EP1165742B1 - Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux - Google Patents

Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux Download PDF

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Publication number
EP1165742B1
EP1165742B1 EP00916991A EP00916991A EP1165742B1 EP 1165742 B1 EP1165742 B1 EP 1165742B1 EP 00916991 A EP00916991 A EP 00916991A EP 00916991 A EP00916991 A EP 00916991A EP 1165742 B1 EP1165742 B1 EP 1165742B1
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EP
European Patent Office
Prior art keywords
phase
weight
formula
bleach
cleaning composition
Prior art date
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Expired - Lifetime
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EP00916991A
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German (de)
English (en)
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EP1165742A2 (fr
Inventor
Horst-Dieter Speckmann
Monika Böcker
Andreas Lietzmann
Christian Nitsch
Jörg Poethkow
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0086—Laundry 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
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • C11D3/40—Dyes ; Pigments
    • 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

Definitions

  • the present invention relates to detergent tablets which contain so-called nitrile quats as bleach activators.
  • the invention relates to such shaped articles as detergent tablets, detergent tablets, in particular detergent tablets for automatic dishwashing, bleaching tablets or water softener tablets with the said bleach activators.
  • Detergent compositions in the form of shaped articles, in particular tablets, have long been known and broadly described in the prior art, although this form of supply has hitherto had no outstanding importance on the market. This is due to the fact that the offer form of the molded body in addition to a number of advantages also has disadvantages that affect both the production and use as well as consumer acceptance.
  • the main advantages of moldings such as the elimination of the metering of the required amount of product by the consumer, the higher density and thus the reduced packaging and storage costs and a not to be underestimated aesthetic aspect are disadvantages such as the dichotomy between acceptable hardness and sufficiently fast disintegration and Dissolution of the moldings and numerous technological difficulties in the production and Verpakkung relativized.
  • the dichotomy between a sufficiently hard molded body and a sufficiently fast disintegration time is a key problem. Since sufficiently stable, ie shape and break resistant moldings can be produced only by relatively high compression pressures, there is a strong compaction of the molding constituents and a consequent delayed disintegration of the molding in the aqueous liquor and thus to a slow release of the active ingredients in washing or cleaning process.
  • the delayed disintegration of the moldings also has the disadvantage that conventional detergent tablets can not be flushed in via the dispensing chamber of household washing machines, since the tablets do not disintegrate in sufficiently fast time into secondary particles which are small enough from the dispensing chamber into the washing drum to be flushed.
  • Bleaching compositions containing nitrile quat-type bleach activators are described in the prior art.
  • European Patent Application EP 303 520 discloses bleaching compositions containing a peroxide and a peracid precursor containing at least one N + -CH 2 -CN or one N + (CH 2 CN) 2 group .
  • Detergent tablets are not mentioned in this document.
  • European Patent Application EP 458 396 also describes bleaching compositions containing a peroxy bleach and a peracid precursor having at least one N + -CH 2 -CN or N + (CH 2 CN) 2 group . Also in this document neither single nor multi-phase detergent tablets are mentioned.
  • washing and cleaning agent tablets which contain, as bleach activators, nitrile quats and have a high hardness and outstanding disintegration properties.
  • This washing and cleaning agent tablets should also be able to be dosed via the dispenser, without the consumer thereby disadvantages by residues in the dispenser and insufficient detergent in the wash liquor grown.
  • the washing and cleaning performance of the moldings according to the invention should also be exemplary. In particular, the storage stability of the moldings and the preservation of the bleaching performance even with long storage should be ensured.
  • the invention relates to single- or multi-phase detergent tablets made of compacted particulate detergent and cleaner, comprising bleach, bleach activator (s) and optionally further detergent and cleaner ingredients, which are characterized in that the moldings or at least one phase thereof as Bleach activator a cationic nitrile of the formula (I) in which R 1 is -H, -CH 3 , a C 2-24 -alkyl or -alkenyl radical, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 alkyl group, or a substituted alkyl or alkenylaryl radical having a C 1-24 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
  • Inventive moldings can be configured as single or multi-phase.
  • the individual phases of the shaped body can have different roughness forms in the context of the present invention.
  • the simplest realization possibility lies in two-layered or multi-layered tablets, each layer of the shaped article representing one phase.
  • multiphase moldings can be found in the drawings of EP-A-0 055 100 (Jeyes) which describes toilet cleaning blocks.
  • the technically most common spatial form of multiphase moldings is the two-layer or multi-layer tablet. In the context of the present invention it is therefore preferred that the phases of the shaped body have the form of layers. Two-, three- and four-layer tablets are preferred within the scope of the present invention.
  • the pH of a 1% strength by weight aqueous solution can be determined in the context of the present invention by preparing a solution of the molding or the phase which contains the cationic nitrile of the formula (I) in demineralized water.
  • the appropriate amount of the molding or the phase is dissolved or suspended in water and determines the pH by known methods such as indicator papers or combination electrodes. Since certain methods of pH determination are temperature-dependent, the values given in the context of the present invention apply to a temperature of the solution or suspension of 20 ° C.
  • the pH of the 1% strength by weight aqueous solution of the shaped body or the phase containing the nitrile quatate is less than 6.
  • the moldings according to the invention may contain the cationic nitriles of the general formula (I) in varying amounts, the amount depending on the intended use of the moldings. So include detergent tablets and detergent tablets for the Machine dishwashing usually less bleach activator than, for example, bleach tablets, which consist largely of bleach and bleach activator. Detergent tablets and detergent tablets which are preferred for the purposes of the present invention are characterized in that they contain the cationic nitrile of the formula (I) in amounts of from 0.1 to 20% by weight, preferably from 0.25 to 15% by weight, and in particular from 0.5 to 10 wt .-%, each based on the molding weight.
  • the detergent tablets according to the invention contain the cationic nitrile of the formula (I) in coarser form.
