WO2000044873A1 - Pastilles detergentes a phases multiples - Google Patents

Pastilles detergentes a phases multiples Download PDF

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Publication number
WO2000044873A1
WO2000044873A1 PCT/EP2000/000385 EP0000385W WO0044873A1 WO 2000044873 A1 WO2000044873 A1 WO 2000044873A1 EP 0000385 W EP0000385 W EP 0000385W WO 0044873 A1 WO0044873 A1 WO 0044873A1
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WO
WIPO (PCT)
Prior art keywords
weight
phase
surfactant
detergent tablets
detergent
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PCT/EP2000/000385
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German (de)
English (en)
Inventor
Andreas Lietzmann
Monika Böcker
Birgit Burg
Hans-Friedrich Kruse
Markus Semrau
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Priority to AU24385/00A priority Critical patent/AU2438500A/en
Publication of WO2000044873A1 publication Critical patent/WO2000044873A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets

Definitions

  • the present invention relates to multi-phase detergent tablets.
  • the invention relates to multi-phase detergent tablets which are used for washing textiles in a household washing machine and are referred to as detergent tablets for short.
  • the form of highly compressed molded articles has a number of advantages which make it desirable to also provide washing and cleaning agents in this form.
  • detergent tablets which are often referred to as detergent tablets for short, which has the particular task of overcoming a central problem of the "tablet" form: the dichotomy between the hardness of the tablets on the one hand and their rate of disintegration on the other hand.
  • Adequate hardness is essential for the packaging, storage, transport and handling of the moldings, while the disintegration properties have a decisive influence on the washing process and a sufficiently rapid disintegration is imperative for the formation of a sufficiently concentrated washing liquor.
  • Multi-phase detergent tablets in which the surfactant content of the individual phases of the shaped body does not vary by more than 3% by weight, based on the weight of the individual phase, are described in the earlier German patent application DE 198 03 409.1 (Henkel KGaA). This avoids differences in hardness, solubility or disintegration time between the individual phases.
  • Multi-phase detergent tablets in which the surfactant content of the individual phases of the shaped body varies by more than 3% by weight, based on the weight of the individual phase, are the subject of the earlier German patent application DE 198 03 410.5 (Henkel KGaA).
  • This application teaches that differences in hardness, solubility or disintegration time between the individual phases can be avoided even in the case of more strongly different surfactant contents in the individual phases if a component with an oil absorption capacity of in the phase (s) with the higher surfactant content at least 20g / 100g is contained in higher quantities than in the phase (s) with a lower surfactant content.
  • the present invention was based on the object of providing multiphase detergent tablets which overcome the disadvantages mentioned.
  • multi-phase detergent tablets are to be provided which have a high hardness and a high rate of disintegration and dissolution in all phases, regardless of how much the surfactant contents vary in the individual phases.
  • multiphase detergent tablets can be produced with an outstanding property profile if, in the case of varying surfactant contents in the individual phases of the surfactant-rich phase (s), larger quantities of one or more are used in the preparation of the premix to be pressed disintegrants containing cellulose are added as the phase (s) with less surfactant.
  • the invention now relates to two-phase or multi-phase detergent tablets made of compressed particulate detergent and detergent, comprising surfactant (s), builder (s) and, if appropriate, further detergent and detergent components in which the surfactant content of the individual phases of the tablets varies by more than 3% by weight, based on the weight of the individual phase, in the phase (s) with the higher surfactant content a cellulose-containing disintegrant which contains a maximum of 10% by weight of particles with a particle size below 200 ⁇ m is contained in higher amounts than in the phase (s) with a lower surfactant content.
