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EP3545067B1 - Sachet contenant un mélange activateur de blanchiment/agent complexant - Google Patents

Sachet contenant un mélange activateur de blanchiment/agent complexant Download PDF

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Publication number
EP3545067B1
EP3545067B1 EP17805165.2A EP17805165A EP3545067B1 EP 3545067 B1 EP3545067 B1 EP 3545067B1 EP 17805165 A EP17805165 A EP 17805165A EP 3545067 B1 EP3545067 B1 EP 3545067B1
Authority
EP
European Patent Office
Prior art keywords
weight
acid
detergent
water
cleaning composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP17805165.2A
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German (de)
English (en)
Other versions
EP3545067A1 (fr
Inventor
Matthias Sunder
Frank Meier
Sheila Edwards
Ulrich Pegelow
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Publication of EP3545067A1 publication Critical patent/EP3545067A1/fr
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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
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid 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
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/361—Phosphonates, phosphinates or phosphonites
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen
    • 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
    • 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
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • 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
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to multiphase detergents and cleaning agents comprising at least one liquid, low-water phase and at least one solid, powdery or granular phase and containing at least one particle containing at least one bleach activator compounded with at least one complexing agent.
  • the present invention is also directed to the use of such agents, to washing and cleaning methods in which such agents are used, and to corresponding washing methods.
  • Detergents and cleaning agents are available to the consumer in a large number of forms.
  • flowable and in particular liquid to gel-like agents have recently become increasingly important.
  • consumers appreciate the quick solubility and the associated quick availability of the ingredients in the washing and cleaning liquor, especially in short programs and at low temperatures.
  • compositions in which the water content in particular is reduced compared to conventional compositions, are increasing.
  • Compositions whose water content is as low as possible, for example less than 20% by weight, are therefore particularly desirable for the consumer.
  • a high washing and cleaning performance is achieved primarily through a combination of liquid and powdery phases in so-called multi-chamber portion bags.
  • a high washing and cleaning performance is also achieved through a combination of gel-like or pasty phases with powder-like phases in so-called single-chamber portion bags.
  • the active bleaching substance of the washing or cleaning agent is in the contain powdery phase.
  • a chemical reaction of the different phases can occur, which in particular includes the degradation of the active bleaching substances. Specifically, this means that the active bleaching substances are activated, which then react with the water-soluble film and other ingredients, such as fragrances and dyes, that are contained in the liquid phase.
  • bleach activators compounded with complexing agents cause chemical stabilization of the entire sachet in the powder phase of a multiphase detergent or cleaning agent.
  • This stabilizing effect is reflected in the fact that the water-soluble film no longer decomposes, nor does the color or odor of the agent change, even after prolonged storage.
  • agents of this type have improved washing or cleaning performance, particularly when the agent is stored for a long period of time.
  • the present invention is directed towards a multi-phase detergent or cleaning agent, comprising at least one liquid, low-water phase and at least one solid, powdery or granular phase, characterized in that the at least one solid, powdery or granular phase contains at least one bleach activator contains, wherein the bleach activator is compounded with at least one complexing agent.
  • the present invention is directed to the use of the agent for washing textiles or cleaning hard surfaces, in particular for machine cleaning of dishes.
  • the present invention also relates to a method for cleaning textiles or hard surfaces, in particular for machine cleaning of dishes, characterized in that a detergent or cleaning agent according to the invention is used.
  • At least one refers to 1 or more, for example 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.
  • phase refers to a part of the agent that differs from another phase of the agent according to the invention, which contains at least two phases, by various features, for example ingredients, physical properties, external appearance, etc.
  • the phases differ in particular with regard to physical properties and here in particular by the state of aggregation, with one phase preferably being liquid under standard conditions (1013 mbar, 20° C.) and the other preferably being solid.
  • standard conditions 1013 mbar, 20° C.
  • the agent according to the invention comprises at least two different phases. Both the at least one first phase and the at least one second phase are described below.
  • each additional phase can correspond either to the at least one first phase, as defined herein, or to the at least one second phase, as defined herein.
  • the compositions of the respective phases that correspond to one another can differ to the extent that the respective definitions given below, both of the at least one first phase and of the at least one second phase, allow it.
  • it may be a three-phase dishwashing detergent having two phases corresponding to the first phase as defined herein and one phase corresponding to the second phase as defined herein.
  • the various phases are packaged in the means described in such a way that they are spatially are separated from each other, are for example in different chambers of a multi-chamber portion bag.
  • low in water means that the composition characterized in this way contains 1 to 20% by weight water, 1 to 15% by weight water, 5-15% by weight water or less than 15% by weight. % or less than 10% by weight of water.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • Liquid as used herein in relation to one of the at least two different phases of the washing or cleaning agent according to the invention, includes all free-flowing compositions and in particular also includes gels and pasty compositions. In particular, the term also includes non-Newtonian liquids that have a yield point.
  • Solid as used herein in relation to one of the at least two different phases of the washing or cleaning agent according to the invention includes all types of free-flowing powders, granules, extrudates, etc., in particular those with a bulk density of 300 g / l to 1200 g /l, in particular 500 g/l to 900 g/l or 600 g/l to 850 g/l.
  • Water-soluble refers to the property of a substance or object that it has a solubility in distilled water, measured at 25°C, of at least 0.1 g/L.
  • the substance and object have a solubility of at least 0.1, at least 1, at least 5, at least 10, at least 50, at least 100, at least 500 g/l, measured at 25 °C.
  • Water-disintegrable means that the substance or object breaks down into small parts within 15, preferably within 10 minutes on contact with water at temperatures between 15 and 60°C and in particular between 20 and 45°C.
  • substantially refers to the respective main characteristic of the substance or article. That's how it can be, im
  • the material composition of an object for example a composition, which contains the respective named substance as the main component.
  • the term means that the main component of the particles is at least one bleach activator as defined herein.
  • the composition (of the particles) can also comprise one or more further components.
  • the respective main component is, in various embodiments, with not less than 50% by weight, preferably not less than 55% by weight, 60% by weight, 65% by weight, 70% by weight. -%, 75%, 80%, 85%, 90% or 95% by weight contained in the composition.
  • it can be a spatial definition of a thing.
  • the particles as described herein which in various embodiments can be, for example, "substantially" spherical, it is thus a question of particles in which the vast majority of the particles are spherical.
  • no less than 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% of the particles are spherical.
  • the present invention relates to a detergent or cleaning agent, in particular a multi-phase detergent or cleaning agent, as defined above.
  • At least one of the phases is a liquid, low-water phase.
  • at least one further phase is a solid, powdery or granular phase.
  • this at least one solid phase is characterized in that it contains at least one bleach activator, the bleach activator being compounded with at least one complexing agent.
  • “compounded” means that the individual particles of the bleach activator are coated/coated with at least one complexing agent.
  • the coating or encapsulation does not have to be complete in relation to the particle surface, but in preferred embodiments the entire surface of the bleach activator particle is coated/encapsulated with the complexing agent.
  • Suitable methods for compounding substances are known in the prior art. Such processes include, but are not limited to, fluid bed granulation processes.
  • the bleach activator is introduced in particle form and then granulated ("compounded") with a solution of the complexing agent, preferably an aqueous solution. In various embodiments, a spray coating method is used for this.
  • the lead activator particles which can have different shapes and sizes, are moved in a fluidized bed and mixed with a liquid (complexing agent solution or suspension) sprayed.
  • a liquid complexing agent solution or suspension
  • the aqueous or organic solvent evaporates and the complexing agent it contains forms the coating layer.
  • Typical particle sizes are 100 micrometers to 3 millimeters.
  • Such a spray coating can be carried out in all fluidized bed systems - typically in batch operation. Continuous processes are also available for some coating applications. It is important to ensure that no liquid bridges form during application in order to avoid unwanted agglomeration.
