EP1051474B1 - Multiphase detergent tablets - Google Patents
Multiphase detergent tablets Download PDFInfo
- Publication number
- EP1051474B1 EP1051474B1 EP98954379A EP98954379A EP1051474B1 EP 1051474 B1 EP1051474 B1 EP 1051474B1 EP 98954379 A EP98954379 A EP 98954379A EP 98954379 A EP98954379 A EP 98954379A EP 1051474 B1 EP1051474 B1 EP 1051474B1
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- EP
- European Patent Office
- Prior art keywords
- shaped bodies
- weight
- phase
- washing
- surfactant
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- 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.)
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Classifications
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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
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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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
Definitions
- the present invention relates to multi-phase detergent tablets.
- the invention relates to multi-phase detergent tablets intended for washing of textiles used in a household washing machine and briefly as detergent tablets be designated.
- EP-A-0 466 485 (Unilever) describes detergent tablets which have resulted from the compression of two granules containing surfactant.
- One granulate contains the total amount of anionic surfactants, while the second surfactant granulate is preferably free of anionic surfactants. This document also does not comment on hardness and / or decay depending on the phase composition.
- the present invention was based on the object of multiphase detergent tablets to provide, which overcome the disadvantages mentioned.
- multi-phase detergent tablets are to be provided, which in all phases have a high hardness as well as a high rate of disintegration and dissolution, regardless of how much the surfactant levels vary in the individual phases.
- the invention now relates to two-phase or multi-phase detergent tablets made of compressed particulate detergent and cleaning agent, comprising Surfactant (s), builder (s) and optionally further detergent and cleaning agent components, in which the surfactant content of the individual phases of the moldings, based on the Weight of the individual phase, varied by more than 3 wt .-%, being in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g / 100g and an average particle size of less than 50 microns, based on the weight the phase is contained in higher amounts than in the phase (s) with a lower surfactant content.
- Surfactant s
- builder s
- optionally further detergent and cleaning agent components in which the surfactant content of the individual phases of the moldings, based on the Weight of the individual phase, varied by more than 3 wt .-%, being in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g
- the variation in the surfactant content means more than 3% by weight, based on the weight of the individual phases, that the absolute values of the surfactant content vary in the phases by more than 3% by weight.
- a 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 more than 3% by weight.
- the Percentage numerical value of the surfactant content of the lower surfactant phase from the percentage numerical value of the Subtracted surfactant content of the respective surfactant-rich phase, the result of each of Phase to phase must be> 3. In a four-phase tablet, this would be at a surfactant level of 12% by weight in the surfactant-poorest phase means that the next phases, for example Report surfactant contents of 15.1% by weight, 18.2% by weight and 21.3% by weight.
- a phase is completely free of Is surfactants (corresponding to a surfactant content of 0% by weight, based on this phase).
- the next phase must then - in order to meet the criteria according to the invention - a surfactant content of more than 3% by weight.
- the individual phases of the laundry detergent according to the invention contain Detergent tablets increasing proportions of component A with an oil absorption capacity of at least 20g / 100g, with the proviso that the more tenis-rich Phase based on the overall composition of the phase a higher proportion of this Has component. It is preferred in the context of the present invention that the content the more surfactant-rich phase (s) on component A by at least 0.3% by weight, preferably by at least 0.5% by weight and in particular by at least 1% by weight on the weight of the individual phase, is higher than in the phase (s) with less surfactant.
- the second phase would contain at least 1.8% by weight (preferably 2.0% by weight and in particular 2.5% by weight) of this component A.
- the third phase of component A depends on the real content thereof Component in the second phase - here too the difference is preferably at least 0.3% by weight, more preferably at least 0.5% by weight and in particular at least 1.0 Wt .-%. The same applies to the fourth phase.
- the second phase compared to the first so much of component A contains that the ratio of this component in the two phases is greater than 1.26. contains
- phase 1 is 1.5% by weight of component A
- phase 2 should be more than that 1.26 times this value, ie contain at least 1.9% by weight of this component.
- a phase that is free of an oil absorption component or is free from surfactants makes relationships mathematical no sense, which is why absolute values in the sense of the preferred embodiments explained above find application of the present invention.
- the oil absorption components contained in the individual surfactant-containing phases of the molded body according to the invention have an oil absorption capacity of at least 20g / 100g. However, preference is given to using oil absorption components which have a higher oil absorption capacity have.
- Detergent tablets are preferred which the component A contained in them has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular has at least 140g / 100g
- the oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, there are British standard methods BS1795 and BS3483: Part B7: 1982, both of which refer to the ISO 787/5 standard.
- BS1795 and BS3483: Part B7: 1982 both of which refer to the ISO 787/5 standard.
- a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm-3) from a burette is added dropwise. After each addition, the powder is mixed intensively with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling.
- the oil absorption capacity is now the amount of the added oil, based on 100g absorbent and is given in ml / 100g or g / 100g, whereby conversions about the density of the linseed oil are easily possible.
- the oil absorption component preferably has the smallest possible average particle size, since the active surface increases with decreasing particle size.
- Preferred washing and Detergent tablets contain a component with an oil absorption capacity of at least 20g / 100g, which preferably has an average particle size of less than 20 ⁇ m has less than 10 microns.
- a large number of substances are suitable as an oil absorption component.
- inorganic and organic substances that have a large oil absorption capacity exhibit.
- examples include finely divided substances obtained by precipitation are called.
- diatomaceous earth (Diatomaceous earth) and finely divided cellulose fibers or derivatives thereof are within the scope of present invention can be used.
- Preferred detergent tablets are characterized in that component A contained in them is selected from silicates and / or aluminosilicates, in particular from the group of silicas and / or Zeolites.
- finely divided zeolites can be used, but also pyrogenic silicas (Aerosil®) or silicas that were obtained by precipitation.
- the individual phases of the shaped body can have different spatial shapes.
- the simplest possible implementation is in two- or multi-layer tablets, with 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. 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 molded body by more than 3 wt .-%, based on the weight of the individual Phase varies and the more surfactant-rich phase (s) contain more oil absorption component than the lower surfactant phase (s).
- the sum is used to determine the surfactant content of the surfactants contained in the phase in question, regardless of the order what type of surfactants it is.
- the surfactants can be incorporated in the individual phases of the shaped bodies in pure form become. This is no problem, for example, with soaps or other easily processable surfactants possible. With many surfactants, however, it is advisable not to incorporate the pure surfactants, but surfactant compounds. These compounds, depending on the application, if possible should have high surfactant contents, can be done by conventional methods such as spray drying, Granulation or compounding can be made. It goes without saying a combination of several surfactant granules or a combination of surfactant granules possible with pure surfactants.
- the surfactant (s) contain surfactant-containing Granules (e) are introduced into the phases of the shaped body.
- each phase Surfactant granules are used. But it is also possible that each phase has its own The surfactant content is obtained from a single granulate, which therefore applies to all phases of the molded body is included. In the context of the present invention, this is a further preferred embodiment, in which the same surfactant granules are used in all phases of the molded body becomes.
- anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Mixtures of are preferred from an application point of view anionic and nonionic surfactants.
- the total surfactant content of the moldings is 5 up to 60% by weight, based on the weight of the shaped body, surfactant contents above 15% by weight are preferred.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably 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 a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent 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.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained.
- preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
- alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous 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.
- 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).
- sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use 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 ones are suitable 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, available.
- the anionic surfactants are preferably in the form of 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 can 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 either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably described in the international patent application Methods described in 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 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 them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) 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 remainder.
- 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 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, which contain anionic (s) and nonionic (s) surfactant (s), application technology Advantages from certain proportions in which the individual surfactant classes are used will result.
- detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is 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 cleaning agents.
- Builders may be included, in particular thus 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 are 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 are Na 2 Si 2 O 5 .
- yH 2 O is preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
- 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 (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O. (1-n) K 2 O. Al 2 O 3 . (2-2.5) SiO 2 .
- the zeolite can be used both as a builder in a granular compound and can also be used for 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.
- phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be.
- the sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.
- Usable organic builders are, for example, the polycarboxylic acids which 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), provided that 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.
- disintegration aids so-called tablet disintegrants
- tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.
- 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 aids, each based on the weight of the molded article.
- 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, viewed formally, 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 pressed.
- 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 WO 98/40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
- the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
- the above-mentioned coarser disintegration aids based on cellulose and 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 As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
- This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses completely dissolve, but leave the crystalline areas (approx. 70%) undamaged.
- a subsequent one Disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and, for example can be compacted into granules with an average particle size of 200 ⁇ m.
- Detergent tablets which are additionally a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, contained are particularly preferred in the context of the present invention.
- a disintegration aid preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, contained are particularly preferred in the context of the present invention.
- Preferred washing and cleaning agents in the context of the present invention are obtained by compressing particulate premixes from at least one surfactant Granules and at least one subsequently mixed powdered component.
- the surfactant-containing granules can be processed using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelleting or compacting getting produced. It is for the later detergent tablets advantageous if the premixes to be pressed have a bulk density, that comes close to the usual compact detergent.
- the premix to be pressed has a bulk density of at least 500 g / l, preferably has at least 600 g / l and in particular above 700 g / l.
- Detergent and cleaning product tablets are within the scope of the present invention preferred, in which the granules particle sizes between 10 and 4000 microns, preferably have between 100 and 2000 microns and in particular between 600 and 1400 microns.
- Another object of the present invention is therefore a method for manufacturing two-phase or multi-phase detergent tablets, which surfactant (s), builders (e) and optionally contain further detergent and cleaning agent components, by pressing known per se, which is characterized in that it is carried out by pressing a particulate premix consisting of at least one surfactant-containing granulate and at least one a subsequently admixed powdery component were obtained, wherein the surfactant content of the individual phases of the moldings, based on the weight of the individual Phase varied by more than 3% by weight and in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g / 100g and an average particle size of less than 50 microns, based on the weight of the phase, in higher Amounts are contained in the phase (s) with a lower surfactant content.
- Preferred processes are characterized in that the granules are made using conventional ones Granulation processes such as mixer and plate granulation, fluid bed granulation, extrusion, Pelleting or compacting were made.
- the granules have particle sizes between 10 and 4000 ⁇ m, preferably between 100 and 2000 ⁇ m and in particular between 600 and 1400 ⁇ m.
- the particle size distribution of the subsequently mixed powder-form processing components can be varied, with methods preferred in which the subsequently mixed powdered component (s) containing component A.
- 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 detergent tablets be an advantage.
- Finely divided powdering agents are known in the art Well-known technology, mostly using zeolites, silicates or other inorganic salts become.
- the premix is preferably "powdered” with finely divided zeolite, faujasite type zeolites are preferred.
- faujasite type zeolite denotes all three zeolites that make up the faujasite subgroup of the zeolite structure group 4 (compare Donald W.
- zeolites Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily belong to the zeolite structure group 4 are used as powdering agents can be used, it being advantageous if at least 50% by weight of the powdering agent are made from a faujasite type zeolite.
- powdering agents can of course have an oil absorption capacity of more have as 20g / 100g, where they can replace or supplement the oil absorption component.
- the powdering agent is used in addition to the oil absorption components and have an oil absorption capacity of more than 20g / 100g, they are at The calculation of the share in the individual phases must of course be taken into account.
- detergent tablets consist of a particulate premix, the granular components and subsequently contains powdered substances, the or one of the subsequently admixed powdered components a zeolite of the faujasite type with particle sizes is below 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1 Makes up% by weight of the premix to be pressed.
- the finely divided processing components with the particle sizes mentioned above can be mixed dry with the premix to be pressed. But it is also possible and preferably, by adding small amounts of liquids to the surface of the "stick" coarser particles.
- These powdering processes are state of the art broadly described and familiar to the expert.
- suitable powdering agents for example nonionic surfactants or aqueous solutions of surfactants or other detergents and cleaning agents be used. In the context of the present invention, it is preferred as a liquid Adhesion promoter between finely divided powdering agent and the coarse particles of perfume use.
- surfactant, builder and disintegration aid can the detergent tablets according to the invention further in detergents usual ingredients from the group of bleaching agents, bleach activators, enzymes, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and contain corrosion inhibitors.
- bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
- bleach activators can be used as the sole component or as an ingredient of Component b) are incorporated.
- 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.
- Substances containing O- and / or N-acyl groups are suitable carry the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
- Multi-acylated alkylenediamines are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
- TAED acylated triazine derivatives
- DADHT 1,5-diacet
- Bleaching catalysts can be incorporated into the moldings. Acting on these substances it is bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt 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 amine complexes can be used as bleaching catalysts.
- Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
- the proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
- the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile that is already soiled previously several times with a detergent according to the invention that this oil and fat-dissolving Contains component that has been 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 on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art 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. Of these, those are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.