  • surfactant s
  • builder s
  • further detergent and detergent components in which the surfactant content of the individual phases of the tablets varies by more than 3% by weight, based on the weight of the individual phase, in the phase (s) with the higher surfactant content a cellulose-containing disintegrant which contains a maximum of 10% by weight of particles with a particle size below 200 ⁇ m is contained in higher amounts than in the phase (
  • the variation in the surfactant content by more than 3% by weight means that the absolute values of the surfactant content in the phases vary by more than 3% by weight. So if one phase contains 20% by weight of surfactant (s), the surfactant content of the other phase (s) must be selected so that the range of variation by the value 20 is more than 3% by weight. In other Words subtract the percentage numerical value of the surfactant content of the surfactant-poor phase from the percentage numerical value of the surfactant content of the respective surfactant-rich phase, the result having to be> 3 from phase to phase.
  • the individual phases of the detergent tablets according to the invention contain increasing proportions of a cellulose-containing disintegration aid which has a maximum of 10% by weight of particles with a particle size of less than 200 ⁇ m, with the proviso that the phase which is richer in surfactant is based on the overall composition of the phase has a higher proportion of this disintegration aid.
  • the content of the cellulose-containing disintegration aid in the surfactant-rich phase (s) by at least 2.5% by weight, preferably by at least 5% by weight and in particular by at least 10% by weight, based on the weight of the disintegration aid, is higher than in the phase (s) with less surfactant.
  • the situation can be clarified as follows: If the phase with the lowest surfactant content contains 1.5% by weight of the cellulose-containing disintegration aid in addition to the 12% by weight of surfactant mentioned, the second phase would contain at least 1.5375% by weight (preferably 1.575% by weight and in particular 1.65% by weight) of this component.
  • the content of cellulose-containing disintegration aid in the third phase depends on the real content of this 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% by weight.
  • the disintegration times of the layers can be adjusted very closely to one another and the problems mentioned above can be avoided.
  • detergent tablets are preferred in which the disintegration times of the layers differ from one another by a maximum of 5 seconds.
  • a cellulose-based disintegration aid based on cellulose a cellulose-containing disintegration aid made from cellulose fibers with a primary fiber length of less than 100 ⁇ m, which has been compacted to a particle spectrum between 200 and 2000 ⁇ m, has proven itself in the context of the present invention. Further information on the cellulose-containing disintegration aid is summarized below.
  • the ratio of the amounts in the individual phases to one another can also be varied.
  • detergent tablets are preferred in which the quantitative ratio of the cellulose-containing disintegration aid between the individual phases is greater than the quantitative ratio of the surfactants between the relevant phases.
  • the second phase compared to the first contains so much cellulose-containing disintegration aid that the ratio of this component in the two phases is greater than 1.26.
  • phase 1 contains 1.5% by weight of the cellulose-containing disintegration aid
  • phase 2 should contain more than 1.26 times this value, ie at least 1.9% by weight of this component.
  • the contents of the other phases in these substances can be varied so that they meet the criteria mentioned.
  • the formation of relationships makes no mathematical sense, which is why absolute values are used here in the sense of the preferred embodiments of the present invention explained above.
  • the cellulose-containing disintegration aid contained in the individual surfactant-containing phases of the molded body which contains a maximum of 10% by weight of particles with a particle size ter has 200 ⁇ m, can be pure cellulose in the particle size range mentioned, but it can also be cogranulates of cellulose and / or cellulose derivatives with other substances, in particular detergent and cleaning agent ingredients.
  • Such auxiliary granules which contain other ingredients in addition to cellulose are described, for example, in German patent applications DE 197 23 028.8, DE 198 53 173.7 and DE 199 01 063.3 (all Henkel KGaA) and can preferably be used in the context of the present invention.
  • the cellulose contained in the cellulose-containing disintegration aid has the formal bratto composition (C 6 H ⁇ 0 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed 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 derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as the cellulose-containing disintegrant.
  • Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted.
  • celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
  • CMC carboxymethyl cellulose
  • the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
  • the cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-containing disintegrant.
  • the cellulose-containing disintegration aid must contain less than 10% by weight of particles with a particle size below 200 ⁇ m.
  • it is preferably converted into a coarser form, for example granulated or compacted.
