Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0047—Detergents in the form of bars or tablets
  • C11D17/0065—Solid detergents containing builders
  • C11D17/0073—Tablets
  • 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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
  • C11D3/18—Hydrocarbons

Definitions

• the present invention relates to the field of machine dishwashing detergents for household dishwashers. It relates to detergent components for use in machine dishwashing detergents (MGSM) and to detergent compositions and detergent tablets containing such components
• MGSM machine dishwashing detergents
• the automatic cleaning of dishes in household dishwashing machines usually includes a fast-forward cycle, a main-wash cycle and a rinse-aid cycle, which are interrupted by intermediate rinse cycles. Most machines can switch on the fast-forward cycle for heavily soiled dishes, but are only selected by the consumer in exceptional cases, so that m Most of the machines have a main rinse cycle, an intermediate rinse cycle with pure water and a rinse aid cycle.
• the temperature of the main rinse cycle varies between 40 and 65 ° C depending on the machine type and program level selection.
• rinse aid cycle rinse aid is added from a metering tank in the machine, which is usually the non-ionic main component Containing surfactants
• Such rinse aids are in liquid form and are widely described in the prior art. Their main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and mild showers These rinse aids often also contain nonionic surfactants, hydrotopes, pH-adjusting agents such as citric acid or scale-inhibiting polymers
• the storage tank in the dishwasher must be filled with rinse aid at regular intervals, whereby one fill is sufficient for 10 to 50 rinse cycles, depending on the machine type. If the tank is forgotten, glasses in particular become stained with limescale and Unsightly toppings. In the prior art there are therefore some proposed solutions for integrating a rinse aid into the detergent for machine dishwashing.
• European patent application EP-A-0 851 024 (Unilever) describes two-layer detergent tablets, the first layer of which contains peroxy bleach, builder and enzyme, while the second layer contains acidifying agents and a continuous medium with a melting point between 55 and 70 ° C. and scale inhibitors contains. Due to the high-melting continuous medium, the acid (s) and scale inhibitor (s) should be released with a delay and cause a rinse aid effect. Powdered machine dishwashing detergents or surfactant-containing rinse aid systems are not mentioned in this document.
• German patent application DE 198 51 426.3 (Henkel KGaA) describes a process for the production of multiphase detergent tablets in which a particulate premix is pressed to give moldings which have a trough which is later made from a meltable melt with a separately produced melt Substance and one or more active substance (s) dispersed or suspended in it.
• the teaching of this document is also tied to the "tablet" offer.
• melt suspensions or emulsions disclosed in the last-mentioned document have long-term stability in need of improvement, especially when incorporating surfactants as active substances.
• the meltable substances should enclose the active substance and protect against premature release. If the emulsion is insufficiently stable, it partially separates in the molten state before metering, which leads to metering accuracy. Slightly more stable emulsions can be dosed, but they partially separate before solidification, so that the active substance is released early in the cleaning cycle.
• this document discloses the use of various aids or stabilizers. If solids are mentioned, however, no statements are made about their physical properties.
• the present invention was based on the object of further developing the teaching of the older German patent application DE 198 51 426.3 and of providing long-term stable mixtures which do not tend to separate during metering and cooling and are therefore effective and stable detergent components deliver These long-term stable mixtures and the detergent components made from them should make all known advantages of the controlled release of ingredients, in particular a rinse aid, usable for powder detergents and detergent tablets
• meltable hydrophobic substances with melting points above 30 ° C., tenside (s) and optionally further ingredients such as colorants and fragrances, etc., if these mixtures have at least 0.1% by weight of finely divided solid (e) included
• the melting point of such mixtures can be specifically adjusted to the desired value by the type and amount of the individual ingredients, in particular the melting points and amounts of meltable substance (s) and tenside (s). Above the melting point, mixtures which are stable to separation are present , below the melting point solidified mixtures in any shape, which are referred to in the present application as detergent components
• the present invention relates to a cleaning agent component which contains a) 10 to 89.9% by weight of surfactant (s), b) 10 to 89.9% by weight of fusible substance (s) with a melting point above 30 ° C. and a lack of water of less than 20 g / l at 20 ° C., c) 0.1 to 15% by weight of one or more solids, d) 0 to 15% by weight of further active substances and / or auxiliaries, with the proviso that at least 90 % By weight of the particles c) have particle sizes below 300 ⁇ m
• detergent component in the context of the present application characterizes solidified melts from the ingredients a) to d), regardless of their shape. “Detergent component” in the sense of the present application are therefore, for example, scales, pills, lozenges, shaped body areas, shaped bodies per se etc.
• both ingredients are separated or melted in a mixture with one another, if necessary combined and stirred with the addition of c) and optional addition of d).
• the melt suspension or emulsion produced in this way which is also referred to below for short as “mixture”, can then be converted into the desired shape.
• Preferred detergent components contain 15 to 80, preferably 20 to 70, particularly preferably 25 to 60 and in particular 30 to 50% by weight of surfactant (s) as ingredient a). All surfactants from the groups of anionic, nonionic, cationic or amphoteric surfactants can be used, preferred detergent components being characterized in that they contain, as ingredient a) anionic and / or nonionic surfactant (s), preferably nonionic (s) surfactant (s) included.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are preferably Cg-u-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as those obtained from with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alkanesulfonates obtained from C] 2- i 8 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci2-C] 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl alcohol, , Myristyl, cetyl or stearyl alcohol or the C ⁇ o-C 2 o-oxo alcohols and those half esters of secondary alcohols of these chain lengths are preferred.
• alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which is biodegradable in the same way as the adequate compounds based on oleochemical raw materials.
• Ci 2 -C 6 alkyl sulfates and Ci 2 -C .5 alkyl sulfates and C -C 5 alkyl sulfates are preferred for washing technology reasons.
• 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C 7-2 ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched C 9 n alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2 - . 8 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain Cs-fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut oil, palm kernel oil or tallow fatty acids, are suitable.
• the anionic surfactants, including the soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri-ethanolamine.
• the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts
• the nonionic surfactants used are preferably alkoxy, advantageously ethoxy, in particular polymeric alcohols, preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably 2-methyl branched or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• the preferred ethoxylated alcohols include, for example, C 12 ⁇ 4 alcohols with 3 EO or 4 EO, C 9 n alcohol with 7 EO, C ⁇ 3] 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C, 2 ig alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ⁇ 2 ⁇ 4 alcohol with 3 EO and C ⁇ 2 ig alcohol with 5 EO
• the specified degrees of ethoxylation represent statistical mean values, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxylates, NRE).
• fatty alcohols with more than 12 EO can also be used Examples include taig fat alcohol with 14 EO, 25 EO, 30 EO or 40 EO
• alkyl glycosides of the general formula RO (G) can also be used as further nonionic surfactants, in which R is a p ⁇ maren straight-chain or methyl-branched, in particular in the 2-position methyl-branched ahphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of ohgome ⁇ s ist x which indicates the distribution of monoglycosides and ohgoglycosides, is any number between 1 and 10, preferably x is 1.2 to 1.4
• nonionic surfactants that are used either as the sole nonionic surfactant or in combination with other nonionic surfactants those are alkoxy-hard, preferably ethoxy-hard or ethoxy-hard and propoxy-hardened fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular methyl fatty acid
• Nonionic surfactants of the ammoxides type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide and fatty acid alkanolamide, may also be suitable.
• the amount of these nonionic surfactants is preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
• 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 alkanolamm and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R represents a linear, branched or cychlene alkyl radical or an aryl radical having 2 to 8 Carbon atoms
• R 2 is a linear, branched or cychschen alkyl residue or an aryl residue or an oxy-alkyl residue with 1 to 8 carbon atoms, with C 4 alkyl- or phenyl radicals are preferred and
• [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxy-hard, preferably ethoxy-hard or propoxy-hard derivatives of this radical
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can be reacted with fatty acid methyl esters in the presence of an alkoxide be converted into the desired polyhydroxy fatty acid amides as a catalyst
• the detergent components according to the invention for machine dishwashing particularly preferably contain nonionic surfactants, in particular nonionic surfactants from the group of alkoxy-etherified alcohols 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) are used per mole of alcohol, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is usually the case with m oxo alcohol radicals
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of natural origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred in particular.
