EP3008158B1 - Granulés combinés sous forme d'agent de blanchiment, procédés de production desdits granulés et leur utilisation - Google Patents

Granulés combinés sous forme d'agent de blanchiment, procédés de production desdits granulés et leur utilisation Download PDF

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Publication number
EP3008158B1
EP3008158B1 EP14723721.8A EP14723721A EP3008158B1 EP 3008158 B1 EP3008158 B1 EP 3008158B1 EP 14723721 A EP14723721 A EP 14723721A EP 3008158 B1 EP3008158 B1 EP 3008158B1
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Prior art keywords
weight
granulate
acid
bleaching agent
granules
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German (de)
English (en)
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EP3008158A1 (fr
Inventor
Gerd Reinhardt
Michael Best
Miriam Ladwig
Andreas Schottstedt
Mathias Groeschen
Sven GEHARD
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Catexel Production GmbH
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Weylchem Wiesbaden GmbH
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3955—Organic bleaching agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • C11D17/0091—Dishwashing tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in 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
    • C11D3/39—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
    • C11D3/391—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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
    • C11D3/391—Oxygen-containing compounds
    • C11D3/3912—Oxygen-containing compounds derived from saccharides
    • 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
    • C11D3/3915—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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
    • 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
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3922—Cyanamides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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

Definitions

  • the present invention relates to bleach co-granules, a process for their preparation and their use in detergents and cleaners, in particular in detergents for dishwashing.
  • dishwashing detergents for machine cleaning.
  • the dishwashing detergents In order to activate these bleaching agents and to achieve a satisfactory bleaching action during cleaning at temperatures of 60 ° C. and below, the dishwashing detergents generally furthermore contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.
  • Bleach catalysts are used in dishwasher detergents for machine cleaning, preferably in the form of prefabricated granules. This is done on the one hand to increase their storage stability, on the other hand, but also to ensure a homogeneous incorporation of tiny amounts of catalyst in the formulations, especially in tablet applications.
  • Bleach catalysts based on various manganese-containing transition metal complexes are z.
  • EP 0 458 397 EP 0 458 398 and EP 0 530 870 described.
  • Process for the preparation of bleach catalyst granules are described in EP 0 544 440 .
  • bleach catalysts are low in most cases.
  • the performance of bleaching agents in dishwasher detergents is therefore higher, if they consist of a combination of a bleach catalyst with a bleach activator.
  • the bleaching effect of the catalyst is effectively supported by the peroxycarboxylic acid formed from the activator.
  • the peroxycarboxylic acid significantly contributes to germ killing on the items to be washed, improves the odor of the wash liquor and prevents the formation of a biofilm in the dishwasher.
  • the combination of bleach catalysts and bleach activators is therefore useful for increasing bleaching performance and ensuring hygiene in the use of bleaching agents in laundry detergents and cleaners.
  • Detergent formulations containing both a bleach activator such as tetraacetylethylenediamine (TAED), nonanoyloxibenzenesulfonate sodium (NOBS) or decanoyloxibenzoic acid (DOBA) and one or more bleach catalysts are known in the art. So z. In EP 0 710 714 a bleaching composition containing TAED, a manganese catalyst and a crystalline layered silicate. These components are added as separate particles to the detergent formulation but not in the form of a uniform co-granule.
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxibenzenesulfonate sodium
  • DOBA decanoyloxibenzoic acid
  • activators and catalysts as separate particles or granules also has disadvantages that can have a negative effect on the bleaching performance.
  • the reactions of the persalt or of the hydrogen peroxide released therefrom with activator and catalyst proceed in parallel. Dissolves the catalyst granules faster than the activator granules, then the persalt is already consumed before it can react with the activator. The same applies to the opposite case.
  • Co-granules of activators and catalysts are also advantageous in order to ensure the homogeneous distribution of both components in the detergent and cleaning agent and to save space in the formulation. Furthermore, the manufacturing costs are reduced, since instead of two different granules, only one co-granulate must be produced.
