EP1319705B1 - Cogranules d'activateur de blanchiment - Google Patents

Cogranules d'activateur de blanchiment Download PDF

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Publication number
EP1319705B1
EP1319705B1 EP02027051A EP02027051A EP1319705B1 EP 1319705 B1 EP1319705 B1 EP 1319705B1 EP 02027051 A EP02027051 A EP 02027051A EP 02027051 A EP02027051 A EP 02027051A EP 1319705 B1 EP1319705 B1 EP 1319705B1
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Prior art keywords
alkyl
prepared
acid
granulates
granules
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EP02027051A
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German (de)
English (en)
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EP1319705A1 (fr
Inventor
Jürgen Dr. Cramer
Johannes Dr. Himmrich
Helmut Dr. Kramer
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Clariant Produkte Deutschland GmbH
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Clariant Produkte Deutschland GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—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
    • 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

Definitions

  • the invention relates to a process for the preparation of bleach activator co-granules of one or more ammonium nitriles and at least one further bleach activator, which react in a wide temperature range of 10 ° C to 70 ° C with a bleaching agent and induce a bleaching action. Furthermore, the granules produced according to the invention are distinguished by improved storage stability and by high active ingredient contents.
  • Bleach activators are important ingredients in compact detergents, patch salts and machine dishwashing detergents.
  • Conventional bleach activators at 40 ° C to 60 ° C, provide a bleaching result comparable to that of cooking by reacting with hydrogen peroxide donors (usually perborates, percarbonates, persilicates and perphosphates) to release an organic peroxycarboxylic acid.
  • the achievable bleaching result is determined by the nature and reactivity of the peroxycarboxylic acid formed, the structure of the bond to be perhydrolyzed, and the water solubility of the bleach activator.
  • Many substances are known in the art as bleach activators. These are usually reactive organic compounds having an O-acyl or N-acyl group already in the washing powder mixture, favored by the residual moisture present, with the bleaching agent such as e.g. Sodium perborate can react when both components are unprotected.
  • bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), nonanoyl-caprolactam phenylsulfonate ester (APES), glucose pentaacetate (GPA), xylose tetraacetate (TAX), acyloxybenzenesulfonates (eg nonanoyloxybenzenesulfonate (NOBS), sodium 4-benzoyloxybenzenesulfonate ( SBOBS), sodium trimethylhexanoyloxybenzenesulfonate (STHOBS), diacetyldioxohexahydrotriazine (DADHT), tetraacetylglucoluril (TAGU), Tetraacetylcyanoic acid (TACA), di-N-acetyldimethylglyoxine (ADMG) and 1-phenyl-3-acetylhydantoin (PAH) and n
  • nitrile quats Ammonium nitriles
  • nitrile quats Compounds of this type and their use as bleach activators in bleaching agents are known in EP-A-0 303 520 .
  • the invention relates to co-granules of one or more ammonium nitriles and at least one further bleach activator, wherein these co-granules are obtained by spraying on the / the further bleach activator (s) an aqueous solution of one or more Ammoniumnitrile (s), the granulated mixture obtained and the moist granules are dried and sieves.
  • Suitable ammonium nitriles are, in particular, compounds of the formula (1) in which R 1 , R 2 , R 3 are identical or different and for linear or branched C 1 -C 24 -alkyl groups, C 2 -C 24 -alkenyl groups or for C 1 -C 4 -alkoxy-C 1 -C 4 - Alkyl groups, substituted or unsubstituted benzyl, or in which R 1 and R 2 together with the nitrogen atom to which they are attached form a ring having 4 to 6 C atoms which is substituted by C 1 -C 5 -alkyl, C 1 - C 5 alkoxy, C 1 - to C 5 alkanoyl, phenyl, Amino, ammonium, cyano, cyanamino, chloro or bromo and in addition to the nitrogen atom may contain one or two oxygen or nitrogen atoms, a group NR 6 or a group R 3 -NR 6 instead of carbon atoms,
  • ammonium nitrites are compounds of the formula 2 wherein R 1 , R 2 and R 3 represent a linear or branched, saturated or unsaturated alkyl group of 1 to 24 carbon atoms, an alkenyl group of 2 to 24 carbon atoms or substituted or unsubstituted benzyl, and A represents any charge-balancing ion, for example, chloride, bromide , iodide, fluoride, sulfate, hydrogensulfate, carbonate, bicarbonate, phosphate, mono- and di-hydrogen phosphate, pyrophosphate, metaphosphate, nitrate, methylsulfate, phosphonate, methylphosphonate, methanedisulfonate, methylsulfonate, ethanesulfonate or for an anion of the formulas R 7 SO 3 ⁇ , R 7 SO 4 ⁇ or R 7 COO ⁇ , wherein R 7 has the meanings given above. Particular
  • R 1 , R 2 and R 3 are each a methyl group.
