EP1051475B1 - Mehrphasige waschmitteltabletten - Google Patents
Mehrphasige waschmitteltabletten Download PDFInfo
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- EP1051475B1 EP1051475B1 EP98954380A EP98954380A EP1051475B1 EP 1051475 B1 EP1051475 B1 EP 1051475B1 EP 98954380 A EP98954380 A EP 98954380A EP 98954380 A EP98954380 A EP 98954380A EP 1051475 B1 EP1051475 B1 EP 1051475B1
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- shaped bodies
- washing
- surfactant
- cleaning composition
- weight
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- 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
Definitions
- the present invention relates to multiphase detergent tablets.
- the invention relates to multiphase detergent tablets suitable for washing of textiles used in a household washing machine and short as detergent tablets be designated.
- EP-A-0 466 485 (Unilever) describes detergent tablets which have resulted from the compression of two surfactant-containing granules.
- a granulate contains the total amount of anionic surfactants, while the second surfactant granules are preferably free of anionic surfactants.
- the present invention was based on the object, multiphase detergent tablets to provide that overcome the disadvantages mentioned.
- multi-phase detergent tablets are to be provided, which in All phases have a high hardness and a high decay and dissolution rate.
- the invention now provides two- or multi-phase detergent tablets of compacted particulate detergent and cleaner, comprising Surfactant (s), builder (s) and optionally other detergent and cleaner ingredients, in which the surfactant content of the individual phases of the molding, in each case based to the weight of each phase, by no more than 1.5 wt .-%, varies.
- the variation means not more than 1.5% by weight, based on the weight of the individual phases, that the absolute values of the surfactant content in the phases to vary by not more than 1.5 wt .-%.
- one phase contains 20% by weight Surfactant (s)
- the surfactant content of the other phase (s) must be selected so that the Width of the variation by the value 20 is at most 1.5% by weight.
- the percentage value of the surfactant content of the least surfactant phase of the percent numerical value subtracted from the surfactant content of the most surfactant phase the result must be ⁇ 1.5.
- the surfactant content of the individual varies Phases by less than 1.5 wt .-%. So are detergent and cleaner tablets preferred in which the surfactant content of the individual phases of the molding is no more as 1 wt .-%, based on the weight of the individual phase varies.
- washing and cleaning agent tablets are preferred in which the Surfactant content of the individual phases of the molding is identical.
- Products to large-scale products which at unit weights, usually Below 100 grams, produced on a ton scale, is a low Fluctuation in the surfactant content of individual phases can not be completely ruled out.
- An "identical" Tenside content in the individual phases is also within the scope of the present invention then when fluctuations of a few tenths of a percent are recorded.
- the individual phases of the shaped body can have different spatial forms in the context of the present invention.
- the simplest realization possibility lies in two-layered or multi-layered tablets, each layer of the shaped article representing one phase.
- multiphase moldings can be found in the drawings of EP-A-0 055 100 (Jeyes) which describes toilet cleaning blocks.
- the technically most widespread spatial form of multiphase moldings is the two-layer or multi-layer tablet. In the context of the present invention it is therefore preferred that the phases of the shaped body have the form of layers.
- the surfactant content of the individual Phases of the molding by not more than 3 wt .-%, based on the weight of the individual Phase, varies.
- the surfactant content is the sum of the in the relevant surfactants, regardless of which type of surfactants it is.
- Contains a phase, for example, anionic and nonionic Surfactants the total surfactant content of the phase is the sum of the amounts of anionic and nonionic surfactants.
- the surfactants can be incorporated in pure form in the individual phases of the moldings become. This is easy, for example, with soaps or other readily processible surfactants possible. For many surfactants, it is recommended not to incorporate the pure surfactants, but surfactant compounds. These compounds, depending on the application as possible should have high surfactant contents, can by conventional methods such as spray drying, Granulation or compounding are produced. Of course, too a combination of several surfactant granules or a combination of surfactant granules possible with pure surfactants.
- surfactant (s) is present over surfactant-containing (s) Granules (e) are introduced into the phases of the shaped body.
- anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. From an application point of view, mixtures are preferred anionic and nonionic surfactants.
- the total surfactant content of the moldings is 5 up to 60% by weight, based on the molding weight, surfactant contents of more than 15% by weight are preferred.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
- alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
- fatty acid glycerine esters are the mono-, di- and triesters and their mixtures to understand how they in the Preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or at the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
- preferred Sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
- Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, 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. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical having an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- 2,3-Alkyl sulfates which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
- EO ethylene oxide
- Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- anionic surfactants are particularly soaps into consideration.
