EP3545067A1 - Sachet contenant un mélange activateur de blanchiment/agent complexant - Google Patents

Sachet contenant un mélange activateur de blanchiment/agent complexant

Info

Publication number
EP3545067A1
EP3545067A1 EP17805165.2A EP17805165A EP3545067A1 EP 3545067 A1 EP3545067 A1 EP 3545067A1 EP 17805165 A EP17805165 A EP 17805165A EP 3545067 A1 EP3545067 A1 EP 3545067A1
Authority
EP
European Patent Office
Prior art keywords
washing
acid
water
cleaning
weight
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.)
Granted
Application number
EP17805165.2A
Other languages
German (de)
English (en)
Other versions
EP3545067B1 (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
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP3545067A1 publication Critical patent/EP3545067A1/fr
Application granted granted Critical
Publication of EP3545067B1 publication Critical patent/EP3545067B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C11D17/06—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
    • C11D17/0008—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
    • C11D17/0039—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 the bleach activator particles described herein which are compounded with at least one complexing agent and multi-phase detergents and cleaners comprising at least one liquid, water-poor to anhydrous phase and at least one solid, powdered or granular phase and containing at least one bleach activator compounded with at least one complexing agent ,
  • the present invention is further directed to the use of such agents, to washing and cleaning processes employing such agents, and to corresponding laundry methods.
  • Detergents and cleaners are available to the consumer in a variety of forms. In addition to the traditional solid funds increasingly flowable and especially liquid to gel increasingly gaining importance. The consumer especially appreciates the rapid solubility and the associated rapid availability of the ingredients in the washing and cleaning liquor, especially in short programs and at low
  • compositions in which in particular the water content is reduced compared to conventional compositions, increases.
  • compositions whose water content is as low as possible, for example less than 20% by weight, are particularly desirable.
  • a high washing and cleaning performance is achieved mainly by a combination of liquid with powdered phases in so-called multi-chamber sachets. Also, a high washing and cleaning performance is achieved by a combination of gelatinous or pasty with powdered phases in so-called single-chamber sachets.
  • the bleach-active substance of the washing or cleaning agent is in the contain powdered phase.
  • Mehrcroportionslessnesssysteme can lead to a chemical reaction of the various phases, which includes in particular the degradation of bleach-active substances. Specifically, this means that the bleaching-active substances are activated, which then react with the water-soluble film and with other ingredients, for example fragrances and dyes, which are contained in the liquid phase. Consequently, it causes discoloration and
  • Bleach activators in the powder phase of a multi-phase detergent or cleaning agent cause a chemical stabilization of the entire sachet. This stabilizing effect manifests itself in the fact that, even with longer storage times, decomposition of the water-soluble film as well as color or odor changes of the agent no longer occur. In addition, such agents have an improved washing or cleaning performance, in particular when the agent is stored for a long time.
  • the present invention is directed to the herein described particles, which comprise substantially at least one bleach activator, characterized in that the at least one bleach activator is compounded with at least one complexing agent.
  • the invention is therefore directed to a multi-phase detergent or cleaning agent comprising at least one liquid, low to anhydrous phase and at least one solid, powdered or granular phase, characterized in that the at least one solid, powdered or granular phase at least a bleach activator, wherein the bleach activator is compounded with at least one complexing agent.
  • the present invention is directed to the use of the fabric laundering agent or hard surface cleaning, in particular for
  • the present invention is further directed to a process 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 which differs from another phase of the agent of the invention containing at least two phases by various features, for example, ingredients, physical properties, appearance, etc.
  • the phases differ in particular with regard to physical properties and in particular by the state of aggregation, one phase preferably being liquid and the other preferably solid under standard conditions (1013 mbar, 20 ° C.)
  • 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 further phase may correspond in each case 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 respectively corresponding phases may differ to the extent permitted by the respective definitions given below of both the at least one first phase and the at least one second phase.
  • 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 made up in the described means such that they are spatially are separated, for example, in different chambers of a
  • Multi-compartment sachet are located.
  • low in water means that the composition thus characterized contains 20% by weight of water or less. In particular, this term covers compositions containing from 1 to 20% by weight of water, from 1 to 15% by weight. % Water, 5-15% by weight of water or less than 15% by weight or less than 10% by weight of water.
  • composition contains less than 5% by weight, more preferably less than 3% by weight, preferably less than 1% by weight of water.
  • the water content as defined herein refers to the water content determined by Karl Fischer titration.
  • Liquid as used herein with reference to one of the at least two different phases of the detergents or cleaners of the invention, includes all flowable ones
  • gels and pasty compositions are also included.
  • the term also includes non-Newtonian fluids having a yield point.
  • Solid as used herein in reference to one of the at least two distinct phases of the detergents or cleaners of the invention includes all types of free-flowing powders, granules, extrudates, etc., especially those having a bulk density of from 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 the 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-disintegratable means that the substance or the object on contact with water at temperatures between 15 and 60 ° C and especially between 20 and 45 ° C within 15, preferably within 10 minutes into small parts.
  • substantially refers to the particular characteristic of the substance or article with respect to a feature of a substance or article Context of the present invention, the material composition of a thing,
  • a composition containing as main ingredient the respective substance mentioned.
  • the term means that the major constituent of the particles is at least one bleach activator as defined herein.
  • the composition may also comprise one or more other ingredients.
  • the respective major constituent in various embodiments, is not less than 50% by weight, preferably not less than 55% by weight, 60% by weight, 65% by weight, 70% by weight. -%, 75 wt .-%, 80 wt .-%, 85 wt .-%, 90 wt .-% or 95 wt .-% in the composition.
  • the particles as described herein which in various embodiments may be, for example, "substantially" spherical, are particles in which the vast majority of the particles are spherical In the context of the present invention, not less than fifty %, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95% of the particles spherical.