  • WO 03/093405 describes co-granules consisting of a bleach catalyst, a bleach activator, and optionally a coating.
  • a manganese (II) complex is mixed with TAED powder and a tallow fatty alcohol ethoxylate (Genapol® T500, Clariant) in a Lödigemischer at 40 to 50 ° C and then by means of an extruder to noodle-shaped granules pressed.
  • Preferred bleach catalysts for the preparation of such co-granules are metal complexes with macrocyclic, bridged ligands, as described in WO 01/64826 and WO 98/39098 are described. These are characterized by a particularly good chemical stability.
  • WO 2010/115581 describes co-granules comprising a) one or more bleach activators, b) one or more bleach catalysts and c) at least 5% by weight of one or more organic acids.
  • Possible binders mentioned are fatty acids, alcohol ethoxylates or polymers.
  • Preferred binder, as can be seen from the examples, is Genapol® T500.
  • bleach catalysts in particular manganese salts, can be converted into storage-stable, odorless co-granules which are suitable for use in detergents and cleaners.
  • co-granules consisting of TAED, [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 .H 2 O and Genapol® T500, prepared according to the teachings of WO 03/093405 or WO 2010/115581 , after a certain storage time have a distinct smell of amines. They are therefore unsuitable for commercial use in household products. It is believed that during production and / or storage of the co-granules at least a small proportion of the manganese complex decomposes, thereby releasing the ligand trimethyltriazacyclononane (TACN), which has a strong amine-like odor.
  • TACN trimethyltriazacyclononane
  • the present invention therefore relates to storage-stable and odorless bleach co-granules according to claim 1, which comprises a bleach activator, a metal-containing bleach catalyst comprising at least one ligand selected from the group consisting of di- or trimethyltriazacyclononanes or derivatives thereof, and a homo- or copolymer based on ( Meth) acrylic acid, or its salts or Operaneutralisate having a pH in the range of 3 to 9, the characteristic feature is seen in that they are prepared in an anhydrous granulation process, preferably by compaction, and that the temperature in the anhydrous granulation process kept below 100 ° C.
  • the bleach co-granule according to the invention is preferably characterized in that it contains no alcohol ethoxylates or ethylene or propylene oxide derivatives.
  • the co-granules according to the invention can be 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-nonanoyloxy or n-lauroyl oxbenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxibenzoic acid (NOBA or DOBA), Carboxylic acid anhydrides, in particular phthalic anhydrides, in
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • nitrile derivatives such as n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators.
  • MMA n-methyl-morpholinium-acetonitrile-methyl sulfate
  • MOR cyanomorpholine
  • bleach activators can also be used.
  • Particularly preferred bleach activators are TAED, NOBS and DOBA.
  • Bleach catalysts used in the context of the present invention are preferably bleach-enhancing transition metal salts or complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.
  • complexes of iron in the oxidation states II or III and the manganese in the oxidation state II, III, IV or IV preferably one or contain several macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, in which R is a hydrocarbon radical having up to 5 C atoms.
  • ligands are used which have nitrogen donor functions.
  • Preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN) or bridged ligands such as 1,2-bis (4,7-dimethyl -1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE), as described, for.
  • EP 0 458 397 EP 0 458 398 .
  • WO 96/06157 or WO 2006/125517 are described.
  • manganese complexes examples include the polynuclear complexes [Mn III 2 ( ⁇ -O) 1 ( ⁇ -OAc) 2 (TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (SO 4 ), [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (OAc) 2 , [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (Cl) 2 , [Mn IV Mn III 2 ( ⁇ -O) 2 (OAc) (Me4-DTE)] (Cl) 2 , Mn IV Mn III 2 ( ⁇ -O) 2 (OAc) (Me4-DTE)] (PF 6 ) 2 or the mononuclear complexes [Mn IV (Me-TACN) (OCH 3
  • the co-granules according to the invention contain a binder in order to ensure cohesion of the co-granules.
  • the binder is characterized in that it is polymers or copolymers of acrylic acid and / or methacrylic acid (referred to in this specification "poly (meth) acrylic acid”), preferably in the form of their salts or in teilneutralinstrumenter form.