- Suitable are 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 of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants including the soaps may be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
- the anionic surfactants are in the form of their sodium or Potassium salts, especially in the form of sodium salts.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols 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 of these, 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 means which, for a particular product, may be an integer or a fractional number.
- 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.
- the degree of oligomerization x, the The distribution of monoglycosides and oligoglycosides is any number between 1 and 10; preferably x is 1.2 to 1.4.
- nonionic surfactants used either alone nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533.
- 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 alkanolamide may 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 them.
- polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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 the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred
- [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy or N-aryloxy-substituted compounds can then, for example, according to the International Application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
- detergent tablets are preferred. contain the anionic (s) and nonionic (s) surfactant (s), with application technology Advantages from certain proportions, in which the individual surfactant classes used will be able to result.
- the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
- builders are the most important ingredients of Detergents and cleaners.
- detergent tablets according to the invention can all commonly used in detergents and cleaning agents Be included builders, especially zeolites, silicates, carbonates, organic cobuilders and -where there are no ecological prejudices against their use-also the phosphates.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline sheet 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 is sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of 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 Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- 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 particularly preferred.
- zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
- the zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates as builders possible, unless such use is avoided for environmental reasons should be.
- Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular the tripolyphosphates.
- Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use for environmental reasons is not objectionable, as well as 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 thereof.
- excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
- Preferred washing and cleaning agent tablets contain from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% of one or more disintegration aids, in each case based on the molding body weight.
- Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 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 is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
- Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
- Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
- the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
- the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of
- the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
- Detergents and cleaning agent tablets which contain disintegrating agents in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO 98/40463 (Henkel). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications.
- the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
- the above-mentioned coarser disintegration aids based on cellulose 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 Rettenmaier.
- Microcrystalline cellulose can be used. This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the amorphous areas (about 30% of the total cellulose mass) of the celluloses attack and complete Dissolve the crystalline areas (about 70%) but leave undamaged. A subsequent one Disaggregation of resulting from the hydrolysis micro-fine celluloses provides the microcrystalline celluloses having primary particle sizes of about 5 microns and for example be compacted into granules with an average particle size of 200 microns.
- Detergents and cleaning agent tablets which additionally contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably granular, cogranulated or compacted form, in amounts of from 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 based on the molding weight, are particularly preferred in the context of the present invention.
- a disintegration aid preferably a disintegration aid based on cellulose, preferably granular, cogranulated or compacted form, in amounts of from 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 based on the molding weight, are particularly preferred in the context of the present invention.
- preferred detergent tablets be obtained by compressing particulate premixes of at least one surfactant-containing Granules and at least one subsequently added powdered component.
- the surfactant-containing granules can be processed by conventional granulation processes such as mixing and plate granulation, fluidized bed granulation, extrusion, pelletizing or compaction getting produced. It is for the later detergent tablets advantageous if the premixes to be compressed have a bulk density, which comes close to the usual compact detergent.
- the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l.
- detergents and cleaning compositions are molded preferred in which the granules particle sizes between 10 and 4000 microns, preferably between 100 and 2000 microns and in particular between 600 and 1400 microns have.
- Another object of the present invention is therefore a process for the preparation two- or multi-phase detergent tablets, surfactant (s), builder (s) and optionally contain other detergent and cleaner ingredients, by pressing known per se, which is characterized in that they by pressing a particulate premix of at least one surfactant-containing granules and at least a subsequently admixed powdery component were obtained, wherein the surfactant content of the individual phases of the moldings, in each case based on the weight of single phase, varied by not more than 1.5 wt .-%.
- Preferred methods are characterized in that the granules over conventional Granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, Pelleting or compaction were made.
- the granules have particle sizes between 10 and 4000 microns, preferably between 100 and 2000 microns, and especially between 600 and 1400 microns.
- the particle size distribution of the subsequently admixed pulverulent processing components can be varied, with detergent tablets preference is given to those in which the subsequently admixed (n) pulverulent component (s) have the same particle size distribution as the granules used.
- the premix may contain finely divided surface treatment agents be "powdered". This may be for the texture and physical properties both the premix (storage, compression) and the finished detergent tablets be beneficial.
- Fine particulate powdering agents are in the state of Technique well known, with mostly zeolites, silicates or other inorganic salts used become.