  • the present invention relates to a washing or cleaning agent, in particular a
  • At least one of the phases is a liquid, water-poor to anhydrous phase.
  • at least one further phase is a solid, powdery or granular phase.
  • this at least one solid phase is characterized by containing at least one bleach activator, wherein the bleach activator is compounded with at least one complexing agent.
  • Bleach activator are coated / coated with the at least one complexing agent.
  • Coating or coating need not be complete with respect to the particle surface, but in preferred embodiments, the entire surface of the bleach activator particle is coated / encased with the complexing agent. Suitable methods of compounding substances are known in the art. Such processes include, but are not limited to, fluidized bed granulation processes. In various embodiments, the bleach activator in particulate form is initially charged and then treated with a solution of the
  • Complexing agent preferably an aqueous solution
  • a spray-coating process is used In this process, the blech activator particles, which may be of different shape and size, are agitated in a fluidized bed with a liquid (complexing agent solution or suspension). The aqueous or organic solvent evaporates, and the complexing agent contained therein forms the coating layer. Typical particle sizes are 100
  • Such spray coating can be carried out in all fluidized bed systems - typically in batch operation. For some coating applications, continuous processes are also available. It is important to ensure that no liquid bridges are formed during application in order to avoid undesirable agglomeration. Depending on the direction in which the particle is sprayed, coating can be carried out in top-spray, tangential-spray, bottom-spray (Wurster process) or in the
  • Fluidized bed system can be performed.
  • the compounding can also be called
  • the bleach activator particles usually very small pulverulent particles, are agitated in the fluidized bed and sprayed with a binder liquid containing the complexing agent. By forming liquid bridges, the particles combine to form agglomerates. The spraying process is continued until the desired size of the agglomerates is reached. Typical sizes of agglomerates range from 100
  • Suitable fluidized bed plants for the mentioned processes are available, for example, from Glatt GmbH (Binzen, DE). Suitable processes are described, for example, in German Patent Application DE 10 2007 051 093 A1.
  • Bleach activator is largely due to the binding of free calcium and iron ions, which lead to activation upon contact with Blleichinatorsubstanzen.
  • the agent according to the invention comes into contact with water, whereby the individual phases of the agent disintegrate. This dissolves the
  • Coating of the bleach activator according to the invention and the bleach-active substances present in the middle are activated.
  • 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 wt .-% to 13 wt .-% in the washing or cleaning agent, each based on the total weight of the detergent or cleaning agent.
  • the at least one complexing agent is a complexing agent, preferably organic complexing agent, containing Ca 2+
  • the determination of the calcium binding capacity is carried out by means of visual turbidity titration
  • 1.00 g of the complexing agent to be tested are weighed into a 250 ml beaker and dissolved with about 100 ml of distilled water. If necessary, the pH of this solution is first raised to about 8-9 with the 1 M NaOH and then exactly 10 ml of 2% Na 2 CO 3 solution are added to the solution. Finally, the pH of the resulting solution is adjusted to 1, 0 with 1 M NaOH and the total volume of the solution is increased to 150 ml.
  • the titration is carried out at 20 ° C by adding portions of Ca acetate solution. until permanent turbidity, wherein smaller volume increments are added towards the end of the titration. During the addition of the titrant is not stirred. The mixture is stirred between the additions and the pH is kept constant with 1 M NaOH. 1 ml of spent Ca-acetate solution corresponds to 25 mg of calcium carbonate.
  • the conversion into calcium binding capacity mg CaO / g is carried out by multiplying the CaCCb binding capacity [mg CaCCb / g] by 0.560.
  • HEDP tetrasodium salt
  • DTPMP heptasodium salt
  • 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 according to the invention.
  • the phosphonates used are preferably aminoalkane and / or hydroxyalkane phosphonates.
  • Aminoalkanephosphonates are preferably diethylenetriaminepentamethylenephosphonate (DTPMP), nitrilotris (methylenephosphonic acid) (NTMP), 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBTC), ethylenediamine tetramethylenephosphonate (EDTMP) and their higher homologs.
  • DTPMP diethylenetriaminepentamethylenephosphonate
  • NTMP nitrilotris
  • PBTC 2-phosphonobutane-1, 2,4-tricarboxylic acid
  • ETMP ethylenediamine tetramethylenephosphonate
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • the polycarboxylates are the salts, in particular the alkali salts, more preferably the sodium salts of polycarboxylic acids, polycarboxylic acids being understood to mean those carboxylic acids which have more than one, in particular two to eight, acid functions, preferably two to six, in particular two or three , carry four or five acid functions throughout the molecule.
  • Preferred polycarboxylic acids are thus dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids and pentacarboxylic acids, in particular di-, tri- and tetracarboxylic acids.
  • the polycarboxylic acids may contain other functional groups, such as
  • Hydroxyl groups carry. These are, for example, 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,
  • 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 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), more preferably MGDA or GLDA.
  • bleach activators compounds which, under perhydrolysis conditions, are aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • TAED tetraacetylethylenediamine
  • DADHT
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • TAED is preferably used according to the invention.
  • 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 phenolsulfonates.
  • the at least one complexing agent is selected from the group consisting of DTPMP, HEDP, MGDA or GLDA, most preferably DTPMP and HEDP, most preferably the at least one complexing agent is 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, most preferably 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 of 5% to 30% by weight, preferably 5 to 25% by weight, especially 5 to 20% by weight, based on the
  • the remainder of the compounded bleach activator consists essentially of the at least one bleach activator.
  • the amount of the at least one bleach activator in the compounded bleach activator is 70 to 95% by weight, preferably 75 to 95% by weight, more preferably 80 to 95% by weight, based on the total weight of the particle.
  • the washing or cleaning agent according to the invention preferably contains at least one bleaching agent.
