EP1794272B1 - Melanges d'agents de blanchiment - Google Patents

Melanges d'agents de blanchiment Download PDF

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Publication number
EP1794272B1
EP1794272B1 EP05784396A EP05784396A EP1794272B1 EP 1794272 B1 EP1794272 B1 EP 1794272B1 EP 05784396 A EP05784396 A EP 05784396A EP 05784396 A EP05784396 A EP 05784396A EP 1794272 B1 EP1794272 B1 EP 1794272B1
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EP
European Patent Office
Prior art keywords
acid
sodium
salts
weight
mixtures
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EP05784396A
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German (de)
English (en)
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EP1794272A1 (fr
Inventor
Gerd Reinhardt
Georg Borchers
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Priority claimed from DE200410053971 external-priority patent/DE102004053971A1/de
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Publication of EP1794272A1 publication Critical patent/EP1794272A1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3935—Bleach activators or bleach catalysts granulated, coated or protected
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/3945—Organic per-compounds

Definitions

  • the invention relates to improved bleaching mixtures for use in detergents, cleaners and disinfectants. More particularly, the invention relates to co-granules of such bleaching compositions having improved bleaching performance on a variety of bleachable soils.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfecting and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 ° C, a sufficiently fast bleaching of soiled textiles.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine and tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles.
  • Diketopiperazines, sulphurylamides and cyanurates furthermore carboxylic acid anhydrides, in particular phthalic anhydride and substituted maleic anhydrides, carboxylic acid esters, in particular sodium-acetoxy-benzenesulphonate, sodium benzoyloxybenzenesulphonate (BOBS), sodium nonanoyloxy-benzenesulphonate (NOBS), sodium isononanoyloxybenzenesulphonate (ISONOBS) and acylated sugar derivatives, like pentaacetylglucose.
  • carboxylic acid esters in particular sodium-acetoxy-benzenesulphonate, sodium benzoyloxybenzenesulphonate (BOBS), sodium nonanoyloxy-benzenesulphonate (NOBS), sodium isononanoyloxybenzenesulphonate (ISONOBS) and acylated sugar derivatives, like pentaacetylglucose.
  • Bleach activators are essential ingredients in powdered or tableted detergents, spot salts or machine dishwashing detergents, in particular being used in granulated form. As a result, their storage stability is significantly increased.
  • the achievable bleaching result is essentially determined by the water solubility of the activator, the structure of the perhydrolysierenden compound, the type and reactivity of the peracid formed, the Granulieryskars and the type of granule production.
  • Bleach activators can be classified into two classes for their reactivity to certain soils, hydrophilic and hydrophobic.
  • hydrophilic bleach activators remove tea or red wine stains
  • hydrophobic activators preferentially discolor oily discolorations such as ketchup and barbecue sauce.
  • many of the soils that occur in daily life do not fall into these classes (eg grass, curry) or are mixtures of various soiling (eg baby food).
  • the application of a single bleach activator usually leads to unsatisfactory results.
  • synergistically acting mixtures of detergent ingredients will be of particular interest in the future.
  • the bleaching optimum of the activator mixtures depends on the type and the mixing ratio of the activators used and on the type of stains to be removed and, according to experience, can not theoretically be calculated in advance. Therefore, there is still much interest in novel bleach activator blends with which synergistic effects can be achieved.
  • these co-granules are used as a bleaching component together with a hydrogen peroxide-generating substance in detergents, cleaners and disinfectants.
  • the ratio of organic peracid to N-acyl compound is 95: 5 to 5:95 wt%, preferably 75:25 to 25:75 wt%.
  • these mixtures are prepared in granulated form.
  • the use of additives and / or coating agents may be beneficial.
  • the proportion of bleach mixtures is 5-98% by weight, preferably 40-95%, the remainder being attributable to additives and / or coating agents.
  • the co-granules are used in combination with hydrogen peroxide or inorganic peroxy compounds.
  • all alkali metal perborates preferably in the form of mono- or tetrahydrate and / or alkali percarbonates, are considered in the first place, with sodium being the preferred alkali metal.