  • the charge-balancing anion may be arbitrary, preferably chloride or methosulfate or a mixture various anions, for example chloride or methosulfate and cumene sulfonate and / or lauryl sulfate and / or Fettklarealkylcarboxylate.
  • Ammonium nitriles according to formula 1 and 2 are characterized by a particularly good bleaching ability in the presence of a bleaching agent at low temperatures in the range of 10 ° C to 50 ° C.
  • ammonium nitriles as a bleach activator in detergents and cleaners but their hygroscopicity and sensitivity to hydrolysis in the presence of alkaline detergent ingredients and a correspondingly low storage stability associated with a great disadvantage.
  • an improvement in the storage stability of ammonium nitriles can be achieved by preparing ammonium nitriles with alkane or paraffin sulfonate, aryl sulfonate, primary alcohol sulfate or fatty acid alkyl carboxylate as counterion by anion exchange by precipitation reaction in polar organic solvents such as methanol and isopropanol.
  • the anion exchange is disadvantageous for ecological and economic reasons; the separation of the solvent from the precipitated product consuming.
  • Another way to prevent hydrolysis of the bleach activators in the presence of alkaline detergent ingredients and to ensure adequate storage stability is via granulation and coating of the bleach activators before use in detergent and cleaner preparations.
  • acetonitrile derivatives in particular cyclic acetonitrile for conversion into solid detergents and cleaners are converted into a solid form by a carrier material with the largest possible surface, for example silica stirred into an aqueous acetonitrile or sprayed the aqueous solution onto the carrier or mixed and the resulting mixture is subjected to drying in vacuo at elevated temperatures.
  • a carrier material with the largest possible surface
  • the granules or particles described in the documents have water contents of up to 20 percent by weight, preferably less than 1 percent by weight.
  • Bleaching agents which contain a bleach activator ammonium nitrile, optionally in admixture with other bleach activators, for example Alkanoyloxybenzolsulfonklare or tetraacetylethylenediamine and an inorganic peroxide and an alkali metal carbonate.
  • bleach activators for example Alkanoyloxybenzolsulfonklare or tetraacetylethylenediamine and an inorganic peroxide and an alkali metal carbonate.
  • the other bleach activators used in the invention are solid and naturally have a different structure than the ammonium nitriles.
  • the preparation of the co-granules according to the invention is carried out by spraying the further bleach activator (s) with an aqueous solution of one or more ammonium nitriles (s) and granulating this mixture.
  • the water content of the granules thus obtained is then reduced to less than 5, preferably less than 2 wt .-%.
  • the removal of the excess water can be done by drying under heat, the temperature the granules expediently does not exceed 100 ° C and is below the melting temperature of the granules. Suitable are dryers that do not adversely affect the granular structure of the product, such as tray, vacuum or fluidized bed dryers.
  • the coarse grain and fine grain content 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 grain size of the granules produced in this way is generally in the range of 100 microns - 2000 microns, preferably 300 microns - 1800 microns, more preferably 600 microns - 1200 microns.
  • the bulk density is in the range of 400 to 700 kg / m 3 .
  • An increase in the bulk density can be achieved by compressing the granules into larger agglomerates, for example in roller compactors, and then comminuted with the aid of mills, toothed disc rollers and / or screening screens.
  • the total amount of all bleach activators, based on the finished, dry co-granules is from 50% by weight to 99% by weight, preferably from 70% by weight to 98% by weight, in particular from 80% by weight to 96% by weight.
  • the proportion by weight of ammonium nitrile, based on the finished, dry co-granules is from 1% by weight to 50% by weight, preferably from 10% by weight to 40% by weight, particularly preferably from 15% by weight to 35% by weight.
  • the co-granules according to the invention additionally contain binders and acid additives which reduce the hydrolysis sensitivity of the ammonium nitrile.
  • Possible 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 Maleic anhydride and acrylic acid, as well as the salts of these polymeric acids.
  • CMC carboxymethylcellulose
  • MC methylcellulose
  • HEC hydroxyethylcellulose
  • film-forming polymers for example polyacrylic acids and copolymers Maleic anhydride and acrylic acid, as well as the salts of these polymeric acids.
  • pulverulent anionic components in particular alkanesulfonates, alkylarylsulfonates, arylsulfonates, in particular cumene, xylene, toluenesulfonate, alkyl ether sulfates, alkyl sulfates, ⁇ -olefinsulfonates and soaps are suitable.
  • the amount of binder, based on the finished granules can be from 1 to 45% by weight, preferably from 5 to 15% by weight.
  • Suitable acid 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 polymers are polyacrylic acid, polymaleic acid or copolymers of acrylic acid and maleic acid.
  • the amount of acidic additive and its concentration is such that the proportion of the acidic additive in the finished granules about 0 to 20 wt .-%, preferably 1 to 15 wt .-%, in particular 1 to 10 wt .-% is.
