EP1056832B1 - Corps moules a plusieurs phases presentant une division de phases optimisee - Google Patents

Corps moules a plusieurs phases presentant une division de phases optimisee Download PDF

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Publication number
EP1056832B1
EP1056832B1 EP98954404A EP98954404A EP1056832B1 EP 1056832 B1 EP1056832 B1 EP 1056832B1 EP 98954404 A EP98954404 A EP 98954404A EP 98954404 A EP98954404 A EP 98954404A EP 1056832 B1 EP1056832 B1 EP 1056832B1
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EP
European Patent Office
Prior art keywords
tablets
oxidation
bleach
substances
bleach activator
Prior art date
Legal status (The legal status 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 status listed.)
Revoked
Application number
EP98954404A
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German (de)
English (en)
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EP1056832A1 (fr
Inventor
Christian Block
Heinz-Manfred Wilsberg
Heinke Jebens
Fred Schambil
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • the present invention relates to detergent tablets which Bleach included.
  • the invention relates to moldings such as Detergent tablets, detergent tablets, bleach tablets or water softener tablets with bleach.
  • a particular problem results from the incorporation of bleaches into washing and Detergent tablets, especially when next to the bleach active ingredients and auxiliaries sensitive to oxidation are introduced into the moldings should. Due to the high density caused by a strong compression of the particulate If premixes are reached, substances that are incompatible with each other are in closer contact with each other than is the case, for example, in a loose powder. This closer contact leads to chemical intolerance of individuals Ingredients have a far more drastic effect than conventional powdery ones Means.
  • European patent application EP 481 792 (Unilever) describes detergent tablets which contain a persalt and a bleach activator, the bleach activator having to have a certain pseudo-first-order perhydrolysis constant. This document teaches that the bleach should preferably be separated from bleach destabilizing ingredients. If the bleaching agent is perborate and a di- or polyacylated amine bleach activator is used, this measure is even mandatory.
  • European patent application EP 481 793 also describes detergent tablets. These contain sodium percarbonate as a bleaching agent, which is spatially separated from all substances that can affect its stability. This document also explicitly refers to the separation of bleach and bleach activator or substances which can be attacked by bleach and thereby lead to a loss of bleaching activity.
  • European patent application EP 395 333 (Unilever) describes tableted detergent compositions which contain sodium perborate and one or more substances from the group of the di- or polyacylated amine bleach activators. Contain enzymes and optical brighteners, whereby the persalt is not separated from the substances from this group.
  • the tablets disclosed in this application are stable and have no loss of bleach or enzyme activity.
  • the present invention was based on the object of washing and To provide detergent tablets that overcome the problems mentioned.
  • the stability problems of substances sensitive to oxidation such as For example, dyes, optical brighteners, fragrances and enzymes are overcome and overcome the loss of activity of the bleach even over long periods of time become.
  • the invention now relates to two-phase or multi-phase washing and Detergent tablets made of compressed particulate washing and Cleaning agents, including builders, bleach, bleach activator (s), oxidation sensitive substances and if necessary, further detergent and cleaning agent components in which the Bleach activator (s) spatially separated from substances sensitive to oxidation in one delimited region of the molded body is / are present.
  • the detergent tablets of the present invention solve this Problem of insufficient stability of both the bleach and the Oxidation sensitive substances by adding oxidation sensitive components destroyed by the bleach and being able to "consume" the bleach, from Bleach activator be spatially separated.
  • At least one contains spatially delimited region the bleach activator and optionally other components that are not are sensitive to oxidation.
  • These non-oxidation sensitive substances come from for example from the group of builders, cobuilders, surfactants, binders, Disintegration aids and complexing agents as well as other optional ones Detergent and cleaning agent components.
  • the spatial delimitation of the bleach activator can be done in many different ways can be achieved. So the delimited region can take the form of a separate layer, one Wrapping or individual deposits, while the oxidation sensitive substances in other layers, in further wrappings or in the core or in the Main matrix of the molded body can be present. Another option is Production of comparatively large granules or extrudates Cover are protected and are distributed over the tablet or tablet.
