WO2005093034A1 - Pastilles a plusieurs phases permettant une meilleure perception de parfum - Google Patents

Pastilles a plusieurs phases permettant une meilleure perception de parfum Download PDF

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Publication number
WO2005093034A1
WO2005093034A1 PCT/EP2005/000371 EP2005000371W WO2005093034A1 WO 2005093034 A1 WO2005093034 A1 WO 2005093034A1 EP 2005000371 W EP2005000371 W EP 2005000371W WO 2005093034 A1 WO2005093034 A1 WO 2005093034A1
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WIPO (PCT)
Prior art keywords
acid
perfume
weight
phase
detergent
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PCT/EP2005/000371
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German (de)
English (en)
Inventor
Maren Jekel
Rolf Bayersdörfer
Arnd Kessler
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO2005093034A1 publication Critical patent/WO2005093034A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0078—Multilayered tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • 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
    • C11D3/50—Perfumes
    • 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
    • C11D3/50—Perfumes
    • C11D3/502—Protected perfumes
    • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay

Definitions

  • the present invention relates to multi-phase detergent tablets.
  • the invention relates to multi-phase RMFK, which are used for the mechanical cleaning of dishes in household dishwashers and are briefly referred to as detergent tablets for machine dishwashing or as tableted MGSM.
  • the automatic cleaning of dishes in household dishwashers usually comprises a pre-wash, a main wash and a rinse cycle, which are interrupted by intermediate wash cycles.
  • the pre-wash cycle for heavily soiled dishes can be activated, but is only selected by the consumer in exceptional cases, so that in most machines a main wash cycle, an intermediate rinse cycle with pure water and a rinse cycle are carried out.
  • the temperature of the main wash cycle varies between 40 and 65 ° C depending on the machine type and program level selection.
  • rinse aids are added from a metering tank in the machine, which usually contain non-ionic surfactants as the main component. Such rinse aids are in liquid form and are widely described in the prior art. Your main task is to prevent limescale and deposits on the cleaned dishes. In addition to water and low-foaming non-surfactants, these rinse aids often also contain hydrotopes, pH-adjusting agents such as citric acid or deposit-inhibiting polymers and often perfume.
  • Machine dishwashing detergents themselves are also often perfumed.
  • the perfume is also pumped out, so that, although the product smells when it is bought, the consumer cannot perceive the scent impression after the cleaning process.
  • the sometimes sensitive fragrances suffer from the drastic conditions in the rinse aid.
  • the "unpleasant smell of lye" which the consumer perceives as unpleasant, is only inadequately masked when the dishwasher is opened.
  • only a small proportion of the cost-intensive fragrances end up where it is supposed to have an effect.
  • German patent application DE 199 48 667 suggests using detergent components which contain 0.1 to 20% by weight of one or more esters, ethers, acetals or ketals of fragrances, 20 to 99.9% by weight of meltable substance (s) with a melting point above 30 ° C and 0 to 60 wt .-% of other active ingredients and / or auxiliaries.
  • meltable substance s
  • the release of these sensitive substances can be controlled in a targeted manner, so that the exposure to the alkaline cleaning liquor and the ambient temperatures is avoided until the meltable substances release the fragrance precursors.
  • the released perfume is exposed to thermal or chemical loads for a significantly shorter period of time, so that less perfume is destroyed by environmental influences.
  • the fragrance compounds disclosed in this document lead to significantly improved fragrance perception and largely prevent the perfume from being pumped out in the meantime, they are cost-intensive to produce, since the fragrances are first esterified, etherified, acetalized or ketlized and then in a melt matrix must be introduced.
  • the present invention relates to two-phase or multi-phase detergent tablets made from compressed particulate detergent or detergent, comprising polymer (s), builder (s), perfume and, if appropriate, further detergent and cleaning agent components, one phase of the tablet based on its weight contains more perfume than the other phase (s) and the more perfume-rich phase of the shaped body contains more polymer (s) than the other phase (s) based on its weight.
  • the detergent tablet consists of at least two phases, one phase being more rich in perfume and polymer than the other phase (s).
  • one phase contains more perfume and more polymer than the other two phases.
  • the perfume and polymer contents relate to the weight of the individual phase.
  • a phase is "richer" in perfume or polymer when the value given in% by weight (based on the phase) for the ingredient in question is greater than the value of the other phase (s).
  • detergent tablets according to the invention are preferred in which the perfume content of the individual phases of the tablet, based on the weight of the individual phase, by more than 0.1% by weight, preferably by more than 0.25% by weight and in particular by more than 0.5% by weight.
  • Preferred detergent tablets according to the invention are characterized in that the polymer content of the individual phases of the tablet, based on the weight of the individual phase, by more than 0.05% by weight, preferably by more than 0.1% by weight, particularly preferably varies by more than 0.2% by weight and in particular by more than 0.5% by weight.
  • the variation by more than 0.1% by weight, based on the weight of the individual phases means that the absolute values of the perfume content in the phases vary by more than 0.1% by weight.
  • the perfume content of the other phase (s) should be selected according to the invention such that the width of the variation around the value 2.0 is at least 0.1% by weight, that is is less than 1.9% by weight or more than 2.1% by weight, in each case based on the phase.
  • the percentage numerical value of the perfume content of the poorest perfume phase is subtracted from the percentage numerical value of the perfume content of the perfume-richest phase, the result having to be> 0.1.
  • the greatest possible difference in the perfume content in the individual phases can be achieved if at least one phase contains perfume, while at least one other phase is free of perfume. This is another preferred embodiment of the present invention.
  • the individual phases of the shaped body can have different spatial shapes.
  • the simplest possible implementation is in two- or multi-layer tablets, with each layer of the shaped body representing a phase.
  • ring core tablets for example, coated tablets or combinations of the named th embodiments possible.
  • Examples of multi-phase moldings can be found in the illustrations in EP-A-0 055 100 (Jeyes), which describes toilet cleaning blocks.
  • the currently widespread spatial form of multi-phase tablets is the two- or multi-layer tablet.
  • the phases of the shaped body have the form of layers.
  • Three-phase molded articles are currently preferably offered by providing a two-phase tray tablet whose tray is filled with a "core" as the third phase. These products have high consumer acceptance and are preferred as three-phase tablets.
  • each phase contains a different perfume
  • the perfume contents differing in the phases.
  • different fragrance impressions can be realized for each individual phase or the composition of the perfumes can be adapted to the other ingredients of the phase in question.
  • the detergent tablets according to the invention have two phases which contain the same perfume in different amounts.
  • perfume-free As already mentioned, the greatest possible difference in perfume content can be achieved by combining perfume-free with perfume-containing phases.
  • the proportion of the individual phases in the total tablet can be varied within wide limits.
  • detergent tablets are preferred in which the two layers of the tablet in a weight ratio of 5 to 95 to 50 to 50, preferably 10 to 90 to 60 to 40 and in particular 15 to 85 to 65 35 stand, the perfume is preferably concentrated in the proportionately lower layer.
  • Phases with a higher fragrance percentage cannot bind them as strongly, i.e. the fragrance is less adherent in the shaped body and can be perceived more intensively by the consumer when the packaged tablet is opened.