  • the binder used 1% dissolved in water, a pH of 3 to 9, but especially between 3.5 and 8.5.
  • poly (meth) acrylates which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility preferred from this group, especially the short-chain poly (meth) acrylates having molecular weights of 2,000 to 10,000 g / mol and preferably from 3,000 to 5,000 g / mol.
  • copolymeric polycarboxylates of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are furthermore preferred.
  • Copolymers of acrylic acid or of methacrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid, have proven to be particularly suitable.
  • Their average molecular weight, based on free acids, is preferably 2,000 to 70,000 g / mol, particularly preferably 20,000 to 50,000 g / mol and particularly preferably 30,000 to 40,000 g / mol.
  • Preferred polymers are Sokalan® CP45 and CP5 from BASF in substantially anhydrous form, preferably in powder or granular form.
  • the polymers may also contain structural units derived from allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid.
  • allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid.
  • biodegradable polymers from more than two different monomer units, for example those which contain structural units from salts of acrylic acid or methacrylic acid and maleic acid and from vinyl alcohol or vinyl alcohol derivatives and sugar derivatives or the structural units from salts of acrylic acid or acrylic acid of methacrylic acid and 2-alkylallylsulfonic acid and of sugar derivatives.
  • copolymers are those which have structural units derived from acrolein and acrylic acid / acrylic acid salts or methacrylic acid / methacrylic acid salts or acrolein and vinyl acetate.
  • the co-granules of the invention may contain substances which are known to enhance the effectiveness of the TACN-containing bleach catalyst. Examples of these are, in particular, oxalic acid, ascorbic acid and glyoxylic acid esters and their acetals or hemiacetals.
  • the co-granules according to the invention are not provided with a protective layer (so-called coating).
  • the co-granules of the invention is additionally provided with a protective layer, whereby the storage stability further improved and the co-granules can optionally be colored.
  • the share of Protective or coating layer on the total granulate should then be at least 5 wt .-%, particularly preferably at least 7 wt .-% and particularly preferably at least 15 wt .-% amount.
  • the upper limit of the content of the protective or coating layer on the total granulate is preferably 30% by weight.
  • Preferred coating layers are solid, organic compounds with film-forming properties, eg. As waxes, polyvinyl alcohols or the substances already used as binders (c).
  • the coating layer may additionally contain small amounts of water-soluble or water-insoluble organic dyes.
  • the powdered active substances are first mixed and then this mixture is compacted, then ground and then optionally sieved into individual grain fractions.
  • the compaction is preferably carried out on so-called roll compactors (eg from Hosokawa-Bepex, Alexanderwerk, Köppern).
  • roll compactors eg from Hosokawa-Bepex, Alexanderwerk, Köppern.
  • the roll profile can be on the one hand produce lumpy pellets or briquettes and on the other hand pressing slugs. While the lumpy pellets are usually separated only from the fine fraction, the slugs must be crushed in a mill to the desired particle size. Typically come as a mill type preferably gentle grinding apparatus, such.
  • sieve and hammer mills eg from the company Hosokawa-Alpine, Hosokawa-Bepex
  • roll mills eg., Fa. Bauermeister, Bühler
  • Characteristic of the bleach co-granules according to the invention is primarily their chemical composition. Nevertheless, it has been proven that the Bleaching effect of bleach co-granules can also be influenced by the influence of physical parameters such as the particle size, the fines content and the Blleichkatalysatorgehalts selected sieve fractions advantageous.
  • preferred bleach co-granules according to the invention are characterized in that the co-granules have an average particle size between 0.1 and 1.6 mm, preferably between 0.2 and 1.2 mm and particularly preferably between 0.3 and 1.0 mm, each measured by sieve analysis.
  • the bleach co-granules according to the invention are suitable for use in all detergents or cleaners, and their use in detergents for dishwashing has proven to be particularly advantageous.