  • at least 90% by weight of the particles of the cationic nitrile of the formula (I) have a particle size of more than 0.2 mm.
  • the particles of the cationic nitrile not only to have more than 90% by weight of particles with sizes above 0.2 mm, but also to contain a relatively high proportion of coarser particles.
  • Preferred washing and cleaning agent tablets are characterized in that at least 40% by weight, preferably at least 50% by weight and in particular at least 60% by weight, of the particles of the cationic nitrile of the formula (I) have a particle size above 0.4 mm have.
  • the proportion of particles with sizes above 200 ⁇ m should preferably be more than 90% by weight, based on the total of the particles of the cationic nitrile.
  • the bleach activators used should in particular be free of too fine or dust fractions, that is to say particularly preferably contain no particles smaller than 0.2 mm in diameter.
  • the cationic nitriles are substantially free of particles with sizes below 0.2 mm.
  • substantially free is understood to mean contents of less than 2% by weight, preferably less than 1% by weight and in particular less than 0.5% by weight, in each case based on the totality of the particles.
  • the cationic nitrile of the formula (I) has an average particle size above 400 ⁇ m, preferably above 500 ⁇ m, more preferably above 600 ⁇ m and in particular above 700 ⁇ m.
  • the general formula (I) includes a variety of cationic nitriles useful in the present invention.
  • the detergent tablets according to the invention comprise cationic nitriles in which R 1 represents methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-butyl Tetradecyl, n-hexadecyl or n-octadecyl stands.
  • R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.
  • preferred cationic nitriles of the formula (I) according to the invention are characterized by their radicals R 1 , R 2 and R 3 : R 1 R 2 R 3 -H -CH 3 -CH 3 -H -CH 2 -CH 3 -CH 3 -H -CH 2 -CH 2 -CH 3 -CH 3 -H -CH (CH 3 ) -CH 3 -CH 3 -H -CH 2 -OH -CH 3 -H -CH 2 -CH 2 -OH -CH 3 -H -CH (OH) -CH 3 -CH 3 -H -CH 2 -CH 2 -OH -CH 3 -H -CH 2 -CH (OH) -CH 3 -CH 3
  • 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 - .
  • the detergent tablets according to the invention contain a system for the "activated bleach", ie both bleach and bleach activator, cationic nitriles being used as the latter according to the invention in order to obtain advantageous shaped body properties to obtain.
  • the detergent tablets according to the invention may also contain further bleach activators, which are also described below.
  • the detergent tablets according to the invention preferably contain the cationic nitriles of the general formula (I) as sole or as main bleach activator, ie at least 50% by weight of the total bleach activators contained in the detergent tablets according to the invention are cationic nitriles of the formula ( I).
  • Bleach activators are added to bleach-containing detergents and cleaners to achieve improved bleaching performance when washed at temperatures of 60 ° C and below.
  • bleach activators to be used in addition to the cationic nitrile it is possible in the context of the present invention to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy- 2,5-dihydrofuran.
  • TAED tetraacet
  • bleach catalysts can also be incorporated into the moldings.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or - carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
  • bleach-enhancing active ingredient combinations obtained by intimately mixing a water-soluble salt of a divalent transition metal can be selected from cobalt, iron, copper and ruthenium and mixtures thereof, a water-soluble ammonium salt and optionally a peroxygen-based oxidizing agent and inert carrier material are available, can be used as bleach catalysts in the present invention. If bleach catalysts are used in the context of the present invention, the abovementioned particle size restrictions also apply to them.
  • a bleach activator particularly preferably used in addition to the cationic nitrile of formula (I) is N, N, N ', N'-tetraacetylethylenediamine, which is widely used in detergents and cleaners. Accordingly, preferred detergent tablets are characterized in that they contain as bleach activators a cationic nitrile of the formula (I) and tetraacetylethylenediamine (TAED).
  • the weight ratios of "nitrile quat” to TAED are preferably in the range of 1: 2 to 10: 1. Particularly preferred in such combinations are 1/3 to 2/3 of the total amount of bleach activator cationic nitrile of the formula (I).
  • the detergent tablets according to the invention contain the bleach activator (s) in amounts of from 0.5 to 30% by weight, preferably from 1 to 20% by weight and in particular from 2 to 15% by weight, based in each case on the entire washing and cleaning agent shaped body, reference being made to the above quantities for the cationic nitrile.
  • bleach activators may vary.
  • bleach activator levels between 0.5 and 10 wt .-%, preferably between 2 and 8 wt .-% and in particular between 4 and 7 wt .-% usual
  • bleach tablets quite higher levels for example between 5 and 30 wt .-%, preferably between 7.5 and 25 wt .-% and in particular between 10 and 20 wt .-% may have.
  • the skilled person is not limited in its formulation freedom and can in this way stronger or weaker bleaching detergent tablets, detergent tablets or bleach tablets by varying the levels of bleach activator and bleach.
  • the bleach activator (s) serve in the detergent tablets according to the invention to activate the bleach or bleach at lower washing or cleaning temperatures and thus to ensure a high bleaching performance even at low temperatures.
  • a bleaching agent sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • bleaching agents Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the tablets.
  • bleaching agents from the group of organic bleaching agents.
  • Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
  • Chlorinating or bromine-releasing substances can also be used as bleaching agents in machine dishwashing moldings.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • sodium percarbonate is the preferred bleaching agent to be used.
  • sodium percarbonate is a non-specific term used for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonate) but hydrogen peroxide adducts of sodium carbonate.
  • the commodity has the average composition 2 Na 2 CO 3 .3 H 2 O 2 and is therefore not peroxycarbonate.
  • Sodium percarbonate forms a white, water-soluble powder with a density of 2.14 gcm -3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.
  • the industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process).
  • aqueous solutions of sodium carbonate and hydrogen peroxide, Kristallisierysstoff (for example, polyphosphates, polyacrylates) and stabilizers are combined and the sodium percarbonate by salting-out agent (mainly sodium chloride) (for example, Mg 2+ ions) like.
  • the precipitated salt which still contains 5 to 12 wt .-% mother liquor, is then removed by centrifugation and dried in fluid bed dryers at 90 ° C.
  • the bulk density of the finished product may vary between 800 and 1200 g / l depending on the manufacturing process.
  • the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature. In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.