  • a bleaching agent is understood, on the one hand, to be a water substance itself and, on the other hand, to any compound which gives hydrogen peroxide in an aqueous medium.
  • sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and peroxygenic salts or peracids which yield H2O2, such as persulfates
  • the inventive compositions can, if desired, bleach from the group of contain organic bleach, although their use is also possible in principle for laundry detergents.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-a-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid , PAP), o- Carboxybenzamidoperoxycaproic acid, N-Nonenylamidoperadipinklare and N-Nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, the diperoxyphthalic acids, 2-Decyldip
  • Chlorine- or bromine-releasing substances can also be used as the bleaching agent, but these are not preferred according to the invention.
  • suitable chlorine or bromine releasing materials are heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • the detergents or cleaning agents may contain from 1 to 35% by weight, preferably from 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15% by weight of bleach, preferably sodium percarbonate, in each case based on the
  • Total weight of the detergent or cleaning agent included Based on the total weight of the solid phase, the amount of bleach in the solid phase, preferably
  • Sodium percarbonate 5 to 50, preferably 10 to 40 wt .-% amount.
  • Cleaning agent further comprises one or more of the substances selected from the group consisting of further complexing agents, further 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, fluorescers, dyes, hydrotropes, foam inhibitors, silicone oils, anti redeposition agents,
  • Grayness inhibitors anti-shrinkage agents, anti-wrinkling agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, Corrosion inhibitors, antistatic agents, bittering agents, ironing auxiliaries, repellents and impregnating agents, swelling and anti-slip agents, plasticizing components and UV absorbers.
  • the washing or cleaning agent according to the invention comprises at least one bleach catalyst.
  • the bleach catalysts include, but are not limited to, sutfonimines and / or bleach-enhancing transition metal salts or transition metal complexes.
  • the candidate transition metal compounds include in particular manganese, iron, cobalt, ruthenium or molybdenum-salene complexes and their N-analogues, manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes.
  • Bleach-enhancing transition metal complexes in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, in usual amounts, preferably in an amount up to 1 wt .-%, in particular from 0.0025 to 0.25 wt -%, and particularly preferably from 0.01 to 0.1 wt .-% are used, each based on the total weight of the detergent or cleaning agent. In special cases, however, more bleach catalyst can 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
  • ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl
  • Detergents or cleaning agents containing at least one bleach catalyst wherein the bleach catalyst is selected from the group of bleach-enhancing transition metal salts and transition metal complexes, preferably the complexes of manganese in the oxidation state
  • macrocyclic ligand having the donor functions N, NR, PR, O and / or S, more 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-triazacyclononane (Me-TACN) or 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane (Me / Me-TACN) are preferred according to the invention.
  • Detergent at least one surfactant selected from the group of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and mixtures of the aforementioned.
  • Suitable anionic surfactants are those of the formula (I)
  • R represents a linear or branched unsubstituted alkylaryl group.
  • Y stands for a monovalent cation or the n-th part of an n-valent cation, the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations Y + may be selected from NhV, Mg 2+ , Y 2 Ca 2+ 2 Mn 2+ , and mixtures thereof.
  • Alkylaryl refers to organic radicals consisting 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 alkylbenzenesulfonates of the formula A-1
  • the compound of formula (I) is preferably the sodium salt of a linear alkyl benzene sulfonate.
  • anionic surfactants are those of the formula (II)
  • R is a linear or branched, substituted or
  • unsubstituted alkyl, aryl or alkylaryl radical preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical.
  • Preferred radicals R are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
  • Particularly preferred radicals R 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 represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • the index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8.
  • X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na + or K + including Na, with Na + being extremely preferred. Additional cations X + can be selected from NH 4 + , Mg 2+ , Y 2 Ca 2+ 2 Mn 2+ , and mixtures thereof.
  • anionic surfactants are the alkyl sulfates of the formula
  • R 2 is a linear or branched, substituted or
  • unsubstituted alkyl radical preferably a linear, unsubstituted alkyl radical, more 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, where the representatives with even number of carbon atoms Atoms are preferred.
  • Particularly preferred radicals R 2 are derived from Ci2-CI8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or of Cio-C2o-oxo alcohols.
  • X represents a monovalent cation or the nth part of an n-valent cation, with the alkali metal ions being preferred, and Na + or K + being preferred, Na + being extremely preferred.
  • Other cations X + can be selected from NhV,
  • these surfactants are selected from fatty alcohol sulfates of formula A-3
  • the content of anionic surfactants is preferably less than 4 wt .-%, more preferably less than 2 wt .-% and in particular less than 1 wt .-%.
  • 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 automatic dishwashing detergents contain nonionic surfactants from the group of the alkoxylated alcohols.
  • Suitable nonionic surfactants are in particular the fatty alcohol alkoxylates.
  • the detergents therefore contain at least one nonionic surfactant of the formula
  • R 3 is a linear or branched, substituted or unsubstituted alkyl radical
  • AO for an ethylene oxide (EO) or propylene oxide (PO) grouping
  • n stands for integers from 1 to 50.
  • 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,
  • 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 represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety.
  • EO ethylene oxide
  • PO propylene oxide
  • m is an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, m is the numbers 2, 3, 4, 5, 6, 7 or 8.
  • a class of useful 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 come from the groups of ethoxylated primary alcohols and mixtures of these surfactants with structurally complicated surfactants such as
  • Polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants).
  • Such (PO / EO / PO) nonionic surfactants are characterized by good foam control.
  • nonionic surfactants are those which contain alternating ethylene oxide and
  • surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows.