  • the ratio of bleaching agent mixture and peroxide compound is 1: 0.5 to 1:20 parts by weight, preferably 1: 1 to 1: 5 parts by weight.
  • the co-granules are used in the detergents according to the invention or, if the detergents are machine dishwashing detergents, in concentrations of 0.1-15%, preferably 1-8%. In stain salts or disinfectants, however, the proportion of the bleach activator mixture can also be up to 50%.
  • bleaching is understood here to mean both the bleaching of dirt located on the textile surface and the bleaching of dirt located in the wash liquor and detached from the textile surface.
  • Bleaching of stains on hard surfaces applies mutatis mutandis the same. Further potential applications can be found in the personal care field z.
  • the activator mixtures according to the invention are used in commercial laundries, in wood and paper bleaching, bleaching of cotton and in disinfectants.
  • the invention relates to a process for the cleaning of textiles as well as hard surfaces, in particular dishes, using said co-granules in combination with the peroxide compound in aqueous, optionally further detergent or cleaning agent components, containing solution, and detergent and cleaning agent for hard surfaces, especially dishwashing detergents, such being preferred for use in machine processes.
  • the preparation of the co-granules can take place in different ways, wherein the state of matter of the active substance at the beginning of the assembly can be of essential importance for the choice of method.
  • the term "packaging" is to be understood here in particular as the granulation of the bleaching mixture.
  • the mixture is present as a solid, there are different ways of packaging. Usually, one or more additives which can have binding, stabilizing and / or supplementary function are added in these processes.
  • the binder material is often added in liquid form, but can also be registered as a solid, which is activated in the granulator by an auxiliary liquid (usually water).
  • the mixer granulation of the components can be carried out in conventional, batch or continuous mixing devices, which are usually rotating Mischorganen are equipped done.
  • a mixer moderately operating devices such.
  • plowshare mixer Lödige KM types, Drais KT types
  • intensive mixers eg Eirich, Schugi, Lödige CB types, Drais K-TT types
  • the residence times in the mixer granulation are preferably 0.5 s to 20 min, more preferably 2 s to 10 min.
  • the liquid plasticizer is intensively mixed with the powdery bleach mixture and optionally the other additives, so that a plastically deformable mass is formed.
  • the mixing step may be in the o.g. Mixing apparatus, but also kneaders or special extruder types (for example Extrud-o-mix from Hosokawa-Bepex Corp.) are possible.
  • the granulation mass is then pressed by means of tools through the nozzle bores of a press die, so that cylindrically shaped extrudates are formed.
  • Suitable apparatuses for the extrusion process are ring roller presses (eg from Schlüter), edge mills (eg from Amandus-Kahl) and extruders, designed as single-shaft machines (eg from Hosokawa-Bepex, Fuji-Paudal) or preferably as twin-screw extruders (eg from Fa. Händle).
  • the choice of the diameter of the nozzle bore depends on the individual case and is typically in the range of 0.7 - 4 mm.
  • the exiting extrudates are to be comminuted by a post-processing step to the desired length or particle size.
  • the particle diameter is between 0.2 mm and 2 mm, preferably between 0.5 mm and 0.8 mm, the particle length in the range of 0.5 mm to 3.5 mm, ideally between 0.9 mm and 2 , 5 mm.
  • the lengths or size adjustment of the granules can be done for example by fixed scraper blades, rotating blades, cutting wires or blades. To round off the cut edges, the granules can subsequently be rounded again in a rounding device (for example from Glatt, Schlüter, Fuji-Paudal).
  • the extrudate is only roughly chipped and the extrudate strands are transferred directly to a ripper.
  • the further granulation takes place in Rondier Kunststoff, in a preferred embodiment, the process is carried out in cascade operation.
  • the size and shape of the particles can be influenced and brought about in the Rondier Kunststoff by several parameters.
  • the molding process is determined by the filling amount, the Temperature of the mixture, the residence time of the mixture in Rondierer, by the rotational speed of the Rondierusion, as well as by the plastic deformability of the mixture. With decreasing filling volume in the rounding device, shorter cylindrical granules and a narrower distribution of the particle sizes are obtained. With decreasing plasticity initially longer granules are obtained, with a further decrease in plasticity, the dust content increases sharply and targeted particle formation can not be achieved.