  • the stability of both layers and their disintegration times can also be adjusted or specifically controlled by varying the perfume content in the layers of the tablet. An additional effect occurs with higher perfume contents in a colored layer, since the color intensity is increased.
  • perfume denotes both individual fragrances and fragrance mixtures in concentrated or with suitable solvents diluted form.
  • perfume oil is also used for the pure fragrance mixture, which is not diluted with solvents.
  • fragrances are essential oils, flower oils, extracts from plant and animal drugs, isolated from natural products, chemically modified (semi-synthetic) and purely synthetic "Fragrances" is the colloquial collective name for those fragrances that trigger a pleasant sensation of smell in humans and are therefore suitable for perfuming detergents and cleaning agents. In a broader sense, essences and aromas can also be added to the fragrances.
  • fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
  • Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate (DMBCA), phenylethyl acetate, benzyl acetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropylate, melyllalpylate, melateylylalpylate, melateylalpylate, melateylalpylate, melateylalpylate, benzylatepylate, melateylalpylate, benzylateolate, melylalpy
  • the linear alkanals with 8 - 18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, lilial and bourgeonal, to the ketones e.g. the jonones, oc-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance.
  • Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil. It is now possible to produce cleaning agents in which the proportion of the perfume which is present in the phase which is richer in perfume and polymer is composed mainly of adhesive odoriferous substances.
  • fragrance In order to be perceptible, a fragrance must be volatile, the molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound , Most odoriferous substances have molecular weights of up to about 200 daltons, while molecular weights of 300 daltons and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are described in "top note”, “heart or middle note” (middle note or body) and “base note” (end note or dry out).
  • the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile
  • more volatile fragrances can be bound, for example, to certain fixatives, which prevents them from evaporating too quickly.
  • fixatives which prevents them from evaporating too quickly.
  • Such a method for fragrance fixation is applied in low density.
  • the subsequent classification of the fragrances into “more volatile” or “adherent” fragrances nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note.
  • Adhesive odoriferous substances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, anise oil, amica flower oil, basil oil, bay oil and berry oil. gamott oil, champaca flower oil, noble fir oil, noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, camomile oil, kale oil, camava oil, camava oil Cardamom oil, cassia oil, pine needle oil, Kopa ⁇ vabalsamöl, coriander oil, Krausem inzeöl, caraway oil, Kuminöl, lavender oil, lemongrass oil, lime oil, mandarin oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, oriban
  • the higher-boiling or solid odorants of natural or synthetic origin can also be used in the context of the present invention as adherent odorants or odorant mixtures, that is to say fragrances.
  • These compounds include the compounds listed below and mixtures thereof: ambrettolide, ⁇ -amyl cinnamic aldehyde, anethole, anisaldehyde, anisyl alcohol, anisole, methyl anthranilate, acetophenone, benzyl acetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, Benzylvalerianat, borneol , Bornyl acetate, ⁇ -bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugeno
  • the more volatile fragrances include, in particular, the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
  • Examples of more volatile fragrances are alkyisothiocyanates (alkyl mustards), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, methyl-n-heptenone, phellandren, phenylacetaldehyde, terpinylacetate, citral, citronellal.
  • alkyisothiocyanates alkyl mustards
  • butanedione butanedione
  • limonene limonene
  • linalool linaylacetate and propionate
  • menthol menthone
  • methyl-n-heptenone phellandren
  • phenylacetaldehyde terpinylacetate
  • citral citronellal.
  • detergent tablets are preferred in which the tablets have total perfume contents of 0.05 to 10% by weight, preferably 0.1 to 5% by weight. and in particular from 0.25 to 1.5% by weight, in each case based on the weight of the shaped body.
  • the detergent tablets according to the invention contain, in addition to perfume, one or more polymer (s).
  • the agents according to the invention contain polymers as an essential component.
  • the molecular weight of these polymers can be 2000 gmol "1 or more.
  • a first embodiment of the present invention preference is given to those polymers which have at least one positive charge, with detergents or cleaning agents which contain 0.02 to 7.5% by weight, preferably 0.05 to 5% by weight, in particular preferably 0.07 to 2.5% by weight and in particular 0.1 to 1% by weight of at least one polymer with a molecular weight of 2000 gmol "1 or above, which has at least one positive charge, are particularly preferred.
  • the aforementioned polymers with a cationic charge can in principle be cationic or amphoteric polymers.
  • Preferred washing or cleaning agents according to the invention are characterized in that the polymer which has cationic monomer units is a cationic polymer and / or an amphoteric polymer.
  • “Cationic polymers” in the sense of the present invention are polymers which carry a positive charge in the polymer molecule. This can be achieved, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain.
  • Particularly preferred cationic polymers come from the groups of quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate Methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.
  • Amphorere polymers in the sense of the present invention also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • Cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a compound of the general formula (I) as monomer unit
  • R 2 and R 3 independently of one another represent an alkyl, hydroxyalkyl or aminoalkyl group in which the alkyl radical is linear or branched and has between 1 and 6 carbon atoms, where it is preferably a methyl group
  • x and y independently of one another represent integers between 1 and 3.
  • X " represents a counter ion, preferably a counter ion from the group chloride, bromide, iodine, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate , p-toluenesulfonate (tosylate), cumene sulfonate, xylene sulfonate, phosphate, citrate, formate, acetate or mixtures thereof.
  • Preferred radicals R 1 and R 4 in the above formula (I) are selected from -CH 3 , -CH 2 - CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, - CH 2 -CH (OH) -CH 3 , -CH (OH ) -CH 2 -CH 3 , and - (CH 2 CH 2 -0) nH.
  • DADMAC diallyldimethylammonium chloride
  • cationic or amphoteric polymers which are particularly preferred in the context of the present application contain a monomer unit of the general formula (II)
  • R 1 HC CR 2 -C (0) -NH- (CH 2 ) x -N + R 3 RR 5 X " (II),
  • R 1 , R 2 , R 3 , R 4 and R 5 independently of one another for a linear or branched, saturated or unsaturated alkyl, or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably for a linear or branched alkyl radical selected from -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , - CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , - CH (OH) -CH 2 -CH 3 , and - (CH 2 CH 2 -0) nH and x represents an integer between 1 and 6.
  • H 2 C C (CH 3 ) -C (0) -NH- (CH 2 ) ⁇ -N + (CH 3 ) 3 X "
  • X " chloride are also referred to as MAPTAC (methyacrylamidopropyl trimethylammonium chloride).
  • washing or cleaning agents preferred according to the invention are characterized in that the polymer c) contains diallyldimethylammonium salts and / or acrylamidopropyltrimethylammonium salts as monomer units.
  • the aforementioned amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic monomer units originate, for example, from the group of the linear or branched, saturated or unsaturated carboxylates, the linear or branched, saturated or unsaturated phosphonates, the linear or branched, saturated or unsaturated sulfates or the linear or branched, saturated or unsaturated sulfonates.
  • Preferred monomer units are acrylic acid, (meth) acrylic acids, (dimethyl) acrylic acid, (ethyl) acrylic acid, cyanoacrylic acid, vinyl essingic acid, allyl acetic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid and their Derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, or the allylphosphonic acids.