  • Detergent tablets which disintegrate in granular or, if appropriate, cogranulated form hold, are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
  • Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
  • a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses, which have primary particle sizes of approximately 5 ⁇ m and can be compacted, for example, into granules with a larger particle size.
  • the cellulose-containing disintegration aid is preferably used in coarser, granulated or compacted form.
  • detergent tablets are preferred in which the cellulose-containing disintegration aid contained therein contains less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight, of particles with a particle size below 400 ⁇ m .
  • the maximum particle size of the disintegration aid is also preferably limited.
  • detergent tablets are preferred in which the cellulose-containing disintegration aid contained therein contains less than 20% by weight, preferably less than 10% by weight and in particular less than 5% by weight, of particles with a particle size contains above 1200 ⁇ m.
  • cellulose-containing disintegration aids can be used, in addition to pure cellulose, also cogranulates or cocompacts of cellulose with other substances. It is preferred here that the cellulose-containing disintegration auxiliaries used consist predominantly of cellulose, that is to say detergent tablets are preferred which are characterized in that this is in them contained cellulose-containing disintegration aid consists of at least 60% by weight, preferably at least 75% by weight and in particular at least 90% by weight of cellulose.
  • 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 shaped body varies by more than 3% by weight, based on the weight of the individual phase, and that the surfactant-rich phase (s) contain more cellulose-containing disintegration aid than that Less surfactant phase (s).
  • the surfactant content the sum of the surfactants contained in the phase in question is used, regardless of the type of surfactant involved. For example, if a phase contains anionic and nonionic surfactants, the total surfactant content of the phase is the sum of the amounts of anionic and nonionic surfactants.
  • the surfactants can be incorporated into the individual phases of the shaped bodies in pure form. This is easily possible, for example, with soaps or other easily workable surfactants. With many surfactants, however, it is advisable not to incorporate the pure surfactants, but rather surfactant compounds. These compounds, which should have as high a surfactant content as possible depending on the application, can be prepared using conventional methods such as spray drying, granulation or compounding. Of course, a combination of several surfactant granules or a combination of surfactant granules (s) with pure surfactants is also possible.
  • the surfactant (s) are introduced into the phases of the shaped bodies via granules (s) containing surfactant.
  • different surfactant granules can now be used for each phase.
  • each phase it is also possible for each phase to obtain its surfactant content from a single granulate, which is thus contained in all phases of the shaped body.
  • this is a further preferred embodiment, in which the same surfactant granules are used in all phases of the shaped body, preference being given to detergent tablets which have two layers and contain the same surfactant granules in different amounts.
  • the simplest conceivable embodiment of the present invention now provides a two-phase tablet in which the phases are present as layers and in which the same surfactant granules are used in different amounts in both layers.
  • These moldings which have two layers and contain the same surfactant granulate, can be easily produced in conventional tablet presses.
  • Anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof can be used in the detergent tablets according to the invention. Mixtures of anionic and nonionic surfactants are preferred from an application point of view.
  • the total surfactant content of the moldings is 5 to 60% by weight, based on the weight of the moldings, with surfactant contents above 15% by weight being 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 as well as disulfonates, such as those obtained from C 12 . 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration. Alkanesulfonates which are derived from C 12 are also suitable.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut 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, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 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 in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 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).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • 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 Highly linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 alcohols with 3 EO or 4 EO, C 9 . n alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C I2 . Ig alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R * for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C M -alkyl or phenyl radicals being preferred and [Z] for a linear poly - Hydroxyalkyl radical, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • detergent tablets are preferred which contain anionic (s) and nonionic (s) surfactant (s), where application-related advantages can result from certain quantitative ratios in which the individual classes of surfactants are used.
  • detergent tablets are particularly preferred in which 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.
  • a further important embodiment of the present invention therefore provides that at least one phase of the shaped body is free from nonionic surfactants.
  • a positive effect can also be achieved by the content of individual phases or of the entire molded body, ie all phases, of certain surfactants.