  • the detergent tablets according to the invention may be monophasic, i. be pressed from a premix to a homogeneous molding.
  • two-phase or multi-phase detergent tablets are preferred in which one phase contains the cationic nitrile of the formula (I) in amounts of 2.5% by weight, preferably 5% by weight and in particular 7 5% by weight, based in each case on the weight of the phase, while the other phase (s) is / are preferably free of the cationic nitrile of the formula (I) and in particular free of all bleach activators.
  • an increased content of certain ingredients, in particular bleach activators can be achieved in a single phase if the content of this ingredient in the other phase (s) is correspondingly reduced without the Total content of the shaped body of this active substance varies.
  • Multiphase moldings have the advantage over single-phase moldings that the pH criterion according to the invention can be realized more easily and universally in one phase than for the entire molding. Due to the low pH that the phase should have after dissolution in water, is a use of higher alkaline raw materials not possible in unlimited quantities, or to avoid according to the invention.
  • an addition of acidifying agents is required in order to have the cationic nitriles of the formula (I) present in the weakly alkaline to slightly acidic medium desired according to the invention.
  • alkaline raw materials that can not be dispensed with are to be incorporated into the compositions, a single-phase tablet would require the use of high amounts of acidifying agent.
  • phase split it is possible to realize both the stabilization of the cationic nitrile advantageous according to the invention and the use of alkaline raw materials, in that the alkaline raw materials such as carbonates, phosphates, silicates, etc. are present in the phase (s) free of the cationic nitrile of the formula (I) are.
  • Delayed release can be achieved, for example, by coating particles or the entire phase, while accelerated release can be achieved, for example, by adding disintegration aids to a phase.
  • accelerated release can be achieved, for example, by adding disintegration aids to a phase.
  • the delayed release of the cationic nitrile of the formula (I) can be realized. If in this case the resolution of the other phase (s) accelerated in relation to the nitrile-containing phase should yield a high pH, this must be compensated by acidifying agent in the nitrile-containing phase, if it is desired that the nitrile should be released in the neutral to slightly acidic medium.
  • the separation of the molding in two or more phases can also be used to separate incompatible ingredients.
  • Two- or multi-phase detergent tablets in which one phase contains the cationic nitrile of formula (I) while another phase contains the total amount of bleach contained in the tablets are preferred in the present invention.
  • bleaching agents and the cationic nitrile of the formula (I) are used, it is also preferable to separate certain ingredients from each other.
  • two- or more-phase detergent tablets are preferred which contain the cationic nitrile of formula (I), bleaching agents and enzymes, which enzymes do not co-incipient in one phase Bleaching agent and the cationic nitrile are included.
  • two- or more-phase detergent tablets which contain the cationic nitrile of formula (I), bleach and silver protectants, the silver protectant not being in phase together with the bleach and cationic nitrile is included.
  • the detergent tablets according to the invention may contain further ingredients whose amounts are determined by the intended use of the tablets.
  • substances from the groups of surfactants, builders and polymers are suitable for use in the detergent tablets according to the invention. It will also be difficult for the person skilled in the art to select the individual components and their quantitative contents.
  • a universal detergent tablet will contain higher levels of surfactant (s), while a bleach tablet may even be dispensed with altogether.
  • the amount of builder (s) used will vary according to the intended use.
  • all builders commonly used in detergents and cleaners may be present, in particular zeolites, silicates, carbonates, organic co-builders and, where there are no ecological prejudices against their use, also the phosphates.
  • Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • Such crystalline sheet silicates are described, for example, in European Patent Application EP-A-0 164 514 .
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
  • amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
  • the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
  • the term "amorphous” is also understood to mean "X-ray amorphous”.
  • the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • Zeolite P is zeolite MAP® (commercial product the company Crosfield) particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 ⁇ (3.5-5.5) H 2 O. can be described.
  • the zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • the alkali metal phosphates with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, in Water very easily soluble powders which lose the water of crystallization on heating and at 200 ° C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in Natiumtrimetaphosphat (Na 3 P 3 O 9 ) and Maddrellsches Salt (see below), go over.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • Sodium potassium tripolyphosphates which are also usable in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • Particularly suitable organic co-builders in the detergent tablets according to the invention are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of washing or Detergents.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,
  • copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are described, for example, in European Patent Applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and International Patent Applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 .
  • an oxidized oligosaccharide according to the German patent application DE-A-196 00 018.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such co-builders are described, for example, in International Patent Application WO 95/20029 .
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Aminoallcanphosphonate preferably come Ethylenendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, eg.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the amount of builder is usually between 10 and 70 wt.%, Preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%.
  • the amount of buildem used is dependent on the intended use, so that bleach tablets may have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and especially between 30 and 55% by weight. ), for example, detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-%, in particular between 17.5 and 37.5 wt .-%).
  • Preferred detergent tablets also contain one or more surfactants.
  • anionic, nonionic, cationic and / or amphoteric surfactants or mixtures thereof may be used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants.
  • the total surfactant content of the molded articles is from 5 to 60% by weight, based on the weight of the molded article, surfactant contents of more than 15% by weight being preferred in the case of detergent tablets, and detergent tablets for automatic dishwashing usually less than 3 wt .-% surfactant.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration.
  • alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • EO ethylene oxide
  • Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.
  • Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are particularly soaps into consideration.
  • Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methylvetzwe costume radicals in the mixture may contain, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are
  • alkoxylated preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are
  • JP 58/217598 are described or preferably after in the international Patent Application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (II) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1-4 alkyl or phenyl radicals are preferred and [Z] is a linear Polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides according to the teaching of international application WO-A-95/07331, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • detergent tablets which contain anionic (s) and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight. % and in particular above 10 wt .-%, each based on the molding weight, have.
  • anionic (s) and / or nonionic surfactant (s) and total surfactant contents above 2.5% by weight, preferably above 5% by weight. % and in particular above 10 wt .-%, each based on the molding weight, have.
  • application-related advantages can result from certain proportions in which the individual classes of surfactants are used.
  • washing and cleaning agent tablets are particularly preferred in which the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
  • anionic surfactants Similar to the nonionic surfactants, the omission of anionic surfactants from individual or all phases may result in washing and cleaning agent tablets which are more suitable for certain fields of application. It is therefore within the scope of the present invention also possible to use detergent tablets in which at least one phase of the tablets is free of anionic surfactants.
  • excipients are understood to mean excipients which are suitable for rapid disintegration of tablets in water or gastric juice and for the release of the drugs in resorbable form.
  • disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used.
  • Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
  • Preferred detergent tablets contain from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, of one or more disintegration aids, in each case based on the weight of the tablet.
  • Preferred disintegrating agents in the context of the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning agent tablets contain such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%.
  • Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
  • Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
  • Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
  • Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
  • Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
  • the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
  • the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
  • the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of
  • the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted.
  • Detergents and cleaning agent tablets which contain disintegrating agents in granular or optionally cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO-A-98/40463 (Henkel). described. These writings are also details to Production of granulated, compacted or cogranulated cellulose explosives to remove.
  • the particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.
  • the above-mentioned coarser disintegration aids based on cellulose described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
  • microcrystalline cellulose can be used as a further disintegrating agent based on cellulose or as a component of this component.
  • This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact.
  • Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 ⁇ m and can be compacted, for example, into granules having an average particle size of 200 ⁇ m.
  • single- or multi-phase detergent tablets are additionally a disintegration assistant, preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molding weight.
  • a disintegration assistant preferably a disintegration assistant based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably 3 to 7 wt .-% and in particular from 4 to 6 wt .-%, each based on the molding weight.
  • the detergent tablets according to the invention may contain one or more substances from the group of builders, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents , optical brighteners, grayness inhibitors, Color transfer inhibitors and corrosion inhibitors. These substances will be described below.
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus cinereus and Humicola insolens
  • enzymatically-derived variants derived from their genetically modified variants e.g., Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt%, preferably 0.5 to about 4.5 wt%.
  • detergent tablets for automatic dishwashing come as enzymes in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glykosylhydrolasen and mixtures of said enzymes in question. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. For bleaching and oxidoreductases can be used.
  • Bacillus subtilis Bacillus subtilis
  • Bacillus licheniformis Bacillus licheniformis
  • Streptomyceus griseus Streptomyceus griseus
  • Coprinus cinereus and Humicola insolens
  • enzymatically-derived variants derived from their genetically modified variants e.g., Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can also be, for example, about 4.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-% amount.
  • Detergent shaped bodies according to the invention for machine dishwashing can contain corrosion inhibitors for protecting the items to be washed or the machine, with particular silver protectants in the area of automatic dishwashing being particularly special Have meaning. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • the detergent tablets may also contain components which positively influence the oil and grease washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component.
  • the preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic Cellulose ethers, as well as known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.
  • the shaped bodies may contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • Dyes and fragrances are added to the detergent tablets according to the invention in order to improve the aesthetic impression of the products and to provide the consumer with a visual and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
  • the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, ⁇ -isomethylionone and Methylcedrylketon to the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol; the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the content of the detergent tablets according to the invention is usually less than 0.01% by weight of dyes, while fragrances may account for up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • Cyclodextrins for example, have proven useful as such carrier materials, wherein the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents can be dyed with suitable dyes.
  • Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers or dishes, so as not to stain them.