- the moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group.
- Farther brighteners of the substituted diphenylstyryl 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 brighteners can be used.
- Dyes and 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 to provide visually and sensory "typical and distinctive" product.
- perfume oils or fragrances individual fragrance compounds, e.g. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g.
- benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- To the etheme include, for example, benzyl ethyl ether, the aldehydes e.g.
- the linear alkanals with 8-18 Carbon atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes like lime and pinene. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance.
- perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources are, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.
- the dye content of the plasticizers according to the invention is usually lower 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.
- the fragrances can be incorporated directly into the agents according to the invention, it can but it may also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume reinforce on the laundry and through a slower fragrance release for long-lasting Ensure the fragrance of the textiles.
- Cyclodextrins for example, have become such carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.
- the detergent tablets according to the invention can be colored with suitable dyes.
- suitable dyes preferred Dyes, the selection of which is not difficult for the person skilled in the art, have a high level Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers to stain. Since the subject of the present invention multi-phase detergent tablets concerns, the coloring of individual phases is of increased importance to underline the different effects of individual phases. Examples for the effectiveness of such coloring and for the success of statements well known from the denture cleaner advertising.
- the moldings according to the invention are first produced by dry Mixing the components of the individual phases, which are partially or completely pre-granulated can, and then bringing information, in particular compression to tablets, whereby conventional methods for the production of multi-phase molded articles can be used can.
- the premixes are used to produce the multiphase moldings according to the invention in a so-called matrix between two stamps to form a solid compressed product compacted.
- This process which is briefly referred to below as tabletting, is structured divided into four sections: metering, compression (elastic deformation), plastic deformation and expelling.
- Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, the lower punch also moves during the pressing process towards the upper stamp while the upper stamp presses down.
- Production quantities are preferably eccentric tablet presses in which the or the stamps are attached to an eccentric disc, which in turn is on an axis a certain rotational speed is mounted. The movement of this ram is comparable to the way a conventional four-stroke engine works.
- the pressing can be done with one upper and one lower stamp; however, several stamps can also be on one Eccentric disk can be attached, the number of die holes correspondingly expanded is.
- the throughputs of eccentric presses vary from a few hundred to depending on the type maximum 3000 tablets per hour.
- rotary tablet presses are selected, on which a so-called Matrix table 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 matrices are also commercially available are available.
- Each die on the die table is assigned an upper and lower stamp, where again the pressure is active only through the upper or lower stamp, but also can be built by both stamps.
- the die table and the stamps move around a common vertical axis, the stamp using rail-like Curve tracks during the circulation in the positions for filling, compression, plastic Deformation and discharge are brought.
- these cam tracks are by additional low-pressure pieces, kidney rails and lift tracks supported.
- the matrix is filled with a rigid one arranged feed device, the so-called filling shoe, which with a storage container for the premixes are connected.
- the pressure on the respective premix is over the Press paths for upper and lower punches individually adjustable, whereby the pressure build-up the stamp shaft heads roll past adjustable pressure rollers.
- Rotary presses can also be used with two or more filling shoes to increase the throughput be provided.
- several filling shoes arranged one behind the other without the slightly pressed first layer is ejected before further filling.
- Appropriate process management is based on this In this way, coated tablets and dot tablets can also be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible.
- Rotary tablet presses can also be or multiple tools can be equipped so that, for example, an outer circle with 50th and an inner circle with 35 holes can be used simultaneously for pressing.
- the Throughputs of modern rotary tablet presses are over one million tablets per Hour.
- Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH presses GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU).
- the hydraulic double-pressure press HPF for example, is particularly suitable 630 from LAEIS, D.
- the moldings can be made in a predetermined spatial shape and size being made up of several phases, i.e. Layers, inclusions or cores and rings exist. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form from the tablet to compact Cylinder pieces with a ratio of height to diameter above 1.
- the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have 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.
- For the Use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can form the portioned compacts as tablets, in cylindrical or cuboid shape may be appropriate, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
- Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, particularly for manufacturing such compacts.
- the spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the molded body can be dosed directly into the induction bowl without a dosing aid dissolves during the induction process. It goes without saying that the Detergent tablets easily possible using a dosing aid.
- Another preferred multi-phase molded body that can be produced has one plate-like or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "multi-phase bolt" at the predetermined breaking points, the represent the short thin segments, broken off and entered into the machine can.
- This principle of the "bar-shaped" shaped detergent can also be used in others geometric shapes, for example vertically standing triangles, which only on one their sides are connected alongside each other, can be realized. Here it offers itself for optical reasons, the triangular base that connects the individual segments, form as one phase, while the triangle tip forms the second phase. A different coloring of both phases is particularly attractive in this embodiment.
- ⁇ 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 breaks the Shaped body caused
- D is the shaped body diameter in meters
- t is the height of the Moldings.
- surfactant-containing granules By mixing surfactant-containing granules with pulverulent preparation components, premixes were produced which were pressed into two-phase detergent tablets in a Korsch tablet press.
- the surfactant granules 1, 2 and 3 were produced in a 130 liter ploughshare mixer (Gebrüder Lödige, Paderbom) and then dried in a fluidized bed dryer. After the coarse particles ( ⁇ 1.6 mm) and the fine particles ( ⁇ 0.4 mm) had been sieved, the surfactant granules were mixed with the preparation components in a paddle mixer.
- the composition of the surfactant granules is shown in Table 1.
- the premixes (surfactant granules + treatment components) were used on a Korsch rotary press produced two-layer detergent tablets, the proportion of the first layer 75% by weight of the total mass and the proportion of the second layer 25% by weight the total mass of the tablet was.
- the diameter of the tablets was 44 mm.
- Tables 2, 3 and 4 below show the compositions of the detergent tablets broken down by phase.
- the values in the columns of the table indicate the amount of the substance in question in the respective phase of the tablet, ie the values in one column add up to 100%.
- the amount of the substance in question in the entire tablet can be easily calculated from the proportion of the individual phases.
- the tablet hardness fluctuated by approx. ⁇ 10%, the disintegration times by approx. 5 seconds.
- the tablet hardness and disintegration times are listed in the respective tables.
- Detergent tablets composition [% by weight], physical data example 1 inventively Comparative example Layer 1 Layer 2 Layer 1 Layer 2 Granules 1 64.0 50.7 64.2 51.3 Sodium perborate monohydrate 23.7 - 23.7 - tetraacetylethylenediamine - 29.0 - 29.0 Enzyme granules * - 10.0 - 10.0 foam inhibitor 3.5 1.1 3.5 1.1 Repelotex-SRP-4 ** 1.1 1.1 1.1 1.1 Perfume 0.5 0.5 0.5 0.5 0.5 0.5 Zeolite A 2.2 1.4 2.0 2.0 cellulose **** 5.0 5.0 5.0 5.0 surfactant 20.03% 15.87% 20.09% 16.06% Surfactant content (tablet) 18.99% 19.09% Difference in surfactant content 4.16% 4.03% Ratio of surfactant levels 1.26: 1 1.25: 1 Ratio zeolite A *** 1.57: 1 1: 1 tablet hardness 36-48 N 39-47 N disintegration time 17-23 s > 60
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Abstract
Description
Die vorliegende Erfindung betrifft mehrphasige Wasch- und Reinigungsmittelformkörper. Insbesondere betrifft die Erfindung mehrphasige Waschmittelformkörper, die zum Waschen von Textilien in einer Haushaltswaschmaschine eingesetzt und kurz als Waschmitteltabletten bezeichnet werden.The present invention relates to multi-phase detergent tablets. In particular, the invention relates to multi-phase detergent tablets intended for washing of textiles used in a household washing machine and briefly as detergent tablets be designated.
Aufgrund der Bequemlichkeit ihrer Dosierung und weiterer Vorteile hinsichtlich Verpackung, Transport und Lagerung hat die Angebotsform hochverdichteter Formkörper eine Vielzahl von Vorteilen, die es wünschenswert erscheinen lassen, in dieser Angebotsform auch Waschund Reinigungsmittel bereitzustellen. Zu Wasch- und Reinigungsmittelformkörpern, die oft kurz als Waschmitteltabletten bezeichnet werden, existiert ein breiter Stand der Technik, der sich insbesondere die Aufgabe stellt, ein zentrales Problem der Angebotsform "Tablette" zu überwinden: Die Dichotomie zwischen der Härte der Formkörper einerseits und ihrer Zerfallsgeschwindigkeit andererseits. Eine ausreichende Härte ist für Verpackung, Lagerung, Transport und Handhabung der Formkörper unerläßlich, während die Zerfallseigenschaften den Waschvorgang entscheidend beeinflussen und ein ausreichend schneller Zerfall für die Bildung einer hinreichend konzentrierten Waschflotte zwingend notwendig ist.Because of the convenience of their dosage and other packaging benefits, Transport and storage, the offer form of highly compressed molded bodies has a variety of advantages that make it seem desirable in this form of washing and washing Provide cleaning agents. To detergent tablets, which often abbreviated as detergent tablets, there is a wide prior art, the in particular the task arises of addressing a central problem of the "tablet" offer form overcome: The dichotomy between the hardness of the molded body on the one hand and its rate of decay on the other hand. Adequate hardness is required for packaging, storage, Transport and handling of the moldings essential while the disintegration properties influence the washing process decisively and a sufficiently fast disintegration for the Formation of a sufficiently concentrated wash liquor is absolutely necessary.
Das Problem, zwischen Härte und Zerfall einen technisch vernünftigen Kompromiß zu finden, wird bei mehrphasigen Formkörpem weiter erschwert: Es kann aus wasch- oder reinigungstechnischen Gründen von Vorteil sein, bestimmte Wasch- und Reinigungsmittelinhaltsstoffe voneinander zu trennen. Diese Trennung bedingt aber ein unterschiedliches physikalisches Eigenschaftsprofil der unterschiedlichen Phasen im Formkörper. So kann im Extremfall die Haftung zwischen den Phasen so gering werden, daß sich mehrphasige Formkörper nicht mehr herstellen lassen. Eine zu unterschiedliche Härte unterschiedlicher Phasen würde dazu führen, daß einzelne Phasen verpackungs-, transport- oder handhabungsbedingt stärker beschädigt werden als andere Phasen. Zusätzlich ist auch eine zu unterschiedliche Zerfalls- und Auflösegeschwindigkeit einzelner Phasen nicht wünschenswert, da sonst Wirkstoffe aus der schlechter zerfallenden bzw. löslichen Phase im Waschprozeß nicht zur Verfügung stehen. Desweiteren kann es wünschenswert sein, daß die einzelnen Phasen des Formkörpers unterschiedliche Tensidgehalte aufweisen, um so eine breitere Möglichkeiten bei der Rezepturauswahl zu besitzen.The problem of finding a technically reasonable compromise between hardness and decay is made more difficult with multi-phase moldings: it can be from washing or cleaning technology Reasons to be beneficial certain detergent ingredients separate from each other. However, this separation requires a different physical Property profile of the different phases in the molded body. In extreme cases, the Adhesion between the phases become so low that multiphase molded articles do not have more manufactured. Too different hardness of different phases would result cause individual phases to be more severely damaged due to packaging, transport or handling than other phases. In addition, there is also a too different decay and The dissolution rate of individual phases is not desirable, since otherwise active substances from the poorer disintegrating or soluble phase in the washing process are not available. Furthermore, it may be desirable that the individual phases of the molded body differ Have surfactant levels, so a wider range of recipe choices to own.
Es ist also bei mehrphasigen Wasch- und Reinigungsmittelformkörpern von zentraler Bedeutung, daß alle Phasen aneinander haften, eine ausreichende und möglichst gleiche Härte sowie ein ausreichend schnelles und möglichst identisches Zerfalls- und Löseprofil zeigen, auch wenn die Tensidgehalte der einzelnen Phasen stark variieren. Lösungsvorschläge zu dieser Problematik werden im Stand der Technik derzeit nicht beschrieben.It is therefore of central importance in the case of multiphase detergent tablets, that all phases adhere to each other, a sufficient and possibly the same hardness and show a sufficiently fast and possibly identical decay and dissolution profile, too if the surfactant levels in the individual phases vary widely. Proposed solutions to this Problems are currently not described in the prior art.