  • a final solidification step is required in which the solvent is removed or the melt is solidified.
  • this step is carried out in a fluidized bed apparatus operating as a dryer or condenser as required.
  • the coarse grain and the fine grain fraction is separated by sieving.
  • the coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.
  • the pulverulent bleaching mixture is optionally mixed with further preferably solid additives and this mixture is compacted, then ground and then optionally sieved into individual grain fractions.
  • additional liquid additives may be added to the mixture to some extent (e.g., up to 10%).
  • compacting aids are water glass, polyethylene glycols, nonionic surfactants, anionic surfactants, polycarboxylate copolymers, modified and / or unmodified celluloses, bentonites, hectorites, saponites and / or other detergent ingredients.
  • 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 Preßschülpen. While the lumpy briquettes Usually only be separated from the fine fraction, the slugs must be crushed in a mill to the desired particle size.
  • mild milling machines such as screen and hammer mills (eg from Hosokawa-Alpine, Hosokawa-Bepex) or roller mills (eg from Bauermeister, Bühler) are preferably used as the mill type.
  • Bleach mixture as a solution or suspension:
  • the bleaching agent mixture is in the form of a solution or suspension, it is above all spray drying or fluidized bed granulation that is suitable for packaging.
  • spray drying usually a spray powder with a particle size ⁇ 200 microns is achieved, this powder can then be processed in a further confectioning step to larger particles.
  • the liquid containing the bleach mixture is transferred directly into a granulate in a fluidized-bed granulation process.
  • one or more additives may be added to the spray liquid, it being possible for these additives to be mixed both liquid and solid.
  • the additives can also have the task of stabilizing or supplementing the actual active substance.
  • optimum preparation of the spray slurry for the spraying process is advantageous, such as, for example, a grinding step for comminuting solid particles, in which frequently toothed disc colloid mills can be used.
  • a dilution and / or temperature control can be carried out.
  • one or more additives may be separately metered into the process in solid form.
  • the dust content of finished granules, as they are usually incurred, can be recycled as a solid in the fluidized bed. This recycling of the dust content is basically possible in all process variants for granulation.
  • the separate solids dosage allows e.g. the targeted supply of a carrier material for receiving sticky active substances.
  • the separate solid feed may prove to be a control tool for granule growth in the process.
  • the described fluidized bed processes can be carried out in apparatuses which are designed both with round and with rectangular geometries.
  • the safety aspect should be particularly considered when selecting a suitable granulation process.
  • the limited thermal stability must also be taken into account, so that processes with potentially increased energy input (mechanical, such as compaction and thermal, such as spray-drying) are to be considered separately and evaluated in this respect.
  • methods can prove to be more advantageous which, by selecting the process conditions and / or the auxiliaries, allow improved control of the energy input.
  • inert materials such as inorganic salts (e.g., sodium sulfate) may have a positive effect on phlegmatization of the peracid.
  • additives can have the following function.
  • alkali metal phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and mixtures of sodium and potassium salts.
  • Useful organic support materials are, for example, the carboxylic acids preferably used in the form of their sodium salts, such as citric acid and nitriloacetate (NTA), ethylenediaminetetraacetic acid.
  • polymeric carboxylates and their salts include, for example, the salts of homopolymeric or copolymeric polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those of 50% to 10% of maleic acid, polyaspartic acid and also polyvinylpyrrolidone and urethanes.
  • the molecular weight of the homopolymers is generally between 1000 and 100,000, that of the Copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • water-soluble polyacrylates which are crosslinked, for example, with about 1% of a polyallyl ether of sucrose and which have a molecular weight of more than one million are also suitable.
  • these are the polymers available under the name Carbopol 940 and 941.
  • Suitable binders are cellulose and starch and their ethers or esters, for example carboxymethylcellulose (CMC), methylcellulose (MC) or hydroxyethylcellulose (HEC) and the corresponding starch derivatives, but also film-forming polymers, for example polyacrylic acids and copolymers of maleic anhydride and acrylic acid, and Salts of these polymer acids.