  • R 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 -Chta, -CH2CH3, -CH2CH2-CH3, CH (CH3) 2 and the indices w, x, y, z are each independently integers 1 to 6
  • nonionic surfactants having a C9-alkyl group with 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units, followed by 1 to 4
  • Preferred nonionic surfactants here are those of the general formula
  • R is -CH (OH) CH 2 O- (AO) w- (A'0) x- (A "0) y - (A '" 0) z R 2 in which
  • R is a straight-chain or branched, saturated or mono- or polyunsaturated C 6-24-alkyl or alkenyl radical
  • R 2 is H or a linear or branched hydrocarbon radical having 2 to 26 carbon atoms;
  • A, ⁇ ', A "and A'" independently of one another are radicals from the group -CH 2 CH 2 , -CH 2 CH 2 -CH 2 , -CH 2 -CH (CH 3 ), -CH 2 -CH 2 -CH 2 -CH 2 , -CH 2 - CH (CH 3 ) -CH 2 -, - CH 2 -CH (CH 2 -CH 3 ),
  • w, x, y and z are values between 0.5 and 120, where x, y and / or z can also be 0.
  • Hydrocarbon radicals having 2 to 30 carbon atoms, preferably 4 to 22
  • Carbon atoms furthermore a linear or branched, saturated or
  • x stands for values between 1 and 90, preferably for values between 30 and 80 and in particular for values between 30 and 60.
  • surfactants of the formula R 0 [CH 2 CH (CH 3) O] x [CH 2 CH 2 O] yCH 2 CH (OH) R 2 in which R is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 is a linear one or branched
  • Hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y is a value of at least 15 stands.
  • nonionic surfactants includes, for example, the C2-26 fatty alcohol (PO) i- (EO) i5-4o-2-hydroxyalkyl ethers, in particular also the coco-fatty alcohol (PO) i (EO) 22-2-hydroxydecyl ethers ,
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 where R and R 2 are linear or branched , saturated or unsaturated, aliphatic or aromatic Hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x is Values between 1 and 30, k and j represent values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula R 0 [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] jOR 2 may be different.
  • R and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22
  • Carbon atoms, with radicals having 8 to 18 carbon atoms are particularly preferred.
  • R 3 H, -Chta or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x> 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • R 1 RO [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 simplified.
  • R 1 R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R and R 2 Have 9 to 14 carbon atoms, R 3 is H and x assumes values of 6 to 15.
  • nonionic surfactants of the general formula R -CH (OH) CH 2 O- (AO) w -R 2 have proved to be particularly effective, in which
  • R for a straight-chain or branched, saturated or on or
  • R 2 is a linear or branched hydrocarbon radical having 2 to 26
  • A is a radical from the group CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH (CH 3 ),
  • w stands for values between 1 and 120, preferably 10 to 80, in particular 20 to 40
  • the group of these nonionic surfactants include, for example, the C4-22 fatty alcohol (EO) io-8o-2-hydroxyalkyl ethers, in particular also the C8-12 fatty alcohol (EO) 22-2-hydroxydecyl ethers and the C4-22 fatty alcohol (EO) 4o 8o-2-hydroxyalkyl ethers.
  • R 2 is hydrogen and R, R 3 , A, A, A ", A '", w, x, y and z are as defined above.
  • compositions described herein which preferably comprise at least one nonionic surfactant, more preferably a nonionic surfactant from the group of hydroxy mixed ethers, contain the further nonionic surfactant in various embodiments in an amount based on the total weight of the composition of at least 1 wt .-%, preferably at least 2.5% by weight.
  • nonionic surfactants which may be included in the described compositions within the meaning 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, for example, alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which is a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • soaps suitable being 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.
  • those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12-18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of 0.1 to 5% by weight. In particular, in the liquid phase, however, higher amounts of soap of usually up to 20 wt .-% may be included.
  • Suitable amphoteric surfactants are, for example, betaines of the formula (R iii) (R iv) (R v) N + CH2COO _ in which R i is an optionally interrupted by hetero atoms or hetero atom groups alkyl radical having 8 to 25, preferably 10 to 21 carbon atoms, and R IV and R v are identical or different alkyl radicals having 1 to 3 carbon atoms, in particular Cio-Cis-alkyl dimethylcarboxymethylbetain and Cn-Ci7-alkylamidopropyl-dimethylcarboxymethylbetain.
  • Suitable cationic surfactants are i.a. the quaternary ammonium compounds of the formula
  • R VI (R VI ) (R vii ) (R viii ) (R ix ) N + X "
  • R vi to R ix for four identical or different, in particular two long and two short-chain, alkyl radicals and X " for an anion , in particular a halide ion, for example, didecyldimethylammonium chloride, Alkylbenzyldidecylammoniumchlorid 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.
  • the agent can be designed with an antimicrobial effect or its possibly existing antimicrobial effect 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 the surfactants, based on the weight of the agent is 1 to 45% by weight, preferably 5 to 25% by weight.
  • the agent according to the invention comprises water-soluble and / or water-insoluble builders, in particular selected from alkali metal aluminosilicate, crystalline
  • Alkali silicate with modulus above monomeric polycarboxylate, polymeric polycarboxylate and their Mixtures, in particular in quantities ranging from 2.5% by weight to 60% by weight.
  • Other builders which may be present in the dishwashing detergent in the amounts mentioned include, 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, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized.
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • acid content is at least 50% by weight.
  • water-soluble organic builders it is also possible to use terpolymers which as monomers two
  • Carboxylic acids and / or salts thereof and as the third monomer vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate are derived from a monoethylenically unsaturated C 3 -C 5 -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 C4-Cs dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 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 also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt may also be a derivative of an allylsulfonic acid which is in the 2-position with a Alkyl radical, preferably with a Ci-C4-alkyl radical, or an aromatic radical which is derived preferably from benzene or benzene derivatives substituted.
  • Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 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 from 15% by weight to 25% by weight, of methallylsulfonic acid and / or methallylsulfonate and, as the third monomer, from 15% by weight to 40% by weight, preferably from 20% by weight to 40% by weight.
