases solvents.

In a further modification of the first variant, two partial gel phases, the A gel phase and the B gel phase, are provided and a third partial phase C, which is not a gel phase, but which, like the B phase described above, leads to a color change of the A and / or or B-gel phase leads. For example, the partial C phase may be a peroxide solution which decolorizes the A and / or B gel phase.

The description of the B gel phase also applies accordingly to the B phase with the modification that the B phase does not have to comprise a gelling agent and no perfume, but a solvent.

All variants with the total gel phase and the partial gel phase A and the part (gel) phase B have in common that in the cooled total gel phase, the partial gel phases or the partial gel phase and the partial phase neither completely homogeneously mix nor are completely separated from each other and / or that in the Gesamtgelphase at least one color gradient, ie a change in the absorbance in the absorption band, of one Part of the gel phase A to another part (gel) phase takes place. There is thus no sharp phase change between the partial gel phase A and the gel phase B, either because the A phase migrates in one direction of the total gel phase and the B phase in the other direction, or because of the hot A-gel phase, the surface of a solid piece of another phase is dissolved, so that the color gradient extends around individual local centers or bits of the B-part (gel) phase.

According to the invention, the cleaning agent in a second variant in the Gesamtgelphase a Farbstoffumschlagsedukt on, wherein the Farbumumumschlagsedukt is at least one chemical substance, which can be converted into a colored or other colored product, for example by reaction with a reactant or by the action of energy, For example, radiation energy such as IR, UV or electron radiation.

The dyestuff transposing agents can be pH indicators, redox indicators, complex indicators, reduction- or oxidation-sensitive dyes or thermal indicators, ie substances, ie at a different pH, in the presence of a redox partner, in the presence of metal ions or complexing agents or another reactant change the color.

The reaction partner for the Farbstoffumschlagsedukt can be located in the adjoining the Gesamtgelphase detergent tablet phase, so that at the interface between Gesamtgelphase and the cleaning agent molding phase, the two reactants, the Farbstoffumschlagsedukt in the Gesamtgelphase and the reactants in the detergent mold phase, with each other to a (different ) -coloured product. As a result of the relative velocity of the total gel phase with respect to the detergent moldings phase, diffusion processes and possibly dissolution processes at the interface, colored courses around the interface area can be achieved. In addition, in another variant of the invention, the reaction partner can also be metered in separately, for example in small amounts into the total gel phase, in order to partially effect a color change, or else into the transition region between the total gel phase and the detergent tablet phase.

As Farbstoffumschlagsedukte also photosensitive substances can serve. The color of photosensitive substances is changeable by irradiation with light of suitable wavelength. After the total gel phase of the composition has cooled down and optionally cut to the desired size, each cleaning agent block can then be irradiated in the desired area of the total gel phase, for example with the aid of a stencil or aperture. In the area not covered by the stencil, a color change occurs. In this case, as a rule, no exact sharp color boundary is achieved, but rather, light scattering leads to soft transitions and color gradients.

The templates used can be any shapes, such as flowers, animals, objects or geometric patterns.

A comparable effect can be achieved with the use of thermoindicators. If an area of the total gel phase is heated after solidification and cutting with the aid of a heated stamp, a change in color occurs at the heated areas. If, for example, infrared radiation is used for heating, the diaphragms and templates already described are applicable. The stamps can be designed in any shape. In general, the temperature at which a color change is achieved is above the temperature that the total liquid gel phase has prior to filling.

In the simplest variant, the total gel phase in the variant with the Farbstoffumschlagsedukt consists of a gel phase, the gelling agent, solvents, fragrances and the Farbstoffumschlagsedukt has. In contrast to the previous variant with the two different partial gel phases with different physical properties. In this variant, the image of the differently colored areas is formed by a chemical reaction following a filling of the gel mass or a photoreaction of areas of the cured total gel phase.

I. The (total) gel phase

The total gel phase, the A gel phase and / or the B gel phase contain gel formers, fragrances and solvents.