Waschmitteltabletten, in denen einzelne Inhaltsstoffe getrennt von anderen vorliegen, werden auch in der EP-A-0 481 793 (Unilever) beschrieben. Die in dieser Schrift offenbarten Waschmitteltabletten enthaltend Natriumpercarbonat, das von allen anderen Komponenten, die seine Stabilität beeinflussen könnten, räumlich getrennt vorliegt. Aussagen über Härte und/oder Zerfall in Abhängigkeit von der Phasenzusammensetzung werden in dieser Schrift nicht gemacht.Detergent tablets in which individual ingredients are present separately from others are also described in EP-A-0 481 793 (Unilever). The detergent tablets disclosed in this document contain sodium percarbonate, which is spatially separated from all other components that could influence its stability. Statements about hardness and / or decay depending on the phase composition are not made in this document.
Die EP-A-0 466 485 (Unilever) beschreibt Waschmitteltabletten, die aus der Verpressung zweier tensidhaltiger Granulate hervorgegangen sind. Hierbei enthält ein Granulat die Gesamtmenge der anionischen Tenside, während das zweite Tensidgranulat vorzugsweise frei von anionischen Tensiden ist. Auch diese Schrift äußert sich nicht über Härte und/oder Zerfall in Abhängigkeit von der Phasenzusammensetzung. EP-A-0 466 485 (Unilever) describes detergent tablets which have resulted from the compression of two granules containing surfactant. One granulate contains the total amount of anionic surfactants, while the second surfactant granulate is preferably free of anionic surfactants. This document also does not comment on hardness and / or decay depending on the phase composition.
Der vorliegenden Erfindung lag nun die Aufgabe zugrunde, mehrphasige Wasch- und Reinigungsmittelformkörper bereitzustellen, die die genannten Nachteile überwinden. Insbesondere sollen mehrphasige Wasch- und Reinigungsmittelformkörper bereitgestellt werden, die in allen Phasen eine hohe Härte sowie eine hohe Zerfalls- und Lösegeschwindigkeit aufweisen, unabhängig davon, wie stark die Tensidgehalte in den einzelnen Phasen variieren.The present invention was based on the object of multiphase detergent tablets to provide, which overcome the disadvantages mentioned. In particular multi-phase detergent tablets are to be provided, which in all phases have a high hardness as well as a high rate of disintegration and dissolution, regardless of how much the surfactant levels vary in the individual phases.
Es wurde nun gefunden, daß sich mehrphasige Wasch- und Reinigungsmittelformkörper mit einem herausragenden Eigenschaftsprofil herstellen lassen, wenn bei variierenden Tensidgehalten in den einzelnen Phasen der/den tensidreicheren Phase(n) bei der Aufbereitung des zu verpressenden Vorgemischs größere Mengen an absorbierenden Stoffen zugegeben werden als der/den tensidärmeren Phase(n).It has now been found that multiphase detergent tablets with have an outstanding property profile produced if the surfactant content varies in the individual phases of the surfactant-rich phase (s) in the preparation of the compressing premix larger amounts of absorbent are added than the less surfactant phase (s).
Gegenstand der Erfindung sind nun zwei- oder mehrphasige Wasch- und Reinigungsmittelformkörper aus verdichtetem teilchenförmigen Wasch- und Reinigungsmittel, umfassend Tensid(e), Gerüststoff(e) sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile, bei denen der Tensidgehalt der einzelnen Phasen der Formkörper, bezogen auf das Gewicht der einzelnen Phase, um mehr als 3 Gew.-%, variiert, wobei in der/den Phase(n) mit dem höheren Tensidgehalt eine Komponente A mit einer Ölabsorptionskapazität von mindestens 20g/100g und einer mittleren Teilchengröße von unter 50 µm, bezogen auf das Gewicht der Phase, in höheren Mengen enthalten ist als in der/den Phase(n) mit niedrigerem Tensidgehalt.The invention now relates to two-phase or multi-phase detergent tablets made of compressed particulate detergent and cleaning agent, comprising Surfactant (s), builder (s) and optionally further detergent and cleaning agent components, in which the surfactant content of the individual phases of the moldings, based on the Weight of the individual phase, varied by more than 3 wt .-%, being in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g / 100g and an average particle size of less than 50 microns, based on the weight the phase is contained in higher amounts than in the phase (s) with a lower surfactant content.
Im Rahmen der vorliegenden Anmeldung bedeutet die Variation des Tensidgehalts um mehr als 3 Gew.-%, bezogen auf das Gewicht der einzelnen Phasen, daß die Absolutwerte des Tensidgehaltes in den Phasen um mehr als 3 Gew.-% variieren. Enthält also eine Phase 20 Gew.-% Tensid(e), so muß der Tensidgehalt der anderen Phase(n) so ausgewählt werden, daß die Breite der Variation um den Wert 20 mehr als 3 Gew.-% beträgt. In anderen Worten wird der Prozent-Zahlenwert des Tensidgehalts der tensidärmeren Phase vom Prozent-Zahlenwert des Tensidgehalts der jeweils tensidreicheren Phase subtrahiert, wobei das Ergebnis jeweils von Phase zu Phase > 3 sein muß. In einer Vierphasentablette würde dies bei einem Tensidgehalt von 12 Gew.-% in der tensidärmsten Phase bedeuten, daß die nächsten Phasen beispielsweise Tensidgehalte von 15,1 Gew.-%, 18,2 Gew.-% und 21,3 Gew.-% ausweisen.In the context of the present application, the variation in the surfactant content means more than 3% by weight, based on the weight of the individual phases, that the absolute values of the surfactant content vary in the phases by more than 3% by weight. So a 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 more than 3% by weight. In other words, the Percentage numerical value of the surfactant content of the lower surfactant phase from the percentage numerical value of the Subtracted surfactant content of the respective surfactant-rich phase, the result of each of Phase to phase must be> 3. In a four-phase tablet, this would be at a surfactant level of 12% by weight in the surfactant-poorest phase means that the next phases, for example Report surfactant contents of 15.1% by weight, 18.2% by weight and 21.3% by weight.
Es ist im Rahmen der vorliegenden Erfindung auch möglich, daß eine Phase völlig frei von Tensiden ist (entsprechend einem Tensidgehalt von 0 Gew.-%, bezogen auf diese Phase). Die nächste Phase muß dann - um den erfindungsgemäßen Kriterien zu genügen - einen Tensidgehalt von mehr als 3 Gew.-% aufweisen.It is also possible in the context of the present invention that a phase is completely free of Is surfactants (corresponding to a surfactant content of 0% by weight, based on this phase). The The next phase must then - in order to meet the criteria according to the invention - a surfactant content of more than 3% by weight.
Mit steigendem Tensidgehalt enthalten die einzelnen Phasen der erfindungsgermäßen Waschund Reinigungsmittelformkörper steigende Anteile einer Komponente A mit einer Ölabsorptionskapazität von mindestens 20g/100g, mit der Maßgabe, daß die jeweils tenisdreichere Phase bezogen auf die Gesamtzusammensetzung der Phase einen höheren Anteil an dieser Komponente aufweist. Es ist im Rahmen der vorliegenden Erfindung bevorzugt, daß der Gehalt der tensidreicheren Phase(n) an der Komponente A um mindestens 0,3 Gew.-%, vorzugsweise um mindestens 0,5 Gew.-% und insbesondere um mindestens 1 Gew.-%, bezogen auf das Gewicht der einzelnen Phase, höher ist als in der/den tensidärmeren Phase(n). Bezogen auf das oben aufgeführte Beispiel des vierphasigen Formkörpers, läßt sich der Sachverhalt folgendermaßen verdeutlichen: Enthält die tensidärmste Phase neben den genannten 12 Gew.-% Tensid 1,5 Gew.-% der Komponente A, so enthielte die zweite Phase mindestens 1,8 Gew.-% (vorzugsweise 2,0 Gew.-% und insbesondere 2,5 Gew.-%) dieser Komponente A. Der Gehalt der dritten Phase an der Komponente A richtet sich dabei nach dem realen Gehalt dieser Komponente in der zweiten Phase - auch hier beträgt die Differenz vorzugsweise mindestens 0,3 Gew.-%, weiter bevorzugt mindestens 0,5 Gew.-% und insbesondere mindestens 1,0 Gew.-%. Analoges gilt für die vierte Phase.As the surfactant content increases, the individual phases of the laundry detergent according to the invention contain Detergent tablets increasing proportions of component A with an oil absorption capacity of at least 20g / 100g, with the proviso that the more tenis-rich Phase based on the overall composition of the phase a higher proportion of this Has component. It is preferred in the context of the present invention that the content the more surfactant-rich phase (s) on component A by at least 0.3% by weight, preferably by at least 0.5% by weight and in particular by at least 1% by weight on the weight of the individual phase, is higher than in the phase (s) with less surfactant. Based the fact can be based on the example of the four-phase shaped body listed above Clarify as follows: contains the phase with the lowest surfactant content in addition to the 12% by weight Surfactant 1.5% by weight of component A, the second phase would contain at least 1.8% by weight (preferably 2.0% by weight and in particular 2.5% by weight) of this component A. The content The third phase of component A depends on the real content thereof Component in the second phase - here too the difference is preferably at least 0.3% by weight, more preferably at least 0.5% by weight and in particular at least 1.0 Wt .-%. The same applies to the fourth phase.
Neben dem absoluten Gehalt der einzelnen Phasen an Tensid(en) und der/den Komponente(n) A, der sich jeweils auf die Zusammensetzung der einzelnen Phase bezieht, ist auch das Verhältnis der Mengen in den einzelnen Phasen zueinander variierbar. Im Rahmen der vorliegenden Erfindung sind Wasch- und Reinigungsmittelformkörper bevorzugt, bei denen das Mengenverhältnis der Komponente A zwischen den einzelnen Phasen größer ist als das Mengenverhältnis der Tenside zwischen den betreffenden Phasen.In addition to the absolute content of the individual phases of surfactant (s) and the component (s) A, which refers to the composition of each phase, is also the ratio the quantities in the individual phases are mutually variable. As part of the present Invention are detergent tablets preferred, in which the quantitative ratio of component A between the individual phases is greater than the quantitative ratio of the surfactants between the relevant phases.
Zieht man zur Verdeutlichung wieder das oben erwähnte Beispiel heran, so beträgt das Verhältnis der Tensidgehalte zwischen Phase 2 und Phase 1 15,1 zu 12,0 = 1,26 zu 1. Hier ist nun bevorzugt, daß die zweite Phase im Vergleich mit der ersten so viel an der Komponente A enthält, daß das Verhältnis dieser Komponente in den beiden Phasen größer als 1,26 ist. Enthält Phase 1 also beispielsweise 1,5 Gew.-% der Komponente A, so soll Phase 2 mehr als das 1,26-fache dieses Wertes, also mindestens 1,9 Gew.-% dieser Komponente enthalten. Je nachdem, wie groß der Gehalt an Tensid und Ölabsorptionskomponente in der einzelnen Phase nun ist, kann man die Gehalte der jeweils anderen Phasen an diesen Stoffen variieren, damit sie den genannten Kriterien genügen. Bei einer Phase, die frei von einer Ölabsorptionskomponente oder frei von Tensiden ist, macht das Bilden von Verhältnissen mathematisch keinen Sinn, weshalb hier Absolutwerte im Sinne der oben erläuterten bevorzugten Ausführungsformen der vorliegenden Erfindung Anwendung finden.If the example mentioned above is used again for clarification, the ratio is the surfactant levels between phase 2 and phase 1 15.1 to 12.0 = 1.26 to 1. Here is now preferred that the second phase compared to the first so much of component A contains that the ratio of this component in the two phases is greater than 1.26. contains For example, if phase 1 is 1.5% by weight of component A, phase 2 should be more than that 1.26 times this value, ie contain at least 1.9% by weight of this component. ever according to the level of surfactant and oil absorption component in each phase now, one can vary the contents of the other phases of these substances so that they meet the criteria mentioned. In a phase that is free of an oil absorption component or is free from surfactants, makes relationships mathematical no sense, which is why absolute values in the sense of the preferred embodiments explained above find application of the present invention.