  • washing and cleaning active moldings is done by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • the mixture to be tableted is compressed directly, ie without preceding granulation.
  • the advantages of this so-called Maistablett ist are their simple and cost-effective application, since no further process steps and consequently no other systems are needed.
  • these advantages are also faced with disadvantages.
  • a powder mixture, which is to be tabletted directly have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die.
  • washing and cleaning agent tablets are based on pulverulent components ("primary particles") which are agglomerated or granulated by suitable processes to form secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting.
  • Another object of the present invention is a process for the preparation of single- or multi-phase detergent tablets by molding one or more particulate premixes in a conventional manner, which is characterized in that the premix for the entire molding or for at least one of the phases is a cationic nitrile of the formula (I) contains, in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br , -OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -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
  • % aqueous solution of the premix concerned is less than 7. If single-phase detergent tablets are prepared, the entire premix must comply with the said pH criterion. In the production of multiphase moldings, by juxtaposing or pressing each other different Vorgemische be obtained, only the premix containing the cationic nitrile of formula (I), in 1 wt .-% aqueous solution has a pH below 7.
  • Preferred embodiments of the method according to the invention can be seen analogously to the detergent tablets according to the invention.
  • processes in which the pH of a 1% strength by weight aqueous solution of the premix for the entire molding or for the phase which contains the cationic nitrile of the formula (I) is below 6 are preferred according to the invention.
  • the pH is more preferably within a narrower range, so that processes in which the pH of a 1 wt .-% aqueous solution of the premix for the entire molding or for the phase containing the cationic Contains nitrile of formula (I), less than 6.5, preferably less than 6.0, more preferably less than 5.5 and in particular less than 5.0, according to the invention further preferred.
  • contents of the pre-mixture of cationic nitrile of 0.25 to 15 and especially from 0.5 to 10 wt .-%, each based on the premix, are preferred.
  • the particle sizes of the cationic nitrile analogously applies the above.
  • Particularly preferred are process variants in which the cationic nitrile of the formula (I) a average particle size above 400 microns, preferably above 500 microns, more preferably above 600 microns and in particular above 700 microns.
  • the premix comprises as cationic nitrile (CH 3 ) 3 N (+) CH 2 -CN X - , where X - is an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p- Toluene sulfonate (tosylate) or xylene sulfonate is selected.
  • preferred detergent tablets are obtained by compressing a particulate premix of at least one surfactant-containing granulate and at least one subsequently admixed pulverulent component.
  • the preparation of the surfactant-containing granules can be carried out by conventional industrial granulation processes such as compaction, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is advantageous for the later detergent tablets if the premix to be compressed has a bulk density which approximates the conventional compact detergent.
  • the particulate premix additionally contains surfactant-containing granules and has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
  • the surfactant-containing granules in preferred process variants also satisfy certain particle size criteria.
  • preferred processes according to the invention are those in which the surfactant-containing granules have 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 surfactant granules preferably also contain excipients, which more preferably originate from the group of builders. Particularly advantageous processes are therefore characterized in that the surfactant-containing granules contain anionic and / or nonionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
  • the premix Before the particulate premix is compressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premixture (storage, compression) and the final detergent and cleaning products.
  • Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used.
  • the premix is "powdered” with finely divided zeolite, with faujasite-type zeolites being preferred.
  • the term "faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structural group 4 (cf.
  • detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be tabletted.
  • the premixes to be compressed may additionally contain one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, Fluorescers, dyes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, color transfer inhibitors and corrosion inhibitors. These substances have been described above.
  • the production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the molding is finally determined, since the compacts due to physical Processes (re-stretching, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used to build up pressure, and the lower punch moves during the pressing on the upper punch, while the upper punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary depending on the type of a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individualized via the pressing paths for upper and lower punches adjustable, wherein the pressure build-up occurs by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drin to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling. By suitable process control are on this.
  • coat and point tablets which have an onion-shell-like construction, wherein in the case of the point tablets the top side of the core or the core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, with upper and lower punches being designed to be rotatable if possible should. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Tableting machines suitable for the purposes of the present invention are obtainable, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), 1st Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment detects the presentation form of the tablet to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent.
  • the formation of the portioned compacts as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of Ein Albanykammcr of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the Ein effetvorgangs.
  • a use of the detergent tablets via a dosing is easily possible and preferred in the context of the present invention.
  • Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered.
  • This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.
  • the various components are not pressed into a single tablet, but that moldings are obtained, the several layers, So at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution.
  • the layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) are reached through the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body
  • outermost layers are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N which results in the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters and t the height of the moldings.