- the premix is "powdered” with finely divided zeolite, wherein faujasite-type zeolites are preferred.
- faujasite-type zeolite denotes all three zeolites that contain the faujasite subgroup of the zeolite structure group 4 (See Donald W.
- mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily belong to the zeolite structure group 4 are as powdering agents can be used, wherein it is advantageous if at least 50 wt .-% of the powdering agent consist of a zeolite of the faujasite type.
- detergent tablets consist of a particulate premix, the granular components and contains subsequently admixed powdery substances, wherein the or one of the later to admixed powdery components, a faujasite-type zeolite having particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and especially below 5 ⁇ m and at least 0.2 wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 % By weight of the premix to be compressed.
- the finely divided treatment components with the above particle sizes can while being dry admixed to the pre-mix to be compressed. It is also possible and preferably by adding small amounts of liquid to the surface of the "stick" coarser particles.
- These powdering processes are in the state of the art broadly described and familiar to the expert.
- liquid components that are used for bonding the powdering agents are suitable, for example, nonionic surfactants or aqueous solutions of surfactants or other detergent ingredients be used. In the context of the present invention it is preferred as liquid Adhesive between finely divided powdering agent and the coarse particle perfume use.
- the detergent tablets according to the invention further in detergents and cleaners typical ingredients from the group of bleaches, bleach activators, enzymes, Perfumes, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- bleach activators can Compounds which, under perhydrolysis conditions, preferably contain aliphatic peroxocarboxylic acids 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted Perbenzoic acid, are used. Suitable substances are the O and / or N-acyl the said C atom number and / or optionally substituted benzoyl groups carry.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
- TAED tetraacet
- Bleaching catalysts are incorporated into the moldings. These substances are it is bleach-enhancing transition metal salts or transition metal complexes such For example, Mn, Fe, Co, Ru or Mo-salene complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
- Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus.
- enzyme mixtures for example from protease and amylase or protease and lipase or protease and Cellulase or cellulase and lipase or protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also proved suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in encapsulating substances be to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings of the invention can, for example about 0, 1 to 5 wt .-%, preferably 0.1 to about 2 wt .-% amount.
- the detergent tablets may also contain components which positively influence the oil and grease washability of textiles (so-called soil repellents). This effect becomes particularly evident when a textile is already soiled previously several times with a detergent according to the invention, this oil and fat dissolving Component contains, was washed.
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and at hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and at hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ethers
- the known from the prior art polymers of phthalic acid and / or terephthalic acid or its derivatives in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
- Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
- the moldings can be used as optical brighteners derivatives of Diaminostilbendisulfonklare or their alkali metal salts. 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 Compounds which, instead of the morpholino group, are a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- brighteners of the substituted diphenylstyrene type may be present, e.g.
- alkali salts 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls.
- mixtures of the aforementioned brightener can be used.
- Dyes and fragrances are added to the inventive compositions to the aesthetic To enhance the impression of the products and to visually and in addition to the performance of the consumer sensory "typical and distinctive" product to provide.
- perfume oils or fragrances may be individual fragrance compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons used become. Fragrance compounds of the ester type are known e.g.
- benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- Ethern include, for example, benzyl ethyl ether, to 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 ionone, ⁇ -isomethylionone and methyl cedryl ketone
- the hydrocarbons mainly include the terpenes like limes and pinas.
- mixtures of different fragrances are preferred used, which together create an appealing scent.
- perfume oils can also contain natural fragrance mixtures, as accessible from plant sources are, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- the fragrances can be incorporated directly into the compositions of the invention, it can but also be beneficial to apply the perfumes on carriers that the adhesion of the perfume intensify on the laundry and through a slower release of fragrance for long-lasting Fragrance of the textiles provide.
- carrier materials are cyclodextrins proven, wherein the cyclodextrin-perfume complexes additionally with other Excipients can be coated.
- the detergent tablets according to the invention can be colored with suitable dyes.
- suitable dyes preferred Dyes, the selection of which does not cause any difficulty for the skilled person, have a high level of Storage stability and insensitivity to the other ingredients of the agent and against light and no pronounced substantivity to textile fibers, not these to stain. Since the subject of the present invention multi-phase detergent tablets is concerned, the coloring of individual phases is of increased importance to underline the different effect of individual phases. Examples for the effectiveness of such colorations and for the success of statements on this are Well known from denture cleaning advertising.
