EP3008158A1 - 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

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Publication number
EP3008158A1
EP3008158A1 EP14723721.8A EP14723721A EP3008158A1 EP 3008158 A1 EP3008158 A1 EP 3008158A1 EP 14723721 A EP14723721 A EP 14723721A EP 3008158 A1 EP3008158 A1 EP 3008158A1
Authority
EP
European Patent Office
Prior art keywords
bleach
granules
weight
acid
cleaning
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
EP14723721.8A
Other languages
German (de)
English (en)
Other versions
EP3008158B1 (fr
Inventor
Gerd Reinhardt
Michael Best
Miriam Ladwig
Andreas Schottstedt
Mathias Groeschen
Sven GEHARD
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.)
Catexel Production GmbH
Original Assignee
Weylchem Wiesbaden GmbH
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 Weylchem Wiesbaden GmbH filed Critical Weylchem Wiesbaden GmbH
Publication of EP3008158A1 publication Critical patent/EP3008158A1/fr
Application granted granted Critical
Publication of EP3008158B1 publication Critical patent/EP3008158B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • 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
    • 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
    • C11D3/39—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 happens on the one hand, in order to increase their storage stability, on the other hand, however, to a homogeneous
  • Bleach catalysts based on various manganese-containing transition metal complexes are z.
  • Processes for the preparation of bleach catalyst granules are disclosed in EP 0 544 440, WO 95/06710 and WO 2008/069935. Characteristic of the processes described therein is the use of large amounts of inert materials as carriers and binders, which are optionally used as melts, this method includes cooling and / or drying stages, which requires the use of additional equipment such as fluidized bed plants.
  • 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.
  • Peroxycarboxylic acid significantly contributes to germ killing on the dishes, improves the smell of the wash 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.
  • TAED tetraacetylethylenediamine
  • NOBS nonanoyloxibenzenesulfonate sodium
  • DOBA decanoyloxibenzoic acid
  • EP 0 710 714 describes 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.
  • 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.
  • Granules only one co-granules 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 with TAED powder and a tallow alcohol ethoxylate (Genapol ® T500, Clariant) were mixed in a Lodige mixer at 40 to 50 ° C and then nudeiförmigen means of an extruder 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. 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
  • binders mentioned are fatty acids, alcohol ethoxylates or polymers.
  • a large number of the bleaching catalysts mentioned in WO 2010/115581, in particular manganese salts, can therefore be converted into storage-stable, odorless co-granules which are suitable for use in detergents and cleaners.
  • Poly (meth) acrylic acid or its salts or partial neutralizers having a pH in the range of 3 to 9 is used.
  • the present invention therefore bleach co-granules containing a bleach activator, a metal-containing bleach catalyst containing at least one ligand from the group di- or Trimethyltriazacyclononane or derivatives thereof, and a homo- or copolymeric polycarboxylate, in particular a homo- or copolymer based of (meth) acrylic acid, or its salts or partial neutralizers having a pH in the range of 3 to 9, whose characteristic feature is that they are produced in an anhydrous granulation process, preferably by compaction, and that the temperature in the anhydrous granulation process is kept below 100 ° C.
  • the bleach co-granule according to the invention is characterized in that it contains no alcohol ethoxylates or ethylene or propylene oxide derivatives.
  • co-granules according to the invention which, based in each case on the total weight of the co-granules,
  • the bleach co-granules according to the invention particularly preferably comprise, based on the total weight of the co-granules,
  • the co-granules according to the invention may 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 phenolsulphonates, in particular n-nonanoyloxy or n-lauroyloxibenzenesulphonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxibenzoic acid (NOBA or DOBA ), Carboxylic anhydrides, in particular phthalic anhydride,
  • SORMAN acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose and
  • acetylated optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam.
  • 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
  • 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.
  • Mono- or dinuclear complexes of the general formulas A or B are preferably used as transition metal complexes in the co-granules according to the invention
  • R H, CH 3 , C 2 H 5 , or C 3 H 7
  • Preferred ligands are 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me-TACN),
  • TACN 4,7-triazacyclononane
  • bridged ligands such as 1, 2-bis- (4,7-dimethyl-
  • Suitable manganese complexes are, for example, the polynuclear complexes
  • the co-granules according to the invention contain a
  • Binders to ensure the cohesion of the co-granules.
  • the binder is characterized in that it is homo- or copolymeric polycarboxylates, in particular 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
  • the binder used 1% dissolved in water, should have a pH of from 3 to 9, but in particular between 3.5 and 8.5, in particular homo- or copolymeric polycarboxylates, preferably For example, preference is given to using polyacrylic acid or polymethacrylic acid, in particular those having an average molar mass of from 500 to 70,000 g / mol.