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Claims (19)

  1. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases en agent de lavage et de nettoyage sous forme de particules, compacté, comprenant un agent de blanchiment, un ou des activateurs de blanchiment ainsi que le cas échéant d'autres constituants d'agents de lavage et de nettoyage caractérisés en ce que les corps façonnés ou au moins une phase de ceux-ci contiennent/contient comme activateur de blanchiment un nitrile cationique de formule (I)
    Figure imgb0013
    dans laquelle R1 représente -H, -CH3, un radical alkyle ou alcényle en C2 à C24, un radical alkyle ou alcényle en C2 à C24 substitué, présentant au moins un substituant du groupe comprenant -Cl, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle présentant un groupe alkyle en C1 à C24 ou un radical alkylaryle ou alcénylaryle substitué, présentant un groupe alkyle en C1 à C24 et au moins un autre substituant sur le cycle aromatique, R2 et R3 sont choisis, indépendamment l'un de l'autre parmi-CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH avec n = 1, 2, 3, 4, 5 ou 6 et X représente un anion, le pH de la solution aqueuse à 1% en poids du corps façonné ou de la phase qui contient le nitrile quaternaire étant inférieur à 7.
  2. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon la revendication 1, caractérisés en ce que le pH de la solution aqueuse à 1 % en poids du corps façonné ou de la phase qui contient le nitrile quaternaire est inférieur à 6.
  3. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon l'une quelconque des revendications 1 ou 2, caractérisés en ce qu'ils contiennent le nitrile cationique de formule (I) en des quantités de 0,1 à 20% en poids, de préférence de 0,25 à 15% en poids et en particulier de 0,5 à 10% en poids, à chaque fois par rapport au poids des corps façonnés.
  4. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon l'une quelconque des revendications 1 à 3, caractérisés en ce qu'ils contiennent comme nitrile cationique de formule (I) un nitrile cationique de formule (la)
    Figure imgb0014
    dans laquelle R4, R5 et R6 sont choisis indépendamment l'un de l'autre parmi -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, R4 pouvant en outre également représenter -H et X représente un anion, où, de préférence R5 = R6 = -CH3 et en particulier R4 = R5 = R6 = -CH3.
  5. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon l'une quelconque des revendications 1 à 4, caractérisés en ce qu'ils contiennent comme nitrile cationique (CH3)3N(+)CH2-CN X-, où X- représente un anion, qui est choisi dans le groupe chlorure, bromure, iodure, hydrogénosulfate, méthosulfate, p-toluènesulfonate (tosylate) ou xylènesulfonate.
  6. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon l'une quelconque des revendications 1 à 5, caractérisés en ce qu'ils contiennent comme activateurs de blanchiment un nitrile cationique de formule (I) et de la tétraacétyléthylènediamine (TAED).
  7. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon l'une quelconque des revendications 1 à 6, caractérisés en ce qu'ils contiennent en outre un adjuvant de désintégration, de préférence un adjuvant de désintégration à base de cellulose, de préférence sous forme granulée, co-granulée ou compactée, en des quantités de 0,5 à 10% en poids, de préférence de 3 à 7% en poids et en particulier de 4 à 6% en poids, à chaque fois par rapport au poids des corps façonnés.
  8. Corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases selon l'une quelconque des revendications 1 à 6, caractérisés en ce qu'ils contiennent un ou des agents tensioactifs anioniques et/ou non ioniques et présentent des teneurs totales en agents tensioactifs supérieures à 2,5% en poids, de préférence supérieures à 5% en poids et en particulier supérieures à 10% en poids, à chaque fois par rapport au poids des corps façonnés.
  9. Corps façonnés d'agent de lavage et de nettoyage à deux phases ou plus selon l'une quelconque des revendications 1 à 8 caractérisés en ce qu'une phase contient le nitrile cationique de formule (I) en des quantités de 2,5% en poids, de préférence de 5% en poids et en particulier de 7,5% en poids, à chaque fois par rapport au poids de la phase, alors que la ou les autres phases sont de préférence exemptes du nitrile cationique de formule (I) et en particulier exemptes de tous les activateurs de blanchiment.
  10. Corps façonnés d'agent de lavage et de nettoyage à deux phases ou plus selon la revendication 9, caractérisés en ce qu'une phase contient le nitrile cationique de formule (I) alors qu'une autre phase contient la quantité totale de l'agent de blanchiment contenu dans les corps façonnés.