- the production of the shaped body according to the invention is initially carried out by the dry Mixing the components of the individual phases, which are pre-granulated in whole or in part can, and then informing, in particular pressing into tablets, wherein Conventional methods for producing multiphase moldings are used can.
- the premixes in a so-called matrix between two stamps to a fixed comprimat compacted. This process, which is referred to below as tabletting, is divided divided into four sections: metering, compaction (elastic deformation), plastic deformation and Ejecting.
- the tabletting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped.
- the lower punch moves during the pressing process on the upper punch, while the upper punch presses down.
- eccentric tablet presses in which the or the punches are attached to an eccentric disc, which in turn on an axis with a certain rotational speed is mounted.
- the movement of these punches is comparable with the operation of a conventional four-stroke engine.
- the compression can with each one upper and lower stamp done, but it can also several stamps on a Eccentric disc be attached, the number of die holes extended accordingly is.
- the throughputs of eccentric presses vary according to type from a few hundred to maximum 3000 tablets per hour.
- rotary tablet presses where on a so-called Matrizentisch a larger number of matrices is arranged in a circle.
- the number of Matrices vary between 6 and 55 depending on the model, although larger dies are also commercially available are available.
- Each die on the die table is assigned a top and bottom stamp, in turn, the pressing pressure active only by the upper or lower punch, but also can be built by both stamp.
- the die table and the stamp move around a common perpendicular axis, with the stamps using rail-like Curved tracks during the circulation in the positions for filling, compaction, plastic Deformation and ejection are brought.
- Concentric presses can be used to increase throughput even with two or more filling shoes be provided.
- For producing two- and multi-layered molded bodies several filling shoes arranged one behind the other without the slightly pressed first layer is ejected before further filling.
- suitable process control are on this Way coat and point tablets produced, the onion-like structure have, in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
- Rotary tablet presses are also available with or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for crimping.
- the Throughputs of modern rotary tablet presses amount to over one million moldings per Hour.
- Tableting machines suitable for the purposes of the present invention are, for example available from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Presses GmbH, Berlin, Mapag Maschinenbau AG, Berne (CH) and Courtoy N.V., Halle (BE / LU).
- the hydraulic double pressure press HPF is particularly suitable 630 of the company LAEIS, D.
- the moldings can be made in a predetermined spatial form and predetermined size are always made up of several phases, i. Layers, inclusions or cores and wrestling exist.
- Layers, inclusions or cores and wrestling exist.
- As a form of space come practically all useful manageable configurations considered, for example, the training as a blackboard, the bar or bar form, Cube, cuboid and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with a circular or oval cross-section.
- This last embodiment covers the presentation form of the tablet up to compact Cylinder pieces with a height to diameter ratio above 1.
- the portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts, which are a plurality of such mass units connect in a compact, in particular by predetermined breaking points the easy separability of portioned smaller units is provided.
- the formation of portioned compacts as tablets, in cylinder or cuboid shape be useful, with a diameter / height ratio in the range from 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 such compacts.
- the spatial form of another embodiment of the moldings is in their dimensions of Ein Titaniere adapted from commercial household washing machines, so that the moldings can be metered directly into the dispensing chamber without dosing aid, where they are dissolves during the flushing process.
- the moldings can be metered directly into the dispensing chamber without dosing aid, where they are dissolves during the flushing process.
- dosing aid where they are dissolves during the flushing process.
- Detergent tablets on a dosing easily possible.
- Another preferred multiphase molding that can be made has one plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, the represent the short thin segments, aborted and entered into the machine can.
- This principle of the "bar-shaped" detergent body can also in other geometric shapes, such as vertical triangles, the only one their sides are connected together, be realized. Here it is for optical reasons, the triangle base connecting the individual segments together, as a phase while the triangle peak forms the second phase. A Different staining of both phases is particularly attractive in this embodiment.
- the detergent tablets After pressing, the detergent tablets have a high stability.
- ⁇ stands for the diametrical fracture stress (DFS) in Pa
- P is the force in N which leads to the pressure exerted on the molding, which causes the breakage of the Form body caused
- D is the molding diameter in meters
- t is the height of Moldings.
- surfactant-containing granules By mixing surfactant-containing granules with pulverulent processing components, premixes were prepared which were pressed in a Korsch tablet press into two-phase detergent tablets.