• Preferred ethoxyli First alcohols include, for example, C 2] 4 alcohols with 3 EO or 4 EO, C 9 ⁇ alcohol with 7 EO, C 3 i 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C, 2 , 8 -Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C .2 ⁇ 4 -alcohol with 3 EO and -C ⁇ 2 ig-alcohol with 5 EO.
• the degrees of ethoxylation given represent statistical mean values that are necessary for a specific
• the product can 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
• Suitable non-toxic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming non-surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants are used which are highly viscous at room temperature, it is preferred that these have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have a waxy consistency at room temperature are also preferred
• Preferred non-ionic surfactants to be used at room temperature originate from the groups of alkoxy-containing non-ionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) -N ⁇ otens ⁇ de are also characterized by good foam control
• the surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol has resulted
• non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C
• particularly preferred detergent components according to the invention contain, as ingredient a), ethoxylated nonionic surfactant (s) which are composed of C () .
• o-monohydroxy alkanols or C 6 - 2 o alkyl phenols or C ⁇ 6-2 o-fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).
• the nonionic surfactant which is solid at room temperature, preferably additionally has propylene oxide units in the molecule.
• Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
• Particularly preferred nonionic surfactants are ethoxy-hardened monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
• Preferred detergent components are characterized in that, as ingredient a), they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the make up the total molecular weight of the nonionic surfactant.
• nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight.
• Nonionic surfactants which can be used with particular preference, are available, for example, from Olin Chemicals under the name Poly Tergent * SLF-18.
• a further preferred cleaning agent components according to the invention contain non-ionic surfactants of the formula as ingredient a)
• R' [CH 2 CH (CH 3 ) 0] x [CH 2 CH 2 0] y [CH 2 CH (OH) R 2 ], in which R represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R "denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y stands for a value of at least 15.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
• x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x> 2, each R 3 in the above formula can be different.
• R and R are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
• H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R J.
• 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 can be different if x> 2.
• the value 3 for x has been chosen here by way of example and may well be larger, the range of variation 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 ! , R 2 and R 3 as defined above and ⁇ stands for numbers 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 have 9 to 14 carbon atoms have, R 3 is H and x assumes values from 6 to 15
• detergent components according to the invention are preferred, the poly (oxyalkyherten) nonionic surfactants of the formula which are end group-capped
• R 1 and R 2 represent linear or branched, saturated or unsaturated, a phatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
• x stands for values between 1 and 30
• k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
• the detergent components according to the invention contain one or more meltable substances which have a melting point above 30 ° C. and are sparingly or not water-soluble. These substances form the “matrix” in which ingredient a) of the detergent components according to the invention is present in a remote distribution. this distribution being stabilized by the special ingredient c).
• preferred detergent components contain 15 to 85 as ingredient b). preferably 20 to 80, particularly preferably 25 to 75 and in particular 30 to 70% by weight of meltable substance (s)
• the temperature at which the detergent components according to the invention release ingredients a) and optionally d) can be varied within wide limits. Below this temperature, the other ingredients are protected from environmental influences
• the meltable substances used in the detergent components according to the invention which on the one hand have the melting or solidification behavior, but on the other hand also the material properties of the casing in the solidified state, i.e. in the detergent components according to the invention.
• the fusible substance Since the cleaning agent component is to be permanently protected against environmental influences during transport or storage, the fusible substance must have a high stability against, for example, shock loads occurring during packaging or transport.
• the fusible substance should therefore either have at least partially elastic or at least plastic properties in order to react to an impact load caused by elastic or plastic deformation and not to break.
• the fusible substance should have a melting range (solidification range) in such a temperature range with the other ingredients the detergent components according to the invention are not exposed to excessive thermal stress.
• the melting range must be sufficiently high to still provide effective protection for the enclosed active substances at at least a slightly elevated temperature.
• the meltable substances have a melting point above 30 ° C., preference being given to detergent components which only contain meltable substances with melting points Above 40 ° C, preferably above 45 ° C and in particular above 50 ° C.
• Particularly preferred detergent components contain as ingredient b) one or more substances with a melting range between 30 and 100 ° C, preferably between 40 and 80 ° C and especially between 50 and 75 ° C
• the meltable substance does not have a sharply defined melting point, as usually occurs with pure, crystalline substances, but instead has a melting range that may include several degrees Celsius
• the fusible substance preferably has a melting range which is between approximately 52.5 ° C. and approximately 80 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not denote the width of the melting range.
• the width of the melting range is preferred at least 1 ° C, preferably about 2 to about 3 ° C
• waxes are understood to mean a number of natural or artificially obtained substances which usually melt above 50 ° C without decomposition and which are relatively low-viscosity and not stringy just above the melting point have a strongly temperature-dependent consistency and solubility
• the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes
• Natural waxes include, for example, vegetable waxes such as candehllaw wax, carnauba wax, japan wax, esparto grass wax. Cork wax, guaruma wax, rice germ oil, sugar cane wax, Ou ⁇ cury wax, or montan wax, deep waxes such as beeswax, shellac wax, walrus, lanolin (wool wax), or root fat, mineral waxes such as Ceresm or Ozoke ⁇ t (earth wax), or petrochemical waxes such as petrolatum. Paraffin waxes or micro waxes
• the chemically modified waxes include, for example, hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes
• Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of substances which meet the stated requirements with regard to the softening point and the lack of water can also be used as Hull material. Suitable synthetic compounds are, for example, higher esters of phthalic acid, in particular dicyclohexyl phthalate, which are commercially available the name Unimoll 8 66 (Bayer AG) is available, also synthetic are suitable prepared waxes from lower carboxylic acids and fatty alcohols, for example Dimv ⁇ styl Tartrat, which is available under the name Cosmacol "ETLP (Condea)
• the shell substance contained in the detergent components according to the invention preferably contains a proportion of paraffin wax.
• Paraffin wax contents (based on the total amount of meltable substance) of are particularly suitable about 12.5% by weight, about 15% by weight or about 20% by weight, with even higher proportions of, for example, more than 30% by weight being particularly preferred.
• the total amount of the meltable substance used consists exclusively made of paraffin wax
• paraffin waxes have the advantage over the other natural waxes mentioned that there is no hydrolysis of the waxes in an alkaline cleaning agent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups
• Paraffin waxes consist mainly of alkanes, and also mediogenic proportions of iso- and cycloalkanes.
• the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C., to fractions of high-melting alkanes in the paraffin If this melting temperature is not reached in the detergent liquor, wax residues on the surfaces to be cleaned or the goods to be cleaned are not desired. Such wax residues generally lead to an unattractive appearance of the cleaned surface and should therefore be avoided
• Preferred detergent components contain as ingredient b) at least one paraffin wax with a melting range from 30 ° C. to 65 ° C.
• the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature is as high as possible.
• With increasing proportion of solid wax components the resistance of the cleaning agent component to impact or friction on other surfaces increases, which leads to long-lasting protection of the active substances.
• High proportions of oils or liquid wax components can weaken the particles lead, whereby pores are opened and the active substances are exposed to the environmental influences mentioned above
• the meltable substance may also contain one or more of the waxes or wax-like substances mentioned above.
• the mixture forming the meltable substance should preferably be such that the detergent component is at least largely water-insoluble.
• the solubility in water should be at a temperature of about 30 ° C. not exceed about 10 mg / 1 and preferably below 5 mg / 1
• the coating should preferably have as little water solubility as possible, even in water at an elevated temperature, in order to avoid as far as possible a temperature-independent release of the active substances.
• Preferred detergent components are therefore characterized in that the water solubility of the ingredient b) at 20 ° C less than 15 g / 1, preferably less than 10 g / 1. is particularly preferably less than 5 g / 1 and in particular less than 2 g / 1. It is particularly preferred if the waterlessness of the ingredient b) is below the measurement limit at 20 ° C., so substance b) is "water-insoluble" in the usual sense
• the detergent components according to the invention contain 0.1 to 15% by weight of one or more solids, at least 90% by weight of the particles of c) having particle sizes below 300 ⁇ m.