  • the coating can be done using the top spray, tangential spray, bottom spray (Wurster process) or rotor process.
  • the processes mentioned can be carried out in a single modern fluidized bed system.
  • the compounding can also take place as a spray agglomeration.
  • the bleach activator particles usually very small powdery particles, are moved in the fluidized bed and sprayed with a binder liquid containing the complexing agent.
  • the particles combine to form agglomerates by forming liquid bridges.
  • the spraying process is continued until the desired size of the agglomerates is reached.
  • Typical sizes of the agglomerates range from 100 micrometers to 3 millimeters, while the starting materials can be in microfine form.
  • Suitable fluidized bed systems for the processes mentioned are available, for example, from Glatt GmbH (Binzen, DE). Suitable methods are for example in the German patent application DE 10 2007 051 093 A1 described.
  • the at least one compounded bleach activator is present in an amount in the range from 1% by weight to 20% by weight, preferably 1% by weight to 15% by weight, in particular 1% by weight to 13% by weight in the detergent or cleaning agent, based in each case on the total weight of the detergent or cleaning agent.
  • the at least one complexing agent is a complexing agent, preferably an organic complexing agent, which contains Ca 2+ with a calcium binding capacity mg CaO/g at 20° C. and pH 10 of at least 100, preferably at least 150, more preferably at least 200. more preferably at least 300, most preferably at least 350.
  • the calcium binding capacity is determined by visual turbidity titration with calcium acetate solution and sodium carbonate in the alkaline range and subsequent conversion to calcium binding capacity mg CaO/g.
  • the titration is carried out at 20° C. by adding Ca acetate solution in portions. until turbidity persists, with smaller volume steps being added towards the end of the titration. There is no agitation during the addition of the titrant. The mixture is stirred between the additions and the pH is kept constant with 1 M NaOH. 1 ml used Ca acetate solution corresponds to 25 mg calcium carbonate.
  • the conversion to calcium binding capacity mg CaO/g is then carried out by multiplying the CaCO 3 binding capacity [mg CaCO 3 / g] by 0.560.
  • the at least one complexing agent is selected from phosphonates, aminocarboxylic acid salts and (polymeric) polycarboxylates and their corresponding acids.
  • phosphonates are not subsumed under the phosphates.
  • Aminoalkane and/or hydroxyalkane phosphonates are preferably used as phosphonates.
  • Diethylenetriaminepentamethylenephosphonate (DTPMP), nitrilotris(methylenephosphonic acid) (NTMP), 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), ethylenediaminetetramethylenephosphonate (EDTMP) and their higher homologues are preferably suitable as aminoalkanephosphonates.
  • NTMP nitrilotris(methylenephosphonic acid)
  • PBTC 2-phosphonobutane-1,2,4-tricarboxylic acid
  • ETMP ethylenediaminetetramethylenephosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • the polycarboxylates are the salts, in particular the alkali metal salts, more preferably the sodium salts, of polycarboxylic acids, polycarboxylic acids being understood as meaning those carboxylic acids which have more than one, in particular two to eight acid functions, preferably two to six, in particular two, three , carry four or five acid functions throughout the molecule.
  • Dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids are therefore preferred as polycarboxylic acids.
  • the polycarboxylic acids can also carry other functional groups, such as hydroxyl groups.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids (preferably aldaric acids, for example galactaric acid and glucaric acid) and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid and mixtures of these.
  • Polymeric polycarboxylates include, for example, poly(acrylic acid), poly(alpha-hydroxyacrylic acid), poly(acrylic acid-co-maleic acid), poly(tetramethylene-1,2-dicarboxylic acid), poly(4-methoxytetramethylene-1,2-dicarboxylic acid), and poly (acrylic acid-co-allyl alcohol).
  • the aminocarboxylic acid salts are the salts, especially the alkali metal salts, more preferably the sodium salts, of aminocarboxylic acids.
  • Particularly preferred representatives of this class are methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), aspartic acid diacetate (ASDA), hydroxyethyliminodiacetate (HEIDA), iminodisuccinate (IDS) and ethylenediamine disuccinate (EDDS), particularly preferably MGDA or GLDA.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, produce aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and/or optionally substituted perbenzoic acid. Substances which carry O- and/or N-acyl groups with the number of carbon atoms mentioned and/or optionally substituted benzoyl groups are suitable.
  • 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 acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5- Diacetoxy-2,5-dihydrofuran and enol esters and
  • TAED Hydrophilically substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. According to the invention, TAED is preferably used as the bleach activator. In various embodiments, TAED is preferably used in particular in combination with a percarbonate bleach, preferably sodium percarbonate.
  • the at least one bleach activator is therefore selected from the group consisting of polyacylated alkylenediamines, acylated triazine derivatives, acylated glycolurils, N-acylimides and acylated phenol sulfonates.
  • the at least one complexing agent is selected from the group consisting of DTPMP, HEDP, MGDA or GLDA, very particularly preferably from DTPMP and HEDP, and the at least one complexing agent is most preferably DTPMP.
  • the at least one complexing agent is selected from the group consisting of the sodium salt of DTPMP, HEDP, MGDA or GLDA, most preferably consisting of the sodium salt of DTPMP or HEDP, most preferably the at least one complexing agent is a sodium salt of DTPMP.
  • the at least one bleach activator is TAED.
  • the complexing agent is selected from the group consisting of DTPMP, HEDP, MGDA or GLDA, very particularly preferably from DTPMP and HEDP, most preferably the complexing agent is DTPMP.
  • the coating amount of the at least one complexing agent on the at least one bleach activator is in the range from 5% by weight to 30% by weight, preferably 5 to 25% by weight, in particular 5 to 20% by weight the total weight of the compounded bleach activator.
  • the remainder of the compounded bleach activator consists essentially of the at least one bleach activator.
  • the amount of at least one bleach activator in the compounded bleach activator is therefore 70 to 95% by weight, preferably 75 to 95% by weight, more preferably 80 to 95% by weight, based in each case on the total weight of the particle.
  • the washing or cleaning agent according to the invention preferably contains at least one bleach.
  • a bleaching agent is understood to mean, on the one hand, hydrogen peroxide itself and, on the other hand, any compound which yields hydrogen peroxide in an aqueous medium.
  • Sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and yield H 2 O 2 in water.
  • bleaches that can be used are peroxopyrophosphates, citrate perhydrates and peracid salts or peracids that supply H 2 O 2 , such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide which can be described by the formula H 2 N-CO-NH 2 H 2 O 2 , can also be used.
  • the agents according to the invention can, if desired, also bleach from the group of contain organic bleaching agents, although in principle they can also be used for laundry detergents.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples being the alkylperoxyacids and the arylperoxyacids.
  • Preferred representatives are (a) peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid , Pap), O-carboxyboxyburoxycapronic acid, n-nonylamideopic acid and n-nonylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarbonic acids, such as 1.12-diperoxy carbonic acid, 1,9-diperoxyazelaina, diperoxybacinsa, di Peroxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1 ,4-
  • Suitable chlorine or bromine releasing materials include, for example, N-bromo- and N-chloro-heterocyclic amides, e.g. trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and/or dichloroisocyanuric acid (DICA) and/or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the detergents or cleaning agents can contain 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably 3.5 to 20% by weight and in particular 5 to 15% by weight of bleach, preferably sodium percarbonate, based in each case on the total weight of the detergent or cleaning agent.
  • the amount of bleaching agent in the solid phase, preferably sodium percarbonate can be 5 to 50% by weight, preferably 10 to 40% by weight.
  • the washing or cleaning agent according to the invention also contains one or more of the substances selected from the group consisting of other complexing agents, other bleach activators, bleach catalysts, anionic, nonionic, cationic and amphoteric surfactants, builders, enzymes, enzyme stabilizers, builders, electrolytes, nonaqueous Solvents, pH adjusters, odor absorbers, deodorizing substances, perfume, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, antiredeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, Corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and non-slip agents, softening components and UV absorbers.