As gel formers, for example, metal soaps of higher fatty acids, in particular the corresponding alkali metal salts such as sodium stearate or sodium oleate, can be used. In addition, other anionic surfactants are also usable, for example alkyl sulfates, alkyl ether sulfates, alkyl ether sulfonates, ethoxylated arylalkyl sulfates, α-olefin sulfonates, β-alkoxyalkanesulfonates, alkylaryl sulfonates, alkylmonoglyceride sulfates, alkylmonoglyceride sulfonates, alkyl carbonates, alkyl ether carboxylates, alkyl phosphates, alkyl ether phosphates, sulfosuccinates, sarcosinates, Octoxynol or nonoxynol phosphates, taurinates, polyoxyethylene fatty acid amide sulfates, isethionates, anionic derivatives of the polyglycol ethoxylates and / or combinations thereof, if these form gels. It is also possible to use as gelling agents nonionic surfactants, such as, for example, ethylene oxide / propylene oxide (EO / PO) block polymers, glycerin ethoxylates, partial glycerol ethoxylates, polyglycol ethoxylates, polyalkoxyalkanes, for example a mixture of alkyl (C20, C22) ethoxylate with 35 EO, alkyl (C22) -ethoxylate with 35 EO or alkyl (C16, C18) -ethoxylate with 30 EO, natural polymers ("gums") such as gum arabic, guar gum, agar agar, pectins, gelatin, Starch, sorbitol, chemically modified or derivatized natural gums such as carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, xanthan, sorbitol derivatives such as dibenzylidenesorbitol and derivatives thereof, starch derivatives such as carboxymethyl starch, hydroxyethyl starch, microbially fermented gums such as dextran, polysaccharide dB-1459 and gelling agents such as methoxypectin, propylene glycol tallowate, triethanolaminalgate, carboxy methyl guar gum, etc., and / or mixtures thereof if they form gels.

It is also possible to use polymers as gelling agents, for example polyalkoxylates (polyacrylic acid, polyacrylic acid derivatives, polymalinates, etc.), polystyrene-ethylene-butylene-styrene copolymers (SEBS), styrene-ethylene-ethylene-propylene-styrene copolymers ( SEEPS), styrene-ethylene-propylene-styrene copolymers (SEPS), styrene-ethylene-propylene copolymers (SEP) and / or combinations thereof, if these form gels.

It is likewise possible to use cationic surfactants as gelling agents, for example salts of aminated fatty acids, alkylpyridinium salts, quaternary ammonium salts, quaternary ethoxylated amines, alkylated ammonium salts, polymeric ammonium salts, arylated ammonium salts, alkylated and arylated ammonium salts, quaternary polydimethylsiloxanes, quaternary silanes and / or combinations from this, as far as these gels form.

It is also possible to use hydrophobic gel formers, for example polyamide resins, in particular ester-terminated polyamide resins, which are described, for example, in US Pat. No. 6,268,466. These resins can form gels with hydrophobic solvents, so that the gel formation with the perfume oils can take place without the addition of solvent, as described in EP 1 553 162. For these gelling agents, the fragrance concentration can be up to 60% by weight of the gel phase.

The proportion of gelling agent in the gel phase depends on the gelling agent used in each case. If metal soaps are used as gel formers, their weight percentage is between 0.5 and

25% by weight and preferably between 1.0% by weight and 20% by weight and more preferably between 1.5% by weight and 15% by weight.

When using polyalkoxyalkanes as gel formers, their proportion is between 10 and 40% by weight, preferably between 15 and 35% by weight, when using natural or synthetic "gums" preferably between 0.1 and 10% by weight are used. The fragrances contained in the (total) gel phase may be pure substances or perfume mixtures, preferably a perfume oil or perfume oil mixture. In the context of the present invention, a perfume is understood to mean a chemical substance which is pleasant to the sense of smell or a corresponding substance mixture of perfumes. No fragrance in the sense of the present invention is a volatile but unpleasant-smelling substance. The proportion of fragrances in the (total) gel phase is preferably at least 2% by weight, preferably between 6% by weight and 50% by weight and particularly preferably between 15% by weight and 35% by weight.

Another essential component of the gel phase is the solvent. In principle, an organic solvent, water or mixtures thereof can be used as solvent. In addition to water, in particular alkylene glycol alkyl ethers such as, for example, propylene glycol n-butyl ether, dipropylene glycol methyl ether or mixtures thereof are suitable as solvents. It is also possible to use as solvents C ₃ -C 5 glycols, propylene carbonates, C ₂ -C 4 -alcohols or polyalkylene glycols, preferably with 200-600-alkylene glycol units, polyalcohols, (2) -methyl-1,3-propanediol, also in mixtures of other solvents , The solvent (s) are generally polar solvents that dissolve the gelling agents. Their percentage is between 5 and 70 wt.%.