• the amounts of c) are within a narrow range , and also the particle sizes are preferably even finer.
• detergent components which contain the ingredient c) in amounts from 0.15 to 12.5, preferably from 0.2 to 10, particularly preferably from 0.25 to 7.5 and contain in particular from 0.3 to 5% by weight, on the other hand at least 90% by weight of the particles from c) in further preferred detergent components have particle sizes below 200 ⁇ m, preferably below 190 ⁇ m, particularly preferably below 175 ⁇ m, in particular below 150 ⁇ m and entirely particularly preferably less than 100 ⁇ m It is particularly preferred if the ingredient c) has no particles at all that have a size greater than 200 ⁇ m, the particle size limit preferably being even further undershot.
• the ingredient c) consists entirely of particles with particle sizes below 200 ⁇ m, preferably less than 175 ⁇ m, particularly preferably less than 150 ⁇ m and in particular less than 100 ⁇ m
• ingredient c) All substances that are solid and that meet the stated particle size are suitable as ingredient c).
• solid means that ingredient c) remains solid even at the processing temperatures of ingredients a) to d) and not during manufacture Melting or melting in other ingredients is preferably used as ingredient c) substances whose melting point is well above the melting point of the cleaning agent component, for example at least 10 ° C. above, preferably at least 25 ° C. above and in particular at least 50 ° C. above It can also be preferred to use infusible substances as ingredient c) at conventional temperatures
• the alkali metal salts of organic acids have been found to be particularly suitable as ingredient c), the sodium and potassium salts being preferred.
• Organic acids, the salts of which are preferred ingredients c) are suitable formic acid, acetic acid, propionic acid, succinic acid, citric acid, fumaric acid, oxalic acid, malonic acid, tartaric acid, etc.
• Particularly preferred detergent components are characterized in that they contain, as ingredient c), alkali metal salts of organic acids, preferably alkane metal acetates and in particular potassium hydroxide
• Another preferred group of substances that can be used as ingredient c) are clay minerals.
• the natural or chemically modified clay minerals can be used.
• Particularly preferred tomers are the bentonites, which are very suitable ingredient c) in the context of the present invention
• Bentomts are contaminated clays that have arisen from the weathering of volcanic tuffs. It is possible to modify the properties of the bentoms according to their intended use. Bentomts are common as a clay component in tropical soil and are mined as a natural bentomite, for example in Wyoming / USA -Bentomt has the most favorable application properties, so that its use in the context of the present invention is preferred.
• Calcmm bentomts originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D.
• the naturally obtained Ca bentomts become artificially through exchange converted from Ca against Na into the more swellable Na bentoms
• montmoon lumps are to the phyllosihcates and here clay minerals belonging to the dioctahedral smectites, the mono-mono-pseudohexagonal crystallize montmoon lumps predominantly form white, gray-white to yellowish, completely Amorphous appearing, slightly friable, swelling in the water, but not becoming plastic, by the general formulas
• Montmo ⁇ llonite have a three-layer structure, which consists of two tetrahedron layers, which are electrostatically cross-linked via the cations of an intermediate octahedron layer.
• the layers are not rigidly connected, but can be reversible incorporation of water (m 2-7 times the amount) and others Swelling substances such as alcohols, glycols, Py ⁇ dm, ⁇ -Picohn, ammonium compounds, hydroxy-alumosihcat ions etc.
• the formulas given above are only approximate formulas, since Montmo ⁇ llomte have a large ion exchange capacity "Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions are exchanged.
• the octahedron layer can also contain Mg 2+ (saponite - trioctahedral sheet silicate) or Fe 3+ (nontronite - dioctahedral sheet silicate). It also contains cations such as Zn 2+ (for Sauconite - trioctahedral sheet silicate), Ni 2 ⁇ (Nickel Sauconite - trioctahedral sheet silicate) and Li + (hectorite - trioctahedral sheet silicate).
• bentonites in the classic sense, that is to say clays with a high montmorillonite content.
• Preferred ingredient c) are phyllosilicates with a montmorillonite content of more than 60% by weight, preferably of more than 75% by weight and in particular of more than 90% by weight, in each case based on the weight of the phyllosilicate. Unless this is undesirable for reasons of cost, pure montmonthonites can also be used with preference. Detergent components which contain pure montmonthonites as bentonite are likewise preferred according to the invention
• the layer spacing of phyllosihcates can be modified by the incorporation of certain compounds, since these - depending on the charge of the elementary layers and on the interlayer cations - can swell, i.e. the base spacing of their three-layer packets through the incorporation of water molecules or long-chain organic molecules on over 15 ⁇ can be enlarged.
• chemically modified bentomites can also be used as ingredient c), preference being given to detergent components which contain bentoms modified by quaternary ammonium compounds
• preferred detergent components contain, as ingredient c), substances from the group of clay marbles, preferably the chemically modified clay marbles and in particular the hydrophobicized bentome
• ionic surfactants Other solids to be used as ingredient c) in the context of the present invention are ionic surfactants, provided they have a sufficiently high melting point and can be brought to the particle size range mentioned. These surfactants have been described in detail above.
• fatty alcohol sulfates are preferred as ingredient c), so that detergent components are preferred which contain, as ingredient c), anionic surfactant (s), preferably fatty alcohol sulfates and in particular 2 g fatty alcohol sulfates
• the detergent components according to the invention can preferably contain, as ingredient d), further active substances and / or auxiliaries from the groups of dyes, fragrances, soil-release polymers, corrosion inhibitors, enzymes, bleaches, bleach activators and complexing agents in amounts of 0 to 10% by weight, preferably from 0.25 to 7.5% by weight, particularly preferably from 0.5 to 5% by weight and in particular from 0.75 to 2.5% by weight, contain colorants and fragrances and the other substances mentioned are customary Ingredients of washing or cleaning agents and are described in detail below As already mentioned above, the physical and chemical properties of the detergent components according to the invention can be varied in a targeted manner by suitable choice of ingredients a) to d).
• those detergent components are preferred which are characterized by a melting point between 50 and 80 ° C, preferably between 52.5 and 75 ° C and in particular between 55 and 65 ° C
• the detergent components according to the invention are solidified mixtures of the ingredients mentioned, which can take on any external shape. It is also possible to absorb the mixtures as a melt onto carrier substances and thus to provide carrier material-based detergent components which, at room temperature, consist of carrier material (s). and a melt solidified on this support material are all solid materials which do not soften at the melt temperature and which also have a sufficiently large absorption capacity for the melt.
• carrier material s
• a melt solidified on this support material are all solid materials which do not soften at the melt temperature and which also have a sufficiently large absorption capacity for the melt.
• Particularly preferred support materials are builders, which are described in detail below
• Another object of the present invention is a process for the production of particulate detergent components, in which a melt of a) 10 to 89.9% by weight of surfactant (s), b) 10 to 89.9% by weight of meltable (n ) Substance (s) with a melting point above 30 ° C and a water solubility of less than 20g / l at 20 ° C, c) 0.1 to 15% by weight of one or more solids, d) 0 to 15% by weight applying further active substances and / or auxiliary substances to one or more carrier materials and processing the mixture in a shaping manner
• a melt suspension or emulsion is first prepared, which may contain further active ingredients and auxiliaries. This is added to a material and processed to give a shape in a mixture with this carrier material
• meltable substance makes up 25 to 85% by weight, preferably 30 to 70% by weight and in particular 40 to 50% by weight of the melt
• the melt can be applied to the carrier material in all conventional mixing devices.
• the shaping processing step for the mixture of melt and carrier material is likewise not subject to any procedural restrictions, so that the person skilled in the art can also choose from the methods familiar to him. In attempts by the applicants, methods have been found turned out to be preferred in which the shaping processing takes place by granulating, compacting, pelleting, extruding or tableting
• the process according to the invention comprises the application of melts from the ingredients a) to d) to carrier material.