Die in den einzelnen tensidhaltigen Phasen des Formkörpers enthaltenen Ölabsorptionskomponenten weisen erfindungsgemäß eine Ölabsorptionskapazität von mindestens 20g/100g auf. Bevorzugt werden jedoch Ölabsorptionskomponenten eingesetzt, die eine höhere Ölabsorptionskapazität besitzen. Es sind dabei Wasch- und Reinigungsmittelformkörper bevorzugt, bei denen die in ihnen enthaltene Komponente A eine Ölabsorptionskapazität von mindestens 50g/100g, vorzugsweise mindestens 80g/100g, besonders bevorzugt mindestens 120g/100g und insbesondere mindestens 140g/100g aufweistThe oil absorption components contained in the individual surfactant-containing phases of the molded body according to the invention have an oil absorption capacity of at least 20g / 100g. However, preference is given to using oil absorption components which have a higher oil absorption capacity have. Detergent tablets are preferred which the component A contained in them has an oil absorption capacity of at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular has at least 140g / 100g
Die Ölabsorptionskapazität ist dabei eine physikalische Eigenschaft eines Stoffes, die sich nach genormten Methoden bestimmen läßt So existieren beispielsweise die britischen Standardmethoden BS1795 und BS3483:Part B7:1982, die beide auf die Norm ISO 787/5 verweisen. Bei den Testmethoden wird eine ausgewogene Probe des betreffenden Stoffes auf einen Teller aufgebracht und tropfenweise mit raffiniertem Leinsamenöl (Dichte: 0,93 gcm-3) aus einer Bürette versetzt. Nach jeder Zugabe wird das Pulver mit dem Öl unter Verwendung eines Spatels intensiv vermischt, wobei die Zugabe von Öl fortgesetzt wird, bis eine Paste von geschmeidiger Konsistenz erreicht ist. Diese Paste sollte fließen bzw. verlaufen, ohne zu krümeln. Die Ölabsorptionskapazität ist nun die Menge des zugetropften Öls, bezogen auf 100g Absorptionsmittel und wird in ml/100g oder g/100g angegeben, wobei Umrechnungen über die Dichte des Leinsamenöls problemlos möglich sind.The oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, there are British standard methods BS1795 and BS3483: Part B7: 1982, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm-3) from a burette is added dropwise. After each addition, the powder is mixed intensively with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100g absorbent and is given in ml / 100g or g / 100g, whereby conversions about the density of the linseed oil are easily possible.
Die Ölabsorptionskomponente besitzt vorzugsweise eine möglichst kleine mittlere Teilchengröße, da mit sinkender Teilchengröße die aktive Oberfläche steigt. Bevorzugte Wasch- und Reinigungsmittelformkörper enthalten dabei eine Komponente mit einer Ölabsorptionskapazität von mindestens 20g/100g, die eine mittlere Teilchengröße von unter 20 µm, vorzugsweise unter 10 µm aufweist.The oil absorption component preferably has the smallest possible average particle size, since the active surface increases with decreasing particle size. Preferred washing and Detergent tablets contain a component with an oil absorption capacity of at least 20g / 100g, which preferably has an average particle size of less than 20 µm has less than 10 microns.
Als Ölabsorptionskomponente eignen sich eine Vielzahl von Stoffen. Es existiert eine große Anzahl sowohl anorganischer als auch organischer Substanzen, die eine genügen große Ölabsorptionskapazität aufweisen. Beispielhaft seien hier feinteilige Stoffe, die durch Fällung gewonnen werden genannt. Als Substanzen finden beispielsweise Silikate, Aluminosilikate, Calciumsilikate, Magnesiumsilikate und Calciumcarbonat Verwendung. Aber auch Kieselgur (Diatomeenerde) und feinteilige Cellulosefasern bzw. Derivate hiervon sind im Rahmen der vorliegenden Erfindung einsetzbar. Bevorzugte Wasch- und Reinigungsmittelformkörper, zeichnen sich dadurch aus, daß die in ihnen enthaltene Komponente A ausgewählt ist aus Silikaten und/oder Aluminosilikaten, insbesondere aus der Gruppe der Kieselsäuren und/oder Zeolithe.A large number of substances are suitable as an oil absorption component. There is a big one Number of both inorganic and organic substances that have a large oil absorption capacity exhibit. Examples include finely divided substances obtained by precipitation are called. For example, silicates, aluminosilicates, Calcium silicates, magnesium silicates and calcium carbonate use. But also diatomaceous earth (Diatomaceous earth) and finely divided cellulose fibers or derivatives thereof are within the scope of present invention can be used. Preferred detergent tablets, are characterized in that component A contained in them is selected from silicates and / or aluminosilicates, in particular from the group of silicas and / or Zeolites.
Hier kommen beispielsweise feinteilige Zeolithe in Frage, aber auch pyrogene Kieselsäuren (Aerosil® ) oder Kieselsäuren, die durch Fällung erhalten wurden.Here, for example, finely divided zeolites can be used, but also pyrogenic silicas (Aerosil®) or silicas that were obtained by precipitation.
Die einzelnen Phasen des Formkörpers können im Rahmen der vorliegenden Erfindung unterschiedliche Raumformen aufweisen. Die einfachste Realisierungsmöglichkeit liegt dabei in zwei- oder mehrschichtigen Tabletten, wobei jede Schicht des Formkörpers eine Phase darstellt. Es ist aber erfindungsgemäß auch möglich, mehrphasige Formkörper herzustellen, in denen einzelne Phasen die Form von Einlagerungen in (eine) andere Phase(n) aufweisen. Neben sogenannten "Ring-Kern-Tabletten" sind dabei beispielsweise Manteltabletten oder Kombinationen der genannten Ausführungsformen möglich. Beispiele für mehrphasige Formkörper finden sich in den Abbildungen der EP-A-0 055 100 (Jeyes), die Toilettenreinigungsblöcke beschreibt. Die technisch derzeit verbreiteste Raumform mehrphasiger Formkörper ist die Zwei- oder Mehrschichttablette. Im Rahmen der vorliegenden Erfindung ist es daher bevorzugt, daß die Phasen des Formkörpers die Form von Schichten aufweisen.In the context of the present invention, the individual phases of the shaped body can have different spatial shapes. The simplest possible implementation is in two- or multi-layer tablets, with each layer of the shaped body representing a phase. However, it is also possible, according to the invention, to produce multiphase molded articles in which individual phases have the form of inclusions in (another) other phase (s). In addition to so-called "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. In the context of the present invention, it is therefore preferred that the phases of the shaped body have the form of layers.
Bei der vorliegenden Erfindung ist es erfindungswesentlich, daß der Tensidgehalt der einzelnen Phasen des Formkörpers um mehr als 3 Gew.-%, bezogen auf das Gewicht der einzelnen Phase, variiert und die tensidreichere(n) Phase(n) mehr Ölsabsorptionskomponente enthalten als die tensidärmere(n) Phase(n). Bei der Ermittlung des Tensidgehalts wird dabei die Summe der in der betreffenden Phase enthaltenen Tenside zugrundegelegt, unabhängig davon, um welchen Typ von Tensiden es sich dabei handelt. Enthält eine Phase beispielsweise anionische und nichtionische Tenside, so ist der Gesamttensidgehalt der Phase die Summe der Mengen an anionischen und nichtionischen Tensiden.In the present invention, it is essential to the invention that the surfactant content of the individual Phases of the molded body by more than 3 wt .-%, based on the weight of the individual Phase, varies and the more surfactant-rich phase (s) contain more oil absorption component than the lower surfactant phase (s). The sum is used to determine the surfactant content of the surfactants contained in the phase in question, regardless of the order what type of surfactants it is. Contains one 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.
Die Tenside können in reiner Form in die einzelnen Phasen der Formkörper eingearbeitet werden. Dies ist beispielsweise bei Seifen oder anderen leicht verarbeitbaren Tensiden problemlos möglich. Bei vielen Tensiden empfiehlt es sich aber, nicht die reinen Tenside einzuarbeiten, sondern Tensidcompounds. Diese Compounds, die je nach Anwendung möglichst hohe Tensidgehalte aufweisen sollten, können dabei durch übliche Verfahren wie Sprühtrocknung, Granulation oder Compoundierung hergestellt werden. Selbstverständlich ist auch eine Kombination mehrerer Tensidgranulate oder eine Kombination von Tensidgranulat(en) mit reinen Tensiden möglich.The surfactants can be incorporated in the individual phases of the shaped bodies in pure form become. This is no problem, for example, with soaps or other easily processable surfactants possible. With many surfactants, however, it is advisable not to incorporate the pure surfactants, but surfactant compounds. These compounds, depending on the application, if possible should have high surfactant contents, can be done by conventional methods such as spray drying, Granulation or compounding can be made. It goes without saying a combination of several surfactant granules or a combination of surfactant granules possible with pure surfactants.
Im Rahmen der vorliegenden Erfindung ist es bevorzugt, daß das/die Tensid(e) über tensidhaltige(s) Granulat(e) in die Phasen der Formkörper eingebracht werden.In the context of the present invention, it is preferred that the surfactant (s) contain surfactant-containing Granules (e) are introduced into the phases of the shaped body.
In weiteren Ausführungsformen der vorliegenden Erfindung können nun für jede Phase unterschiedliche Tensidgranulate eingesetzt werden. Es ist aber auch möglich, daß jede Phase ihren Tensidgehalt aus einem einzigen Granulat bezieht, das somit in allen Phasen des Formkörpers enthalten ist. Dies ist im Rahmen der vorliegenden Erfindung eine weitere bevorzugte Ausführungsform, bei der in allen Phasen der Formkörper das gleiche Tensidgranulat eingesetzt wird.In further embodiments of the present invention can now be different for each phase Surfactant granules are used. But it is also possible that each phase has its own The surfactant content is obtained from a single granulate, which therefore applies to all phases of the molded body is included. In the context of the present invention, this is a further preferred embodiment, in which the same surfactant granules are used in all phases of the molded body becomes.
Die einfachste denkbare Ausführungsform der vorliegenden Erfindung sieht nun eine zweiphasige Tablette vor, in der die Phasen als Schichten vorliegen und in der in beiden Schichten das gleiche Tensidgranulat in unterschiedlichen Mengen eingesetzt wird. Diese Formkörper, die zwei Schichten aufweisen, welche das gleiche Tensidgranulat enthalten, lassen sich in herkömmlichen Tablettenpressen problemlos herstellen.The simplest conceivable embodiment of the present invention now sees a two-phase Tablet in which the phases are in layers and in which in both layers the same surfactant granules are used in different amounts. These moldings, which have two layers, which contain the same surfactant granulate, can be in easily manufacture conventional tablet presses.
In den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern können anionische, nichtionische, kationische und/oder amphotere Tenside beziehungsweise Mischungen aus diesen eingesetzt werden. Bevorzugt sind aus anwendungstechnischer Sicht Mischungen aus anionischen und nichtionischen Tensiden. Der Gesamttensidgehalt der Formkörper liegt bei 5 bis 60 Gew.-%, bezogen auf das Formkörpergewicht, wobei Tensidgehalte über 15 Gew.-% bevorzugt sind.In the detergent tablets according to the invention, anionic, nonionic, cationic and / or amphoteric surfactants or mixtures of these are used. Mixtures of are preferred from an application point of view anionic and nonionic surfactants. The total surfactant content of the moldings is 5 up to 60% by weight, based on the weight of the shaped body, surfactant contents above 15% by weight are preferred.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkem- oder Talgfettsäuren geeignet.Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably 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 a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem namen DAN® erhalten werden können, sind geeignete Aniontenside.As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut 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 this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The 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.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.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.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Other 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. 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). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkem- oder Talgfettsäuren, abgeleitete Seifengemische.Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable 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.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kaliumoder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natriumoder Kaliumsalze, insbesondere in Form der Natriumsalze vor.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, available. The anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.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 can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, 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). In addition to these nonionic surfactants, 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.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In addition, 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.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden.Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably described in the international patent application Methods described in WO-A-90/13533.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Also 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 them.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I), in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II), in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R1 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.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 remainder.
[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielweise nach der Lehre der internationalen Anmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.[Z] is preferably obtained by reductive amination of 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 reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
Im Rahmen der vorliegenden Erfindung sind Wasch- und Reinigungsmittelformkörper bevorzugt, die anionische(s) und nichtionische(s) Tensid(e) enthalten, wobei anwendungstechnische Vorteile aus bestimmten Mengenverhältnissen, in denen die einzelnen Tensidklassen eingesetzt werden, resultieren können.In the context of the present invention, detergent tablets are preferred, which contain anionic (s) and nonionic (s) surfactant (s), application technology Advantages from certain proportions in which the individual surfactant classes are used will result.
So sind beispielsweise Wasch- und Reinigungsmittelformkörper besonders bevorzugt, bei denen 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.For example, detergent tablets are particularly preferred which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably is between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
Es kann aus anwendungstechnischer Sicht Vorteile haben, wenn bestimmte Tensidklassen in einigen Phasen der Wasch- und Reinigungsmittelformkörper oder im gesamten Formkörper, d.h. in allen Phasen, nicht enthalten sind. Eine weitere wichtige Ausführungsform der vorliegenden Erfindung sieht daher vor, daß mindestens eine Phase der Formkörper frei von nichtionischen Tensiden ist.From an application point of view, it can have advantages if certain classes of surfactants are used some phases of the detergent tablets or in the entire tablet, i.e. in all phases, are not included. Another important embodiment of the present The invention therefore provides that at least one phase of the shaped body is free of nonionic Is surfactants.