  • the Introducing the alkyl polyglycosides described above has proven to be advantageous, so that detergent tablets are preferred in which at least one phase of the tablets contains alkyl polyglycosides.
  • washing and cleaning agent foam bodies according to the invention can contain all of the builders customarily used in washing and cleaning agents, 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 ⁇ 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na ⁇ O ,; 'yH 2 O is preferred, it being possible for ⁇ -sodium disilicate to be obtained, for example, by the process described in international patent application WO-A-91/08171.
  • the dissolution delay compared to conventional amorphous sodium silicates can be done in different ways, for example have been caused by surface treatment, compounding, compacting / compaction or overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ® and by the formula
  • the zeolite can be used both as a builder in a granular compound and can also be used for a type of "powdering" of the entire mixture to be compressed, usually using both ways of incorporating the zeolite into the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Coun- ter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.
  • Usable organic builders are, for example, the polycarboxylic acids 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 this.
  • 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.
  • washable and cleaning-active molded articles is carried out by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • a mixture to be tabletted is pressed directly, ie without prior granulation.
  • the advantages of this so-called direct tableting are its simple and inexpensive application, since no further process steps and consequently no further plants are required.
  • these advantages are offset by disadvantages.
  • a powder mixture that is to be tabletted directly must have sufficient plastic deformability and have good flow properties; furthermore, it must not show any tendency to segregate during storage, transport and filling of the die.
  • detergent tablets are extremely difficult to master with many substance mixtures, so that direct tableting is not often used, particularly in the production of detergent tablets.
  • the usual way of manufacturing detergent tablets is therefore based on powdery components ("primary particles"), which can be prepared using suitable components. drive to secondary particles with a larger particle diameter are agglomerated or granulated. These granules or mixtures of different granules are then mixed with individual powdery additives and fed to the tableting.
  • the die is gradually filled with different premixes.
  • a slight application of pressure between the pre-mix filling can have advantages for the next layer. Such a pre-compression with shaping is even almost indispensable in the production of shaped cores or coated tablets.
  • Preferred detergent tablets in the context of the present invention are obtained by pressing particulate premixes of at least one surfactant-containing granulate and at least one subsequently admixed powdery component.
  • the surfactant-containing granules can be produced using conventional granulation processes such as mixer and plate granulation, fluidized bed granulation, extrusion, pelletizing or compacting. It is advantageous for the later detergent tablets if the premixes to be pressed have a bulk density that comes close to that of conventional compact detergents. In particular, it is preferred that the premix to be pressed has a bulk density of at least 500 g / 1, preferably at least 600 g / 1 and in particular above 700 g / 1.
  • laundry detergent and cleaning agent film bodies are preferred in which 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 admixed pulverulent preparation components can also be varied, preference being given to detergent tablets in which the subsequently admixed pulverulent component (s) contain the cellulose-containing disintegration aid.
  • the premix Before the particulate premix is pressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This can be advantageous for the nature and physical properties of both the premix (storage, pressing) and the finished detergent tablets. Fine powdering agents are well known in the art, mostly zeolites, silicates or other inorganic salts being used. However, the premix is preferably “powdered” with finely divided zeolite, zeolites of the faujasite type being preferred.
  • zeolite-type zeolite denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (see Donald W. Breck: “Zeolite Molecular Sieves”, John Wiley & Sons, New York) , London, Sydney, Toronto, 1974, page 92).
  • zeolite X zeolite Y and faujasite and mixtures of these compounds can also be used, the pure zeolite X being preferred.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily have to belong to the zeolite structural group 4, can be used as powdering agents, it being advantageous if at least 50% by weight of the powdering agent is used a zeolite of the faujasite type.
  • detergent tablets consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the or one of the subsequently admixed pulverulent components being a zeolite of the faujasite type with particle sizes below 100 ⁇ m, is preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be pressed.
