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EP1322743B1 - Pastilles a cavite et procede de fabrication desdites pastilles - Google Patents

Pastilles a cavite et procede de fabrication desdites pastilles Download PDF

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Publication number
EP1322743B1
EP1322743B1 EP01969736A EP01969736A EP1322743B1 EP 1322743 B1 EP1322743 B1 EP 1322743B1 EP 01969736 A EP01969736 A EP 01969736A EP 01969736 A EP01969736 A EP 01969736A EP 1322743 B1 EP1322743 B1 EP 1322743B1
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EP
European Patent Office
Prior art keywords
weight
laundry
acid
cavity
detergent tablets
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01969736A
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German (de)
English (en)
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EP1322743A1 (fr
Inventor
Thomas Holderbaum
Bernd Richter
Christian Nitsch
Rolf Bayersdörfer
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE2000148058 external-priority patent/DE10048058A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C11D1/721—End blocked ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups

Definitions

  • the invention relates to detergent tablets in the form of well tablets, i. Tablets having at least one cavity on one of their surfaces.
  • the invention also relates a method of making well tablets or well tabs. It is in a (usually the upper) side of a large volume tablet imprinted a trough, which in a subsequent Confectioning be filled with a different material, in particular poured out can.
  • the present invention relates to washing or cleaning agent tablets comprising at least one cavity, wherein the content of the tablets of nonionic surfactants having a melting point above 20 ° C 5.5 to 25 % By weight, based in each case on the tablet.
  • nonionic surfactants in the stated amounts leads to a reduction in the Appearances on the non-planning pressing tool and a significantly reduced occurrence edge chipping phenomena at the trough edges.
  • a corresponding composition of the phase comprising the cavity, i. of the premix which comes into contact with the non-planned ram at the final crimping.
  • the first premix is only slightly compressed by pressing with the stamp, no adhesion or occur here Edge break phenomena on. Only at the final compression, the forces are so great that the problems mentioned are to be feared.
  • Another object of the present invention are therefore also multi-phase washing or Detergent tablets comprising at least one cavity, wherein the content of the phase, the the cavity has, to nonionic surfactants having a melting point above 20 ° C 5.5 to 25 wt .-%, is.
  • the vertical has lateral boundary surfaces (possibility of ejection from the die).
  • the bottom and "top” surfaces are horizontal, i. they and the edge surface (s) are orthogonal each other.
  • Tablets having at least one cavity (so-called mortar tablets), possess this cavity for the reasons mentioned above at its top or bottom.
  • the lower punch and thus the Bottom
  • the upper punch at least one survey which impresses the cavity in the top of the tablet.
  • the tablets according to the invention may be any geometric shape in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disc-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, octagonal and octagonal prismatic and rhombohedral forms are preferred. Also completely irregular bases like arrow or animal shapes, trees, clouds can be realized. Indicates the basic shaped body Corners and edges, so these are preferably rounded. As an additional optical Differentiation is an embodiment with rounded corners and beveled (“chamfered”) Edges preferred.
  • the shape of the trough can be chosen freely, with tablets being preferred in which at least a trough a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segmented, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, pentagonal, pentagonal, octagonal, prismatic and rhombohedral Can take shape. Also completely irregular trough shapes like arrow or animal forms, trees, Clouds can be realized. As with the basic moldings are wells with rounded Corners and edges or with rounded corners and chamfered edges preferred.
  • Such wells which have a cone, have advantages in later Filling operations, so that tablets according to the invention, in soft angle as explained above between 90 and 120 °, preferably between 91 and 110 °, more preferably between 92 and 100 ° and in particular between 93 and 98 °, are preferred.
  • the size of the trough or cavity in comparison to the entire shaped body depends on the desired use of the shaped body. Depending on whether and with which substances in which aggregate states the trough or cavity is to be filled, the size of the trough vary. Regardless of the purpose, washing and cleaning tablets are used preferred in which the volume ratio of base molding to trough volume in the range from 1: 1 to 100: 1, preferably from 2: 1 to 80: 1, more preferably from 3: 1 to 50: 1 and especially from 4: 1 to 30: 1.
  • washing or Detergent tablets in which the surface of the cavity opening is 1 to 25%, preferably 2 to 20%, more preferably 3 to 15% and in particular 4 to 10% of the total surface makes up the tablet.
  • the overall shaped body has dimensions of 20 ⁇ 20 ⁇ 40 mm and thus a total surface area of 40 cm 2
  • well fillings are preferred which have a surface area of 0.4 to 10 cm 2 , preferably 0.8 to 8 cm 2 , more preferably of 1.2 to 6 cm 2 and in particular from 1.6 to 4 cm 2 .
  • the well tablets according to the invention contain nonionic surfactant (s).
  • nonionic surfactant s
  • the total surfactant content of detergent tablets is 5.5 to 60 Wt .-%, based on the molding weight, with surfactant contents above 15 wt .-% preferred are.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • the surfactants of the sulfonate type are preferably C 9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters.
  • fatty acid glycerol esters are the mono-, di- and triesters and their mixtures to understand how they are in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example, the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
  • 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps may be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
  • the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • surfactants are usually low-foaming surfactants nonionic surfactants used.
  • nonionic surfactants used in detergent tablets according to the invention therefore have Representatives of the groups of anionic, cationic or amphoteric surfactants a lower Importance.
  • the detergent tablets according to the invention comprise nonionic surfactants from the group of the alkoxylated alcohols.
  • nonionic surfactants preference is given to using 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, 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.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon 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 alone nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide may be suitable.
  • the amount of these nonionic surfactants is preferably no longer than that of the ethoxylated fatty alcohols, especially not more than half of them.
  • polyhydroxy fatty acid amides of the formula (I) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R '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 oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy or N-aryloxy-substituted compounds can then be converted by reaction with fatty acid methyl esters converted in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides become.
  • the automatic dishwashing detergent tablets according to the invention contains a nonionic surfactant which has a melting point above Room temperature.
  • the washing or cleaning agent tablets contain nonionic surfactant (s) having a melting point above 20 ° C, preferably above of 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, in amounts of 5.5 to 25 wt .-%, preferably from 5.5 to 20 wt .-%, preferably from 6.0 to 17.5 wt .-%, especially preferably from 6.5 to 15 wt .-% and in particular from 7.0 to 12.5 wt .-%, each based on the tablet or the phase that has the cavity.
  • Suitable nonionic surfactants are, for example, low-foaming nonionic surfactants which Room temperature can be solid or highly viscous. Become highly viscous at room temperature Nonionic surfactants used, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Also Niotenside, the at Room temperature waxy consistency, are preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures thereof
  • Surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Drawing such (PO / EO / PO) nonionic surfactants Beyond that 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.
  • nonionic surfactant (s) is / are ethoxylated nonionic surfactant (s) selected from C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol were obtained (n), are therefore preferred.
  • 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 bis to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Surfactants.
  • Detergents or cleaning tablets, the ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25 wt .-%, preferably up to 20 Wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant are preferred embodiments of the present invention.
  • Nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which in addition Having polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part such nonionic surfactant molecules preferably makes up more than 30% by weight, especially preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight such nonionic surfactants.
  • nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 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 of a block copolymer 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 preference are, for example available 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 for a value of at least 15 is detergent tablets, which are characterized in that they nonionic surfactants of 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
  • 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 ] j 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, with the variation width increasing with increasing x values and including, for example, 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.
  • detergent or detergent tablets are preferred, which are characterized in that they or the phase having the cavity 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 ] j 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, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • nonionic surfactants from group a) have already been described in detail above, with particular preference for the automatic dishwashing compositions containing the abovementioned mixtures, C 12-14 fatty alcohols with 5EO and 4PO and C 12-18 fatty alcohols with an average of 9 EO have proven to be outstanding. With similar preference end-capped nonionic surfactants, in particular C 12-18 fatty alcohol-9 EO-butyl ether, can be used.
  • Surfactants from group b) show outstanding clear rinse effects and reduce stress corrosion cracking on plastics. Furthermore, they have the advantageous property that their network behavior is constant over the entire usual temperature range. Particularly preferred the surfactants from the group b) hydroxyl-containing alkoxylated alcohols, as described in EP 300 305 are described, the disclosure of which is expressly incorporated herein. All there Hydroxymischether disclosed are invariably with preference as a surfactant from the group b) in the According to the invention preferred dishwashing detergents contain.
  • nonionic surfactant s / e
  • the surfactants may, for example, in the molten state on the otherwise ready-to-use pre-mix to be compressed are sprayed on or the premix in the form of compounds or surfactant formulations. Especially it is preferred to use particulate premixes of high-surfactant particles, so-called "rinse aid particles" admit.
  • Particularly preferred rinse aid particles contain as carrier (e) a) one or more substances from the groups of phosphates, carbonates, bicarbonates and / or silicates in quantities of From 25 to 85% by weight, preferably from 35 to 82.5% by weight and in particular from 45 to 80% by weight, each based on the weight of the particulate rinse aid, contains These substances described below.
  • the alkali metal phosphates are particularly preferred as support materials for the rinse aid particles.
  • 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, moreover, 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 is acidic; 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 according to the invention just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also 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 are used according to the invention.
  • Preferred washing or Detergent tablets contain carbonate (s) and / or bicarbonate (s), preferably Alkali carbonates, more preferably sodium carbonate, in amounts of 25 to 75 wt .-%, preferably from 30 to 60 wt .-% and in particular from 35 to 50 wt .-%, each based on the mass of rinse aid particles contained in them.
  • Silicates which, instead of or in addition to the said phosphates and / or Carbonates / bicarbonates may be included in the detergent tablets are Silicates, wherein the alkali metal silicates and including 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 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x has 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.
  • washing or cleaning agent tablets according to the invention can be used as carrier materials or in the remaining solid matrix also contain zeolites, with preferred agents no zeolite as Carrier material in the rinse aid particles and particularly preferred detergent tablets even do not contain any zeolite.
  • zeolites with preferred agents no zeolite as Carrier material in the rinse aid particles and particularly preferred detergent tablets even do not contain any zeolite.