• the melt and carrier material (s) may contain varying amounts in the resulting rinse aid particles.
• Preferred processes are characterized in that a mixture of 5 to 50% by weight %, preferably 10 to 45% by weight, particularly preferably 15 to 40% by weight and in particular 20 to 35% by weight of a melt of the ingredients a) to d) and 50 to 95% by weight, preferably 55 to 90% by weight %, particularly preferably 60 to 85% by weight and in particular 65 to 80% by weight of carrier material (s) is processed to give shape
• the detergent components according to the invention can also be formulated without carrier material, so that they consist only of the ingredients a) to d). Chen-shaped detergent components according to the invention have in particular preserved the pilling, pastilizing and scaling by means of cooling rolls
• Another object of the present invention is therefore, in a first embodiment, a process for the production of spilled detergent components, in which a melt of a) 10 to 89.9% by weight of surfactant (s), b) 10 to 89.9% by weight meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20g / l at 20 ° C, c) 0.1 to 15% by weight of one or more solids, d) 0 to 15 % By weight of further active ingredients and / or auxiliaries in a cold gas stream
• the method according to the invention comprises the production of granular bodies from fusible substances, the melt being sprayed from the ingredients a) to d) at the top of a tower in a defined droplet size, solidifying in free fall and the particles being on Bottom of the tower accumulate as granules
• all gases can be used as the cold gas flow, the temperature of the gas being below the melting temperature of the melt.
• cooled gases are often used, for example with frozen air or even liquid nitrogen, which is sprayed into the spray tower
• the grain size of the resulting particles can be varied by the choice of the droplet size, particle sizes which are technically simple to implement being in the range from 0.5 to 2 mm, preferably around 1 mm
• a further embodiment of the present invention therefore provides a process for the production of pastilhered detergent components, in which a melt of a) 10 to 89.9% by weight surfactant (s), b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20g / l at 20 ° C, c) 0.1 to 15% by weight one or more solids, d) 0 to 15% by weight of further active ingredients and / or auxiliaries metered onto chilled pastil plates
• the pastilheren which is sometimes also referred to as pelleting, comprises the metering of the melt from the ingredients a) to d) onto rotating, inclined plates which have a temperature below the melting temperature of the melt and are preferably cooled below room temperature. Process variants can also be carried out here where the pastil plate is frozen. However, measures must be taken to prevent the moisture from condensing
• Pastil production produces larger particles which have sizes between 2 and 10 mm, preferably between 3 and 6 mm, in the technically customary processes
• Another object of the present invention is therefore a process for producing particulate detergent components, in which a melt is made from a) 10 to 89.9% by weight.
• cooling rollers enables the desired particle size range to be set without problems, which can also be less than 1 mm, for example 200 to 700 ⁇ m, in the method according to the invention
• Multi-phase shaped bodies can also be produced by producing shaped bodies with cavities, for example troughs or through holes, and subsequently filling these cavities with other shaped bodies.
• the “basic shaped body”, ie the tablet, which has a cavity has the composition of a detergent tablet, while the molded part contained in the cavity is a molded part that has been pressed from prills, pastilles or scales.
• the two molded parts can adhere to one another by gluing the two molded parts together, but it is also possible pressing the molded bodies into or into one another. It is also possible to insert one into the other, in which the adhesion is achieved by the geometric configuration of the cavity and the filling
• the production of the shaped bodies by separate production (pressing) of a basic shaped body a) and a core shaped body b), which is preferably pressed from prills of the detergent components according to the invention, the joining and the final compression of both parts is preferred
• molded bodies from particulate detergent components according to the invention can be carried out by conventional tableting processes. These are described in detail below
• the shaped bodies can be produced in a predetermined spatial shape and a predetermined size. Practically all practical configurations can be considered as the spatial shape, for example the design as a board, the rod or bar shape, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical shapes circular or oval cross-section
• This last embodiment covers the presentation form from the tablet to compact cylindrical pieces with a ratio of height to diameter above 1
• the shaped body produced can take on any geometric shape, in particular concave, convex, biconcave, biconvex, cubic tetragonal, orthorhombic, cylindrical, spherical, cylindrical segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, five-elhpsoid, five octagonal-prismatic and rhombohedral shapes are preferred.
• Completely irregular basic surfaces such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the molded body has corners and edges, these are preferably rounded.
• An additional optical differentiation is an embodiment with rounded corners Corners and chamfered ("chamfered”) edges preferred
• the detergent components according to the invention can be given directly to the hand of the consumer, so that they can also be added to the detergent as required. However, in addition to the fixed dosage form and the addition to the same dosage compartment, this additional dosing step has minimized the advantages over liquid rinse aid. to mix the detergent components according to the invention with particulate machine-made dishwashing agents or to incorporate them into moldings
• Another object of the present invention is therefore the use of particulate detergent components composed of a) 10 to 89.9% by weight of surfactant (s), b) 10 to 89.9% by weight of meltable substance (s) a melting point above 30 ° C and a water solubility of less than 20g / l at 20 ° C, c) 0.1 to 15% by weight of one or more solids, d) 0 to 15% by weight of further active substances and / or auxiliaries in cleaning agents for machine dishwashing
• Another object of the present invention is also a particulate machine dishwashing agent containing builders and optionally further detergent ingredients which contain particulate detergent components which, based on their weight, a) 10 to 89.9% by weight surfactant (s), b) 10 to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C and a water solubility of less than 20g / l at 20 ° C, c) 0.1 to 15% by weight of one or several solids, d) contain 0 to 15% by weight of further active substances and / or auxiliaries
• ingredients of the machine dishwashing detergents are described below. In part, these can also be contained as ingredient d) or carrier material in the detergent components according to the invention
• the most important ingredients of machine dishwashing agents are builders.
• all builders usually used in detergents and cleaning agents can be present, in particular zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological concerns about their use - Also the phosphates.
• the builders mentioned below are all suitable as support materials for the detergent components according to the invention, as has already been explained above
• Suitable small, layered sodium silicates have the general formula NaMS ⁇ O 2 +] H 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values for x 2, 3 or 4 are such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3 ⁇ -Nat ⁇ umdisihkate Na 2 S ⁇ 2 0-, yH 2 0 is preferred, wherein ß-Nat ⁇ umdisihkat can be obtained for example by the method described in international patent application WO-A-91/08171
• Amorphous sodium silicates with a module Na 2 0 S ⁇ 0 of 1 2 to 1 3.3, preferably of 1 2 to 1 2.8 and in particular of 1 2 to 1 2.6, which are loosely delayed and have secondary washing properties, can also be used
• Conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compaction or by overdrying.
• the term “amorphous” also means "X-ray amorphous”.
• the femk ⁇ stalline, synthetic and bound water-containing Zeohth is preferably Zeohth A and / or P.
• Zeohth MAP R (commercial product from Crosfield) is particularly preferred as Zeohth P.
• Zeohth X and mixtures of A, X and / or P are also commercially suitable is available and can preferably be used in the context of the present invention, for example also co-aluminum from Zeohth X and Zeohth A (about 80% by weight Zeohth X), which is sold by CONDEA Augusta S p A under the brand name VEGOBOND AX R and through the formula
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; Coulter Counter measurement method) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water
• the alkali metal phosphates are of the greatest importance in the detergent and cleaning agent industry, with particular preference for pentanate or pentakahium phosphate (sodium or potassium polyphosphate).
• Alkahmetallphosphate is the general term for the alkahmetal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO) n and orthophosphoric acid H 1 P0 in addition to high molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent lime deposits on machine parts or lime encrustations in tissues and also contribute to the cleaning performance
• Sodium dihydrogen phosphate, NaH 2 P0 exists as a dihydrate (density 1.91, preferably 3 , melting point 60 °) and as a monohydrate (density 2.04 gcm 3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (Dmat ⁇ umhydrogendiphosphat, Na 2 H 2 P 2 0 7 ), at higher temperature in sodium metaphorate (Na 3 P 3 0 9 ) and Maddrell's salt (see below), NaH 2 P0 4 reacts with acid; it occurs when phosphoric acid is adjusted to pH 4.5 with sodium hydroxide solution and the mash is sprayed.