  • % of a carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol.
  • the dishwashing detergents can contain as further builders in particular also phosphonates, which according to the invention are not subsumed under the phosphates.
  • the phosphonate compound used is preferably a hydroxyalkane and / or aminoalkane phosphonate.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • Phosphonates are contained in the compositions preferably in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.3 to 8% by weight, in each case based on the total weight of the dishwashing detergent.
  • machine dishwashing detergents are preferred according to the invention in that the dishwashing detergent contains citric acid or a salt of citric acid and that the weight fraction of citric acid or of the salt of citric acid is preferably 1 to 40 wt.%, Preferably 10 to 25 wt between 15 and 22 wt .-% is.
  • phosphate-free builders are aminocarboxylic acids and / or their salts. Particularly preferred members of this class are
  • Methylglycinediacetic acid (MGDA) or its salts Methylglycinediacetic acid (MGDA) or its salts, and glutamic diacetic acid (GLDA) or its salts or ethylenediaminediacetic acid (EDDS) or its salts.
  • GLDA glutamic diacetic acid
  • EDDS ethylenediaminediacetic acid
  • Very particular preference is GLDA or its salts.
  • the content of these aminocarboxylic acids or their salts, in particular GLDA sodium salt for example, between 0, 1 and 25 wt .-% is preferred between 5 and 25 wt .-% and in particular between 15 and 25 wt .-% amount.
  • Aminocarboxylic acids and their salts can be used, for example, together with the abovementioned builders, in particular together with citrate and the abovementioned phosphonates.
  • polycarboxylic acids mentioned 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.
  • Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents. In other embodiments, amounts close to said upper limit are preferably employed 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 agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the stated upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 ⁇ m, and preferably consist of at least 80% by weight of particles having a size of less than 10 ⁇ m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful 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 may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2 O.sub.x + VH.sub.2O, 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5-yH 2 O
  • x is a number from 1, 9 to 2.1
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
  • Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in another preferred embodiment of detergents.
  • Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate 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, in each case based 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 especially 1: 1 to 2: 1.
  • inorganic builder it is possible for further water-soluble or water-insoluble inorganic substances to be used in the compositions together with this or used in the process according to the invention.
  • suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof.
  • additional inorganic material may be present in amounts up to 70% by weight.
  • the dishwashing agents according to the invention may further comprise a sulfopolymer as further builder.
  • the proportion by weight of the sulfopolymer in the total weight of the dishwashing agent according to the invention is preferably from 0.1 to 20 wt .-%, in particular from 0.5 to 18 wt .-%, particularly preferably 1, 0 to 15 wt .-%, in particular from 4 to 14 wt .-%, especially from 6 to 12 wt .-%.
  • the sulfopolymer is usually used in the form of an aqueous solution, the aqueous solutions typically containing 20 to 70 wt .-%, in particular 30 to 50 wt .-%, preferably about 35 to 40 wt .-% sulfopolymers.
  • the sulfopolymer used is preferably a copolymeric polysulfonate, preferably a hydrophobically modified copolymeric polysulfonate.
  • the copolymers may have two, three, four or more different monomer units.
  • Preferred copolymeric polysulfonates contain not only sulfonic acid group-containing monomer (s) but also at least one monomer selected from the group consisting of unsaturated carboxylic acids.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, ⁇ -cyanoacrylic acid, crotonic acid, ⁇ -phenyl-acrylic acid, maleic acid,
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfo - Propylmethacrylat, sulfomethacrylamide, sulfomethylmethacrylamide and mixtures of said acids or their water-
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • the monomer distribution of the copolymers preferably used in the case of copolymers which contain only monomers containing carboxylic acid groups and monomers containing sulfonic acid groups is preferably in each case from 5 to 95% by weight, with the proportion of
  • Sulfonic acid group-containing monomers 50 to 90 wt .-% and the proportion of
  • the molecular weight of the sulfo copolymers preferably used can be varied in order to adapt the properties of the polymers to the desired end use.
  • Preferred dishwashing detergents are characterized in that the copolymers have molecular weights from 2000 to 200,000 gmol "1, preferably from 4000 to 25,000 gmol" 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 builder, wherein in particular the solid, powdery or granular phase contains 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 which act as softeners.
  • cationic, anionic and amphoteric polymers can be used in automatic dishwashing detergents in addition to nonionic polymers.
  • the sulfo (co) polymers described above are, for example, anionic polymers.
  • amphoteric polymers furthermore have, in addition to a positively charged group in the polymer chain, negatively charged groups or monomer units, for example, these may be carboxylic acids, sulfonic acids or phosphonic acids.
  • Preferred polymers which can be used are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the
  • Alkylacrylamide / methylmethacrylic acid copolymers the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid / alkylaminoalkyl (meth) acrylic acid Copolymers, the alkylacrylamide / alkymethacrylate / Alkylaminoethylmethacrylat / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally other ionic or nonionic monomers.
  • Further usable polymers come from the group of acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali metal and ammonium salts, the acrylamido alkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.
  • the abovementioned 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 in preferred embodiments.
  • the enzyme used or the enzymes used can in one
  • any enzyme known in the art capable of exhibiting catalytic activity in a detergent or cleaning agent is suitable, and includes but is not limited to, for example, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin-cleaving Enzymes, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
  • proteases amylases, lipases, cellulases, hemicellulases, mannanases, pectin-cleaving Enzymes, tannases, xylanases, xanthanases, ⁇ -glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases and mixtures thereof.
  • proteases amylases, lipa
  • Embodiment is the at least one enzyme selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof. These enzymes are, in principle, of natural origin, but starting from the natural molecules, improved variants are available for use in detergents or cleaners, which are preferably used accordingly.