  • laundry detergent tablets according to the invention is the use of zeolite however preferred.
  • Zeolites have the general formula M 2 / n O ⁇ Al 2 O 3 ⁇ x SiO 2 ⁇ y H 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.
  • the "primary binding units” AlO 4 tetrahedra and SiO 4 tetrahedra
  • secondary binding units which are in the form of single or multiple rings.
  • 4-, 6- and 8-membered rings (referred to as S4R, S6R and S8R) occur in different zeolites, others are joined via four- and six-membered double ring prisms (most common types: D4R as quadrangular or D6R as hexagonal prism ).
  • These "secondary subunits” combine different polyhedra called Greek letters. The most common is a Dahlflächner, which is composed of six squares and eight equilateral hexagons and which is referred to as " ⁇ ". With these units, a variety of different zeolites can be realized. So far, 34 natural zeolite minerals and about 100 synthetic zeolites have been known.
  • the best known zeolite, zeolite 4 A is a cubic composite of ⁇ -cages linked by D4R subunits. It belongs to the zeolite structure group 3 and its three-dimensional network has pores of 2.2 ⁇ and 4.2 ⁇ size, the formula unit in the unit cell can be with Na 12 [(AlO 2 ) 12 (SiO 2 ) 12 ] ⁇ 27 H 2 O describe.
  • faujasite-type zeolites are preferably used. Together with zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double-six-membered subunit D6R (cf. Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974 , page 92).
  • the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5.
  • the latter two synthetic zeolites have no mineral analogs.
  • Faujasite-type zeolites are composed of ⁇ -cages linked tetrahedrally via D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities of about 13 ⁇ diameter and can be represented by the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] . 264 H 2 O.
  • the network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 47% void volume). (All data from: Donald W. Breck: "Zeolite Molecular Sieves", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176 , 177 ).
  • faujasite-type zeolite denotes all three zeolites forming the faujasite subgroup of zeolite structure group 4.
  • X are also zeolite Y and faujasite as well as mixtures of these compounds can be used according to the invention, wherein the pure zeolite X is preferred
  • mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, the not necessarily belong to the zeolite structure group 4, can be used according to the invention, the advantages of the method according to the invention are particularly evident when at least 50% by weight of the powdering agent consists of a faujasite-type zeolite.
  • the aluminum silicates used in the washing or cleaning tablets according to the invention are commercially available, and the methods of their presentation are in Standard monographs are described.
  • Examples of commercially available X-type zeolites can be described by the following formulas: Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .xH 2 O, K 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .xH 2 O, Ca 40 Na 6 [(AlO 2 ) 86 (SiO 2 ) 106 ] xH 2 O, Sr 21 Ba 22 [(AlO 2) 86 (SiO 2) 106] ⁇ x H 2 O,
  • x can take values between 0 and 276 and have pore sizes of 8.0 to 8.4 ⁇ .
  • a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) which is marketed by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® is also commercially available and preferably usable in the context of the process according to the invention and by the formula nNa 2 O • (1-n) K 2 O • Al 2 O 3 • (2 - 2.5) SiO 2 • (3.5-5.5) H 2 O can be described.
  • Y-type zeolites are commercially available us can be, for example, by the formulas Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] xH 2 O, K 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] xH 2 O, where x is numbers between 0 and 276 and has pore sizes of 8.0 ⁇ .
  • the abovementioned builder substances can be used as carrier materials in the rinse aid particles be included, or they may be additional or only part of the "other" Washing or cleaning tablets.
  • the rinse aid particles contained in the washing or Detergent tablets can be used nonionic surfactant (s) already have been described in detail above.
  • the inventive Detergents or cleansing tablets contain the nonionic surfactant (s) in the form of separate rinse aid particles those tablets are preferred in which the particulate rinse aid as nonionic Surfactants b) Mixtures of alkoxylated alcohols and hydroxy mixed ethers in amounts of From 10 to 35% by weight, preferably from 10.5 to 30% by weight and in particular from 11 to 20% by weight, each based on the weight of the particulate rinse aid contains.
  • the well tablets according to the invention may contain further ingredients which are either as Active ingredients or excipients localized in the rinse aid particles or incorporated in other ways in the agents are. These substances are described below and may each be further Active ingredients or auxiliaries may be contained in the rinse aid particles, but they may also be added or only exclusively part of the "remaining" mortar tablets.
  • the particulate Klarspüier as further active ingredients and / or auxiliaries c) a or more substances from the groups of dyes, fragrances, defoamers, polymers, scale inhibitors, Silver protectants, enzymes and / or mixtures thereof in amounts of 5 to 60 Wt .-%, preferably from 10 to 50 wt .-% and in particular from 15 to 30 wt .-%, respectively based on the weight of the particulate rinse aid.
  • bleaching agents In addition to the substances mentioned above, bleaching agents, bleach activators, co-builders, Chelating and complexing agents, water-softening substances, acidifying and / or alkalizing agents as well as adjusting, separating and anti-caking agents as constituents of the mortar tablets according to the invention prefers. In the case of the first three substances mentioned, it is advantageous not to use them into the rinse aid particles.
  • wellbill tablets according to the invention are preferred, which are characterized are that they continue to contain one or more substances from the groups of surfactants, enzymes, Bleaching agents, bleach activators, corrosion inhibitors, scale inhibitors, cobuilders color and / or Fragrances, soil release polymers, optical brighteners, color transfer or grayness inhibitors in amounts of 25 to 70 wt .-%, preferably from 30 to 60 wt .-% and in particular from 40 to 50 wt .-%, each based on the weight of the total composition.
  • 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 peroxygenic salts or peracids which yield H 2 O 2 , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid.
  • bleaching agents it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the compositions.
  • Bleaching agents from the group of organic bleaching agents can also be used in the compositions according to the invention.
  • 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-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldip
  • chlorine or bromine-releasing materials are, for example, heterocyclic N-bromine and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as Potassium and sodium are considered.
  • heterocyclic N-bromine and N-chloroamides for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with cations such as Potassium and sodium are considered.
  • DICA dichloroisocyanuric acid
  • salts such as Potassium and sodium are considered.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • bleach activators can be incorporated.
  • Bleach activators that For example, compounds that support one or more of the bleaching agent's effects N- or O-acyl groups, such as substances from the class of anhydrides, the ester, 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 compounds which are aliphatic under perhydrolysis conditions
  • Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used.
  • suitable Substances which contain O- and / or N-acyl groups of said C 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, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-
  • TAED
  • Bleaching catalysts are incorporated. These substances are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are known as Bleach catalysts usable.
  • Bleach activators from the group of the multiply acylated alkylenediamines in particular Tetraacetylethylenediamine (TAED), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, especially 2 to 8 wt .-% and especially preferably 2 to 6 wt .-% based on the total agent used.
  • TAED Tetraacetylethylenediamine
  • N-acylimides especially N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonan
  • Bleach-enhancing transition metal complexes in particular with 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, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025% to 1% and more preferably from 0.01% to 0.25% by weight, each based on the total agent used. But in special cases can be more Bleach activator can be used.
  • Further preferred well tablets are characterized in that they silver protectants the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, 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 total agent included.
  • the corrosion inhibitors mentioned can be used to protect the items to be washed or the machine are also incorporated into the well tablets, wherein in the field of machine dishwashing Silver protectants have a special meaning.
  • Can be used the known Substances of the prior art.
  • especially silver protectants can be selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and the transition metal salts or complexes.
  • benzotriazole and / or alkylaminotriazole are to be used.
  • One finds in cleaner formulations In addition, frequently active chlorine-containing agents that corrode the silver surface can significantly reduce.
  • chlorine-free cleaner are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes.
  • organic redox-active compounds such as di- and trihydric phenols, eg. Hydroquinone, Pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these connection classes.
  • salt and complex inorganic compounds such as salts
  • the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • Transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and the Manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the dishes be used.
  • hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures the enzymes mentioned in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains.
  • Oxidoreductases are used. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens and enzymatically derived from their genetically modified variants Agents.
  • subtilisin-type proteases and in particular proteases used from Bacillus lentus.
  • 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 been found to be 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 encapsulating substances to them to protect against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on the total mean amount.
  • compositions of the invention are, for example Co-builders, dyes, fragrances, soil-release compounds, soil repellents, antioxidants, Fluorescers, foam inhibitors, silicone and / or paraffin oils. These substances will be described below.
  • Useful organic builders are, for example, those usable in the form of their sodium salts
  • Polycarboxylic acids understood by polycarboxylic acids such carboxylic acids which carry more than one acidity function.
  • these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use of ecological Reasons are not objectionable, as well as mixtures of these.
  • Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids have besides their builder effect typically also the property of an acidifying component and thus also serve for Setting a lower and milder pH of detergents or cleaners.
  • citric acid succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.
  • Suitable builders are polymeric polycarboxylates, for example the alkali metal salts the polyacrylic acid or the polymethacrylic acid, for example those with a relative Molecular weight of 500 to 70000 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 polystyrosulfonic 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, this group may again, the short-chain polyacrylates, the molecular weights of 2000 to 10,000 g / mol, and especially preferably from 3000 to 5000 g / mol, have to be preferred.
  • copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • copolymeric polycarboxylates in particular those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • acrylic acid with maleic acid the 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
  • Their 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 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution become.
  • the content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
  • the polymers may also allylsulfonic, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
  • biodegradable polymers of more than two different Monomer units for example those containing as monomers salts of acrylic acid and the Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.
  • copolymers are those containing as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties also a bleach-stabilizing Have effect.
  • polyacetals which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C atoms and at least 3 hydroxyl groups, can be obtained.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes be performed.
  • they are hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, especially from 2 to 30 preferred, wherein DE a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is.
  • DE dextrose equivalent
  • Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins having higher molecular weights in the range of 2000 to 30,000 g / mol.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one atcohol 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 cobuilders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts.
  • EDDS ethylenediamine-N, N'-disuccinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable quantities 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 at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Aminoalkanphosphonate are preferably Ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral reacting sodium salts, eg.