  • Preferred amphoteric polymers that can be used come from the group of the alkyl acrylamide / acrylic acid copolymers, the alkyl acrylamide / methacrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid copolymers, the alkyl acrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylate - mid / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylate / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and
  • Zwitterionic polymers which can be used with preference come from the group of acrylamidoalkyl trialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts, acrylamidoalkyl trialkylammonium chloride / methacrylic acid copolymers and their alkali and ammonium salts and methacroylethylbetaine / methacrylate copolymers.
  • amphoteric polymers which, in addition to one or more anionic monomers, comprise methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride as cationic monomers.
  • amphoteric polymers come from the group of methacrylamidoalkyl trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylic amidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and methacrylamidoalkyltrialkyllammonium chloride (hd) dimethylammonium chloride / Alkyl (meth) acrylic acid copolymers and their alkali and ammonium salts.
  • amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid Copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers and their alkali and ammonium salts.
  • compositions according to the invention are therefore characterized in that they comprise at least one copolymer of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionic monomers
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • H 2 C CH-X-S0 3 H (IVa)
  • H 2 C C (CH 3 ) -X-S0 3 H (IVb)
  • H0 3 SX- (R 6 ) C C (R 7 ) - X-S0 3 H (IVc)
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenlsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate , Sulfomethacrylamide, sulfomethyl methacrylamide and water-soluble salts of the acids mentioned.
  • ionic or nonionic monomers are, in particular, ethylenically unsaturated compounds.
  • the group iii) monomer content of the polymers used according to the invention is preferably less than 20% by weight, based on the polymer. Polymers to be used with particular preference consist only of monomers of groups i) and ii).
  • copolymers are made of
  • R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH-substituted alkyl or alkenyl radicals as defined above or represents -COOH or -COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
  • Particularly preferred copolymers consist of i) one or more unsaturated carboxylic acids from the group consisting of acrylic acid, methacrylic acid and / or maleic acid ii) one or more monomers of the formulas IVa, IVb and / or IVc containing sulfonic acid groups:
  • H 2 C CH-X-S0 3 H (IVa)
  • H 2 C C (CH 3 ) -X-S0 3 H (IVb)
  • H0 3 SX- (R 6 ) C C (R 7 ) - X-S ⁇ 3 H (IVc)
  • the copolymers can contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • compositions according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula V.
  • compositions according to the invention are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the sulfonic acid group-containing acrylic acid derivative is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the compositions according to the invention is also preferred and is characterized in that the compositions contain one or more copolymers which have structural units of the formula VI
  • acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule to be changed.
  • Compositions according to the invention which contain one or more copolymers which have structural units of the formula VII
  • compositions which are characterized in that they contain one or more copolymers which have structural units of the formula VIII
  • compositions according to the invention which are characterized in that they contain one or more copolymers, the structural units of the formula VIII
  • m - [HOOCCH-CHCOOH] m - [CH 2 -C (CH 3 ) C (0) 0-Y-S0 3 H] p - (IX), contain, in which m and p each represent an integer between 1 and 2000 and Y represents a spacer group which is selected from substituted or unsubstituted aliphatic, aromatic or araliphatic hydrocarbon radicals having 1 to 24 carbon atoms, spacer groups in which Y for -0- (CH 2 ) n - with n 0 to 4, for -0- (C 6 H 4 ) -, for -NH- C (CH 3 ) 2 - or -NH-CH (CH 2 CH 3 ) - stands, are preferred.
  • compositions according to the invention which contain one or more copolymers which have structural units of the formulas IV and / or V and / or VI and / or VII and / or VIII and / or IX are preferred
  • the sulfonic acid groups in the polymers may be wholly or partly in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • Corresponding compositions which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
  • the monomer distribution of the copolymers used in the compositions according to the invention is preferably 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight, of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred ,
  • compositions according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred compositions are characterized in that the copolymers have molar masses of 2,000 to 200,000 gmol "1 , preferably 4,000 to 25,000 gmol " 1 and in particular 5,000 to 15,000 gmol "1 .
  • the abovementioned polymers are also outstandingly suitable as perfume carriers, provided that the perfume is not to be incorporated by spraying onto a particulate premix - more details can be found below in the description of the process according to the invention.
  • polymeric carboxylates described below as cobuilders are used as polymers.
  • the polymers contained in the agents according to the invention are in pre-assembled form.
  • the following is suitable for packaging the polymers: encapsulation of the polymers by means of water-soluble or water-dispersible coating agents, preferably by means of water-soluble or water-dispersible natural or synthetic polymers; - Encapsulation of the polymers by means of water-insoluble, meltable coating agents, preferably by means of water-insoluble coating agents from the group of waxes or paraffins with a melting point above 30 ° C; - The co-granulation of the polymers with inert carrier materials, preferably with carrier materials from the group of active washing or cleaning substances, particularly preferably from the group of builders (builders) or cobuilders.
  • the detergent tablets according to the invention can also contain one or more surfactant (s). These come from the groups of anionic, nonionic, cationic and / or amphoteric surfactants, with nonionic surfactants being clearly preferred in the context of automatic dishwashing and Surfactants from the other groups are used only in minor amounts or preferably not at all.
  • surfactant come from the groups of anionic, nonionic, cationic and / or amphoteric surfactants, with nonionic surfactants being clearly preferred in the context of automatic dishwashing and Surfactants from the other groups are used only in minor amounts or preferably not at all.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C 9 . 13- Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 12 . 18 -monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates from C 2 - 18 are obtained, for example, alkanes by sulfochlorination or sulfoxidation and 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 the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsu! Fates of the chain length mentioned which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 5 alkyl sulfates are preferred from a washing-technical point of view.
  • 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
  • 21 alcohols such as 2-methyl-branched C 9-1 alcohols containing on average 3.5 mol ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO, are also 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.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-0 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • non-ionic surfactants are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 . 14 -alcohols with 3 EO or 4 EO, C 9 . ⁇ alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 . 18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 - alcohol with 3 EO and C 12 - .8 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols can also be used can be used with more than 12 EO. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
  • Alkypolyglycosides which can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
  • Linear alkyl polyglucosides, ie alkyl polyglycosides, which consist of a glucose residue and an n-alkyl chain, are preferably used.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • RCO for an aliphatic acyl radical with 6 to 22 carbon atoms
  • R ⁇ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
  • [Z] for a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