  • a preferred embodiment of the present invention provides that the delimited region, which contains the bleach activator, not alone, but in Mixture with other non-oxidation sensitive substances.
  • preferred Detergent tablets contain the in the delimited region Bleach activator and other non-oxidation sensitive ingredients of washing and Detergents.
  • the delimited region Bleach activator and at least part of the total amount in the molded body contains builders and ionic surfactants.
  • Particularly preferred washing and Detergent tablets have a delimited region that is in addition to Bleach activator one or more substances from the group of builders, cobuilders, Contains surfactants, binders, disintegration aids and complexing agents.
  • the applicant assumes that the separation of the oxidation-sensitive substances from the bleach activator has the effect that the access of water or hydrogen peroxide to the oxidation-sensitive substances in the absence of bleach activators does not lead to a drastic destruction of these compounds. If, on the other hand, bleach activator and oxidation-sensitive substances are present within a region, under the influence of the bleach activator from migrating H 2 O or H 2 O 2, significantly more bleach-active species (for example peracetic acid) are formed, which lead to the destruction of the oxidation-sensitive compounds. Since H 2 O 2 is consumed in this way, further bleaching agent disintegrates until an equilibrium concentration of H 2 O 2 is reached again in the shaped body. This process is prevented by the separation of bleach activator and oxidation-sensitive substances, that the bleach activator does not migrate even in the molded article and that the bleach-active species that arise when bleach activator and H 2 O 2 come into contact are obviously less prone to migration.
  • bleach-active species for example peracetic acid
  • Preferred moldings are not made from a mixture of individual powders, but instead at least partially from compounds, i.e. a mixture of fewer granules.
  • the primary particles of the components are agglomerated into secondary particles that in turn are compressed into tablets.
  • the secondary particles that make up the bleach activator contain, are separated from and sensitive to oxidation sensitive substances Not to form highly bleach-active species in the vicinity of the oxidation-sensitive Substances contribute.
  • oxidation-sensitive substances are understood to mean those substances which can be oxidatively decomposed by means of H 2 O 2 or more bleach-active compounds which are formed from H 2 O 2 and bleach activators.
  • Such substances are, in particular, dyes which completely fade or change their color in an unacceptable manner, optical brighteners in which the destruction of the molecule leads to the loss of the lightening effect, fragrances which are decomposed oxidatively to odorless or even malodorous compounds and enzymes whose Oxidation products no longer show any catalytic activity.
  • oxidation sensitive substances within the scope of the present invention must be separated from the bleach activator by the bleach activator in a delimited region of the molded body is present, the oxidation-sensitive Fabrics are easily in intimate contact with the bleach, without doing so To take damage.
  • the defined region that contains the bleach activator can also additionally contain bleach, it being within the scope of the present invention it is preferred that the delimited region (which contains the bleach activator) is free of Bleach (s).
  • the delimited region which contains the bleach activator
  • the bleach can be easily mixed with the Oxidation-sensitive substances are mixed, so that detergent tablets are preferred in which bleaching agents and oxidation-sensitive Substance (s) are present together in a region of the shaped bodies.
  • the essence of the present invention requires that the molded body contain substances sensitive to oxidation, since their destruction and the resultant Loss of bleach in activity should be prevented.
  • This Oxidation-sensitive substances have already been explained in more detail above, but can also be selected from groups other than those mentioned above.
  • detergent tablets which, as substances sensitive to oxidation, contain one or more substances from the Group of dyes, optical brighteners, fragrances and enzymes included.
  • Bleach activators are incorporated into detergents and detergents to aid in washing to achieve an improved bleaching effect at temperatures of 60 ° C. and below. According to the invention, these bleach activators are located in a defined region of the Shaped body.
  • As bleach activators compounds that are under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used.
  • Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED Tetraacetylethylenediamine
  • bleaching catalysts can be incorporated into the moldings.
  • these Fabrics are bleach-enhancing transition metal salts or Transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with tripod ligands containing N and Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • substances from the group of Bleaching catalysts to bleach activators i.e. the bleaching catalysts are also in the or a delimited region of the molded body.