  • other complexing agents other bleach activators, bleach catalysts, anionic, nonionic, cationic and amphoteric surfactants, builders, enzymes, enzyme stabilize
  • the washing or cleaning agent according to the invention contains at least one bleach catalyst.
  • the bleach catalysts include, inter alia, sulfonimines and/or bleach-boosting transition metal salts or transition metal complexes.
  • the transition metal compounds in question include, in particular, manganese, iron, cobalt, ruthenium or molybdenum salen complexes and their N-analog compounds, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron , cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, cobalt, iron, copper and ruthenium amine complexes.
  • Bleach-boosting transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and/or Ru, can be used in customary amounts, preferably in an amount of up to 1% by weight, in particular from 0.0025 to 0. 25% by weight and particularly preferably from 0.01 to 0.1% by weight are used, based in each case on the total weight of the detergent or cleaning agent. In special cases, however, more bleach catalyst can also be used.
  • Complexes of manganese in the oxidation state II, III, IV or IV which preferably contain one or more macrocyclic ligand(s) with the donor functions N, NR, PR, O and/or S, are particularly preferably used.
  • Ligands which have nitrogen donor functions are preferably used.
  • bleach catalyst(s) in the agents according to the invention which contain 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN ), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me-TACN) and /or 2-methyl-1,4,7-triazacyclononane (Me/TACN).
  • Me-TACN 1,4,7-trimethyl-1,4,7-triazacyclononane
  • TACN 1,4,7-triazacyclononane
  • TACD 1,5,9-trimethyl-1,5,9-triazacyclododecane
  • Me/Me-TACN 2-methyl-1,4,7-triazacyclononane
  • Me/TACN 2-methyl-1,4,7-triazacyclononane
  • Detergents or cleaning agents which contain at least one bleach catalyst, the bleach catalyst being selected from the group of bleach-boosting transition metal salts and transition metal complexes, preferably the complexes of manganese in oxidation state II, III, IV or IV, the one or more macrocyclic (s) ligand (en) with the donor functions N, NR, PR, O and/or S, particularly preferably the macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7 -triazacyclononane (TACN), 1,5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (Me/Me -TACN) and/or 2-methyl-1,4,7-triazacyclononane (Me/TACN), most preferably the ligands 1,4,7-trimethyl-1,4,7-triazacyclonan
  • the washing or cleaning agent according to the invention contains at least one surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures of the aforementioned.
  • Suitable anionic surfactants are those of the formula (I) R-SO 3 - Y + (I).
  • R represents a linear or branched unsubstituted alkylaryl radical.
  • Y stands for a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations Y + can be selected from NH 4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
  • Alkylaryl refers to organic radicals composed of an alkyl radical and an aromatic radical. Typical examples of such radicals include, but are not limited to, alkylbenzene radicals such as benzyl, butylbenzene radicals, nonylbenzene radicals, decylbenzene radicals, undecylbenzene radicals, dodecylbenzene radicals, tridecylbenzene radicals, and the like.
  • such surfactants are selected from linear or branched alkyl benzene sulfonates of formula A-1 in which R' and R" together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms.
  • R' and R" together contain 9 to 19, preferably 11 to 15 and in particular 11 to 13 carbon atoms.
  • a very particularly preferred representative can be described by the formula A-1a:
  • the compound of formula (I) is preferably the sodium salt of a linear alkyl benzene sulphonate.
  • anionic surfactants are those of the formula (II) R 1 -O-(AO) n -SO 3 - X + (II).
  • R 1 is a linear or branched, substituted or unsubstituted alkyl, aryl or alkylaryl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred.
  • radicals R 1 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety.
  • the index n is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. n is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X is a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations X+ can be selected from NH 4+ , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof .
  • anionic surfactants that can be used are the alkyl sulfates of the formula R2 -O- SO3 - X + (III).
  • R 2 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred.
  • radicals R 2 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • X represents a monovalent cation or the nth part of an n-valent cation, preference being given to the alkali metal ions and including Na + or K + , with Na + being extremely preferred. Further cations X + can be selected from NH 4 + , 1 ⁇ 2 Zn 2+ , 1 ⁇ 2 Mg 2+ , 1 ⁇ 2 Ca 2+ , 1 ⁇ 2 Mn 2+ , and mixtures thereof.
  • the content of anionic surfactants is preferably less than 4% by weight, particularly preferably less than 2% by weight and in particular less than 1% by weight. Dishwashing detergents which do not contain anionic surfactants are particularly preferred.
  • Low-foaming nonionic surfactants are preferably used, in particular alkoxylated, especially ethoxylated, low-foaming nonionic surfactants.
  • the machine dishwashing detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols.
  • R 3 is a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical.
  • Preferred radicals R 2 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, the representatives with an even number of C atoms are preferred.
  • radicals R 3 are derived from C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from C 10 -C 20 oxo alcohols.
  • AO stands for an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably for an ethylene oxide moiety.
  • the index m is an integer from 1 to 50, preferably from 1 to 20 and in particular from 2 to 10. m is very particularly preferably the numbers 2, 3, 4, 5, 6, 7 or 8.
  • nonionic surfactants which can be used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are accordingly alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.
  • Surfactants to be used with preference come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with surfactants with a more complex structure, such as polyoxypropylene/polyoxyethylene/polyoxypropylene ((PO/EO/PO) surfactants).
  • Such (PO/EO/PO) nonionic surfactants are distinguished by good foam control.
  • nonionic surfactants are those which have alternating ethylene oxide and alkylene oxide units.
  • preference is in turn given to surfactants with EO-AO-EO-AO blocks, in which case one to ten EO or AO groups are bonded to one another before a block of the other groups follows.
  • nonionic surfactants of the general formula preferably in which R 1 is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24 -alkyl or -alkenyl radical; each group R 2 or R 3 is independently selected from -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , CH(CH 3 ) 2 and the indices w, x, y, z are independent of one another are integers from 1 to 6.
  • nonionic surfactants having a C 9-15 alkyl radical containing 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units.
  • R 1 O[CH 2 CH(CH 3 )O] x [CH 2 CH 2 O] y CH 2 CH(OH)R 2
  • R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
  • R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x has values between 0.5 and 1.5 and y has a value of at least 15.
  • the group of these nonionic surfactants includes, for example, the C 2-26 fatty alcohol (PO) 1 -(EO) 15-40 -2-hydroxyalkyl ethers, in particular also the C 8-10 fatty alcohol (PO) 1 -(EO) 22 -2 -hydroxydecyl ether.
  • nonionic surfactants are the end-capped poly(oxyalkylated) nonionic surfactants of the formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 in which R 1 and R 2 is linear or branched, saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is values between 1 and 30, k and j for values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 1 O[CH 2 CH(R 3 )O] x [CH 2 ] k CH(OH)[CH 2 ] j OR 2 can be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
  • H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different.
  • the value 3 for x was selected here as an example and can certainly be larger, with the range of variation increasing with increasing x values and including, for example, a large number of (EO) groups combined with a small number of (PO) groups, or vice versa .
  • R 1 , R 2 and R 3 are as defined above and x is a number from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • the group of these nonionic surfactants includes, for example, the C 4-22 fatty alcohol (EO) 10-80 -2-hydroxyalkyl ethers, in particular the C 8-12 fatty alcohol (EO) 22 -2-hydroxydecyl ether and the C 4-22 fatty alcohol (EO) 40-80 -2-hydroxyalkyl ether.
  • the agents described herein which preferably comprise at least one nonionic surfactant, particularly preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the other nonionic surfactant in various embodiments in an amount based on the total weight of the agent of at least 1% by weight, preferably at least 2.5% by weight.