  • the finely divided processing components with the particle sizes mentioned above can be dry mixed into the premix to be pressed. However, it is also possible and preferred to "stick" them to the surface of the coarser particles by adding small amounts of liquid substances.
  • liquid components that are suitable for promoting the adhesion of the powdering agents for example nonionic surfactants or aqueous solutions of surfactants or other washing and cleaning agent ingredients.
  • perfume it is preferred to use perfume as the liquid adhesion promoter between the finely divided powdering agent and the coarse-grained particles.
  • the detergent tablets according to the invention can contain further ingredients customary in detergents and cleaning agents from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical agents Brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors included.
  • bleaching agents that 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 that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleach activators can be incorporated into one or more phases.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 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 special n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED tetraacetylethylene diamine
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules in the shaped bodies according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • laundry detergent and cleaning product tablets may 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 is soiled, which has already been washed several times with a detergent according to the invention contains oil and fat-dissolving component, was washed.
  • the preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • the moldings can contain derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino grappa, contain a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g.
  • Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visually and sensorially "typical and unmistakable" product in addition to performance.
  • Individual fragrance compounds for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycineate, allyl cycloproxylhexylateyl pylylateyl pylylateyl pylylateyl pylylateyl pylylateyl pylylatepylatepylate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkali nale with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones, for example the jonones, oc-isomethylionone and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, phenanylethyl, alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citras, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • the dye content of the plasticizers according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the entire formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the detergent tablets can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them. Since the object of the present invention relates to multi-phase detergent tablets, the coloring of individual phases occurs are of increasing importance in order to underline the different effects of individual phases. Examples of the effectiveness of such coloring and of the success of statements on this are well known from the denture cleaner advertising.
  • the moldings according to the invention are first produced by dry mixing the constituents of the individual phases, which can be wholly or partially pregranulated, and then informing them, in particular pressing them into tablets, it being possible to use conventional methods for producing multiphase moldings.
  • the premixes are compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to as tableting in the following, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are fastened to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies is arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is an upper and lower Assigned stamps, whereby the press track can be actively built up only by the upper or lower stamp, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compaction, plastic deformation and ejection by means of rail-like cam tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premixes.
  • the pressure on the respective premix can be individually adjusted via the pressure paths for the upper and lower punches, with the build-up of the pressure occurring when the punch shaft heads roll past adjustable pressure rollers.
  • Rotary presses can also be equipped with two or more filling shoes to increase the throughput.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses survey over a million tablets per hour.
  • Tableting machines suitable within the scope of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen GmbH, Berlin, Mapag Maschinenbau AG, Bern (CH) and Courtoy NV, Halle (BE / LU).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. is particularly suitable.
  • the moldings can be made in a predetermined spatial shape and size, always consisting of several phases, i.e. Layers, inclusions or cores and rings exist. Practically all sensibly manageable configurations come into consideration as spatial form, for example, the training as a board, the rod or. Bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces and in particular cylindrical designs with a 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 designed as separate individual elements that correspond to the predetermined dosage of the detergents and / or cleaning agents. It is also possible, however, to form compacts which connect a plurality of such mass units in one compact, the portioned smaller units being easy to separate, in particular by predetermined predetermined breaking points.
  • the portioned compacts as tablets, in cylinder or cuboid form can be expedient, 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, in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped body is adapted in its dimensions to the induction chamber of commercially available household washing machines, so that the shaped bodies can be dosed directly into the induction chamber without metering aid, where they dissolve during the induction process.
  • the detergent tablets can also be used without problems using a metering aid.
  • Another preferred multi-phase molded body that can be produced has a plate-like or plate-like structure with alternately thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, which represent the short thin segments, are broken off and can be entered into the machine.
  • This principle of the "bar-shaped" molding detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side. For optical reasons, it makes sense to design the triangular base that connects the individual segments as one phase, while the triangle tip forms the second phase. Different coloring of both phases is particularly attractive in this embodiment.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametrical fracture sfress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body, which causes the molded body to break
  • D is the molded body diameter in meters and t 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, Paderborn) 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 treatment components in a paddle mixer.