  • the agents contain enzymes preferably in total amounts of 1 ⁇ 10 6 to 5 wt .-% based on active protein.
  • the protein concentration can be determined by known methods, for example the BCA method or the biuret method.
  • the enzyme is in an amount of 0.01 to 10 wt .-%, preferably 0.01 to 5 wt .-% in the inventive composition, based on the
  • the protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
  • BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
  • the determination of the active protein concentration takes place via a titration of the active sites using a suitable irreversible inhibitor (for proteases, for example phenylmethylsulfonyl fluoride (PMSF)) and determination of the residual activity (compare M. Bender et al., J. Am. Chem. Soc , 24 (1966), pp. 5890-5913).
  • PMSF phenylmethylsulfonyl fluoride
  • proteases are among the most technically important enzymes of all. They cause the degradation of protein-containing stains on the items to be cleaned.
  • proteases of the subtilisin type (subtilases, subtilopeptidases, EC 3.4.21 .62) are particularly important, which are serine proteases due to the catalytically active amino acids. They act as unspecific Endopeptidases and hydrolyze any acid amide bonds, which are located inside of peptides or proteins. Their pH optimum is usually in the clearly alkaline range.
  • Subtilases are naturally produced by microorganisms. Of these, in particular, the subtilisins formed and secreted by Bacillus species are to be mentioned as the most important group within the subtilases.
  • subtilisin-type proteases preferably used in washing 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,
  • Proteases are selectively or randomly modified by methods known from the prior art and 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. Thus, correspondingly optimized variants are known for most 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 improved for use in dishwashing further developments of the aforementioned amylases.
  • the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).
  • lipases or cutinases in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors.
  • lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L.
  • enzymes can be used which are termed hemicellulases
  • pectinases pectinases
  • pectin esterases pectate lyases
  • xyloglucanases xylanases
  • pullulanases and ß-glucanases.
  • ß-glucanases the licheninases in particular should be mentioned.
  • Oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese, may be used to increase the bleaching effect.
  • Peroxidases, dioxygenases or laccases phenol oxidases, polyphenol oxidases
  • the agent according to the invention preferably comprises at least one enzyme selected from the group comprising proteases, amylases, lipases, hemicellulases, cellulases, ⁇ -glucanases,
  • An enzyme can be particularly protected during storage against damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
  • damage such as inactivation, denaturation or disintegration such as by physical influences, oxidation or proteolytic cleavage.
  • inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
  • Dishwashing agents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
  • the enzymes to be used may also be formulated together with adjuncts, such as from fermentation.
  • the enzymes are preferably used as enzyme liquid formulation (s).
  • the enzymes are usually not provided in the form of the pure protein, but rather in the form of stabilized, storable and transportable preparations. To this
  • Prefabricated preparations include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers or further auxiliaries.
  • the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or
  • Chemical-impermeable protective layer is coated.
  • further active ingredients for example 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 by applying polymeric
  • the enzyme protein forms only a fraction of the total weight of conventional enzyme preparations.
  • Preferably used protease and / or amylase preparations contain between 0.1 and 40 wt .-%, preferably between 0.2 and 30 wt .-%, particularly preferably between 0.4 and 20 wt .-% and in particular between 0 , 8 and 10 wt .-% of the enzyme protein.
  • Total weight 0, 1 to 12 wt .-%, preferably 0.2 to 10 wt .-% and in particular 0.5 to 8 wt .-% enzyme preparations.
  • the agent according to the invention may comprise one or more enzyme stabilizers.
  • compositions described herein may also include enzyme stabilizers.
  • stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted
  • Phenylboronic in particular 4-formylphenyl-boronic acid, or the salts or esters of said compounds.
  • peptide aldehydes that is oligopeptides with a reduced C-terminus, especially those of 2 to 50 monomers are 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 suitable.
  • enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C12, such as succinic acid, other dicarboxylic acids or salts of said acids. Also end phenomenonver notese Fatty acid amide alkoxylates are suitable for this purpose. Other enzyme stabilizers are known to those skilled in the 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 perfumes within the scope of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouli, rose or ylang-ylang oil.
  • Solvents which are suitable for the compositions used according to the invention are generally water-miscible organic solvents, such as, without limitation, monohydric 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
  • the washing or cleaning agent may contain such organic solvents in amounts of up to at most 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 in the form of a
  • Pre-assembled multi-compartment sachet In this case, the liquid and the solid phase are in different chambers of the sachet.
  • Such prefabricated metering units preferably comprise the necessary for a cleaning cycle amount of washing or cleaning-active substances.
  • Preferred metering units have a weight between 12 and 35 g, preferably between 14 and 29 g and in particular between 16 and 26 g.
  • the volume of the aforementioned metering units and their spatial form are chosen with particular preference so that a metering of the prefabricated units on the metering a Washer or dishwasher is guaranteed.
  • the volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 14 and 25 ml.
  • the detergents and cleaners in particular the prefabricated metering units, have a water-soluble sheath with particular preference.
  • the water-soluble coating is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends.
  • the wrapper may be formed of one or two or more layers of the water-soluble film material.
  • the water-soluble film material of the first layer and the further layers, if present, may be the same or different. Particularly preferred are films which, for example, can be glued and / or sealed to packages such as hoses or cushions after being filled with an agent.
  • the water-soluble packaging has at least two or more chambers, in each of which one of the at least two different phases, as defined herein, is contained.
  • the amount of agent preferably corresponds to the full or half dose needed for a washing or cleaning cycle.
  • the washing or cleaning agent according to the invention may be characterized in that it is in a water-insoluble, water-soluble or water-disintegratable packaging, in particular in a polyvinyl alcohol-containing film, wherein 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 polyvinyl alcohol-containing film, are separated from each other.