  • nonionic surfactants which may be included in the compositions described for the purposes of the present invention include, but are not limited to, alkyl glycosides, alkoxylated fatty acid alkyl esters, amine oxides, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, polyhydroxy fatty acid amides and alkoxylated alcohols.
  • Suitable nonionic surfactants are alkyl glycosides of the general formula RO(G) x , where R is a primary straight-chain or methyl-branched aliphatic radical, especially methyl-branched in the 2-position, having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol is, which is a glucose unit with 5 or 6 carbon 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 from 1.2 to 1.4.
  • 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 alkanolamide type can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
  • Suitable surfactants are the polyhydroxy fatty acid amides known as PHFA.
  • soaps with saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, being suitable.
  • those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • the liquid phase in particular can also contain higher amounts of soap, generally up to 20% by weight.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii )(R iv )(R v )N + CH 2 COO - , in which R iii is an alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms and which is optionally interrupted by heteroatoms or heteroatom groups, and R iv and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular C 10 -C 18 -alkyldimethylcarboxymethylbetaine and C 11 -C 17 -alkylamidopropyldimethylcarboxymethylbetaine.
  • Suitable cationic surfactants include the quaternary ammonium compounds of the formula (R vi )(R vii )(R viii )(R ix )N + X-, where R vi to R ix are four of the same or different types, in particular two long and two short-chain alkyl radicals and X- is an anion, especially a halide ion, for example didecyldimethylammonium chloride, alkylbenzyldidecylammonium chloride and mixtures thereof.
  • Suitable cationic surfactants are the quaternary surface-active compounds, in particular with a sulfonium, phosphonium, iodonium or arsonium group, which are also known as antimicrobial agents.
  • quaternary surface-active compounds with an antimicrobial effect, the agent can be designed with an antimicrobial effect or its antimicrobial effect, which may already be present due to other ingredients, can be improved.
  • the at least one surfactant is preferably contained in the at least one liquid phase of the washing and cleaning agent according to the invention.
  • the total amount of surfactants, based on the weight of the composition is 1 to 45% by weight, preferably 5 to 25% by weight.
  • the agent according to the invention contains a water-soluble and/or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and their Mixtures, especially in amounts ranging from 2.5% to 60% by weight.
  • a water-soluble and/or water-insoluble builder in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and their Mixtures, especially in amounts ranging from 2.5% to 60% by weight.
  • Other builders that can be present in the dishwashing detergent in the amounts mentioned are, in particular, the complexing agents mentioned in connection with the compounding of the bleach activator, as well as carbonates and mixtures of these substances.
  • the water-soluble organic builder substances include in particular those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which also may contain small proportions of polymerizable substances without carboxylic acid functionality as polymerized units.
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g/mol and 200,000 g/mol, and that of the copolymers between 2000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol, based on the free acid .
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g/mol to 100,000 g/mol.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth)acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, of (meth)acrylic acid and/or (meth)acrylate, particularly preferably acrylic acid and/or acrylate, and maleic acid and/or maleate and 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and/or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is substituted in the 2-position with a Alkyl radical, preferably with a C 1 -C 4 alkyl radical, or an aromatic radical, which is preferably derived from benzene or benzene derivatives, is substituted.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight, of (meth)acrylic acid and/or (meth)acrylate, particularly preferably acrylic acid and/or acrylate, 10% by weight to 30% by weight, preferably 15% by weight to 25% by weight, of methallyl sulfonic acid and/or methallyl sulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight.
  • % of a carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, and sucrose being particularly preferred.
  • the use of the third monomer incorporates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a relative molecular mass of between 1000 g/mol and 200000 g/mol, preferably between 2000 g/mol and 50000 g/mol and in particular between 3000 g/mol and 10000 g/mol.
  • the dishwashing detergents can also contain, in particular, phosphonates as a further builder, which according to the invention are not subsumed under the phosphates.
  • a hydroxyalkane and/or aminoalkane phosphonate is preferably used as the phosphonate compound.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues.
  • the detergents contain phosphonates preferably in amounts of 0.1 to 10% by weight, in particular in amounts of 0.3 to 8% by weight, based in each case on the total weight of the dishwashing detergent.
  • automatic dishwashing detergents are therefore preferred, characterized in that the dishwashing detergent contains citric acid or a salt of citric acid and that the proportion by weight of the citric acid or the salt of citric acid is preferably 1 to 40% by weight, preferably 10 to 25% by weight and in particular is between 15 and 22% by weight.
  • aminocarboxylic acids and/or their salts are aminocarboxylic acids and/or their salts. Particularly preferred representatives of this class are methylglycinediacetic acid (MGDA) or its salts and glutamicdiacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts. GLDA or its salts are very particularly preferred.
  • the content of these aminocarboxylic acids or their salts, in particular GLDA sodium salt can be between 0.1 and 25% by weight, for example between 5 and 25% by weight and in particular between 15 and 25% by weight.
  • Aminocarboxylic acids and their salts can be used, for example, together with the aforementioned builders, in particular together with citrate and the aforementioned phosphonates.
  • polycarboxylic acids are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular aqueous, compositions. In other embodiments, amounts close to the upper limit mentioned are preferably used in solid, powdered or granular compositions.
  • crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. deployed.
  • the crystalline detergent grade aluminosilicates particularly zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • suitable aluminosilicates do not have any particles with a particle size of more than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size of less than 10 ⁇ m. Your calcium binding capacity, according to the information in the German patent specification DE 24 12 837 can be determined is in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates which can be used as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8.
  • Amorphous alkali metal silicates of this type are commercially available, for example, under the name Portil® .
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x+1 ⁇ yH 2 O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x has the value 2 or 3 in the general formula mentioned.
  • both ⁇ - and ⁇ -sodium disilicates are preferred.
  • Practically anhydrous crystalline alkali metal silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali metal silicates can also be used in the compositions described herein.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents.
  • alkali metal silicates are preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali metal silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is then preferably 4:1 to 10:1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.
  • water-soluble or water-insoluble inorganic substances can be present in the agents used together with the builder or used in processes according to the invention.
  • the alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and mixtures thereof are suitable in this connection.
  • Such additional inorganic material may be present in amounts up to 70% by weight.
  • the dishwashing detergents according to the invention can also contain a sulfopolymer as an additional builder.
  • the proportion by weight of the sulfopolymer in the total weight of the dishwashing detergent according to the invention is preferably from 0.1 to 20% by weight, in particular from 0.5 to 18% by weight, particularly preferably from 1.0 to 15% by weight, in particular from 4 to 14% by weight, especially from 6 to 12% by weight.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70% by weight, in particular 30 to 50% by weight, preferably about 35 to 40% by weight, of sulfopolymers.
  • a copolymeric polysulfonate preferably a hydrophobically modified copolymeric polysulfonate, is preferably used as the sulfopolymer.
  • the copolymers can have two, three, four or more different monomer units.
  • preferred copolymeric polysulfonates contain at least one monomer from the group of unsaturated carboxylic acids.
  • the unsaturated carboxylic acid(s) used is/are particularly preferably unsaturated carboxylic acids of the formula R 1 (R 2 )C ⁇ C(R 3 )COOH, in which R 1 to R 3 independently represent —H, —CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH 2 , -OH or -COOH as defined above or for -COOH or -COOR 4 where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenylacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, methylenemalonic acid, sorbic acid, cinnamic acid or mixtures thereof.
  • unsaturated dicarboxylic acids can also be used.
  • Particularly preferred sulfonic acid group-containing monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3- Methacrylamido-2-hydroxy-propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propen1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate , sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of the acids mentioned or their
  • some or all of the sulfonic acid groups can be present in neutralized form, i.e. the acidic hydrogen atom of the sulfonic acid group in some or all of the sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular sodium ions.