  • the co-granules according to the invention contain binders and / or acidic additives, it is possible to proceed by premixing these components together with the further bleach activator (s).
  • This step can be carried out in conventional, batch or continuous mixing devices, which are usually equipped with rotating mixing devices, for example in a plowshare mixer. Depending on the effectiveness of the mixing device, the mixing times for a homogeneous mixture are generally between 30 seconds and 5 minutes.
  • this mixture is moistened with an aqueous solution of one or more ammonium nitriles at temperatures of about 20 to 80 ° C. It is then granulated, dried and sieved as indicated above.
  • binders and / or acidic additives to the aqueous solution of ammonium nitrile (s) and to spray the aqueous solution onto the further bleach activator (s).
  • the binder (s) can also be premixed with the further bleach activator (s) and sprayed with the solution of the ammonium nitrile (s) containing acidic additives or, conversely, by passing the further bleach activator (s) ) is premixed with the acidic additives and the binder (s) sprayed within the aqueous solution of the / Ammoniumnitrile (s).
  • the aqueous solution of ammonium nitrile (s) may also contain anionic components, in particular alkanesulfonates, alkylarylsulfonates, arylsulfonates, in particular cumene, xylene, toluenesulfonate, alkyl ether sulfates, alkyl sulfates, ⁇ -olefinsulfonates and soaps in parts by weight of from 0 to 3, preferably 0.5 to 2, more preferably 1 to 2, based on the ammonium nitrile contained in the co-granules.
  • the preparation can also be carried out in such a way that all components are mixed dry and then the mixture is granulated with addition of water.
  • a mixture of dry components with one or more water-moist solid (s) can be mixed and granulated.
  • the resulting co-granules themselves, but in particular the resulting fines, as well as the pulverulent milled coarse fraction can be used as the carrier material to which in turn with intensive mixing aqueous nitrile quat solution is metered.
  • This process is freely repeatable within the physico-chemical properties of the resulting co-granules.
  • the co-granules obtained according to the invention are suitable directly for use in detergents and cleaners. In a particularly preferred form of use, however, they can be provided with a coating shell according to methods known per se. For this purpose, the co-granules are coated in an additional step with a film-forming substance, whereby the product properties can be significantly influenced.
  • Suitable coating agents are all film-forming substances, such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, polyethylene glycols and polyalkylene glycols.
  • the application of the coating materials is usually carried out by spraying the molten or dissolved in a solvent coating materials.
  • the coating material can be applied in amounts of 0 to 30 wt .-%, preferably from 5 to 15 wt .-%, based on the total weight, on the granule core according to the invention.
  • the storage stability and hygroscopicity can be further improved and the reaction kinetics can be specifically influenced so as to prevent interactions between the bleach activator and the enzyme system at the beginning of the washing process.
  • co-granules of the invention may contain other suitable additives, such as anionic and nonionic surfactants, which contribute to a faster dissolution of the co-granules of the invention, and bleach stabilizers such as phosphonates and polyphosphonates.
  • suitable additives such as anionic and nonionic surfactants, which contribute to a faster dissolution of the co-granules of the invention, and bleach stabilizers such as phosphonates and polyphosphonates.
  • Preferred anionic surfactants are alkali metal salts, ammonium salts, amine salts and salts of amino alcohols of the following compounds: alkyl ether sulfates, alkylamide sulfates and ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylamide sulfonates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, alkylpolyglycerol carboxylates, alkyl phosphates, alkyl ether phosphates, alkyl sarcosinates, alkyl polypeptides, Alkylamidopolypeptidates, alkylisethionates, alkyltaurates, alkylpolyglycolethercarboxylic acids or fatty acids, such as
  • Preferred nonionic surfactants are polyethoxylated, polypropoxylated or polyglycerolated ethers of fatty alcohols, polyethoxylated, polypropoxylated and polyglycerolated fatty acid esters, polyethoxylated esters of fatty acids and of sorbitol, polyethoxylated or polyglycerolated fatty amides.
  • suitable additives are complexing agents and transition metal complexes, such as iron, cobalt or manganese-containing metal complexes as in EP-A-0 458 397 and EP-A-0 458 398 described.
  • additives are substances which react with the peroxycarboxylic acid released from the activator in the wash liquor to form reactive intermediates, such as dioxiranes or oxaziridines, and in this way can increase the reactivity.
  • substituing compounds are correspondingly ketones and sulfonimines US-A-3 822 114 and EP-A-0 446 982 ,
  • the amount of the additive depends in particular on its nature.
  • acidifying additives and organic activators to increase the performance of the peracid in amounts of 0 to 20 wt .-%, in particular in amounts of 1 to 10 wt .-%, based on the total weight, added, metal complexes in concentrations in the ppm range.
  • the co-granules according to the invention are distinguished by a very good storage stability in pulverulent washing, cleaning and disinfectant formulations. They are ideal for use in heavy-duty detergents, stain salts, machine dishwashing detergents, powdered all-purpose cleaners and denture cleaners.