Umgekehrt kann aber auch durch den Gehalt einzelner Phasen oder des gesamten Formkörpers, d.h. aller Phasen, an bestimmten Tensiden ein positiver Effekt erzielt werden. Das Einbringen der oben beschriebenen Alkylpolyglycoside hat sich dabei als vorteilhaft erwiesen, so daß Wasch- und Reinigungsmittelformkörper bevorzugt sind, in denen mindestens eine Phase der Formkörper Alkylpolyglycoside enthält.Conversely, however, the content of individual phases or of the entire molded body, i.e. all phases, a positive effect can be achieved on certain surfactants. The bringing in the alkyl polyglycosides described above have proven to be advantageous, so that detergent tablets are preferred in which at least one phase the molded body contains alkyl polyglycosides.
Ähnlich wie bei den nichtionischen Tensiden können auch aus dem Weglassen von anionischen Tensiden aus einzelnen oder allen Phasen Wasch- und Reinigungsmittelformkörper resultieren, die sich für bestimmte Anwendungsgebiete besser eignen. Es sind daher im Rahmen der vorliegenden Erfindung auch Wasch- und Reinigungsmittelformkörper denkbar, bei denen mindestens eine Phase der Formkörper frei von anionischen Tensiden ist.Similar to the nonionic surfactants can also be left out of anionic Surfactants from individual or all phases of detergent tablets result that are more suitable for certain areas of application. It is therefore in the frame the present invention also conceivable detergent tablets, which at least one phase of the shaped body is free of anionic surfactants.
Neben den waschaktiven Substanzen sind Gerüststoffe die wichtigsten Inhaltsstoffe von Wasch- und Reinigungsmitteln. In den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern können dabei alle üblicherweise in Wasch- und Reinigungsmitteln eingesetzten Gerüststoffe enthalten sein, insbesondere also Zeolithe, Silikate, Carbonate, organische Cobuilder und -wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen- auch die Phosphate. In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the detergent tablets according to the invention can all be used in washing and cleaning agents Builders may be included, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.
Geeignete kristalline, schichtförmige Natriumsilikate besitzen die allgemeine Formel NaMSixO2x+1 .yH2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5 . yH2O bevorzugt, wobei β-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/08171 beschrieben ist.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 are 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. In particular, both β- and δ-sodium disilicates are Na 2 Si 2 O 5 . yH 2 O is preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/ Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamorphe Silikate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE-A- 44 00 024 beschrieben. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate. Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. 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. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the 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. However, 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.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist
vorzugsweise Zeolith A und/oder P. Als Zeolith P wird Zeolith MAP® (Handelsprodukt der
Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen
aus A, X und/oder P. Kommerziell erhältlich und im Rahmen der vorliegenden Erfindung
bevorzugt einsetzbar ist beispielsweise auch ein Co-Kristallisat aus Zeolith X und Zeolith A
(ca. 80 Gew.-% Zeolith X), das von der Firma CONDEA Augusta S.p.A. unter dem Markennamen
VEGOBOND AX® vertrieben wird und durch die Formel
Selbstverständlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Geeignet sind insbesondere die Natriumsalze der Orthophosphate, der Pyrophosphate und insbesondere der Tripolyphosphate.It goes without saying that the generally known phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bemsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Um den Zerfall hochverdichteter Formkörper zu erleichtern, ist es möglich, Desintegrationshilfsmittel, sogenannte Tablettensprengmittel, in diese einzuarbeiten, um die Zerfallszeiten zu verkürzen. Unter Tablettensprengmitteln bzw. Zerfallsbeschleunigem werden gemäß Römpp (9. Auflage, Bd. 6, S. 4440) und Voigt "Lehrbuch der pharmazeutischen Technologie" (6. Auflage, 1987, S. 182-184) Hilfsstoffe verstanden, die für den raschen Zerfall von Tabletten in Wasser oder Magensaft und für die Freisetzung der Pharmaka in resorbierbarer Form sorgen.Usable organic builders are, for example, the polycarboxylic acids which 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), provided that 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. In order to facilitate the disintegration of highly compressed moldings, disintegration aids, so-called tablet disintegrants, can be incorporated into them in order to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184), tablet disintegrants or disintegration accelerators are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in resorbable form.
Diese Stoffe, die auch aufgrund ihrer Wirkungs als "Spreng"mittel bezeichnet werden, vergrößem bei Wasserzutritt ihr Volumen, wobei einerseits das Eigenvolumen vergrößert (Quellung), andererseits auch über die Freisetzung von Gasen ein Druck erzeugt werden kann, der die Tablette in kleinere Partikel zerfallen läßt. Altbekannte Desintegrationshilfsmittel sind beispielsweise Carbonat/Citronensäure-Systeme, wobei auch andere organische Säuren eingesetzt werden können. Quellende Desintegrationshilfsmittel sind beispielsweise synthetische Polymere wie Polyvinylpyrrolidon (PVP) oder natürliche Polymere bzw. modifizierte Naturstoffe wie Cellulose und Stärke und ihre Derivate, Alginate oder Casein-Derivate.These substances, which are also referred to as "explosives" due to their effectiveness, increase their volume in the event of water ingress, on the one hand increasing their own volume (swelling), on the other hand, a pressure can be generated via the release of gases, which the tablet disintegrates into smaller particles. Well-known disintegration aids are for example carbonate / citric acid systems, with other organic acids also being used can be. Swelling disintegration aids are, for example, synthetic Polymers such as polyvinyl pyrrolidone (PVP) or natural polymers or modified natural products such as cellulose and starch and their derivatives, alginates or casein derivatives.
Bevorzugte Wasch- und Reinigungsmittelformkörper enthalten 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-% eines oder mehrerer Desintegrationshilfsmittel, jeweils bezogen auf das Formkörpergewicht.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 aids, each based on the weight of the molded article.
Als bevorzugte Desintegrationsmittel werden im Rahmen der vorliegenden Erfindung Desintegrationsmittel auf Cellulosebasis eingesetzt, so daß bevorzugte Wasch- und Reinigungsmittelformkörper ein solches Desintegrationsmittel auf Cellulosebasis in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-% enthalten. Reine Cellulose weist die formale Bruttozusammensetzung (C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei aus ca. 500 bis 5000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von 50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate einsetzen. In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC), Celluloseester und -ether sowie Aminocellulosen. Die genannten Cellulosederivate werden vorzugsweise nicht allein als Desintegrationsmittel auf Cellulosebasis eingesetzt, sondern in Mischung mit Cellulose verwendet. Der Gehalt dieser Mischungen an Cellulosederivaten beträgt vorzugsweise unterhalb 50 Gew.-%, besonders bevorzugt unterhalb 20 Gew.-%, bezogen auf das Desintegrationsmittel auf Cellulosebasis. Besonders bevorzugt wird als Desintegrationsmittel auf Cellulosebasis reine Cellulose eingesetzt, die frei von Cellulosederivaten ist.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, viewed formally, is a β-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. However, 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.
Die als Desintegrationshilfsmittel eingesetzte Cellulose wird vorzugsweise nicht in feinteiliger Form eingesetzt, sondern vor dem Zumischen zu den zu verpressenden Vorgemischen in eine gröbere Form überführt, beispielsweise granuliert oder kompaktiert. Wasch- und Reinigungsmittelformkörper, die Sprengmittel in granularer oder gegebenenfalls cogranulierter Form enthalten, werden in den deutschen Patentanmeldungen DE 197 09 991 (Stefan Herzog) und DE 197 10 254 (Henkel) sowie der internationalen Patentanmeldung WO 98/40463 (Henkel) beschrieben. Diesen Schriften sind auch nähere Angaben zur Herstellung granulierter, kompaktierter oder cogranulierter Cellulosesprengmittel zu entnehmen. Die Teilchengrößen solcher Desintegrationsmittel liegen zumeist oberhalb 200 µm, vorzugsweise zu mindestens 90 Gew.-% zwischen 300 und 1600 µm und insbesondere zu mindestens 90 Gew.-% zwischen 400 und 1200 µm. Die vorstehend genannten und in den zitierten Schriften näher beschriebenen gröberen Desintegrationshilfsmittel auf Cellulosebasis sind im Rahmen der vorliegenden Erfindung bevorzugt als Desintegrationshilfsmittel einzusetzen und im Handel beispielsweise unter der Bezeichnung Arbocel® TF-30-HG von der Firma Rettenmaier erhältlich.The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. Detergent tablets which contain disintegrants in granular or, 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 WO 98/40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned coarser disintegration aids based on cellulose and 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.
Als weiteres Desintegrationsmittel auf Cellulosebasis oder als Bestandteil dieser Komponente kann mikrokristalline Cellulose verwendet werden. Diese mikrokristalline Cellulose wird durch partielle Hydrolyse von Cellulosen unter solchen Bedingungen erhalten, die nur die amorphen Bereiche (ca. 30% der Gesamt-Cellulosemasse) der Cellulosen angreifen und vollständig auflösen, die kristallinen Bereiche (ca. 70%) aber unbeschadet lassen. Eine nachfolgende Desaggregation der durch die Hydrolyse entstehenden mikrofeinen Cellulosen liefert die mikrokristallinen Cellulosen, die Primärteilchengrößen von ca. 5 µm aufweisen und beispielsweise zu Granulaten mit einer mittleren Teilchengröße von 200 µm kompaktierbar sind.As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose will obtained by partial hydrolysis of celluloses under such conditions that only the attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses completely dissolve, but leave the crystalline areas (approx. 70%) undamaged. A subsequent one Disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and, for example can be compacted into granules with an average particle size of 200 μm.
Wasch- und Reinigungsmittelformkörper, die 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, sind im Rahmen der vorliegenden Erfindung besonders bevorzugt.Detergent tablets, which are additionally a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 up to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body, contained are particularly preferred in the context of the present invention.
Die Herstellung wasch- und reinigungsaktiver Formkörper geschieht durch Anwendung von Druck auf ein zu verpressendes Gemisch, das sich im Hohlraum einer Presse befindet. Im einfachsten Fall der Formkörperherstellung, die nachfolgend vereinfacht Tablettierung genannt wird, wird die zu tablettierende Mischung direkt, d.h. ohne vorhergehende Granulation verpreßt. Die Vorteile dieser sogenannten Direkttablettierung sind ihre einfache und kostengünstige Anwendung, da keine weiteren Verfahrensschritte und demzufolge auch keine weiteren Anlagen benötigt werden. Diesen Vorteilen stehen aber auch Nachteile gegenüber. So muß eine Pulvermischung, die direkt tablettiert werden soll, eine ausreichende plastische Verformbarkeit besitzen und gute Fließeigenschaften aufweisen, weiterhin darf sie während der Lagerung, des Transports und der Befüllung der Matrize keinerlei Entmischungstendenzen zeigen. Diese drei Voraussetzungen sind bei vielen Substanzgemischen nur außerordentlich schwierig zu beherrschen, so daß die Direkttablettierung insbesondere bei der Herstellung von Wasch- und Reinigungsmittel-tabletten nicht oft angewendet wird. Der übliche Weg zur Herstellung von Wasch- und Reinigungsmitteltabletten geht daher von pulverförmigen Komponenten ("Primärteilchen") aus, die durch geeignete Verfahren zu Sekundärpartikeln mit höherem Teilchendurchmesser agglomeriert bzw. granuliert werden. Diese Granulate oder Gemische unterschiedlicher Granulate werden dann mit einzelnen pulverförmigen Zuschlagstoffen vermischt und der Tablettierung zugeführt. Je nach Ausgestaltung der Phasen der mehrphasigen Wasch- und Reinigungsmittelformkörper wird die Matrize dabei schrittweise mit unterschiedlichen Vorgemischen befüllt. Bei der Herstellung mehrschichtiger Tabletten kann eine leichte Druckanwendung zwischen der Befüllung mit dem Vorgemisch für die nächste Schicht Vorteile haben. Bei der Herstellung von Ring-Kern-Formkörpern oder Manteltabletten ist eine solche Vorverpressung mit Formgebung sogar nahezu unerläßlich.The production of washing and cleaning-active moldings is done by using Pressure on a mixture to be pressed, which is located in the cavity of a press. in the simplest case of molded article production, which is referred to below simply as tableting the mixture to be tabletted is directly, i.e. without previous granulation pressed. The advantages of this so-called direct tableting are its simple and inexpensive Application, since no further process steps and therefore no further Attachments are needed. However, these advantages are offset by disadvantages. So a powder mixture that is to be tabletted directly must have sufficient plastic deformability possess and have good flow properties, furthermore it may be used during the Storage, transportation and filling of the die have no tendency to separate demonstrate. These three requirements are only extraordinary for many substance mixtures difficult to master, so that direct tableting, especially in the manufacture of Detergent tablets are not often used. The usual way of making detergent tablets are therefore based on powdery components ("Primary particles"), which by means of suitable processes to secondary particles with higher Particle diameter can be agglomerated or granulated. These granules or mixtures different granules are then made with individual powdered additives mixed and fed to the tableting. Depending on the design of the phases of the multi-phase Detergent and cleaning product tablets are gradually made with different molds Premixes filled. When making multilayer tablets, one can apply light pressure between the pre-mix filling for the next shift Have advantages. One of them is in the production of ring-core shaped articles or coated tablets such pre-pressing with shaping is almost indispensable.