  • metal ions preferably alkali metal ions and in particular sodium ions.
  • the monomer distribution of the copolymers preferably used is preferably 5 to 95% by weight in each case, and the proportion of the sulfonic acid group-containing monomer is particularly preferably 50 to 90% by weight. and the proportion of the carboxylic acid group-containing monomer is 10 to 50% by weight, the monomers here preferably being selected from those mentioned above.
  • the molar mass of the sulfo-copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired application.
  • Preferred dishwashing detergents are characterized in that the copolymers have molecular weights of from 2000 to 200,000 gmol -1 , preferably from 4000 to 25,000 gmol -1 and in particular from 5000 to 15,000 gmol -1 .
  • the washing or cleaning agent according to the invention contains at least one sulfopolymer as a builder, with the solid, powdery or granular phase in particular containing the sulfopolymer.
  • other polymers can be used in the compositions of the invention.
  • the group of suitable polymers includes, in particular, the washing or cleaning-active polymers, for example the rinse-aid polymers and/or polymers that act as softeners.
  • the washing or cleaning-active polymers for example the rinse-aid polymers and/or polymers that act as softeners.
  • cationic, anionic and amphoteric polymers can also be used in machine dishwashing detergents.
  • the sulfo(co)polymers described above are, for example, anionic polymers.
  • Amphoteric polymers within the meaning of the present invention also have negatively charged groups or monomer units in addition to a positively charged group in the polymer chain. These groups can be, for example, carboxylic acids, sulfonic acids or phosphonic acids.
  • Preferred polymers that can be used come from the group of alkylacrylamide/acrylic acid copolymers, alkylacrylamide/methacrylic acid copolymers, alkylacrylamide/methylmethacrylic acid copolymers, alkylacrylamide/acrylic acid/alkylaminoalkyl (meth)acrylic acid copolymers, alkylacrylamide/methacrylic acid/alkylaminoalkyl (meth) -acrylic acid copolymers, the alkyl acrylamide / methyl methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkyl acrylamide / alkyl methacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
  • acrylamidoalkyltrialkylammonium chloride/acrylic acid copolymers and their alkali metal and ammonium salts acrylamidoalkyltrialkylammonium chloride/methacrylic acid copolymers and their alkali metal and ammonium salts and methacroylethylbetaine/methacrylate copolymers.
  • the aforementioned organic and/or inorganic builder substances are preferably contained in the at least one solid phase of the agent according to the invention.
  • the agents of the present invention contain one or more enzymes.
  • the enzyme or enzymes used can be present in an enzyme preparation or enzyme composition.
  • any enzyme known in the prior art that can develop a catalytic activity in a detergent or cleaning agent is suitable as an enzyme and includes, without being limited thereto, for example proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin-splitting enzymes Enzymes, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
  • the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof.
  • these enzymes are of natural origin, but based on the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.
  • the agents preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5% by weight, based on active protein.
  • the protein concentration can be determined using known methods, for example the BCA method or the Biuret method.
  • the enzyme is contained in the agent according to the invention in an amount of 0.01 to 10% by weight, preferably 0.01 to 5% by weight, based on the total weight of the agent.
  • the protein concentration can be determined using known methods, for example the BCA method (bicinchoninic acid; 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the Biuret method.
  • the active protein concentration is determined via a titration of the active centers using a suitable irreversible inhibitor (for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (cf. M. Bender et al., J. Am. Chem. Soc. 88, 24 (1966), pp. 5890-5913 ).
  • a suitable irreversible inhibitor for proteases, for example, phenylmethylsulfonyl fluoride (PMSF)
  • proteases are among the most technically important enzymes of all. They break down proteinaceous soiling on the items to be cleaned. Among these, in turn, proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21.62) are particularly important, which are serine proteases because of the catalytically active amino acids. They act as non-specific Endopeptidases and hydrolyze any acid amide bonds that are inside peptides or proteins. Their optimum pH is usually in the clearly alkaline range. Subtilases are naturally produced by microorganisms. Among these, the subtilisins formed and secreted by Bacillus species should be mentioned in particular as the most important group within the subtilases.
  • subtilisin-type proteases preferably used in detergents and dishwashing detergents are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the protease from Bacillus lentus, in particular from Bacillus lentus DSM 5483, subtilisin DY and the the subtilases, but no longer the subtilisins in the narrower sense, thermitase, proteinase K and the proteases TW3 and TW7, as well as variants of the proteases mentioned, which have an altered amino acid sequence compared to the starting protease.
  • Proteases are modified in a targeted or random manner using methods known from the prior art and are thus optimized, for example, for use in detergents and dishwashing detergents. These include point mutagenesis, deletion or insertion mutagenesis, or fusion with other proteins or protein parts. Correspondingly optimized variants are known for most of the proteases known from the prior art.
  • amylases examples include the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases which have been improved for use in dishwashing detergents. Furthermore, for this purpose, the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • Lipases or cutinases can also be used, in particular because of their triglyceride-splitting activities, but also in order to generate peracids in situ from suitable precursors. These include, for example, the lipases originally available from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the D96L amino acid substitution.
  • oxidoreductases for example oxidases, oxygenases, catalases, peroxidases such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, Dioxygenases or laccases (phenol oxidases, polyphenol oxidases) are used.
  • organic, particularly preferably aromatic, compounds that interact with the enzymes are additionally added in order to increase the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).
  • the agent according to the invention preferably contains at least one enzyme selected from the group consisting of proteases, amylases, lipases, hemicellulases, cellulases, ⁇ -glucanases, perhydrolases and oxidoreductases.
  • An enzyme can be protected against damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • damage such as, for example, inactivation, denaturation or decomposition, for example due to physical influences, oxidation or proteolytic cleavage, particularly during storage.
  • inhibition of proteolysis is particularly preferred, particularly if the agents also contain proteases.
  • Dishwashing detergents may contain stabilizers for this purpose; the provision of such means represents a preferred embodiment of the present invention.
  • the enzymes to be used can also be packaged together with accompanying substances, for example from the fermentation.
  • the enzymes are preferably used as enzyme liquid formulation(s).
  • the enzymes are not provided in the form of the pure protein, but rather in the form of stabilized preparations that can be stored and transported.
  • These ready-made preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, low in water and/or mixed with stabilizers or other auxiliaries.
  • the enzymes can be encapsulated for both the solid and the liquid dosage form, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer, or in the form of capsules, for example those in which the enzymes are enclosed as in a set gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and/or chemical impermeable protective layer.
  • additional active ingredients such as stabilizers, emulsifiers, pigments, bleaches or dyes are applied.
  • Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
  • such granules for example due to the application of polymeric film formers, produce little dust and are stable in storage due to the coating.
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Protease and/or amylase preparations used with preference contain between 0.1 and 40% by weight, preferably between 0.2 and 30% by weight, particularly preferably between 0.4 and 20% by weight and in particular between 0 , 8 and 10% by weight of the enzyme protein.
  • Dishwashing detergents which, based in each case on their total weight, contain 0.1 to 12% by weight, preferably 0.2 to 10% by weight and in particular 0.5 to 8% by weight of enzyme preparations are particularly preferred.
  • the agent according to the invention can have one or more enzyme stabilizers.
  • compositions herein may also include enzyme stabilizers.
  • stabilizers are reversible protease inhibitors.
  • Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are often used for this purpose, including above all derivatives with aromatic groups, such as ortho-, meta- or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of said compounds.
  • Peptide aldehydes ie oligopeptides with a reduced C-terminus, in particular those composed of 2 to 50 monomers, are also used for this purpose.
  • Peptidic reversible protease inhibitors include ovomucoid and leupeptin.
  • Specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are also suitable for this.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanolamine and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C 12 such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. Also end group closed Fatty acid amide alkoxylates are suitable for this purpose. Other enzyme stabilizers are known to those skilled in the art from the prior art.
  • the at least one enzyme is preferably contained in the at least one solid phase of the agent according to the invention.
  • Perfume oils or fragrances which can be used in the context of the present invention are individual odorant compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance note. Perfume oils of this type can also contain natural mixtures of fragrances, such as those obtainable from vegetable sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • Solvents suitable for the compositions employed in the present invention are generally water-miscible organic solvents such as, without limitation, mono- or polyhydric alcohols, alkanolamines, or glycol ethers.
  • the solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol mono
  • the washing or cleaning agent can contain such organic solvents in amounts of up to a maximum of 50% by weight, preferably up to 20% by weight, based on the total weight of the composition.
  • the detergents and cleaning agents described herein are preferably prepackaged in the form of a multi-chamber portion bag.
  • the liquid and the solid phase are in different chambers of the sachet.
  • Such prepackaged dosing units preferably comprise the amount of washing or cleaning active substances required for one cleaning cycle.
  • Preferred dosage units weigh between 12 and 35 g, preferably between 14 and 29 g and in particular between 16 and 26 g.
  • the volume of the aforementioned dosing units and their shape are chosen with particular preference so that a dosing of the pre-assembled units on the metering chamber washing machine or dishwasher is guaranteed.
  • the volume of the dosage unit is therefore preferably between 10 and 35 ml, preferably between 14 and 25 ml.
  • the detergents and cleaning agents in particular the prefabricated dosing units, particularly preferably have a water-soluble coating.
  • envelope and “packaging” are to be understood identically, unless the context indicates otherwise.
  • the water-soluble cover is preferably formed from a water-soluble film material which is selected from the group consisting of polymers or polymer mixtures.
  • the cover can be formed from one or from two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if any, can be the same or different. Films are particularly preferred which can be glued and/or sealed to form packaging such as tubes or pillows after they have been filled with an agent.
  • the water-soluble packaging has at least two or more chambers, each of which contains one of the at least two different phases, as defined herein.
  • a first chamber contains liquid agent and a second chamber contains solid agent.
  • the amount of agent preferably corresponds to the full or half dose required for a washing or cleaning cycle.
  • the washing or cleaning agent according to the invention can be characterized in that it is in a water-insoluble, water-soluble or water-disintegratable packaging, in particular in a film containing polyvinyl alcohol, in particular the at least one liquid and the at least one solid phase through the water-soluble or water-dispersible packaging , in particular the film containing polyvinyl alcohol, are separated from one another.
  • the washing or cleaning agent according to the invention can be characterized in that it is in a water-insoluble, water-soluble or water-disintegratable packaging, in particular in a polyvinyl alcohol-containing film, with the at least one gel-like or pasty phase and the at least one solid phase in particular being in the same Chamber of the water-soluble or water-dispersible packaging, in particular the film containing polyvinyl alcohol.
  • Water-soluble or water-disintegrable packaging is very preferred.
  • the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer.
  • Water-soluble coatings containing polyvinyl alcohol or a Contain polyvinyl alcohol copolymer have good stability with a sufficiently high water solubility, especially cold water solubility.
  • Suitable water-soluble films for producing the water-soluble covering are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol -1 .
  • Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are correspondingly produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol % and in particular 82 to 88 mol %.
  • the polyvinyl alcohol degree of hydrolysis is at least 85 mole percent, preferably at least 88 mole percent, more preferably at least 90 mole percent, most preferably at least 98 mole percent.
  • polyvinyl alcohol is a copolymer of vinyl alcohol and vinyl acetate, with the monomer ratio in the polymer depending on the degree of hydrolysis of the vinyl acetate.
  • the polyvinyl alcohol polymer is considered a homopolymer.
  • copolymer or terpolymer is used when the polymer contains other monomers in addition to vinyl alcohol and vinyl acetate.
  • the polyvinyl alcohol degree of hydrolysis is 85 mol% or more, preferably 88 mol% or more, more preferably 90 mol% or more
  • the polyvinyl alcohol is preferably a copolymer.
  • polyvinyl alcohol includes mixtures of polyvinyl alcohol and polyvinyl alcohol copolymers. Copolymers may include 2-acrylamido-2-methylpropane sulfonic acid (AMPS). Also included are terpolymers of polyvinyl alcohol. Preferably, the polyvinyl alcohol is a copolymer that includes AMPS.
  • AMPS 2-acrylamido-2-methylpropane sulfonic acid
  • the polyvinyl alcohol degree of hydrolysis is usually at least 90 mole percent.
  • the degree of hydrolysis is at least 95 mole percent, more preferably at least 98 mole percent.
  • the polyvinyl alcohol may comprise a mixture of polyvinyl alcohol and a monomer selected from the list consisting of 2-arylamido-1-methylpropane sulfonic acid, 2-methylacrylamido-2-methylpropane sulfonic acid, and alkali metal salts thereof.
  • the content of sulfonic acid group units in the modified polyvinyl alcohol is preferably 0.1 to 20% by mole, more preferably 0.5 to 10% by mole, most preferably 1 to 5% by mole.
  • the mechanical properties as a water-soluble film are also important. Sufficient strength and flexibility of the foil are necessary, especially in the case of a small thickness of 10 to 100 ⁇ m. Therefore, the viscosity-average degree of polymerization (hereinafter referred to as degree of polymerization) of the modified PVA is preferably 300 to 10,000, more preferably 500 to 8,000, very preferably 900 to 2000, still more preferably 1000 to 1800. In the case of a degree of polymerization of less than 300, the strength of the film becomes lower. In the case of a degree of polymerization of more than 10,000, the viscosity of the solution becomes so high during the production of the film that the workability is deteriorated.
  • the degree of polymerization averaged over the viscosity can be calculated by measuring the Staudinger factor [ ⁇ ] (dl/g).
  • the Staudinger factor is determined at 30° C. in aqueous NaCl solution (1 M) using a capillary viscometer.
  • a synthesis can take place, for example, as follows.
  • a methanolic solution of sodium hydroxide is added to a methanolic solution of a copolymer prepared by the copolymerization of vinyl acetate and sodium acrylamido-2-methylpropanesulfonate in methanol.
  • the copolymer is hydrolyzed to give a modified PVA having a sulfonic acid group.
  • the modified PVA thus obtained most preferably has a degree of polymerization of 1,300, a degree of hydrolysis of 98 mol% and a sulfonic acid group content of 1.5 mol%.
  • the polyvinyl alcohol can also be present as a terpolymer.
  • the second film comprises a copolymer of polyvinyl alcohol having 0 to 10 mole percent residual acetate and 1 to 6 mole percent of a non-hydrolyzable anionic comonomer selected from the group consisting of acrylic acid, methacrylic acid, cis- 2-butenoic acid, 3-butenoic acid, cinnamic acid, phenylcinnamic acid, pentenoic acid, methylenemalonic acid, acrylamide, maleic acid, itaconic acid, the alkali metal and ammonium salts thereof.
  • a non-hydrolyzable anionic comonomer selected from the group consisting of acrylic acid, methacrylic acid, cis- 2-butenoic acid, 3-butenoic acid, cinnamic acid, phenylcinnamic acid, pentenoic acid, methylenemalonic acid, acrylamide, maleic acid, itaconic acid, the alkali metal and ammonium salts
  • the vinyl acetate-co-itaconic acid copolymer is prepared under nitrogen in methanol solvent using 2,2'-azobis(isobutyronitrile) (AIBN) as the initiator. Alcoholysis of this copolymer is carried out in methanolic sodium hydroxide and the recovered vinyl alcohol-co-itaconic acid (sodium salt) copolymer is ground, washed to remove residual sodium acetate and dried.
