EP1390463B1 - Elements moules de produits de lavage a phase viscoelastique - Google Patents

Elements moules de produits de lavage a phase viscoelastique Download PDF

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Publication number
EP1390463B1
EP1390463B1 EP02732618A EP02732618A EP1390463B1 EP 1390463 B1 EP1390463 B1 EP 1390463B1 EP 02732618 A EP02732618 A EP 02732618A EP 02732618 A EP02732618 A EP 02732618A EP 1390463 B1 EP1390463 B1 EP 1390463B1
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Prior art keywords
weight
acid
detergent
phase
preferred
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German (de)
English (en)
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EP1390463A1 (fr
Inventor
Dieter Legel
Birgit Burg
Gerhard Blasey
Berthold Schreck
Peter Schmiedel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets

Definitions

  • the present invention relates to detergent tablets which have at least one viscoelastic phase.
  • the customary production of detergent tablets comprises the preparation of particulate premixes which are compressed into tablets by tabletting methods known to those skilled in the art.
  • the starting substances can not regularly be tabletted directly, but must be converted by upstream process steps, such as granulation, in a tablettable form, which means additional time and expense.
  • the incorporation of surfactants is problematic in this regard, with the anionic surfactants additionally presents the problem that the obtained in the preparation of the surfactants acid form of the anionic surfactants by further neutralization steps only in the active substance (the salt) must be transferred.
  • the supply form of the compressed tablet implies that the ingredients are in direct physical proximity to each other, resulting in undesirable reactions, instabilities, inactivities or loss of active ingredient in incompatible substances.
  • German patent application DE197 52 711 A1 is a process for the granulation of LAS pastes.
  • the present invention relates to a detergent or cleaning agent shaped article comprising a viscoelastic phase which, based on its weight, contains 40 to 85% by weight of alkylbenzenesulfonate (e) and whose storage modulus is between 40,000 and 800,000 Pa, characterized that the viscoelastic phase is surrounded by two tableted phases.
  • a viscoelastic phase which, based on its weight, contains 40 to 85% by weight of alkylbenzenesulfonate (e) and whose storage modulus is between 40,000 and 800,000 Pa, characterized that the viscoelastic phase is surrounded by two tableted phases.
  • Viscoelastic substances are to be classified in the range between solids and liquids. Whereas for an ideal-elastic solid in arbitrary deformations the stress is directly proportional to the strain and independent of the rate of deformation (Hooke's Law), for an ideal-viscous liquid Newton's Law, i. the stress in a linear shear rate is proportional to the rate of deformation, but independent of the amount of deformation.
  • Viscoelastic fabrics have both viscous and elastic behavior, wherein the elastic portion is described on a deformation acting on a viscoelastic substance by the storage module, while the viscous portion is referred to as loss modulus.
  • the memory module G 'as well as the loss modulus G can be correlated with the deformation work reversibly stored per oscillation period or irreversibly dissipated.
  • the determination of the elastic or viscous portions of a reaction of viscoelastic substances at a defined rate gradient is achieved in vibration viscometers using a Couette measuring system.
  • These measuring systems can be structured differently.
  • cylinder / cylinder measuring systems, plate / plate measuring systems or cone / plate measuring systems can be used.
  • the outer cylinder In a coaxial cylinder measuring system, the outer cylinder is subjected to an oscillating movement, whereby the angular velocity of the outer cylinder changes sinusoidally with time.
  • a substance located in the annular gap between the outer cylinder and the inner cylinder receives from the outer cylinder an oscillating variable speed gradient depending on the frequency and amplitude.
  • the inner cylinder On the inner cylinder a resulting thrust chip voltage signal, which varies with the same frequency but has a different amplitude and is more or less phase-shifted with respect to the input signal to the outer cylinder.
  • the differences between the input signal on the outer cylinder and the output signal on the inner cylinder are influenced, inter alia, by the elastic component.
  • the mathematical treatment of the data allows the determination of the storage modulus G 'and the loss modulus G "G' is a measure of the energy stored in the substance to be measured and thus of the elastic component, while G" is a measure of the heat converted to viscous flow and with it lost energy.
  • Storage and loss modulus measurements can be carried out computer-assisted in coaxial cylinder systems, for example with a HAAKE Rotovisco RV 20 with the CV 100 measuring system at 20 ° C. (Couette system).