  • the washing or cleaning agent according to the invention can thereby
  • waterdisintegrierbaren packaging in particular in a polyvinyl alcohol-containing film, wherein in particular the at least one gel or pasty and the at least one solid phase in the same chamber of the water-soluble or water-dispersible packaging, in particular the polyvinyl alcohol-containing film, are.
  • Most preferred are water-soluble or water-disintegratable packaging.
  • the water-soluble coating be polyvinyl alcohol or a
  • Water-soluble coatings containing polyvinyl alcohol or a Containing polyvinyl alcohol copolymer have a good stability with a sufficiently high water solubility, in particular cold water solubility on.
  • Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose
  • Molecular weight in the range of 10,000 to 1,000,000 gmol "1 , preferably from 20,000 to 500,000 gmol 1 , more preferably from 30,000 to 100,000 gmol -1 and in particular from 40,000 to 80,000 gmol 1 .
  • polyvinyl alcohol is usually carried out by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible.
  • polyvinyl alcohol copolymers which are prepared in accordance with polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.
  • the degree of polyvinyl alcohol hydrolysis is at least 85 mole%, preferably at least 88 mole%, even more preferably at least 90 mole%, most preferably at least 98 mole%.
  • Polyvinyl alcohol is strictly speaking a copolymer of vinyl alcohol and vinyl acetate, the monomer ratio in the polymer depending on the degree of hydrolysis of the vinyl acetate. However, in the nomenclature used herein, the polyvinyl alcohol polymer is considered a homopolymer.
  • copolymer or terpolymer is used when in addition to the vinyl alcohol and vinyl acetate other monomers are included in the polymer.
  • the polyvinyl alcohol hydrolysis degree is 85 mol% or more, preferably 88 mol% or more, still 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-methylpropanesulfonic acid (AMPS). Also included are terpolymers of polyvinyl alcohol. Preferably, the polyvinyl alcohol is a copolymer comprising AMPS. When copolymers or terpolymers are used, the degree of polyvinyl alcohol hydrolysis is usually at least 90 mol%. Preferably, the degree of hydrolysis is at least 95 mole%, more preferably at least 98 mole%.
  • AMPS 2-acrylamido-2-methylpropanesulfonic acid
  • the polyvinyl alcohol may comprise a mixture of polyvinyl alcohol and a monomer selected from the list consisting of 2-aerylamido-1-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid and alkali metal salts thereof.
  • the content of sulfonic acid group units in the modified polyvinyl alcohol is preferably 0.1 to 20 mol%, more preferably 0.5 to 10 mol%, most preferably 1 to 5 mol%.
  • the mechanical properties as a water-soluble film are also important. Sufficient strength and flexibility of the film are necessary, especially in the case of a small thickness of 10 to 100 ⁇ . Therefore, the degree of polymerization averaged over the viscosity (herein referred to as
  • Degree of polymerization of the modified PVA is preferably 300 to 10,000, more preferably 500 to 8000, more preferably 900 to 2000, even 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 during the production of the film becomes so high that the processability 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. The viscosity averaged
  • a synthesis can be carried out, for example, as follows.
  • Copolymerization of vinyl acetate and sodium acrylamido-2-methylpropanesulfonate in methanol is added. This hydrolyzes the copolymer 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 may be present as a terpolymer.
  • the second film comprises a copolymer of polyvinyl alcohol having from 0 to 10 mole percent of residual acetate and from 1 to 6 mole percent of a non-hydrolyzable anionic co-monomer 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.
  • the vinyl acetate-co-ltaconic acid copolymer is prepared under nitrogen in methanol as a solvent using 2,2'-azobis (isobutyronitrile) (AIBN) as an initiator. Alcoholysis of this copolymer is carried out in methanolic sodium hydroxide solution and the recovered
  • Vinyl alcohol-co-ltaconic acid (sodium salt) copolymer washed to remove residual sodium acetate, and dried.
  • the preferred degree of polymerization of the vinyl alcohol co-lactaconic acid (sodium salt) copolymer is preferably such that the viscosity of a freshly prepared 4% aqueous solution at 20 ° C is in a range of from about 5 to about 45 MPa ⁇ s (cps). More preferably, the viscosity is in the range of 1 to 30 mPas and more preferably in the range of 15 to 25 mPas.
  • the viscosities described herein are determined for a freshly prepared 4% aqueous solution at 20 ° C with a Brookfield LV viscometer with a UL adapter according to EN ISO 15023-2: 2006 Appendix E Brookfield Test Method.
  • the preferred degree of incorporation of itaconic acid comonomer in the vinyl alcohol-co-lactaconic acid (sodium salt) copolymer is in the range of from about 1.5 to about 11 mole percent. More preferably, the degree of incorporation is in the range of 2.5 to 8.5 mole percent, and more preferably in the range of 4-6 mole percent.
  • the preferred degree of hydrolysis of the vinyl alcohol-co-itaconic acid (sodium salt) copolymer of the present invention, as converted as a percentage of vinyl acetate units to vinyl alcohol units, is in the range of about 98 to 100%.
  • the polyvinyl alcohol polymer is a copolymer with a sulfonate monomer, preferably AMPS, or is a terpolymer with AMPS and another monomer.
  • sulfonic acid monomers which act as stronger acids over carboxylic acid monomers, react less strongly with the hydroxy groups of the vinyl alcohol monomers in the polymer.
  • the water solubility of the resulting polymers is more independent of pH changes and inorganic salts.
  • (Meth) acrylic acid-containing (co) polymers polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid or mixtures of the above polymers may be added.
  • a preferred additional polymer is polylactic acids.
  • Preferred polyvinyl alcohol copolymers include, in addition to vinyl alcohol, dicarboxylic acids as further monomers.
  • Suitable dicarboxylic acids are itaconic acid and mixtures thereof, wherein
  • Itaconic acid is preferred.