  • the preferred degree of polymerization of the vinyl alcohol-co-itaconic acid (sodium salt) copolymer is preferably such that the viscosity of a freshly prepared 4% aqueous solution at 20°C ranges from about 5 to about 45 MPa.s (cps). The viscosity is more preferably in the range from 11 to 30 mPas and particularly preferably in the range from 15 to 25 mPas.
  • the viscosities described herein are determined for a freshly prepared 4% aqueous solution at 20° C. using a Brookfield LV viscometer with a UL adapter in accordance with EN ISO 15023-2:2006 Annex E Brookfield Test Method.
  • the preferred level of incorporation of itaconic acid comonomer in the vinyl alcohol-co-itaconic acid (sodium salt) copolymer ranges from about 1.5 to about 11 mole percent. More preferably, the level of incorporation is in the range of 2.5 to 8.5 mole percent and most preferably is in the range of 4-6 mole percent.
  • the polyvinyl alcohol polymer is a copolymer with a sulfonate monomer, preferably AMPS, or is a terpolymer with AMPS and another monomer.
  • a polyvinyl alcohol-containing film material suitable for producing the water-soluble casing can also have a polymer selected from the group consisting of (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above Polymers can be added.
  • a preferred additional polymer are polylactic acids.
  • preferred polyvinyl alcohol copolymers include dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid and mixtures thereof, with itaconic acid being preferred.
  • Polyvinyl alcohol copolymers which are also preferred include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its ester.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.
  • the film material contains further additives.
  • the film material can contain, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerol, sorbitol, mannitol or mixtures thereof.
  • Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, anti-blocking agents, anti-adhesive agents or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages according to the invention are films sold by MonoSol LLC, for example under the designations M8630, M8315, M8720, C8400 or M8900.
  • Other suitable films include Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL films from Aicello Chemical Europe GmbH or Kuraray VF-HP films.
  • the corresponding use of the washing or cleaning agent according to the invention is also a subject of the invention.
  • the invention also relates to a textile washing or dishwashing method, in particular a machine dishwashing method, in which a washing or cleaning agent according to the invention is used.
  • the subject matter of the present application is therefore also a method for cleaning textiles or hard surfaces, such as dishes, in a washing machine or dishwasher, in which the agent according to the invention is used while running through a washing or dishwashing program before the start of the main dishwashing or washing cycle or in the Course of the main wash or wash cycle is metered into the interior of a washing machine or dishwasher.
  • the dosing or the agent according to the invention can be introduced into the interior of the washing machine or dishwasher manually, but the agent is preferably metered into the interior of the washing machine or dishwasher by means of the metering chamber. How
  • the disclosed particles comprising at least one bleach activator, wherein the at least one bleach activator is compounded with at least one complexing agent.
  • the complexing agent and/or the bleach activator are preferably defined and compounded as already described above in connection with the agents according to the invention and can also be produced in the manner described there.
  • the particles consist essentially or exclusively of bleach activator and chelating agent, preferably in the ratios indicated above, i.e. the amount of chelating agent is from 5 to 30% by weight of the total weight of the particle.
  • the at least one complexing agent is selected from the group consisting of the sodium salt of DTPMP, HEDP, MGDA or GLDA.
  • the at least one chelating agent is selected from the group consisting of the sodium salt of DTPMP and HEDP.
  • the at least one bleach activator is TAED.
  • the particles described herein are characterized in that they are approximately spherical.
  • the particles described herein are further characterized in that the mean particle diameter of the particles is in the range of 300-1000 ⁇ m.
  • the detergents according to the invention containing the particles described herein are characterized in that they are storage-stable and, even after a relatively long period of time, neither the particles themselves nor the detergents or cleaning agents in which they are contained undergo discoloration or a change in fragrance.
  • the detergents have good washing or cleaning performance even after prolonged storage, especially if they contain bleaching agents. The agent thus remains visually attractive over a long period of time and has improved cleaning or washing performance.
  • TAED granules ex Warwick were compounded in a Glatt AGT 200 fluidized bed with a DTPMP phosphonate solution (diethylene triamine pentamethylene phosphonic acid heptasodium salt, Dequest 2066, ex thermPhos).
  • the fluidized bed temperature was chosen so that there was no agglomeration of the TAED granules.
  • the resulting TAED-DTPMP compound had a DTPMP content of 13.0% by weight.
  • A1-A3 Two powder mixtures A1-A3 were produced in a tumble mixer by dry mixing of the individual granules.
  • A1 contains the TAED complexing compound according to the invention.
  • A2 is without a complexing agent and
  • A3 is a composition in which a complexing agent has been added separately as granules.
  • 1-Hydroxyethane-1,1-diphosphonic acid tetrasodium salt was used as HEPD.
  • composition B A liquid phase of composition B was prepared.
  • Soil release polymer 1.4 Perfume 1.7 dye 0.01 Water 8.39
  • the recipe contains 8.39% by weight of water from additives and raw materials. All ingredient information as active substance.
  • Diethylenetriaminepentamethylenephosphonic acid heptasodium salt was used as DTPMP.
  • the sachets produced were stored at 40° C. in a closed screw-top jar. After storage, a sample is taken from the powder chambers and subjected to a TAM (Thermal Activity Monitor) measurement. The sample is stored isothermally at 40 °C and the heat flow from this sample is determined over time. Exothermic decomposition reactions of the bleaching components take place. The greater the heat flow of the sample, the more unstable the bleaching components. For better comparability, the heat flow is taken as a measure after 48 hours of storage. A fresh powder mixture not packaged as a sachet is also examined in the TAM. A1 A2 A3 TAM fresh powder [ ⁇ w/g] 11.7 13.0 14.0 TAM of a powder after 7 days storage in a sachet at 40 °C [ ⁇ w/g] 22.5 58.1 56.8
  • composition A1 according to the invention shows the same stability as comparison mixtures A2 and A3.
  • the stability of the mixture A1 is significantly higher than the comparable mixtures without complexing agent and with admixed complexing agent.
  • TAED granules ex Warwick were compounded with a complexing agent solution in a Glatt fluidized bed.
  • the fluidized bed temperature was chosen so that there was no agglomeration of the TAED granules.
  • MGDA trisodium ⁇ -DL-alanine diacetate, Trilon M
  • GLDA tetrasodium-N,N-bis(carboxylatomethyl)-L-glutamate, Dissolvine
  • the resulting TAED complexing agent compounds had a complexing agent content of 10.0% by weight.
  • MGDA trisodium ⁇ -DL-alanine diacetate, Trilon M
  • GLDA tetrasodium-N,N-bis(carboxylatomethyl)-L-glutamate, Dissolvine

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Claims (14)

  1. Produit de lavage ou de nettoyage à plusieurs phases, comprenant au moins une phase liquide, contenant 1 à 20 % en poids d'eau, le terme liquide englobant toutes les phases fluides, en particulier également les gels et les compositions pâteuses, et au moins une phase solide, pulvérulente ou granulaire, caractérisé en ce que la au moins une phase solide, pulvérulente ou granulaire contient au moins une particule comprenant au moins un activateur de blanchiment, le au moins un activateur de blanchiment étant mélangé avec au moins un agent complexant.
  2. Produit de lavage ou de nettoyage selon la revendication 1, caractérisé en ce que le au moins un agent complexant est choisi dans le groupe constitué par les phosphonates, les sels d'acides aminocarboxyliques et les polycarboxylates (polymères) ainsi que leurs acides correspondants.
  3. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 2, caractérisé en ce que ledit au moins un activateur de blanchiment est choisi dans le groupe constitué par les alkylènediamines polyacylées, les dérivés de triazine acylés, les glycoluriles acylés, les N-acylimides, et les phénolsulfonates acylés.