  • the co-granules according to the invention are used in combination with a source of hydrogen peroxide.
  • a source of hydrogen peroxide examples include perborate monohydrate, perborate tetrahydrate, percarbonates, alkali persulfates, persilicates and percitrates, with sodium being the preferred alkali metal, as well as hydrogen peroxide adducts of urea or amine oxides.
  • peroxycarboxylic acids for example dodecanedioic acid or phthalimidopercarboxylic acids, which may optionally be substituted on the aromatic, may be present.
  • Bleach stabilizers such as phosphonates, borates, or metaborates and metasilicates, and magnesium salts such as magnesium sulfate may be advantageous.
  • formulation according to the prior art may comprise other detergent ingredients such as surfactants of nonionic, anionic, cationic or amphoteric nature, organic and inorganic builders and co-builders, enzymes, bleach activators, bleach catalysts, salts, optical brighteners, grayness inhibitors, foam inhibitors, sequestering agents and Fragrances and dyes.
  • surfactants of nonionic, anionic, cationic or amphoteric nature organic and inorganic builders and co-builders, enzymes, bleach activators, bleach catalysts, salts, optical brighteners, grayness inhibitors, foam inhibitors, sequestering agents and Fragrances and dyes.
  • Preferred nonionic surfactants are fatty alcohol ethoxylates containing from about 1 to about 25 moles of ethylene oxide.
  • the alkyl chain of the aliphatic alcohols may be linear or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols containing an alkyl chain of 10 to 20 carbons with 2 to 18 moles of ethylene oxide per mole of alcohol.
  • the alkyl chain can be saturated or unsaturated.
  • the alcohol ethoxylates may have a narrow homolog distribution of the ethylene oxide ("narrow range ethoxylates") or a broad homolog distribution of the ethylene oxide ("broad range ethoxylates").
  • nonionic surfactants of this type are Tergitol TM 15-S-9 (condensation product of a C11-C15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol TM 24-L-NMW (condensation product of a C 12 -C 14 linear primary alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution). Also included in this product class are the Genapol TM brands from Clariant GmbH.
  • nonionic surfactants in question such as polyethylene, polypropylene, polybutylene and Polypentylenoxidaddukte of fatty alcohols having 8-22 carbon atoms and alkylphenols having 6 to 12 carbon atoms in the alkyl chain, addition products of ethylene oxide with a hydrophobic base formed from the condensation of propylene oxide with propylene glycol or addition products of ethylene oxide with a reaction product of propylene oxide and ethylenediamine.
  • Suitable amine oxides are in particular C 10 -C 18 -alkyldimethylamine oxides and C 8 -C 12 -alkoxyethyl-dihydroxyethylamine oxides.
  • Suitable anionic surfactants are, in particular, straight-chain and branched alkyl sulfates, sulfonates, carboxylates, phosphates, alkyl ester sulfonates, arylalkyl sulfonates, alkyl ether sulfates and mixtures of the abovementioned compounds. In the following, some of the candidate types of anionic surfactants will be described in more detail.
  • Alkyl ester sulfonates are linear esters of C 8 -C 20 carboxylic acids (ie, fatty acids) which are sulfonated by SO 3 as described in U.S. Pat. The Journal of the American Oil Chemists Society, 52 (1975), pp. 323-329 described.
  • Suitable starting materials are natural fatty derivatives, such as tallow or palm oil fatty acid.
  • Alkyl sulfates are water-soluble salts or acids of the formula ROSO 3 M, wherein R preferably has a C 10 -C 24 -hydrocarbon radical, preferably an alkyl or hydroxyalkyl radical having 10 to 20 C atoms, particularly preferably a C 12 -C 18 -alkyl or Represents hydroxyalkyl.
  • M is hydrogen or a cation, for example an alkali metal cation (eg sodium, potassium, lithium) or ammonium or substituted ammonium, for example a methyl, dimethyl and trimethylammonium cation or a quaternary ammonium cation, such as tetramethylammonium and dimethylpiperidinium cation and quaternary ammonium cations, derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof.
  • Alkyl chains with C 12 -C 16 are preferred for low washing temperatures (eg below about 50 ° C) and alkyl chains with C 16 -C 18 preferably for higher washing temperatures (eg above about 50 ° C).
  • the alkyl ether sulfates are water-soluble salts or acids of the formula RO (A) m SO 3 M, where R is an unsubstituted C 10 -C 24 -alkyl or hydroxyalkyl radical with 10 to 24 carbon atoms, preferably a C 12 -C 20 -alkyl or hydroxyalkyl radical, more preferably a C 12 -C 18 -alkyl or hydroxyalkyl radical.
  • A is an ethoxy or propoxy moiety
  • m is a number greater than 0, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3
  • M is a hydrogen atom or a cation such as for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium, or a substituted ammonium cation.