  • As a builder is from the class of phosphonates preferred to use HEDP.
  • the aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it may, especially if the means also bleach may be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.
  • the agents according to the invention can be whole or partially (e.g., only single layers or the well fill) colored with suitable dyes become.
  • Preferred dyes the selection of which does not cause any difficulty for the skilled person, have a high storage stability and insensitivity to the other ingredients the agent and against light and no pronounced substantivity to the treated Substrates such as crockery parts, so as not to stain them.
  • Preferred for use in laundry detergent tablets according to the invention are all colorants which are in Washing process can be oxidatively destroyed as well as mixtures thereof with suitable blue Dyes, so-called blue tint. It has proved to be advantageous to use dyes which are in Water or at room temperature in liquid organic substances are soluble.
  • anionic colorants e.g. anionic nitrosofarads.
  • a possible dye is, for example, naphthol green (Color Index (Cl) Part 1: Acid Green 1, part 2: 10020), which is known as Commercial product, for example, as Basacid® Green 970 from BASF, Ludwigshafen, available is, as well as mixtures of these with suitable blue dyes.
  • Pigmosol® Blue 6900 (Cl 74160), Pigmosol® Green 8730 (Cl 74260), Basonyl® Red 545 FL (Cl 45170), Sandolan® Rhodamine EB400 (Cl 45100), Basacid® Yellow 094 (Cl 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, Cl Acidblue 221)), Nylosan® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan® Blue (Cl Acid Blue 182, CAS 12219-26-0) for use.
  • 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, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically selected.
  • the suitable concentration of the colorant in detergents or cleaners is typically between 10 -3 and 10 -4 % by weight.
  • Fragrances are added to the compositions of the invention to give the aesthetic impression of Improve products and give the consumer a visual and in addition to the performance of the product sensory "typical and distinctive" product to provide.
  • perfume oils or fragrances may be individual fragrance compounds, e.g. the synthetic products of the type the esters, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the ionone, ⁇ -isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes Limes and pinas. However, preference is given to using mixtures of different fragrances, which together create an appealing scent.
  • perfume oils can also be natural Fragrance mixtures as available from vegetable sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, Olibanumöl, Galbanumöl and Labdanumöl as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.
  • the content of the detergents according to the invention of fragrances is up to 2 Wt .-% of the total formulation.
  • the fragrances can be directly in the agents according to the invention but it may also be advantageous to apply the perfumes to carriers, which increase the adhesion of the perfume on the laundry and by a slower fragrance release ensure a long-lasting fragrance of the textiles.
  • carrier materials for example Cyclodextrins proven, the cyclodextrin-perfume complexes additionally with other excipients can be coated.
  • foam inhibitors which can be used in the inventive compositions come for example, soaps, paraffins or silicone oils, optionally on support materials can be applied.
  • the detergent tablets according to the invention may contain one or more optical (s) Contain brightener. These substances, which are also called “whiteners” are used in modern Detergent used since even freshly washed and bleached white laundry a slightly yellowish.
  • Optical brighteners are organic dyes that are part of the invisible Convert UV radiation of sunlight into longer wavelength blue light. The emission This blue light complements the "gap" in the light reflected from the textile, so that one with optical Brightener treated textile makes the eye whiter and brighter because of the mechanism of action of brighteners presupposes their application to the fibers, a distinction is made according to the "to be colored" Fibers, for example, brighteners for cotton, polyamide or polyester fibers.
  • Brighteners suitable for incorporation into detergents are essentially included therein five structural groups on the stilbene, the diphenylstilbene, the coumarin-quinoline, the diphenylpyrazole group and the group of 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 similar compounds which replace the Morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group.
  • brighteners of the substituted type can be used Diphenylstyryls 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) -diphenyls. Also mixtures The aforementioned brightener can be used.
  • tablet disintegrants In order to facilitate the disintegration of highly compressed tablets, it is possible disintegration aids, so-called tablet disintegrants to incorporate into this to shorten the disintegration times. These Substances are suitable, for example, for the release of individual tablet areas accelerate other areas.
  • tablet disintegrants and decay accelerators are understood to be excipients for the rapid disintegration of tablets in water or gastric juice and provide for the release of the pharmaceuticals in absorbable form.
  • Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration aids, in each case based on the weight of the tablet.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents in the present invention, 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 formally represents a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5,000 Glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of
  • the cellulose used as disintegration assistant is preferably not in finely divided form but before blending into the pre-mixes to be pressed into a coarser one Form transferred, for example, granulated or compacted.
  • the particle sizes of such disintegrating agents are usually above 200 microns, preferably at least 90 wt .-% between 300 and 1600 microns and in particular at least 90 wt .-% between 400 and 1200 microns.
  • coarser Disintegrationstoskar Cellulosic are preferred in the context of the present invention as disintegration aids and commercially available, for example, under the name Arbocel® TF-30-HG available from Rettenmaier.
  • microcrystalline cellulose As another disintegrating agent based on cellulose or as a component of this component can microcrystalline cellulose.
  • This microcrystalline cellulose is made by partial Obtained hydrolysis of celluloses under such conditions that only the amorphous regions (ca. 30% of the total cellulose mass) of the celluloses attack and completely dissolve the crystalline ones Areas (about 70%) but leave undamaged.
  • preferred washing and cleaning agent tablets additionally a disintegration aid, preferably a cellulose disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, respectively based on the weight of the tablet.
  • a disintegration aid preferably a cellulose disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, respectively based on the weight of the tablet.
  • the detergent tablets according to the invention can moreover be a gas-evolving Effervescent system incorporated into one or more of the masses to be processed incorporated becomes.
  • the gas-evolving effervescent system may consist of a single substance, which releases a gas on contact with water. Among these compounds is in particular the To name magnesium peroxide, which releases oxygen on contact with water.
  • the gas-releasing effervescent system itself comprises at least two components, which react with each other to form gas. While here a variety of systems thinking and is executable that release, for example, nitrogen, oxygen or hydrogen, the both in the detergent and cleaner tablets used according to the invention be selected on the basis of economic as well as ecological aspects.
  • preferred Effervescent systems consist of alkali metal carbonate and / or bicarbonate as well an acidifying agent which is suitable from the Aikatimetailsalzen in aqueous solution of carbon dioxide release.
  • the sodium and potassium salts are made Cost reasons over the other salts clearly preferred. Of course you have to not the respective pure alkali metal carbonates or bicarbonates are used; Rather, mixtures of different carbonates and bicarbonates from washing technical Interest be preferred.
  • washing and cleaning agent tablets are used as effervescent 2 to 20 wt .-%, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or -hydrogencarbonats and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% an Acidisersstoffs, each based on the total tablets used.
  • the salary individual masses of the substances mentioned may well be higher.
  • Acidifying agents which release carbon dioxide from the alkali salts in aqueous solution are for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
  • organic Acidaimssstoff used, wherein the citric acid is a particularly preferred Acidiser.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • detergent tablets and cleansing agent tablets are preferred those as Acidisersmittel in the effervescent system, a substance from the group of organic di-, tri-and Oligocarbon Acid or mixtures of these are used.
  • Grayness inhibitors have the task of removing the dirt removed from the fiber in the fleet to keep it suspended and thus prevent the dirt from being rebuilt.
  • These are water-soluble colloids mostly organic nature suitable, for example, the water-soluble salts polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids or the Cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble, Acidic group-containing polyamides are suitable for this purpose.
  • soluble starch preparations and other than the above starch products e.g. degraded starch, aldehyde levels, etc.
  • polyvinylpyrrolidone is useful.
  • cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of 0.1 to 5 wt .-%, based on the means used
  • the well tablets synthetic crease inhibitors contain. These include, for example, synthetic products based on fatty acids, Fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols which usually reacted with ethylene oxide, or products based on lecithin or modified Organophosphate.
  • the well tablets may contain antimicrobial agents.
  • antimicrobial agents Here one differentiates depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungiostats and fungicides, etc.
  • Important substances include, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and Phenolmercuriacetat, which can be completely dispensed with these compounds.
  • the agents can antioxidants contain.
  • 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 improved drainage of formed charges.
  • External antistatic agents are usually substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. This mostly surfactant antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) Divide antistatic agents.
  • the lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect is achieved.
  • Silicone derivatives are used. These additionally improve the rinsing behavior of the Agent 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 completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, optionally be derivatized and are then amino-functional or quaternized or Si-OH-, Have Si-H and / or Si-Cl bonds.
  • the viscosities of the preferred silicones are included 25 ° C in the range between 100 and 100,000 centistokes, with the silicones in quantities between 0.2 and 5 wt .-%, based on the total agent can be used.
  • the mortar tablets according to the invention may also contain UV absorbers on apply the treated textiles and improve the lightfastness of the fibers.
  • Links, which have these desired properties are, for example, by non-radiative Deactivation of effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position.
  • substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanic acid suitable.
  • the mortar tablets according to the invention are particularly suitable for further ingredients in the To incorporate cavity.
  • a liquid poured into the trough caused by cooling, solidification, chemical reaction, delayed water retention, Change the rheological properties, etc. is solidified.
  • particulate To provide fillings for the cavity, which are fastened in the cavity by adhesion promoter become.
  • a special case of this is the insertion of a single particle (hereinafter also referred to as "core"), either by the use of adhesion promoters or by physical Forces in the cavity are liable.
  • core single particle
  • a particulate premix can enter the trough pressed in and also form a phase there.
  • adhesion promoters When using adhesion promoters can these are introduced into the well either before the dosage of the cavity filling, or afterwards ( “Spray effect”).
  • the application of adhesion promoters is particularly necessary if the subsequently applied active substances alone do not have sufficient adhesiveness to remain at least partially in the cavity and the mechanical loads to withstand packaging, transport and handling without abrasion.
  • the bonding agent Thus, in the case of cores that are not sufficiently adhesive, it is used to "stick" these substances or compounds.
  • Melting of one or more substances with a melting range of 40 ° C to 75 ° C are as Adhesion promoters preferred.