- the surfactant granules 1, 2 and 3 were produced in a 130 liter ploughshare mixer (Gebrüder Lödige, Paderborn) and then dried in a fluidized bed dryer. After screening off the coarse fractions ( ⁇ 1.6 mm) and the fines ( ⁇ 0.4 mm), the surfactant granules were mixed with the conditioning components in a paddle mixer.
- the composition of the surfactant granules is shown in Table 1.
- Two-layer detergent tablets were prepared from the premixes (surfactant granules + preparation components) on a Korsch rotary press, the proportion of the first layer being 75% by weight of the total mass and the proportion of the second layer being 25% by weight of the total mass of the tablet.
- the diameter of the tablets was 44 mm.
- Tables 2, 3 and 4 the compositions of the laundry detergent tablets are indicated by phases.
- the values in the columns of the table indicate the amount of the respective substance in the respective phase of the tablet, ie the values in one column add up to 100%. The amount of the substance in question throughout the tablet can be easily calculated from the proportion of each phase.
- Tablet hardness varied by about ⁇ 10%, the disintegration times by about 5 seconds. Tablet hardness and decay times are listed in the respective tables.
- Detergent tablets composition [wt%], phys.
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Description
Die Zusammensetzung der Tensidgranulate zeigt Tabelle 1.
Tensidgranulate [Gew.-%] | |||
Granulat 1 | Granulat 2 | Granulat 3 | |
C9-13-Alkylbenzolsulfonat | 21,2 | 18,6 | 19,4 |
C12-18-Fettalkoholsulfat | 8,5 | 5,4 | 5,2 |
C12-18-Fettalkohol mit 7 EO | - | 5,7 | 4,8 |
C12-16-Alkylglucosid Oligomerisierungsgrad 1,1 | - | - | 1,0 |
Seife | 1,6 | 1,6 | 1,6 |
Natriumcarbonat | 17,0 | 16,6 | 17,0 |
Natriumsilikat | 5,6 | 5,4 | 5,6 |
Zeolith A (wasserfreie Aktivsubstanz) | 28,5 | 29,9 | 28,5 |
optischer Aufheller | 0,3 | 0,3 | 0,3 |
Na-Hydroxyethan-1,1-diphosphonat | 0,8 | 0,8 | 0,8 |
Acrylsäure-Maleinsäure-Copolymer | 5,6 | 5,4 | 5,6 |
Wasser, Salze | Rest | Rest | Rest |
In den nachfolgenden Tabellen 2, 3 und 4 sind die Zusammensetzungen der Waschmitteltabletten nach Phasen gegliedert angegeben. Die Werte in den Spalten der Tabelle geben dabei die Menge des betreffenden Stoffes in der jeweiligen Phase der Tablette an, d.h. die Werte in eine Spalte addieren sich auf 100 %. Die Menge des betreffenden Stoffes in der gesamten Tablette läßt sich aus dem Anteil der einzelnen Phasen daraus mühelos errechnen. Entsprechend der unterschiedlichen Tablettengewichte (37,5 g ± 1%, bedingt durch geringe Schwankungen bei der Zuführung des Vorgemischs in die Matrize der Presse) schwankten die Tablettenhärten um ca. ± 10%, die Zerfallszeiten um ca. 5 Sekunden. Die Tablettenhärten und -zerfallszeiten sind in den jeweiligen Tabellen mit aufgeführt.