Im Rahmen der vorliegenden Erfindung bevorzugte Wasch- und ReinigungsmitteIformkörper werden durch Verpressen teilchenförmiger Vorgemische aus mindestens einem tensidhaltigen Granulat und mindestens einer nachträglich zugemischten pulverförmigen Komponente erhalten. Die tensidhaltigen Granulate können dabei über übliche Granulierverfahren wie Mischer- und Tellergranulation, Wirbelschichtgranulation, Extrusion, Pelletierung oder Kompaktierung hergestellt werden. Es ist dabei für die späteren Wasch- und Reinigungsmittelformkörper von Vorteil, wenn die zu verpressenden Vorgemische ein Schüttgewicht aufweisen, das dem üblicher Kompaktwaschmittel nahe kommt Insbesondere ist es bevorzugt, 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. Ein weiterer Vorteil kann aus einer engeren Teilchengrößenverteilung der eingesetzten Tensidgranulate resultieren. Im Rahmen der vorliegenden Erfinduing sind Wasch- und Reinigungsmittelformkörper bevorzugt, bei denen die Granulate Teilchengrößen zwischen 10 und 4000 µm, vorzugsweise zwischen 100 und 2000 µm und insbesondere zwischen 600 und 1400 µm aufweisen.Preferred washing and cleaning agents in the context of the present invention are obtained by compressing particulate premixes from at least one surfactant Granules and at least one subsequently mixed powdered component. The surfactant-containing granules can be processed using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelleting or compacting getting produced. It is for the later detergent tablets advantageous if the premixes to be pressed have a bulk density, that comes close to the usual compact detergent. In particular, it is preferred that the premix to be pressed has 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 result from a narrower particle size distribution of the surfactant granules used. Detergent and cleaning product tablets are within the scope of the present invention preferred, in which the granules particle sizes between 10 and 4000 microns, preferably have between 100 and 2000 microns and in particular between 600 and 1400 microns.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung zwei- oder mehrphasiger Wasch- und Reinigungsmittelformkörper, welche Tensid(e), Gerüststoff(e) sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile enthalten, durch an sich bekanntes Verpressen, das dadurch gekennzeichnet ist, 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, bezogen auf das Gewicht der einzelnen Phase, um mehr als 3 Gew.-% variiert und in der/den Phase(n) mit dem höheren Tensidgehalt eine Komponente A mit einer Ölabsorptionskapazität von mindestens 20g/100g und einer mittleren Teilchengröße von unter 50 µm, bezogen auf das Gewicht der Phase, in höheren Mengen enthalten ist als in der/den Phase(n) mit niedrigerem Tensidgehalt. Another object of the present invention is therefore a method for manufacturing two-phase or multi-phase detergent tablets, which surfactant (s), builders (e) and optionally contain further detergent and cleaning agent components, by pressing known per se, which is characterized in that it is carried out by pressing a particulate premix consisting of at least one surfactant-containing granulate and at least one a subsequently admixed powdery component were obtained, wherein the surfactant content of the individual phases of the moldings, based on the weight of the individual Phase varied by more than 3% by weight and in the phase (s) with the higher surfactant content a component A with an oil absorption capacity of at least 20g / 100g and an average particle size of less than 50 microns, based on the weight of the phase, in higher Amounts are contained in the phase (s) with a lower surfactant content.
Bezüglich der Variation des Tensidgehalts und bevorzugter Werte gelten die vorstehenden Angaben analog auch für das erfindungsgemäße Verfahren.The above applies to the variation of the surfactant content and preferred values Analogous information also for the method according to the invention.
Bevorzugte Verfahren sind dabei dadurch gekennzeichnet, daß die Granulate über übliche Granulierverfahren wie Mischer- und Tellergranulation, Wirbelschichtgranulation, Extrusion, Pelletierung oder Kompaktierung hergestellt wurden. In besonders bevorzugten Verfahren weisen die Granulate Teilchengrößen zwischen 10 und 4000 µm, vorzugsweise zwischen 100 und 2000 µm und insbesondere zwischen 600 und 1400 µm auf.Preferred processes are characterized in that the granules are made using conventional ones Granulation processes such as mixer and plate granulation, fluid bed granulation, extrusion, Pelleting or compacting were made. In particularly preferred processes the granules have particle sizes between 10 and 4000 μm, preferably between 100 and 2000 µm and in particular between 600 and 1400 µm.
Auch die Teilchengrößenverteilung der nachträglich zugemischten pulverförmigen Aufbereitungskomponenten kann variiert werden, wobei Verfahren bevorzugt sind, bei denen die nachträglich zugemischte(n) pulverförmige(n) Komponente(n) die Komponente A enthalten.The particle size distribution of the subsequently mixed powder-form processing components can be varied, with methods preferred in which the subsequently mixed powdered component (s) containing component A.
Vor der Verpressung des teilchenförmigen Vorgemischs zu Wasch- und Reinigungsmittelformkörpern kann das Vorgemisch mit feinteiligen Oberflächenbehandlungsmitteln "abgepudert" werden. Dies kann für die Beschaffenheit und physikalischen Eigenschaften sowohl des Vorgemischs (Lagerung, Verpressung) als auch der fertigen Wasch- und Reinigungsmittelformkörper von Vorteil sein. Feinteilige Abpuderungsmittel sind im Stand der Technik altbekannt, wobei zumeist Zeolithe, Silikate oder andere anorganische Salze eingesetzt werden. Bevorzugt wird das Vorgemisch jedoch mit feinteiligem Zeolith "abgepudert", wobei Zeolithe vom Faujasit-Typ bevorzugt sind. Im Rahmen der vorliegenden Erfindung kennzeichnet der Begriff "Zeolith vom Faujasit-Typ" alle drei Zeolithe, die die Faujasit-Untergruppe der Zeolith-Strukturgruppe 4 bilden (Vergleiche Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974. Seite 92). Neben dem Zeolith X sind also auch Zeolith Y und Faujasit sowie Mischungen dieser Verbindungen einsetzbar, wobei der reine Zeolith X bevorzugt ist.Before pressing the particulate premix into detergent tablets can 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 detergent tablets be an advantage. Finely divided powdering agents are known in the art Well-known technology, mostly using zeolites, silicates or other inorganic salts become. However, the premix is preferably "powdered" with finely divided zeolite, faujasite type zeolites are preferred. Within the scope of the present invention The term "faujasite type zeolite" denotes all three zeolites that make up the faujasite subgroup of the zeolite structure group 4 (compare Donald W. Breck: "Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974. Page 92). In addition to zeolite X, there are also zeolite Y and faujasite and mixtures of these Compounds can be used, the pure zeolite X being preferred.
Auch Mischungen oder Cokristallisate von Zeolithen des Faujasit-Typs mit anderen Zeolithen, die nicht zwingend der Zeolith-Strukturgruppe 4 angehören müssen, sind als Abpuderungsmittel einsetzbar, wobei es von Vorteil ist, wenn mindestens 50 Gew.-% des Abpuderungsmittels aus einem Zeolithen vom Faujasit-Typ bestehen.Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which do not necessarily belong to the zeolite structure group 4 are used as powdering agents can be used, it being advantageous if at least 50% by weight of the powdering agent are made from a faujasite type zeolite.
Diese Abpuderungsmittel können selbstverständlich eine Ölsabsorptionskapazität von mehr als 20g/100g aufweisen, wobei sie die Ölabsorptionskomponente ersetzen oder ergänzen können. Wenn die Abpuderungsmittel zusätzlich zu den Ölabsorptionskomponenten eingesetzt werden und eine Ölabsorptionskapazität von mehr als 20g/100g aufweisen, sind sie bei der Berechnung des Anteils in den einzelnen Phasen selbstverständlich zu berücksichtigen.These powdering agents can of course have an oil absorption capacity of more have as 20g / 100g, where they can replace or supplement the oil absorption component. When the powdering agent is used in addition to the oil absorption components and have an oil absorption capacity of more than 20g / 100g, they are at The calculation of the share in the individual phases must of course be taken into account.
Im Rahmen der vorliegenden Erfindung sind Wasch- und Reinigungsmittelformkörper bevorzugt, die aus einem teilchenförmigen Vorgemisch bestehen, das granulare Komponenten und nachträglich zugemischte pulverförmige Stoffe enthält, wobei 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.In the context of the present invention, detergent tablets are preferred, which consist of a particulate premix, the granular components and subsequently contains powdered substances, the or one of the subsequently admixed powdered components a zeolite of the faujasite type with particle sizes is below 100 µm, preferably below 10 µm and in particular below 5 µm and at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1 Makes up% by weight of the premix to be pressed.
Die feinteiligen Aufbereitungskomponenten mit den obengenannten Teilchengrößen können dabei dem zu verpressenden Vorgemisch trocken zugemischt werden. Es ist aber auch möglich und bevorzugt, sie durch Zugabe geringer Mengen flüssiger Stoffe an die Oberfläche der gröberen Teilchen "anzukleben". Diese Abpuderungsverfahren sind im Stand der Technik breit beschrieben und dem Fachmann geläufig. Als flüssige Komponenten, die sich zur Haftvermittlung der Abpuderungsmittel eignen, können beispielsweise nichtionischen Tenside oder wäßrige Lösungen von Tensiden oder anderen Wasch- und Reinigungsmittelinhaltsstoffen eingesetzt werden. Im Rahmen der vorliegenden Erfindung ist es bevorzugt, als flüssigen Haftvermittler zwischen feinteiligem Abpuderungsmittel und den grobkörnigen Teilchen Parfüm einzusetzen.The finely divided processing components with the particle sizes mentioned above can be mixed dry with the premix to be pressed. But it is also possible and preferably, by adding small amounts of liquids to the surface of the "stick" coarser particles. These powdering processes are state of the art broadly described and familiar to the expert. As liquid components that are used for adhesion mediation suitable powdering agents, for example nonionic surfactants or aqueous solutions of surfactants or other detergents and cleaning agents be used. In the context of the present invention, it is preferred as a liquid Adhesion promoter between finely divided powdering agent and the coarse particles of perfume use.
Neben den genannten Bestandteilen Tensid, Builder und Desintegrationshilfsmittel, können die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper weitere in Wasch- und Reinigungsmittel übliche Inhaltsstoffe aus der Gruppe der Bleichmittel, Bleichaktivatoren, Enzyme, Duftstoffe, Parfümträger, Fluoreszenzmittel, Farbstoffe, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, optischen Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren und Korrosionsinhibitoren enthalten.In addition to the ingredients mentioned, surfactant, builder and disintegration aid can the detergent tablets according to the invention further in detergents usual ingredients from the group of bleaching agents, bleach activators, enzymes, Fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, Anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and contain corrosion inhibitors.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure.Among the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
Um beim Waschen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren als alleiniger Bestandteil oder als Inhaltsstoff der Komponente b) eingearbeitet werden. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran.To improve the bleaching effect when washing at temperatures of 60 ° C and below To achieve, bleach activators can be used as the sole component or as an ingredient of Component b) are incorporated. 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. Substances containing O- and / or N-acyl groups are suitable carry the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine, are preferred (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch sogenannte Bleichkatalysatoren in die Formkörper eingearbeitet werden. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts can be incorporated into the moldings. Acting on these substances it is bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt 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 amine complexes can be used as bleaching catalysts.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere jedoch Cellulase-haltige Mischungen von besonderem Interesse. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate in den erfindungsgemäßen Formkörpem kann beispielsweise etwa 0, 1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen.Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules in the moldings according to the invention can, for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
Zusätzlich können die Wasch- und Reinigungsmittelformkörper auch Komponenten enthalten, welche die Öl- und Fettauswaschbarkeit aus Textilien positiv beeinflussen (sogenannte soil repellents). Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfindungsgemäßen Waschmittel, das diese öl- und fettlösende Komponente enthält, gewaschen wurde. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxy-propylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Besonders bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und der Terephthalsäure-Polymere.In addition, the detergent tablets can also contain components which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile that is already soiled previously several times with a detergent according to the invention that this oil and fat-dissolving Contains component that has been washed. Among the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers of phthalic acid known from the prior art 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. Of these, those are particularly preferred sulfonated derivatives of phthalic acid and terephthalic acid polymers.