• Dmat ⁇ umhydrogendiphosphat, Na 2 H 2 P 2 0 7 weakly acidic diphosphate
• Na 3 P 3 0 9 sodium metaphorate
• Maddrell's salt see below
• Kahum dihydrogen phosphate (primary or monobasic potassium phosphate, Kahumbiphosphat, KDP), KH P0, is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) x ] and is light soluble in water
• Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.
• Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K HPO 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals that like a dodecahydrate a density of 1.62 "3 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 39-0% P 2 0 5 ), a density of 2.536 gcm " .
• Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or three-base potassium phosphate), K P0, is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It occurs, for example, when heating Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 0 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815- 1.836 like " 3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 0 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• Potassium diphosphate (potassium pyrophosphate), IC 1 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 "3 , which is soluble in water, the pH of which is 1% Solution at 25 ° is 10.4.
• Sodium and potassium phosphates in which one cyclic representatives, the sodium and potassium metaphosphates and chain-like types that can differentiate between sodium and potassium polyphosphates. Especially for the latter, a large number of terms are used. Melt or glow phosphates, Graham's salt, Ku ⁇ ol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates
• 100 g of water about 17 g of the salt free from salt water are dissolved at room temperature, about 20 g at 60 °, about 32 g at 100 °, and after heating the solution to 100 ° for two hours, about 8% is formed by hydrolysis.
• sodium polyphosphate potassium polyphosphate or mixtures of these two, and mixtures of sodium polyphosphate and sodium polyphosphate or mixtures of sodium polyphosphate and sodium phosphate and sodium polyphosphate and mixtures of sodium polyphosphate and mixtures of sodium polyphosphate and mixtures of sodium polyphosphate
• Organic cobuilders which can be used in the machine dishwashing agents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below
• Usable organic scent substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood as meaning those carboxylic acids which carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acid and mixtures thereof
• the acids themselves can also be used.
• the acids typically also have the property of an acid component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
• citric acid, amber acid, glutaric acid, adipic acid are used here to call gluconic acid and any mixtures of these
• Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid. for example those with a molecular weight of 500 to 70,000 g / mol
• the molar masses given for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were basically determined by means of gel permeation chromatography (GPC), using an UV detector. The measurement was carried out against an external polyacrylic acid standard , which provides realistic molecular weight values due to its structural relationship with the investigated polymers. These figures deviate significantly from the molecular weight figures for which polystyrene sulfonic acids are used as standard.
• Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight> acrylic acid and 50 to 10% by weight maleic acid have proven to be particularly suitable.
• Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 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.
• the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers ,
• copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• polymeric aminodicarboxylic acids their salts or their precursor substances.
• Polyaspartic acids or their salts and derivatives are particularly preferred which, in addition to cobuilder properties, also have a bleach-stabilizing effect.
• Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
• DE dextrose equivalent
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• Such oxidized dextrins and processes for their preparation are described in detail in the prior art.
• a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
• Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
• Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in the form of lactones and which contain min. contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups
• phosphonates are, in particular, hydroxyalkane or ammoalkane phosphonates.
• hydroxyalkane phosphonates l-hydroxyethane-l, l-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as a sodium salt, the dinate salt being neutral and the tetrasodium salt being alkaline (pH 9).
• the preferred ammoalkane phosphonates are ethylenediammetetramethylenephosphonate (EDTMP), diethylenetammammententamethylenephosphonate (DTPMP) and their higher homologs.
• HEDP is preferably used as a builder from the phosphonate class.
• the ammoalkane phosphonates also have a pronounced heavy metal content. Accordingly, especially if the agents also contain bleach, bev be preferred to use ammoalkane phosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned
• Preferred particulate machine dishwashing detergents according to the invention contain builders in amounts of from 20 to 80% by weight, preferably from 25 to 75% by weight and in particular from 30 to 70% by weight, in each case based on the weight of the agent
• Preferred particulate machine dishwashing agents furthermore contain one or more substances from the groups of bleaching agents, bleach activators, bleach catalysts, surfactants, Ko ⁇ osionsinhibitoren, polymers, dyes and fragrances, pH adjusting agents, complexing agents and the enzymes
• bleaching agents which can be used are, for example, sodium pumperborate tetrahydrate and sodium piperborate monohydrate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates , Peroxophthalate, Diperazelamsaure, Phthaloimmopersaure or Diperdodecandisaure
• “Nat ⁇ umper carbonate” is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but are hydrogen peroxide adducts with sodium carbonate.
• the merchandise has the average composition 2 Na 2 CO; 3 H 2 0 2 and is not a peroxycarbonate Nat ⁇ umpercarbonat like forming a white water-soluble powder of density 2.14 3 that easily m Nat ⁇ umcarbonat and bleaching or oxidizing oxygen decays
• the industrial production of sodium pumper carbonate is predominantly produced by precipitation from an aqueous solution (so-called wet process).
• aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium pumper carbonate by means of salting-out agents (mainly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ Ions) precipitated
• salting-out agents mainly sodium chloride
• crystallization aids for example polyphosphates, polyacrylates
• stabilizers for example Mg 2+ Ions
• the precipitated salt which still contains 5 to 12% by weight of mother liquor, is then decentred and dried in fluidized bed dryers at 90 ° C.
• the bulk weight of the finished product can vary between 800 and 1200 g / 1 depending on the manufacturing process
• Detergents according to the invention can also contain bleaching agents from the group of organic bleaching agents.
• Typical organic bleaching agents are the diacyl peroxides, for example dibenzoyl peroxide.
• Other typical organic bleaching agents are the peroxy acids, examples of which include the alkyl peroxy acids and the aryl peroxy acids.
• Preferred representatives are ( a) the peroxybenzoic acid and its ⁇ ngsubstituted derivatives, such as alkyl-peroxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the ahphatic or substituted ahphatic peroxyacids, such as peroxylauric acid, peroxysteane-phoxythanoic acid, ⁇ -phyphthanoic acid [ ⁇ -phthalamine], (PAP)], o-carboxybenzamido-peroxycaproic acid, N-nonenylamidoperadipmsaure and N-nonenylamidopersuccmate, and (c) aliphatic and arahphatic peroxydicarboxylic acids, such as 1,12-di-peroxycarboxylic acid, 1, 9-di-peroxy-aceyl-diperoxyacrylic acid, oxy-diperoxy-azo-diperoxyacrylic acid, PHth
• Chlorine or bromine-releasing substances can also be used as bleaching agents in the inventive detergents for machine dishwashing.
• Suitable chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo- and N-chloramides, for example trichlorosocyanuric acid, trichloroisocyanuric acid,
• Dibromoisocyanuric acid and / or dichlorosocyanuric acid (DICA) and or their salts with cations such as potassium and sodium are also suitable.
• Hydantom compounds, such as 1,3-dichloro-5,5-dimethylhydantanthoin, are also suitable.
• the bleaching agents mentioned can also be introduced into the automatic machine dishwashing agents according to the invention, partially to achieve “post-bleaching", using the detergent components according to the invention, where they constitute ingredient d)
• Bleach activators which support the action of the bleaching agents are, for example, compounds which contain one or more N or O-Acvl groups, such as substances from the class of anhydrides, the esters, the imides and the acyherten imidazoles or oximes Tetraacetylethylene diamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhexylene diamine TAHD, but also pentaacetyl glucose PAG, l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine DADHT and isatoic anhydride ISA.
• N or O-Acvl groups such as substances from the class of anhydrides, the esters, the imides and the acyherten imidazoles or oximes Tetraacetylethylene diamine TAED, tetraacetylmethylene diamine TAMD and tetraacetylhe
• Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• bleach catalysts can also be incorporated into the detergents for automatic dishwashing.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
• Bleach activators from the group of multi-acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N- Nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts up to 10% by weight o , in particular 0.1% by weight to 8% by weight, particularly 2 to 8% by weight and particularly preferably 2 to 6% by weight, based on the total composition.