  • R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms
  • Cu alkyl or phenyl radicals being preferred
  • [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical ,
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • surfactants are generally suitable as surfactants.
  • the nonionic surfactants described above, and above all the low-foaming nonionic surfactants are preferred for this purpose.
  • the alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols.
  • alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C 10 to C 8 , preferably between C 12 and C 16 , such as Cn- , C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols).
  • C 10 to C 8 preferably between C 12 and C 16 , such as Cn- , C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 -alcohols.
  • n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation, depending on the reaction conditions.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • a final etherification with short-chain alkyl groups leads to the substance class of the "closed" alcohol ethoxylates, which can also be used in the sense of the invention.
  • very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
  • nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants.
  • surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
  • washing or cleaning agents according to the invention are preferred which contain surfactants of the general formula III as nonionic surfactant (s)
  • R 1 represents a straight-chain or branched, saturated or mono- or polyunsaturated C 6 - 24 alkyl or alkenyl radical
  • each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
  • the preferred nonionic surfactants of the formula III can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
  • the radical R 1 in formula I above can vary depending on the origin of the alcohol. If native sources are used, the radical R 1 has an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or Oleyl alcohol are preferred.
  • Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • washing or cleaning compositions according to the invention are preferred in which R 1 in formula I for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.
  • butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
  • R 2 or R 3 are selected independently of one another from -CH 2 CH 2 -
  • CH 3 or -CH (CH 3 ) 2 are suitable.
  • Preferred washing or cleaning agents are characterized in that R 2 or R 3 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
  • nonionic surfactants which have a C 9 . 15 - alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
  • the washing or cleaning agents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43, 3 ° C.
  • Suitable, in addition to the nonionic surfactants contained in the compositions according to the invention, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature originate from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols and mixtures of these surfactants with structurally more complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic 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.
  • a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms, (C ⁇ .
  • particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C 6 . 20 monohydroxyalkanols or C 6 . 20 -alkylphenols or C 16-2 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).
  • ethoxylated nonionic surfactant consist of C 6 . 20 monohydroxyalkanols or C 6 . 20 -alkylphenols or C 16-2 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 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 ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part 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 molar mass of such nonionic surfactants.
  • Preferred detergents or cleaning agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total Make up the 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 comprises 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 that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
  • a further preferred washing or cleaning agent according to the invention contains nonionic surfactants of the formula
  • R 1 0 [CH 2 CH (CH 3 ) 0] x [CH 2 CH 2 0] y [CH 2 CH (OH) R 2 ], in which R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.
  • nonionic surfactants are the end group-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 1 and R 2 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 3 .
  • 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 1 0 [CH 2 CH (R 3 ) 0] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 , R 2 and R 3 are as defined above and x represents 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 has 9 to 14 C atoms, R 3 represents H and x assumes values from 6 to 15.
  • washing or cleaning agents according to the invention are preferred, 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, with surfactants of the type
  • x represents numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
  • Anionic, cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent.
  • the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
  • the detergent tablets according to the invention surfactant (s), preferably nonionic surfactant (s), in amounts of 0.5 to 10 wt .-%, preferably from 0.75 to 7, 5 wt .-% and in particular from 1, 0 to 5 wt .-%, each based on the total agent.
  • the agents according to the invention particularly preferably contain exclusively nonionic surfactant (s) and are accordingly free from anionic surfactants, cationic and amphoteric surfactants.
  • Particularly preferred detergent tablets according to the invention are characterized in that the tablets contain only nonionic surfactant (s) as surfactant (s), the nonionic surfactant (s) preferably being at least 40%, particularly preferably at least 60% and in particular at least 75% its weight is contained in the more perfume phase.
  • Agents according to the invention are particularly preferred, characterized in that the moldings contain only nonionic surfactant (s) as surfactant (s), the nonionic surfactant (s) preferably being at least 80%, particularly preferably at least 90% and in particular at least 95% of its weight is contained in the more perfume phase.
  • two-phase or multiphase detergent tablets made from compressed particulate detergent or cleaning agent, comprising polymer (s), builder (s), perfume, surfactant (s) and, if appropriate, further detergent and cleaning agent components , wherein one phase of the shaped body contains more perfume based on its weight than the other phase (s), characterized in that the phase with more perfume of the shaped body contains more polymer (s) and more surfactant (s) based on its weight, than the other phase (s).
  • detergent tablets are preferred which consist of two phases and in which the quotient of the difference in the perfume contents and the difference in the polymer contents is less than 2, preferably less than 1 and in particular less than 0.5.
  • the detergent tablets according to the invention contain builders as a further constituent.
  • Preferred detergent tablets according to the invention contain, in addition to the ingredients mentioned above, one or more substances from the group of cobuilders, bleaches, bleach activators, enzymes, dyes, corrosion inhibitors, or another conventional constituent of detergents and cleaning agents. These ingredients are described below.
  • all builders normally used in detergents and cleaning agents can be incorporated into the washing and cleaning agents, in particular silicates, carbonates, organic cobuilders and also the phosphates.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2x + 1 ⁇ 2 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.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 "yH 2 0 are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates.
  • Preferred alkali metal ions are sodium and / or potassium ions.
  • Compounds made of, for example, carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can also be present as separate components in the finished compositions. It is of course also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons.
  • alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.
  • Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) n and orthophosphoric acid H 3 P0 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to 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, preferably " 3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 0 7 ) at 200 ° C, and at higher temperatures in sodium trimetaphosphate (Na 3 P 3 0 9 ) and Maddrell's salt (see below).
  • NaH 2 P0 4 is acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with a Naronauge and the mash is sprayed.
  • Potassium hydrogen phosphate primary or monobasic potassium phosphate, potassium biphoshate, KDP