In the non-polar gelling agent from the class of polyamide resins and other more nonpolar Gelbild ner preferably nonpolar solvents or perfume oils are used as solvents.

The total content of solvents in the gel phase is determined by the amount of solvent required for the gel formation with the respective gelling agent. The total solvent content of the gel phase includes water contained in other ingredients, for example, the water content of the added foamer. If a metal soap is used as gelling agent, the total solvent content is at least 15% by weight, preferably more than 20% by weight. As the solvent, for example, 0 to 40 wt.% Water together with 0 to 50 wt.% Organic solvent, for example 20 to 25 wt.% Water and 30 to 40 wt.% Organic solvent, preferably from the group the alkylene glycol alkyl ethers, polyalcohols or perfume oils or mixtures thereof.

The concentration ranges indicated for the solvents may relate to one or more of the partial gel phases as well as to the total gel phase.

If the fragrances are liquid, the fragrance components are also included in the solvent proportions.

The dyes in the gel phases may be selected from the group of acid, mordant, disperse, natural, food, leather, direct, sulfur, vat, development, reactive, solvent dyes, basic or organic dyes which pigments, optical brightener, color development intermediates and pigments are selected.

The proportion of the dye in the gel phases should be at least 0% by weight to 10% by weight, preferably 0% by weight to 5% by weight and more preferably between 0% by weight and 1% by weight, based on the total gel phase.

For example, if the total gel phase comprises a dye donor, it may be selected from the group of metal salts such as ferric chloride or Cu (II) salts, complexing agents such as potassium thiocyanate or ammonia, redox indicators such as ferroin, which exhibits a reversible turnover or resazurin showing an irreversible envelope, or the pH indicators such as phenolphthalein / NaOH, the reducing agent such as sodium thiosulfate or the oxidizing agent such as hydrogen peroxide or sodium percarbonate.

The proportion of Farbstoffumschlagsedukts in the Gesamtgelphase is usually between 0 wt.% And 20 wt.%, Preferably between 0 wt.% And 10 wt.% And particularly preferably between 0 wt.% And 5 wt.%. The gel phase may additionally comprise one or more foaming agents, such as, for example, betaines, alkoxylated alkyl ether sulfates or lactobionic acid derivatives, for example fatty acid amidopropyl betaine having a C 5 -C 21 fatty acid moiety, for example cocoamidopropyl betaine, alkali metal or ammonium salts of lauryl ether sulfates having from 1 to 5 EO, Lactobionococylamide, Lactobionooleyl- amide, Lactobionotalgamid etc. or mixtures thereof. These foaming agents can be introduced extremely well into the gel phase. Particularly preferred is the use of liquid super-expanders, namely the betaines and the lauryl ether sulfates. If, in addition, a foamer is used in the gel phase, its proportion is preferably up to 10% by weight, preferably 3% by weight to 7% by weight.

If desired, the gel phase may further di-, oligo- or polyhydroxy compounds or their ethers such as glycol, 1,2- or 1,3-dihydroxypropane, 1,2-, 1,3-, 2,3- or 1,4-dihydroxybutane, the isomers of dihydroxyisobutane, dihydroxypentane, etc., glycerol, pentaerythritol, penta or hexahydroxy compounds or polyhydroxy ethers such as polymethylene or polypropylene glycol in a proportion of up to 20 wt.% To the formation of poorly soluble residues by To prevent dehydration of the gel, to accelerate the dissolution process and to achieve a reasonably smooth surface of the gel phase. Also, the gel phase may additionally contain preservatives, e.g. Hydroxybenzoic acid alkyl esters such as methyl or propyl hydroxybenzoate, generally between 0 and 1% by weight.

To control the dissolution rate, hydrophobicizing agents, such as, for example, coconut fatty acid monoethanolamide or other known hydrophobicizing agents, may additionally be added to the gel phase; preference is given to using 0% by weight to 10% by weight of hydrophobicizing agent. In principle, the hydrophobic perfume oils contained in the gel phase also contribute to a reduction in the dissolution rate.

Furthermore, the gel phase can contain further customary constituents, such as surfactants, in particular foaming surfactants, which do not have an excessively high wetting power, so that they are not bound to the fragrances to be released. , disinfectants or salts for controlling the dissolution rate include.