  • substituted ammonium cations are methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, as well as those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like.
  • C 12 -C 18 -alkyl polyethoxylate (1.0) sulfate, C 12 -C 18 -alkyl polyethoxylate (2,25) sulfate, C 12 -C 18 -alkyl polyethoxylate (3, 0) sulfate, C 12 -C 18 alkyl polyethoxylate (4.0) sulfate, wherein the cation is sodium or potassium.
  • anionic surfactants useful in detergents and cleaners are C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of pyrolysis products of alkaline earth metal citrates, as described, for example, in US Pat British Patent GB 1,082,179 , Alkyl glycerol sulfates, fatty acyl glycerol sulfates, oleyl glycerol sulfates, alkyl phenol ether sulfates, linear or branched alkyl benzene sulfonates, primary and secondary paraffin sulfonates, alkyl phosphates, alkyl ether phosphates, isethionates such as acyl isethionates, N-acyl taurides, alkyl succinamates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and uns
  • Monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 12 -C 18 diesters), acyl sarcosinates, sulfates of alkyl polysaccharides such as sulfates of alkyl polyglycosides, branched primary alkyl sulfates and alkyl polyethoxycarboxylates such as those of the formula RO (CH 2 CH 2 ) k CH 2 COO - M + wherein R is a C 8 -C 22 alkyl, k is a number from 0 to 10 and M is a soluble salt-forming cation.
  • Resin acids or hydrogenated resin acids such as rosin or hydrogenated rosin or tall oil resins and tall oil rosin acids are also useful. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A variety of such surfactants are also in U.S. Patent 3,929,678 claimed.
  • amphoteric surfactants which can be used in the formulations of the present invention are, above all, those which are broadly described as derivatives of aliphatic secondary and tertiary amines in which the aliphatic radical can be linear or branched and in which one of the aliphatic radicals Substituents containing from 8 to 18 carbon atoms and an anionic, water-soluble group, such as Carboxy, sulfonate, sulfate, phosphate or phosphonate contains.
  • Preferred amphoteric surfactants are monocarboxylates and dicarboxylates such as cocoamphocarboxypropionate, cocoamidocarboxypropionic acid, cocoamphocarboxyglycinate (also referred to as cocoamphodiacetate) and cocoamphoacetate.
  • amphoteric surfactants are alkyl dimethyl betaines, alkylamido betaines and alkyl dipolyethoxy betaines having an alkyl radical which may be linear or branched, having from 8 to 22 carbon atoms, preferably from 8 to 18 carbon atoms and more preferably from 12 to. 18 carbon atoms. These compounds are for example marketed by Clariant GmbH under the trade name Genagen ® CAB and LAB.
  • cationic surfactants are quaternary ammonium compounds, ester quats, ether quats, hydroxyethyl quats, ethoxylated quats, in particular quaternized fatty acid alkanolamine ester salts and dialkylaminopropylamine ester salts.
  • Suitable organic and inorganic builders are neutral or, in particular, alkaline salts which are able to precipitate or complex calcium ions.
  • Suitable and in particular ecologically acceptable builder substances such as fine-crystalline, synthetic hydrous zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g, find a preferred use.
  • sheet silicates and amorphous silicates are also preferred.
  • alkali metal phosphates which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • Trisodium phosphate Trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of 5 to 1000, in particular 5 to 50, and mixtures of sodium and potassium salts.
  • Useful organic builders are, for example, the carboxylic acids preferably used in the form of their sodium salts, such as citric acid, nitriloacetate (NTA) and ethylenediaminetetraacetic acid, if such use is unobjectionable for ecological reasons and phosphonic and polyphosphonic acids.
  • 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% maleic acid, as well as polyaspartic acid and also polyvinylpyrrolidone and urethanes.
  • the molecular weight of the homopolymers is generally between 1000 and 100,000, those of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid, in particular water-soluble polyacrylates are suitable, for example, about 1% of a Polyallylethers of sucrose are cross-linked and have a molecular weight above one million. Examples of these are the polymers available under the name Carbopol 940 and 941.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, pullinases, cutinases, and cellulases or mixtures thereof.
  • the enzymes can be adsorbed to carrier substances and / or embedded in encapsulating substances.
  • Suitable substances are those which carry O- and / or N-acyl groups and / or optionally benzoyl groups.
  • TAED polyacylated alkylenediamines
  • TAED acylated triazine derivatives
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU acylated glycolurils, in particular tetraacetylglycoluril
  • N-acylimides especially N-nonanoylsuccinimide (NOSI )
  • Carboxylic acid anhydrides in particular phthalic anhydride
  • acylated polyhydric alcohols in particular triacetin, ethylene glycol diacetate, 2,5-diacet
  • GAA glucose pentaacetate
  • TAX xylose tetraacetate
  • NOBS nonanoyloxybenzenesulfonate
  • SBOBS sodium 4-benzoyloxybenzenesulfonate
  • STHOBS sodium trimethylhexanoyloxybenzenesulfonate
  • TACA tetraacetylcyanoic acid
  • ADMG di-N-acetyldimethylglyoxine
  • PAH 1-phenyl- 3-acetylhydantoin
  • APES nonanoyl-caprolactam phenylsulfonate ester
  • NOPS nonanoylphenylsulphonate ester
  • NTA nitrilotriacetate
  • quaternary ammonium nitrile compounds quaternary ammonium nitrile compounds.