  • a plate In the measuring system of two opposing plates, a plate can be subjected to an oscillating movement, wherein the speed of the plate changes sinusoidally with time.
  • a substance located in the gap between the plates receives from the exciter plate an oscillating variable speed gradient depending on frequency and amplitude. Then, a resulting shear stress signal can be measured on the measuring plate, which varies with the same frequency, but has a different amplitude and is more or less phase-shifted with respect to the input signal to the exciter plate.
  • the differences between the input signal to the excitation plate and the output signal at the measuring plate are influenced, inter alia, by the elastic component.
  • the measurements of the sizes G 'and G " were carried out with the UDS 2000 rheometer from Paar Physika according to the plate-plate measuring system 25 mm, 2 mm gap, at 20 ° C.
  • the loss modulus of the viscoelastic phase is within narrower limits.
  • washing or cleaning agent shaped bodies according to the invention are preferred in which the storage modulus of the viscoelastic phase is 50,000 to 750,000 Pa, preferably 60,000 to 700,000 Pa, particularly preferably 70,000 to 650,000 Pa and in particular 80,000 to 600,000 Pa.
  • the loss modulus is smaller than the storage modulus, ie G '> G ".
  • Preferred detergent tablets according to the invention are those in which the storage modulus of the viscoelastic phase is at least twice as large, preferably at least four times as great loss modulus.
  • a resulting shear stress signal can be measured, which varies with the same frequency but has a different amplitude and more or less with respect to the input signal at the outer cylinder is strongly out of phase.
  • detergent tablets are provided in which the phase shift of the viscoelastic phase is 0 to 30 °, preferably 0 to 20 ° and in particular ⁇ 17 °.
  • a particular advantage of the detergent tablets according to the invention lies in the fact that the advantages of a gel detergent (good washing performance due to the high proportion of surfactant) can be combined with the convenient handling of solid dosage forms.
  • the viscoelastic phase is under ordinary storage conditions in an almost solid consistency, without sacrificing the usual gel wash detergent good solubility under washing conditions.
  • Further general advantages of this type of detergent are the lack of drying of the surfactant-containing phase after the neutralization of the starting fatty acids (e.g., ABS) and the greater formulation flexibility.
  • the viscoelastic phase therefore contains large amounts of surfactant (s), preferably anionic surfactant (s).
  • Preferred detergent tablets or detergent tablets according to the invention are those which are characterized in that the viscoelastic phase, based on their weight, contains 40 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 to 85% by weight and in particular 65 to 82 wt .-% surfactant (s).
  • anionic surfactants are the most important class of surfactants, while these have only a minor importance in automatic dishwashing detergents. It is therefore particularly advantageous to use anionic surfactants in products according to the invention which are provided for textile washing.
  • the invention allows the use of non-neutralized raw materials, which are further processed directly to the viscoelastic phase, without previously by time-consuming and costly process steps in granules or similar. have to be transferred.
  • Preferred anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated secies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-oc
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 , 1% by weight C 18 " ), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight C) 12 , 15 wt .-% C 14 , 7 wt .-% C 16 , 2 wt .-% C 18 , 15 wt .-% C 18 , 1 wt .-% C 18 " ), tallow fatty acid (about 3 wt % C 14 , 26% by weight C 16 , 2% by weight C 16 ' , 2% by weight C 17 , 17% by weight C 18 , 44% by weight C 18' , 3% by
  • Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention.
  • Their alkali metal salts, in particular sodium salts the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • the quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in specific cascade, falling film, or tube bundle reactors.
  • alkyl ether sulfuric acids which can be used according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, have a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acidic hydrolysis) these sultones react Hydroxylalkanesulfonklaren or alkene sulfonic acids, both of which can also be used as anionic surfactant acids.
  • alkyl benzene sulfonates as powerful anionic surfactants have been known since the thirties of our century. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
  • ABSS alkylbenzenesulfonic acid
  • C 8-16 -, preferably C 9-13 -alkylbenzenesulfonic acids are preferred according to the invention as anionic surfactant in acid form. It is further preferred in the context of the present invention to use C 8-16 , preferably C 9-13 , alkylbenzenesulfonic acids derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene.
  • alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13 -alkyl benzene sulfonic acids used have a content of 2-phenyl isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form may be used alone or in admixture with each other.
  • the anionic surfactant in acid form prior to conversion into the viscoelastic phase further, preferably, acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 Wt .-% and in particular from 2 to 10 wt .-%, in each case based on the weight of the mixture to be reacted, mixed.
  • Suitable acid reactants in the context of the present invention are not only the “surfactant acids” but also the stated fatty acids, phosphonic acids, polymer acids or partially neutralized polymeric acids and “builder acids” and “complex builder acids” (details later in the text) alone and in any desired mixtures.
  • the ingredients of detergents and cleaners are especially acidic detergents and cleaners ingredients, so for example phosphonic acids which are in neutralized form (phosphonates) as incrustation inhibitors part of many detergents and cleaners.
  • the use of (partially neutralized) polymer acids such as polyacrylic acids, according to the invention is possible. But it is also possible to mix acid-stable ingredients with the anionic surfactant acid.
  • viscoelastic phase contains from 50 to 82.5% by weight and in particular from 60 to 80% by weight of alkylbenzenesulfonate (s), based on their weight.
  • the neutralized form can be produced directly during the formation of the viscoelastic phase by mixing appropriate amounts of anionic acid, water and neutralizing agent and optionally other ingredients. The temperature increases, and the mixture is easily processable at this temperature. Upon cooling, the viscoelastic phase forms, which is characterized by handling stability, shelf life and good solubility. In preferred embodiments of the present invention, the viscoelastic phase additionally contains nonionic surfactants.
  • detergent tablets or detergent tablets according to the invention are preferred in which the viscoelastic phase, based on their weight, contains 0 to 20% by weight, preferably 0.5 to 15% by weight and in particular 1 to 10% by weight of nonionic surfactant (e) contains.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either 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 having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula II, wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula III, in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 Carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl 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 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 or detergent tablets which contain anionic (s) and nonionic surfactant (s) are preferred, technical advantages resulting from certain ratios in which the individual classes of surfactants are used.
  • washing and cleaning agent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • surfactant (s) preferably anionic (s) and / or nonionic surfactant (s)
  • amounts of from 5 to 40% by weight preferably from 7.5 to 35% by weight .-%, particularly preferably from 10 to 30 wt .-% and in particular from 12.5 to 25 wt .-%, in each case based on the weight of the molded article.
  • anionic surfactants Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets, which are more suitable for certain applications. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.
  • surfactants in automatic dishwashing detergent tablets is preferably restricted to the use of small amounts of nonionic surfactants.
  • Detergent tablets preferably to be used as detergent tablets are characterized in that they contain total surfactant contents below 5% by weight, preferably below 4% by weight, more preferably below 3% by weight and in particular below 2 wt .-%, each based on their total weight, have.
  • surfactants only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents.
  • representatives of the groups of the anionic, cationic or amphoteric surfactants are less significant.
  • inventive detergent tablets for automatic dishwashing contain nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • the detergent tablets in the case of detergent tablets according to the invention or dishwashing detergent tablets, it is preferred for the detergent tablets to comprise a nonionic surfactant which has a melting point above room temperature, preferably a nonionic surfactant having a melting point above 20 ° C.
  • a nonionic surfactant having a melting point above 20 ° C.
  • nonionic surfactants have melting points above 25 ° C, particularly preferably used nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also distinguished by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight.
  • -% one Block copolymers of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which can be used with particular advantage are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred surfactant can be defined by the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ] in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, the variation width increasing with increasing x values and for example, includes a large number (EO) groups combined with a small number (PO) groups, or vice versa.
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • ingredients that may be part of the viscoelastic phase for example, bleaches, bleach activators, enzymes, dyes and fragrances, optical brighteners, etc. are described below.
  • products according to the invention which contain at least one viscoelastic phase at least one tabletted phase are particularly attractive, which is why detergent tablets according to the invention additionally have at least one tabletted phase which, based on their weight, contains from 10 to 80% by weight. , preferably 20 to 75 wt .-% and in particular 30 to 70 wt .-% builder (s), are preferred.
  • These detergent tablets according to the invention contain, at least in the tableted phase, builders which preferably originate from the groups of zeolites, silicates, carbonates, bicarbonates, phosphates and polymers.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ).
  • Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 reacts angry; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH 2 PO 4 , is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • phosphates are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Further ingredients which may be present in the detergent tablets instead of or in addition to phosphates are carbonates and / or bicarbonates, preference being given to the alkali metal salts and, in particular, the potassium and / or sodium salts.
  • Preferred detergent tablets contain carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, more preferably sodium carbonate, in amounts of from 5 to 50% by weight, preferably from 7.5 to 40% by weight and in particular of 10 to 30 wt .-%, each based on a tableted phase.
  • silicates the alkali metal silicates and especially the amorphous and / or crystalline potassium and / or sodium disilicates are preferred.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 yH 2 O are preferred.
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • preferred detergent tablets contain silicate (s), preferably alkali metal silicates, more preferably crystalline or amorphous alkali disilicates, in amounts of from 3 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the mass of the tableted phase (s).
  • silicate preferably alkali metal silicates, more preferably crystalline or amorphous alkali disilicates, in amounts of from 3 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the mass of the tableted phase (s).
  • Zeolites have the general formula M 2 / n O.Al 2 O 3 .xSiO 2 .yH 2 O in which M is a cation of valency n, x stands for values which are greater than or equal to 2 and y can assume values between 0 and 20.
  • the zeolite structures are formed by linking AlO 4 tetrahedra with SiO 4 tetrahedra, this network being occupied by cations and water molecules. The cations in these structures are relatively mobile and can be exchanged to varying degrees by other cations.
  • the intercrystalline "zeolitic" water can be released continuously and reversibly, while with some zeolite types, structural changes are accompanied by water release or uptake.
  • Preferred detergent tablets are characterized in that they contain zeolite (s), preferably zeolite A, zeolite P, zeolite X and mixtures thereof, in amounts of from 0 to 60% by weight, preferably from 1 to 40% by weight. and in particular from 3 to 30% by weight.
  • zeolite preferably zeolite A, zeolite P, zeolite X and mixtures thereof, in amounts of from 0 to 60% by weight, preferably from 1 to 40% by weight. and in particular from 3 to 30% by weight.
  • the detergent tablets according to the invention may contain further ingredients customary in detergents and cleaners from the group of bleaches, bleach activators, disintegration aids, dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti redeposition agents, grayness inhibitors, Color transfer inhibitors and corrosion inhibitors.
  • Disintegration aids are especially in tableted phases preferred ingredients.
  • disintegration aids so-called tablet disintegrating agents
  • Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the tableted phase (s).
  • Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. But also celluloses in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom, can be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivative
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • preferred detergent tablets also contain a disintegration aid, preferably a disintegration aid 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 wt .-%, each based on the weight of the tableted phase (s).
  • a disintegration aid preferably a disintegration aid 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 wt .-%, each based on the weight of the tableted phase (s).
  • the detergent tablets according to the invention may moreover contain a gas-evolving effervescent system which is incorporated in one or more of the tableted phases.
  • the gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water.
  • the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While here a variety of systems is thinkable and executable that release, for example, nitrogen, oxygen or hydrogen, the bubble system used in the detergent tablets according to the invention can be selected both on the basis of economic as well as ecological aspects.
  • Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.
  • the alkali metal carbonates or bicarbonates the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
  • the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred for washing technical interest.
  • the effervescent system is 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of an Acidisersstoffs, in each case based on the entire molded body used.
  • Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts.
  • Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • Sokalan® DCS commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).
  • detergent tablets and cleansing agent tablets in which a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures thereof is used as the acidifying agent in the effervescent system.
  • sodium percarbonate is a non-specific term used for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonate) but hydrogen peroxide adducts of sodium carbonate.
  • the commercial product has the average composition 2 Na 2 CO 3 ⁇ 3 H 2 O 2 and is therefore no peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
  • bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • perbenzoates peroxophthalates
  • diperazelaic acid diperazelaic acid
  • phthaloimino peracid diperdodecanedioic acid.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenz-amidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-di-peroxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, Decyl
  • Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • bleach activators can be incorporated.
  • Bleach activators which support the action of the bleaching agents are, for example, compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes.