Preferably, the melting point of the gel phase - to ensure a dimensionally stable storage and transport of the agent - at least 40 ° C, preferably at least 50 ° C. By means of these minimum melting points, cooling times of the second phase required during production can be reduced prior to pouring in the gel phase.

The ratio of A-gel phase to B-gel phase in the total gel phase may be between 1:20 and 20: 1, preferably between 1:10 and 10: 1, and more preferably between 1: 2 and 2: 1.

II. The detergent tablet phase

A detergent tablet is understood to mean a solid body, which is preferably produced by extrusion, compression or solidification from a melt in accordance with the usual production processes of rim blocks.

The detergent tablet containing at least 10% surfactants is for cleaning and may contain a perfume to perfume the toilet.

The detergent tablet comprises surfactants to achieve the desired cleaning effect. These surfactants should be well wetting surfactants, thus preferably anionic or nonionic surfactants, to achieve the desired cleaning. In principle, all known anionic surfactants are suitable. The anionic surfactants used are preferably alkylbenzenesulfonates, alkyl sulfates, fatty alcohol sulfates and fatty alcohol ether sulfates. Preferably, the alkyl group or fatty acid moiety comprises between 8 and 18 carbon atoms. As alkylbenzenesulfonate, for example, sodium alkyl (C10-C13) - benzenesulfonate can be used. The use of amphoteric surfactants is also possible.

Furthermore, the detergent tablet may contain salts for the regulation of the consistency and the rinsing behavior. In general, these salts are inorganic salts, which are preferably selected from the group of the alkali and alkaline earth salts of sulfuric acids, phosphoric acids, nitrogen acids, carbonic acid, halogen acids such as HCl or mixtures thereof. The proportion of these salts in the detergent tablet may be up to 80% by weight, preferably about 20 to 50% by weight. It is particularly preferred to use as salts sodium chloride or sodium sulfate or a mixture thereof.

In addition, the detergent tablet may comprise lignin or lignin sulfonate as a filler.

The detergent tablet may further comprise extrusion aids, preferably up to a level of 15% by weight. For example, alkylpolyethylene glycol ethers having up to 40 EO, but also other known extrusion aids, such as, for example, cellulose and its derivatives, can be used as extrusion aids.

Furthermore, the detergent tablet may include dyes and pigments such as titanium dioxide, but optionally also disinfectants, preservatives, bleaches, activators, enzymes, complexing agents and acids.

If the total gel phase has a Farbstoffumschlagsedukt, the detergent molding may contain the reactant. The reactant, depending on the Farbstoffumschlagsedukt an acid, a base, a reducing agent, an oxidizing agent, a complexing agent or a metal ion. Examples of the formation of colored complexes of metal ions as Farbstoffumschlagsedukt and reactants (or vice versa) are, for example, iron (III) / thiocyanate, copper (II) / chloride (formation of green tetrachlorocuprate) or copper (II) / ammonia. Preferably, the detergent tablets should have as few congruences as possible to provide as few diffusion barriers as possible.

In addition to the surfactant-containing, generally extruded detergent tablets, the second phase may in principle also be a soap phase. However, the soap phase should then in any case in addition to the Alkancarbonsäuresalzen also include other surfactants.

In addition, the detergent tablet may in principle also be a phase comprising water-soluble or water-dispersing polymers, which comprises surfactants.

III. Compositions according to the invention

The inventive piece-shaped means may be shaped differently, for example q uaderförmig or cylindric. However, other forms are possible, such as those shown in Community Design No 748975.

Usually, the agent is shaped so that it can be introduced into a conventional, attachable to the edge of the toilet Bares Toilettenkörbchen.

In general, the agent consists of the detergent moldings whose proportion to the agent should be at least 10% by weight, preferably at least 50% by weight and more preferably at least 60% by weight.

The proportion of the total gel phase is thus at most 90% by weight, preferably at most 50% by weight and particularly preferably at most 40% by weight of the composition. The surface of the agent should consist predominantly of the detergent tablet phase, so that a maximum of 60% of the total surface area, preferably at most 50% of the total surface area, and more preferably at most 40% of the total surface area of the agent is formed by the total gel phase.