  • the detergent formulations may also include EP 446 982 and EP 453 003 contain known sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts.
  • salts or adjusting agents for example, sodium sulfate, sodium carbonate or sodium silicate (water glass) are used.
  • Further constituents of the detergent formulation may be optical brighteners, for example derivatives of diaminostilbene disulfonic acid or its alkali metal salts and foam inhibitors such as fatty acid alkyl ester alkoxylates, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and their mixtures with silanated silica. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicone oil, paraffin oil or waxes.
  • foam inhibitors are to a granular, in water soluble or dispersible carrier substance bound.
  • the salts of polyphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), ethylenediamine tetramethylene phosphonic acid (EDTMP) and diethylene triamine pentamethylene phosphonic acid (DTPMP) can be added.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • ETMP ethylenediamine tetramethylene phosphonic acid
  • DTPMP diethylene triamine pentamethylene phosphonic acid
  • further additives are sodium borate, cellulose and starch and their ethers or esters, sucrose, polydextrose and polymeric additives.
  • a ploughshare mixer FKM 130 D Lödige, 18.6 kg of tetraacetylethylenediamine (TAED) and 1.4 kg of carboxymethylcellulose (CMC) were intensively mixed at a mixing tool speed of 135 rpm for a period of 5 minutes. Subsequently, in the same ploughshare mixer at a mixing tool speed of 135 rpm and a rotating cutter head in the middle part of the mixer at a speed of 2800 rpm, an aqueous solution consisting of 2.0 kg N, N, N was added to this powder premix.
  • TAED tetraacetylethylenediamine
  • CMC carboxymethylcellulose
  • Trimethyl (N-nitrilomethyl) ammonium methosulfate 0.5 kg partially neutralized copolymer of acrylic acid and maleic acid, 2.4 kg of cumene sulfonate and 5.1 kg of water at a temperature of 75 ° C over a period of 10 min directly metered onto the cutter head and then mixed for a further 2 min and granulated.
  • the moist granules were then transferred to a fluidized bed dryer and dried with gas inlet temperatures of 100 ° C to a residual water content of 2%.
  • the coarse fraction (7.6 kg over 1400 ⁇ ) from the first pass was ground with a FitzMill and, together with the fine fraction (10.9 kg under 500 ⁇ ) from the 1st pass and 5.4 kg fresh TAED / CMC. (93: 7)
  • Trimethyl (N-nitrilomethyl) ammonium methosulfate 0.5 kg partially neutralized copolymer of acrylic acid and maleic acid, 2.4 kg of cumene sulfonate and 5.1 kg of water at a temperature of 75 ° C over a period of 10 min directly metered onto the cutter head and then mixed for a further 2 min and granulated.
  • the moist granules were then transferred to a fluidized bed dryer and dried with gas inlet temperatures of 100 ° C to a residual water content of 2%. This gave 7.8 kg of granules with a particle size distribution of 500-1400 ⁇ and 12.9 kg fines ⁇ 500 microns and 8.6 kg coarse fraction> 1400 ⁇ .
  • the granules with the grain size of 500 - 1400 ⁇ has a bulk density of about 495 g / l.
  • the coarse fraction (8.6 kg over 1400 ⁇ ) from the 2nd pass was ground with a FitzMill and, together with the fine fraction (12.9 kg under 500 ⁇ ) from the second pass and 5.4 kg fresh TAED / CMC. (93: 7)
  • the moist granules were then transferred to a fluidized bed dryer and dried with gas inlet temperatures of 100 ° C to a residual water content of 2%.
  • the coarse fraction (9.7 kg over 1400 ⁇ ) from the 3rd run was ground with a FitzMill and, together with the fines (14.2 kg under 500 ⁇ ) from the 3rd run and 5.4 kg fresh TAED / CMC (93: 7)
  • an aqueous solution consisting of 2.0 kg N, N, N was added to this powder premix.
  • Trimethyl (N-nitrilomethyl) ammonium methosulfate 0.5 kg partially neutralized copolymer of acrylic acid and maleic acid, 2.4 kg of cumene sulfonate and 5.1 kg of water at a temperature of 75 ° C over a period of 10 min directly metered onto the cutter head and then mixed for a further 2 min and granulated.
  • the moist granules were then transferred to a fluidized bed dryer and dried with gas inlet temperatures of 100 ° C to a residual water content of 2%. This gave 9.3 kg granules with a particle size distribution of 500- 1400 ⁇ and 14.9 kg fines ⁇ 500 microns and 10.2 kg coarse fraction> 1400 ⁇ .