• TAED tetraacetylethylenediamine
• N-acylimides in particular N- Nonanoylsuccinimide (NOSI)
• NOSI N- Nonanoylsuccinimide
• 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 consisting of manganese and / or cobalt salts and / or complexes, particularly preferably cobalt (amrnine ) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, of manganese sulfate are used in customary amounts, preferably in an amount of up to 5% by weight, in particular 0.0025 % By weight to 1% by weight and particularly preferably from 0.01% by weight to 0.25% by weight, in each case based on the total composition. But in special cases, more bleach activator can be used.
• Suitable enzymes in the cleaning agents according to the invention are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch. Oxidoreductases can also be used for bleaching. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as stains containing protein, fat or starch
• protease and amylase or protease and lipase or lipolytically active enzymes for example of protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest.
• Known cutinases are examples of such lipolytically active enzymes.
• Peroxidases or oxidases have also proven to be suitable in some cases.
• Suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and pectinases.
• the enzymes can be absorbed on dyestuffs or embedded in meltable substances in order to protect them against premature decomposition.
• the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight -%
• Dyes and fragrances can be added to the machine dishwashing agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with visually and sensory "typical and unmistakable" product as well as performance.
• perfume moles or fragrances individual fragrance compounds, e.g. B the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
• Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethylsobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbynyl acetate, phenylethylbenzate acetate, benzyl formate acetate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl sahylate.
• Ethyl for example, benzyl ethyl ether, aldehydes, for example, linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, cyclamenaldehyde, cyclamenaldehyde itronellal, lilial and bourgeonal, to the ketones eg the ionone, ⁇ -isomethyhonone and methylcedryl ketone, to the alcohols anethole, citronellol, eugenol, geramol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and Pmen However, preference is given to using mixtures of different odoriferous substances which together produce an appealing fragrance.
• Such perfume moles can also contain natural odoriferous substance mixtures as are obtainable from plant sources, for example Pme, citrus, jasmine, patchouly, rose or ylang-ylang-oil Also suitable are muscatel, sageiol, chamomile oil, clove oil, mehssenol, mint, cinnamon leaf oil, lmdenblutenol, juniper beerol, vetiverol, ohbanumol, galbanumol and labdanumol as well as orange blutenol, nerohol, orange peel oil and sand
• the fragrances can be incorporated directly into the cleaning agents according to the invention, but it can also be advantageous to apply the fragrances to carriers.
• Cyclodextins for example, have been found to be such carrier materials, and the cyclodextine-perfume complexes can additionally be coated with further auxiliaries Also an in- Corporation of the fragrances as ingredient d) into the detergent components according to the invention is possible and leads to a fragrance impression when the machine is opened.
• the agents according to the invention can be dyed with suitable dyes.
• Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and are insensitive to the other ingredients of the agents and to light as well as no pronounced substantivity towards the substrates to be treated with the agents, such as glass, ceramic or plastic, so as not to stain them.
• the cleaning agents according to the invention can contain anti-corrosion agents to protect the items to be washed or the machine, silver protection agents in particular being of particular importance in the field of automatic dishwashing.
• anti-corrosion agents to protect the items to be washed or the machine
• silver protection agents in particular being of particular importance in the field of automatic dishwashing.
• the known substances of the prior art can be used.
• silver protection agents selected from the group of the t ⁇ azoles, the benzot ⁇ azoles, the bisbenzot ⁇ azoles, the aminot ⁇ azoles, the alkylaminot ⁇ azoles and the transition metal salts or complexes can be used.
• Benzot ⁇ azol and / or alkylaminot ⁇ azole are particularly preferably to be used.
• detergent formulations frequently contain agents containing active chlorine which can significantly reduce the corroding of the silver surface.
• oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these compound classes.
• Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
• transition metal salts which are selected from the group consisting of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammm) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
• Zmkverbmdonne can also be used to prevent corrosion on the wash ware
• the particulate machine dishwashing agents according to the invention can contain the detergent components according to the invention in varying amounts, the content depending on the composition of the detergent components and depending on what is desired High or low application success.
• Preferred particulate machine dishwashing detergents contain the particulate detergent component in amounts of 0.5 to 30% by weight, preferably 1 to 25% by weight and in particular 3 to 15% by weight, in each case based on the total agent
• composition of the detergent components according to the invention can be designed in such a way that they do not dissolve in the main wash cycle (and also in optional pre-wash cycles) or only dissolve to a minor extent.
• Household items Dishwashing machines contain the water or cleaning solution before the detergent solution after the individual cleaning cycles pumps out of the machine, a sieve insert which is intended to prevent the pump from becoming blocked by dirt residues.
• the size and shape of the detergent components according to the invention are now preferably designed such that they do not pass through the sieve insert of the dishwasher even after the cleaning cycle, ie after exposure to movement in the machine and the cleaning solution This ensures that there are detergent components in the dishwasher in the rinse aid cycle, which release the active substance (s) under the action of the warmer water and bang the desired rinse aid effect.
• Particulate machine dishwashing agents preferred in the context of the present invention are characterized in that the particulate detergent component has particle sizes between 1 and 40 mm, preferably between 1.5 and 30 mm and in particular between 2 and 20 mm.
• the detergent components with the above-mentioned sizes can protrude from the matrix of the other particulate ingredients, but the other particles can also have sizes that lie in the range mentioned, so that overall a cleaning agent is formulated that consists of large detergents.
• Detergent and detergent component particles exist, in particular, if the detergent components according to the invention are colored, for example have a red, blue, yellow or yellow color, it is advantageous for the appearance of the product, that is to say the entire detergent, if the detergent components are visibly larger than that Matrix of the particles of the other ingredients of the cleaning agent.
• particle-shaped machine dishwashing agents are preferred which (without considering the particle-shaped cleaning agent component) have particle sizes between 100 and 6000 ⁇ m, preferably up to 4500 ⁇ m and in particular between 100 and 3000 ⁇ m, with particle sizes between in particular 300 and 2500 ⁇ m and in particular between 400 and 2000 ⁇ m are particularly preferred
• the cleaning agents according to the invention are formulated as a powder mixture, partial segregation can occur on the one hand when the package is shaken, especially when the sizes of the cleaning agent component and cleaning agent mat are very different, on the other hand the dosage can be different in two successive cleaning cycles because the consumer does not Always the same amount of detergent and detergent component should be metered in. If it is desired to use the same amount per cleaning cycle, this can be achieved by packaging the agents according to the invention in sachets made of water-soluble film, which is also familiar to the person skilled in the art characterized in that a dosing unit is welded into a bag made of water-soluble film and is a subject of the present invention
• the melt can be made from the ingredients a) to d) Formulate as a phase of a shaped body that has, for example, the FO ⁇ of a layer, a core-shaped insert, etc.
• Another object of the present invention is thus a multi-phase detergent tablet for machine dishwashing, containing builders and optionally further detergent ingredients, in which at least one phase consists of a) 10 to 89.9% by weight of surfactant (s), b) 10 up to 89.9% by weight of meltable substance (s) with a melting point above 30 ° C. and a water solubility of less than 20 g / l at 20 ° C., c) 0.1 to 15% by weight of a or several solids, d) 0 to 15% by weight of further active substances and / or auxiliary substances.
• the individual phases of the shaped body can have different spatial shapes.
• the simplest way of reacting here is in two- or multi-layer tablets, each layer of the shaped body representing a phase.
• ring-core tablets coated tablets or combinations of the above-mentioned embodiments are possible, for example.
• Examples of multi-phase moldings can be found in the illustrations of EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks.
• the currently most widespread spatial form of multi-phase tablets is the two- or multi-layer tablet.
• it is therefore preferred that the phases of the shaped body have the shape of layers and the shaped body is 2-, 3- or 4-phase.
• the shaped bodies according to the invention can assume any geometric shape, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoidal, five-, seven- and octagonal-prismatic and rhombohedral shapes are preferred. Completely irregular surfaces such as arrow or animal shapes, trees, clouds, etc. can also be realized. If the shaped bodies according to the invention have corners and edges, these are preferably emptied. As an additional opti- see Differentiation, an embodiment with chamfered corners and chamfered (“chamfered”) edges is preferred.