In a particularly preferred variant, the agent is cylindrical with a thickness of about 1.4 cm and a diameter of 5 cm, with the multicolor Gesamtgelphase is in the center, which is surrounded by the detergent moldings phase annular.

To prepare the composition according to the invention, the constituents of the detergent tablet are mixed and extruded in a continuous process into a hollow body, preferably in the form of an infinite tube. At the same time via one or more nozzles of the hollow body, in particular the inner cavity of the tube, with the molten gel of Gesamtgelphase or two or more nozzles each of the molten gels of Teilgelphasen filled together in the cavity. After sufficient solidification of Gesamtgelphase the agent can be cut into the desired shape.

If desired, in addition to the Gesamtgelphase also another phase can be added to the cavity.

The invention will be described in more detail below with reference to exemplary embodiments. Embodiments of various A and B gel phases

Table 1 below shows embodiments of different A and B gel phases that differ in both color and density.

Table 1

To prepare the A or B gel phases, the solid components are first melted and then the solvents and colorants are melted. Substances added. The liquid mass can then be used in the further production process.

The liquid A and B gel phases can be metered together via separate nozzles into the cavity in the detergent tablet, where they gradually separate again due to the different densities.

The density was measured by weighing a defined volume.

Exemplary embodiments of various gel phases with dye-precipitated silica

Table 2

To prepare the gels, the solid components are first melted and then the solvents and dyes and finally the Farbumschlagsedukte added. The liquid mass can then be used in the further production process. III. Exemplary Embodiments of Various Detergent Moldings (RMFK)

Table 3 To prepare the detergent tablet, all ingredients are mixed and then extruded.

IV. List of chemicals used

In the above experiments, the chemicals listed in the table below were used:

Phenolphthalein C20H14O4 Sigma Aldrich

Sodium chloride NaCl Solvay

Trisodium citrate CeHsNasO? Jungbunzlauer

Sodium sulfate Na ₂ SO ₄ Lenzing

Polyethylene glycol 6000 DS PEG 6000 Clariant

Titanium Dioxide T1O2 CSC Jäckle chemistry

V. Embodiments of the multicolor agent with A and

B gel phases of different densities with detergent tablet phase

For a first preferred embodiment, a part of the total gel phase consisting of 50% gel A and 50% of one of the gels Bl to B4 according to Table 1 and three parts of the detergent molding phase RMFK 5 from Table 3 are used. The two liquid gels A and B are injected together into the cavity located in the detergent molding.

In an alternative, the dye in gel formulation A or Bl to B4 may be omitted.

VI. Embodiments of the multicolor agent with A and

B gel phases of different viscosity and temperature

In a further preferred embodiment, the A gel phase is poured according to Table 1 and cut after solidification in approximately equal pieces with a maximum edge length of 5 mm.

The cavity of the detergent tablet according to embodiment RMFK5 in Table 3 is filled simultaneously with the pieces of the A gel phase and a liquid A or B gel phase according to Example A or B1 to B4 in Table 1.

Insofar as the agent is made up of solid particles and the hot liquid gel phase of the same formulation, eg the A gel phase, only a single formulation of the partial gel phase is required. Due to the different conditions of solidification of the solidified pieces of the A gel phase and the other solidification conditions of the moving A gel phase in the cavity, the means are characterized even when the same gel phase is used, by an appealing interesting appearance.

VII. Exemplary Embodiment of a Multicolor Agent Having a Gel Phase with a Color-Changing Primer and Reactant a) In a first variant, the alkaline composition RMFK1 from Table 3 is used as the detergent component and the gel 2 with phenolphthalein from Table 2 is used as the total gel phase. In the transition region between the total gel phase and the detergent tablet phase, the reaction of phenolphthalein with the NaOH results in a violet coloration. b) In a further variant, the RMFK 4 from Table 3 with the complex salt FeC and as the total gel phase Gel 1 with thiocyanate from Table 2 is used as detergent tablet. In the transition region between total gel phase and detergent tablet phase, a red color is obtained. C) In a further variant, the detergent tablet RMKF3 from Table 3 is used with hydrogen peroxide with gel 3 from Table 2 as total gel phase. The gel 3 comprises two different dyes, the blue oxidation-sensitive Liquitint Royale MX and the oxidation-stable quinoline yellow, the color of the gel 3 is therefore green. At the phase boundary to the detergent tablet, the sodium percarbonate oxidizes and decolorizes the oxidation-sensitive Liquitint Royale MX, so that the gel phase 3 in the edge region is colored yellow.