Waschmitteltabletten: Zusammensetzung [Gew.-%], phys. Daten | ||||
Beispiel 1 | ||||
erfindungsgemäß | Vergleichsbeispiel | |||
Schicht 1 | Schicht 2 | Schicht 1 | Schicht 2 | |
Granulat 1 | 60,0 | 60,0 | 64,2 | 51,3 |
Natriumperborat-Monohydrat | 23,7 | - | 23,7 | - |
Tetraacetylethylendiamin | 2,6 | 22,5 | - | 29,0 |
Enzymgranulat* | - | 10,0 | - | 10,0 |
Schauminhibitor | 4,7 | - | 3,5 | 1,1 |
Repelotex-SRP-4** | 1,5 | - | 1,1 | 1,1 |
Parfüm | 0,5 | 0,5 | 0,5 | 0,5 |
Zeolith A | 2,0 | 2,0 | 2,0 | 2,0 |
Cellulose*** | 5,0 | 5,0 | 5,0 | 5,0 |
Tensidgehalt | 18,78 % | 18,78 % | 20,09 % | 16,05 % |
Tensidgehalt (Tablette) | 18,78 % | 19,08 % | ||
Tablettenhärte | 43 - 55 N | 39 - 47 N | ||
Zerfallszeit | 13 - 18 s | > 60 s |
Waschmitteltabletten: Zusammensetzung [Gew.-%], phys. Daten | ||||
Beispiel 2 | ||||
erfindungsgemäß | Vergleichsbeispiel | |||
Schicht 1 | Schicht 2 | Schicht 1 | Schicht 2 | |
Granulat 2 | 60,0 | 60,1 | 66,8 | 41,1 |
Natriumperborat-Monohydrat | 17,8 | 17,8 | 17,8 | 17,8 |
Tetraacetylethylendiamin | 10,1 | - | - | 29,0 |
Enzymgranulat* | - | 10,0 | 3,3 | - |
Schauminhibitor | 3,5 | 3,5 | 3,5 | 3,5 |
Repelotex-SRP-4** | 1,1 | 1,1 | 1,1 | 1,1 |
Parfüm | 0,5 | 0,5 | 0,5 | 0,5 |
Zeolith A | 2,0 | 2,0 | 2,0 | 2,0 |
Cellulose*** | 5,0 | 5,0 | 5,0 | 5,0 |
Tensidgehalt | 18,78% | 18,81% | 20,91 % | 12,86% |
Tensidgehalt (Tablette) | 18,79 % | 18,90 % | ||
Tablettenhärte | 40 - 50 N | 37 - 49 N | ||
Zerfallszeit | 16 - 22 s | > 60 s |
Waschmitteltabletten: Zusammensetzung [Gew.-%], phys. Daten | ||||
Beispiel 3 | ||||
erfindungsgemäß | Vergleichsbeispiel | |||
Schicht 1 | Schicht 2 | Schicht 1 | Schicht 2 | |
Granulat 3 | 60,1 | 60,1 | 66,3 | 42,5 |
Natriumperborat-Monohydrat | 14,5 | 27,8 | 7,0 | 50,0 |
Tetraacetylethylendiamin | 10,0 | - | 9,8 | - |
Enzymgranulat | 3,3 | - | 3,3 | - |
Schauminhibitor | 3,5 | 3,5 | 4,7 | - |
Repelotex-SRP-4 | 1,1 | 1,1 | 1,4 | - |
Parfüm | 0,5 | 0,5 | 0,5 | 0,5 |
Zeolith A | 2,0 | 2,0 | 2,0 | 2,0 |
Cellulose | 5,0 | 5,0 | 5,0 | 5,0 |
Tensidgehalt der.Schicht | 19,23 % | 19,23 % | 21,22 % | 13,60 % |
Tensidgehalt (Tablette) | 19,23 % | 19,32 % | ||
Tablettenhärte | 43 - 51 N | 38 - 47 N | ||
Zerfallszeit | 13 - 17 s | > 60 s |
Claims (20)
- Zwei- oder mehrphasige Wasch- und Reinigungsmittelformkörper aus verdichtetem teilchenförmigen Wasch- und Reinigungsmittel, umfassend Tensid(e), Gerüststoff(e) sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile, dadurch gekennzeichnet, daß der Tensidgehalt der einzelnen Phasen des Formkörpers, jeweils bezogen auf das Gewicht der einzelnen Phase, um nicht mehr als 1,5 Gew.-% variiert.
- Wasch- und Reinigungsmittelformkörper nach Anspruch 1, dadurch gekennzeichnet, daß der Tensidgehalt der einzelnen Phasen des Formkörpers um nicht mehr als 1 Gew.-%, bezogen auf das Gewicht der einzelnen Phase, variiert.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der Tensidgehalt der einzelnen Phasen des Formkörpers identisch ist.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Phasen des Formkörpers die Form von Schichten aufweisen.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das/die Tensid(e) über tensidhaltige(s) Granulat(e) in die Phasen der Fonnkörper eingebracht werden.
- Wasch- und Reinigungsmittelformkörper nach Anspruch 5, dadurch gekennzeichnet, daß in allen Phasen der Formkörper das gleiche Tensidgranulat eingesetzt wird.
- Wasch- und Reinigungsmittelformkörper nach Anspruch 4 und 6, dadurch gekennzeichnet, daß die Formkörper zwei Schichten aufweisen, die das gleiche Tensidgranulat enthalten.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß sie anionische(s) und nichtionische(s) Tensid(e) enthalten.