  • the Moldings according to the invention contain, in each case based on the total Shaped body, between 0.5 and 30 wt .-%, preferably between 1 and 20 wt .-% and in particular between 2 and 15% by weight of one or more bleach activators or Bleach catalysts. Depending on the intended use of the molded article produced these amounts vary.
  • Bleach activator contents between 0.5 and 5% by weight, preferably between 1 and 4 Wt .-% and in particular between 2 and 3.5 wt .-% usual, during Bleach tablets definitely higher contents, for example between 5 and 30 wt .-%, preferably between 7.5 and 25% by weight and in particular between 10 and 20 Can have wt .-%.
  • the expert is not free in his formulation restricted and can be more or less bleaching in this way Manufacture detergent tablets, detergent tablets or bleach tablets, by varying the levels of bleach activator and bleach.
  • a particularly preferred bleach activator is N, N, N ', N'-tetraacetylethylenediamine, widely used in detergents and cleaning agents Accordingly, preferred detergent tablets are characterized in that as the bleach activator tetraacetylethylenediamine in the above mentioned amounts is used.
  • the detergent tablets of the present invention contain one or more bleaches.
  • bleaches include sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agents are also used in varying amounts in the detergent tablets according to the invention.
  • Usual contents are between 5 and 50% by weight, preferably between 10 and 40% by weight and in particular between 15 and 35% by weight, in each case based on the entire molded body.
  • the content of these substances in the shaped bodies depends on the intended use of the shaped bodies.
  • conventional universal detergents in tablet form contain between 5 and 30% by weight, preferably between 7.5 and 25% by weight and in particular between 12.5 and 22.5% by weight of bleach
  • the contents of bleach or bleach booster tablets are between 15 and 50% by weight. %, preferably between 22.5 and 45% by weight and in particular between 30 and 40% by weight.
  • the oxidation-sensitive substances preferably originate the group of dyes, optical brighteners, fragrances and enzymes. These groups are specified in more detail below.
  • the aesthetic impression of the detergent tablets according to the invention To improve, they can be colored with suitable dyes become.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art prepares, have a high storage stability and insensitivity to the rest Inhalation substances of the means and genen light and no pronounced substantivity compared to textile fibers so as not to stain them. Since the subject of the present Invention relates to multi-phase detergent tablets, comes Coloring individual phases is of increasing importance to the different To emphasize the effect of individual phases. Examples of the effectiveness of such Colorings and for the success of statements on this are from the denture cleaner advertising well known.
  • Preferred for use in the detergent tablets according to the invention are all colorants that are oxidatively destroyed in the washing process and mixtures of these with suitable blue dyes, so-called blue toners, It has proven to be advantageous to use colorants in water or at Room temperature are soluble in liquid organic substances.
  • anionic colorants e.g. anionic nitroso dyes.
  • a possible one Colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1: Part 2: 10020), which as a commercial product, for example as Basacid® Green 970 from Fa. BASF, Ludwigshafen, is available, as well as mixtures of these with suitable blue Dyes.
  • Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260). Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E.
  • colorants When choosing the colorant, care must be taken to ensure that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. In the case of colorants which are readily water-soluble, for example the above-mentioned Basacid® green or the above-mentioned Sandolan® blue, colorant concentrations are typically selected in the range from a few 10 -2 to 10 -3 % by weight.
  • the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 -3 to 10 -4 % by weight.
  • the moldings can be optical brighteners as oxidation-sensitive substances
  • Type of derivatives of diaminostilbenedisulfonic acid or its alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed connections that instead the morpholino group a diethanolamino group, a methylamino group, a Wear anilino group or a 2-methoxyethylamino group. Can continue Present brighteners of the substituted diphenylstyryl type, e.g.
  • the optical brighteners are in the invention Detergent tablets in concentrations between 0.01 and 1% by weight, preferably between 0.05 and 0.5% by weight and in particular between 0.1 and 0.25 % By weight, based in each case on the entire shaped body.