  • the Schmelz supportive canyon Solidification behavior on the other hand, however, the material properties in the solidified area at ambient temperature.
  • the "stuck" active substances during transport or storage permanently should, it has a high stability against, for example, in packaging or transport have occurring impact loads.
  • the bonding agents should therefore either at least partially have elastic or at least plastic properties in order to an occurring Impact stress by elastic or plastic deformation to respond and not to break.
  • the Adhesion promoters should have a melting range (solidification range) in such a temperature range have, in which the applied active materials are not exposed to high thermal stress become.
  • the melting range must be sufficiently high to at least slightly elevated temperature nor to provide effective adhesion of the applied active ingredients.
  • the coating substances preferably have a melting point above 30 ° C.
  • the width the melting range of the primer also has an immediate effect on the Procedure: The provided with primer body must in the following Process step are brought into contact with the applied active substances, In the meantime, the adhesion must not be lost. After absorption of the active substances the adhesion should be reduced as quickly as possible in order to avoid unnecessary loss of time or Caking and stagnation in subsequent process steps or handling and Avoid packaging. In the case of the use of melts, the reduction of the Adherence by cooling (for example, blowing cold air) are supported.
  • adhesion promoters do not have a sharply defined melting point show how it usually occurs in pure, crystalline substances, but one under Circumstances have several degrees Celsius melting range.
  • the adhesion promoters preferably have a melting range of between about 45 ° C and about 75 ° C is. That is, in the present case, that the melting range within the specified Temperature interval occurs and does not denote the width of the melting range.
  • the width of the melting range is at least 1 ° C, preferably about 2 to about 3 ° C.
  • waxes are usually met by so-called waxes.
  • “Waxing” is understood to mean a number of natural or artificial substances, usually melt above 40 ° C without decomposition and relatively little above the melting point low viscosity and non-stringy. They have a strong temperature-dependent Consistency and solubility.
  • the waxes are divided into three groups, the natural waxes, chemical modified waxes and the synthetic waxes.
  • Natural waxes include, for example, vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwax), or raffia fat, mineral waxes such as ceresin or Ozokerite (ground wax), or petrochemical waxes such as petrolatum, paraffin waxes or Microcrystalline waxes.
  • vegetable waxes such as candelilla wax, Carnauba wax, japan wax, esparto wax, cork wax, guaruma wax, rice germ oil wax, Sugar cane wax, ouricury wax, or montan wax
  • animal waxes such as beeswax, Shellac wax, spermaceti, lanolin (woolwa
  • the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
  • Synthetic waxes are generally polyalkylene waxes or polyalkylene glycol waxes Understood.
  • Compounds which can also be used as adhesion promoters are compounds from other classes of substances, which are the meet the requirements regarding the softening point.
  • suitable synthetic Compounds for example, have higher esters of phthalic acid, in particular Dicyclohexyl phthalate, which is commercially available under the name Unimoll® 66 (Bayer AG), proved.
  • waxes from lower carboxylic acids and Fatty alcohols for example dimyristyl tartrate, sold under the name Cosmacol® ETLP (Condea)
  • synthetic or partially synthetic esters of lower alcohols are also available Fatty acids can be used from natural sources.
  • Tegin® 90 falls into this class of substances (Goldschmidt), a glycerol monostearate palmitate.
  • shellac for example shellac KPS three-ring SP (Kalkhoff GmbH) can be used according to the invention as a primer.
  • wax alcohols are higher molecular weight, water-insoluble Fatty alcohols with usually about 22 to 40 carbon atoms.
  • the waxy alcohols come for example in the form of wax esters of higher molecular weight fatty acids (wax acids) as the main constituent many natural waxes.
  • wax alcohols are lignoceryl alcohol (1-tetracosanol), Cetyl alcohol, myristyl alcohol or melissyl alcohol.
  • adhesion promoters to be applied may also contain wool wax alcohols, among which Triterpenoid- and steroid alcohols, such as lanolin, understands, for example, under the Trade name Argowax® (Pamentier & Co) is available. Also at least proportionately as Component of the adhesion promoter can be used in the context of the present invention Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds.
  • the adhesion promoters preferably contain paraffin wax in the predominant proportion. It means that preferably at least 50% by weight of the adhesion promoters, preferably more, of paraffin wax consist. Particularly suitable are paraffin wax contents in the adhesion promoter of about 60 wt .-%, about 70 wt .-% or about 80 wt .-%, with even higher levels of, for example, more than 90 wt .-% are particularly preferred.
  • Paraffin waxes have, compared to the other mentioned, natural waxes in the context of present invention has the advantage that in an alkaline detergent environment no Hydrolysis of waxes takes place (as can be expected, for example, in the Wachsestem) since Paraffin wax contains no hydrolyzable groups
  • Paraffin waxes consist mainly of alkanes, as well as low levels of iso and Cycloalkanes.
  • the paraffin to be used according to the invention preferably has substantially no constituents having a melting point of more than 70 ° C, more preferably more than 60 ° C on. Shares of high-melting alkanes in the paraffin can fall below this Melting temperature in the cleaning agent unwanted wax residue on the zu leave cleansing surfaces or the goods to be cleaned. Such wax residues usually lead to an unsightly appearance of the cleaned surface and therefore should be avoided.
  • the content of the paraffin wax used is at ambient temperature (in the Usually about 10 to about 30 ° C) solid alkanes, isoalkanes and cycloalkanes as high as possible.
  • With increasing proportion of fixed Wax constituents increases the strength of the adhesive layer against shocks or Friction on other surfaces, resulting in a longer-lasting clinging of the wrapped Active ingredients results in high levels of oils or liquid wax components can lead to a Weakening of the particle adhesion, whereby the adhered active substances differ from the shaped body to solve.
  • the adhesion promoters may contain one or more of the above mentioned waxes or waxy substances.
  • the bonding agents should be such that the "adhesive layer" is at least largely insoluble in water.
  • the solubility in water at a temperature of about 30 ° C should not exceed about 10 mg / l, and preferably below 5 mg / l.
  • the Adhesion promoters the lowest possible solubility in water, even in water at elevated temperature, have as possible to a temperature-independent release of the coated active ingredients largely avoided.
  • the adhesion promoters can be pure substances or substance mixtures. In the latter case, the Melt contain varying amounts of adhesion promoters and excipients.
  • the principle described above serves the delayed detachment of the "glued" Active substances at a certain time, for example in the cleaning of a Dishwasher and can be particularly advantageous to use when in the main rinse with lower temperature (for example 55 ° C) is rinsed, so that the active substance from the Adhesive layer is only released in the rinse cycle at higher temperatures (about 70 ° C).
  • the said principle can also be reversed to the effect that the active substance (s) of The adhesive layer does not delay, but accelerates to be released.
  • This can be easier Achieve way in that as a primer not Lenseverzögerer, sondem dissolution accelerator be used so that the adhered active substances do not dissolve more slowly from the molding, but faster.
  • preferred adhesion promoters are readily soluble in water for rapid release.
  • the Water solubility of the adhesion promoter can be significantly increased by certain additives, for example, by incorporation of slightly soluble salts or effervescent systems.
  • Such Dissolution-accelerated adhesion promoter (with or without additives of further solubility improvers) lead to a rapid detachment and release of the active substances at the beginning of the Cleaning cycle.
  • the release acceleration can also be achieved or supported by certain geometric factors become. Detailed comments can be found below.
  • Polyethylene glycols which can be used according to the invention are polymers of ethylene glycol which are of general formula III H- (O-CH 2 -CH 2 ) n -OH satisfy, where n can assume values between 1 (ethylene glycol) and over 100,000.
  • n can assume values between 1 (ethylene glycol) and over 100,000.
  • Decisive in the assessment of whether a polyethylene glycol is used according to the invention, is the state of aggregation of the PEG, ie the melting point of the PEG must be above 30 ° C, so that the monomer (ethylene glycol) and the lower oligomers with n 2 to approx 16 can not be used because they have a melting point below 30 ° C.
  • polyethylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights.
  • polyethylene glycols there are various nomenclatures that can lead to confusion.
  • Technically common is the indication of the average relative molecular weight following the indication "PEG”, so that "PEG 200” characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210.
  • the commercially available polyethylene glycols PEG 1550, PEG 3000, PEG 4000 and PEG 6000 are preferably used in the context of the present invention.
  • polyethylene glycols for example under the trade name Carbowax® PEG 540 (Union Carbide), Emkapol® 6000 (ICI Americas), Lipoxol® 3000 MED (HUBS America), Polyglycol® E-3350 (Dow Chemical), Lutrol® E4000 (BASF) and the corresponding trade names with higher numbers.
  • PEG and PPG are of course also Other substances can be used provided they have a sufficiently high water solubility and a Melting point above 30 ° C.
  • Preferred adhesion promoters according to the invention are one or more substances from the groups the paraffin waxes, preferably with a melting range of 50 ° C to 55 ° C, and / or the Polyethylene glycols (PEG) and / or polypropylene glycols (PPG) and / or the natural waxes and / or the fatty alcohols.
  • the paraffin waxes preferably with a melting range of 50 ° C to 55 ° C
  • PEG Polyethylene glycols
  • PPG polypropylene glycols
  • adhesion promoters In addition to melting, other substances can be applied as adhesion promoters.
  • concentrated salt solutions are suitable after application of the active ingredients Crystallization or evaporation / evaporation are transferred into an adhesion-promoting salt crust.
  • supersaturated solutions or solutions can also be used of salts in solvent mixtures.
  • adhesion promoters are solutions or suspensions of water-soluble or dispersible polymers, preferably polycarboxylates.
  • the substances mentioned were further already described above due to their co-builder characteristics.
  • adhesion promoters are solutions of water-soluble substances the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, gelatin and mixtures thereof.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n in small proportions also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but especially by alkaline-channeled transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. These technical processes also make PVAL accessible. which contain a predeterminable residual amount of acetate groups.
  • PVAL e.g., Mowiol® grades from Hoechst
  • PVAL e.g., Mowiol® grades from Hoechst
  • the water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Reduce borax and thus set specifically to desired values.