  • KH 2 P0 4 is a white salt with a density of 2.33 "3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KP0 3 ) ⁇ ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0, is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gladly “3 , water loss at 95 °), 7 mol. (Density 1, 68 gladly “ 3 , melting point 48 ° with loss of 5 H 2 0) and 12 mol. Water ( Density 1, 52 like “3 , melting point 35 ° with loss of 5 H 2 0), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 0 7 when heated.
  • Disodium hydrogen phosphate is lost by neutralizing phosphoric acid with soda solution Using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HP0 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 are colorless crystals which, as dodeca- hydrate, have a density of 1.62 "3 and a melting point of 73-76 ° C (decomposition), as deca- hydrate (corresponding to 19-20 % P 2 0 5) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 0 5) a density of 2.536 like "3 alseisen.
  • Trisodium phosphate is in Water is readily soluble in 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 3 P0 4 , 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 Heating of Thomas slag with coal and potassium sulfate Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred to the 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 water loss). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 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. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 0 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 value being 1 % solution at 25 ° is 10.4.
  • Sodium and potassium phosphates in which a distinction can be made between cyclic representatives, the sodium and potassium metaphoshates, and chain-like types, the sodium and potassium polyphosphates. A large number of names are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • About 17 g of the salt of water free of water of crystallization dissolve in 100 g of water at room temperature, about 20 g at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (> 23% P 2 0 5 , 25% K 2 0). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. Sodium potash also exists umtripolyphosphates, which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:
  • these can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
  • Washing or cleaning agents preferred in the context of the present invention contain no sodium and / or potassium hydroxide. Dispensing with sodium and / or potassium hydroxide as the alkali source has proven to be particularly advantageous if zinc gluconate, zinc formate and zinc acetate are used as zinc salts. .
  • Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates.
  • the polymers can also be part of the active substance-containing matrix, but they can also be contained in the agents according to the invention completely independently of this. The substance classes mentioned are described below.
  • Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean 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, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
  • Polymeric polycarboxylates are also suitable as builders; these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
  • GPC gel permeation chromatography
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information deviates significantly from the molecular weight information, for which polystyrene sulfonic acids are used as standard.
  • the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.
  • Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
  • the copolymers containing sulfonic acid groups are described in detail below.
  • sulfonic acid group-containing polymers described above can of course also be present in the agents according to the invention, without necessarily having to be part of the active ingredient-containing matrix.
  • polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
  • the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
  • Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or Sokalan ® PA25 (BASF).
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 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 of more than two different monomer units are also particularly preferred, 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.
  • builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
  • Polyaspartic acids or their salts and derivatives are particularly preferred.
  • 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.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. 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.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylenediamine-N, N'-disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
  • Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used 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 lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. They are preferably in the form of the neutral sodium salts, e.g. B.
  • HEDP is preferably used as the builder from the class of the phosphonates.
  • the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • all compounds that are able to form complexes with alkaline earth metal ions can be used as cobuilders.
  • Agents according to the invention are characterized in the context of the present application in that they contain builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably of 1 to 95 % By weight, particularly preferably from 5 to 90% by weight and in particular from 10 to 80% by weight, in each case based on the composition.
  • Bleaching agents and bleach activators are important components of detergents and cleaning agents, and a detergent and cleaning agent can contain one or more substances from the groups mentioned within the scope of the present invention.
  • Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H 2 0 2 in water.
  • Other useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate.
  • Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
  • the merchandise has the average composition 2 Na 2 C0 3 -3 H 2 ⁇ 2 and is therefore not peroxycarbonate.
  • Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 "3 , which easily disintegrates into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate 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 percarbonate is precipitated by salting-out agents (predominantly sodium chloride), crystallization aids (for example polyphosphates, polyacrylates) and stabilizers (for example Mg 2+ ions).
  • the precipitated salt which is still 5 to 12 Contains wt .-% mother liquor, is then centrifuged and dried in fluid bed dryers at 90 ° C.
  • the bulk density of the finished product can vary between 800 and 1200 g / l depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating.
  • Detergents for automatic dishwashing can also contain bleaches from the group of organic bleaches.
  • Typical organic bleaching agents that can be used as ingredients in the context of the present invention are the diacyl peroxides, such as e.g. Dibenzoyl.
  • Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -Phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxyacid, diperoxyacidoxyacid, diperoxyacidoxyacid, Diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dia
  • chlorine or bromine-releasing substances can also be used as bleaching agents for machine dishwashing.
  • Suitable materials which release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chlorioramides, for example trichloroisocyanuric acid, tbromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
  • Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.
  • bleaching agents preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight, preferably from 1 to 30% by weight, particularly preferably from 2.5 to 25% by weight and in particular from 5 to 20% by weight, in each case based on the total composition.
  • bleaching agents preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40%
  • 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. Substances are suitable which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • bleach catalysts can also be incorporated into the cleaning agents according to the present invention.
  • 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.
  • agents are preferred to use one or more substances from the group of bleach activators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), of acylated phenolsulfonates, in particular n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20% by weight, preferably 0.5 to 15% by weight % and in particular from 1 to 10 wt .-%, each based on the total agent.
  • TAED tetraacetylethylene diamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOSI)
  • NOSI N-nonanoylsucc
  • the bleach activators preferred in the context of the present invention also include the “nitrile quats”, cationic nitriles of the formula (IV), R 1