  • Fragrances are added to the agents according to the invention in order to improve the aesthetics Improve impression of the products and the consumer in addition to the softness performance a visually and sensorially "typical and distinctive" product is available put.
  • perfume oils or fragrances individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and type Hydrocarbons are used. Fragrance compounds are of the ester type e.g.
  • the ethers include, for example, benzyl ethyl ether and the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
  • the ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone
  • the hydrocarbons mainly include terpenes such as limonene and pinene.
  • mixtures of different fragrances are preferably used, which together create an appealing fragrance.
  • perfume oils can also contain natural fragrance mixtures as they are available from plant sources are, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
  • 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 content of the inventive washing and Detergent tablets on Duris up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials have become
  • cyclodextrins have proven to be the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to prevent them from premature decomposition protect.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the Shaped bodies according to the invention can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight.
  • spatial separation is understood to mean that the separate layer, covering or individual insert which contains the bleach activator is completely free of the oxidation-sensitive substances mentioned.
  • this can be achieved, for example, by producing a separate secondary granulate which, in addition to the bleach activator, contains only substances which are not sensitive to oxidation and which, after mixing with other constituents and / or compounds, is pressed to give shaped articles.
  • the production of a two- or multi-layer tablet in which only one layer contains bleach activator is also conceivable. Oxidation-sensitive substances can then be used in the other layer (s).
  • the delimited region of the shaped bodies is in the form of a separate layer, an envelope or individual inserts, the embodiment as a multilayer shaped body being particularly preferred.
  • the individual phases of the molded body can have different spatial shapes within the scope of the present invention.
  • the simplest possible implementation is in two- or multi-layer tablets, each layer of the shaped body representing a phase.
  • ring core tablets coated tablets or combinations of the above-mentioned embodiments are possible, for example.
  • Examples of multi-phase moldings can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks.
  • the currently most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet.
  • the washing and Detergent tablets contain other ingredients, the amounts of which vary according to Align the intended use of the molded body. So are especially fabrics from the Groups of surfactants, builders and polymers for use in the Detergent tablets according to the invention are suitable. The professional there will be no difficulties here either, the individual components and their To select quantities. So a universal detergent tablet becomes larger quantities of surfactant (s) contained, while in the case of bleach tablets on their use may even be dispensed with entirely. Also the amount of builder (s) that used varies depending on the intended use.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 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, 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, 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 disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
  • Amorphous sodium silicates with a Na 2 O: SiO 2 modulus from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which are delayed in dissolution and have secondary washing properties, can also be used.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by 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 provide 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 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 (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula Na 2 O.
  • zeolite can be used both as a builder in a granular compound and as a kind 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 Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate.
  • the amount of builders is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. Again, the amount of builders used depends on Intended use, so that bleach tablets higher amounts of builders may have (for example between 20 and 70 wt .-%, preferably between 25 and 65 wt .-% and in particular between 30 and 55 wt .-%), for example Detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight us in particular between 17.5 and 37.5% by weight).
  • 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.
  • Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view.
  • the total surfactant content of the shaped bodies is 5 to 60% by weight, based on the weight of the shaped body, with surfactant contents above 15% by weight being preferred
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent ones receives alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained.
  • Preferred sulfonated fatty acid glycerol esters are Sulfation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.
  • alkali and, in particular, the sodium salts of the sulfuric acid semiesters of the C 12 -C 18 fatty alcohols are used as alk (en) yl sulfates.
  • alk (en) yl sulfates Myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are 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. used.
  • 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 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 including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
  • 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 can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • 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.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic Surfactants used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or preferably according to that in international patent application WO-A-90 13533 described methods are produced.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I). in the RCO for an aliphatic acyl radical having 6 to 22 carbon atoms.
  • R 1 represents hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] stands 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). in which 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 and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.
  • 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
  • [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 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.
  • detergent tablets are shaped preferred which contain anionic (s) and nonionic (s) surfactant (s), wherein application technology advantages from certain proportions, in which the individual classes of surfactants can be used.
  • detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10. is preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • An embodiment of the present invention therefore provides that at least one phase the molded body is free of nonionic surfactants.
  • the content of individual phases or the entire phase can also be used Molded body, i.e. all phases, achieved a positive effect on certain surfactants become.
  • the introduction of the alkyl polyglycosides described above has proven to be proven to be advantageous, so that detergent tablets are preferred, in which contains at least one phase of the shaped body alkyl polyglycosides.
  • tablet disintegrants it is possible to facilitate the disintegration of highly compressed moldings. Incorporate disintegration aids, so-called tablet disintegrants, to reduce disintegration times. According to Römpp (9th edition, vol. 6 p. 4440) and Voigt "Textbook of pharmaceutical technology" (6, edition, 1987, p. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for the rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
  • Disintegration aids are, for example, carbonate / citric acid systems, wherein other organic acids can also be used.
  • overflowing Disintegration aids are, for example, synthetic polymers such as Polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as Cellulose and starch and their derivatives, alginates or casein derivatives.
  • Preferred detergent 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 aid, each based on the weight of the molded 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, is a ⁇ -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 hydroxy 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 are 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 cellulose-based disintegrant.
  • 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 compressed.
  • Detergent tablets which contain disintegrants in granular or, if appropriate, 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 PCT / EP 98/1203 (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-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.
  • microcrystalline cellulose As a further disintegrant based on cellulose or as part of it Component can be used microcrystalline cellulose.
  • This microcrystalline Cellulose is made by partial hydrolysis of celluloses under such conditions get that only the amorphous areas (about 30% of the total cellulose mass) of the Attack and completely dissolve celluloses, but the crystalline areas (approx. 70%) leave undamaged.
  • a subsequent disaggregation by hydrolysis emerging micro-fine cellulosic supplies the microcrystalline celluloses that Have primary particle sizes of about 5 microns and, for example, to granules with a average particle size of 200 microns are compactible.
  • Detergent tablets which are also a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight in each case on the weight of the shaped body are included in the scope of the present invention particularly preferred.
  • a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight in each case on the weight of the shaped body are included in the scope of the present invention particularly preferred.
  • bleach activator bleach, bleach, and oxidation-sensitive Substance
  • surfactant builder and disintegration aid
  • Detergent tablets more in detergents usual ingredients from the group of foam inhibitors, silicone oils, Anti-redeposition agents, graying inhibitors, color transfer inhibitors and Corrosion inhibitors included.
  • the detergent tablets can also contain components contain, which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly with an inventive Detergent containing this oil and fat-dissolving component has been washed.
  • the preferred oil- and fat-dissolving components include, for example, nonionic Cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 up to 15 wt .-%, based in each case on the nonionic cellulose ether, and that from the Polymers of phthalic acid and / or terephthalic acid known in the prior art or, of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these.
  • the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.
  • Preferred detergent tablets in the context of the present invention are made by compressing particulate premixes at least one surfactant-containing granulate and at least one subsequently admixed powdery component obtained.
  • the surfactant-containing granules can using conventional granulation processes such as mixer and plate granulation, Fluid bed granulation, extrusion, pelleting or compacting become. It is for the later detergent tablets from Advantage if the premixes to be pressed have a bulk density that corresponds to the usual compact detergent comes close. In particular, it is preferred that that be compressing premix a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular above 700 g / l.
  • Another advantage can from a narrower particle size distribution of the surfactant granules used result.
  • washing and Preferred detergent tablets in which the granules have particle sizes between 10 and 4000 ⁇ m, preferably between 100 and 2000 ⁇ m and in particular have between 600 and 1400 ⁇ m.
  • the premix with finely divided surface treatment agents be "powdered”. This can affect the nature and physical properties of the premix (storage, pressing) as well as the finished washing and Detergent tablets can be advantageous.
  • Fine powdering agents are in the State of the art, mostly zeolites, silicates or other inorganic Salts are used.
  • the premix is preferred with finely divided zeolite "powdered", with zeolites of the faujasite type being preferred.