  • the rheological properties PVAL solutions can be modified by changing the molecular weight or concentration adjust to the desired values, depending on how the solution is applied as a primer shall be.
  • Polyvinylpyrrolidones referred to as PVP for short, may be represented by the general formula describe.
  • PVP are prepared by radical polymerization of 1-vinylpyrrolidone.
  • commercial PVP have molecular weights in the range of about 2500-750,000 g / mol and are called white, hygroscopic Powder or offered as aqueous solutions.
  • Gelatine is a polypeptide (molecular weight: approx. 15,000-> 250,000 g / mol), primarily by hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline Conditions is won.
  • the amino acid composition of gelatin corresponds largely that of the collagen from which it was obtained and varies depending on it Provenance.
  • the use of gelatin as the water-soluble coating material is particularly useful in the Pharmaceutical in the form of hard or soft gelatin capsules extremely widespread.
  • adhesion promoters from the group starch are also preferred and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.
  • Starch is a homoglycan, wherein the glucose units are linked ⁇ -glycosidically.
  • Strength is composed of two components of different molecular weight: from about 20-30% straight chain Amylose (M.W., about 50,000-150,000) and 70-80% branched-chain amylopectin (M.W. 300,000-2,000,000), in addition there are still small amounts of lipids, phosphoric acid and cations contain. While the amylose due to binding in 1,4-position long, helical, forms chains with about 300-1200 glucose molecules, the chain branches in the Amylopectin after an average of 25 glucose building blocks by 1,6-binding to a branch-like Formations with about 1500-12000 molecules of glucose.
  • starch derivatives by polymer-analogous reactions of starch are available.
  • Such chemically modified starches include, for example, products of esterifications or etherifications in which hydroxy-hydrogen atoms were substituted.
  • strengths in which the hydroxy groups have been replaced by functional groups that are not bound by an oxygen atom can be used as starch derivatives.
  • 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.
  • Cellulosic adhesion promoters usable in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • Preferred adhesion promoters which can be used as aqueous solution consist of a Polymer having a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 daltons, and more particularly between 10,000 and 100,000 daltons.
  • the after drying the bonding agent between the individual molding body areas (Muldenwandung and second Part) present layer of the adhesion promoter preferably has a thickness of 1 to 150 microns, preferably from 2 to 100 ⁇ m, particularly preferably from 5 to 75 ⁇ m and in particular from 10 up to 50 ⁇ m, up.
  • the active substances can be applied in solid, highly viscous or plastic form become.
  • the Metering accuracy with which a certain amount of additional active substance is applied different high. In general, this dosing accuracy when applying crumbs with a certain fluctuation range of approx. +/- 10%.
  • active substances for those in the cavity solid crumbles to be introduced have proven to be particularly effective in the washing or cleaning should dissolve quickly, for example, enzymes.
  • the crumbs can be produced in different shapes and sizes.
  • under “crumbling” is also the gluing of a single metering unit in the cavity to understand, with this single metering unit naturally has a higher volume as the single volume of dosing units, which are introduced several times into the cavity.
  • a hemispherical crumb in the context of the present invention Mulde be glued.
  • other forms for "Sprinkles” and moldings such as cubes, cuboids, Semi-ellipsoids, cylinder segments, prisms, etc. are thinkable and realizable.
  • the number of crumbs, which in the trough glued is greater than 1.
  • Such sprinkles then advantageously have the dimensions conventional washing and cleaning agent in powder, granule, extrudate, flake or platelet form and are glued in multiple numbers.
  • a particularly preferred embodiment of the present invention provides that the Muldentablette has a cavity whose bottom and / or side surfaces optionally with adhesion promoter be provided, after which a separately prepared and in the cavity matching shaped body is glued.
  • the application of the adhesion promoter can also be individual surfaces of the To be adhered molded body.
  • the cavity in the well tablet can - as already mentioned - have any shape. she can divide the shaped body, i. an opening at the top and bottom of the molding but it can also be a cavity that does not pass through the entire molded body, the opening of which is only visible on a molded body side.
  • adhesion promoter can either in the molding with cavity or in the molding take place, which fills the cavity. Bonding agent is preferred in the cavity of the molding brought in.
  • adhesion promoter on preferably an area of the individual metering unit can be done in different ways. For example, it is possible to use the separate dosing unit in the dipping process one-sidedly with adhesive to wet and then in the cavity to place. This technology is technologically easy to implement, but carries the risk that Adhesive contaminates the surface of the molding with cavity. The amount of glue can controlled in this variant by varying the rheological properties of the adhesion promoter become.
  • adhesion promoters on preferably to apply an area of the individual metering unit is this metering unit past adhesive dosing systems and then place in the cavity. This is achieved by adhesion promoter dosing nozzles, impregnated with primer brushes or Nonwovens or by rolling.
  • adhesion promoter dosing nozzles impregnated with primer brushes or Nonwovens or by rolling.
  • the latter method design is particularly easy to implement, that the separate dosing unit has only a small contact surface to the roller
  • the adhesion promoter can be dosed from the interior of the roller, but it is also possible, the bonding agent at a point from the point of contact of the roller with the separate metering units away, apply to the roller.
  • the filling of the cavity can fill the cavity completely, but it can also fill the cavity stand out or only partially fill them, leaving the imagination of the product developers no Limits are set.
  • the Shape of the trough or the hole and the shape of the separate dosing unit can be varied Produce molded body variations that are visually very different from each other.
  • the adhesion of the separate metering unit in the cavity decreases with decreasing Touchpad. Maximum adhesion between the two moldings is achieved if the molded body and the separate dosing unit without gaps fit together form-fitting.
  • four-phase moldings can be produced by two biphasic moldings (inventive two-phase mold body and two-phase "Kem") are interconnected.
  • composition of the second part optionally to be introduced into the cavity are the design possibilities also no limits.
  • the second part can also contain several ingredients or in themselves a complete detergent or cleaning composition be. It is particularly preferred in the context of the present invention, if the second part is made up so that it in the washing or cleaning process an additional Effect unfolds.
  • automatic dishwashing detergents it is preferred to use "kernels" to be used in the well tablets which serve the function of a "pre-rinse phase", a "performance booster” or a "final rinse phase", i.
  • ingredients in the first case, for example, enzymes, in the second case, for example Bleaching agent and in the third case, for example, surfactants or scale-inhibiting polymers or Acids. It is particularly preferred to incorporate ingredients in the "core” which the make additional dosage unnecessary otherwise necessary means, for example Rinse aid or regenerating salt. In the former case, the "core” represents a final rinse phase, in In the latter case, salt substitutes are incorporated into the "core” necessary for binding the Provide water hardness and thus allow rinsing with hard water, without causing limescale on the dishes or machine parts comes.
  • Washing or cleaning agent tablets according to the invention are therefore particularly preferred additionally have a second part, the shape of a core or on or in the first part ("base tablet") glued body and preferably one or more substances from the group of builders, acidifiers, chelating agents or scale-inhibiting agents Contains polymers.
  • Chelating agents are substances that form cyclic compounds with metal ions, where a single Ligand occupies more than one coordination site on a central atom, i. H. at least "bidentate" is. In this case, normally stretched verbs are formed by complex formation over a lon to rings closed. The number of bound ligands depends on the coordination number of the central lone.
  • chelate complex images within the scope of the present invention are for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complexing polymers ie polymers which are either in the Main chain or self-supporting to this functional groups that act as ligands can and with suitable metal atoms usually to form chelate complexes react,. are used according to the invention.
  • the polymer-bound ligands of the resulting Metal complexes can come from just one macromolecule or different ones Belong to polymer chains. The latter leads to the networking of the material, provided that the complex-forming Polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of conventional complex-forming polymers are iminodiacetic acid, Hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic, amidoxime, aminophosphoric, (cycl.) Polyamino, mercapto, 1,3-dicarbonyl and crown ether radicals with z. T. very specific. Activities towards ions of different metals.
  • Many base polymers too commercially significant complexing polymers are polystyrene, polyacrylates, polyacrylonitriles, Polyvinyl alcohols, polyvinylpyridines and polyethyleneimines.
  • natural polymers like cellulose, Starch or chitin are complexing polymers. In addition, these may be due to polymer analogues Transformations are provided with additional ligand functionalities.
  • polycarboxylic acids a) are in the context of this patent application carboxylic acids - also monocarboxylic acids - understood, in which the sum of carboxyl and contained in the molecule Hydroxyl groups is at least 5.
  • Complexing agent from the group of nitrogen-containing polycarboxylic acids, especially EDTA, are preferred.
  • these Komplexbilner are at least partially as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts become.
  • salts are alkali, ammonium or alkylammonium salts, especially sodium salts, preferred.
  • the scale-inhibiting polymers as an ingredient of the second part are in particular Detergent tablets preferred, characterized in that the second part one or more scale-inhibiting polymers from the group of cationic homoders Copolymers, in particular hydroxypropyltrimethylammonium guar; Copolymers of aminoethyl methacrylate and acrylamide, copolymers of dimethyldiallylammonium chloride and acrylamide, Polymers with imino groups, polymers, which are quaternized as monomer units Ammoniumalkylmethacrylat phenomenon cationic polymers of monomers such as trialkylammonium alkyl (meth) acrylate or -acrylamide; Dialkyldiallyldiammoniumsalze; polymer-analogous reaction products of ethers or esters of polysaccharides having pendant ammonium groups, in particular Guar, cellulose and starch derivatives; Polyadducts of ethylene oxide with ammonium groups; quatern
  • ionic or nonionic monomers are in particular ethylenically unsaturated Compounds considered.
  • the content is preferably that used according to the invention Polymers of monomers of group iii) less than 20 wt .-%, based on the polymer.
  • Particularly preferred polymers contained in the second part consist only of monomers of Groups i) and ii).
  • the copolymers contained in the second part may contain the monomers from groups i) and ii) and, where appropriate, (iii) in varying amounts, all representatives of the Group i) with all representatives from group ii) and all representatives from the group iii) can be combined.
  • Particularly preferred polymers have certain structural units on, which are described below.