  • Commercial products are, for example Sokalan ® CP 5 or 45, Sokalan CP 12 S or 13 S. CP
  • Surfactants in particular anionic and nonionic surfactants, surfactant compounds, di- and polysaccharides, cyclodextrins, meltable polyesters, polyalkylene glycols, in particular polyethylene, polypropylene glycols, particularly preferably polyethylene glycols having molecular weights of from 1000 to 10,000, preferably from 3,000 to 6,000, may also be used as binders and granulating aids , particularly preferably 4000, fatty acids, in particular saturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, eg Coconut, palm kernel or tallow fatty acids derived mixtures, soaps, especially saturated fatty acid soaps and waxes are used.
  • fatty acids in particular saturated fatty acids, such as lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic
  • Preferred anionic surfactants are alkali salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl sulfates, alkyl ether sulfates, alkylamide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkanesulfonates, ⁇ -olefinsulfonates, alkylarylsulfonates, arylsulfonates, in particular cumene, xylene, toluenesulfonate alkylamide sulfonates, Alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkyl amide sulfosuccinates, Alkyl sulfoacetates, alkyl polyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates,
  • Suitable nonionic surfactants are polyethoxylated, polypropoxylated and polyglycerinated fatty acid alkyl esters, polyethoxylated esters of fatty acids and sorbitol, polyethoxylated or polyhydroxy fatty acid amides of the formula R 2 -CO-N (R 3 ) -Z, in which R 2 CO is an aliphatic acyl radical with 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and Z is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups, but also alkyl glycosides of the general formula RO (G) x used where R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms, and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose
  • Suitable acidic additives are sulfuric acid, sodium hydrogensulfate, phosphoric acid, sodium hydrogenphosphate, phosphonic acids and their salts, carboxylic acids or their salts, such as citric acid in anhydrous or hydrated form, glycolic acid, succinic acid, succinic anhydride, glutaric acid, glutaric anhydride, adipic acid, adipic anhydride, maleic acid, maleic anhydride or Lactic acid, but also acidic polymers.
  • Particularly suitable acidic additives are polyacrylic acid, polymaleic acid or copolymers of acrylic acid and maleic acid (Sokalan ® grades).
  • the granules obtained according to the invention are suitable directly for use in detergents and cleaners.
  • they can be provided with a coating shell according to methods known per se.
  • the granules are coated in an additional step with a film-forming substance, whereby the product properties can be significantly influenced.
  • further substances which do not soften or melt in this area can be in dissolved or suspended form, for example homo-, cobalt- or graft copolymers of unsaturated carboxylic acids and / or sulfonic acids and their derivatives Alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone; mono- and polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 carbon atoms and salts thereof; Silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates.
  • the content of coating substance can be from 1 to 30% by weight, preferably from 5 to 15% by weight, based on the coated granules.
  • mixers mechanically induced fluidized bed
  • fluidized bed apparatuses pneumatically induced fluidized bed
  • a mixer e.g. Ploughshare mixers (continuous and batchwise), ring layer mixers or even Schugi mixers possible.
  • the tempering can be carried out using a mixer in a granule preheater and / or in the mixer directly and / or in a fluidized bed downstream of the mixer.
  • Granulated coolers or fluid bed coolers can be used to cool the coated granules.
  • the heat treatment takes place via the hot gas used for fluidization.
  • the granules coated by the fluidized-bed method can be cooled by a granulate cooler or a fluidized-bed cooler, similar to the mixing method. Both in the mixing process and in the fluidized bed process, the coating substance can be sprayed on a single-component or a Zweistoffdüsvorraum.
  • the optional tempering consists in a heat treatment at a temperature of 30 to 100 ° C, but equal to or below the melting or softening temperature of the respective shell substance. Preference is given to working at a temperature which is just below the melting or softening temperature.
  • the bleach mixtures according to the invention can be used in detergents, cleaners and disinfectants together with hydrogen peroxide or inorganic peroxy compounds.
  • Essential components of such detergents, cleaners and disinfectants will be listed below.