  • R 3 in which R 1 for -H, -CH 3 , a C 2 . 24 alkyl or alkenyl radical, a substituted C 2 - 24 alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical with a C 24 alkyl group, or for a substituted alkyl or alkenylaryl radical having a C 1-4 alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) - CH 3 , -CH 2 -CH 2 -CH 2 -OH,
  • General formula (XXI) includes a large number of cationic nitriles which can be used in the context of the present invention.
  • the detergent tablets according to the invention particularly advantageously contain cationic nitriles in which R 1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical.
  • R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.
  • radicals R 1 to R 3 are identical, for example (CH 3 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH (CH 3 )) 3 N (+) CH 2 -CN X “ , or (HO -CH 2 -CH 2 ) 3 N (+) CH 2 -CN X " , where X " is preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is selected.
  • Detergents and cleaning agents preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XXI) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the weight of the shaped body.
  • Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, grease or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. For bleaching or to inhibit the transfer of color oxidoreductases can also be used.
  • hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases help to remove stains such as protein, grease or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color
  • Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and from their genetically modified variants are particularly suitable.
  • Proteases of the subiiisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, 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.
  • Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different cellulase types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
  • Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , each based on the total mean.
  • Dyes preferred in the context of the present invention the selection of which does not pose any difficulty for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
  • Preferred for use in the washing and cleaning agents according to the invention are all colorants which can be oxidatively destroyed in the cleaning process, and also mixtures of these with suitable blue dyes, so-called blue tones. It has proven to be advantageous to use colorants which are soluble in water or in liquid organic substances at room temperature.
  • anionic colorants for example anionic nitroso dyes, are suitable.
  • One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
  • Pigmosol ® Blue 6900 (Cl 74160), Pigmosol ® Green 8730 (Cl 74260), Basonyl ® Red 545 FL (Cl 45170), Sandolan ® Rhodamine EB400 (Cl 45100), Basacid ® Yellow 094 (Cl 47005), Sicovit ® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ® Blau GLW (CAS 12219-32-8, Cl A- cidblue 221)), Nylosan ® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan ® Blue (Cl Acid Blue 182, CAS 12219-26-0).
  • the colorant When choosing the colorant, it must be ensured that the colorants do not have too strong an affinity for the textile surfaces and especially for synthetic fibers. At the same time, when choosing suitable colorants, it must also be taken into account that colorants have different stabilities against oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the washing or cleaning agents varies. For highly soluble dyes, for example, the above-mentioned Basacid ® Green or the above-mentioned Sandolan Blue ®, are typically selected dye concentrations in the range of some 10 "2 to 10" 3 wt .-%.
  • the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 "3 to 10" 4 wt .-% ,
  • Detergents for machine dishwashing can contain corrosion inhibitors to protect the items to be washed or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing.
  • the known substances of the prior art can be used.
  • silver protective agents selected from the group consisting of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkyl laminotriazoles and the transition metal salts or complexes can be used.
  • Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
  • active chlorine-containing agents that corrode the silver surface are often found in cleaner formulations can significantly reduce.
  • 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 classes of compounds.
  • 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 of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) -Complexes, the chlorides of cobalt or manganese and manganese sulfate as well as the manganese complexes
  • Me-MeTACN Mn III (m-0) (m-0AC) 2 Mn ll l (Me-MeTACN)] 2+ (PF 6 ') 2 - wherein MeTACN for 1, 4,7-trimethyl-1 , 4,7-triazacyclononan and Me-MeTACN stands for 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane, and zinc compounds can also be used to prevent corrosion on the wash ware.
  • a preferred agent for providing corrosion protection for glassware during cleaning and / or rinsing operations of a dishwasher is zinc in oxidized form, i.e. Zinc compounds in which zinc is cationic.
  • Zinc compounds in which zinc is cationic are also preferred.
  • magnesium salts are also preferred.
  • both soluble and poorly or insoluble zinc or magnesium compounds can be used.
  • Preferred compositions according to the invention contain one or more magnesium and / or zinc salt (s) of at least one monomeric and / or polymeric organic acid.
  • the acids in question preferably originate from the group of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the Amino acids and / or the polymeric carboxylic acids, the unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acids with at least 8 carbon atoms and / or resin acids.
  • magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be present, as described above, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of the unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, sugar acids, hydroxy acids, oxo acids, amino acids and / or polymeric carboxylic acids are preferred.
  • the acids mentioned below are again preferred within these groups:
  • benzoic acid 2-carboxybenzoic acid (phthalic acid), 3-carboxybenzoic acid (isophthalic acid), 4-carboxybenzoic acid (terephthalic acid), 3,4-dicarboxybenzoic acid (trimellitic acid), 3,5-dicarboxybenzoic acid (Trimesionklare).
  • sugar acids galactonic acid, mannonic acid, fructonic acid, arabinonic acid, xylonic acid, ribonic acid, 2-deoxy-ribonic acid, alginic acid.
  • hydroxy acids hydroxyphenylacetic acid (mandelic acid), 2-hydroxypropionic acid (lactic acid), hydroxysuccinic acid (malic acid), 2,3-
  • Dihydorxybutanedioic acid (tartaric acid), 2-hydroxy-1, 2,3-propanetricarboxylic acid (citric acid), ascorbic acid, 2-hydroxybenzoic acid (salicylic acid), 3,4,5-trihydroxybenzoic acid (gallic acid).
  • oxo acids 2-oxopropionic acid (pyruvic acid), 4-oxopentanoic acid (levulinic acid).
  • amino acids From the group of amino acids: alanine, valine, leucine, isoleucine, proline, tryptophan, phenylalanine, methionine, glycine, serine, tyrosine, threonine, cysteine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, histidine.
  • polymeric carboxylic acids polyacrylic acid, polymethacrylic acid, alkyl acrylamide / acrylic acid copolymers, alkyl acrylamide / methacrylic acid copolymers, alkyl acrylate / methyl methacrylic acid copolymers, copolymers of unsaturated carboxylic acids, vinyl acetate / crotonic acid copolymers, vinyl pyrrolidone / vinyl pyrrolidone / vinyl acrylate copolymers.
  • the spectrum of the zinc salts of organic acids, preferably organic carboxylic acids preferred according to the invention, extends from salts which are sparingly or not soluble in water, ie have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, up to such salts which have a solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C. water temperature).
  • the first group of zinc salts includes, for example, zinc citrate, zinc oleate and zinc stearate
  • the group of soluble zinc salts includes, for example, zinc formate, zinc acetate, zinc lactate and zinc gluconate:
  • compositions according to the invention contain at least one zinc salt, but no magnesium salt of an organic acid, it preferably being at least one zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group consisting of zinc stearate, zinc oleate, zinc gluconate and zinc acetate , Zinc lactate and / or zinc citrate.
  • Zinc ricinoleate, zinc abietate and zinc oxalate can also be used with preference
  • Another object of the present invention is a method for producing multiphase detergent tablets by compression molding known per se.
  • Particulate premixes which contain different amounts of perfume, characterized in that the more perfume-based premix contains more polymer (s) than the other premix (s), based on its weight.