  • 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 especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid
  • Methacrylic acid and 50 to 10 wt .-% maleic acid. Their middle one
  • Molecular weight is preferably 2,000 to 70,000 g / mol, more preferably 20,000 to 50,000 g / mol, and most 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. Also particularly preferred are biodegradable polymers of more than two different monomer units,
  • 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.
  • Sulfonic acid-containing polymers in particular copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally further ionic or nonionic monomers.
  • 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.
  • Co-granules are not provided with a protective layer (so-called coating).
  • Co-granules additionally provided with a protective layer, whereby the storage stability further improved and the co-granules can be optionally 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
  • the coarse grain fraction is again fed to the mill, the fine grain content, however, again the compaction. to
  • Classification of the granules can common screening machines such. As tumble screen or vibrating screens (eg., From Allgaier, Sweco, Vibra) are used.
  • tumble screen or vibrating screens eg., From Allgaier, Sweco, Vibra
  • 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 more 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 washing and
  • Detergents and preferably detergents for dishwashing are preferably dishwashing.
  • Another object of the present invention are also washing and
  • Detergent preferably means for machine dishwashing, comprising a bleach co-granule according to the invention.
  • Preferred detergents and cleaners according to the invention in particular the means for machine washing of crockery, contain the inventive compositions
  • Bleach co-granules in amounts between 0.1 and 10 wt .-%, preferably in amounts between 0.2 and 8 wt .-% and particularly 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.
  • Detergents in particular the detergents for dishwashing, 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.
  • detergents and cleaners in particular detergents for dishwashing, contain
  • iii) from 0.5 to 6% by weight of a bleach co-granule according to the invention, and iv) from 0 to 50% by weight of further additives, such as enzymes, alkali carriers,
  • surfactants such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, in each case based on the total weight of the washing and cleaning agent.
  • 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.
  • Cleaning agents in particular the means for the mechanical cleaning of Dishes, in principle, all builders commonly used in such compositions in question, for example, alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. examples for this are
  • Trisodium phosphate Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate,
  • Pentasodium triphosphate so-called sodium hexametaphosphate
  • 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.
  • Other possible 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 are disclosed in particular in US Pat
  • Polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are, for example Sokalan ® CP 5, CP 10 and PA 30 from BASF.
  • suitable co-builder polymers of native origin include oxidized starch and
  • Polyamino acids such as polyglutamic acid or polyaspartic acid.
  • Other possible 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.
  • Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimate in the washing and
  • Crockery, adjusted pH can also be present corresponding to the said co-builder salts acids.
  • Particularly preferred builder components in phosphate-free formulations are methylglycine (. MDGA, such as Trilon M ®, BASF), L-glutamic acid, N, N, (biscarboxymethyl) - (tertra sodium salt GLDA,
  • Preferred peroxygen compounds are perborates and percarbonates, especially the corresponding sodium salts of these compounds.
  • Proteases, amylases, pullulanases, cutinases and / or lipases which may be present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, may contain proteases, amylases, pullulanases, cutinases and / or lipases.
  • proteases such as BLAP TM, Optimase TM, Opticlean TM, Maxacal TM,
  • Lipolase TM Lipomax TM, Lumafast TM and / or Lipozym 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.
  • washing and cleaning agents according to the invention in particular the means for the machine cleaning of dishes, the usual
  • Alkaline carriers such as alkali silicates, alkali carbonates and / or
  • Alkali metal bicarbonates The alkali carriers commonly used include carbonates, bicarbonates and alkali metal silicates having a molar ratio of S1O2 / M2O
  • 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. be included.
  • 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. In a further preferred embodiment of the invention are in the
  • Detergents and cleaning agents according to the invention in particular the detergents for dishwashing, 20 to 60 wt .-% of water-soluble organic builder, in particular Alkaiicitrat, 3 to 20 wt .-% Aikaiicarbonat and 3 to 40 wt .-% Alkalidisilikat included.
  • 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 Granulieryffen. Your amount can be up to
  • extremely low-foam compounds are used in particular for means for the automatic cleaning of dishes.
  • These preferably include Ci 2 -C 8 -Alkylpolyethylenglykolpolypropylen glycol ethers each having up to 8 mol
  • Alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides The presence of amine oxides, betaines and ethoxylated alkylamines is also possible. pH regulators