• moldings which contain the cleaning agent component according to the invention in the form of other phases. It has proven useful here to produce base moldings which have one or more cavities and to fill the melt from the constituents a) to d) of the cleaning agent component according to the invention into the cavity and allow it to be stoked there.
• This manufacturing process results in preferred multi-phase detergent molded articles, which consist of a basic article having a cavity and an at least partially contained part of the cavity.
• the cavity in the molded part of such molded bodies according to the invention can have any shape. It can cut through the shaped body, i.e. have an opening on different sides, for example on the top and bottom of the molded body, but it can also be a cavity that does not extend through the entire molded body, the opening of which is only visible on one side of the molded body.
• the shape of the cavity can also be freely selected within wide limits. For reasons of process economy, through holes, the openings of which lie on opposite surfaces of the molded body, and troughs with an opening on one side of the molded body have proven successful.
• the cavity has the shape of a through hole, the openings of which are located on two opposing molded surfaces.
• the shape of such a through hole can be chosen freely, whereby molded bodies are preferred in which the through hole has circular, elliptical, triangular, rectangular, square, pentagonal, hexagonal, seven-sided or octagonal horizontal sections. Completely irregular hole shapes such as arrow or animal shapes, trees, clouds etc. can also be realized. As with the molded bodies, in the case of angular holes, those with chamfered corners and edges or with chamfered corners and chamfered edges are preferred.
• Molded bodies with a rectangular or square base and circular holes can be produced, as can molded bodies with octagonal holes, whereby there are no limits to the variety of possible combinations. Because of Process economy and aesthetic consumer perception are particularly preferred molded bodies with a hole, in which the molded body surface and the hole cross section have the same geometric shape, for example molded bodies with a square base area and a centrally incorporated square hole. Ring-shaped bodies, ie circular shaped bodies with a circular hole, are particularly preferred.
• the shaped bodies according to the invention can also assume any geometrical shape in this embodiment, in particular concave, convex, biconcave, biconvex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral , pyramidal, ellipsoidal, pentagonal, octagonal and octagonal-prismatic as well as rhombohedral shapes are preferred.
• Completely irregular base surfaces such as arrow or animal shapes, trees, clouds etc. can also be realized they are preferably capped.
• the shape of the trough can also be chosen freely, preference being given to shaped bodies in which at least one trough is a concave, convex, cubic, tetragonal, orthorhombic, cylindrical, spherical, segment-like, disk-shaped, tetrahedral, dodecahedral, octahedral, conical, pyramidal, ellipsoid , five-, seven- and octagonal-prismatic and rhombohedral shape can take.
• Completely irregular trough shapes such as arrow or animal shapes, trees, clouds etc. can also be realized.
• troughs with chamfered corners and edges or with chamfered corners and chamfered edges are preferred.
• the part at least partially contained in the cavity consists solely of the ingredients a) to d) of the detergent components.
• detergent components based on carrier material are preferred, in which the part from a) 10 to 89.9% by weight of surfactant (s) contained in the cavity, b) 10 to 89.9% by weight of meltable substance (s) ( en) with a melting point above 30 ° C and a water solubility of less than 20g / l at 20 ° C, c) 0.1 to 15% by weight of one or more solids, d) 0 to 15% by weight of other active ingredients and / or auxiliary substances
• the size of the trough or the through hole compared to the entire molded body depends on the intended use of the molded body. Depending on how much more active substance the remaining hollow volume is to be filled with and whether a smaller or larger amount of detergent component should be contained, the large size can the cavity vary Irrespective of the intended use, detergent tablets are preferred in which the volume ratio of the pressed part (“basic tablet”) to the cleaning agent component 2 1 to 100 1, preferably 3 1 to 80 1, particularly preferably 4 1 to 50 1 and in particular 5 1 to 30 1
• the mass ratio of the two parts can also be specified, the two values correcting each other via the densities of the base molding or the cleaning agent component.
• detergent molding bodies according to the invention are preferred, in which the weight ratio from Basisformko ⁇ er to cleaning agent component 1 1 to 100 1, preferably 2 1 to 80 1, particularly preferably 3 1 to 50 1 and in particular 4 1 to 30 1
• Analogous statements can also be made for the surfaces which are respectively visible from the base molding or from the detergent component.
• detergent tablets are preferred, in which the externally visible surface of the cleaning agent component is 1 to 25%, preferably 2 to 20 %, particularly preferably 3 to 15% and in particular 4 to 10% of the total surface of the molded body
• the cleaning agent component and the basic molded body are preferably optically distinguishable. In addition to the optical differentiation, application-technical advantages can be achieved by different solubilities of the different molded body regions.
• Detergent and cleaning agent molded bodies in which the cleaning agent component dissolves faster than the basic molded body are preferred according to the invention on the one hand, the solubility of the cleaning agent component can be accelerated in a targeted manner, on the other hand, the release of certain ingredients from the cleaning agent component can lead to advantages in the washing or cleaning process
• detergent tablets according to the invention are also preferred, in which the detergent component dissolves later than the basic tablet, and performance advantages from this delayed release can be achieved, for example, by using a slower-soluble detergent component to release active substance (s) only in later rinse cycles
• slow-release detergent components can make it easier for further active substance (s) to be available in the final rinse cycle.
• Additional substances such as michiometric surfactants, acidifying agents, soil-release polymers, etc. can also be used to improve the final rinse results an incooration of perfume is possible without any problems, because of its delayed release, the "lye smell" that often occurs when opening the machine can be eliminated in dishwasher machines.
• the ingredients acidification Detergents, soil-release polymers, etc. are then based on the detergent components according to the invention, ingredients d)
• the basic shaped body has a high specific weight of detergent and cleaning agent shaped bodies, which are characterized in that the basic shaped body has a density above 1000 gdm 3 . preferably above 1025 gdm 3 , particularly preferably above 1050 gdm 3 and in particular above 1100 gdm 3 , are preferred according to the invention
• disintegration aids so-called tablet disintegrants
• auxiliary substances which are necessary for the rapid disintegration of tablets in water or gastric juice and for the Ensure release of the pharmaceuticals in an absorbable form.
• Preferred makesmittelformkö ⁇ er contain from 0.5 to 10 wt .-%, preferably 3 to 7 wt .-% and in particular 4 to 6 wt .-% 0 of one or more disintegration aids, based on the Formgro ⁇ erori. If only the basic molded article contains disintegration aids, the information given relates only to the weight of the basic molded article. When disintegration aids are inco ⁇ orated in the detergent components according to the invention, those count as ingredients d).
• Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain.
• Pure cellulose has the formal gross composition (C 6 H ⁇ o0 5 ) n and is formally considered a ß-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose.
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. But also celluloses. in which the hydroxy groups Functional groups that are not bound via an oxygen atom can be used as cellulose derivatives.
• the category of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• the cellulose derivatives mentioned are preferably not used alone as cellulose-based disintegration agents, but are used in a mixture with cellulose.
• the cellulose derivative content of these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free from cellulose derivatives is particularly preferably used as the disintegrant based on cellulose.
• the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be treated.
• Detergent tablets containing disintegrants in granular or optionally cogranuherter form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogran-disintegrated cellulose disintegrants.
• the particle sizes of such disintegration agents are mostly above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
• the above-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel "TF-30-HG from the Rettenmaier company.
• Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component.
• This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged.
• a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline Celluloses which have primary particle sizes of approx. 5 ⁇ m and can be compacted, for example, into granules with an average particle size of 200 ⁇ m.
• Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranuhered or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the weight of the molded article.
• a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranuhered or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the weight of the molded article.
• the detergent tablets according to the invention can also contain a gas-developing shower system both in the base tablet and in the detergent component.
• the gas-developing shower system can consist of a single substance that releases a gas when it comes into contact with water.
• magnesium peroxide should be mentioned in particular, which releases oxygen on contact with water.