  • the term "faujasite type zeolite” denotes all three Zeolites that form the faujasite subgroup of the zeolite structure group 4 (compare Donald W.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with others Zeolites, which do not necessarily have to belong to the zeolite structure group 4, are as Powdering agent can be used, it being advantageous if at least 50% by weight of the Powdering agent consist of a zeolite of the faujasite type.
  • detergent tablets are shaped preferred, which consist of a particulate premix, the granular Contains components and subsequently mixed powdery substances, the or one of the subsequently mixed powdered components is a zeolite from Faujasite type with particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and is in particular below 5 ⁇ m and is at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be pressed accounts.
  • the finely divided processing components with the above-mentioned particle sizes can be dry mixed into the premix to be pressed. But it is also possible and preferred, by adding small amounts of liquid substances to the "Glue" the surface of the coarser particles.
  • These powdering processes are in State of the art broadly described and familiar to the expert.
  • a liquid Components that are suitable for promoting adhesion of the powdering agents can for example nonionic surfactants or aqueous solutions of surfactants or others Detergent and cleaning agent ingredients are used.
  • the moldings according to the invention are first produced by dry means Mixing the components of the individual phases, the whole or partially pre-granulated and subsequent information, in particular compression into tablets, being based on conventional processes for producing multiphase moldings can be used.
  • the premixes are molded in a so-called die between two Stamping compressed to a solid compressed. This process, briefly below called tableting, is divided into four sections: dosage, Compression (elastic deformation), plastic deformation and ejection.
  • the tableting takes place in commercially available tablet presses, which in principle include Single or double stamps can be equipped. In the latter case, not only the upper stamp is used to build up pressure, the lower stamp also moves during the pressing process towards the upper punch, while the upper punch is down suppressed.
  • Eccentric tablet presses are preferred for small production quantities used, in which the stamp or stamps are attached to an eccentric, the in turn is mounted on an axis with a certain rotational speed. The Movement of this ram is with the operation of a usual four-stroke engine comparable. The pressing can be done with an upper and lower stamp However, several stamps can also be attached to an eccentric disc, the Number of die holes has been expanded accordingly.
  • the throughputs of Eccentric presses vary from a few hundred to a maximum of 3000 tablets depending on the type per hour.
  • rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle.
  • the number of matrices varies between 6 and 55, depending on the model, with larger ones as well Matrices are commercially available.
  • Each die on the die table is a top and Assigned lower stamp, whereby again the pressure is active only by the upper or Lower stamp, but can also be built up by both stamps.
  • the Matrix table and the stamp move around a common vertical Axis, the stamp with the help of rail-like cam tracks during circulation in the positions for filling, compression, plastic deformation and discharge to be brought.
  • Rotary presses can also be used with two or more to increase the throughput Filling shoes are provided. For the production of two-layer and multi-layer molded articles several filling shoes are arranged one behind the other without the slightly pressed the first layer is ejected before further filling.
  • suitable Process control can also be used to produce coated tablets and tablets have an onion-shell-like structure, the in the case of the point tablets Top of the core or core layers is not covered and therefore visible remains.
  • Rotary tablet presses are also available with single or multiple tools can be equipped so that, for example, an outer circle with 50 and an inner circle with 35 Bores can be used for pressing at the same time.
  • the throughputs are more modern Rotary tablet presses are over one million tablets per hour.
  • Suitable tableting machines are within the scope of the present invention for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am Lake. KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU).
  • the hydraulic one is particularly suitable Double printing press HPF 630 from LAEIS, D.
  • the moldings can be in a predetermined spatial shape and a predetermined size are manufactured, whereby they always consist of several phases, i.e. Layers, inclusions or cores and rings. Practically all of them come in useful form manageable configurations into consideration, for example training as a blackboard, the rod or bar shape, cubes, cuboids and corresponding room elements with levels Side surfaces and in particular cylindrical configurations with a circular or oval cross section.
  • This last embodiment covers the form of presentation from the tablet to compact cylinder pieces with a ratio of height to Diameter above 1.