  • the organic acid of the bleach co-granules of the present invention performs a protective function and inhibits the reaction of alkaline detergent ingredients with the alkali-labile and hydrolysis-sensitive bleach activators and bleach catalysts of the bleach co-granules of the present invention.
  • Another object of the present invention is therefore the use of a bleach co-granules according to the invention for the production of detergents and cleaners and preferably of agents for the automated cleaning of dishes.
  • Another subject of the present invention are also detergents and cleaners, preferably detergents for dishwashing, comprising a bleach co-granules according to the invention.
  • Preferred detergents and cleaners according to the invention in particular the detergents for dishwashing, contain the bleach co-granules according to the invention in amounts of between 0.1 and 10% by weight, preferably in amounts of between 0.2 and 8% by weight. % and more preferably in amounts between 0.5 and 6 wt .-%.
  • the detergents and cleaners according to the invention in particular the compositions for the automatic cleaning of dishes, which may be in the form of granules, powdered or tablet-like solids but also in liquid or pasty form, may in principle all known and in addition to the co-granules of the invention Means usual ingredients included.
  • the detergents and cleaners according to the invention in particular the compositions for the automated cleaning of dishes, may in particular contain builder substances, peroxygen compounds, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and further auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators.
  • the bleach co-granules according to the invention are suitable both for use in phosphate-containing and phosphate-free formulations.
  • Such an agent is especially lower alkaline, d. H. its 1% by weight solution has a pH in the range of 8 to 11.5 and preferably 9 to 11.
  • alkali metal phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal phosphates examples include trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Their amounts may range from 15 to about 65% by weight, preferably from 20 to 60% by weight, based on the total agent.
  • water-soluble builder components in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the type of the polycarboxylates of native or synthetic origin, which act as co-builders, in particular in hard water regions.
  • organic polymers of the type of the polycarboxylates of native or synthetic origin which act as co-builders, in particular in hard water regions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • water-soluble builder components are naturally occurring hydroxycarboxylic acids such as mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid.
  • the preferred organic water-soluble builder components include the salts of citric acid, especially sodium citrate.
  • citric acid especially sodium citrate.
  • sodium citrate anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable.
  • Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the said co-builder salts may also be present.
  • Particularly preferred builder components in phosphate-free formulations are methylglycine diacetate (MDGA, eg Trilon® M, BASF), L-glutamic acid, N, N, (biscarboxymethyl) -tertra sodium salt (GLDA, Dissolvine® DL, Akzo Nobel), sodium Polyaspartates (Baypure®, Lanxess) or iminodisuccinic acid salts (Baypure®, Lanxess).
  • Preferred peroxygen compounds are perborates and percarbonates, especially the corresponding sodium salts of these compounds.
  • the enzymes present in the detergents and cleaners of the invention include proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM, amylases such as Termamyl TM, Amylase-LT TM, Maxamyl TM, Duramyl TM and / or lipases such as Lipolase TM, Lipomax TM, Lumafast TM and / or Lipozyme TM.
  • proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM, Maxapem TM, Durazym TM, Purafect TM OxP, Esperase TM and / or Savinase TM
  • the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, preferably in amounts of up to 10% by weight and more preferably in amounts of from 0.05 to 5% by weight, with particular preference being given be used against oxidative degradation stabilized enzymes.
  • the detergents and cleaners according to the invention in particular the means for the automated cleaning of dishes, preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates may be present in amounts of up to 40% by weight. in particular from 3 to 30% by weight, based on the total weight of the washing and cleaning agent.
  • the alkali carrier system preferably used in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight and preferably from 5 to 40 wt .-% may be included.
  • the detergents and cleaners according to the invention in particular the detergents for dishwashing, from 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, from 3 to 20% by weight of alkali metal carbonate and 3 contain up to 40 wt .-% Alkalidisilikat.
  • Surfactants in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the detergents and cleaners according to the invention, in particular the detergents for dishwashing, where appropriate, as a wetting agent and optionally in the context of Production of these agents serve as Granulieryaku.
  • Their amount may be up to 20 wt .-%, preferably up to 10 wt .-% and is more preferably in the range of 0.5 to 5 wt .-%, based in each case on the total weight of the washing and cleaning agent.