  • polyvinyl alcohol copolymers include, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt or its esters.
  • Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylates, methacrylates or mixtures thereof.
  • the film material contains further additives.
  • the film material may include, for example, plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol,
  • Additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, detackifiers, or mixtures thereof.
  • Suitable water-soluble films for use in the water-soluble coatings of the water-soluble packaging according to the invention are films sold by the company MonoSol LLC, for example under the designation M8630, M8315, M8720, C8400 or M8900.
  • Other suitable films include films named Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the films VF-HP from Kuraray.
  • washing or cleaning agent according to the invention is likewise an object of the invention.
  • the invention relates to a Textilwasch- or
  • Dishwashing process in particular automatic dishwashing process, in which a detergent or cleaning agent according to the invention is used.
  • the subject of the present application is therefore also a process for the cleaning of textiles or hard surfaces, such as crockery, in a washing machine or dishwasher, wherein the agent according to the invention during the passage of a washing or Geschirr Hughesprogramms before the beginning of Hauptpül- or wash passage or im Course of Hauptpül- or wash passage is metered into the interior of a washing machine or dishwasher.
  • Dishwasher can be done manually, but preferably the agent is metered by means of the metering chamber into the interior of the washing machine or dishwasher.
  • the present invention is also directed to the particles described herein.
  • the particles according to the invention comprise at least one
  • Bleach activator wherein the at least one bleach activator is compounded with at least one complexing agent.
  • the complex image 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 prepared in the manner described there.
  • the particles consist essentially or exclusively of bleach activator and chelating agent, preferably in the above ratios, i. the amount of the complexing agent is 5 to 30 wt .-% 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 complexing agent is selected from the group consisting of the sodium salt of DTPMP and HEDP. In different of these
  • Embodiments is the at least one bleach activator TAED.
  • the particles described herein are characterized by being 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 ⁇ .
  • the detergents and cleaners according to the invention comprising the particles described herein are distinguished by their storage stability and, even after a relatively long period of time, no discoloration or fragrance change occurs either with the particles themselves or with the detergents or cleaners in which they are present.
  • the agents have good washing or cleaning performance even after long storage, especially when they contain bleach.
  • the agent remains visually attractive over a long period of time and has improved cleaning or washing performance.
  • TAED granules ex Warwick was compounded in a Glatt AGT 200 fluidized bed with a DTPMP phosphonate solution (diethylenetriaminepentamethylenephosphonic acid heptasodium salt, Dequest 2066, ex thermPhos).
  • the fluidized bed temperature was chosen so that there was no agglomeration of the TAE D granules.
  • the resulting TAED-DTPMP compound had a DTPMP content of 13.0 wt%.
  • Two powder blends A1-A3 were prepared in a tumble mixer by dry blending the individual granules.
  • A1 contains the TAED complexing agent compound according to the invention.
  • A2 is without a complexing agent and
  • A3 is a composition in which a complexing agent is added separately as granules.
  • 1-Hydroxyethane-1, 1-diphosphonic acid tetrasodium salt was used as HEPD.
  • a liquid phase of composition B was prepared.
  • the recipe contains 8.39 wt .-% water from addition and raw materials. All ingredient information as active ingredient. Diethylenetriaminepentamethylenephosphonic acid heptasodium salt was used as DTPMP.
  • the produced sachets were stored at 40 ° C in a closed screw-capped glass. After storage, a sample is taken from the powder chambers and fed to a TAM (Thermal Activity Monitor) measurement. The sample is stored isothermally at 40 ° C and determines the heat flow from this sample over time. It's exothermic
  • the inventive composition A1 freshly shows the same stability as the
  • TAED granules ex Warwick was compounded in a smooth fluid bed with a complexing agent solution.
  • the fluidized bed temperature was chosen so that it is none
  • TAED complexing agents trisodium-a-DL-alanine diacetate, Trilon M
  • GLDA tetrasodium N, N-bis (carboxylatomethyl) -L-glutamate, dissolvins
  • MGDA trisodium-a-DL-alanine diacetate, Trilon M
  • GLDA tetrasodium N, N-bis (carboxylatomethyl) -L-glutamate, dissolvins
  • MGDA trisodium-a-DL-alanine diacetate, Trilon M
  • GLDA tetrasodium N, N-bis (carboxylatomethyl) -L-glutamate, dissolvins
  • the resulting TAED complexant compounds had a complexing agent content of 12.0% by weight.
  • Enzyme preparation (protease, amylase) 2.00-8.00

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Abstract

L'invention concerne un mélange activateur de blanchiment/agent complexant ainsi qu'un agent de lavage et de nettoyage multiphasique comprenant au moins une phase liquide, allant de faiblement aqueuse à anhydre et au moins une phase solide, pulvérulente ou granulaire et contenant au moins un activateur de blanchiment mélangé à au moins un agent complexant. La présente invention concerne en outre l'utilisation de ce type d'agent dans des procédés de lavage et de nettoyage dans lequel on utilise ce type d'agents ainsi que ces procédés de lavage.
EP17805165.2A 2016-11-25 2017-11-22 Sachet contenant un mélange activateur de blanchiment/agent complexant Active EP3545067B1 (fr)

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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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WO2018138124A1 (fr) * 2017-01-24 2018-08-02 Henkel Ag & Co. Kgaa Dose de détergent comprenant au moins deux phases
DE102020212099A1 (de) * 2020-09-25 2022-03-31 Henkel Ag & Co. Kgaa Konzentrierte fließfähige Waschmittelzubereitung mit verbesserten Eigenschaften

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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
EP2397539B1 (fr) * 2010-06-15 2013-03-27 The Procter & Gamble Company Poche à compartiments multiples
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
DE102016223472A1 (de) 2018-05-30

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