  • TAED tetraacetylethylenediamine
  • TAMD tetraacetylmethylenediamine
  • TAHD tetraacetylhexylenediamine
  • PAG pentaacetylglucose
  • DADHT 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are the O- and / or N-acyl groups of said carbon atom number and / or optionally bear substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • bleach catalysts can also be incorporated.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of the manganese sulfate are added in conventional amounts, preferably in an amount of up to 5% by weight, in particular of 0.0025% by weight. -% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can be used.
  • Further preferred automatic dishwashing detergent tablets are characterized in that at least one phase contains silver protectants from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes, more preferably benzotriazole and / or alkylaminotriazole , in amounts of 0.01 to 5 wt .-%, preferably from 0.05 to 4 wt .-% and in particular from 0.5 to 3 wt .-%, each based on the mass.
  • the corrosion inhibitors mentioned can also be incorporated to protect the items to be washed or the machine, with silver protectants being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art.
  • silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
  • cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • corrosion inhibitors are used in multiphase moldings, it is preferable to separate them from the bleaching agents.
  • Detergent tablets in which one of the phases contains bleach while another contains anticorrosion agent are therefore preferred.
  • Detergent tablets according to the invention in which one of the phases contains bleach while another contains enzymes are also preferred.
  • Suitable enzymes include in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • cellulases and other glycosyl hydrolases can be removed by removal of pilling and microfibrils for color retention and to increase the softness of the textile.
  • oxidoreductases for bleaching or inhibiting color transfer.
  • bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • hydrolases In automatic dishwashing detergent tablets, other enzymes are naturally used to account for the different treated substrates and contaminants.
  • those from the classes of the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned come into question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus cinereus and Humicola insolens
  • enzymatically-derived variants derived from their genetically modified variants e.g., Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on the phase in which they are used.
  • ingredients that may be part of one or more phase (s) include cobuilders, dyes, optical brighteners, fragrances, soil release compounds, soil repellents, antioxidants, fluorescers, foam inhibitors, silicone and / or paraffin oils, dye transfer inhibitors, graying inhibitors , Waschkraftverlochr etc .. These substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may, especially if the Agents also contain bleach, it is preferable to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.
  • the detergent tablets according to the invention can be wholly or partially dyed with suitable dyes. Special optical effects can be achieved if the individual phases are colored differently in the case of moldings of several phases.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the treated substrates such as textile fibers or dishes so as not to stain them.
  • Preferred for use in detergent tablets according to the invention are all colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable are, for example, anionic colorants, e.g. anionic nitrosofarads.
  • a possible colorant is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is available as a commercial product, for example as Basacid® Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes.
  • Pigmosol® Blue 6900 (Cl 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI 47005), Sicovit® Patent Blue 85 E 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acid Blue 183), Pigment Blue 15 (Cl 74160), Supranol® Blue GLW (CAS 12219-32-8, CI Acidblue 221 ), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan® Blue (CI Acid Blue 182, CAS 12219-26-0).
  • the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® green or the abovementioned Sandolan® blue, Typically, colorant concentrations ranging from a few 10 -2 to 10 -3 wt% are selected.
  • the suitable concentration of the colorant in detergents or cleaners is typically between 10 -3 and 10 -4 % by weight.
  • the detergent tablets according to the invention may contain one or more optical brighteners. These fabrics, also called “whiteners", are used in modern laundry detergents because even freshly washed and bleached white laundry has a slight yellow tinge.
  • Optical brighteners are organic dyes that convert part of the invisible UV radiation of sunlight into longer-wavelength blue light. The emission of this blue light complements the "gap" in the light reflected from the textile so that a fabric treated with optical brightener appears whiter and brighter to the eye. Since the mechanism of action of brighteners requires their application to the fibers, a distinction is made depending on the "fibers to be dyed", for example, brighteners for cotton, polyamide or polyester fibers.
  • the commercially available brighteners suitable for detergent incorporation essentially comprise five structural groups on the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazoline and the combination of benzoxazole or benzimidazole with conjugated systems.
  • Suitable are e.g. Salts of 4,4'-bis [(4-anilino-6-morpholino-s-triazin-2-yl) amino] -stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl).
  • Mixtures of the aforementioned brightener can be used.
  • Fragrances are added to the compositions according to the invention in order to improve the aesthetic impression of the products and to provide the consumer, in addition to the performance of the product, a visually and sensory "typical and unmistakable" product.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and methyl cedrylketone , among the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the content of perfume in the washing and cleaning agent tablets produced according to the invention is up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • Suitable foam inhibitors which can be used in the compositions according to the invention are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber from being suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble, Acidic group-containing polyamides are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the compositions
  • compositions according to the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, - alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • compositions prepared according to the invention may contain antimicrobial agents.
  • antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungiostats and fungicides, etc.
  • Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although it is entirely possible to do without these compounds.
  • the agents may contain antioxidants.
  • This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.
  • Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges.
  • External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents.
  • silicone derivatives can be used in the compositions according to the invention. These additionally improve the rinsing behavior of the agents by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are in the range between 100 and 100,000 centistokes at 25 ° C, wherein the silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.
  • compositions according to the invention may also contain UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the detergent tablets according to the invention completely dissolve in the washing or cleaning cycle, wherein - as mentioned above - it can have advantages if the different regions have different dissolution rates.
  • detergent tablets are preferred in which the pH of a 1% strength by weight solution in water is in the range from 8 to 12, preferably from 9 to 11 and in particular from 9.5 to 10.
  • the moldings according to the invention are those in which the viscoelastic phase is surrounded by two tableted phases.
  • the layer structure offers.
  • such a preferred shaped article according to the invention has the form of a three-layer tablet whose outer layers are tabletted, while the middle layer is the viscoelastic phase.
  • the outer "lid” may also consist of multilayer tablets, and also the viscoelastic phase may be composed of several - possibly differently composed - viscoelastic phases.
  • Preferred herein are detergent tablets according to the invention which have two tableted phases which have the form of layers, the viscoelastic phase being localized as a third layer between the tableted layers.
  • the tablettability of the tableted phases and their hardness / solubility profile can be improved if their surfactant content is kept as low as possible.
  • the design of the three-layer tablet described above is particularly attractive in terms of optics when the viscoelastic layer is 0.1 to 0.6 times, preferably 0.15 to 0.5 times and in particular 0.2 to 0.4 times the total tablet height.
  • the premix can be composed of a wide variety of substances as described above.
  • the premixes to be tabletted in process step a physical parameters of the premixes can be chosen such that advantageous moldings properties result.
  • tabletting particulate premixes are compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction, plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the Particles of the premix pressed closer to each other, wherein the void volume decreases continuously within the filling between the punches.
  • From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • some of the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • the lower punch is usually not moved during the pressing process.
  • the resulting tablet has a hardness gradient, i. harder in the areas closer to the upper punch than in the areas closer to the lower punch.
  • such tablets are preferably oriented such that the "softer" side lies inside, ie. comes into contact with the viscoelastic phase. The "hard” side then lies outside and causes a high stability. In this way, stable and fast-dissolving tablets can be obtained with reduced overall compressive forces.
  • rotary tablet presses are selected in which a larger number of dies are 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 commercially available.
  • Each die on the die table is assigned a top and bottom stamp, again the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drik to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • the "lid” in the context of the present invention also multi-phase, in particular multi-layered, ausgestalten.
  • two-layered tablets as a "lid", wherein the layer of the respective two-layer tablet, which has contact with the viscoelastic phase, in their composition and thickness can also be selected as a "barrier layer", which is a penetration of ingredients from the or into the viscoelastic phase.
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of Ein Titanauersch of commercial household washing machines or the dosing of commercial dishwashers, so that the moldings can be metered without dosing directly into the dispenser, where they dissolve during the dispensing process, or from where they are released during the cleaning process.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N leading to the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters
  • t the height of the moldings.
  • the viscoelastic phases are stable, readily storable and readily soluble in cold and warm water.
  • tableted phase 1 tableted phase 2 (Min in%) (Max in%) (Min in%) (Max in%)

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Claims (11)

  1. Corps moulé d'agent de lavage ou de nettoyage, comprenant une phase viscoélastique qui contient, rapportés à son poids, à concurrence de 40 à 85 % en poids, un ou plusieurs alkylbenzènesulfonates, et dont le module de stockage s'élève entre 40.000 et 800.000 Pa, caractérisé en ce que la phase viscoélastique est entourée par deux phases transformées en comprimés.