  • extremely low-foam compounds are used in particular for means for the automatic cleaning of dishes.
  • These include preferably C 12 -C 18 -Alkylpolyethylenglykolpolypropylen-glycol ethers each having up to 8 moles of ethylene oxide and propylene oxide in the molecule.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol with the C chain length C 6 -C 14 . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.
  • detergents and cleaning agents in particular the means for the machine cleaning of dishes, system and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, Malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides.
  • Such pH regulators are present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, preferably not more than 10% by weight and more preferably from 0.5 to 6% by weight, based in each case on the total weight of the agent.
  • the organic solvents which can be used in the detergents and cleaners of the invention, in particular the detergents for dishwashing, in particular when in liquid or pasty form include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
  • Such water-miscible solvents are present in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, preferably in an amount not exceeding 20% by weight and more preferably from 1 to 15% by weight.
  • crystalline layered silicates and / or zinc salts are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na 2 Si 22 O 45 .xH 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 .xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ⁇ xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 .xH 2 O, Makatite).
  • Na-SKS z.
  • Na-SKS-1 Na 2 Si 22 O 45 .xH 2 O, Kenyaite
  • Na-SKS-2 Na 2 Si 14 O 29 .xH 2 O, magadiite
  • Na-SKS-3 Na 2 Si 8 O 17 ⁇ xH 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 .xH 2 O, Makatite
  • Na-SKS-5 alpha-Na 2 Si 2 O 5
  • Na-SKS-7 beta-Na 2 Si 2 O 5 , natrosilite
  • Na-SKS-9 NaHSi 2 O 5 ⁇ H 2 O
  • Na-SKS-10 NaHSi 2 O 5 ⁇ 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 delta-Na 2 Si 2 O 5
  • the detergents and cleaners according to the invention in particular the detergents for dishwashing, have an amount of the crystalline layered silicate of preferably from 0.1 to 20% by weight, more preferably from 0.2 to 15 Wt .-% and particularly preferably 0.4 to 10 wt .-%, each based on the total weight of the composition on.
  • detergents and cleaners according to the invention in particular means for machine dishwashing, contain at least one zinc or bismuth salt, preferably selected from the group of organic zinc salts, more preferably selected from the group of soluble organic zinc salts selected from the group of soluble zinc salts of monomeric or polymeric organic acids and most preferably selected from zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate.
  • bismuth salts such.
  • B. bismuth acetates are used.
  • washing and cleaning agents in particular to means for machine dishwashing, in which the amount of zinc salt, based on the total weight of this agent, is from 0.1 to 10% by weight, preferably 0.2 up to 7 wt .-% and particularly preferably 0.4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.
  • silver corrosion inhibitors can be used in detergents and cleaners according to the invention, in particular detergents for dishwashing machines.
  • Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, cobalt or cerium salts and / or complexes in which the abovementioned Metals depending on the metal in one of the oxidation states II, III, IV, V or VI.
  • the detergents and cleaners according to the invention in particular the means for the automated cleaning of dishes, for example in the presence of anionic surfactants, foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4 Wt .-% of a foam suppressant compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklaamide, and other further known commercially available defoamer may be added.
  • a foam suppressant compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettklareamide, and other further known commercially available defoamer may be added.
  • washing and cleaning agents according to the invention in particular the means for the machine cleaning of dishes, as further ingredients, for example from the prior art for such agents known sequestering agents, electrolytes, additional peroxygen activators, dyes or fragrances such.
  • sequestering agents for example from the prior art for such agents known sequestering agents, electrolytes, additional peroxygen activators, dyes or fragrances such.
  • the preparation of the solid detergents and cleaners according to the invention presents no difficulties and can in principle be carried out in a known manner, for example by spray drying or granulation, with peroxygen compound and co-granules according to the invention optionally being separated later be added.
  • the anhydrous granulation according to the invention takes place at temperatures below 100 ° C, in particular at temperatures between 25 and 90 ° C.