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • the sulfonic acid groups can be completely or partially in neutralized form, i.e. that the acidic acid of the sulfonic acid group in some or all sulfonic acid groups against metal ions, preferably alkali metal ions and in particular against sodium ions, can be exchanged.
  • metal ions preferably alkali metal ions and in particular against sodium ions.
  • the monomer distribution in the copolymers according to the invention contained in the second part is in the case of copolymers which contain only monomers from groups i) and ii), preferably in each case 5 to 95 wt .-% i) or ii), particularly preferably 50 to 90 wt .-% monomer from the group i) and 10 to 50 wt .-% of monomer from group ii), each based on the polymer.
  • terpolymers particular preference is given to those which contain from 20 to 85% by weight of monomer Group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer Group iii).
  • the molecular weight of the polymers according to the invention contained in the second part can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the parent application detergent tablets according to the invention may also be designed multiphase, wherein the content of the phase, the the cavity has, on nonionic surfactants from 5.5 to 25 wt .-%, is.
  • Both the as- The multiphase washing or cleaning agent tablets according to the invention can additionally a second part having the shape of a core or one on the first Part ("base tablet") glued body has and preferably one or more substances from the group of builders, acidifiers, chelating agents or scale-inhibiting agents Contains polymers.
  • cleaning agents according to the invention are preferred which, in addition to the nonionic surfactants have a content of sulfonic acid-containing polymers.
  • inventive Means of this embodiment causes the after the main rinse cycle and the intermediate rinses in the machine remaining amounts of surfactants adequate drainage behavior in the final rinse cycle, so that the effluent from the wash water leaves no stains during drying.
  • the sulfonic acid group-containing polymer used acts as an effective softener, so that can be rinsed with non-softened water even in high hardness areas without it comes to coverings on the dishes or machine.
  • the rinse requires when using this inventive agent is not charged with additional intentionally added rinse aid to be, and also on the use of regenerating salt can be omitted.
  • the products described in this additional application are thus genuine '3in1' products, which are the Combine cleaner, rinse aid and regenerating salt in one medium.
  • sulfonated Cpolymere in a second part, which has already been as "core” in the surfactant-rich mortar tablet ("base tablet”) is inserted or glued.
  • base tablet surfactant-rich mortar tablet
  • sulfonated copolymers can be incorporated not only in the “core” but also in the base tablet, cores optionally present in the base tablets, the copolymer (s) contain or be free from it.
  • the sulfonated copolymer (s) in amounts of 0.25 to 50 wt .-%, preferably from 0.5 to 35% by weight, more preferably from 0.75 to 20% by weight and especially from 1 to 15 wt .-%, each based on the total tablet included.
  • washing or cleaning agent tablets which contain one or more copolymers which are structural units of the formulas VII and / or VIII and / or IX and / or X and / or XI and / or XII are also preferred - [CH 2 -CHCOOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -CHC (O) -Y-SO 3 H] p - - [CH 2 -CHCOOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH 3 ) C (O) -Y-SO 3 H] p - - [CH 2 -C (CH 3 ) COOH] m - [CH 2 -C (CH
  • Particularly preferred sulfonic acid-containing monomers are as already above mentions 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propane-sulfonic acid, 2-acrylamido-2-methyl-1-propane-sulfonic acid, 2-Methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, Allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, Methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propen-1-sulfonic acid, Styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamid, sulfomethylmethacrylamide and water-soluble salts
  • a "core” in the surfactant-rich depression tablet glued which also contain the sulfonated or the copolymer (s) can.
  • those detergent or detergent tablets are preferred, in addition to a second part having the shape of a core or one on the first part ("base tablet") glued body and - based on the weight of the core - 1 to 80 wt .-%, preferably 2.5 to 70 wt .-%, particularly preferably 5 to 60 wt .-% and in particular 10 to 50% by weight of the sulfonated copolymer (s / e).
  • the tablets themselves may contain the sulfonated copolymer (s).
  • inventive Detergents or detergent tablets preferred in which the well tablet ("Base tablet") based on their weight 0.5 to 30 wt .-%, preferably 1 to 25 wt .-%, especially preferably from 2.5 to 20% by weight and in particular from 4 to 15% by weight of the sulphonated one Copolymer (s / e) contains.
  • the polymer is particularly advantageous not uniformly distributed in core and base tablet, but is mainly localized in the base tablet
  • washing or cleaning agent tablets according to the invention are preferred in which both the base tablet and the core contain the sulfonated copolymer (s), wherein at least 50% by weight, preferably at least 60% by weight and in particular at least 65% % By weight of the total sulfonated copolymer (s / e) contained in the tablet in the base tablet is included.
  • washing or cleaning agent tablets according to the invention are not required, so that both the base tablet and optionally contained Core no coating is required to effect a rinse effect and on regenerating salt to be able to do without.
  • Particularly preferred washing or cleaning agent tablets according to the invention are therefore characterized in that the core has no coating.
  • agents according to the invention have been found to be particularly suitable in addition to the sulfonated copolymers other homo- and / or copolymeric polycarboxylic acids or contain polycarboxylates.
  • sulfonated copolymers with heteroatom-containing Polymers or copolymers, especially those with amino or phosphono groups.
  • washing or cleaning agent tablets according to the invention are particularly preferred, which additionally 0.1 to 30 wt .-% homo- and / or copolymeric polycarboxylic acids or their salts and / or heteroatom-containing polymers / copolymers, in particular those having amino or phosphono groups contain.
  • Another object of the present invention is a process for the preparation of washing or Detergent tablets having at least one cavity, wherein a particulate premix, its content of nonionic surfactants having a melting point above 20 ° C 5.5 to 25 wt .-%, each based on the premix, is pressed in a conventional manner to depression tablets.
  • Another object of the present invention is Therefore, a method for producing multiphase washing or cleaning agent tablets with at least one cavity, in which several particulate premixes in per se known Be pressed into well tablets, wherein the content of the premix, the final compression the tablet is contacted with the stamp for the injection of the cavity, a Content of nonionic surfactants of from 5.5 to 25% by weight, in each case based on the premix, having a melting point above 20 ° C. having.
  • the tableting of the mono- or multiphase well tablets is analogous to conventional Tablettings, except that the pressing surface of at least one press ram is not is plan, but has at least one survey that the cavity (s) in the inventive Molded body. It has proved to be advantageous if the compressed premix meets certain physical criteria. For example, preferred methods characterized in that to be compressed particulate premixes a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
  • the particle size of the compressed premix preferably satisfies certain criteria: Processes in which particulate premixes have particle sizes between 100 and 2000 ⁇ m, preferably between 200 and 1800 microns, more preferably between 400 and 1600 microns and especially between 600 and 1400 ⁇ m, are preferred according to the invention. One more Narrowed particle size in the premixes to be compressed may be more advantageous for obtaining Molded body properties are set.
  • the inventive Method to be compressed particulate premixes have a particle size distribution at, wherein less than 10 wt .-%, preferably less than 7.5 wt .-% and in particular less than 5 wt .-% of the particles are greater than 1600 microns or less than 200 microns.
  • Particularly advantageous process variants are characterized in that the to be compressed particulate premixtures a Particle size distribution, wherein more than 30 wt .-%, preferably more than 40 wt .-% and more preferably more than 50% by weight of the particles have a particle size between 600 and 1000 have ⁇ m.
  • the process preferred according to the invention is not specified limited that only a particulate premix is pressed into a shaped body. Rather, this process step can also be extended to the effect that in known per se Way multilayer molded body produces by mixing two or more premixes prepares that are pressed together. In this case, the first-filled premix becomes light pre-compressed to get a smooth top and after filling in the second premix Endverpreßt the finished molded body. In the case of three-layered or multi-layered shaped bodies, the following occurs each pre-mix addition, one more pre-compression before adding the last pre-mix the molding is end-pressed.
  • the cavity described above is in Basic shaped body a trough, so that preferred embodiments of the first invention Method characterized in that multilayer moldings having a trough, be prepared in a conventional manner by several different particulate Premixes are pressed together. This must (if the upper punch the non-plane Preßstempel is) only the last premix meet the criteria of the invention - it can however, it may be desired that several or all premixes, despite otherwise different composition contain at least 5 wt .-% of nonionic surfactant (s).
  • s nonionic surfactant
  • the production of the moldings takes place first by the dry mixing of the ingredients, which may be pre-granulated in whole or in part, and subsequent informing, in particular Compress to tablets, using conventional methods.
  • Preparation of the shaped bodies according to the invention is the premix in a so-called template compressed between two stamps to a fixed compressed. This process, in the following short referred to as tableting, is divided into four sections: dosage, compaction (elastic deformation), 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 molded body by the position of the lower punch and the shape of the pressing tool can be determined.
  • the constant dosage even at high Moldings throughputs are preferably via volumetric metering of the premix reached.
  • the upper punch touches the pre-mix and continues to lower in the direction of the lower punch. In this compression, the particles become of the premix is pressed closer to each other, wherein the void volume within the Filling between the punches decreases continuously.
  • the tableting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch to Pressure build-up used, also the lower punch moves during the pressing process on the Upper stamp too, while the upper punch presses down.
  • Eccentric tablet presses are preferably used, in which the one or the stamp on an eccentric disc are fixed, which in turn on an axis with a certain rotational speed is mounted. The movement of these punches is the operation of a usual Four-stroke engine comparable.
  • the compression can each with a top and bottom stamp take place, but it can also be attached more stamp on an eccentric disc, wherein the number of die holes is extended accordingly.
  • the throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses where on a so-called Matrizentisch a larger number of matrices is arranged in a circle.
  • the number of matrices varies from 6 to 55 depending on the model, although larger dies are commercially available.
  • Each die on the die table is assigned a top and bottom stamp, again the pressing pressure active only by the upper or lower punch, but also constructed by both stamp can be.
  • the die table and the punches move around a common vertical standing axis, wherein the punches by means of rail-like cam tracks during the Circulated to positions for filling, compaction, plastic deformation and ejection become.