  • the detergents and cleaners may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • surfactants are present in detergent compositions according to the invention in proportions of preferably 1 wt .-% to 50 wt .-%, in particular from 3 wt .-% to 30 wt .-%, whereas in hard surface cleaner usually lower proportions, that is Amounts up to 20 wt .-%, in particular up to 10 wt .-% and preferably in the range of 0.5 wt .-% to 5 wt .-% are included.
  • Dishwashing detergents typically use low-foam compounds.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those of monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of alpha-sulfo fatty acids for example the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by sulfonating the methyl esters of fatty acids of vegetable and / or animal origin having 8 to 20 carbon atoms be prepared in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts.
  • alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 8 -C 20 -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis.
  • 2,3-alkyl sulfates which, for example, according to the US patents US 3,234,158 and US 5 075 041 are prepared, are suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols containing on average 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -fatty alcohols with 1 up to 4 EO.
  • EO ethylene oxide
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosinate).
  • anionic surfactants are in particular soaps, for example in amounts of 0.2 to 5 wt .-%, into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants may be more organic in the form of their sodium, potassium or ammonium salts and as soluble salts Bases such as mono-, di- or triethanolamine, are present.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Anionic surfactants are preferably present in detergents according to the invention in amounts of from 0.5 to 10% by weight and in particular in amounts of from 5 to 25% by weight.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position , or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and 6 for one Glykoseiki with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen; an alkyl or hydroxyalkyl radical. with 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl having 3 to 1 0 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R4 for a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1 -C 4 alkyl or phenyl radicals being preferred, and [Z] a linear polyhydroxyalkyl radical whose alkyl chain has at least two Is substituted hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-allyloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with others nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide and the fatty acid alkanolamides may also be suitable.
  • surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953 . WO 95/19954 and WO 95/19955 to be discribed. Other surfactant types may have dendrimeric structures.
  • a detergent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • water-soluble inorganic builder materials are in particular alkali metal silicates and polymeric alkali metal phosphates, in the form of their alkaline, neutral or acidic sodium or potassium salts may be considered. Examples of these are 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.
  • water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50 wt .-%.
  • the detergent grade crystalline sodium aluminosilicates particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X.
  • Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable builder substances are also crystalline alkali metal silicates, which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates with a molar ratio Na 2 O: SiO 2, of 1: 2 to 1: 2.8.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na 2 Si x O 2 ⁇ + 1 .
  • YH 2 O is used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and are preferred values for x 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate are preferred.
  • amorphous silicates practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • agents according to the invention are used granular compound of alkali silicate and alkali carbonate, as it is available, for example, under the name Nabion® commercially.
  • alkali metal aluminosilicate in particular zeolite
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is preferably 1:10 to 10: 1.
  • the weight ratio is from amorphous alkali metal silicate to crystalline alkali metal silicate, preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • Such builder substances are preferably present in agents according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid.
  • Polyphosphonic acids especially aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid can also be used.
  • polymeric (poly) carboxylic acids in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Also suitable are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as Vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1000 and 200,000.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 wt .-% aqueous solutions are used. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1 to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular water-containing agents.
  • Suitable water-soluble builder components in hard surface cleaners according to the invention are in principle all builders customarily used in detergents for dishwashing, for example the abovementioned alkali metal phosphates. Their amounts can range up to about 60 wt .-%, in particular 5 to 20 wt .-%, based on the total agent.
  • water-soluble builder components are, in addition to polyphosphonates and Phosphonatalkylcarboxylaten for example, organic polymers of the synthetic or synthetic type of the above-mentioned type of polycarboxylates, which act as a co-builder in hard water regions, and naturally occurring Hvdroxycarbon Acid such as mono-, dihydroxysuccinic, alpha-hydroxypropionic and gluconic.
  • Preferred organic builder components include the salts of citric acid, especially sodium citrate.
  • sodium citrate anhydrous tri-sodium 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.