  • Inventive detergents and cleaners in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • the detergents and cleaning agents according to the invention are preferably in the form of powdered, granular or tablet-like preparations which are known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, which in particular enzymes, bleaching agents and the bleach catalyst are expected, can be prepared.
  • the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example eccentric presses or rotary presses Range of 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • a tablet produced in this way has a weight of 15 to 40 g, in particular 20 to 30 g, with a diameter of 35 up to 40 mm.
  • the preparation of detergents and cleaners according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / l, in particular corresponding inventive means for the machine cleaning of dishes, can thereby take place, that mixed in a first process step, the builder components with at least a proportion of liquid mixture components to increase the bulk density of this premix and subsequently - optionally after an intermediate drying - the other ingredients of the agent, including the inventive co-granules, with the thus obtained Pre-mix united.
  • Means for the automatic cleaning of dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. The addition is carried out by hand or by means of suitable metering devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.
  • a machine wash program is expediently supplemented and terminated by a few intermediate rinses with clear water following a cleaning cycle and a rinse cycle with a customary rinse aid. After drying, when using agents according to the invention, a completely clean and hygienically perfect dishes are obtained.
  • the storage behavior was investigated in a typical detergent powder formulation.
  • the co-granules were incorporated into IEC-A basic washing powder so that the finished formulation contained 2% of co-granules.
  • the commercial binder granules were first ground to a particle size of 200 to 1000 microns.
  • Bleach activator TAED, bleach catalyst 1-3 and solid binder were mixed in the amounts shown in Table 1 in a Eyrisch mixer and then compacted by means of a Bepex laboratory compactor. The resulting slugs were crushed by means of an Alexanderwerk sieve mill at 1.25 mm and fractionated by means of Sweco sieve at 200 to 1040 microns. Batch size: 5 to 7 kg.
  • the table shows an overview of the co-granules 1 to 4 according to the invention
  • Co-granules 1 2 3 4 substances bleach TAED TAED TAED TAED Bleach catalyst *) Complex 1 Complex 1 Complex 2 Complex 3 binder Sokalan® CP 45 G Sokalan® CP5G Sokalan® CP 45 G Sokalan® CP5G Addition of organic acid - - - oxalic acid composition bleach % 85 75 79 80 bleach catalyst % 3 2 1 2 binder % 12 23 20 17 Organic acid % - - - 1 TAED tetraacetylethylenediamine *) Complex 1 [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (PF 6 ) 2 .H 2 O, prepared according to EP 0 458 397 *) Complex 2 [Mn IV 2 ( ⁇ -O) 3 (Me-TACN) 2 ] (OAc) 2, prepared according to WO 2006/125517 *) Complex 3 [Mn
  • the storage behavior was investigated in a typical detergent powder formulation.
  • the co-granules were incorporated into IEC-A basic washing powder, so that the finished formulation contained 2% co-granules.

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Claims (14)

  1. Cogranulé d'agent de blanchiment stable au stockage et sans odeur contenant, chaque fois par rapport au poids total du cogranulé,
    a) de 50 à 90 % en poids d'un ou plusieurs activateurs de blanchiment ;
    b) de 0,01 à 10 % en poids d'un ou plusieurs catalyseurs de blanchiment contenant un métal qui comporte au moins un ligand choisi dans le groupe constitué du di- ou du triméthyltriazacyclononane ou de leurs dérivés ; et
    c) de 5 à 40 % en poids d'un ou plusieurs polymères ou copolymères de l'acide acrylique et/ou de l'acide méthacrylique ou de leurs sels ou neutralisats partiels ayant une valeur de pH dans la plage de 3 à 9, mesurée sous forme de 1 % en poids dissout dans l'eau, en tant qu'agent liant,
    caractérisé en ce qu'il est fabriqué dans un processus de granulation anhydre, de préférence par compactage, et que la température lors du processus de granulation anhydre est maintenue en dessous de 100 °C.
  2. Cogranulé d'agent de blanchiment selon la revendication 1, caractérisé en ce qu'il est exempt d'éthoxylate d'alcool ou de dérivés d'oxyde d'éthylène ou de propylène.