  • these curved paths by additional Low pressure pieces, Nierderzugschienen and Aushebebahnen supported.
  • the filling the die takes place via a rigidly arranged supply device, the so-called filling shoe, the is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, whereby the pressure build-up by passing the stamp shank heads past adjustable pressure rollers.
  • Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle must be run through.
  • suitable process control coat and point tablets can be produced in this way, which have a onion-bowl-like 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.
  • 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 at the same time for pressing to be used. The throughputs of modern rotary tablet presses are over one Million moldings per hour.
  • Tableting machines suitable for the purposes of the present invention are available, for example at the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Packaging Systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Presses AG, Berlin, as well as Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bem (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
  • Hydraulic double pressure press HPF 630 of the company LAEIS, D is particularly suitable.
  • Tabletting tools are for example by the companies Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
  • Other providers are e.g. the Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).
  • the moldings can - as already mentioned above - in a predetermined spatial form and be made of a predetermined size.
  • the training as a blackboard the bar or bar form, Cube, cuboid and corresponding room elements with flat side surfaces and in particular cylindrical embodiments with a circular or oval cross-section.
  • These last embodiment detects the presentation form of the tablet up to compact cylinder pieces with a height to diameter ratio above 1.
  • the various components do not become a single tablet be pressed, but that moldings are obtained, the more layers, so at least two layers. It is also possible that these different layers have different dissolution rates. This can be advantageous application technology Properties of the moldings result. For example, if components in the moldings are mutually negative influence, so it is possible, the one Integrate component in the faster soluble layer and the other component into one incorporate slower soluble layer so that the first component has already reacted, when the second goes into solution.
  • the layer structure of the molded body can be both stacked take place, wherein a solution process of the inner layer (s) at the edges of the molding already it then happens when the outer layers are not yet completely dissolved, but it can also a complete encasement of the inner layer (s) by the further outer layer (s) Layer (s) are achieved, resulting in a prevention of premature solution of components the inner layer (s) leads.
  • a shaped body consists of at least three layers, so two outer and at least one inner layer, wherein at least in one of the inner layers a peroxy bleach is contained, while in the stacked one Shaped body, the two outer layers and the envelope-shaped body the outermost
  • layers are free of peroxy bleach.
  • peroxy bleach and optionally existing bleach activators and / or enzymes spatially in one Separate molded bodies from each other.
  • the washing or cleaning agent tablets After pressing, the washing or cleaning agent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P ist the force in N, which leads to the pressure exerted on the molding
  • the breakage of the molding D is the shape diameter in meters
  • t is the height of the moldings.
  • the detergent tablets according to the invention can be packaged after production, wherein the use of certain packaging systems has proven particularly useful since these packaging systems on the one hand increase the storage stability of the ingredients, in the case of moldings with cavities and inserted second part on the other hand surprisingly long-term adhesion of the Significantly improve trough filling.
  • a further subject of the present invention is therefore a combination of (one or more) washing or cleaning agent tablets according to the invention and a packaging system containing the washing or cleaning agent tablet (s), the packaging system having a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85%.
  • the packaging system of the combination of detergent tablet (s) and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system at 23 ° C and a relative Equilibrium moisture content of 85% is stored.
  • the temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
  • the moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity").
  • the measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested.
  • the relative equilibrium moisture in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C.
  • the absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is expressed in g / m 3 .
  • saturation content For example, 1 m 3 of air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor.
  • the relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature.
  • the relative equilibrium humidity of 85% at 23 ° C can be, for example, in laboratory chambers with humidity control to +/- 2% r.L. depending on the device type. set exactly. Also over saturated Solutions of certain salts form in closed systems at a given temperature constant and well-defined relative humidities resulting in the phase equilibrium between partial pressure of water, saturated solution and soil body based.
  • washing or cleaning agent tablet (s) and packaging system can, of course, in turn in secondary packaging, such as cardboard or trays, with no secondary requirements on the secondary packaging have to be asked.
  • secondary packaging such as cardboard or trays
  • Packaging systems preferred in the present invention have a moisture vapor transmission rate of from 0.5 g / m 2 / day to less than 15 g / m 2 / day.
  • the packaging system of the combination according to the invention encloses depending on the embodiment of the invention one or more washing or cleaning agent tablet (s). It is according to the invention preferred to make either a shaped body such that it is an application unit of the washing or cleaning agent, and to pack this tablet individually, or to pack the number of tablets in a packaging unit, which in sum is an application unit includes.
  • a target dosage of 80 g detergent or cleaning agent it is According to the invention, it is possible to prepare an 80 g washing or cleaning agent tablet and to package individually, but it is also possible according to the invention, two 40 g each heavy To pack washing or cleaning agent tablets in a packaging in order to form a product according to the invention Combination to arrive.
  • combinations also include three, four, five or even more washing or cleaning agent tablets contained in a packaging unit.
  • two or three more detergent tablets in a package different compositions exhibit. In this way it is possible to spatially separate certain components to separate, for example, to avoid stability problems.
  • the packaging system of the combination according to the invention can be made of the most diverse Materials exist and assume any external forms. For economic reasons and however, for ease of processing, packaging systems are preferred which the packaging material has a low weight, easy to work and inexpensive is.
  • the packaging system consists of a Bag or bag of single-layer or laminated paper and / or plastic film.
  • the washing or cleaning agent tablets may be unsorted, i. as a loose bed, in a bag of the materials mentioned are filled. It is for aesthetic reasons and preferably for sorting the combinations in secondary packaging, the detergent tablets one by one or several sorted into sacks or bags to fill.
  • the term "flow pack” has become common in the art. Such "flow packs” can then - optionally again sorted - optionally be packed in outer packaging, which underlines the compact form of the tablet.
  • the preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become.
  • Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded.
  • Plastic films which can be used in the context of the present invention as a packaging system, for example, in Hans Domining House "The Plastics and their properties", 3rd edition , VDI Verlag, Dusseldorf, 1988 , page 193 indicated.
  • the figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.
  • particularly preferred combinations contain as a packaging system a bag or bag of single-layer or laminated plastic film with a Thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.
  • packaging system indicates in the context of the present invention is always the primary packaging of Detergents or shaped bodies, i. the packaging, which on its inside directly with the Shaped surface is in contact. At an optional secondary packaging are no requirements provided so that all the usual materials and systems can be used here.
  • the washing or cleaning agent tablets of the invention Combination depending on their intended use further ingredients of Waschoder Detergents in varying amounts. Regardless of the purpose of the tablets it is inventively preferred that the detergent tablets or a detergent Equilibrium moisture content of less than 30% at 35 ° C / exhibit.
  • the relative equilibrium humidity of the washing or cleaning agent tablets can after the following methods A water-impermeable 1-liter jar with a lid, which has a closable opening for the introduction of samples was, with a total of 300 g washing or cleaning agent tablets are filled and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of vessel and substance.
  • the water vapor pressure in the room above the moldings can then with a hygrometer (Hygrotest 6100, Testoterm Ltd., England).
  • the water vapor pressure is now measured every 10 minutes until two consecutive values show no deviation (equilibrium humidity).
  • the o.g. Hygrometer allows a direct display of the recorded values in% relative humidity.
  • compositions according to the invention can be used in all household dishwashing machines be used, with respect to the program choice, there are no limitations.
  • the beneficial effects are found in both low-temperature programs such as 45 ° C programs or Achieved at 50/55 ° C or 60/65 ° C programs.
  • Another object of the present invention is therefore a method for the purification of Dishes in a domestic dishwasher, in which one or more inventive Detergent tablet (s) is introduced into the main cleaning cycle of the machine.
  • the introduction into the main cleaning gear can by filling the dosing with the tablet (s), wherein by opening the dosing after a possible Vorthesesgang the tablet (s) is released into the machine. It is alternatively possible bring the tablet (s) directly into the machine and thus already in an optional Pre-cleaning procedure to release active substance. Alternatively, it can also be on a Vorthesesgang be waived.
  • inventive methods in which the Klarspttlgang the machine is carried out without the deliberate addition of further rinse aid are therefore preferred.
  • cleaner encompasses liquid commercially available rinse aids which are from Consumers given at intervals of several rinsing cycles in a reservoir of the machine must be released and programmatically released from there. This intentional addition a rinse aid and the required for this second dosing step at intervals of some rinse cycles are not required by the use of the agents according to the invention.
  • step b) the additional deliberate dosage of commercially available rinse aid is not required so that processes are preferred in which in step b) no further rinse aid intentionally is added.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicinal Preparation (AREA)

Claims (23)

  1. Pastilles de produits de lavage ou de nettoyage, comprenant au moins une cavité, caractérisées en ce que la teneur des pastilles en agents tensioactifs non ioniques avec un point de fusion supérieur à 20°C s'élève de 5,5 à 25 % en poids, toujours par rapport aux pastilles.
  2. Pastilles de produits de lavage ou de nettoyage à plusieurs phases, comprenant au moins une cavité, caractérisées en ce que la teneur de la phase qui présente la cavité en agents tensioactifs non ioniques avec un point de fusion supérieur à 20°C s'élève de 5,5 à 25 % en poids.
  3. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1ou 2, caractérisées en ce que la cavité présente des parois de délimitation latérales qui sont orthogonales par rapport à la surface de base.
  4. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 3, caractérisées en ce que la surface de l'ouverture de la cavité constitue de 1 à 25 %, de préférence de 2 à 20 %, de façon particulièrement préférée de 3 à 15 % et en particulier de 4 à 10 % de la surface totale de la pastille.
  5. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 4, caractérisées en ce qu'elles contiennent un ou plusieurs agents tensioactifs non ioniques avec un point de fusion supérieur à 25°C, de façon particulièrement préférée compris entre 25 et 60°C et en particulier entre 26,6 et 43,3°C, à des quantités de 5,5 à 20 % en poids, de préférence de 6,0 à 17,5 % en poids, de façon particulièrement préférée de 6,5 à 15 % en poids et en particulier de 7,0 à 12,5 % en poids, toujours par rapport à la pastille respectivement à la phase qui présente la cavité.