Die Formkörper können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.The moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid 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, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Farther brighteners of the substituted diphenylstyryl type may be present, e.g. the 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 brighteners can be used.
Farb- und Duftstoffe werden den erfindungsgemäßen Mitteln zugesetzt, um den ästhetischen Eindruck der Produkte zu verbessern und dem Verbraucher neben der Weichheitsleistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethem zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl.Dyes and 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 to provide visually and sensory "typical and distinctive" product. As perfume oils or fragrances, individual fragrance compounds, e.g. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are e.g. benzyl acetate, Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenylglycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. To the etheme include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 Carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes like lime and pinene. However, mixtures of different fragrances are preferred used, which together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those obtainable from plant sources are, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.
Üblicherweise liegt der Gehalt der erfindungsgemäßen Weichmacher an Farbstoffen unter 0,01 Gew.-%, während Duftstoffe bis zu 2 Gew.-% der gesamten Formulierung ausmachen können.The dye content of the plasticizers according to the invention is usually lower 0.01% by weight, while fragrances make up up to 2% by weight of the total formulation can.
Die Duftstoffe können direkt in die erfindungsgemäßen Mittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.The fragrances can be incorporated directly into the agents according to the invention, it can but it may also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume reinforce on the laundry and through a slower fragrance release for long-lasting Ensure the fragrance of the textiles. Cyclodextrins, for example, have become such carrier materials proven, the cyclodextrin-perfume complexes additionally with others Auxiliaries can be coated.
Um den ästhetischen Eindruck der erfindungsgemäßen Wasch- und Reinigungsmittelformkörper zu verbessern, können sie mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasem, um diese nicht anzufärben. Da der Gegenstand der vorliegenden Erfindung mehrphasige Wasch- und Reinigungsmittelformkörper betrifft, kommt der Einfärbung einzelner Phasen eine erhöhte Bedeutung zu, um den unterschiedlichen Wirkcharakter einzelner Phasen zu unterstreichen. Beispiele für die Wirksamkeit solcher Einfärbungen und für den Erfolg von Aussagen hierzu sind aus der Gebißreinigerwerbung hinlänglich bekannt. For the aesthetic impression of the detergent tablets according to the invention To improve, they can be colored with suitable dyes. preferred Dyes, the selection of which is not difficult for the person skilled in the art, have a high level Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers to stain. Since the subject of the present invention multi-phase detergent tablets concerns, the coloring of individual phases is of increased importance to underline the different effects of individual phases. Examples for the effectiveness of such coloring and for the success of statements well known from the denture cleaner advertising.
Die Herstellung der erfindungsgemäßen Formkörper erfolgt zunächst durch das trockene Vermischen der Bestandteile der einzelnen Phasen, die ganz oder teilweise vorgranuliert sein können, und anschließendes Informbringen, insbesondere Verpressen zu Tabletten, wobei auf herkömmliche Verfahren zur Herstellung mehrphasiger Formkörper zurückgegriffen werden kann. Zur Herstellung der erfindungsgemäßen mehrphasigen Formkörper werden die Vorgemische in einer sogenannten Matrize zwischen zwei Stempeln zu einem festen Komprimat verdichtet. Dieser Vorgang, der im folgenden kurz als Tablettierung bezeichnet wird, gliedert sich in vier Abschnitte: Dosierung, Verdichtung (elastische Verformung), plastische Verformung und Ausstoßen.The moldings according to the invention are first produced by dry Mixing the components of the individual phases, which are partially or completely pre-granulated can, and then bringing information, in particular compression to tablets, whereby conventional methods for the production of multi-phase molded articles can be used can. The premixes are used to produce the multiphase moldings according to the invention in a so-called matrix between two stamps to form a solid compressed product compacted. This process, which is briefly referred to below as tabletting, is structured divided into four sections: metering, compression (elastic deformation), plastic deformation and expelling.
Die Tablettierung erfolgt in handelsüblichen Tablettenpressen, die prinzipiell mit Einfachoder Zweifachstempeln ausgerüstet sein können. Im letzteren Fall wird nicht nur der Oberstempel zum Druckaufbau verwendet, auch der Unterstempel bewegt sich während des Preßvorgangs auf den Oberstempel zu, während der Oberstempel nach unten drückt. Für kleine Produktionsmengen werden vorzugsweise Exzentertablettenpressen verwendet, bei denen der oder die Stempel an einer Exzenterscheibe befestigt sind, die ihrerseits an einer Achse mit einer bestimmten Umlaufgeschwindigkeit montiert ist. Die Bewegung dieser Preßstempel ist mit der Arbeitsweise eines üblichen Viertaktmotors vergleichbar. Die Verpressung kann mit je einem Ober- und Unterstempel erfolgen; es können aber auch mehrere Stempel an einer Exzenterscheibe befestigt sein, wobei die Anzahl der Matrizenbohrungen entsprechend erweitert ist. Die Durchsätze von Exzenterpressen variieren ja nach Typ von einigen hundert bis maximal 3000 Tabletten pro Stunde.Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, the lower punch also moves during the pressing process towards the upper stamp while the upper stamp presses down. For little ones Production quantities are preferably eccentric tablet presses in which the or the stamps are attached to an eccentric disc, which in turn is on an axis a certain rotational speed is mounted. The movement of this ram is comparable to the way a conventional four-stroke engine works. The pressing can be done with one upper and one lower stamp; however, several stamps can also be on one Eccentric disk can be attached, the number of die holes correspondingly expanded is. The throughputs of eccentric presses vary from a few hundred to depending on the type maximum 3000 tablets per hour.
Für größere Durchsätze wählt man Rundlauftablettenpressen, bei denen auf einem sogenannten Matrizentisch eine größere Anzahl von Matrizen kreisförmig angeordnet ist. Die Zahl der Matrizen variiert je nach Modell zwischen 6 und 55, wobei auch größere Matrizen im Handel erhältlich sind. Jeder Matrize auf dem Matrizentisch ist ein Ober- und Unterstempel zugeordnet, wobei wiederum der Preßdruck aktiv nur durch den Ober- bzw. Unterstempel, aber auch durch beide Stempel aufgebaut werden kann. Der Matrizentisch und die Stempel bewegen sich um eine gemeinsame senkrecht stehende Achse, wobei die Stempel mit Hilfe schienenartiger Kurvenbahnen während des Umlaufs in die Positionen für Befüllung, Verdichtung, plastische Verformung und Ausstoß gebracht werden. An den Stellen, an denen eine besonders gravierende Anhebung bzw. Absenkung der Stempel erforderlich ist (Befüllen, Verdichten, Ausstoßen), werden diese Kurvenbahnen durch zusätzliche Niederdruckstücke, Nierderzugschienen und Aushebebahnen unterstützt. Die Befüllung der Matrize erfolgt über eine starr angeordnete Zufuhreinrichtung, den sogenannten Füllschuh, der mit einem Vorratsbehälter für die Vorgemische verbunden ist. Der Preßdruck auf das jeweilige Vorgemisch ist über die Preßwege für Ober- und Unterstempel individuell einstellbar, wobei der Druckaufbau durch das Vorbeirollen der Stempelschaftköpfe an verstellbaren Druckrollen geschieht.For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table 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 matrices are also commercially available are available. Each die on the die table is assigned an upper and lower stamp, where again the pressure is active only through the upper or lower stamp, but also can be built by both stamps. The die table and the stamps move around a common vertical axis, the stamp using rail-like Curve tracks during the circulation in the positions for filling, compression, plastic Deformation and discharge are brought. In places where one is special serious raising or lowering of the stamp is necessary (filling, compacting, Eject), these cam tracks are by additional low-pressure pieces, kidney rails and lift tracks supported. The matrix is filled with a rigid one arranged feed device, the so-called filling shoe, which with a storage container for the premixes are connected. The pressure on the respective premix is over the Press paths for upper and lower punches individually adjustable, whereby the pressure build-up the stamp shaft heads roll past adjustable pressure rollers.
Rundlaufpressen können zur Erhöhung des Durchsatzes auch mit zwei oder mehreren Füllschuhen versehen werden. Zur Herstellung zwei-und mehrschichtiger Formkörper werden mehrere Füllschuhe hintereinander angeordnet, ohne daß die leicht angepreßte erste Schicht vor der weiteren Befüllung ausgestoßen wird. Durch geeignete Prozeßführung sind auf diese Weise auch Mantel- und Punkttabletten herstellbar, die einen zwiebelschalenartigen Aufbau haben, wobei im Falle der Punkttabletten die Oberseite des Kerns bzw. der Kemschichten nicht überdeckt wird und somit sichtbar bleibt. Auch Rundlauftablettenpressen sind mit Einfach- oder Mehrfachwerkzeugen ausrüstbar, so daß beispielsweise ein äußerer Kreis mit 50 und ein innerer Kreis mit 35 Bohrungen gleichzeitig zum Verpressen benutzt werden. Die Durchsätze moderner Rundlauftablettenpressen betragen über eine Million Formkörper pro Stunde.Rotary presses can also be used with two or more filling shoes to increase the throughput be provided. For the production of two-layer and multi-layer moldings several filling shoes arranged one behind the other without the slightly pressed first layer is ejected before further filling. Appropriate process management is based on this In this way, coated tablets and dot tablets can also be produced, which have an onion-shell-like structure have, whereby in the case of the point tablets the top of the core or the core layers is not covered and therefore remains visible. Rotary tablet presses can also be or multiple tools can be equipped so that, for example, an outer circle with 50th and an inner circle with 35 holes can be used simultaneously for pressing. The Throughputs of modern rotary tablet presses are over one million tablets per Hour.
Im Rahmen der vorliegenden Erfindung geeignete Tablettiermaschinen sind beispielsweise erhältlich bei den Firmen Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Köln, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) sowie Courtoy N.V., Halle (BE/LU). Besonders geeignet ist beispielsweise die Hydraulische Doppeldruckpresse HPF 630 der Firma LAEIS, D.Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH presses GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy N.V., Halle (BE / LU). The hydraulic double-pressure press HPF, for example, is particularly suitable 630 from LAEIS, D.
Die Formkörper können dabei in vorbestimmter Raumform und vorbestimmter Größe gefertigt werden, wobei sie immer aus mehreren Phasen, d.h. Schichten, Einschlüssen oder Kernen und Ringen bestehen. Als Raumform kommen praktisch alle sinnvoll handhabbaren Ausgestaltungen in Betracht, beispielsweise also die Ausbildung als Tafel, die Stab- bzw. Barrenform, Würfel, Quader und entsprechende Raumelemente mit ebenen Seitenflächen sowie insbesondere zylinderförmige Ausgestaltungen mit kreisförmigem oder ovalem Querschnitt. Diese letzte Ausgestaltung erfaßt dabei die Darbietungsform von der Tablette bis zu kompakten Zylinderstücken mit einem Verhältnis von Höhe zu Durchmesser oberhalb 1.The moldings can be made in a predetermined spatial shape and size being made up of several phases, i.e. Layers, inclusions or cores and rings exist. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well as in particular cylindrical configurations with circular or oval cross-section. This last embodiment covers the presentation form from the tablet to compact Cylinder pieces with a ratio of height to diameter above 1.
Die portionierten Preßlinge können dabei jeweils als voneinander getrennte Einzelelemente ausgebildet sein, die der vorbestimmten Dosiermenge der Wasch- und/oder Reinigungsmittel entspricht. Ebenso ist es aber möglich, Preßlinge auszubilden, die eine Mehrzahl solcher Masseneinheiten in einem Preßling verbinden, wobei insbesondere durch vorgegebene Sollbruchstellen die leichte Abtrennbarkeit portionierter kleinerer Einheiten vorgesehen ist. Für den Einsatz von Textilwaschmitteln in Maschinen des in Europa üblichen Typs mit horizontal angeordneter Mechanik kann die Ausbildung der portionierten Preßlinge als Tabletten, in Zylinder- oder Quaderform zweckmäßig sein, wobei ein Durchmesser/Höhe-Verhältnis im Bereich von etwa 0,5 : 2 bis 2 : 0,5 bevorzugt ist. Handelsübliche Hydraulikpressen, Exzenterpressen oder Rundläuferpressen sind geeignete Vorrichtungen insbesondere zur Herstellung derartiger Preßlinge.The portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have 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. For the Use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can form the portioned compacts as tablets, in cylindrical or cuboid shape may be appropriate, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, particularly for manufacturing such compacts.