Claims

claims

Sanitary cleaning and perfuming means comprising at least two phases, the first phase being a total gel phase comprising gelling agents, fragrances and solvents and the second phase being a non-gelled detergent molding comprising surfactants,

characterized,

that the total gel phase comprises partial gel phases, namely at least one partial gel phase of a color A (A gel phase) and a partial gel phase of color B (B gel phase), and the A gel phase of the B gel phase before curing of the total gel phase in the color and in distinguishes at least one other physical property,

or

in that the total gel phase comprises a dye transferant, the dye transferant being at least one chemical substance which can be converted into a colored or otherwise colored product, in particular by reaction with a reactant or by the action of energy

Sanitary area cleaning and perfuming means comprising at least two phases, the first phase being a total gel phase comprising gelling agents, fragrances and solvents, and the second phase being a non-gelled detergent forming body comprising surfactants, characterized in that the total gel phase before curing comprises a liquid partial gel phase of a color A (liquid A gel phase) and solid pieces of the partial gel phase A or a partial gel phase of a color B (B gel phase).

Sanitary cleaning and scenting agent comprising at least two phases, the first phase being a total gel phase comprising gelling agents, perfumes and solvents and the second phase being a non-gelled detergent molding comprising surfactants, characterized in that the Total gel phase a partial gel phase of a color A (A gel phase) and a subphase of color B (B phase), which is not a gel phase, and the A gel phase is different from the B phase before the total gel phase is cured in the color and in at least one other physical property which causes separation and the partial phase of color B is not statistically distributed in the cured total gel phase.

4. Composition according to one of claims 1 to 3, characterized in that the differing physical property of the A gel phase and B (gel) phase, the density, the viscosity, the physical state, the solubility, the magnetic and / or electrical properties and / or the hydrophilicity and / or their internal energy and / or their entropy or else the temperature dependence of these physical quantities.

5. Composition according to one of the preceding claims, characterized in that the A-gel phase and the B (gel) phase have a different density or the A-gel phase is present in pieces.

6. Composition according to one of the preceding claims, characterized in that the ratio of A-gel phase to B (gel) phase in the total gel phase is between 1:20 and 20: 1.

7. Composition according to one of the preceding claims, characterized in that the proportion of the dye in the gel phases between 0 and 10 wt.%, Preferably between 0 and 5 wt.% And particularly preferably between 0 and 1 wt.% Is.

8. Composition according to one of the preceding claims, characterized in that in the cooled Gesamtgelphase the Teilgelphasen or the Teilgelphase and the subphase neither completely homogeneous mix nor are completely separated from each other and / or that in the Gesamtgelphase at least one color, ie a change in the extinction in the absorption band, from one region of the partial gel phase A to another part (gel) phase takes place.

9. Composition according to claim 1, characterized in that the colorant Umschlagedukt a pH indicator, redox indicator, complex indicator, a reduction- or oxidation-sensitive dye, a thermal indicator or a photosensitive substance or any other substance in the presence of the reactant the color changes, wherein the reactant may be an acid, a base, a reducing agent, an oxidizing agent, a complexing agent or a metal ion.

10. Composition according to claim 1 or claim 9, characterized in that the proportion of Farbstoffumschlagsedukts in the gel phases between 0 wt.% And 20 wt.%, Preferably between 0 wt.% And 10 wt.% And particularly preferably between 0 wt. % and 5% by weight.

11. Composition according to one of the preceding claims, characterized in that the Gesamtgelphase is substantially transparent and / or a heterogeneous mixture of the A-gel phase and the B (gel) phase is.

12. Composition according to one of the preceding claims, characterized in that the non-gelled detergent shaped article is an extruded detergent shaped article or a soap phase.

13. A process for preparing a composition according to any one of claims 1 to 12, characterized in that the ingredients of the detergent tablet are mixed and extruded in a continuous process to a hollow body, simultaneously filled via one or more nozzles of the hollow body with the molten gel of Gesamtgelphase or via two or more nozzles each of the molten gels of Teilgelphasen be filled together in the cavity.

14. The method according to claim 13, characterized in that the agent is cut to sufficient solidification of Gesamtgelphase in the desired shape.