  11. Corps façonnés d'agent de lavage et de nettoyage à deux phases ou plus selon l'une quelconque des revendications 9 ou 10, caractérisés en ce qu'ils contiennent le nitrile cationique de formule (I), un agent de blanchiment et des enzymes, les enzymes n'étant pas contenues dans une phase, ensemble avec l'agent de blanchiment et le nitrile cationique.
  12. Corps façonnés d'agent de lavage et de nettoyage à deux phases ou plus selon l'une quelconque des revendications 9 à 11, caractérisés en ce qu'ils contiennent le nitrile cationique de formule (I), un agent de blanchiment et un agent de protection de l'argent, l'agent de protection de l'argent n'étant pas contenu dans une phase, ensemble avec l'agent de blanchiment et le nitrile cationique.
  13. Procédé pour la préparation de corps façonnés d'agent de lavage et de nettoyage à une ou plusieurs phases par la compression avec façonnage d'un ou de plusieurs prémélanges sous forme de particules de manière connue en soi, caractérisé en ce que le prémélange contient, pour l'ensemble du corps façonné ou pour au moins une des phases, un nitrile cationique de formule (I)
    Figure imgb0015
    dans laquelle R1 représente -H, -CH3, un radical alkyle ou alcényle en C2 à C24, un radical alkyle ou alcényle en C2 à C24 substitué, présentant au moins un substituant du groupe comprenant -Cl, -Br, -OH, -NH2, -CN, un radical alkylaryle ou alcénylaryle présentant un groupe alkyle en C1 à C24 ou un radical alkylaryle ou alcénylaryle substitué, présentant un groupe alkyle en C1 à C24 et au moins un autre substituant sur le cycle aromatique, R2 et R3 sont choisis, indépendamment l'un de l'autre parmi-CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH avec n = 1, 2, 3, 4, 5 ou 6 et X représente un anion, le pH d'une solution aqueuse à 1% en poids du prémélange respectif étant inférieur à 7.
  14. Procédé selon la revendication 13, caractérisé en ce que le pH d'une solution aqueuse à 1% en poids du prémélange pour l'ensemble du corps façonné ou pour la phase qui contient le nitrile cationique de formule (I) est inférieur à 6.
  15. Procédé selon l'une quelconque des revendications 13 ou 14, caractérisé en ce que le prémélange contient comme nitrile cationique (CH3)3N(+)CH2-CN X- où X- représente un anion qui est choisi dans le groupe chlorure, bromure, iodure, hydrogénosulfate, méthosulfate, p-toluènesulfonate (tosylate) ou xylènesulfonate.
  16. Procédé selon l'une quelconque des revendications 13 à 15, caractérisé en ce que le prémélange sous forme de particules contient en outre un ou des granulats contenant un ou des agents tensioactifs et présente une densité apparente d'au moins 500 g/l, de préférence d'au moins 600 g/l et en particulier d'au moins 700 g/l.
  17. Procédé selon la revendication 16, caractérisé en ce que le granulat contenant un ou des agents tensioactifs présente des grosseurs de particules entre 100 et 2000 µm, de préférence entre 200 et 1800 µm, de manière particulièrement préférée entre 400 et 1600 µm et en particulier entre 600 et 1400 µm.
  18. Procédé selon l'une quelconque des revendications 16 ou 17, caractérisé en ce que le granulat contenant un ou des agents tensioactifs contient des agents tensioactifs anioniques et/ou non ioniques ainsi que des adjuvants et présente des teneurs totales en agent(s) tensioactif(s) d'au moins 10% en poids, de préférence d'au moins 20% en poids et en particulier d'au moins 25% en poids.
  19. Procédé selon l'une quelconque des revendications 13 à 18, caractérisé en ce que le prémélange sous forme de particules contient en outre une ou plusieurs substances du groupe comprenant les agents de blanchiment, les activateurs de blanchiment, les enzymes, les agents de réglage du pH, les parfums, les supports de parfum, les agents de fluorescence, les colorants, les inhibiteurs de mousse, les huiles de silicone, les agents d'anti-redépôt, les azurants optiques, les inhibiteurs du jaunissement, les inhibiteurs de transfert de couleur et les inhibiteurs de corrosion.
EP00916991A 1999-03-31 2000-03-22 Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux Expired - Lifetime EP1165742B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19914812 1999-03-31
DE19914812A DE19914812A1 (de) 1999-03-31 1999-03-31 Ein- oder mehrphasige Wasch- und Reinigungsmittelformkörper mit speziellen Bleichaktivatoren
PCT/EP2000/002533 WO2000060035A2 (fr) 1999-03-31 2000-03-22 Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux

Publications (2)

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EP1165742A2 EP1165742A2 (fr) 2002-01-02
EP1165742B1 true EP1165742B1 (fr) 2006-01-25

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EP00916991A Expired - Lifetime EP1165742B1 (fr) 1999-03-31 2000-03-22 Corps moules d'agents de lavage et de nettoyage monophases ou multiphases comportant des activateurs de blanchiment speciaux

Country Status (8)

Country Link
EP (1) EP1165742B1 (fr)
JP (1) JP2002541302A (fr)
KR (1) KR20010110469A (fr)
AU (1) AU3814200A (fr)
CA (1) CA2303638A1 (fr)
DE (2) DE19914812A1 (fr)
ES (1) ES2255995T3 (fr)
WO (1) WO2000060035A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US10870818B2 (en) 2018-06-15 2020-12-22 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid
US11053459B2 (en) 2015-04-03 2021-07-06 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MXPA05006578A (es) * 2002-12-18 2005-08-16 Procter & Gamble Activador organico.
EP1433839B2 (fr) * 2002-12-24 2015-04-01 Dalli-Werke GmbH & Co. KG Compositions de lavage et nettoyage optimisées pour un effet amélioré de blanchiment à basse température
DE10314441A1 (de) * 2003-03-31 2004-10-21 Henkel Kgaa Bleichaktivator-Compounds
JP7252601B2 (ja) 2019-02-08 2023-04-05 株式会社ニイタカ 固形洗浄剤組成物、カートリッジ洗浄剤、洗浄方法、及び、微生物の除菌方法又は菌叢凝塊の除去方法

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GB9011618D0 (en) * 1990-05-24 1990-07-11 Unilever Plc Bleaching composition
GB9012001D0 (en) * 1990-05-30 1990-07-18 Unilever Plc Bleaching composition
GB9022724D0 (en) * 1990-10-19 1990-12-05 Unilever Plc Detergent compositions
ES2155613T3 (es) * 1995-07-13 2001-05-16 Reckitt Benckiser Nv Producto en forma de tableta para lavavajillas.
DE19758183A1 (de) * 1997-12-30 1999-07-01 Henkel Kgaa Waschaktiver Formkörper mit spezifischer Oberfläche
KR100630289B1 (ko) * 1998-12-15 2006-09-29 헨켈 코만디트게젤샤프트 아우프 악티엔 고형 세제 중의 표백 활성제로서의 입상 아세토니트릴유도체

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9783766B2 (en) 2015-04-03 2017-10-10 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US10557106B2 (en) 2015-04-03 2020-02-11 Ecolab Usa Inc. Enhanced peroxygen stability using anionic surfactant in TAED-containing peroxygen solid
US11053459B2 (en) 2015-04-03 2021-07-06 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US11731889B2 (en) 2015-04-03 2023-08-22 Ecolab Usa Inc. Enhanced peroxygen stability in multi-dispense TAED-containing peroxygen solid
US10870818B2 (en) 2018-06-15 2020-12-22 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid
US11193093B2 (en) 2018-06-15 2021-12-07 Ecolab Usa Inc. Enhanced peroxygen stability using fatty acid in bleach activating agent containing peroxygen solid

Also Published As

Publication number Publication date
KR20010110469A (ko) 2001-12-13
WO2000060035A3 (fr) 2001-01-04
DE50012128D1 (de) 2006-04-13
EP1165742A2 (fr) 2002-01-02
AU3814200A (en) 2000-10-23
JP2002541302A (ja) 2002-12-03
CA2303638A1 (fr) 2000-09-30
DE19914812A1 (de) 2000-10-05
ES2255995T3 (es) 2006-07-16
WO2000060035A2 (fr) 2000-10-12

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