  • the detergents and cleaning agents according to the invention in particular the means for the automated cleaning of dishes, system and environmentally friendly 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
  • Alkalihydrogensulfate, or bases in particular ammonium or alkali hydroxides.
  • pH regulators are in the detergents and cleaners of the invention, in particular the means for the mechanical cleaning of
  • Dishes preferably not more than 10 wt .-% and particularly preferably from 0.5 to 6 wt .-%, based, in each case, on the total weight of the composition.
  • 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
  • Detergents and cleaning agents according to the invention in particular in the means for the automated cleaning of dishes, preferably in a quantity not above
  • Detergents and cleaning agents according to the invention in particular the means for the automated cleaning of dishes, corresponding inhibitors are used.
  • Particularly advantageous here are crystalline layered silicates and / or zinc salts.
  • the crystalline layered silicates are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na 2 Si 22 O 5 .xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 4 O 29 x H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 Oi 7 xH 2 O) or 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 05
  • 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 0 5
  • an amount of the crystalline layered silicate of preferably 0.1 to 20 wt.%, particularly preferably 0.2 to 15 wt.% and particularly preferably 0, 4 to 10 wt .-%, each based on the
  • Detergents in particular means for the automated cleaning of dishes, 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, more preferably selected from the group of soluble zinc salts monomeric or polymeric organic acids and most preferably selected from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate,
  • Zinc abietate, zinc valerate and zinc p-toluenesulfonate Alternatively or in combination with these zinc salts 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 metals mentioned are present in one of the oxidation states II, III, IV, V or VI, depending on the metal.
  • 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 % By weight of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations,
  • hydrophobized silica added to bis-fatty acid amides and other further known commercially available defoamers.
  • 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.
  • Spray drying or granulation wherein peroxygen compound and inventive co-granules are optionally added separately later.
  • 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 cleaners 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 mixing in the more sensitive
  • Components which in particular enzymes, bleach and the bleach catalyst can be expected, can be produced.
  • 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 from 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.
  • 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 useful by some on the
  • Citric acid were placed in a laboratory mixer, mixed and placed on the
  • T 70 - 75 ° C added.
  • the mixture was regranulated for a few minutes, then cooled to room temperature and sieved to remove coarse and fines of 200 - 1.600 ⁇ .
  • 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 mixture was transferred to a glass bottle and with the lid closed under climatic conditions
  • 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 a Sweco sieve at 200 to 1040 ⁇ m. Batch size: 5 to 7 kg.
  • the table shows an overview of the co-granules 1 to 4 according to the invention
  • Sokalan ® CP copolymers of acrylic acid commercial product of BASF
  • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Granulés combinés sous forme d'agent de blanchiment, comprenant un activateur de blanchiment, un catalyseur 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 un polycarboxylate homopolymère ou copolymère, ou leurs sels ou neutralisats partiels ayant une valeur pH située entre 3 et 9. Lesdits granulés combinés sous forme d'agent de blanchiment sont fabriqués lors d'un processus de granulation anhydre, de préférence par compactage, pendant lequel la température est maintenue au-dessous de 100 °C. La présente invention concerne également l'utilisation desdits granulés combinés sous forme d'agent de blanchiment dans des produits de nettoyage pour le lavage en machine de vaisselle, et un produit de nettoyage contenant lesdits granulés combinés.
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)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013010549.8A DE102013010549A1 (de) 2013-06-15 2013-06-15 Bleichmittel-Co-Granulate
PCT/EP2014/001265 WO2014198369A1 (fr) 2013-06-15 2014-05-09 Granulés combinés sous forme d'agent de blanchiment, procédés de production desdits granulés et leur utilisation

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EP3008158A1 true EP3008158A1 (fr) 2016-04-20
EP3008158B1 EP3008158B1 (fr) 2017-12-13

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US (1) US9902922B2 (fr)
EP (1) EP3008158B1 (fr)
DE (1) DE102013010549A1 (fr)
DK (1) DK3008158T3 (fr)
ES (1) ES2657279T3 (fr)
WO (1) WO2014198369A1 (fr)

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PL3050953T3 (pl) 2015-02-02 2019-07-31 The Procter And Gamble Company Kompozycja detergentu
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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Publication number Publication date
US20160152929A1 (en) 2016-06-02
WO2014198369A1 (fr) 2014-12-18
US9902922B2 (en) 2018-02-27
ES2657279T3 (es) 2018-03-02
DK3008158T3 (en) 2018-03-26
EP3008158B1 (fr) 2017-12-13
DE102013010549A1 (de) 2014-12-18

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