  • the enzymes optionally contained in the agents according to the invention include proteases, amylases, pullulanases, cellulases, cutinases and / or lipases, for example proteases such as BLAP®, Optimal®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Savinase®, amylases such as Termamy®, amylase-LT, Maxamyl®, Duramyl®, Purafectel OxAm, cellulases such as Celluzyme®, Carezyme®, K-AC® and / or lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®.
  • proteases such as BLAP®, Optimal®, Opticlean®, Maxacal®, Maxapem®, Durazym®, Purafect® OxP, Esperase® and / or Sa
  • the enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in detergents and cleaners according to the invention in amounts of up to 10% by weight, in particular from 0.05 to 5% by weight, enzymes which are particularly preferably stabilized against oxidative degradation being used.
  • Machine dishwashing detergents according to the invention preferably comprise the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates.
  • Alkali silicates can in amounts of up to 40 wt .-%, in particular 3 to 30 wt. -% of total resources.
  • the alkali carrier system preferably used in cleaning agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which may be present in an amount of up to 50% by weight, preferably 5 to 40% by weight.
  • inventive means for the automatic cleaning of dishes are 20 to 60 wt .-% of water-soluble organic builder, in particular alkali citrate, 3 to 20 wt .-% alkali carbonate and 3 to 40 wt .-% Alkalidisilikat included.
  • silver corrosion inhibitors can be used in dishwashing detergents according to the invention.
  • 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, molybdenum, vanadium or cerium salts and / or complexes, as well as Salts and / or complexes of the metals present in the complexes suitable according to the invention with other than in formula (I) predetermined ligands.
  • the agents 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-regulating compound, preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • a foam-regulating compound preferably from the group consisting of silicones, paraffins, paraffin-alcohol combinations , Hydrophobicized silicic acids, Bisfettklareamide and mixtures thereof and other other known commercially available foam inhibitors are added.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • mixtures of paraffins and Bistearylethylenediamide preferred.
  • Further optional ingredients in the compositions according to the invention are, for example, perfume oils.
  • organic solvents which can be used in the compositions according to the invention, especially if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C 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 preferably present in the detergents according to the invention not more than 20% by weight, in particular from 1 to 15% by weight.
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular 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 metal hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides, such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, contain.
  • system- and environmentally compatible acids in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid
  • mineral acids in particular sulfuric acid or alkali metal hydrogensulfates, or bases, in particular ammonium or alkali metal hydroxides
  • pH regulators are preferably not more than 10 wt .-%,
  • compositions according to the invention are preferably in the form of pulverulent, granular or tablet-like preparations which are prepared in a manner known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and admixing the more sensitive components, in particular enzymes, bleaches and the bleach catalyst are to be expected, can be prepared.
  • Solutions according to the invention 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.
  • compositions 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 can also be achieved by using the builder components with at least a proportion of liquid mixture components in a first process stage while increasing the bulk density of this premix and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the bleach catalyst, combined with the thus obtained premix.
  • compositions according to the invention in tablet form, the procedure is preferably such that all ingredients are mixed together in a mixer and the mixture by means of conventional tablet presses, such as Exzeriterpressor or rotary presses, with pressing pressures in the range of 200 ⁇ 10 5 Pa to 1500 ⁇ 10 5 Pa pressed.
  • This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strengths of normally over 150 N.
  • a tablet produced in this way has a weight of 1-5 g to 40 g, in particular from 20 g to 30 g; at a diameter of 3-5 mm to 40 mm.
  • PAP phthalimidoperoxycaproic acid
  • TAED tetaacetylethylenediamine
  • PAP phthalimidoperoxycaproic acid
  • TAED tetaacetylethylenediamine
  • the bleaching performance of the individual activators and of the mixtures according to the invention was investigated in a Linitest apparatus (Fa. Out) at 40.degree.
  • a Linitest apparatus Fa. Out
  • 5 g / l of a bleach-free basic detergent (WMP, WFK, Krefeld) and 0.7 g / l of sodium percarbonate (Degussa) were dissolved in water of hardness grade 3.
  • activator, peracid or their mixture were added.
  • the washing time was 30 min.
  • Curry, grass, tea and tomato on cotton BC-4, CS-8, BC-1 and CS-20, WFK, Krefeld.