  4. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 3, caractérisé en ce que la quantité de revêtement dudit au moins un agent complexant sur ledit au moins un activateur de blanchiment est comprise entre 5 % et 25 % en poids, de préférence entre 5 % et 20 % en poids, en particulier entre 5 % et 15 % en poids, par rapport au poids total de l'activateur de blanchiment compoundé.
  5. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 4, caractérisé en ce que ledit au moins un agent complexant est choisi dans le groupe constitué par le sel de sodium de DTPMP, HEDP, MGDA ou GLDA.
  6. Produit de lavage ou de nettoyage selon l'une quelconque des revendications 1 à 5, caractérisé en ce que ledit au moins un activateur de blanchiment est le TAED.
  7. Produit de lavage ou de nettoyage selon l'une des revendications 1 à 6, caractérisé en ce que la quantité de la au moins une particule se situe dans la plage de 1 % en poids à 20 % en poids, de préférence de 1 % en poids à 15 % en poids, en particulier de 1 % en poids à 13 % en poids, par rapport au poids total du produit de lavage ou de nettoyage.
  8. Produit de lavage ou de nettoyage selon l'une des revendications 1 à 7, caractérisé en ce que le produit de lavage ou de nettoyage contient au moins un agent de blanchiment, la phase solide, pulvérulente ou granulaire contenant notamment l'agent de blanchiment.
  9. Produit de lavage ou de nettoyage selon l'une des revendications 1 à 8, caractérisé en ce que le produit de lavage ou de nettoyage contient au moins un catalyseur de blanchiment, le catalyseur de blanchiment étant choisi dans le groupe des sels de métaux de transition et des complexes de métaux de transition renforçant le blanchiment, de préférence des complexes du manganèse au degré d'oxydation II, III, IV ou IV, qui contiennent un ou plusieurs ligand(s) macrocyclique(s) avec les fonctions donneur N, NR, PR, O et/ou S, de préférence les ligands macromoléculaires 1,4,7-triméthyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1,5,9-triméthyl-1,5,9-triazacyclododécane (Me-TACD), 2-méthyl-1,4,7-triméthyl-1,4,7-triazacyclononane (Me/Me-TACN) et/ou le 2-méthyl-1,4,7-triazacyclononane (Me/TACN), de préférence les ligands 1,4,7-triméthyl-1,4,7-triazacyclononane (Me-TACN) ou 1,2,4,7-tétraméthyl-1,4,7-triazacyclononane (Me/Me-TACN).
  10. Produit de lavage ou de nettoyage selon l'une des revendications 1 à 9, caractérisé en ce que le produit de lavage ou de nettoyage contient au moins un sulfopolymère comme adjuvant, la phase solide, pulvérulente ou granulaire contenant notamment le sulfopolymère.
  11. Produit de lavage ou de nettoyage selon l'une des revendications 1 à 10, caractérisé en ce qu'il se trouve dans un emballage insoluble dans l'eau, soluble dans l'eau ou pouvant être dispersé dans l'eau, en particulier dans un film contenant de l'alcool polyvinylique, la au moins une phase liquide et la au moins une phase solide étant séparées l'une de l'autre par l'emballage soluble dans l'eau ou pouvant être dispersé dans l'eau, en particulier le film contenant de l'alcool polyvinylique.
  12. Produit de lavage ou de nettoyage selon l'une des revendications 1 à 10, caractérisé en ce qu'il se trouve dans un emballage insoluble dans l'eau, soluble dans l'eau ou pouvant être dispersé dans l'eau, en particulier dans un film contenant de l'alcool polyvinylique, la au moins une phase gélifiée ou pâteuse et la au moins une phase solide se trouvant dans le même compartiment de l'emballage soluble dans l'eau ou pouvant être dispersé dans l'eau, en particulier du film contenant de l'alcool polyvinylique.
  13. Utilisation du produit de lavage ou de nettoyage selon l'une des revendications 1 à 12 pour le lavage de textiles ou le nettoyage de surfaces dures, en particulier pour le nettoyage en machine de la vaisselle.
  14. Un procédé pour le lavage ou le nettoyage de textiles ou de surfaces dures, en particulier pour le nettoyage en machine de la vaisselle, caractérisé en ce que dans au moins une étape du procédé consiste à appliquer un produit de lavage ou de nettoyage selon l'une des revendications 1 à 12.
EP17805165.2A 2016-11-25 2017-11-22 Sachet contenant un mélange activateur de blanchiment/agent complexant Active EP3545067B1 (fr)

Applications Claiming Priority (2)

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DE102016223472.2A DE102016223472A1 (de) 2016-11-25 2016-11-25 Mehrkammer-Portionsbeutel mit Bleichaktivator/Komplexbildner-Compound
PCT/EP2017/080015 WO2018095956A1 (fr) 2016-11-25 2017-11-22 Sachet contenant un mélange activateur de blanchiment/agent complexant

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EP3545067A1 EP3545067A1 (fr) 2019-10-02
EP3545067B1 true EP3545067B1 (fr) 2023-08-16

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EP (1) EP3545067B1 (fr)
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WO (1) WO2018095956A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2018138119A1 (fr) * 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Dose de détergent comprenant au moins deux phases
DE102018212208A1 (de) * 2018-07-23 2020-01-23 Henkel Ag & Co. Kgaa Mehrphasiger Reinigungsmittelpouch
DE102020212099A1 (de) * 2020-09-25 2022-03-31 Henkel Ag & Co. Kgaa Konzentrierte fließfähige Waschmittelzubereitung mit verbesserten Eigenschaften
DE102023000332A1 (de) 2023-02-03 2024-08-08 Ovidiu Dicoi Fest-/Flüssig-Waschmittel

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
CA2141586A1 (fr) * 1992-08-01 1994-02-17 Anthony Dovey Compositions precurseurs de blanchiment a base de peroxyacide
DE19704634A1 (de) * 1997-02-07 1998-08-27 Henkel Kgaa pH-gesteuerte Freisetzung von Waschmittelkomponenten
DE102004012568A1 (de) * 2004-03-12 2005-12-08 Henkel Kgaa Bleichaktivatoren und Verfahren zu ihrer Herstellung
DE102005041967A1 (de) * 2005-09-03 2007-03-08 Clariant Produkte (Deutschland) Gmbh Granulare Bleichaktivator-Mischungen
DE102006018780A1 (de) * 2006-04-20 2007-10-25 Henkel Kgaa Granulat eines sensitiven Wasch- oder Reinigungsmittelinhaltsstoffs
DE102006036896A1 (de) * 2006-08-04 2008-02-07 Henkel Kgaa Wasch- oder Reinigungsmittel mit größenoptimierten Bleichwirkstoffteilchen
DE102007051093A1 (de) 2007-10-24 2009-04-30 Henkel Ag & Co. Kgaa Wasch- oder Reinigungsmittelcompounds und deren Herstellung
ES2414859T3 (es) * 2010-06-15 2013-07-23 The Procter & Gamble Company Bolsa multicompartimental
EP2527421A1 (fr) * 2011-05-23 2012-11-28 The Procter & Gamble Company Poche à dose unitaire hydrosoluble comprenant un agent chélatant
DE102014202221A1 (de) * 2014-02-06 2015-08-06 Henkel Ag & Co. Kgaa Mehrphasiges vorportioniertes Reinigungsmittel
GB201402257D0 (en) * 2014-02-10 2014-03-26 Revolymer Ltd Novel Peracid - containing particle
PL3190168T3 (pl) * 2016-01-06 2019-10-31 Dalli Werke Gmbh & Co Kg Powlekany katalizator bielenia

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US11220660B2 (en) 2022-01-11
US20190276779A1 (en) 2019-09-12
WO2018095956A1 (fr) 2018-05-31
EP3545067A1 (fr) 2019-10-02
DE102016223472A1 (de) 2018-05-30

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