  • the portioned compacts can each be separated Individual elements can be formed, the predetermined dosage of the washing and / or Corresponds to detergent. But it is also possible. Training compacts, which connect a plurality of such mass units in one compact, wherein the easy separability in portions by predetermined predetermined breaking points smaller units is provided.
  • the portioned compacts as tablets, in cylindrical or cuboid form are expedient, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred, commercially available hydraulic presses.
  • Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it detaches itself during the induction process.
  • a metering aid where it detaches itself during the induction process.
  • the detergent tablets are easily possible via a dosing aid.
  • Another preferred multi-phase molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, which represent the short thin segments, broken off and can be entered into the machine.
  • This principle of the "bar-shaped" molded article detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides. For optical reasons, it makes sense to design the triangular base that connects the individual segments as one phase, while the triangle tip forms the second phase. Different coloring of both phases is particularly attractive in this embodiment.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the shaped body causes
  • D is the shaped body diameter in meters
  • t is the height of the moldings.
  • Two-phase detergent tablets which were in the form of a two-layer tablet, were produced by compressing particulate premixes. By selecting the relevant premixes, one of the two phases was colored blue, while the other phase remained white. The blue coloring was achieved on the one hand by coloring a TAED-containing phase (V1, V2), the TAED being additionally colored blue in the case of comparative example 2.
  • the bleach-containing phase was colored, while the phase containing the bleach activator remains white.
  • Table 1 The composition of the detergent tablets, based in each case on the respective phase, is shown in Table 1.
  • Detergent tablets composition [% by weight] V1 V2 E1 blueness phase white phase tab blueness phase white phase tab blueness phase white phase tab Phase tab Phase fraction [%] 23.3 76.6 100 23.3 76.6 100 28.0 72.0 100 Na Percarbonate - 42.0 32,20 - 42.0 32,20 42.0 27.0 31,20 TAED 50.0 - 11.67 - - - 13.5 9.73 TAED - - - 50.0 - 11.67 - - - Na SKS6 5.84 5.84 5.84 5.84 5.84 3.49 4.04 5.84 3.49 4.15 NaHCO 3 16.0 26.16 23,79 16.0 28.51 25.59 24.33 30.0 28.41 citric acid 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 20.0 PEG 4000 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5 3.5
  • the contact dye / bleach activator is most intense in V1 and V2, the Contact dye / bleach is most intense at E1.
  • the tablets produced were individually packed in polypropylene bags ("flow pack") and stored for 4 weeks at 30 ° C. After storage, the blue phases show the Comparative examples V1 and V2 clear and uneven bleaching and white Spots, while E1 shows a homogeneous blue phase with no significant brightening.

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Claims (9)

  1. Article moulé détergent et nettoyant à deux ou plusieurs phases, fait de produits détergents et nettoyants particulaires compactés, comprenant une ou plusieurs substances d'ossature, agent de blanchiment, activateur de blanchiment, substances sensibles à l'oxydation ainsi que le cas échéant d'autres constituants détergents et nettoyants,
    caractérisé en ce que
    le ou les activateurs de blanchiment se présentent spatialement séparés des substances sensibles à l'oxydation dans une région délimitée de l'article moulé.
  2. Article moulé détergent et nettoyant selon la revendication 1,
    caractérisé en ce que
    la région délimitée contient l'activateur de blanchiment et d'autres constituants non sensibles à l'oxydation d'agents détergents et nettoyants.
  3. Article moulé détergent et nettoyant selon l'une des revendications 1 ou 2,
    caractérisé en ce que
    la région délimitée contient l'activateur de blanchiment ainsi qu'une ou plusieurs substances du groupe des agents d'ossature, coauxillaire, agent tensioactif, liant, adjuvants de désintégration et formateurs de complexes.
  4. Article moulé détergent et nettoyant selon l'une des revendications 1 à 3,
    caractérisé en ce que
    la région délimitée est pourvue d'agent(s) de blanchiment.