  • the granules with the particle size of 500 - 1400 ⁇ has a bulk density of about 510 g / l.
  • Nitrilquat spray powder consisting of 7.44 kg of N, N, N-trimethyl (N-nitrilomethyl) ammonium methosulfate, 8.93 kg of cumene sulfonate, 1, 86 kg of partially neutralized copolymer of acrylic acid and maleic acid and 0.37 kg of water
  • CMC carboxymethylcellulose
  • a ploughshare mixer FKM 130 D Lödige, 18.6 kg of tetraacetylethylenediamine (TAED) and 1.55 kg of carboxymethylcellulose (CMC) were intensively mixed at a mixing tool speed of 135 rpm for a period of 5 minutes. Subsequently, in the same ploughshare mixer with a mixing tool speed of 135 rpm and switched on, rotating cutter head in the middle part of the mixer at a speed of 2800 U / min on this powder premix 3.5 kg of water over a period of 10 min directly on The knife head is metered in and then mixed for a further 2 min and granulated.
  • TAED tetraacetylethylenediamine
  • CMC carboxymethylcellulose
  • the moist granules were then transferred to a fluidized bed dryer and dried with gas inlet temperatures of 100 ° C to a residual water content of 2%. 5.8 kg of granules having a particle size distribution of 500-1400 ⁇ m and 11.8 kg of fine fraction ⁇ 500 ⁇ m and 3.0 kg of coarse fraction> 1400 ⁇ m were obtained.
  • the granules with the grain size of 500 - 1400 microns has a bulk density of about 470 g / l.
  • the Petri dishes filled as described above were then stored open in a climatic cabinet at a temperature of 38 ° C and a relative humidity of 80% for 5 days. After a storage time of 1, 2 and 5 days, the residual content of activator was determined by iodometric titration and set in percent relative to the initial content used. Storage time [days] TAED / nitrile quat / CMC TAED / CMC + nitrile quat / CMC 0 100% 100% 1 89% 81% 2 78% 66% 5 46% 32%
  • the TAED / nitrile quat / CMC co-granulate according to the invention has a better storage stability than a mixture of TAED / CMC granules and nitrile quat / CMC granules with similar overall composition.
  • the TAED / nitrile quat / CMC-co-granules according to the invention absorb less water in the same storage period than a mixture of TAED / CMC granules and nitrile quat / CMC granules with similar overall composition.
  • the TAED / nitrile quat / CMC co-granulate according to the invention after storage in a detergent formulation, achieves better bleaching performance at 20 ° C. and 40 ° C. than a mixture of TAED / CMC granules stored in a detergent formulation over the same period of time and nitrile quat / CMC granules of similar overall composition.

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Claims (14)

  1. Procédé de fabrication de cogranulés d'activateur de blanchiment constitué d'un ou plusieurs nitriles d'ammonium et d'au moins un autre activateur de blanchiment,
    caractérisé en ce qu'
    on pulvérise une solution aqueuse d'un ou plusieurs nitriles d'ammonium sur l'autre activateur de blanchiment, on granule le mélange obtenu et on sèche et tamise le granulé humide.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on fabrique les granulés qui contiennent, comme nitriles d'ammonium, des composés de formule (1)
    Figure imgb0007
     dans laquelle R1, R2, R3 sont identiques ou différents et représentent des groupes alkyle en C1 à C24 linéaires ou ramifiés, des groupes alcényle en C2 à C24 ou des groupes alcoxy en C1 à C4-alkyle en C1 à C4, un groupe benzyle substitué ou non substitué, ou dans laquelle R1 et R2 forment avec l'atome d'azote, sur lequel ils sont liés, un cycle comportant de 4 à 6 atomes de C, qui peut être substitué par un groupe alkyle en C1 à C5, alcoxy en C1 à C5, alcanoyle en C1 à C5, phényle, amino, ammonium, cyano, cyanamino, chlore ou brome et peuvent contenir, en plus de l'atome d'azote, à la place des atomes de carbone, un ou deux atomes d'oxygène ou d'azote, un groupe N-R6 ou un groupe R3-N-R6, R6 étant un atome d'hydrogène, un groupe alkyle en C1 à C5, un groupe alcényle en C2 à C5, alcynyle en C2 à C5, phényle, aralkyle en C7 à C9, cycloalkyle en C5 à C7, alcanoyle en C1 à C6, cyanométhyle ou cyan, R4 et R5 représentant un atome d'hydrogène, un groupe alkyle en C1 à C4, alcényle en C1 à C4, alcoxy en C1 à C4-alkyle en C1 à C4, phényle ou alkylphényle en C1 à C3, de préférence un atome d'hydrogène, un groupe méthyle ou phényle, en particulier R4 représentant un atome d'hydrogène lorsque R5 ne représente pas un atome d'hydrogène, et A représente un anion, par exemple un chlorure, un bromure, un iodure, un fluorure, un sulfate, un hydrogénosulfate, un carbonate, un hydrogénocarbonate, un phosphate, un mono et dihydrogénophosphate, un pyrophosphate, un métaphosphate, un nitrate, un sulfate de méthyle, un phosphonate, un phosphonate de méthyle, un disulfonate de méthane, un sulfonate de méthyle, un sulfonate d'éthane ou bien un anion des formules R7SO3 e, R7SO4 e ou R7COOe, dans lesquelles R7 représente un groupe alkyle en C1 à C20, de préférence un groupe alkyle en C10 à C18 et, en plus aussi un groupe alkylphényle en C1 à C18.