  • the perfume can be introduced into the moldings according to the invention in different ways.
  • the simplest way is that the perfume is sprayed onto the premix (s) and introduced into the perfume-containing phase (s). Since the premixes to be pressed into the respective phases are usually mixtures of different particulate and, if appropriate, liquid or pasty substances, the perfume can simply be metered in in the mixing step. A fine distribution, for example spraying, is preferable to simple pouring.
  • the perfume can - especially if nonionic surfactants are used as surfactants - also mixed with the surfactant and applied to the premixes in a mixture with the latter.
  • fragrances it is also possible to apply the fragrances to carrier substances before adding them to the respective premix, or to increase their adhesion in a suitable manner.
  • Cyclodextrin-perfume complexes or encapsulated perfumes are suitable for this.
  • Methods in which the perfume is introduced into the perfume-containing phase (s) by adding such solid fragrance preparation forms to the premix (s) are also preferred.
  • Suitable carrier materials are, for example, the builder substances mentioned above, but also polymers from the group of the above-mentioned cobuilders.
  • a particularly suitable perfume carrier is the above-described polymer containing sulfonic acid groups.
  • a carrier material containing perfume and optionally surfactant or polymer is introduced into the particulate premix.
  • This preferably has perfume contents of 1 to 60% by weight, particularly preferably 10 to 50% by weight and in particular 12 to 40% by weight, in each case based on its weight.
  • the perfume-containing material additionally contains surfactant, preferably nonionic surfactant, the surfactant content is preferably from 20 to 60% by weight, particularly preferably from 25 to 55% by weight and in particular from 30 to 45% by weight, in each case based on the Weight of the carrier material. In the latter cases, the perfume content is accordingly at the lower end of the above range.
  • the bulk density of the loaded materials is preferably at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
  • the loaded carrier material has particle sizes between 100 and 2000 ⁇ m, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
  • the particulate premix additionally contains one or more substances from the group of bleaching agents, bleach activators, disintegration aids, enzymes, pH regulators, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, Contains color transfer inhibitors and corrosion inhibitors.
  • the moldings according to the invention are first produced by dry mixing the constituents of the individual phases, which can be wholly or partially pregranulated, and then informing them, in particular pressing them into tablets, in which case conventional methods for producing multiphase moldings can be used.
  • the premixes are compacted in a so-called die between two punches to form a solid compressed product. This process, which is briefly referred to below as tableting, is divided into four sections: metering, compression (elastic deformation), plastic deformation and ejection.
  • Tableting takes place in commercially available tablet presses, which can in principle be equipped with single or double punches. In the latter case, not only is the upper stamp used to build up pressure, the lower stamp also moves towards the upper stamp during the pressing process, while the upper stamp presses down.
  • eccentric tablet presses are preferably used, in which the punch or stamps are attached to an eccentric disc, which in turn is mounted on an axis with a certain rotational speed. The movement of these rams is comparable to that of a conventional four-stroke engine.
  • the pressing can take place with one upper and one lower punch, but several punches can also be attached to one eccentric disk, the number of die holes being correspondingly increased.
  • the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of matrices are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are also commercially available.
  • Each die on the die table is assigned an upper and lower punch, and again the pressure can be built up actively only by the upper or lower punch, but also by both stamps.
  • the die table and the stamps move about a common vertical axis, the stamps being brought into the positions for filling, compression, plastic deformation and ejection by means of rail-like curved tracks during the rotation.
  • these cam tracks are supported by additional low-pressure pieces, low-tension rails and lifting tracks.
  • the die is filled via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix.
  • the pressing pressure on the premix can be individually adjusted via the pressing paths for the upper and lower punches, the pressure being built up by rolling the punch shaft heads past adjustable pressure rollers.
  • Rotary presses can also be equipped with two filling shoes to increase the throughput, with only a semicircle having to be run through to produce a tablet.
  • several filling shoes are arranged one behind the other without the slightly pressed first layer being ejected before further filling.
  • jacket and dot tablets can also be produced in this way, which have an onion-shell-like structure, the top side of the core or the core layers not being covered in the case of the dot tablets and thus remaining visible.
  • Rotary tablet presses can also be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses are over one million tablets per hour.
  • Tableting machines suitable in the context of the present invention are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Hörn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Ro-maco GmbH, Worms.
  • Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (Sl ).
  • the hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkmaschinee are, for example, from the companies Adams Tablettierwerkmaschinee, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Hörn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
  • Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (Sl).
  • the moldings can be manufactured in a predetermined spatial shape and size, whereby they always consist of several phases, ie layers, inclusions or cores and rings. Practically all practical configurations can be considered as the spatial form, for example, the design as a board, the shape of bars or bars, cubes, cuboids and corresponding spatial elements with flat side surfaces, and in particular cylindrical configurations with a circular or oval cross-section. This last embodiment covers the presentation form from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can each be designed as separate individual elements which correspond to the predetermined dosage of the detergents and / or cleaning agents.
  • the portioned compacts can be designed as tablets, in cylindrical or cuboid form, with a diameter / height ratio in the range from about 0.5: 2 to 2: 0.5 is preferred.
  • Commercial hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for the production of such compacts.
  • the spatial shape of another embodiment of the shaped bodies is adapted in its dimensions to the induction chamber of commercial household washing machines, so that the shaped bodies can be metered directly into the induction chamber without metering aid, where they dissolve during the induction process.
  • the detergent tablets can also be used without problems using a metering aid.
  • Another preferred multi-phase molded body that can be produced has a plate-like or plate-like structure with alternating thick long and thin short segments, so that individual segments of this "multi-phase bar" at the predetermined breaking points, which represent the short thin segments, broken off and can be entered into the machine.
  • This principle of the "bar-shaped" shaped body detergent can also be implemented in other geometric shapes, for example vertically standing triangles, which are connected to one another only on one of their sides along the side. For optical reasons, it makes sense to design the triangular base that connects the individual segments as one phase, while the triangle tip forms the second phase. Different coloring of both phases is particularly attractive in this embodiment.
  • the breaking strength of cylindrical shaped bodies can be determined via the measured variable of the diametrical breaking load. This can be determined according to
  • ⁇ stands for diametral fracture stress (DFS) in Pa
  • P is the force in N that leads to the pressure exerted on the molded body that causes the molded body to break
  • D is the molded body diameter in meters and t the height of the moldings.