  2. Corps moulé d'agent de lavage ou de nettoyage selon la revendication 1, caractérisé en ce que le module de stockage de la phase viscoélastique s'élève de 50.000 à 750.000 Pa, de préférence de 60.000 à 700.000 Pa, de manière particulièrement préférée de 70.000 à 650.000 Pa et en particulier de 80.000 à 600.000 Pa.
  3. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le module de stockage de la phase viscoélastique est au moins deux fois, de préférence au moins quatre fois supérieur au module de perte.
  4. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le décalage de phase de la phase viscoélastique s'élève de 0 à 30°, de préférence de 0 à 20° et, en particulier est ≤ 17°.
  5. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la phase viscoélastique contient, rapportés à son poids, à concurrence de 40 à 95 % en poids, de préférence à concurrence de 50 à 90 % en poids, de manière particulièrement préférée à concurrence de 60 à 85 % en poids, et en particulier à concurrence de 65 à 82 % en poids, un ou plusieurs agents tensioactifs.
  6. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la phase viscoélastique contient, rapportés à son poids, à concurrence de 50 à 82,5 % en poids, et en particulier à concurrence de 60 à 80 % en poids, un ou plusieurs alkylbenzènesulfonates.
  7. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la phase viscoélastique contient, rapportés à son poids, à concurrence de 0 à 20 % en poids, de préférence à concurrence de 0,5 à 15 % en poids et en particulier à concurrence de 1 à 10 % en poids, un ou plusieurs agents tensioactifs non ioniques.
  8. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'il présente au moins une phase transformée en comprimés qui, rapportés à son poids, contient, à concurrence de 10 à 80 % en poids, de préférence à concurrence de 20 à 75 % en poids et en particulier à concurrence de 30 à 70 % en poids, un ou plusieurs builders.
  9. Corps moulé d'agent de lavage ou de nettoyage selon la revendication 8, caractérisé en ce qu'il présente deux phases transformées en comprimés, qui possèdent la forme de couches, la phase viscoélastique étant disposée, à titre de troisième couche, entre les couches transformées en comprimés.
  10. Corps moulé d'agent de lavage ou de nettoyage selon l'une quelconque des revendications 8 ou 9, caractérisé en ce que la ou les phases transformées en comprimés contiennent, chaque fois rapportés à leur poids, à concurrence de moins de 15 % en poids, de préférence à concurrence de moins de 7 % en poids, de manière particulièrement préférée à concurrence de moins de 3 % en poids, un ou plusieurs agents tensioactifs, et en particulier aucun agent tensioactif.
  11. Corps moulé d'agent de lavage ou de nettoyage (« comprimé à trois couches ») selon l'une quelconque des revendications 9 ou 10, caractérisé en ce que la couche viscoélastique représente de 0,1 à 0,6 fois, de préférence de 0,15 à 0,5 fois et en particulier de 0,2 à 0,4 fois la hauteur totale du comprimé.
EP02732618A 2001-04-25 2002-04-16 Elements moules de produits de lavage a phase viscoelastique Expired - Lifetime EP1390463B1 (fr)

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DE10120441A DE10120441C2 (de) 2001-04-25 2001-04-25 Waschmittelformkörper mit viskoelastischer Phase
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ES2313539T3 (es) * 2005-03-23 2009-03-01 Unilever N.V. Composiciones de detergente en forma de pastillas.
EP1746151A1 (fr) * 2005-07-20 2007-01-24 Unilever N.V. Pastilles de composition détergente
EP3033410A1 (fr) 2013-08-14 2016-06-22 Budich International GmbH Tablette détergente à plusieurs phases
US8877240B1 (en) 2014-01-09 2014-11-04 Chemlink Laboratories, Llc Tablet binding compositions
DE102021203328A1 (de) * 2021-04-01 2022-10-06 Henkel Ag & Co. Kgaa Waschmittelportionseinheit
DE102021203326A1 (de) * 2021-04-01 2022-10-06 Henkel Ag & Co. Kgaa Waschmittelportionseinheit

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EP1390463A1 (fr) 2004-02-25
DE50208499D1 (de) 2006-11-30
ATE342957T1 (de) 2006-11-15
US20040127373A1 (en) 2004-07-01
US7598217B2 (en) 2009-10-06
ES2274976T3 (es) 2007-06-01
DE10120441A1 (de) 2002-11-07
WO2002086047A1 (fr) 2002-10-31
DE10120441C2 (de) 2003-09-04

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