  • the remission difference measured with an Elrepho machine, after washing compared to unwashed one.
  • PAP phthalimidoperoxycaproic acid
  • TAED tetraacetylethylenediamine
  • the experiments were carried out in a Miele Novotronic W927 in a short cycle at 40 ° C.
  • 72 g basic laundry detergent (WMP, WFK, Krefeld), 12 g percarbonate (Degussa) and 5 g TAED or 2.5 g or a mixture of 2.5 g TAED and 1.25 g PAP were used per wash.
  • the test soiling was a multi-stem swatch (EMPA).
  • EMPA multi-stem swatch
  • a 45% aqueous Sokalan CP45 solution (commercial product BASF AG) were mixed at room temperature with about 312 g of water and diluted to 20% polymer content. Subsequently, 138.3 g of TAED powder (without pre-comminution) were gradually added, and the resulting suspension was treated with the Ultra-Turrax for about 10 minutes in order to comminute the TAED crystals.
  • the suspension prepared in this way had a somewhat increased viscosity and had to be stirred constantly to avoid sedimentation.
  • the PAP amount of 138.3 g and TAED amount of 138.3 g required for completing the formulation was initially charged together with 178.5 g of sodium sulfate (anhydrous grade) in the laboratory fluidized bed.
  • the material was fluidized with a gas volume flow of about 22 - 31 m 3 / h, the gas inlet temperature was about 60 - 65 ° C.
  • 588 g of the spray slurry were sprayed into the fluidized bed. In this case, a temperature in the fluidized bed of about 45 - 53 ° C was established.
  • the removed product was fractionated on a laboratory sieve (type Retsch AS 200 control) in order to separate out fine particles ⁇ 200 ⁇ m and coarse particles> 1400 ⁇ m from the target product.
  • the finished granules were present with a composition of about 39.3% TAED, about 19.7% PAP, about 25% Na sulfate and about 16% polymer binder.

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  • Detergent Compositions (AREA)

Claims (5)

  1. Co-granulats, constitués par
    a) un composé de formule (1)
    Figure imgb0005
     où n signifie les nombres 3, 4 ou 5,
    b) de la tétraacétyléthylènediamine et/ou de la 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine, ainsi que le cas échéant des substances support solides, des liants, des adjuvants de granulation, des additifs acides et des substances d'enrobage.
  2. Co-granulats selon la revendication 1, constitués par 5 à 95% en poids du composé de formule 1 et par 95 à 5% en poids de tétraacétyléthylènediamine et/ou de 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine.
  3. Co-granulats selon la revendication 1, constitués par 25 à 75% en poids du composé de formule 1 et par 75 à 25% en poids de tétraacétyléthylènediamine et/ou de 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine.
  4. Co-granulats selon la revendication 1, constitués par 60 à 40% en poids du composé de formule 1 et par 40 à 60% en poids de tétraacétyléthylènediamine et/ou de 1,5-diacétyl-2,4-dioxo-1,3,5-hexahydrotriazine.
  5. Agent de lavage, de nettoyage et de désinfection contenant un co-granulat selon la revendication 1 ainsi que du peroxyde d'hydrogène ou un composé peroxy inorganique.
EP05784396A 2004-09-08 2005-09-03 Melanges d'agents de blanchiment Not-in-force EP1794272B1 (fr)

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DE200410053971 DE102004053971A1 (de) 2004-11-09 2004-11-09 Bleichmittel-Mischungen
PCT/EP2005/009490 WO2006027179A1 (fr) 2004-09-08 2005-09-03 Melanges d'agents de blanchiment

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US7709437B2 (en) * 2006-04-27 2010-05-04 Oci Chemical Corp. Co-granulates of bleach activator-peroxide compounds
JP5883294B2 (ja) * 2011-11-22 2016-03-09 菱江化学株式会社 漂白剤、洗浄漂白剤及び殺菌剤
WO2014161582A1 (fr) * 2013-04-04 2014-10-09 Ecolab Inc. Composition améliorée de désinfection sporicide à faible odeur

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WO2006027179A1 (fr) 2006-03-16
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