  6. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 5, caractérisées en ce que le ou les agents tensioactifs non ioniques est ou sont des agents tensioactifs non ioniques éthoxylés qui ont été obtenus à partir de monohydroxyalcanols en C6 à C20 ou d'alkylphénols en C6 à C20, ou d'alcools gras en C16 à C20 et de plus de 12 moles, de préférence de plus de 15 moles et en particulier plus de 20 moles d'oxyde d'éthylène par mole d'alcool.
  7. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 6, caractérisées en ce qu'elles, respectivement la phase qui présente la cavité, contiennent des agents tensioactifs non ioniques éthoxylés et propoxylés dans lesquels les unités oxyde de propylène dans la molécule constituent jusqu'à 25 % en poids, de préférence jusqu'à 20 % en poids et en particulier jusqu'à 15 % en poids de l'ensemble de la masse molaire de l'agent tensioactif non ionique.
  8. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 7, caractérisées en ce qu'elles, respectivement la phase qui présente la cavité, contiennent des agents tensioactifs non ioniques de formule R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2] dans laquelle R1 représente un radical hydrocarboné aliphatique linéaire ou ramifié avec de 4 à 18 atomes de carbone ou des mélanges de tels corps, R2 représente un radical hydrocarboné linéaire ou ramifié avec de 2 à 26 atomes de carbone ou des mélanges de tels corps, et x prend des valeurs comprises entre 0,5 et 1,5 et y prend une valeur d'au moins 15.
  9. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 8, caractérisées en ce qu'elles, respectivement la phase qui présente la cavité, contiennent des agents tensioactifs non ioniques poly(oxyalkylés) bloqués à leur groupe d'extrémité, de formule R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2 dans laquelle R1 et R2 représentent des radicaux hydrocarbonés linéaires ou ramifiés, saturés ou insaturés, aliphatiques ou aromatiques, avec de 1 à 30 atomes de carbone, R3 représente H ou un radical méthyle, éthyle, n-propyle, iso-propyle, n-butyle, 2-butyle ou 2-méthyl-2-butyle, x prend des valeurs comprises entre 1 et 30, k et j prennent des valeurs comprises entre 1 et 12, de préférence entre 1 et 5, où l'on préfère les agents tensioactifs du type R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2 dans lesquels x représente des nombres allant de 1 à 30, de préférence de 1 à 20 et en particulier de 6 à 18.
  10. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 9, caractérisées en ce qu'elles contiennent
    a) 1,0 à 4,0 % en poids d'agents tensioactifs non ioniques du groupe des alcools alcoxylés,
    b) 4,0 à 24,0 % en poids d'agents tensioactifs non ioniques du groupe des alcools alcoxylés contenant des groupes hydroxyle (« hydroxy éthers mixtes »),
    toujours par rapport à l'ensemble de la pastille respectivement de la phase qui présente la cavité.
  11. Pastilles de produits de lavage ou de nettoyage selon la revendication 10, contenant
    a) 1,5 à 3,5 % en poids, de préférence 1,75 à 3,0 % en poids et en particulier 2,0 à 2,5 % en poids d'agents tensioactifs non ioniques du groupe des alcools alcoxylés,
    b) 4,5 à 20,0 % en poids, de préférence 5,0 à 15,0 % en poids et en particulier 7,0 à 10,0 % en poids d'agents tensioactifs non ioniques du groupe des alcools alcoxylés contenant des groupes hydroxyle (« hydroxy éthers mixtes »),
    toujours par rapport à l'ensemble de la pastille respectivement de la phase qui présente la cavité.
  12. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 11, caractérisées en ce qu'elles présentent en outre une seconde partie qui possède la forme d'un noyau ou d'un corps collé sur respectivement dans la première partie (« pastille de base ») et contient de préférence un ou plusieurs corps du groupe des produits d'ossature, des agents d'acidification, des formateurs de complexes de chélates ou des polymères inhibant les dépôts.
  13. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 12, caractérisées en ce qu'elles contiennent en outre de 0,1 à 70 % en poids de copolymères
    i) d'acides carboxyliques insaturés
    ii) de monomères contenant des groupes acide sulfonique
    iii) le cas échéant d'autres monomères ioniques ou non ionogènes.
  14. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 13, caractérisées en ce qu'elles contiennent le ou les copolymères sulfonés à des quantités de 0,25 à 50 % en poids, de préférence de 0,5 à 35 % en poids, de façon particulièrement préférée de 0,75 à 20 % en poids et en particulier de 1 à 15 % en poids, toujours par rapport à l'ensemble de la pastille.
  15. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 14, caractérisées en ce qu'elles contiennent un ou plusieurs copolymères qui contiennent les unités structurales de formules VII et/ou VIII et/ou IX et/ou X et/ou XI et/ou XII -[CH2-CHCOOH]m-[CH2-CHC(O)-Y-SO3H]p- -[CH2-C(CH3)COOH]m-[CH2-CHC(O)-Y-SO3H]p- -[CH2-CHCOOH]m-[CH2-C(CH3)C(O)-Y-SO3H]p- -[CH2-C(CH3)COOH]m-[CH2-C(CH3)C(O)-Y-SO3H]p- -[HOOCCH-CHCOOH]m-[CH2-CHC(O)-Y-SO3H]p- -[HOOCCH-CHCOOH]m-[CH2-C(CH3)C(O)O-Y-SO3H]p- dans lesquelles m et p représentent à chaque fois un nombre entier naturel compris entre 1 et 2000 et Y représente un groupe d'espacement qui est choisi parmi des radicaux hydrocarbonés aliphatiques, aromatiques ou araliphatiques substitués ou non substitués avec de 1 à 24 atomes de carbone, où l'on préfère les groupes d'espacement dans lesquels Y représente -O-(CH2)n- avec n = 0 à 4, -O-(C6H4)-, -NH-C(CH3)2- ou -NH-CH(CH2CH3)-.
  16. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 15, caractérisées en ce qu'elles présentent en outre une seconde partie qui a la forme d'un noyau ou d'un corps collé sur respectivement dans la première partie (« pastille de base ») et qui contient - par rapport au poids du noyau - de 1 à 80 % en poids, de préférence de 2,5 à 70 % en poids, de façon particulièrement préférée de 5 à 60 % en poids et en particulier de 10 à 50 % en poids du ou des copolymères sulfonés.
  17. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 16, caractérisées en ce que la pastille comportant une dépression (« pastille de base ») contient, par rapport à son poids, de 0,5 à 30 % en poids, de préférence de 1 à 25 % en poids, de façon particulièrement préférée de 2,5 à 20 % en poids et en particulier de 4 à 15 % en poids du ou des copolymères sulfonés.
  18. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 16 ou 17, caractérisées en ce qu'aussi bien la pastille de base que le noyau contiennent le ou les copolymères sulfonés, où au moins 50 % en poids, de préférence au moins 60 % en poids et en particulier au moins 65 % en poids du ou des copolymères sulfonés contenus au total dans la pastille sont contenus dans la pastille de base.
  19. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 16 à 18, caractérisées en ce que le noyau ne présente pas de revêtement.
  20. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 19, caractérisées en ce qu'elles contiennent en outre de 0,1 à 30 % en poids d'acides polycarboxyliques homo- et/ou copolymères, respectivement de leurs sels et/ou de polymères/copolymères contenant des hétéroatomes, en particulier ceux qui contiennent des groupes amino ou phosphono.
  21. Pastilles de produits de lavage ou de nettoyage selon l'une des revendications 1 à 18, caractérisées en ce qu'elles contiennent en outre de 0,1 à 30 % en poids de polymères/copolymères contenant des groupes amino ou phosphono.
  22. Procédé de fabrication de pastilles de produits de lavage ou de nettoyage avec au moins une cavité, caractérisé en ce qu'on comprime de façon connue un prémélange en forme de particules, dont la teneur en agents tensioactifs non ioniques avec un point de fusion supérieur à 20°C s'élève de 5,5 à 25 % en poids, toujours par rapport au prémélange, pour obtenir des pastilles comportant une dépression.
  23. Procédé de fabrication de pastilles de produits de lavage ou de nettoyage à plusieurs phases avec au moins une cavité, dans lequel on comprime de façon connue plusieurs prémélanges en forme de particules pour donner des pastilles présentant une dépression, caractérisé en ce que la teneur du prémélange que l'on met en contact, lors du pressage final des pastilles, avec le poinçonnement de la cavité, présente une teneur en agents tensioactifs non ioniques avec un point de fusion supérieur à 20°C comprise entre 5,5 et 25 % en poids, toujours par rapport au prémélange.
EP01969736A 2000-09-28 2001-09-19 Pastilles a cavite et procede de fabrication desdites pastilles Expired - Lifetime EP1322743B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE10048058 2000-09-28
DE2000148058 DE10048058A1 (de) 2000-09-28 2000-09-28 Muldentabletten und Verfahren zu ihrer Herstellung
DE10108153A DE10108153A1 (de) 2000-09-28 2001-02-20 Muldentabletten und Verfahren zu ihrer Herstellung
DE10108153 2001-02-20
PCT/EP2001/010807 WO2002026926A1 (fr) 2000-09-28 2001-09-19 Pastilles a cavite et procede de fabrication desdites pastilles

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EP1322743A1 EP1322743A1 (fr) 2003-07-02
EP1322743B1 true EP1322743B1 (fr) 2004-11-17

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US (1) US7205266B2 (fr)
EP (1) EP1322743B1 (fr)
AT (1) ATE282688T1 (fr)
AU (1) AU2001289894A1 (fr)
DE (2) DE10108153A1 (fr)
ES (1) ES2232663T3 (fr)
WO (1) WO2002026926A1 (fr)

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ATE282688T1 (de) 2004-12-15
DE10108153A1 (de) 2002-10-24
EP1322743A1 (fr) 2003-07-02
WO2002026926A1 (fr) 2002-04-04
US7205266B2 (en) 2007-04-17
ES2232663T3 (es) 2005-06-01
US20030186828A1 (en) 2003-10-02
AU2001289894A1 (en) 2002-04-08

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