  3. Cogranulé d'agent de blanchiment selon la revendication 1, caractérisé en ce qu'il contient, par rapport au poids total du cogranulé,
    a) de 65 à 85 % en poids d'un ou plusieurs activateurs de blanchiment ;
    b) de 0,05 à 6 % en poids d'un ou plusieurs catalyseurs de blanchiment contenant un métal qui comporte au moins un ligand choisi dans le groupe constitué du di- ou du triméthyltriazacyclononane ou de leurs dérivés ; et
    c) de 10 à 30 % en poids d'un ou plusieurs agents liants à base d'acides poly(métha)acryliques ou de leurs sels ayant une valeur de pH dans la plage de 3 à 9, mesurée sous forme de 1 % en poids dissout dans l'eau.
  4. Cogranulé d'agent de blanchiment selon au moins l'une des revendications 1 à 3, caractérisé en ce qu'il contient en tant qu'activateur de blanchiment du composant a) de l'alkylène diamine polyacylée, en particulier de la tétraacétyléthylènediamine (TAED), des dérivés de triazine acylés, en particulier de la 1,5-diacétyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), des glycoluriles acylés, en particulier du tétraacétylglycolurile (TAGU), des N-acylimides, en particulier du N-nonanoylsuccinimide (NOSI), des phénolsulfonates acylés, en particulier du n-nonanoyloxy- ou du n-lauroyloxybenzolsulfonate (NOBS ou LOBS), des acides phénol-carboxyliques acylés, en particulier de l'acide nonanoyloxy- ou décanoyloxybenzoïque (NOBA ou DOBA), des anhydrides d'acides carboxyliques, en particulier de l'anhydride phtalique, des alcools polyvalents acylés, en particulier de la triacétine, du diacétate d'éthylène glycol et du 2,5-diacétoxy-2,5-dihydrofurane ainsi que du sorbitol et du mannitol acétylés, respectivement leurs mélanges (SORMAN), des dérivés d'oses acylés, en particulier du pentaacétylglucose (PAG), du pentaacétylfructose, du tétraacétylxylose et de l'octaacétyllactose ainsi que de la glucamine et de la gluconolactone acétylées, éventuellement N-alkylées, et/ou des lactames N-acylés, par exemple du N-benzoylcaprolactame.
  5. Cogranulé d'agent de blanchiment selon au moins l'une des revendications 1 à 4, caractérisé en ce que le catalyseur de blanchiment est choisi dans le groupe constitué des complexes de manganèse qui contiennent au moins un ligand de la formule A ou B
    Figure imgb0004
     avec R= H, CH3, C2H5 ou C3H7.
  6. Cogranulé d'agent de blanchiment selon au moins l'une des revendications 1 à 5, caractérisé en ce que le catalyseur de blanchiment contenant un métal est choisi dans le groupe constitué de :
    [MnIII 2(µ-O)1(µ-OAc)2(Me-TACN)2](PF6)2, [MnIV 2(µ-O)3(Me-TACN)2](PF6)2·H2O, [MnIV 2(µ-O)2(M-OAc)(Me4-DTE)]Cl2, [MnIV(Me-TACN)(OCH3)3]PF6 ou [MnIV(Me-TACN)(acac)OCH3]PF6.
  7. Cogranulé d'agent de blanchiment selon au moins l'une des revendications 1 à 6, caractérisé en ce qu'il contient comme agent liant du composant c) un polymère ou copolymère de l'acide (méth)acrylique, de préférence sous la forme de leurs sels ou sous forme partiellement neutralisée, l'agent liant présentant, dissout à 1 % dans l'eau, une valeur de pH dans la plage de 3,5 à 8,5.
  8. Cogranulé d'agent de blanchiment selon au moins l'une des revendications 1 à 7, caractérisé en ce que l'agent liant est un acide polyacrylique ou un acide polyméthacrylique ayant une masse molaire moyenne comprise entre 500 et 70 000 g/mol ou un copolymère de l'acide polyacrylique ou de l'acide polyméthacrylique avec de l'acide maléique contenant de 50 à 90 % en poids d'acide acrylique ou d'acide méthacrylique et de 50 à 10 % en poids d'acide maléique.