Die Raumform einer anderen Ausführungsform der Formkörper ist in ihren Dimensionen der Einspülkammer von handelsüblichen Haushaltswaschmaschinen angepaßt, so daß die Formkörper ohne Dosierhilfe direkt in die Einspülkammer eindosiert werden können, wo sie sich während des Einspülvorgangs auflöst. Selbstverständlich ist aber auch ein Einsatz der Waschmittelformkörper über eine Dosierhilfe problemlos möglich.The spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the molded body can be dosed directly into the induction bowl without a dosing aid dissolves during the induction process. It goes without saying that the Detergent tablets easily possible using a dosing aid.
Ein weiterer bevorzugter mehrphasiger Formkörper, der hergestellt werden kann, hat eine platten- oder tafelartige Struktur mit abwechselnd dicken langen und dünnen kurzen Segmenten, so daß einzelne Segmente von diesem "Mehrphasen-Riegel" an den Sollbruchstellen, die die kurzen dünnen Segmente darstellen, abgebrochen und in die Maschine eingegeben werden können. Dieses Prinzip des "riegelförmigen" Formkörperwaschmittels kann auch in anderen geometrischen Formen, beispielsweise senkrecht stehenden Dreiecken, die lediglich an einer ihrer Seiten längsseits miteinander verbunden sind, verwirklicht werden. Hier bietet es sich aus optischen Gründen an, die Dreiecksbasis, die die einzelnen Segmente miteinander verbindet, als eine Phase auszubilden, während die Dreiecksspitze die zweite Phase bildet. Eine unterschiedliche Anfärbung beider Phasen ist in dieser Ausführungsform besonders reizvoll.Another preferred multi-phase molded body that can be produced has one plate-like or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "multi-phase bolt" at the predetermined breaking points, the represent the short thin segments, broken off and entered into the machine can. This principle of the "bar-shaped" shaped detergent can also be used in others geometric shapes, for example vertically standing triangles, which only on one their sides are connected alongside each other, can be realized. Here it offers itself for optical reasons, the triangular base that connects the individual segments, form as one phase, while the triangle tip forms the second phase. A different coloring of both phases is particularly attractive in this embodiment.
Nach dem Verpressen weisen die Wasch- und Reinigungsmittelformkörper eine hohe Stabilität
auf. Die Bruchfestigkeit zylinderförmiger Formkörper kann über die Meßgröße der diametralen
Bruchbeanspruchung erfaßt werden. Diese ist bestimmbar nach
Hierin steht σ für die diametrale Bruchbeanspruchung (diametral fracture stress, DFS) in Pa, P ist die Kraft in N, die zu dem auf den Formkörper ausgeübten Druck führt, der den Bruch des Formkörpers verursacht, D ist der Formkörperdurchmesser in Meter und t ist die Höhe der Formkörper. Here σ 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 breaks the Shaped body caused, D is the shaped body diameter in meters and t is the height of the Moldings.
Durch Abmischung von tensidhaltigen Granulaten mit pulverförmigen Aufbereitungskomponenten
wurden Vorgemische hergestellt, die in einer Korsch-Tablettenpresse zu zweiphasigen
Waschmitteltabletten verpreßt wurden. Die Tensidgranulate 1, 2 und 3 wurden dabei
in einem 130-Liter-Pflugscharmischer (Gebrüder Lödige, Paderbom) hergestellt und anschließend
in einem Wirbelschichttrockner getrocknet. Nach dem Absieben der Grobanteile (≥ 1,6
mm) und der Feinanteile (≤ 0,4 mm) wurden die Tensidgranulate mit den Aufbereitungskomponenten
in einem Paddelmischer vermischt.
Die Zusammensetzung der Tensidgranulate zeigt Tabelle 1.
The composition of the surfactant granules is shown in Table 1.
Aus den Vorgemischen (Tensidgranulat + Aufbereitungskomponenten) wurden auf einer Korsch-Rundläuferpresse zweischichtige Waschmitteltabletten hergestellt, wobei der Anteil der ersten Schicht 75 Gew.-% der Gesamtmasse und der Anteil der zweiten Schicht 25 Gew.-% der Gesamtmasse der Tablette betrug. Der Durchmesser der Tabletten betrug 44 mm.The premixes (surfactant granules + treatment components) were used on a Korsch rotary press produced two-layer detergent tablets, the proportion of the first layer 75% by weight of the total mass and the proportion of the second layer 25% by weight the total mass of the tablet was. The diameter of the tablets was 44 mm.
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
einer 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.
Claims (23)
- Two- or multiphase washing and cleaning composition shaped bodies made of compacted particulate washing and cleaning composition comprising surfactant(s), builder(s) and optionally further washing and cleaning composition constituents, characterized in that the surfactant content of the individual phases of the shaped bodies, based on the weight of the individual phase, varies by more than 3% by weight, where, in the phase(s) with the higher surfactant content, a component A with an oil-absorption capacity of at least 20 g/100 g and an average particle size of less than 50 µm, based on the weight of the phase, is present in larger amounts than in the phase(s) with a lower surfactant content.
- Washing and cleaning composition shaped bodies according to Claim 1, characterized in that the content of component A in the phase(s) with a higher surfactant content is at least 0.3% by weight, preferably at least 0.5% by weight and in particular at least 1% by weight, based on the weight of the individual phase, higher than that in the phase(s) with a lower surfactant content.
- Washing and cleaning composition shaped bodies according to one of Claims 1 or 2, characterized in that the relative quantitative ratio of component A between the individual phases is greater than the relative quantitative ratio of the surfactants between the relevant phases.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 3, characterized in that the component A present therein has an oil-absorption capacity of at least 50 g/100 g, preferably at least 80 g/100 g, particularly preferably at least 120 g/100 g and in particular at least 140 g/100 g.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 4, characterized in that the component A present therein has an average particle size of less than 20 µm, preferably less than 10 µm.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 5, characterized in that the component A present therein is chosen from silicates and/or aluminosilicates, in particular from the group of silicas and/or zeolites.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 6, characterized in that the phases of the shaped body have the form of layers.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 7, characterized in that the surfactant(s) are introduced into the phases of the shaped bodies via surfactant-containing granulate(s).
- Washing and cleaning composition shaped bodies according to Claim 8, characterized in that the same surfactant granulate is used in all of the phases of the shaped bodies.
- Washing and cleaning composition shaped bodies according to Claim 8 and 9, characterized in that the shaped bodies have two layers which contain the same surfactant granulate in different amounts.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 10, characterized in that they comprise anionic and nonionic surfactant(s).
- Washing and cleaning composition shaped bodies according to Claim 11, characterized in that 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.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 12, characterized in that at least one phase of the shaped bodies is free from nonionic surfactants.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 13, characterized in that at least one phase of the shaped bodies comprises alkyl polyglycosides.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 14, characterized in that at least one phase of the shaped bodies is free from anionic surfactants.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 15, characterized in that they additionally comprise a disintegration auxiliary, preferably a disintegration auxiliary based on cellulose, preferably in 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 shaped body weight.
- Washing and cleaning composition shaped bodies according to one of Claims 1 to 16, further comprising one or more substances from the group of bleaches, bleach activators, enzymes, pH extenders, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, colour transfer inhibitors and corrosion inhibitors.
- Process for the preparation of two- or multiphase washing and cleaning composition shaped bodies which comprise surfactant(s), builder(s) and optionally further washing and cleaning composition constituents by compression known per se, characterized in that they have been obtained by compression of a particulate premix made of at least one surfactant-containing granulate and at least one subsequently mixed-in pulverulent component, where the surfactant content of the individual phases of the shaped bodies, based on the weight of the individual phase, varies by more than 3% by weight and, in the phase(s) with the higher surfactant content a component A with an oil-absorption capacity of at least 20 g/100 g and an average particle size of less than 50 µm, based on the weight of the phase, is present in larger amounts than in the phase(s) with a lower surfactant content.
- Process according to Claim 18, characterized in that the granulates have been prepared by means of customary granulation processes, such as mixer granulation and plate granulation, fluidized-bed granulation, extrusion, pelleting or compaction.
- Process according to one of Claims 18 or 19, characterized in that the granulates have particle sizes between 10 and 4000 µm, preferably between 100 and 2000 µm and in particular between 600 and 1400 µm.
- Process according to one of Claims 18 to 20, characterized in that the subsequently mixed-in pulverulent component(s) comprise the component A.
- Process according to one of Claims 18 to 21, characterized in that 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.
- Process according to one of Claims 18 to 22, characterized in that one of the subsequently mixed-in pulverulent components is a zeolite of the faujasite type with particle sizes below 100 µm, preferably below 10 µm and in particular below 5 µm and constitutes 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 compressed.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19803410A DE19803410A1 (en) | 1998-01-28 | 1998-01-28 | Multiphase laundry detergent tablets exhibiting high hardness and rapid disintegration |
DE19803410 | 1998-01-28 | ||
PCT/EP1998/006403 WO1999038948A1 (en) | 1998-01-28 | 1998-10-08 | Multiphase detergent tablets |
CA002313227A CA2313227A1 (en) | 1998-01-28 | 2000-07-28 | Multiphase detergent tablets |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1051474A1 EP1051474A1 (en) | 2000-11-15 |
EP1051474B1 true EP1051474B1 (en) | 2004-02-11 |
Family
ID=25681924
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98954379A Revoked EP1051474B1 (en) | 1998-01-28 | 1998-10-08 | Multiphase detergent tablets |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP1051474B1 (en) |
JP (1) | JP2002501977A (en) |
AT (1) | ATE259413T1 (en) |
CA (1) | CA2313227A1 (en) |
DE (1) | DE19803410A1 (en) |
WO (1) | WO1999038948A1 (en) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19901063A1 (en) * | 1999-01-14 | 2000-07-20 | Henkel Kgaa | Aid granules for washing and cleaning active moldings |
DE19903288A1 (en) * | 1999-01-28 | 2000-08-03 | Henkel Kgaa | Multi-phase detergent tablets |
GB9918087D0 (en) * | 1999-08-02 | 1999-10-06 | Mcbride Robert Ltd | Detergent tablets |
DE19944222A1 (en) * | 1999-09-15 | 2001-03-29 | Cognis Deutschland Gmbh | Detergent tablets |
US6686327B1 (en) * | 1999-10-09 | 2004-02-03 | Cognis Deutschland Gmbh & Co. Kg | Shaped bodies with improved solubility in water |
DE19953793A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Surfactant granules with an improved dissolution rate |
DE19953792A1 (en) * | 1999-11-09 | 2001-05-17 | Cognis Deutschland Gmbh | Detergent tablets |
DE19962885A1 (en) * | 1999-12-24 | 2001-07-05 | Cognis Deutschland Gmbh | Detergent tablets with improved disintegration properties |
CN107177429A (en) * | 2016-03-11 | 2017-09-19 | 华北制药秦皇岛有限公司 | It is a kind of be easy to carry, laundry sheet easy to use and its preparation technology |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3541146A1 (en) * | 1985-11-21 | 1987-05-27 | Henkel Kgaa | MULTILAYERED DETERGENT TABLETS FOR MACHINE DISHWASHER |
GB9015504D0 (en) * | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergents composition |
GB9022724D0 (en) * | 1990-10-19 | 1990-12-05 | Unilever Plc | Detergent compositions |
DE4404279A1 (en) * | 1994-02-10 | 1995-08-17 | Henkel Kgaa | Tablet with builder substances |
GB9422895D0 (en) * | 1994-11-14 | 1995-01-04 | Unilever Plc | Detergent compositions |
AU6413096A (en) * | 1995-07-13 | 1997-02-10 | Joh. A. Benckiser Gmbh | Dish washer product in tablet form |
DE19758811B4 (en) * | 1997-03-11 | 2008-12-18 | Henkel Ag & Co. Kgaa | Detergent pellet |
DE19710254A1 (en) * | 1997-03-13 | 1998-09-17 | Henkel Kgaa | Shaped or active cleaning moldings for household use |
-
1998
- 1998-01-28 DE DE19803410A patent/DE19803410A1/en not_active Withdrawn
- 1998-10-08 AT AT98954379T patent/ATE259413T1/en not_active IP Right Cessation
- 1998-10-08 EP EP98954379A patent/EP1051474B1/en not_active Revoked
- 1998-10-08 WO PCT/EP1998/006403 patent/WO1999038948A1/en not_active Application Discontinuation
- 1998-10-08 JP JP2000529409A patent/JP2002501977A/en active Pending
-
2000
- 2000-07-28 CA CA002313227A patent/CA2313227A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
ATE259413T1 (en) | 2004-02-15 |
JP2002501977A (en) | 2002-01-22 |
EP1051474A1 (en) | 2000-11-15 |
WO1999038948A1 (en) | 1999-08-05 |
CA2313227A1 (en) | 2000-10-08 |
DE19803410A1 (en) | 1999-07-29 |
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