- Wasch- und Reinigungsmittelformkörper nach Anspruch 8, dadurch gekennzeichnet, daß das Verhältnis von Aniontensid(en) zu Niotensid(en) zwischen 10:1 und 1:10, vorzugsweise zwischen 7,5:1 und 1:5 und insbesondere zwischen 5:1 und 1:2 beträgt.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß mindestens eine Phase der Formkörper frei von nichtionischen Tensiden ist.
- Wasch- und Reinigungsmittelformikörper nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß mindestens eine Phase der Formkörper Alkylpolyglycoside enthält.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß mindestens eine Phase der Formkörper frei von anionischen Tensiden ist.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß sie zusätzlich ein Desintegrationshilfsmittel, vorzugsweise ein Desintegrationshilfsmittel auf Cellulosebasis, vorzugsweise in granularer, cogranulierter oder kompaktierter Form, in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise von 3 bis 7 Gew.-% und insbesondere von 4 bis 6 Gew.-%, jeweils bezogen auf das Formkörpergewicht, enthalten.
- Wasch- und Reinigungsmittelformkörper nach einem der Ansprüche 1 bis 13, enthaltend weiterhin einen oder mehrere Stoffe aus der Gruppe der Gerüststoffe, Bleichmittel, Bleichaktivatoren, Enzyme, pH-Stellmittel, Duftstoffe, Parfümträger, Fluoreszenzmittel, Farbstoffe, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, optischen Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren und Korrosionsinhibitoren.
- Verfahren zur Herstellung zwei- oder mehrphasiger Wasch- und Reinigungsraittelformkörper, welche Tensid(e), Gerüststoff(e) sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile enthalten, durch an sich bekanntes Verpressen, dadurch gekennzeichnet, daß sie durch Verpressen eines teilchenförmigen Vorgemischs aus mindestens einem tensidhaltigen Granulat und mindestens einer nachträglich zugemischten pulverförmigen Komponente erhalten wurden, wobei der Tensidgehalt der einzelnen Phasen der Formkörper, jeweils bezogen auf das Gewicht der einzelnen Phase, um nicht mehr als 1,5 Gew.-% variiert.
- Verfahren nach Anspruch 15, dadurch gekennzeichnet, daß die Granulate über übliche Granulierverfahren wie Mischer- und Tellergranulation, Wirbelschichtgranulation, Extrusion, Pelletierung oder Kompaktierung hergestellt wurden.
- Verfahren nach einem der Ansprüche 15 oder 16, dadurch gekennzeichnet, daß die Granulate Teilchengrößen zwischen 10 und 4000 µm, vorzugsweise zwischen 100 und 2000 µm und insbesondere zwischen 600 und 1400 µm aufweisen.
- Verfahren nach einem der Anspüuche 15 bis 17, dadurch gekennzeichnet, daß die nachträglich zugemischte(n) pulverförmige(n) Komponente(n) die gleichen Teilchengrößenverteilung aufweisen wie die eingesetzten Granulate.
- Verfahren nach einem der Anspüuche 15 bis 18, dadurch gekennzeichnet, daß das zu verpressende Vorgemisch ein Schüttgewicht von mindestens 500 g/l, vorzugsweise mindestens 600 g/l und insbesondere oberhalb von 700 g/l, aufweist.