  3. Procédé selon la revendication 1, caractérisé en ce qu'on fabrique les granulés contenant, comme nitrile d'ammonium, un composé de formule (2)
    Figure imgb0008
     dans laquelle R1, R2 et R3 représentent un groupe alkyle linéaire ou ramifié, saturé ou insaturé comportant de 1 à 24 atomes de carbone, un groupe alcényle comportant de 2 à 24 atomes de carbone ou un groupe benzyle substitué ou non substitué et A représente un ion quelconque équilibrant la charge, par exemple un chlorure, un bromure, un iodure, un fluorure, un sulfate, un hydrogénosulfate, un carbonate, un hydrogénocarbonate, un phosphate, un mono et dihydrogénophosphate, un pyrophosphate, un métaphosphate, un nitrate, un sulfate de méthyle, un phosphonate, un phosphonate de méthyle, un disulfonate de méthane, un sulfonate de méthyle, un sulfonate d'éthane ou bien représente un anion des formules R7SO3 e, R7SO4 e ou R7COOe, dans lesquelles R7 a les mêmes significations que ci-dessus.
  4. Procédé selon la revendication 1, caractérisé en ce qu'
    on fabrique les granulés qui contiennent, en plus, de la N,N,N',N'-tétraacétyléthylènediamine (TAED), de l'ester de sulfonate de nonanoyle-caprolactame-phényle (APES), du pentaacétate de glucose (GPA), du tétraacétate de xylose (TAX), des sulfonates d'acyloxybenzène, de la diacétyldioxohexahydrotriazine (DADHT), du glucolurile tétraacétylé (TAGU), de l'acide cyanique tétraacétylé (TACA), la di-N-acétyldiméthylglyoxine (ADMG) et de la 1-phényl-3-acétylhydantoïne (PAH) ou du nitrilotriacétate (NTA).
  5. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent un ou plusieurs liants et/ou un ou plusieurs additifs acides.
  6. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent, en plus de la cellulose et/ou de l'amidon ainsi que leurs éthers ou esters, et/ou des polymères filmogènes et/ou des composants anioniques du groupe des sulfonates d'alcane, des sulfonates d'aryle, des sulfonates d'alkylaryle, des éthersulfates d'alkyle, des sulfates d'alkyle, des sulfonates d'alpha-oléfine et des savons, en tant que liant.
  7. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent de 1 à 45 % en poids d'un ou plusieurs liants par rapport au cogranulé total.
  8. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent de l'acide sulfurique, de l'hydrogénosulfate de sodium, de l'acide phosphorique, de l'hydrogénophosphate de sodium, des acides phosphoniques et des acides polyphosphoniques et/ou leurs sels, des acides carboxyliques et/ou leurs sels, de l'acide glycolique, de l'acide succinique, de l'anhydride de l'acide succinique, de l'acide glutarique, de l'anhydride de l'acide glutarique, de l'acide adipique, de l'anhydride de l'acide adipique, de l'acide maléique, de l'anhydride de l'acide maléique et/ou de l'acide lactique et/ou des polymères acides en tant qu'additif acide.
  9. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent en plus de 0 à 20 % en poids d'un ou plusieurs additifs acides par rapport au cogranulé total.
  10. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent de 50 à 99 % en poids d'activateur de blanchiment, par rapport au cogranulé total.
  11. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent de 70 à 98 % en poids d'activateur de blanchiment, par rapport au cogranulé total.
  12. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui contiennent de 80 à 96 % en poids d'activateur de blanchiment par rapport au cogranulé total.
  13. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés qui sont enveloppés de 0 à 30 % en poids d'une substance filmogène.
  14. Procédé selon la revendication 1,
    caractérisé en ce qu'
    on fabrique les granulés que l'on compresse en agglomérats plus gros pour augmenter la densité apparente et que l'on broie ensuite.
EP02027051A 2001-12-15 2002-12-03 Cogranules d'activateur de blanchiment Expired - Lifetime EP1319705B1 (fr)

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DE10161766A DE10161766A1 (de) 2001-12-15 2001-12-15 Bleichaktivator-Co-Granulate
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