  9. Cogranulé d'agent de blanchiment selon au moins l'une des revendications 1 à 8, caractérisé en ce que le cogranulé d'agent de blanchiment est muni d'une couche protectrice.
  10. Procédé de fabrication d'un cogranulé d'agent de blanchiment selon l'une des revendications 1 à 9, dans lequel les substances actives sous forme de poudre sont d'abord mélangées et dans lequel le mélange est ensuite compacté, après cela broyé puis éventuellement criblé en différentes fractions granulométriques, la température lors du processus de granulation anhydre étant maintenue en dessous de 100 °C et le compactage étant de préférence réalisé sur des compacteurs à cylindres.
  11. Utilisation d'un cogranulé d'agent de blanchiments selon l'une des revendications 1 à 9 pour fabriquer des produits de lavage et de nettoyage, de préférence de produits pour le nettoyage à la machine de vaisselle.
  12. Produit de lavage et de nettoyage, de préférence produit pour le nettoyage à la machine de vaisselle, contenant un cogranulé d'agent de blanchiment selon l'une des revendications 1 à 9.
  13. Produit de lavage et de nettoyage selon la revendication 12, caractérisé en ce qu'il contient le cogranulé d'agent de blanchiment dans une quantité dans la plage de 0,1 à 10 % en poids, de préférence dans une quantité dans la plage de 0,2 à 8 % en poids et particulièrement de préférence dans une quantité dans la plage de 0,5 à 6 % en poids par rapport au poids total du produit de lavage et de nettoyage.
  14. Produit de lavage et de nettoyage selon au moins l'une des revendications 12 à 13, caractérisé en ce que qu'il contient
    i) de 15 à 65 % en poids, de préférence de 20 à 60 % en poids d'un composant adjuvant hydrosoluble,
    ii) de 5 à 25 % en poids, de préférence de 8 à 17 % en poids d'un composé peroxygéné,
    iii) de 0,5 à 6 % en poids d'un cogranulé d'agent de blanchiments selon l'une des revendications 1 à 9 et
    iv) de 0 à 50 % en poids d'autres additifs tels que des enzymes, des supports alcalins, des tensioactifs, de régulateurs de pH, des solvants organiques ou d'autres substances auxiliaires telles que des inhibiteurs de corrosion du verre, des inhibiteurs de corrosion de l'argent et des régulateurs de mousse,
    chaque fois par rapport au poids total du produit de lavage et de nettoyage.
EP14723721.8A 2013-06-15 2014-05-09 Granulés combinés sous forme d'agent de blanchiment, procédés de production desdits granulés et leur utilisation Active EP3008158B1 (fr)

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EP3050953B1 (fr) 2015-02-02 2018-12-26 The Procter and Gamble Company Composition de détergent
EP3050951A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Procédé de lavage de vaisselle
EP3050952A1 (fr) * 2015-02-02 2016-08-03 The Procter and Gamble Company Procédé de lavage de vaisselle
DE102015016402A1 (de) 2015-12-18 2017-06-22 Weylchem Wiesbaden Gmbh Feinteilige Bleichkatalysatoren, Verfahren zu deren Herstellung und deren Verwendung
DE102017004742A1 (de) 2017-05-17 2018-11-22 Weylchem Wiesbaden Gmbh Beschichtete Granulate, deren Verwendung und Wasch- und Reinigungsmittel enthaltend diese
DE102020001458A1 (de) * 2020-03-06 2021-09-09 WeylChem Performance Products GmbH Wasch- und Reinigungsmittel, Verfahren zum Desinfizieren und deren Verwendung
EP4008765A1 (fr) 2020-12-07 2022-06-08 WeylChem Performance Products GmbH Compositions comprenant des composés triazacycliques protonés et agent de blanchiment et agent de nettoyage les contenant

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