  5. Article moulé détergent et nettoyant selon l'une des revendications 1 à 4,
    caractérisé en ce que
    l'agent de blanchiment et la ou les substances sensibles à l'oxydation se présentent ensemble dans une région de l'article moulé.
  6. Articles moulés détergents et nettoyants selon l'une des revendications 1 à 5,
    caractérisés en ce que
    les articles moulés contiennent comme substances sensibles à l'oxydation une ou plusieurs substances du groupe des colorants, des éclaircissants optiques, des parfums et des enzymes.
  7. Articles moulés détergents et nettoyants selon l'une des revendications 1 à 6,
    caractérisé en ce qu'
    on utilise comme activateur de blanchiment la tétraacétyl éthylène diamine.
  8. Articles moulés détergents et nettoyants selon l'une des revendications 1 à 7,
    caractérisés en ce que
    la région délimitée des articles moulés possède la forme d'une couche séparée, d'un enrobage ou d'inclusions isolées.
  9. Articles moulés détergents et nettoyants selon l'une des revendications 1 à 8,
    caractérisés en ce qu'
    ils contiennent en outre un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulaire, cogranulée ou compactée, à des quantités de 0,5 à 10 % en poids, de préférence de 3 à 7 % en poids et en particulier de 4 à 6 % en poids, toujours par rapport au poids de l'article moulé.
EP98954404A 1998-02-16 1998-10-13 Corps moules a plusieurs phases presentant une division de phases optimisee Revoked EP1056832B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19806220 1998-02-16
DE19806220A DE19806220A1 (de) 1998-02-16 1998-02-16 Mehrphasen-Formkörper mit optimiertem Phasensplit
PCT/EP1998/006473 WO1999041350A1 (fr) 1998-02-16 1998-10-13 Corps moules a plusieurs phases presentant une division de phases optimisee
CA002315253A CA2315253A1 (fr) 1998-02-16 2000-08-17 Corps forme polyphase avec division optimale de la phase

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EP1056832B1 true EP1056832B1 (fr) 2002-08-28

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CA (1) CA2315253A1 (fr)
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GB9911949D0 (en) * 1999-05-21 1999-07-21 Unilever Plc Detergent compositions
DE19925518B4 (de) * 1999-06-04 2016-06-30 Henkel Ag & Co. Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit Parfüm sowie Verfahren zu ihrer Herstellung
DE19959589A1 (de) * 1999-12-10 2001-07-12 Henkel Kgaa Mehrphasige Reinigungsmitteltabletten
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US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US11407965B2 (en) * 2017-07-31 2022-08-09 Dow Global Technologies Llc Detergent additive
EP3805346B1 (fr) * 2019-10-08 2024-08-14 The Procter & Gamble Company Procédé de lavage de tissu

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Publication number Priority date Publication date Assignee Title
GB911204A (en) * 1960-07-28 1962-11-21 Unilever Ltd Bleaching compositions
DE2263939C2 (de) * 1972-07-03 1983-01-13 Henkel KGaA, 4000 Düsseldorf Zur Verwendung in perhydrathaltigen Textilwaschmitteln geeignete Bleichaktivator-Tablette
US4460490A (en) * 1980-12-18 1984-07-17 Jeyes Group Limited Lavatory cleansing blocks
AU647736B2 (en) * 1989-04-24 1994-03-31 Unilever Plc Detergent compositions
CA2053433C (fr) * 1990-10-19 1997-03-25 Michael Joseph Garvey Compositions de detergents
GB9022724D0 (en) * 1990-10-19 1990-12-05 Unilever Plc Detergent compositions

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DE19806220A1 (de) 1999-08-19
ATE222949T1 (de) 2002-09-15
EP1056832A1 (fr) 2000-12-06
CA2315253A1 (fr) 2000-10-28
JP2002503760A (ja) 2002-02-05
HUP0100816A2 (hu) 2001-08-28
CN1284990A (zh) 2001-02-21
SK12032000A3 (sk) 2001-02-12
CZ20002997A3 (cs) 2001-08-15
PL342342A1 (en) 2001-06-04
WO1999041350A1 (fr) 1999-08-19

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