  • the composition of the surfactant granules is shown in Table 1.
  • Two-layer detergent tablets were produced on a Korsch rotary press from the premixes (surfactant granules + preparation components), the proportion of the first layer being 75% by weight of the total mass and the proportion of the second layer being 25% by weight of the total mass of the tablet.
  • the diameter of the tablets was 44 mm, the total amount of cellulose was always 5% by weight, based on the total shaped body.
  • 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, i.e. the values in a 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.
  • Repelotex-SRP-4 is a terephthalic acid-ethylene glycol-polyethylene glycol ester from Rhönen-Poulenc.
  • the shaped articles according to the invention despite the same content of cellulose-containing disintegration aid (based on the entire shaped article), have significantly shorter disintegration times than the comparative examples.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des détergents et nettoyants sous forme de corps moulés, à deux phases ou à phases multiples, à base de détergent et nettoyant particulaire compacté, comprenant un(des) tensioactif(s), un(des) adjuvant(s) de lavage, ainsi qu'éventuellement d'autres constituants de détergents et de nettoyants, dans lesquels la teneur en tensioactif des phases individuelles du corps moulé varie de plus de 3 % par rapport au poids de la phase individuelle. La(les) phase(s) dont la teneur en tensioactif(s) est la plus élevée contient(contiennent) un agent de désintégration à base de cellulose, qui présente au plus 10 % en poids de particules dont la taille est inférieure à 200 mu m, dans des quantités plus élevées que la(les) phase(s) à moindre teneur en tensioactif(s). Ces détergents et nettoyants sous forme de corps moulés présentent de meilleures propriétés de décomposition, tout en ayant des duretés plus marquées.
PCT/EP2000/000385 1999-01-28 2000-01-19 Pastilles detergentes a phases multiples WO2000044873A1 (fr)

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AU24385/00A AU2438500A (en) 1999-01-28 2000-01-19 Multiphase detergent tablets

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DE1999103288 DE19903288A1 (de) 1999-01-28 1999-01-28 Mehrphasige Waschmitteltabletten
DE19903288.2 1999-01-28

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EP1496105A1 (fr) * 2003-07-10 2005-01-12 Unilever N.V. Compositions détergentes

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DE19925518B4 (de) * 1999-06-04 2016-06-30 Henkel Ag & Co. Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit Parfüm sowie Verfahren zu ihrer Herstellung
GB9918087D0 (en) * 1999-08-02 1999-10-06 Mcbride Robert Ltd Detergent tablets
GB9922594D0 (en) * 1999-09-23 1999-11-24 Unilever Plc Cleaning compositions
WO2002033036A1 (fr) * 2000-10-18 2002-04-25 Unilever N.V. Composition de lavage
DE10134310A1 (de) * 2001-07-14 2003-01-30 Henkel Kgaa Mehrphasiger Formkörper mit schneller Löslichkeit
DE102004051557A1 (de) * 2004-10-22 2006-04-27 Henkel Kgaa Wasch- oder Reinigungsmitteldosiereinheit
EP2519622A4 (fr) * 2009-12-31 2013-06-05 Rhodia China Co Ltd Association de polymère et de tensioactif pour lessive améliorée
US20200181542A1 (en) * 2017-06-30 2020-06-11 Novozymes A/S Enzyme Slurry Composition

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JPH04164999A (ja) * 1990-10-29 1992-06-10 Kao Corp 錠剤型洗剤
DE19710254A1 (de) * 1997-03-13 1998-09-17 Henkel Kgaa Wasch- oder reinigungsaktive Formkörper für den Gebrauch im Haushalt
WO1998055583A1 (fr) * 1997-06-06 1998-12-10 Unilever Plc Compositions de nettoyage
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EP1496105A1 (fr) * 2003-07-10 2005-01-12 Unilever N.V. Compositions détergentes

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