- Verfahren nach einem der Ansprüche 15 bis 19, dadurch gekennzeichnet, daß die bzw. eine der nachträglich zugemischten pulverförmigen Komponenten ein Zeolith vom Faujasit-Typ mit Teilchengrößen unterhalb 100µm, vorzugsweise unterhalb 10µm und insbesondere unterhalb 5µm ist und mindestens 0,2 Gew.-%, vorzugsweise mindestens 0,5 Gew.-% und insbesondere mehr als 1 Gew.-% des zu verpressenden Vorgemischs ausmacht.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803409A DE19803409A1 (de) | 1998-01-28 | 1998-01-28 | Mehrphasige Waschmitteltabletten |
DE19803409 | 1998-01-28 | ||
PCT/EP1998/006406 WO1999038949A1 (de) | 1998-01-28 | 1998-10-08 | Mehrphasige waschmitteltabletten |
CA002313294A CA2313294A1 (en) | 1998-01-28 | 2000-07-28 | Multiphase detergent tablets |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1051475A1 EP1051475A1 (de) | 2000-11-15 |
EP1051475B1 true EP1051475B1 (de) | 2005-02-02 |
Family
ID=25681927
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98954380A Revoked EP1051475B1 (de) | 1998-01-28 | 1998-10-08 | Mehrphasige waschmitteltabletten |
Country Status (12)
Country | Link |
---|---|
EP (1) | EP1051475B1 (de) |
JP (1) | JP2002501978A (de) |
CN (1) | CN1284125A (de) |
AT (1) | ATE288470T1 (de) |
CA (1) | CA2313294A1 (de) |
CZ (1) | CZ20002779A3 (de) |
DE (2) | DE19803409A1 (de) |
ES (1) | ES2236957T3 (de) |
HU (1) | HUP0101577A2 (de) |
PL (1) | PL341767A1 (de) |
SK (1) | SK11132000A3 (de) |
WO (1) | WO1999038949A1 (de) |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE19944218A1 (de) * | 1999-09-15 | 2001-03-29 | Cognis Deutschland Gmbh | Waschmitteltabletten |
DE10006306A1 (de) * | 2000-02-12 | 2001-08-23 | Buck Chemie Gmbh | Wirkstoff-Tablette, insbesondere als Reiniger- und/oder Entkalkertablette |
EP1319058B1 (de) * | 2000-09-20 | 2006-02-01 | Reckitt Benckiser Inc. | Verbesserungen in enzyme enthaltende tabletten |
US6852681B1 (en) * | 2004-01-13 | 2005-02-08 | Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. | Compositions and process for preparing cleansing bars comprising low levels of soluble surfactant for enhanced fragrance deposition/longevity |
CN102782112A (zh) * | 2009-12-31 | 2012-11-14 | 罗地亚(中国)投资有限公司 | 用于改进洗衣性能的聚合物和表面活性剂的组合 |
CN106281736A (zh) * | 2016-08-11 | 2017-01-04 | 孔令超 | 一种超浓缩清水型洗衣片及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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DE3541146A1 (de) * | 1985-11-21 | 1987-05-27 | Henkel Kgaa | Mehrschichtige reinigungsmitteltabletten fuer das maschinelle geschirrspuelen |
JPH0674440B2 (ja) * | 1986-03-27 | 1994-09-21 | ライオン株式会社 | 錠剤型洗剤 |
JPH06108099A (ja) * | 1992-09-30 | 1994-04-19 | Lion Corp | タブレット洗剤組成物 |
CA2226143C (en) * | 1995-07-13 | 2007-11-20 | Joh. A. Benckiser Gmbh | Dish washer product in tablet form |
-
1998
- 1998-01-28 DE DE19803409A patent/DE19803409A1/de not_active Withdrawn
- 1998-01-28 DE DE29824160U patent/DE29824160U1/de not_active Expired - Lifetime
- 1998-10-08 JP JP2000529410A patent/JP2002501978A/ja active Pending
- 1998-10-08 WO PCT/EP1998/006406 patent/WO1999038949A1/de active IP Right Grant
- 1998-10-08 EP EP98954380A patent/EP1051475B1/de not_active Revoked
- 1998-10-08 CN CN98813211.7A patent/CN1284125A/zh active Pending
- 1998-10-08 CZ CZ20002779A patent/CZ20002779A3/cs unknown
- 1998-10-08 PL PL98341767A patent/PL341767A1/xx unknown
- 1998-10-08 HU HU0101577A patent/HUP0101577A2/hu unknown
- 1998-10-08 AT AT98954380T patent/ATE288470T1/de not_active IP Right Cessation
- 1998-10-08 SK SK1113-2000A patent/SK11132000A3/sk unknown
- 1998-10-08 ES ES98954380T patent/ES2236957T3/es not_active Expired - Lifetime
-
2000
- 2000-07-28 CA CA002313294A patent/CA2313294A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
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JP2002501978A (ja) | 2002-01-22 |
DE29824160U1 (de) | 2000-08-10 |
HUP0101577A2 (hu) | 2001-09-28 |
PL341767A1 (en) | 2001-05-07 |
ATE288470T1 (de) | 2005-02-15 |
SK11132000A3 (sk) | 2001-02-12 |
DE19803409A1 (de) | 1999-07-29 |
WO1999038949A1 (de) | 1999-08-05 |
CA2313294A1 (en) | 2000-10-09 |
ES2236957T3 (es) | 2005-07-16 |
CZ20002779A3 (cs) | 2001-10-17 |
CN1284125A (zh) | 2001-02-14 |
EP1051475A1 (de) | 2000-11-15 |
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