• the gas-releasing bubble system in turn consists of at least two components that react with one another to form gas. While a large number of systems are conceivable and executable here, which release nitrogen, oxygen or hydrogen, for example, the toilet system used in the detergent tablets according to the invention can be selected on the basis of both economic and ecological considerations.
• Preferred effervescent systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable for releasing carbon dioxide from the alkali metal salts in aqueous solution.
• the alkali metal carbonates or bicarbonates the sodium and potassium salts are clearly preferred over the other salts for reasons of cost.
• the pure alkali metal carbonates or bicarbonates in question do not have to be used; rather, mixtures of different carbonates and bicarbonates may be preferred for reasons of washing technology.
• shaped detergent bodies 2 to 20% by weight, preferably 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or bicarbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of an acidifying agent, in each case based on the total mold. used
• 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.
• organic acidifying agents are preferably used, citric acid being a particularly preferred but also other suitable acidifying agent Mono-, Ohgo- and Polycarbonsauren From this group again preferred are tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well as polyacrylic acid.
• Organic sulfonic acids such as amidosulfonic acid can also be used commercially and is also preferably used as an acidifying agent within the scope of the present invention R DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight)
• detergent form bodies in which a substance from the group of organic di-, T ⁇ - and ohgocarboxylic acids or mixtures of these are used as acidifying agents in the shower system
• the particulate detergents and / or detergents and detergent moldings according to the invention - like the detergent components according to the invention per se - can be packed after manufacture, the use of certain packaging systems having been particularly successful.
• Another aspect of the present invention is a combination of (a) particle-shaped remediation agent (s) according to the invention and / or (a) washing or cleaning agent-shaped body (s) according to the invention and a packaging system containing the cleaning agent and / or the washing and cleaning agent shaped body, the packaging system having a moisture vapor permeability rate of 0.1 g / m / day to less than 20 g / m "/ day if the packaging system is stored at 23 ° C. and a relative equilibrium humidity of 85%
• the packaging system of the combination of cleaning agent component and / or cleaning agent and / or washing and cleaning agent mold body (s) and packaging system has According to the invention, a moisture vapor permeability rate of 0.1 g / m " / day to less than 20 g / m / day if the packaging system is stored at 23 ° C. and a relative equilibrium humidity of 85%.
• the temperature and humidity conditions mentioned are Pmf conditions, which are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ⁇ 1 ° C, 85 ⁇ 2% rel.
• the moisture vapor permeability rate of a given packaging system or material can be determined according to further standard methods and is also, for example, in the ASTM standard E-96- 53T ("Test for measurement Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature and Humidity") description
• the common method of measurement strives for the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere is stored re, wherein the container at the top with the sealed test Mate ⁇ al is from the surface of the container which is sealed with the test Mate ⁇ al (Permeationsflache), the weight increase of Calciumchlo ⁇ ds and exposure time let the foundedsdampf miclasstechniksrate by
• A is the area of the material to be tested in cm 2
• x is the weight increase of calcium chloride in g
• y is the exposure time in h
• the relative equilibrium humidity is 85% when measuring the moisture vapor permeability rate in the context of the present invention) 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 specified in g / m. For example, 1 m of air at 17 ° is saturated with 14.4 g of water vapor, at a temperature of 11 ° a saturation already exists with 10 g of water vapor.
• the relative humidity is expressed as a percentage Ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature.
• the relative equilibrium humidity of 85% at 23 ° C can be adjusted to +/- 2% r.L. in laboratory chambers with humidity control, for example, depending on the device type. adjust exactly. Even over saturated solutions of certain salts, constant and well-defined relative air humidities form in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the soil.
• the combinations according to the invention can of course in turn be packed in secondary packaging, for example cardboard boxes or trays, with no further requirements having to be made of the secondary packaging.
• the secondary packaging is therefore possible, but not necessary.
• Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m / day to less than 15 g / no / day.
• the packaging system of the combination according to the invention includes a certain amount of detergent component according to the invention, a certain amount of a particulate detergent composition or one or more detergent tablets. It is preferred according to the invention either to design a shaped body in such a way that it comprises an application unit of the detergent and cleaning agent, and to individually package this shaped body, or to pack the number of shaped bodies in a packaging unit, which in total comprises one application unit.
• the packaging system of the combination according to the invention can consist of a wide variety of materials and can take on any external shape. For economic reasons and for reasons of easier processing, packaging systems are preferred in which the packaging material is light in weight, easy to process and inexpensive.
• the packaging system consists of a sack or pouch made of single-layer or laminated paper and / or plastic foil.
• the detergent tablets can be unsorted, i.e. as a loose fill, be filled into a bag made of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the detergent and cleaning agent form bodies individually or in several m bags or sacks.
• the term "flow pack” has become common in the art for individual application units of the detergent tablets which are located in a sack or bag. Such "flow packs” can then - again preferably sorted - optionally be packed in secondary packaging , which underlines the compact offer form of the molded body
• the sacks or bags made of single-layer or laminated paper or plastic film which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as an inflated bag without a central seam or as a bag with a central seam, which are sealed by heat (hot fusion), adhesives or adhesive tapes ,
• Single-layer bag or sack material are the known papers, which may or may not be impregnated, and plastic films, which may or may not be co-extruded.
• Plastic films which can be used as a packaging system in the context of the present invention are given, for example, in Hans Domimnghaus "D ⁇ e Kunststoffe und their properties", 3 edition, VDI Verlag, Düsseldor 1988, page 193.
• Packaging system in the context of the present invention always characterizes the primary packaging of the cleaning agent component.
• Detergent composition or molded article i.e. the packaging that is in direct contact on the inside with the cleaning agent component, detergent composition or mold body surface. No requirements are placed on an optional secondary packaging, so that all usual materials and systems can be used here
• the detergent components, detergent compositions or detergent and cleaning agent form bodies of the combination according to the invention contain, depending on their intended use, further ingredients of detergents and cleaning agents in varying amounts. Regardless of the intended use of the detergent or molding compound, it is preferred according to the invention that the detergent (s) or the or the detergent and cleaning agent form body has a relative equilibrium moisture content of less than 30% at 35 ° C.
• the relative equilibrium moisture content of the detergents or detergent tablets can be determined using conventional methods, the following procedure being chosen in the context of the present investigations.
• a water-impermeable 1-liter container with a lid, which has a closable opening for introducing samples has been filled with a total of 300 g of detergent and cleaning agent shaped bodies and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of the vessel and substance.
• the water vapor pressure in the space above the shaped bodies can then be measured with a hygrometer (Hygrotest 6100, Testoterm Ltd , England) The water vapor pressure is now measured every 10 minutes until two successive values show no deviation (equilibrium moisture) The above-mentioned hygrometer allows the recorded values to be displayed directly in% relative humidity
• a cleaning method for cleaning dish in a dishwashing machine is characterized in that one or more particle shapes according to the invention (s )
• Detergent and / or one or more detergent or cleaning agent moldings according to the invention insert the metering chamber of the winder and let a winding program run, in the course of which the metering chamber opens and the detergent (s) and / or the mold (s) are dissolved, em further object of the present invention
• the dosing chamber can also be dispensed with in the cleaning method according to the invention and the detergent components or detergent compositions according to the invention or the molding body (s) according to the invention can be inserted, for example, into the cutlery basket.
• a dosing aid for example a basket, which is attached in the winding space
• a cleaning method for cleaning dishes in a dishwasher is characterized in that one or more detergent particles and / or one or more detergent tablets according to the invention, with or without a metering aid, are used placed in the winding space of the winding machine and running a winding program, in the course of which the cleaning agent (s) and / or the mold body (s) are dissolved, a further subject of the present invention Examples:
• V2 C ⁇ 2 _ ⁇ 8 fatty alcohol sulfate, 90%> 200 ⁇ m, average particle size 300 ⁇ m ***** polyglycerol poly 12 hydroxystearate
• the nonionic surfactant was heated to 85 ° C, the paraffin was added with stirring and the remaining ingredients were added last.
• the stability of the suspension / emulsion was assessed at 85 ° C. by switching off the stirrer and visual assessment.

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