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

Abstract

L'objet de la présente invention est d'améliorer la perception de parfum, même après la fin d'un programme de lavage lors du lavage de vaisselle à la machine. A cet effet, on prépare des corps moulés de lavage ou de nettoyage à deux phases ou plus constitués de produits de lavage ou de nettoyage sous forme de particules compactées qui contiennent un ou plusieurs polymères, un ou plusieurs adjuvants de lavage, du parfum et éventuellement d'autres constituants de produits de lavage ou de nettoyage. Une phase du corps moulé contient plus de parfum par rapport à son poids que la ou les autres phases) et la phase plus riche en parfum du corps moulé contient plus de polymère(s) par rapport à son poids que la ou les autres phases.
PCT/EP2005/000371 2004-03-09 2005-01-15 Pastilles a plusieurs phases permettant une meilleure perception de parfum WO2005093034A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004011256.8 2004-03-09
DE200410011256 DE102004011256B4 (de) 2004-03-09 2004-03-09 Mehrphasentabletten mit verbesserter Duftwahrnehmung

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EP2187796B2 (fr) † 2007-09-10 2021-03-24 Henkel AG & Co. KGaA Procédé de nettoyage

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DE102005043188A1 (de) * 2005-09-09 2007-03-22 Henkel Kgaa Verbrauchsprodukte mit wechselnden Geruchsbildern
DE102015215135A1 (de) 2015-08-07 2017-02-09 Henkel Ag & Co. Kgaa WC-Stein und WC-Körbchen
DE102016110069A1 (de) * 2016-05-31 2017-11-30 Aloys F. Dornbracht Gmbh & Co. Kg Duschvorrichtung

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WO1999027069A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Pastille de detergent
WO2000052130A1 (fr) * 1999-03-04 2000-09-08 The Procter & Gamble Company Pastilles detergentes
WO2000052127A1 (fr) * 1999-03-03 2000-09-08 Henkel Kommanditgesellschaft Auf Aktien Procede de production de corps moules detergents et nettoyants a phases multiples
DE19925518A1 (de) * 1999-06-04 2000-12-07 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit Parfüm
US6551981B1 (en) * 1998-07-17 2003-04-22 Patrizio Ricci Detergent tablet

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DE19856213A1 (de) * 1998-12-05 2000-06-08 Henkel Kgaa Punkttabelle
DE19948667A1 (de) * 1999-10-08 2001-04-12 Henkel Kgaa Reinigungsmittelkomponente mit doppelkontrollierter Duftfreisetzung
DE10032612A1 (de) * 2000-07-07 2002-02-14 Henkel Kgaa Klarspülmittel II

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WO1999027069A1 (fr) * 1997-11-26 1999-06-03 The Procter & Gamble Company Pastille de detergent
US6551981B1 (en) * 1998-07-17 2003-04-22 Patrizio Ricci Detergent tablet
WO2000052127A1 (fr) * 1999-03-03 2000-09-08 Henkel Kommanditgesellschaft Auf Aktien Procede de production de corps moules detergents et nettoyants a phases multiples
WO2000052130A1 (fr) * 1999-03-04 2000-09-08 The Procter & Gamble Company Pastilles detergentes
DE19925518A1 (de) * 1999-06-04 2000-12-07 Henkel Kgaa Mehrphasige Wasch- und Reinigungsmittelformkörper mit Parfüm

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2187796B2 (fr) † 2007-09-10 2021-03-24 Henkel AG & Co. KGaA Procédé de nettoyage

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DE102004011256A1 (de) 2005-09-29

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